U.S. patent application number 13/640911 was filed with the patent office on 2013-05-02 for particles, particle dispersion, particle-dispersed resin composition, producing method therefor, resin molded article, producing method therefor, catalyst particles, catalyst solution, catalyst composition, catalyst molded article, titanium complex, titanium oxide particles and producing method ther.
This patent application is currently assigned to NITTO DENKO CORPORATION. The applicant listed for this patent is Takahiro Fukuoka, Saori Fukuzaki, Yoshiharu Hatakeyama, Junichi Nagase, Tatsuki Nagatsuka, Shusaku Shibata. Invention is credited to Takahiro Fukuoka, Saori Fukuzaki, Yoshiharu Hatakeyama, Junichi Nagase, Tatsuki Nagatsuka, Shusaku Shibata.
Application Number | 20130109770 13/640911 |
Document ID | / |
Family ID | 45323843 |
Filed Date | 2013-05-02 |
United States Patent
Application |
20130109770 |
Kind Code |
A1 |
Hatakeyama; Yoshiharu ; et
al. |
May 2, 2013 |
PARTICLES, PARTICLE DISPERSION, PARTICLE-DISPERSED RESIN
COMPOSITION, PRODUCING METHOD THEREFOR, RESIN MOLDED ARTICLE,
PRODUCING METHOD THEREFOR, CATALYST PARTICLES, CATALYST SOLUTION,
CATALYST COMPOSITION, CATALYST MOLDED ARTICLE, TITANIUM COMPLEX,
TITANIUM OXIDE PARTICLES AND PRODUCING METHOD THEREFOR
Abstract
Organic-inorganic composite particles that can be dispersed in a
solvent and/or a resin as primary particles having an organic group
on the surface of inorganic particles, the organic-inorganic
composite particles having negative birefringence.
Inventors: |
Hatakeyama; Yoshiharu;
(Osaka, JP) ; Fukuoka; Takahiro; (Osaka, JP)
; Nagase; Junichi; (Osaka, JP) ; Shibata;
Shusaku; (Osaka, JP) ; Nagatsuka; Tatsuki;
(Osaka, JP) ; Fukuzaki; Saori; (Osaka,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Hatakeyama; Yoshiharu
Fukuoka; Takahiro
Nagase; Junichi
Shibata; Shusaku
Nagatsuka; Tatsuki
Fukuzaki; Saori |
Osaka
Osaka
Osaka
Osaka
Osaka
Osaka |
|
JP
JP
JP
JP
JP
JP |
|
|
Assignee: |
NITTO DENKO CORPORATION
Ibaraki-shi, Osaka
JP
|
Family ID: |
45323843 |
Appl. No.: |
13/640911 |
Filed: |
April 11, 2011 |
PCT Filed: |
April 11, 2011 |
PCT NO: |
PCT/JP2011/059040 |
371 Date: |
December 31, 2012 |
Current U.S.
Class: |
521/61 ; 106/447;
106/463; 502/150; 502/159; 502/162; 521/189; 524/131; 524/287;
524/300; 534/15; 554/1; 556/19; 556/51; 562/496 |
Current CPC
Class: |
C07F 5/00 20130101; C08K
9/04 20130101; C01F 11/183 20130101; C07F 5/003 20130101; B01J
2531/66 20130101; B01J 31/38 20130101; C07F 3/003 20130101; C07F
19/00 20130101; B01J 2531/46 20130101; B01J 31/2221 20130101; B01J
2231/005 20130101; B01J 31/28 20130101; B01J 31/2208 20130101; C07F
7/28 20130101; B01J 31/26 20130101; B01J 31/06 20130101; C07F 3/00
20130101 |
Class at
Publication: |
521/61 ; 502/150;
502/162; 502/159; 106/447; 106/463; 524/300; 524/287; 524/131;
521/189; 534/15; 562/496; 554/1; 556/19; 556/51 |
International
Class: |
C07F 3/00 20060101
C07F003/00; C07F 7/28 20060101 C07F007/28; C07F 19/00 20060101
C07F019/00; B01J 31/38 20060101 B01J031/38; C07F 5/00 20060101
C07F005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 12, 2010 |
JP |
2010-091577 |
Jul 30, 2010 |
JP |
2010-172309 |
Jul 30, 2010 |
JP |
2010-172310 |
Apr 8, 2011 |
JP |
2011-086371 |
Apr 8, 2011 |
JP |
2011-086701 |
Apr 8, 2011 |
JP |
2011-086803 |
Claims
1-10. (canceled)
11. Organic-inorganic composite particles that can be dispersed in
a solvent and/or a resin as primary particles having an organic
group on the surface of inorganic particles, the organic-inorganic
composite particles having negative birefringence.
12. The particles according to claim 11, wherein the inorganic
particles comprise a carbonate containing an alkaline earth metal
and/or a composite oxide containing an alkaline earth metal.
13. The particles according to claim 11, wherein the primary
particles are obtained by surface-treating the inorganic particles
with an organic compound, and the organic compound contains a
binding group capable of binding to the surface of the inorganic
particles and a hydrophobic group and/or a hydrophilic group
serving as the organic group.
14. The particles according to claim 11, having an aspect ratio of
1000 or less.
15. The particles according to claim 11, having a maximum length of
200 .mu.m or less.
16. The particles according to claim 11, obtained by hydrothermal
synthesis.
17. The particles according to claim 16, wherein an inorganic
compound for forming inorganic particles and the organic compound
are subjected to a hydrothermal synthesis.
18. The particles according to claim 16, wherein a metal hydroxide
containing an alkaline earth metal, a carbonic acid source and the
organic compound are subjected to a hydrothermal synthesis.
19. The particles according to claim 18, wherein the carbonic acid
source is formic acid and/or urea.
20. The particles according to claim 16, wherein a metal hydroxide
containing an alkaline earth metal, a metal complex and the organic
compound are subjected to a hydrothermal synthesis.
21. The particles according to claim 16, wherein the hydrothermal
synthesis is performed in the presence of a pH adjusting agent.
22. The particles according to claim 11, obtained by subjecting an
inorganic compound for forming inorganic particles to a high
temperature treatment in an organic compound containing the organic
group.
23. The particles according to claim 11, subjected to wet
classification using the solvent.
24. A particle dispersion comprising a solvent and particles that
are dispersed as primary particles in the solvent, wherein the
particles are organic-inorganic composite particles having an
organic group on the surface of inorganic particles and have
negative birefringence.
25. A particle-dispersed resin composition comprising a resin and
particles that are dispersed as primary particles in the resin,
wherein the particles are organic-inorganic composite particles
having an organic group on the surface of inorganic particles and
have negative birefringence.
26. A resin molded article formed of a particle-dispersed resin
composition comprising a resin and particles that are dispersed as
primary particles in the resin, wherein the particles are
organic-inorganic composite particles having an organic group on
the surface of inorganic particles and have negative
birefringence.
27. The resin molded article according to claim 26, being an
optical film.
28. A particle-dispersed resin composition comprising a resin and
organic-inorganic composite particles having an organic group on
the surface of inorganic particles, wherein the organic-inorganic
composite particles have at least a configuration that does not
allow the inorganic particles to contact with each other by steric
hindrance of the organic group and are dispersed as primary
particles in the resin.
29. The particle-dispersed resin composition according to claim 28,
wherein the resin has a functional group, and the organic group and
the functional group both have a hydrophilic group or a hydrophobic
group.
30. The particle-dispersed resin composition according to claim 28,
wherein the resin contains a highly oriented resin.
31. The particle-dispersed resin composition according to claim 28,
wherein the organic group contains a plurality of homologous
organic groups.
32. The particle-dispersed resin composition according to claim 28,
wherein the organic group contains a plurality of heterologous
organic groups.
33. A particle-dispersed resin molded article molded from a
particle-dispersed resin composition comprising a resin and
organic-inorganic composite particles having an organic group on
the surface of inorganic particles, wherein the organic-inorganic
composite particles have at least a configuration that does not
allow the inorganic particles to contact with each other by steric
hindrance of the organic group and are dispersed as primary
particles in the resin.
34. A method for producing a particle-dispersed resin composition,
the method comprising: blending a resin and organic-inorganic
composite particles having an organic group on the surface of
inorganic particles such that the organic-inorganic composite
particles are dispersed as primary particles in the resin by steric
hindrance of the organic group.
35. The method for producing a particle-dispersed resin composition
according to claim 34, wherein the organic-inorganic composite
particles are produced in a hot solvent.
36. The method for producing a particle-dispersed resin composition
according to claim 34, wherein the organic-inorganic composite
particles are produced in hot high pressure water.
37. A method for producing a particle-dispersed resin molded
article, the method comprising: producing a particle-dispersed
resin molded article by molding a particle-dispersed resin
composition obtained by blending a resin and organic-inorganic
composite particles having an organic group on the surface of
inorganic particles such that the organic-inorganic composite
particles are dispersed as primary particles in the resin by steric
hindrance of the organic group.
38. Catalyst particles comprising inorganic particles with a
catalytic action and an organic group that binds to the surface of
the inorganic particles, and having a configuration that does not
allow the inorganic particles to contact with each other by steric
hindrance of the organic group.
39. The catalyst particles according to claim 38, having a
catalytic action for a gas and/or a liquid.
40. The catalyst particles according to claim 38, having a
photocatalytic action for a gas and/or a liquid.
41. The catalyst particles according to claim 38, dispersed as
primary particles in a solvent and/or a resin.
42. The catalyst particles according to claim 38, containing a
plurality of mutually different types of organic groups.
43. The catalyst particles according to claim 38, wherein the
organic group is bound to the surface of the inorganic particles
via a binding group, and the binding group contains a phosphoric
acid group and/or a phosphoric acid ester group.
44. The catalyst particles according to claim 38, wherein the
inorganic particles contain an oxide.
45. The catalyst particles according to claim 38, wherein the
inorganic particles contain at least one oxide selected from the
group consisting of TiO.sub.2, WO.sub.3 and SrTiO.sub.3.
46. The catalyst particles according to claim 45, wherein the
inorganic particles further contain at least one inorganic
substance selected from the group consisting of Pt, Pd, Cu, CuO,
RuO.sub.2 and NiO.
47. The catalyst particles according to claim 38, wherein the
catalyst particles have an average maximum length of 450 nm or
less.
48. The catalyst particles according to claim 38, obtained by
surface-treating an inorganic substance and/or a complex thereof
with an organic compound containing the organic group.
49. The catalyst particles according to claim 48, wherein the
inorganic substance and/or the complex are surface-treated with the
organic compound in hot high pressure water.
50. The catalyst particles according to claim 48, wherein the
inorganic substance and/or the complex are surface-treated in the
organic compound heated to a high temperature.
51. A catalyst solution comprising a solvent and catalyst particles
dispersed in the solvent, wherein the catalyst particles contain
inorganic particles with a catalytic action and an organic group
that binds to the surface of the inorganic particles, and the
catalyst particles have a configuration that does not allow the
inorganic particles to contact with each other by steric hindrance
of the organic group.
52. A catalyst composition comprising a resin and catalyst
particles dispersed in the resin, wherein the catalyst particles
contain inorganic particles with a catalytic action and an organic
group that binds to the surface of the inorganic particles, and the
catalyst particles have a configuration that does not allow the
inorganic particles to contact with each other by steric hindrance
of the organic group.
53. A catalyst molded article formed of a catalyst composition
comprising a resin and catalyst particles dispersed in the resin,
wherein the catalyst particles contain inorganic particles with a
catalytic action and an organic group that binds to the surface of
the inorganic particles, and the catalyst particles have a
configuration that does not allow the inorganic particles to
contact with each other by steric hindrance of the organic
group.
54. The catalyst molded article according to claim 53, being an
optical film.
55. A resin molded article having micropores formed by removing
organic-inorganic composite particles from a particle-containing
resin molded article comprising a resin and the organic-inorganic
composite particles that comprises inorganic particles and an
organic group that binds to the surface of the inorganic particles
and having a configuration that does not allow the inorganic
particles to contact with each other by steric hindrance of the
organic group.
56. The resin molded article according to claim 55, wherein the
organic-inorganic composite particles have an average maximum
length of 400 nm or less.
57. The resin molded article according to claim 55, wherein in the
particle-containing resin molded article, the organic-inorganic
composite particles are dispersed as primary particles in the
resin.
58. The resin molded article according to claim 55, wherein the
particle-containing resin molded article has a phase separated
structure formed of a resin phase composed of the resin and a
particle phase that is composed of the organic-inorganic composite
particles and phase-separated from the resin phase.
59. The resin molded article according to claim 58, wherein the
phase separated structure is a bicontinuous phase separated
structure in which the particle phase is three-dimensionally
continuous.
60. The resin molded article according to claim 55, wherein the
organic-inorganic composite particles partially remain.
61. The resin molded article according to claim 60, wherein the
proportion of remaining organic-inorganic composite particles
increases toward one side of the resin molded article.
62. The resin molded article according to claim 55, wherein the
organic group contains a plurality of mutually different organic
groups.
63. A method for producing a resin molded article, the method
comprising the steps of: preparing organic-inorganic composite
particles that comprise inorganic particles and an organic group
that binds to the surface of the inorganic particles and having a
configuration that does not allow the inorganic particles to
contact with each other by steric hindrance of the organic group;
blending the organic-inorganic composite particles with a resin so
as to prepare a particle-containing resin composition and forming a
particle-containing resin molded article from the
particle-containing resin composition; and forming micropores
formed by removing the organic-inorganic composite particles from
the particle-containing resin molded article.
64. The method for producing a resin molded article according to
claim 63, wherein the step of preparing organic-inorganic composite
particles involves surface-treating an inorganic material with an
organic compound in hot high pressure water.
65. The method for producing a resin molded article according to
claim 63, wherein the step of preparing organic-inorganic composite
particles involves surface-treating an inorganic material in a hot
organic compound.
66. A titanium complex comprising a titanium atom as a central atom
and a hydroxycarboxylic acid having a total of 7 or more carbon
atoms as a ligand.
67. The titanium complex according to claim 66, wherein the
hydroxycarboxylic acid is a hydroxyalkanoic acid having a total of
7 or more carbon atoms.
68. The titanium complex according to claim 67, wherein the
hydroxyalkanoic acid is linear.
69. The titanium complex according to claim 66, wherein the
hydroxycarboxylic acid is a hydroxymonocarboxylic acid.
70. The titanium complex according to claim 66, wherein the
hydroxycarboxylic acid is a monohydroxycarboxylic acid.
71. The titanium complex according to claim 66, wherein the
hydroxycarboxylic acid has a total of 13 or fewer carbon atoms.
72. The titanium complex according to claim 66, wherein the
hydroxycarboxylic acid is 2-hydroxycarboxylic acid and/or
3-hydroxycarboxylic acid.
73. Titanium oxide particles obtained by treating a titanium
complex comprising a titanium atom as a central atom and a
hydroxycarboxylic acid having a total of 7 or more carbon atoms as
a ligand in hot high pressure water.
74. A method for producing titanium oxide particles including
treating a titanium complex comprising a titanium atom as a central
atom and a hydroxycarboxylic acid having a total of 7 or more
carbon atoms as a ligand in hot high pressure water.
Description
TECHNICAL FIELD
[0001] The present invention relates to particles, a particle
dispersion, a particle-dispersed resin composition and a resin
molded article, and more particularly to a particle dispersion, a
particle-dispersed resin composition and a resin molded article
that are for use in various applications including optical
applications, and particles that can be dispersed therein.
[0002] The present invention also relates to a particle-dispersed
resin composition, a particle-dispersed resin molded article, and
producing methods therefor.
[0003] The present invention also relates to catalyst particles, a
catalyst solution, a catalyst composition and a catalyst molded
article, and more particularly to catalyst particles, a catalyst
solution, a catalyst composition and a catalyst molded article that
have a catalytic action.
[0004] The present invention also relates to a resin molded article
and a producing method therefor.
[0005] The present invention also relates to a titanium complex,
titanium oxide particles and a producing method therefor, and more
particularly to a titanium oxide particle producing method, a
titanium complex that can be used in the producing method, and
titanium oxide particles prepared by the producing method.
BACKGROUND ART
[0006] It is conventionally known that nanometer-sized particles
(nanoparticles) are used in optical materials.
[0007] For example, a method has been proposed in which
organomodified fine particles are obtained by subjecting fine
particles of a metal oxide such as SiO.sub.2 or TiO.sub.2 and an
organic modifier to a hydrothermal synthesis (see, for example,
Patent Document 1 listed below).
[0008] Also, it is long known that oxides such as titanium oxide
exert a photocatalytic action.
[0009] For example, it is known that oxides such as titanium oxide,
strontium titanate and tungsten oxide decompose organic substances
by their photocatalytic action (see, for example, Non-Patent
Document 1 listed below).
[0010] It is also long known that porous resin obtained by
porosifying resin exhibits various physical properties due to
porosification, in addition to the physical properties inherent to
resin.
[0011] For example, a method has been proposed in which porous
polyimide resin is obtained by blending polyethylene glycol
dimethyl ether with a polyimide resin precursor so as to prepare a
mixed resin solution, forming a coating and then bringing the
coating into contact with hot high pressure carbon dioxide so as to
extract polyethylene glycol dimethyl ether (see, for example,
Patent Document 2 listed below).
[0012] The porous polyimide resin disclosed in Patent Document 2
has uniformly formed pores (cells), and the dielectric constant of
the porous polyimide resin is set lower than that of non-porous
polyimide resin.
[0013] It is also long known that titanium oxide particles for use
in various industrial products are prepared in organic solvents or
the like. Meanwhile, from a view point of reducing the
environmental load in recent years, various methods are being
studied to prepare titanium oxide particles in water, which imposes
little load to the environment as compared to organic solvents or
the like.
[0014] To produce such titanium oxide, for example, a titanium
oxide particle producing method has been proposed in which titanium
oxide particles are prepared by treating a titanium complex
containing glycolic acid as a ligand in hot high pressure water
(see, for example, Non-Patent Document 2 listed below).
CITATION LIST
Patent Documents
[0015] Patent Document 1: Japanese Unexamined Patent Publication
No. 2005-194148 [0016] Patent Document 2: Japanese Unexamined
Patent Publication No. 2003-26850
Non-Patent Documents
[0016] [0017] Non-Patent Document 1: Journal of Surface Science
Society of Japan, vol. 24, No. 1, pp. 13 to 18, 2003 [0018]
Non-Patent Document 2: Koji Tomita et al., "A Water-Soluble
Titanium Complex for the Selective Synthesis of Nanocrystalline
Brookite, Rutile, and Anatase by a Hydrothermal Method", Angewandte
Chemie Int. Ed., 2006, vol. 45, pp. 2378 to 2381
DISCLOSURE OF THE INVENTION
Problems to be Solved
[0019] Particles for use in the above-described applications are
required to have various characteristics, in addition to excellent
optical characteristics.
[0020] Also, depending on the combination of organomodified fine
particles and resin, a problem may arise in that the organomodified
particles coagulate.
[0021] Also, depending on the application and purpose of catalysts,
there are cases where after preparation of a catalyst resin
composition by blending the oxide proposed in Non-Patent Document 1
mentioned above with a resin, a molded article is formed of the
catalyst resin composition.
[0022] The molded article, however, is problematic in that it is
easily degraded by the catalytic action of the oxide because the
resin is in contact with the oxide in the molded article.
[0023] Also, there is another problem in that the oxide easily
coagulates in the resin during preparation of the resin
composition, resulting in poor clarity.
[0024] Meanwhile, in recent years, there is demand for porous resin
having small-sized pores (cells). To address this demand, for
example, attempts are made in which inorganic fine particles having
a small particle size are blended with resin, and thereafter the
inorganic fine particles are extracted.
[0025] However, blending inorganic fine particles with resin
results in coagulation of the inorganic fine particles in the
resin. Consequently, small-sized pores (cells) cannot be formed,
and thus the porous resin will be opaque. Furthermore, the
mechanical strength of the porous resin is insufficient and
flexibility is poor, as a result of which a problem arises in that
it is not possible to form a self-standing film.
[0026] Also, there is demand of wanting to design the arrangement
of pores (cells) in porous resin.
[0027] Normally, titanium oxide particles are white, but the
titanium oxide particles prepared by the titanium oxide particle
producing method disclosed in Non-Patent Document 2 described above
are colored (brown) due to a decomposition product of the ligand
(decomposition product of glycolic acid) of the titanium complex
that has been decomposed in hot high pressure water.
[0028] Also, in the case of preparing nano-sized titanium oxide
particles, it is very difficult to separate the titanium oxide
particles from the water-soluble ligand (glycolic acid) remaining
from the production of the titanium complex.
[0029] For this reason, in the case of using such titanium oxide
particles in optical applications, it is necessary to remove the
color of the titanium oxide particles (the decomposition product of
the ligand) and the residual ligand, which makes the titanium oxide
particle producing process complex.
[0030] A first object of the present invention is to provide
particles that have excellent optical characteristics and excellent
dispersibility, a particle dispersion, a particle-dispersed resin
composition and a resin molded article.
[0031] A second object of the present invention is to provide a
particle-dispersed resin composition that contains
organic-inorganic composite particles uniformly dispersed in a
resin, a particle-dispersed resin molded article, and producing
methods therefor.
[0032] A third object of the present invention is to provide
catalyst particles that have excellent dispersibility in a solvent
and/or a resin, a catalyst solution in which catalyst particles are
dispersed in a solvent and that has excellent clarity, and a
catalyst composition and a catalyst molded article in which
degradation of the resin is suppressed and that have excellent
clarity.
[0033] A fourth object of the present invention is to provide a
resin molded article that has excellent clarity and excellent
mechanical strength, and a producing method therefor.
[0034] A fifth object of the present invention is to provide a
titanium oxide particle producing method with which the
environmental load as well as coloring of titanium oxide particles
can be reduced, a titanium complex that can be used in the
producing method, and titanium oxide particles prepared by the
producing method.
Means for Solving the Problem
[0035] A first group of inventions for achieving the first object
is as follows.
[0036] Specifically, particles according to the present invention
are organic-inorganic composite particles that can be dispersed in
a solvent and/or a resin as primary particles having an organic
group on the surface of inorganic particles, the organic-inorganic
composite particles having negative birefringence.
[0037] Also, with the particles of the present invention, it is
preferable that the inorganic particles are composed of a carbonate
containing an alkaline earth metal and/or a composite oxide
containing an alkaline earth metal.
[0038] Also, with the particles of the present invention, it is
preferable that the primary particles are obtained by
surface-treating the inorganic particles with an organic compound,
and the organic compound contains a binding group capable of
binding to the surface of the inorganic particles and a hydrophobic
group and/or a hydrophilic group serving as the organic group.
[0039] Also, it is preferable that the particles of the present
invention have an aspect ratio of 1000 or less.
[0040] Also, it is preferable that the particles of the present
invention have a maximum length of 200 .mu.m or less.
[0041] Also, it is preferable that the particles of the present
invention are obtained by hydrothermal synthesis.
[0042] Also, with the particles of the present invention, it is
preferable that an inorganic compound for forming inorganic
particles and the organic compound are subjected to a hydrothermal
synthesis.
[0043] Also, with the particles of the present invention, it is
preferable that a metal hydroxide containing an alkaline earth
metal, a carbonic acid source and the organic compound are
subjected to a hydrothermal synthesis.
[0044] Also, with the particles of the present invention, it is
preferable that the carbonic acid source is formic acid and/or
urea.
[0045] Also, with the particles of the present invention, it is
preferable that a metal hydroxide containing an alkaline earth
metal, a metal complex and the organic compound are subjected to a
hydrothermal synthesis.
[0046] Also, with the particles of the present invention, it is
preferable that the hydrothermal synthesis is performed in the
presence of a pH adjusting agent.
[0047] Also, it is preferable that the particles of the present
invention are obtained by subjecting an inorganic compound for
forming inorganic particles to a high temperature treatment in an
organic compound containing the organic group.
[0048] Also, it is preferable that the particles of the present
invention are subjected to wet classification using the
solvent.
[0049] A particle dispersion according to the present invention
contains a solvent and particles that are dispersed as primary
particles in the solvent, and the particles are organic-inorganic
composite particles having an organic group on the surface of
inorganic particles and have negative birefringence.
[0050] A particle-dispersed resin composition according to the
present invention contains a resin and particles that are dispersed
as primary particles in the resin, and the particles are
organic-inorganic composite particles having an organic group on
the surface of inorganic particles and have negative
birefringence.
[0051] A resin molded article according to the present invention is
formed of a particle-dispersed resin composition containing a resin
and particles that are dispersed as primary particles in the resin,
and the particles are organic-inorganic composite particles having
an organic group on the surface of inorganic particles and have
negative birefringence.
[0052] Also, it is preferable that the resin molded article of the
present invention is an optical film.
[0053] A second group of inventions for achieving the second object
is as follows.
[0054] Specifically, a particle-dispersed resin composition
according to the present invention contains a resin and
organic-inorganic composite particles having an organic group on
the surface of inorganic particles, and the organic-inorganic
composite particles have at least a configuration that does not
allow the inorganic particles to contact with each other by steric
hindrance of the organic group and are dispersed as primary
particles in the resin.
[0055] Also, with the particle-dispersed resin composition of the
present invention, it is preferable that the resin has a functional
group, and the organic group and the functional group both have a
hydrophilic group or a hydrophobic group.
[0056] Also, with the particle-dispersed resin composition of the
present invention, it is preferable that the resin contains a
highly oriented resin.
[0057] Also, with the particle-dispersed resin composition of the
present invention, it is preferable that the organic group contains
a plurality of homologous organic groups.
[0058] Also, with the particle-dispersed resin composition of the
present invention, it is preferable that the organic group contains
a plurality of heterologous organic groups.
[0059] A particle-dispersed resin molded article according to the
present invention is molded from a particle-dispersed resin
composition containing a resin and organic-inorganic composite
particles having an organic group on the surface of inorganic
particles, and the organic-inorganic composite particles have at
least a configuration that does not allow the inorganic particles
to contact with each other by steric hindrance of the organic group
and are dispersed as primary particles in the resin.
[0060] A method for producing a particle-dispersed resin
composition according to the present invention includes blending a
resin and organic-inorganic composite particles having an organic
group on the surface of inorganic particles such that the
organic-inorganic composite particles are dispersed as primary
particles in the resin by steric hindrance of the organic
group.
[0061] With the method for producing a particle-dispersed resin
composition of the present invention, it is preferable that the
organic-inorganic composite particles are produced in a hot
solvent. It is also preferable that the organic-inorganic composite
particles are produced in hot high pressure water.
[0062] A method for producing a particle-dispersed resin molded
article according to the present invention includes producing a
particle-dispersed resin molded article by molding a
particle-dispersed resin composition obtained by blending a resin
and organic-inorganic composite particles having an organic group
on the surface of inorganic particles such that the
organic-inorganic composite particles are dispersed as primary
particles in the resin by steric hindrance of the organic
group.
[0063] A third group of inventions for achieving the third object
is as follows.
[0064] Specifically, catalyst particles according to the present
invention contain inorganic particles with a catalytic action and
an organic group that binds to the surface of the inorganic
particles, and have a configuration that does not allow the
inorganic particles to contact with each other by steric hindrance
of the organic group.
[0065] It is preferable that the catalyst particles of the present
invention have a catalytic action for a gas and/or a liquid.
[0066] Also, it is preferable that the catalyst particles of the
present invention have a photocatalytic action for a gas and/or a
liquid.
[0067] Also, it is preferable that the catalyst particles of the
present invention are dispersed as primary particles in a solvent
and/or a resin.
[0068] Also, it is preferable that the catalyst particles of the
present invention contain a plurality of mutually different types
of organic groups.
[0069] Also, with the catalyst particles of the present invention,
it is preferable that the organic group is bound to the surface of
the inorganic particles via a binding group, and the binding group
contains a phosphoric acid group and/or a phosphoric acid ester
group.
[0070] Also, with the catalyst particles of the present invention,
it is preferable that the inorganic particles contain an oxide.
[0071] Also, with the catalyst particles of the present invention,
it is preferable that the inorganic particles contain at least one
oxide selected from the group consisting of TiO.sub.2, WO.sub.3 and
SrTiO.sub.3, and also contain at least one inorganic substance
selected from the group consisting of Pt, Pd, Cu, CuO, RuO.sub.2
and NiO.
[0072] Also, with the catalyst particles of the present invention,
it is preferable that the catalyst particles have an average
maximum length of 450 nm or less.
[0073] Also, it is preferable that the catalyst particles of the
present invention are obtained by surface-treating an inorganic
substance and/or a complex thereof with an organic compound
containing the organic group. It is also preferable that the
inorganic substance and/or the complex are surface-treated with the
organic compound in hot high pressure water, or that the inorganic
substance and/or the complex are surface-treated in the organic
compound heated to a high temperature.
[0074] A catalyst solution according to the present invention
contains a solvent and catalyst particles dispersed in the solvent,
the catalyst particles contain inorganic particles with a catalytic
action and an organic group that binds to the surface of the
inorganic particles, and the catalyst particles have a
configuration that does not allow the inorganic particles to
contact with each other by steric hindrance of the organic
group.
[0075] A catalyst composition according to the present invention
contains a resin and catalyst particles dispersed in the resin, the
catalyst particles contain inorganic particles with a catalytic
action and an organic group that binds to the surface of the
inorganic particles, and the catalyst particles have a
configuration that does not allow the inorganic particles to
contact with each other by steric hindrance of the organic
group.
[0076] A catalyst molded article according to the present invention
is formed of a catalyst composition containing a resin and catalyst
particles dispersed in the resin, the catalyst particles contain
inorganic particles with a catalytic action and an organic group
that binds to the surface of the inorganic particles, and the
catalyst particles have a configuration that does not allow the
inorganic particles to contact with each other by steric hindrance
of the organic group.
[0077] It is preferable that the catalyst molded article of the
present invention is an optical film.
[0078] A fourth group of inventions for achieving the fourth object
is as follows.
[0079] Specifically, a resin molded article according to the
present invention has micropores formed by removing
organic-inorganic composite particles from a particle-containing
resin molded article containing a resin and the organic-inorganic
composite particles that contain inorganic particles and an organic
group that binds to the surface of the inorganic particles and have
a configuration that does not allow the inorganic particles to
contact with each other by steric hindrance of the organic
group.
[0080] With the resin molded article of the present invention, it
is preferable that the organic-inorganic composite particles have
an average maximum length of 400 nm or less.
[0081] Also, with the resin molded article of the present
invention, it is preferable that in the particle-containing resin
molded article, the organic-inorganic composite particles are
dispersed as primary particles in the resin, or that the
particle-containing resin molded article has a phase separated
structure formed of a resin phase composed of the resin and a
particle phase that is composed of the organic-inorganic composite
particles and phase-separated from the resin phase, and the phase
separated structure is a bicontinuous phase separated structure in
which the particle phase is three-dimensionally continuous.
[0082] Also, with the resin molded article of the present
invention, it is preferable that the organic-inorganic composite
particles partially remain, and the proportion of remaining
organic-inorganic composite particles increases toward one side of
the resin molded article.
[0083] Also, with the resin molded article of the present
invention, it is preferable that the organic group contains a
plurality of mutually different organic groups.
[0084] A method for producing a resin molded article according to
the present invention includes the steps of: preparing
organic-inorganic composite particles that contain inorganic
particles and an organic group that binds to the surface of the
inorganic particles and have a configuration that does not allow
the inorganic particles to contact with each other by steric
hindrance of the organic group; blending the organic-inorganic
composite particles with a resin so as to prepare a
particle-containing resin composition and forming a
particle-containing resin molded article from the
particle-containing resin composition; and forming micropores
formed by removing the organic-inorganic composite particles from
the particle-containing resin molded article.
[0085] With the method for producing a resin molded article of the
present invention, it is preferable that the step of preparing
organic-inorganic composite particles involves surface-treating an
inorganic material with an organic compound in hot high pressure
water, or that the step of preparing organic-inorganic composite
particles involves surface-treating an inorganic material in a hot
organic compound.
[0086] A fifth group of inventions for achieving the fifth object
is as follows.
[0087] Specifically, a titanium complex according to the present
invention contains a titanium atom as a central atom and a
hydroxycarboxylic acid having a total of 7 or more carbon atoms as
a ligand.
[0088] With the present invention, it is preferable that the
hydroxycarboxylic acid is a hydroxyalkanoic acid having a total of
7 or more carbon atoms.
[0089] Also, with the present invention, it is preferable that the
hydroxyalkanoic acid is linear.
[0090] Also, with the present invention, it is preferable that the
hydroxycarboxylic acid is a hydroxymonocarboxylic acid.
[0091] Also, with the present invention, it is preferable that the
hydroxycarboxylic acid is a monohydroxycarboxylic acid.
[0092] Also, with the present invention, it is preferable that the
hydroxycarboxylic acid has a total of 13 or fewer carbon atoms.
[0093] Also, with the present invention, it is preferable that the
hydroxycarboxylic acid is 2-hydroxycarboxylic acid and/or
3-hydroxycarboxylic acid.
[0094] Titanium oxide particles according to the present invention
are obtained by treating a titanium complex containing a titanium
atom as a central atom and a hydroxycarboxylic acid having a total
of 7 or more carbon atoms as a ligand in hot high pressure
water.
[0095] A method for producing titanium oxide particles according to
the present invention includes treating a titanium complex
containing a titanium atom as a central atom and a
hydroxycarboxylic acid having a total of 7 or more carbon atoms as
a ligand in hot high pressure water.
Effect of the Invention
[0096] The particles of the present invention can be dispersed as
primary particles in a solvent and/or a resin, and therefore have
excellent dispersibility in a solvent and/or a resin.
[0097] Accordingly, in the particle dispersion, particle-dispersed
resin composition and resin molded article of the present
invention, the particles are dispersed with good uniformity.
[0098] As a result, the resin molded article of the present
invention can reliably have excellent optical characteristics.
[0099] The method for producing a particle-dispersed resin
composition and the method for producing a particle-dispersed resin
molded article of the present invention enable organic-inorganic
composite particles to be dispersed in a resin with ease and
uniformity by using a simple method in which the resin and the
organic-inorganic composite particles are blended such that the
organic-inorganic composite particles are dispersed as primary
particles in the resin by steric hindrance of the organic
group.
[0100] Accordingly, because the organic-inorganic composite
particles are uniformly dispersed in the resin, the
particle-dispersed resin composition and particle-dispersed resin
molded article of the present invention have excellent clarity and
are suitably used in various industrial applications including
optical applications.
[0101] The catalyst particles of the present invention have a
configuration that does not allow the inorganic particles to
contact with each other by steric hindrance of the organic group,
and therefore can be uniformly dispersed in a solvent and/or a
resin.
[0102] Also, the catalyst solution of the present invention in
which the catalyst particles of the present invention are dispersed
in a solvent can enhance clarity because the catalyst particles are
uniformly dispersed.
[0103] Furthermore, with the catalyst composition of the present
invention in which the catalyst particles of the present invention
are dispersed in a resin, as well as the catalyst molded article of
the present invention formed of the catalyst composition, the
inorganic particles cannot easily come into direct contact with the
resin due to the configuration based on the steric hindrance of the
organic group of the catalyst particles. Accordingly, the catalytic
action for a gas or a liquid can be exerted while degradation of
the resin of the catalyst composition and the catalyst molded
article is suppressed.
[0104] As a result, the catalyst composition of the present
invention and the catalyst molded article of the present invention
can exert various catalytic actions such as a detoxification
action, a deodorization action, a disinfectant (or in other words,
antimicrobial or germicidal) action, a dirt repellent action and a
decomposition action while having excellent durability.
[0105] Also, the catalyst composition of the present invention and
the catalyst molded article of the present invention can enhance
clarity because the catalyst particles are uniformly dispersed.
[0106] As a result, the catalyst molded article of the present
invention can be used in various optical applications and various
construction material applications.
[0107] The resin molded article of the present invention obtained
by the method for producing a resin molded article of the present
invention has excellent clarity and excellent mechanical
strength.
[0108] Accordingly, the resin molded article of the present
invention can be used in various industrial applications including
optical applications as a resin molded article having excellent
clarity and excellent reliability.
[0109] Also, the titanium complex of the present invention contains
a hydroxycarboxylic acid having a total of 7 or more carbon atoms
as a ligand. For this reason, even when titanium oxide particles
are prepared in hot high pressure water, decomposition of the
ligand is suppressed, and thus coloring of the titanium oxide
particles can be reduced.
[0110] Therefore, according to the present invention, it is
possible to reduce coloring of titanium oxide particles while
reducing the environmental load.
BRIEF DESCRIPTION OF THE DRAWINGS
[0111] FIG. 1 shows an image-processed FE-SEM micrograph obtained
in Example 1-1;
[0112] FIG. 2 shows an image-processed FE-SEM micrograph obtained
in Comparative Example 1-2;
[0113] FIG. 3 shows an image-processed TEM micrograph obtained in
Example 1-17;
[0114] FIG. 4 shows an image-processed FE-SEM micrograph obtained
in Example 1-29;
[0115] FIG. 5 shows an image-processed FE-SEM micrograph obtained
in Comparative Example 1-3;
[0116] FIG. 6 shows an image-processed FE-SEM micrograph obtained
in Example 1-47;
[0117] FIG. 7 shows an image-processed TEM micrograph obtained in
Example 1-55;
[0118] FIG. 8 shows an image-processed TEM micrograph obtained in
Comparative Example 1-4;
[0119] FIG. 9 shows an image-processed FE-SEM micrograph obtained
in Example 1-56;
[0120] FIG. 10 shows a particle size distribution of particles in a
particle dispersion obtained in Preparation Example 1-1;
[0121] FIG. 11 shows an image-processed FE-SEM micrograph of a
cross section of a resin molded article in which particles obtained
in Example 1-36 are dispersed;
[0122] FIG. 12 shows an image-processed FE-SEM micrograph of a
cross section of a resin molded article in which particles obtained
in Comparative Example 1-2 are dispersed;
[0123] FIG. 13 shows an image-processed FE-SEM micrograph of a
cross section of an optical film in which particles obtained in
Example 1-36 are dispersed;
[0124] FIG. 14 shows an image-processed FE-SEM micrograph of a
cross section of an optical film in which particles obtained in
Comparative Example 1-2 are dispersed;
[0125] FIG. 15 shows an image-processed TEM micrograph of
organic-inorganic composite particles obtained in Preparation
Example 2-1;
[0126] FIG. 16 shows an image-processed TEM micrograph of a cut
surface of a film obtained in Example 2-1;
[0127] FIG. 17 shows an image-processed TEM micrograph of a cut
surface of a film obtained in Example 2-2;
[0128] FIG. 18 shows an image-processed TEM micrograph of a cut
surface of a film obtained in Example 2-3;
[0129] FIG. 19 shows an image-processed TEM micrograph of a cut
surface of a film obtained in Example 2-4;
[0130] FIG. 20 shows an image-processed TEM micrograph of a cut
surface of a film obtained in Example 2-7;
[0131] FIG. 21 shows an image-processed TEM micrograph of a cut
surface of a film obtained in Example 2-8;
[0132] FIG. 22 shows an image-processed TEM micrograph of a cut
surface of a film obtained in Example 2-11;
[0133] FIG. 23 shows an image-processed TEM micrograph of a cut
surface of a film obtained in Example 2-13;
[0134] FIG. 24 shows an image-processed TEM micrograph of a cut
surface of a film obtained in Example 2-14;
[0135] FIG. 25 shows UV-visible absorption spectra at the start of
irradiation with light and 30 minutes, 1 hour, 2 hours, 3 hours and
4 hours after the irradiation, obtained in Example 3-10;
[0136] FIG. 26 shows UV-visible absorption spectra at the start of
irradiation with light and 5 minutes, 10 minutes, 15 minutes, 30
minutes, 1 hour and 2 hours after the irradiation, obtained in
Example 3-66;
[0137] FIG. 27 shows an image-processed TEM micrograph of a porous
film obtained in Example 4-6;
[0138] FIG. 28 shows an image-processed TEM micrograph of a porous
film obtained in Example 4-7; and
[0139] FIG. 29 shows an image-processed TEM micrograph of a porous
film obtained in Example 4-13.
EMBODIMENT OF THE INVENTION
[0140] Hereinafter, first to fifth embodiments will be sequentially
described that respectively correspond to the first to fifth groups
of inventions that are included in the present invention and
related to each other.
First Embodiment
[0141] Embodiment corresponding to the inventions of particles, a
particle dispersion, a particle-dispersed resin composition and a
resin molded article, which are included in the first group of
inventions
[0142] The particles of the present invention are organic-inorganic
composite particles that can be dispersed in a solvent and/or a
resin as primary particles having an organic group on the surface
of inorganic particles, and have negative birefringence.
[0143] Specifically, the primary particles are obtained as
organic-inorganic composite particles obtained by surface-treating
inorganic particles with an organic compound.
[0144] That is, the inorganic compound (inorganic material) for
forming inorganic particles has negative birefringence (minus
birefringence) and can be, for example, a carbonate containing an
alkaline earth metal and/or a composite oxide containing an
alkaline earth metal.
[0145] Examples of the alkaline earth metal include beryllium (Be),
magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium
(Ra) and the like. Magnesium and strontium are preferable. The
alkaline earth metals can be used singly or in a combination of two
or more.
[0146] Specific examples of the carbonate containing an alkaline
earth metal include beryllium carbonate, magnesium carbonate,
calcium carbonate, strontium carbonate, barium carbonate, radium
carbonate and the like. These carbonates can be used singly or in a
combination of two or more.
[0147] Examples of the composite oxide containing an alkaline earth
metal include alkaline earth metal salts of metal acids such as
alkaline earth metal titanates, alkaline earth metal ferrates,
alkaline earth metal stannates and alkaline earth metal zirconates.
The composite oxides can be used singly or in a combination of two
or more. Alkaline earth metal titanates are preferable.
[0148] Examples of alkaline earth metal titanates include beryllium
titanate (BeTiO.sub.3), magnesium titanate (MgTiO.sub.3), calcium
titanate (CaTiO.sub.3), strontium titanate (SrTiO.sub.3), barium
titanate (BaTiO.sub.3), radium titanate (RaTiO.sub.3) and the like.
The alkaline earth metal titanates can be used singly or in a
combination of two or more.
[0149] The organic compound is, for example, a hydrophobic organic
compound and/or a hydrophilic organic compound that imparts
hydrophobicity and/or hydrophilicity to the surface of the
inorganic particles. Specifically, the organic compound contains a
binding group capable of binding to the surface of the inorganic
particles and a hydrophobic group and/or a hydrophilic group.
[0150] The binding group is selected as appropriate according to
the type of inorganic particles, and examples thereof include
functional groups such as carboxyl group, phosphoric acid group
(--PO(OH).sub.2, phosphono group), amino group and sulfo group.
[0151] One or more of these binding groups may be contained in the
organic compound.
[0152] The hydrophobic group contained in the hydrophobic organic
compound can be, for example, a hydrocarbon group having 4 to 20
carbon atoms, and examples thereof include alkyl group, alkenyl
group, alkynyl group, cycloalkyl group, cycloalkenylalkylene group,
aryl group, aralkyl group and the like.
[0153] Examples of the alkyl group include linear or branched alkyl
groups having 4 to 20 carbon atoms such as butyl, isobutyl,
sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl,
octyl, 2-ethylhexyl, 3,3,5-trimethylhexyl, isooctyl, nonyl,
isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and icosyl.
A linear or branched alkyl group having 6 to 18 carbon atoms is
preferable.
[0154] Examples of the alkenyl group include alkenyl groups having
4 to 20 carbon atoms such as hexenyl, octenyl, nonenyl, decenyl,
undecenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl and
icosenyl.
[0155] Examples of the alkynyl group include alkynyl groups having
4 to 20 carbon atoms such as hexynyl, heptynyl, octynyl, decynyl,
undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl,
hexadecynyl, heptadecynyl and octadecynyl.
[0156] Examples of the cycloalkyl group include cycloalkyl groups
having 4 to 20 carbon atoms such as cyclohexyl, cycloheptyl,
cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and
cyclododecyl.
[0157] Examples of the cycloalkenylalkylene group include
norbornene decyl (norboneryl decyl,
bicyclo[2.2.1]hepta-2-enyl-decyl) and the like.
[0158] Examples of the aryl group include aryl groups having 6 to
20 carbon atoms such as phenyl, xylyl, naphthyl and biphenyl.
[0159] Examples of the aralkyl group include aralkyl groups having
7 to 20 carbon atoms such as benzyl, phenylethyl, phenylpropyl,
diphenylmethyl, phenylbutyl, phenylpentyl, phenylhexyl and
phenylheptyl.
[0160] The hydrophobic group is preferably an alkyl group, an
alkenyl group, a cycloalkyl group, a cycloalkenylalkylene group or
an aralkyl group.
[0161] Specific examples of the hydrophobic organic compound
include alkyl group-containing compounds such as hexanoic acid,
3,3,5-trimethylhexanoic acid, decanoic acid, decylamine, lauric
acid, decylphosphonic acid, trioctylphosphinoxide; alkenyl
group-containing compounds such as 10-undecenoic acid, oleic acid;
cycloalkyl group-containing compounds such as cyclohexanepentanoic
acid (cyclohexylpentanoic acid), cyclopentanedecanoic acid;
cycloalkenylalkylene group-containing compounds such as norbornene
decanoic acid; aralkyl group-containing compounds such as
6-phenylhexanoic acid, and the like.
[0162] The hydrophilic group contained in the hydrophilic organic
compound can be a hydroxyl group, a carbonyl groups or the like.
One or more of the hydrophilic groups may be contained in the
hydrophilic organic compound.
[0163] Specific examples of the hydrophilic organic compound
include hydroxyl group-containing compounds (monohydroxycarboxylic
acids or esters thereof) such as ethyl 6-hydroxyhexanoate,
4-hydroxyphenylacetic acid and 3-(4-hydroxyphenyl)propionic acid;
carbonyl group-containing compounds (or in other words,
monocarbonylcarboxylic acids) such as 4-oxovaleric acid; and the
like.
[0164] The hydrophobic group and/or the hydrophilic group serve as
the organic group that is present on the surface of the inorganic
particles of the organic-inorganic composite particles.
[0165] The particles of the present invention can be obtained by
subjecting the inorganic compound and the organic compound to a
reaction treatment, preferably, a high temperature treatment.
[0166] Specifically, the particles of the present invention can be
obtained by subjecting the inorganic compound and the organic
compound to a high temperature treatment in water under high
pressure (hydrothermal synthesis: hydrothermal reaction) or by
subjecting the inorganic compound to a high temperature treatment
in the organic compound (high temperature treatment in the organic
compound). In short, the particles of the present invention can be
obtained by surface-treating the surface of inorganic particles
formed by the inorganic compound with the organic group.
[0167] In the hydrothermal synthesis, for example, the inorganic
compound and the organic compound are reacted under
high-temperature and high-pressure conditions in the presence of
water (first hydrothermal synthesis).
[0168] Specifically, first, a reaction system is prepared under
high-temperature and high-pressure conditions by placing the
inorganic compound, the organic compound and water in a
pressure-resistant airtight container and heating them.
[0169] The proportions of respective components per 100 parts by
weight of the inorganic compound are as follows: the proportion of
the organic compound is, for example, 5 to 160 parts by weight and
preferably 10 to 110 parts by weight; and the proportion of water
is, for example, 200 to 1000 parts by weight and preferably 400 to
700 parts by weight.
[0170] If the proportion of the organic compound is below the above
range, the degree of progress of the surface modification reaction
will be small, which may result in poor dispersibility in a solvent
and/or a resin. If, on the other hand, the proportion of the
organic compound exceeds the above range, the surface modification
reaction will proceed sufficiently, but due to the excessive use of
organic compound, the cost may increase.
[0171] If the proportion of water is below the above range,
although the reaction will proceed, coarse particles (for example,
with a maximum length of approximately 0.2 to 0.8 mm) which may be
unsuitable for optical applications will be obtained.
[0172] If, on the other hand, the proportion of water exceeds the
above range, the concentration of the inorganic compound will be
excessively high, and the intended particles may not be
produced.
[0173] The density of the organic compound is usually 0.8 to 1.1
g/mL, and thus the proportion of the organic compound in terms of
volume is, for example, 10 to 150 mL and preferably 20 to 100 mL
per 100 g of the inorganic compound.
[0174] Also, the number of moles of the organic compound can be,
for example, 0.01 to 1000 mol and preferably 0.1 to 10 mol per mol
of metal contained in the inorganic compound.
[0175] Also, the density of water is usually approximately 1 g/mL,
and thus the proportion of water in terms of volume is, for
example, 200 to 1000 mL and preferably 400 to 700 mL per 100 g of
the inorganic compound.
[0176] If the proportions of the organic compound and water fall
within the above ranges, the surface of inorganic particles can be
reliably surface-treated.
[0177] Specific reaction conditions for the hydrothermal reaction
are as follows. The heating temperature is, for example, 100 to
500.degree. C. and preferably 200 to 400.degree. C.
[0178] If the heating temperature is below the above range, the
hydrothermal reaction will not proceed sufficiently, as a result of
which the inorganic compound may remain. If, on the other hand, the
heating temperature exceeds the above range, although the
hydrothermal reaction will proceed, an excessive amount of heat
will be generated, and thus the cost and the environmental load may
increase.
[0179] The pressure is, for example, 10 to 50 MPa, and preferably
20 to 40 MPa.
[0180] If the pressure is below the above range, the hydrothermal
reaction will not proceed sufficiently, as a result of which the
inorganic compound may remain. If, on the other hand, the pressure
falls within the above range, the hydrothermal reaction will
proceed and the level of safety can be enhanced.
[0181] The reaction time is, for example, 1 to 200 minutes and
preferably 3 to 150 minutes.
[0182] If the reaction time is below the above range, the
hydrothermal reaction will not proceed sufficiently, as a result of
which the inorganic compound may remain. If, on the other hand, the
reaction time exceeds the above range, although the hydrothermal
reaction will proceed, the particle growth will also proceed to
give coarse particles which may be unsuitable for optical
applications. Also, due to the long reaction time, the cost may
increase.
[0183] After the hydrothermal reaction, the airtight container is
cooled, and then, for example, a precipitate precipitated on the
bottom wall of the airtight container or a deposit adhering to the
inner wall of the airtight container is recovered.
[0184] The precipitate is obtained by, for example, sedimentation
separation in which the reaction product is settled by gravity or a
centrifugal field. Preferably, the precipitate is obtained as a
precipitate of the reaction product by centrifugal sedimentation
(centrifugal separation) in which the reaction product is settled
by a centrifugal field.
[0185] The deposit is recovered by, for example, a scraper
(spatula) or the like.
[0186] The reaction product can also be recovered (separated) by
adding a solvent to wash away an unreacted organic compound (or in
other words, dissolving the organic compound in the solvent) and
thereafter removing the solvent.
[0187] As the solvent, for example, an alcohol such as methanol,
ethanol, propanol or isopropanol or a ketone such as acetone or
methyl ethyl ketone can be used, and an alcohol is preferably
used.
[0188] The washed reaction product is separated from the solvent
(supernatant liquid) by, for example, filtration, decantation or
the like, and recovered.
[0189] In this manner, the particles are obtained.
[0190] The particles of the present invention can also be obtained
by subjecting a metal hydroxide containing an alkaline earth metal,
a carbonic acid source and an organic compound to a hydrothermal
synthesis (second hydrothermal synthesis).
[0191] Examples of the alkaline earth metal contained in the metal
hydroxide containing an alkaline earth metal include the same
alkaline earth metals as those of the carbonates listed above.
[0192] Specific examples of the metal hydroxide include beryllium
hydroxide, magnesium hydroxide, calcium hydroxide, strontium
hydroxide, barium hydroxide, radium hydroxide and the like.
[0193] The carbonic acid source is, for example, formic acid and/or
urea.
[0194] Examples of the organic compound include the same organic
compounds as those used in the first hydrothermal synthesis
described above.
[0195] In the second hydrothermal synthesis, the metal hydroxide,
the carbonic acid source and the organic compound are reacted under
high-temperature and high-pressure conditions in the presence of
water.
[0196] The proportions of respective components per 100 parts by
weight of the metal hydroxide are as follows: the proportion of the
carbonic acid source is, for example, 5 to 140 parts by weight and
preferably 10 to 70 parts by weight; the proportion of the organic
compound is, for example, 4 to 550 parts by weight and preferably
15 to 330 parts by weight; and the proportion of water is, for
example, 150 to 2500 parts by weight and preferably 300 to 500
parts by weight.
[0197] If the proportion of the carbonic acid source is below the
above range, the concentration of the metal hydroxide will be
excessively low, and the particles may not be obtained. If, on the
other hand, the proportion of the carbonic acid source exceeds the
above range, although the reaction will proceed, coarse particles
which may be unsuitable for optical applications will be
obtained.
[0198] If the proportion of the organic compound is below the above
range, the surface modification reaction will not proceed
sufficiently, which may result in poor dispersibility in a solvent
and/or a resin. If, on the other hand, the proportion of the
organic compound exceeds the above range, the surface modification
reaction will proceed sufficiently, but due to the excessive use of
organic compound, the cost may increase.
[0199] If the proportion of water is below the above range,
although the reaction will proceed, coarse particles which may be
unsuitable for optical applications will be obtained. If, on the
other hand, the proportion of water exceeds the above range, the
concentration of the metal hydroxide will be excessively high, and
the intended particles may not be produced.
[0200] The density of the carbonic acid source is usually 1.1 to
1.4 g/mL, and thus the proportion of the carbonic acid source in
terms of volume is, for example, 5 to 100 mL and preferably 10 to
50 mL per 100 g of the metal hydroxide. Also, the number of moles
of the carbonic acid source may be, for example, 0.4 to 100 mol,
preferably 1.01 to 10.0 mol and more preferably 1.05 to 1.30 mol
per mol of the metal hydroxide.
[0201] Also, the proportion of the organic compound in terms of
volume is, for example, 5 to 500 mL, and preferably 20 to 300 mL
per 100 g of the metal hydroxide, and the number of moles of the
organic compound may be, for example, 0.01 to 10000 mol and
preferably 0.1 to 10 mol per mol of the metal hydroxide.
[0202] Also, the proportion of water in terms of volume is, for
example, 150 to 2500 mL and preferably 300 to 500 mL per 100 g of
the metal hydroxide.
[0203] If the proportions of the organic compound and water fall
within the above ranges, the surface of inorganic particles can be
reliably surface-treated.
[0204] The reaction conditions for the second hydrothermal
synthesis are the same as those for the first hydrothermal
synthesis described above.
[0205] Furthermore, in the present invention, the particles of the
present invention can also be obtained by subjecting a metal
hydroxide containing an alkaline earth metal, a metal complex and
an organic compound to a hydrothermal synthesis (third hydrothermal
synthesis).
[0206] Examples of the metal hydroxide containing an alkaline earth
metal include the same metal hydroxides containing an alkaline
earth metal as those used in the second hydrothermal synthesis
described above.
[0207] The metal element contained in the metal complex is a metal
element that constitutes a composite oxide with the alkaline earth
metal contained in the metal hydroxide, and examples thereof
include elemental titanium, elemental iron, elemental tin,
elemental zirconium and the like. Elemental titanium is
preferable.
[0208] Examples of the ligand of the metal complex include
monohydroxycarboxylic acids such as 2-hydroxyoctanoic acid and the
like.
[0209] Examples of the metal complex include 2-hydroxyoctanoic acid
titanate and the like. The metal complex can be obtained by
preparation from the metal element and the ligand.
[0210] Examples of the organic compound include the same organic
compounds as those used in the first hydrothermal synthesis
described above.
[0211] In the third hydrothermal synthesis, the metal hydroxide,
the metal complex and the organic compound are reacted under
high-temperature and high-pressure conditions in the presence of
water.
[0212] The proportions of respective components per 100 parts by
weight of the metal complex are as follows: the proportion of the
metal hydroxide is, for example, 1 to 50 parts by weight and
preferably 5 to 30 parts by weight; the proportion of the organic
compound is, for example, 4 to 550 parts by weight and preferably
15 to 330 parts by weight; and the proportion of water is, for
example, 200 to 1000 parts by weight and preferably 300 to 700
parts by weight.
[0213] If the proportion of the metal hydroxide is below the above
range, the concentration of the metal hydroxide will be excessively
low, and the particles may not be obtained. If, on the other hand,
the proportion of the metal hydroxide exceeds the above range,
although the surface modification reaction will proceed, coarse
particles which may be unsuitable for optical applications will be
obtained.
[0214] If the proportion of the organic compound is below the above
range, the surface modification reaction will not proceed
sufficiently, which may result in poor dispersibility in a solvent
and/or a resin. If, on the other hand, the proportion of the
organic compound exceeds the above range, the surface modification
reaction will proceed sufficiently, but due to the excessive use of
organic compound, the cost may increase.
[0215] If the proportion of water is below the above range,
although the reaction will proceed, coarse particles which may be
unsuitable for optical applications will be obtained. If, on the
other hand, the proportion of water exceeds the above range, the
concentration of the metal hydroxide will be excessively high, and
the intended particles may not be produced.
[0216] The proportion of the organic compound in terms of volume
is, for example, 5 to 500 mL and preferably 20 to 300 mL per 100 g
of the metal complex, and the number of moles of the organic
compound may be 0.01 to 1000 per mol of the organic compound.
[0217] The proportion of water in terms of volume is, for example,
200 to 1000 mL and preferably 300 to 700 mL per 100 g of the metal
complex.
[0218] If the proportions of the organic compound and water fall
within the above ranges, the surface of inorganic particles can be
reliably surface-treated.
[0219] The reaction conditions for the third hydrothermal synthesis
are the same as those for the first hydrothermal synthesis
described above.
[0220] Furthermore, the above hydrothermal syntheses (first, second
and third hydrothermal syntheses) may also be carried out in the
presence of a pH adjusting agent.
[0221] Preferably, the second hydrothermal synthesis is carried out
in the presence of a pH adjusting agent.
[0222] The pH adjusting agent can be an alkali or acid.
[0223] Examples of the alkali include inorganic alkalis such as
potassium hydroxide and sodium hydroxide; organic alkalis such as
ammonia; and the like. Examples of the acid include inorganic acids
such as sulfuric acid, nitric acid and hydrochloric acid; organic
acids such as formic acid and acetic acid; and the like.
[0224] Preferably, an alkali is used.
[0225] The pH of the reaction system is set to, for example, 8 to
12 by using the pH adjusting agent.
[0226] It is thereby possible to set the average particle size of
the resulting particles in the desired range, more specifically, to
a smaller value. Accordingly, the particles having a small average
particle size (or lengthwise length LL and sideways length SL,
which will be described later) can be suitably used in optical
applications.
[0227] Examples of the inorganic compound subjected to the high
temperature treatment in the organic compound include the same
inorganic compounds as those listed above.
[0228] In the high temperature treatment in the organic compound,
the inorganic compound and the organic compound are blended and
heated under, for example, normal atmospheric pressure
conditions.
[0229] The proportion of the organic compound is, for example, 10
to 10000 parts by weight and preferably 100 to 1000 parts by weight
per 100 parts by weight of the inorganic compound. The proportion
of the organic compound in terms of volume is, for example, 10 to
10000 mL and preferably 100 to 1000 mL per 100 g of the inorganic
compound.
[0230] The heating temperature is, for example, a temperature above
100.degree. C., preferably 125.degree. C. or higher and more
preferably 150.degree. C. or higher, and usually for example,
300.degree. C. or lower, and preferably 275.degree. C. or
lower.
[0231] The heating time is, for example, 1 to 60 minutes and
preferably 3 to 30 minutes.
[0232] The particles (primary particles) thus obtained are mostly
acicular, with a lengthwise length (maximum length) LL of, for
example, 200 .mu.m or less, preferably 5 nm to 200 .mu.m, more
preferably 10 nm to 50 .mu.m and even more preferably 40 nm to 10
.mu.m and a sideways length (minimum length) SL of, for example, 1
nm to 20 .mu.m, preferably 3 nm to 10 .mu.m and more preferably 5
nm to 5 .mu.m.
[0233] In particular, the particles (primary particles) obtained by
hydrothermal synthesis in the presence of a pH adjusting agent have
a lengthwise length LL of, for example, 1 nm to 20 .mu.m and
preferably 10 nm to 10 .mu.m and a sideways length SL of, for
example, 0.5 nm to 2 .mu.m and preferably 1 nm to 1 .mu.m.
[0234] If the lengthwise length LL is below the above range, the
particles will be too small, which may result in poor physical
strength. If, on the other hand, the lengthwise length LL exceeds
the above range, good optical characteristics will be obtained, but
the particles may be crushed when mixed with a resin or the
like.
[0235] If the sideways length SL is below the above range, the
particles will be too small, which may result in poor physical
strength. If, on the other hand, the sideways length SL exceeds the
above range, a sufficient aspect ratio may not be obtained.
[0236] The particles have an aspect ratio of, for example, 1000 or
less, specifically, 1 to 1000, preferably 3 to 100 and more
preferably 5 to 30.
[0237] If the aspect ratio is below the above range, poor optical
characteristics will be obtained. If, on the other hand, the aspect
ratio exceeds the above range, good optical characteristics will be
obtained, but the particles may be crushed when mixed with a resin
or the like.
[0238] The particles thus obtained are unlikely to coagulate in a
dry state, and even if the particles appear coagulated in a dry
state, the coagulation (formation of secondary particles) will be
reliably prevented in a particle dispersion and/or a
particle-dispersed resin composition, which will be described next,
and therefore the particles are dispersed as primary particles
substantially uniformly in a solvent and/or a resin.
[0239] The particles obtained in the above-described manner can be
subjected to wet classification.
[0240] Specifically, a solvent is added to the particles, and the
resulting mixture is stirred and allowed to stand still, and
thereafter separated into a supernatant and a precipitate. As the
solvent, the same solvents as those listed above can be used.
[0241] After that, the supernatant is recovered to give particles
having a small particle size.
[0242] With the wet classification, the lengthwise length LL of the
resulting particles can be adjusted to, for example, 10 nm to 400
nm and preferably 20 nm to 200 nm, and the sideways length SL can
be adjusted to, for example, 1 nm to 100 nm and preferably 5 nm to
50 nm.
[0243] If the lengthwise length LL is below the above range, the
particle will be too small, which may result in poor physical
strength. If, on the other hand, the lengthwise length LL exceeds
the above range, good optical characteristics will be obtained, but
the particles may be crushed when mixed with a resin or the
like.
[0244] If the sideways length SL is below the above range, the
particles will be too small, which may result in poor physical
strength. If, on the other hand, the sideways length SL exceeds the
above range, a sufficient aspect ratio may not be obtained.
[0245] There is no particular limitation on the solvent for
dispersing the particles obtained above. Examples thereof include
the solvents used in washing described above, and other examples
include halogenated hydrocarbons such as chloroform,
dichloromethane, 1,1,1-trichloroethane, chlorobenzene and
dichlorobenzene; alkanes such as pentane, hexane and heptane;
cycloalkanes such as cyclopentane and cyclohexane; esters such as
ethyl acetate; polyols such as ethylene glycol and glycerin;
aromatic hydrocarbons such as benzene, toluene and xylene; ethers
such as tetrahydrofuran; nitrogen-containing compounds such as
N-methylpyrrolidone, pyridine, acetonitrile and dimethylformamide;
and the like.
[0246] These solvents can be used singly or in a combination of two
or more.
[0247] The proportion of the solvent is not particularly limited,
and the concentration of the particles in the particle dispersion
is adjusted to, for example, 0.1 to 70 wt % and preferably 1 to 50
wt %.
[0248] If the concentration of the particles in the particle
dispersion is below the above range, the particle dispersion will
be too dilute, and thus sufficient optical characteristics may not
be obtained when mixed with a resin or the like. If, on the other
hand, the concentration of the particles in the particle dispersion
exceeds the above range, the dispersibility will be low.
[0249] In order to disperse the particles in the solvent, the
particles and the solvent are blended, and the resulting mixture is
stirred.
[0250] As a result, in the particle dispersion, the particles are
uniformly dispersed as primary particles in the solvent, or in
other words, without coagulation of the particles.
[0251] There is no particular limitation on the resin for
dispersing the particles, and examples thereof include
thermosetting resins, thermoplastic resins and the like.
[0252] Examples of thermosetting resins include epoxy resin,
polyimide resin (thermosetting polyimide resin), phenol resin, urea
resin, melamine resin, diallyl phthalate resin, silicone resin,
urethane resin (thermosetting urethane resin) and the like.
[0253] Examples of thermoplastic resins include polyolefin (for
example, polyethylene, polypropylene, ethylene-propylene copolymer
and the like), acrylic resin (for example, polymethyl methacrylate
and the like), polyvinyl acetate, ethylene-vinylacetate copolymer
(EVA), polyvinyl chloride, polystyrene, polyacrylonitrile,
polyamide (PA; nylon), polycarbonate, polyacetal, polyester (for
example, polyarylate, polyethylene terephthalate (PET) and the
like), polyphenylene oxide, polyphenylene sulfide, polysulfone,
polyether sulfone, polyether ether ketone (PEEK), polyallylsulfone,
thermoplastic polyimide resin, thermoplastic urethane resin,
polyaminobismaleimide, polyamideimide, polyetherimide,
bismaleimidetriazine resin, polymethylpentene, fluorine resin,
liquid crystal polymer, olefin-vinyl alcohol copolymer, ionomer,
polyarylate, acrylonitrile-ethylene-styrene copolymer (AES),
acrylonitrile-butadiene-styrene copolymer (ABS),
acrylonitrile-styrene copolymer (AS) and the like.
[0254] These resins can be used singly or in a combination of two
or more.
[0255] Among the resins, a thermoplastic resin is preferable, and
polyetherimide and polyester are more preferable.
[0256] The resin (specifically, thermoplastic resin) has a melting
temperature of, for example, 200 to 300.degree. C. and a softening
temperature of, for example, 150 to 280.degree. C.
[0257] In order to disperse the particles in the resin, for
example, at least the particles and the resin are blended, and the
resulting mixture is stirred.
[0258] Preferably, the particles, the solvent and the resin are
blended, the resulting mixture is stirred to prepare a
particle-dispersed resin solution, and thereafter the solvent in
the particle-dispersed resin solution is removed. Blending a
solvent allows the particles to be more uniformly dispersed in the
resin.
[0259] Specifically, a resin solution and/or a resin dispersion
that has been dissolved and/or dispersed in a solvent are/is
blended with the particle dispersion.
[0260] As the solvent used in preparation of the resin solution
and/or the resin dispersion, the same solvents as those listed
above can be used. The proportion of the solvent is adjusted to,
for example, 40 to 2000 parts by weight and preferably 50 to 1000
parts by weight per 100 parts by weight of the resin solution
and/or the resin dispersion.
[0261] If the proportion of the solvent is below the above range,
the resin solution or the resin dispersion will be too viscous,
making its application difficult, and also the dispersibility of
the particles will be low. If, on the other hand, the proportion of
the solvent exceeds the above range, the resin solution or the
resin dispersion will be too dilute and the viscosity is too small,
making it difficult to apply the resin solution or the resin
dispersion so as to be thick.
[0262] The proportion between the resin solution and/or the resin
dispersion and the particle dispersion is adjusted such that the
proportion of the particles is, for example, 0.1 to 240 parts by
weight and preferably 5 to 100 parts by weight per 100 parts by
weight of the resin (solids content). In other words, the
concentration of the particles in the particle-dispersed resin
composition is adjusted to 0.1 to 70 wt % and preferably 1 to 50 wt
%.
[0263] If the proportion of the particles is below the above range,
the particle-dispersed resin composition will be too dilute, and
thus sufficient optical characteristics may not be obtained in the
particle-dispersed resin composition. If, on the other hand, the
proportion of the particles exceeds the above range, the
dispersibility of the particles will be low.
[0264] After that, the particle-dispersed resin composition is
dried by application of heat at, for example, 40 to 60.degree. C.
to remove the solvent, and thereby a particle-dispersed resin
composition is obtained.
[0265] After that, the particle-dispersed resin composition is
injected into a metal mold or the like and then subjected to, for
example, heat molding such as heat pressing, whereby the resin
molded article of the present invention can be obtained.
[0266] As heat pressing, for example, vacuum pressing is used. The
conditions are as follows: the temperature is greater than or equal
to the melting temperature or softening temperature of the resin,
specifically, 100 to 300.degree. C. and preferably 150 to
250.degree. C.; and the pressing pressure is, for example, 20 to
1000 MPa and preferably 40 to 80 MPa.
[0267] If the heating temperature is below the above range, it may
not be possible to soften the resin. If, on the other hand, the
heating temperature exceeds the above range, the resin may be
thermally decomposed, and also the cost may increase due to an
excessive amount of heat generated.
[0268] If the pressing pressure is below the above range, the resin
may not be sufficiently deformed (molded). If, on the other hand,
the pressing pressure exceeds the above range, the resin can be
sufficiently molded, but the pressing pressure will be excessively
high, which may increase the cost.
[0269] The resin molded article of the present invention can be
obtained by (application method) applying the particle-dispersed
resin solution onto a support plate by using, for example, an
application method such as spin coating or roll coating,
subsequently removing the solvent at the same temperature as
described above, and then if necessary curing the resultant by
application of heat so as to form a coating that is made of the
particle-dispersed resin composition, and if necessary further
drying the coating.
[0270] Furthermore, the resin molded article of the present
invention can also be obtained by an extrusion method in which the
particle-dispersed resin composition is extruded by an extruding
machine or the like.
[0271] As a result, in the resin molded article, the particles are
uniformly dispersed as primary particles in the resin, or in other
words, without coagulation of the particles.
[0272] The resin molded article of the present invention has
various applications including, for example, optical applications,
electronic and electrical applications and mechanical applications.
In the case of electronic and electrical applications, for example,
the resin molded article of the present invention is used as a
flexible substrate or the like.
[0273] Preferably, the resin molded article of the present
invention is used in optical applications, specifically, as an
optical fiber, an optical disc, a light guide plate, an optical
film or the like.
[0274] The thickness of the optical film is, for example, 1 to 100
.mu.m and preferably 5 to 50 .mu.m.
[0275] If the thickness of the optical film is below the above
range, sufficient optical characteristics may not be obtained. If,
on the other hand, the thickness of the optical film exceeds the
above range, although sufficient optical characteristics can be
obtained, it may be difficult to form a uniform film and the cost
may increase.
[0276] In the case where the resin molded article is used as an
optical film, the resin molded article is formed into a film
suitable for optical applications by the application method, or in
other words, an optical film is obtained.
[0277] The particles of the present invention can be dispersed as
primary particles in a solvent and/or a resin, and therefore have
excellent dispersibility in a solvent and/or a resin.
[0278] Accordingly, in the particle dispersion and the
particle-dispersed resin composition of the present invention, the
particles are dispersed with good uniformity.
[0279] Moreover, the particles of the present invention have
negative birefringence.
[0280] Accordingly, the resin molded article of the present
invention can reliably have excellent optical characteristics and
thus is useful as an optical member, in particular, as an optical
film.
[0281] More specifically, the particles of the present invention
have a particle size (lengthwise length LL and sideways length SL)
that is smaller than the wavelength of light (for example, 380 to
800 nm in the case of visible light) and are dispersed in the resin
molded article of the present invention, and therefore negative
birefringence can be imparted to the optical film with excellent
reliability.
[0282] For this reason, the optical film of the present invention
can be suitably used in phase difference plates or polarizing
plates for plasma display panels or liquid crystal televisions, or
the like.
Second Embodiment
[0283] Embodiment corresponding to the inventions of a
particle-dispersed resin composition, a particle-dispersed resin
molded article and producing methods therefor, which are included
in the second group of inventions
[0284] The particle-dispersed resin composition of the present
invention contains a resin and organic-inorganic composite
particles.
[0285] Examples of the resin include thermosetting resins,
thermoplastic resins and the like.
[0286] Examples of thermosetting resins include polycarbonate
resin, epoxy resin, thermosetting polyimide resin (including
thermosetting fluorine-based polyimide resin), phenol resin, urea
resin, melamine resin, diallyl phthalate resin, silicone resin,
thermosetting urethane resin and the like.
[0287] Examples of thermoplastic resins include olefin resin,
acrylic resin, polystyrene resin, polyester resin,
polyacrylonitrile resin, maleimide resin, polyvinyl acetate resin,
ethylene-vinylacetate copolymer, polyvinyl alcohol resin, polyamide
resin, polyvinyl chloride resin, polyacetal resin, polyphenylene
oxide resin, polyphenylene sulfide resin, polysulfone resin,
polyether sulfone resin, polyether ether ketone resin,
polyallylsulfone resin, thermoplastic polyimide resin (including
thermoplastic fluorine-based polyimide resin), thermoplastic
urethane resin, polyetherimide resin, polymethylpentene resin,
cellulose resin, liquid crystal polymer, ionomer and the like.
[0288] These resins can be used singly or in a combination of two
or more.
[0289] In the case where excellent mechanical strength needs to be
imparted to the particle-dispersed resin molded article molded from
a particle-dispersed resin composition, the resin is preferably a
highly oriented resin having high orientation, and specific
examples thereof include olefin resin, acrylic resin, polystyrene
resin, polyester resin, polyvinyl alcohol resin, thermoplastic
polyimide resin, polyetherimide resin, liquid crystal polymer and
the like.
[0290] Examples of the olefin resin include cyclic olefin resin,
chain olefin resin and the like. Cyclic olefin resin is
preferable.
[0291] Examples of the cyclic olefin resin include polynorbornene,
ethylene-norbornene copolymers, and derivative thereof.
[0292] Examples of the chain olefin resin include polyethylene,
polypropylene, ethylene-propylene copolymer and the like.
[0293] Examples of the acrylic resin include polymethyl
methacrylate and the like.
[0294] Examples of the polyester resin include polyarylate,
polyethylene terephthalate, polyethylene naphthalate and the
like.
[0295] The polyvinyl alcohol resin is obtained by, for example,
complete or partial saponification of polyvinyl acetate resin
obtained by polymerizing vinyl monomers containing vinyl acetate as
a primary component by an appropriate method. The saponification
degree of polyvinyl alcohol resin is, for example, 70 to 99.99 mol
% and preferably 70 to 99.9 mol %.
[0296] The resin preferably has a functional group. Examples of the
functional group include hydrophilic groups such as carboxyl group
and hydroxyl group; hydrophobic groups such as hydrocarbon group;
and the like.
[0297] The organic-inorganic composite particles are particles that
can be dispersed as primary particles in a solvent (described
later) and/or a resin and that have an organic group on the surface
of the inorganic particles. Specifically, the organic-inorganic
composite particles are obtained by surface-treating inorganic
particles with an organic compound. The organic-inorganic composite
particles can be used singly or in a combination of two or
more.
[0298] The inorganic substance for forming inorganic particles can
be a metal composed of a metal element such as a main group element
or a transition element, a nonmetal composed of a nonmetal element
such as boron or silicon, an inorganic compound containing a metal
element and/or a nonmetal, or the like.
[0299] Examples of the metal element and the nonmetal element
include elements that are located on the left side and the lower
side of a border line that is assumed to pass through boron (B) of
the IIIB group, silicon (Si) of the IVB group, arsenic (As) of the
VB group, tellurium (Te) of the VIB group and astatine (At) of the
VIIB group on the long-form periodic table (IUPAC, 1989), as well
as the elements that are located on the border line. Specific
examples thereof include the group IIIA elements such as Sc and Y;
the group WA elements such as Ti, Zr, and Hf; the group VA elements
such as V, Nb, and Ta; the group VIA elements such as Cr, Mo, and
W; the group VIIA elements such as Mn and Re; the group VIIIA
elements such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt; the group
IB elements such as Cu, Ag, and Au; the group IIB elements such as
Zn, Cd, and Hg; the group IIIB elements such as B, Al, Ga, In, and
Tl; the group IVB elements such as Si, Ge, Sn, and Pb; the group VB
elements such as As, Sb, and Bi; the group VIB elements such as Te
and Po; the lanthanide series elements such as La, Ce, Pr, and Nd;
the actinium series elements such as Ac, Th, and U; and the
like.
[0300] The inorganic compound can be, for example, a hydrogen
compound, a hydroxide, a nitride, a halide, an oxide, a carbonate,
a sulfate, a nitrate, a metal complex, a sulfide, a carbide, a
phosphorus compound, or the like. The inorganic compound may be a
composite compound such as, for example, an oxynitride or a
composite oxide.
[0301] The inorganic substance is preferably an inorganic compound,
and more preferable examples include an oxide, a composite oxide, a
carbonate, a sulfate and the like.
[0302] Examples of the oxide include metal oxides, and preferable
examples include titanium oxide (titanium dioxide, titanium oxide
(IV), titania: TiO.sub.2), cerium oxide (cerium dioxide, cerium
oxide (IV), ceria: CeO.sub.2) and the like.
[0303] The oxides can be used singly or in a combination of two or
more.
[0304] The composite oxide is a compound consisting of oxygen and a
plurality of elements, and the plurality of elements may be a
combination of at least two elements selected from the elements
other than oxygen contained in the oxides listed above, the group I
elements, and the group II elements.
[0305] Examples of the group I elements include alkali metals such
as Li, Na, K, Rb, and Cs. Examples of the group II elements include
the same alkaline earth metals as those listed in the first
embodiment.
[0306] Preferable examples of the combination of a plurality of
elements include combinations that contain at least a group II
element such as a combination of a group II element and a group IVB
element, a combination of a group II element and a group VIIIB
element, and a combination of a group II element and a group IVA
element.
[0307] Examples of the composite oxide containing at least a group
II element include alkaline earth metal titanates, alkaline earth
metal zirconates, alkaline earth metal ferrates, alkaline earth
metal stannates, and the like.
[0308] Preferable composite oxides are alkaline earth metal
titanates.
[0309] Examples of alkaline earth metal titanates include the same
alkaline earth metal titanates as those listed in the first
embodiment.
[0310] The composite oxides can be used singly or in a combination
of two or more.
[0311] In the carbonate, the element that combines with carbonic
acid can be, for example, an alkali metal, an alkaline earth metal
or the like. The alkali metal and the alkaline earth metal can be
the same alkali metals and alkaline earth metals as those listed
above.
[0312] The element that combines with carbonic acid is preferably
an alkaline earth metal.
[0313] Specifically, the carbonate is preferably a carbonate
containing an alkaline earth metal, and examples of such a
carbonate include the same carbonates as those listed in the first
embodiment. These carbonates can be used singly or in a combination
of two or more.
[0314] The sulfate is a compound consisting of a sulfate ion
(SO.sub.4.sup.2-) and a metal cation (more specifically, a compound
formed by substitution of the hydrogen atoms of sulfuric acid
(H.sub.2SO.sub.4) with a metal), and the metal contained in the
sulfate can be, for example, an alkali metal, an alkaline earth
metal or the like. The alkali metal and the alkaline earth metal
can be the same alkali metals and alkaline earth metals as those
listed above.
[0315] The metal is preferably an alkaline earth metal.
[0316] Specifically, preferable sulfates are sulfates containing an
alkaline earth metal, and examples of such sulfates include
beryllium sulfate, magnesium sulfate, calcium sulfate, strontium
sulfate, barium sulfate, radium sulfate and the like. Barium
sulfate is preferable.
[0317] These sulfates can be used singly or in a combination of two
or more.
[0318] The organic compound is, for example, an organic
group-introducing compound that introduces (disposes) an organic
group on the surface of inorganic particles. Specifically, the
organic compound contains a binding group capable of binding to the
surface of inorganic particles and an organic group.
[0319] The binding group may be selected as appropriate according
to the type of inorganic particles, and examples thereof include
functional groups such as carboxyl group, phosphoric acid group
(--PO(OH).sub.2, phosphono group), amino group, sulfo group,
hydroxyl group, thiol group, epoxy group, isocyanate group (cyano
group), nitro group, azo group, silyloxy group, imino group,
aldehyde group (acyl group), nitrile group, vinyl group
(polymerizable group), and the like. Preferable examples include
carboxyl group, phosphoric acid group, amino group, sulfo group,
hydroxyl group, thiol group, epoxy group, azo group, vinyl group,
and the like. More preferable examples include carboxyl group and
phosphoric acid group.
[0320] The carboxyl group includes a carboxylic acid ester group
(carboxy ester group).
[0321] The phosphoric acid group includes a phosphoric acid ester
group (phosphonate group).
[0322] One or more of these binding groups are contained in the
organic compound. Specifically, the binding group is bound to a
terminal or a side chain of the organic group.
[0323] The binding group is selected as appropriate according to
the type of inorganic particles. Specifically, when the inorganic
particles contain cerium oxide, strontium carbonate and/or barium
sulfate, for example, a carboxyl group is selected. When the
inorganic particles contain titanium oxide, for example, a
phosphoric acid group is selected.
[0324] The organic group includes, for example, a hydrocarbon group
such as an aliphatic group, an alicyclic group, an araliphatic
group or an aromatic group, or the like.
[0325] The aliphatic group includes, for example, a saturated
aliphatic group, an unsaturated aliphatic group and the like.
[0326] Examples of the saturated aliphatic group include alkyl
groups having 1 to 20 carbon atoms and the like.
[0327] Examples of the alkyl group include linear or branched alkyl
groups (paraffin hydrocarbon groups) having 1 to 20 carbon atoms
such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
sec-butyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl,
octyl, 2-ethylhexyl, 3,3,5-trimethylhexyl, isooctyl, nonyl,
isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and icosyl,
and the like. A linear or branched alkyl group having 4 to 18
carbon atoms is preferable.
[0328] Examples of the unsaturated aliphatic group include alkenyl
groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20
carbon atoms, and the like.
[0329] Examples of the alkenyl group include alkenyl groups (olefin
hydrocarbon groups) having 2 to 20 carbon atoms such as ethenyl,
propenyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl,
undecenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl
(oleyl) and icosenyl.
[0330] Examples of the alkynyl group include alkynyl groups
(acetylene hydrocarbon groups) having 2 to 20 carbon atoms such as
ethynyl, propynyl, butyryl, pentynyl, hexynyl, heptynyl, octynyl,
decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl,
pentadecynyl, hexadecynyl, heptadecynyl and octadecynyl.
[0331] Examples of the alicyclic group include cycloalkyl groups
having 4 to 20 carbon atoms, cycloalkenylalkylene groups having 7
to 20 carbon atoms, and the like.
[0332] Examples of the cycloalkyl group include cyclobutyl,
cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,
cyclodecyl, cycloundecyl, cyclododecyl and the like.
[0333] Examples of the cycloalkenylalkylene group include
norbornene decyl (norboneryl decyl,
bicyclo[2.2.1]hept-2-enyl-decyl) and the like.
[0334] Examples of the araliphatic group include aralkyl groups
having 7 to 20 carbon atoms such as benzyl, phenylethyl,
phenylpropyl, phenylbutyl, phenylpentyl, phenylhexyl, phenylheptyl
and diphenylmethyl.
[0335] Examples of the aromatic group include aryl groups having 6
to 20 carbon atoms such as phenyl, xylyl, naphthyl and
biphenyl.
[0336] The organic group is used as a hydrophobic group for
imparting hydrophobicity to the surface of inorganic particles.
[0337] Accordingly, the organic compounds containing a hydrophobic
group described above are used as hydrophobic organic compounds for
hydrophobic treatment of inorganic particles.
[0338] Specific examples of such hydrophobic organic compounds in
the case where the binding group is a carboxyl group include
aliphatic group-containing carboxylic acids including saturated
aliphatic group-containing carboxylic acids (saturated fatty acids)
such as hexanoic acid and decanoic acid and unsaturated aliphatic
group-containing carboxylic acids (unsaturated fatty acids) such as
oleic acid, and the like. Other specific examples of hydrophobic
organic compounds in the case where the binding group is a carboxyl
group include alicyclic group-containing carboxylic acids
(alicyclic carboxylic acids) such as cyclohexyl monocarboxylic
acid, araliphatic group-containing carboxylic acids (araliphatic
carboxylic acids) such as 6-phenylhexanoic acid, aromatic
group-containing carboxylic acids (aromatic carboxylic acids) such
as benzoic acid and toluenecarboxylic acid, and the like.
[0339] Specific examples of hydrophobic organic compounds in the
case where the binding group is a phosphoric acid group (including
phosphoric acid ester group), aliphatic group-containing phosphate
esters including saturated aliphatic group-containing phosphate
esters such as ethyl octylphosphonate and ethyl
decylphosphonate.
[0340] The organic compound can also be used as a hydrophilic
organic compound for hydrophilic treatment of inorganic particles.
In this case, the organic group contained in the hydrophilic
organic compound includes any of the above hydrocarbon groups and a
hydrophilic group that binds to the hydrocarbon group.
[0341] That is, in the hydrophilic organic compound, the
hydrophilic group is bound to a terminal (the terminal (the other
terminal) opposite the terminal that is bound to the binding group
(one terminal)) or a side chain of the hydrocarbon group.
[0342] The hydrophilic group is a functional group having a
polarity (or in other words, polar group), and examples thereof
include a carboxyl group, a hydroxyl group, a phosphoric acid
group, an amino group, a sulfo group, a carbonyl group, a cyano
group, a nitro group, an aldehyde group, a thiol group and the
like. One or more of the hydrophilic groups are contained in the
hydrophilic organic compound.
[0343] Examples of the organic group containing a carboxyl group
(carboxyl group-containing organic group) include carboxyaliphatic
groups including carboxysaturated aliphatic groups such as
3-carboxypropyl, 4-carboxybutyl, 6-carboxyhexyl, 8-carboxyoctyl and
10-carboxydecyl and carboxyunsaturated aliphatic groups such as
carboxybutenyl, and the like. Other examples of the organic group
containing a carboxyl group include carboxyalicyclic groups such as
carboxycyclohexyl, carboxyaraliphatic groups such as
carboxyphenylhexyl, carboxyaromatic groups such as carboxyphenyl,
and the like.
[0344] Examples of the organic group containing a hydroxyl group
(hydroxyl group-containing organic group) include hydroxysaturated
aliphatic groups (hydroxy aliphatic groups) such as 4-hydroxybutyl,
6-hydroxylhexyl and 8-hydroxyoctyl, hydroxyaraliphatic groups such
as 4-hydroxybenzyl, 2-(4-hydroxyphenyl)ethyl,
3-(4-hydroxyphenyl)propyl and 6-(4-hydroxyphenyl)hexyl,
hydroxyaromatic groups such as hydroxy phenyl, and the like.
[0345] Examples of the organic group containing a phosphoric acid
group (phosphoric acid group-containing organic group) include
phosphonosaturated aliphatic groups (phosphonoaliphatic groups)
such as 6-phosphonohexyl, phosphonoaraliphatic groups such as
6-phosphonophenylhexyl, and the like.
[0346] Examples of the organic group containing an amino group
(amino group-containing organic group) include aminosaturated
aliphatic groups (aminoaliphatic groups) such as 6-aminohexyl,
aminoaraliphatic groups such as 6-aminophenylhexyl, and the
like.
[0347] Examples of the organic group containing a sulfo group
(sulfo group-containing organic group) include sulphosaturated
aliphatic groups (sulphoaliphatic groups) such as 6-sulphohexyl,
sulphoaraliphatic groups such as 6-sulphophenylhexyl, and the
like.
[0348] Examples of the organic group containing a carbonyl group
(carbonyl group-containing organic group) include oxosaturated
aliphatic groups (oxoaliphatic groups) such as 3-oxopentyl, and the
like.
[0349] Examples of the organic group containing a cyano group
(cyano group-containing organic group) include cyanosaturated
aliphatic groups (cyanoaliphatic groups) such as 6-cyanohexyl, and
the like.
[0350] Examples of the organic group containing a nitro group
(nitro group-containing organic group) include nitrosaturated
aliphatic groups (nitroaliphatic groups) such as 6-nitrohexyl, and
the like.
[0351] Examples of the organic group containing an aldehyde group
(aldehyde group-containing organic group) include aldehydesaturated
aliphatic groups (aldehydealiphatic groups) such as
6-aldehydehexyl, and the like.
[0352] Examples of the organic group containing a thiol group
(thiol group-containing organic group) include thiolsaturated
aliphatic groups (thiolaliphatic groups) such as 6-thiolhexyl, and
the like.
[0353] Specifically, the organic compound containing a hydrophilic
group can be, for example, a carboxyl group-containing organic
compound, a hydroxyl group-containing organic compound, a
phosphoric acid group-containing organic compound, an amino
group-containing organic compound, a sulfo group-containing organic
compound, a carbonyl group-containing organic compound, a cyano
group-containing organic compound, a nitro group-containing organic
compound, an aldehyde group-containing organic compound, a thiol
group-containing organic compound, and the like.
[0354] The carboxyl group-containing organic compound can be, for
example, a dicarboxylic acid or the like in the case where both the
binding group and the hydrophilic group are carboxyl groups.
Examples of the dicarboxylic acid include aliphatic dicarboxylic
acids including saturated aliphatic dicarboxylic acids such as
propanedioic acid (malonic acid), butanedioic acid (succinic acid),
hexanedioic acid (adipic acid), octanedioic acid, decanedioic acid
(sebacic acid) and unsaturated aliphatic dicarboxylic acids such as
itaconic acid; alicyclic dicarboxylic acids such as cyclohexyl
dicarboxylic acid; araliphatic dicarboxylic acids such as
6-carboxyphenyl hexanoic acid; aromatic dicarboxylic acids such as
phthalic acid, terephthalic acid and isophthalic acid; and the
like. Also, the carboxyl group-containing organic compound can be a
carboxyl group-containing phosphate ester or the like in the case
where the binding group is a carboxyl group and the hydrophilic
group is a phosphoric acid ester group (in the case where the
inorganic particles include, for example, cerium oxide, strontium
carbonate or barium sulfate), or in the case where the binding
group is a phosphoric acid ester group and the hydrophilic group is
a carboxyl group (in the case where the inorganic particles
include, for example, zinc oxide or barium sulfate). Specific
examples thereof include ethyl carboxydecylphosphate, ethyl
carboxyoctylphosphate, and the like.
[0355] The hydroxyl group-containing organic compound can
specifically be, for example, a monohydroxyl carboxylic acid in the
case where the binding group is a carboxyl group and the
hydrophilic group is a hydroxyl group (in the case where the
inorganic particles include, for example, cerium oxide, strontium
carbonate or barium sulfate). Specific examples of the monohydroxyl
carboxylic acid include 4-hydroxybutanoic acid, 6-hydroxyhexanoic
acid, 8-hydroxyoctanoic acid, 4-hydroxyphenylacetic acid,
3-(4-hydroxyphenyl)propionic acid, 6-(4-hydroxyphenyl)hexanoic
acid, hydroxybenzoic acid, and the like.
[0356] The phosphoric acid group-containing organic compound can
be, for example, a monophosphonocarboxylic acid in the case where
the binding group is a carboxyl group and the hydrophilic group is
a phosphoric acid group (in the case where the inorganic particles
include, for example, cerium oxide, strontium carbonate or barium
sulfate). Specific examples thereof include 6-phosphonohexanoic
acid, 6-phosphonophenylhexanoic acid, as well as the carboxyl
group-containing phosphate esters listed above.
[0357] The amino group-containing organic compound can specifically
be, for example, a monoaminocarboxylic acid in the case where the
binding group is a carboxyl group and the hydrophilic group is an
amino group (in the case where the inorganic particles include, for
example, cerium oxide, strontium carbonate or barium sulfate).
Specific examples thereof include 6-aminohexanoic acid,
6-aminophenylhexanoic acid, and the like.
[0358] The sulfo group-containing organic compound can specifically
be, for example, a monosulfocarboxylic acid in the case where the
binding group is a carboxyl group and the hydrophilic group is a
sulfo group (in the case where the inorganic particles include, for
example, cerium oxide, strontium carbonate or barium sulfate).
Specific examples thereof include 6-sulfohexanoic acid,
6-sulfophenylhexanoic acid, and the like.
[0359] The carbonyl group-containing organic compound can
specifically be, for example, a monocarbonylcarboxylic acid in the
case where the binding group is a carboxyl group and the
hydrophilic group is a carbonyl group (in the case where the
inorganic particles include, for example, cerium oxide, strontium
carbonate or barium sulfate). Specific examples thereof include
4-oxovaleric acid, and the like.
[0360] The cyano group-containing organic compound can specifically
be, for example, a monocyanocarboxylic acid in the case where the
binding group is a carboxyl group and the hydrophilic group is a
cyano group (in the case where the inorganic particles include, for
example, cerium oxide, strontium carbonate or barium sulfate).
Specific examples thereof include 6-cyano hexanoic acid, and the
like.
[0361] The nitro group-containing organic compound can specifically
be, for example, a mononitrocarboxylic acid in the case where the
binding group is a carboxyl group and the hydrophilic group is a
nitro group (in the case where the inorganic particles include, for
example, cerium oxide, strontium carbonate or barium sulfate).
Specific examples thereof include 6-nitro hexanoic acid, and the
like.
[0362] The aldehyde group-containing organic compound can
specifically be, for example, a monoaldehydecarboxylic acid in the
case where the binding group is a carboxyl group and the
hydrophilic group is an aldehyde group (in the case where the
inorganic particles include, for example, cerium oxide, strontium
carbonate or barium sulfate). A specific example is
6-aldehydehexanoic acid.
[0363] The thiol group-containing organic compound can specifically
be, for example, a monothiolcarboxylic acid in the case where the
binding group is a carboxyl group and the hydrophilic group is a
thiol group (in the case where the inorganic particles include, for
example, cerium oxide, strontium carbonate or barium sulfate).
Specific examples include 6-thiolhexanoic acid, and the like.
[0364] The same or mutually different organic groups may be
used.
[0365] In the case where mutually different organic groups are
used, or in other words, the organic group contains a plurality of
different types of organic groups, a plurality of homologous
organic groups and/or a plurality of heterologous organic groups
are contained.
[0366] Examples of the homologous organic groups include a
combination of a plurality of aliphatic groups, a combination of a
plurality of alicyclic groups, a combination of a plurality of
araliphatic groups and a combination of a plurality of aromatic
groups. Other examples of the homologous organic groups include a
combination of a plurality of carboxyaliphatic groups, a
combination of a plurality of carboxyalicyclic groups, a
combination of a plurality of carboxyaraliphatic groups, a
combination of a plurality of carboxyaromatic groups, a combination
of a plurality of hydroxy aliphatic groups, a combination of a
plurality of hydroxyaraliphatic groups, a combination of a
plurality of hydroxyaromatic groups, a combination of a plurality
of phosphonoaliphatic groups, a combination of a plurality of
phosphonoaraliphatic groups, a combination of a plurality of
aminoaliphatic groups, a combination of a plurality of
aminoaraliphatic groups, a combination of a plurality of
sulphoaliphatic groups, a combination of a plurality of
sulphoaraliphatics, a combination of a plurality of oxoaliphatic
groups, a combination of a plurality of cyanoaliphatic groups, a
combination of a plurality of nitroaliphatic groups, a combination
of a plurality of aldehydealiphatic groups, a combination of a
plurality of thiolaliphatic groups, and the like.
[0367] As the homologous organic groups, a preferable example is a
combination of a plurality of aliphatic groups, a more preferable
example is a combination of a plurality of saturated aliphatic
groups, and a particularly preferable example is a combination of a
saturated aliphatic group having less than 10 carbon atoms and a
saturated aliphatic group having 10 or more carbon atoms,
specifically, a combination of hexyl and decyl.
[0368] When the organic group contains a plurality of homologous
organic groups, a plurality of organic groups having different
sizes (lengths or/and dimensions, or in other words, the number of
carbon atoms) are contained in the organic group. Accordingly, in a
space between adjacent larger organic groups, a resin molecule
enters a gap (pocket) formed in accordance with the smaller organic
group, and the interaction between the larger organic group and the
resin molecule can be enhanced. As a result, the dispersibility of
the organic-inorganic composite particles can be enhanced.
[0369] Examples of the heterologous organic groups include a
combination of at least two different groups selected from the
group consisting of an aliphatic group, an alicyclic group, an
araliphatic group, an aromatic group, a carboxyaliphatic group, a
carboxyalicyclic group, a carboxyaraliphatic group, a
carboxyaromatic group, a hydroxy aliphatic group, a
hydroxyaraliphatic group, a hydroxyaromatic group, a
phosphonoaliphatic group, a phosphonoaraliphatic group, an
aminoaliphatic group, an aminoaraliphatic group, a sulphoaliphatic
group, a sulphoaraliphatic group, an oxoaliphatic group, a
cyanoaliphatic group, a nitroaliphatic group, an aldehydealiphatic
group and a thiolaliphatic group.
[0370] A preferable example of the heterologous organic groups is a
combination of an araliphatic group and an aromatic group, and a
more preferable example is a combination of an araliphatic group
having 7 to 15 carbon atoms and an aromatic group having 6 to 12
carbon atoms, specifically, a combination of phenylhexyl and
phenyl.
[0371] Another preferable example of the heterologous organic
groups is a combination of an aliphatic group and a hydroxy
aliphatic group, a more preferable example is a combination of a
saturated aliphatic group and a hydroxysaturated aliphatic group,
and a particularly preferable example is a combination of a
saturated aliphatic group having 10 or more carbon atoms and a
hydroxysaturated aliphatic group having less than 10 carbon atoms,
specifically, a combination of decyl and 6-hydroxyhexyl.
[0372] As long as the organic group contains a plurality of
heterologous organic groups, when the resin is prepared as a
mixture of a plurality of resin components, the organic group can
exert excellent compatibility with the resin molecules of the
respective resin components having excellent compatibility with the
organic groups of the respective groups. Accordingly, the
interaction between the organic groups and the resin molecules of
the resin components can be enhanced. As a result, the
dispersibility of the organic-inorganic composite particles can be
enhanced.
[0373] The organic groups are present on the surface of inorganic
particles in the organic-inorganic composite particles.
Specifically, the organic groups are bound to the surface of
inorganic particles via a binding group. Also, the organic groups
extend from the surface of inorganic particles toward the outside
of the inorganic particles via the binding group.
[0374] The organic-inorganic composite particles are produced by
subjecting an inorganic substance and an organic compound to a
reaction treatment, preferably to a high temperature treatment.
[0375] The high temperature treatment is carried out in a solvent.
As the solvent, for example, water and any of the organic compounds
listed above can be used.
[0376] Specifically, the organic-inorganic composite particles are
obtained by subjecting an inorganic substance and an organic
compound to a high temperature treatment in water under high
pressure conditions (hydrothermal synthesis: hydrothermal
reaction), or subjecting an inorganic substance to a high
temperature treatment in an organic compound (high temperature
treatment in an organic compound). In other words, the
organic-inorganic composite particles are obtained by
surface-treating the surface of inorganic particles formed by an
inorganic substance with an organic compound.
[0377] In the hydrothermal synthesis, for example, the inorganic
substance and the organic compound are reacted under
high-temperature and high-pressure conditions in the presence of
water (first hydrothermal synthesis).
[0378] The inorganic substance subjected to the first hydrothermal
synthesis is preferably a carbonate or a sulfate.
[0379] Specifically, first, a reaction system is prepared under
high-temperature and high-pressure conditions by placing the
inorganic substance, the organic compound and water in a
pressure-resistant airtight container and heating them.
[0380] The proportions of respective components per 100 parts by
mass of the inorganic substance are as follows: the proportion of
the organic compound is, for example, 1 to 1500 parts by mass,
preferably 5 to 500 parts by mass and more preferably 5 to 250
parts by mass; and the proportion of water is, for example, 50 to
8000 parts by mass, preferably 80 to 6600 parts by mass and more
preferably 100 to 4500 parts by mass.
[0381] The density of the organic compound is usually 0.8 to 1.1
g/mL, and thus the proportion of the organic compound is, for
example, 1 to 1500 mL, preferably 5 to 500 mL and more preferably 5
to 250 mL per 100 g of the inorganic substance.
[0382] Also, the number of moles of the organic compound may be,
for example, 0.01 to 1000 mol, preferably 0.02 to 50 mol, and more
preferably 0.1 to 10 mol per mol of the inorganic substance.
[0383] In the case where the organic compound contains a plurality
of (for example, two) different types of organic groups,
specifically, the molar ratio between an organic compound
containing one type of organic groups and an organic compound
containing the other type of organic group is, for example, 10:90
to 99.9:0.1 and preferably 20:80 to 99:1.
[0384] Also, the density of water is usually approximately 1 g/mL,
and thus the proportion of water is, for example, 50 to 8000 mL,
preferably 80 to 6600 mL, and more preferably 100 to 4500 mL per
100 g of the inorganic substance.
[0385] Specific reaction conditions for the hydrothermal reaction
are as follows. The heating temperature is, for example, 100 to
500.degree. C. and preferably 200 to 400.degree. C. The pressure
is, for example, 0.2 to 50 MPa, preferably 1 to 50 MPa and more
preferably 10 to 50 MPa. The reaction time is, for example, 1 to
200 minutes and preferably 3 to 150 minutes. In the case where a
continuous reactor is used, the reaction time can be set to one
minute or less.
[0386] The reaction product obtained by the above reaction includes
a precipitate that mostly precipitates in water and a deposit that
adheres to the inner wall of the airtight container.
[0387] The precipitate is obtained by, for example, sedimentation
separation in which the reaction product is settled by gravity or a
centrifugal field. Preferably, the precipitate is obtained as a
precipitate of the reaction product by centrifugal sedimentation
(centrifugal separation) in which the reaction product is settled
by a centrifugal field.
[0388] The deposit is recovered by, for example, a scraper
(spatula) or the like.
[0389] The reaction product can also be recovered (separated) by
adding a solvent to wash away an unreacted organic compound (or in
other words, dissolving the organic compound in the solvent) and
thereafter removing the solvent.
[0390] The solvent can be, for example, an alcohol (hydroxyl
group-containing aliphatic hydrocarbon) such as methanol, ethanol,
propanol or isopropanol, a ketone (carbonyl group-containing
aliphatic hydrocarbon) such as acetone, methyl ethyl ketone,
cyclohexanone or cyclopentanone, an aliphatic hydrocarbon such as
pentane, hexane or heptane, a halogenated aliphatic hydrocarbon
such as dichloromethane, chloroform or trichloroethane, a
halogenated aromatic hydrocarbon such as chlorobenzene or
dichlorobenzene, an ether such as tetrahydrofuran, an aromatic
hydrocarbon such as benzene, toluene or xylene, an aqueous pH
adjusting solution such as aqueous ammonia, or the like. An alcohol
is preferable.
[0391] The washed reaction product is separated from the solvent
(supernatant liquid) by, for example, filtration, decantation or
the like, and recovered. After that, the reaction product is dried
by, for example, application of heat, an air stream or the like if
necessary.
[0392] In this manner, the organic-inorganic composite particles
having an organic group on the surface of inorganic particles are
obtained.
[0393] In the first hydrothermal synthesis, the inorganic substance
before reaction and the inorganic substance after reaction that
forms inorganic particles are the same.
[0394] Alternatively, by subjecting an inorganic substance
(starting material) and an organic compound to a hydrothermal
synthesis, it is also possible to obtain organic-inorganic
composite particles containing inorganic particles formed of an
inorganic substance that is different from the inorganic substance
serving as the starting material (second hydrothermal
synthesis).
[0395] The inorganic substance subjected to the second hydrothermal
synthesis can be, for example, a hydroxide, a metal complex, a
nitrate, a sulfate or the like. A hydroxide and a metal complex are
preferable.
[0396] In the hydroxide, the element (element that constitutes a
cation that combines with a hydroxyl ion (OH.sup.-)) contained in
the hydroxide can be the same as the element that combines with
oxygen in an oxide listed above.
[0397] Specifically, the hydroxide can be, for example, titanium
hydroxide (Ti(OH).sub.4) or cerium hydroxide (Ce(OH).sub.4).
[0398] In the metal complex, the metal element contained in the
metal complex is a metal element that constitutes a composite oxide
with the metal contained in the hydroxide, and examples thereof
include titanium, iron, tin, zirconium and the like. Titanium is
preferable.
[0399] The ligand of the metal complex can be, for example, a
monohydroxycarboxylic acid such as 2-hydroxyoctanoic acid, or the
like.
[0400] Examples of the metal complex include 2-hydroxyoctanoic acid
titanate and the like. The metal complex can be obtained by
preparation from a metal element and a ligand described above.
[0401] As the organic compound, for example, the same organic
compounds as those that can be used in the first hydrothermal
synthesis described above can be used.
[0402] In the second hydrothermal synthesis, the inorganic
substance and the organic compound are reacted under
high-temperature and high-pressure conditions in the presence of
water.
[0403] The proportions of respective components per 100 parts by
mass of the inorganic compound are as follows: the proportion of
the organic compound is, for example, 1 to 1500 parts by mass,
preferably 5 to 500 parts by mass, and more preferably 5 to 250
parts by mass; and the proportion of water is, for example, 50 to
8000 parts by mass, preferably 80 to 6600 parts by mass, and more
preferably 80 to 4500 parts by mass.
[0404] The proportion of the organic compound is, for example, 0.9
to 1880 mL, preferably 4.5 to 630 mL, and more preferably 4.5 to
320 mL per 100 g of the hydroxide, and the number of moles of the
organic compound may be, for example, 0.01 to 10000 mol, and
preferably 0.1 to 10 mol per mol of the hydroxide.
[0405] The proportion of water is, for example, 50 to 8000 mL,
preferably 80 to 6600 mL, and more preferably 5 to 4500 mL per 100
g of the hydroxide.
[0406] The reaction conditions for the second hydrothermal
synthesis are the same as those for the first hydrothermal
synthesis described above.
[0407] In this manner, the organic-inorganic composite particles
containing an organic group on the surface of inorganic particles
formed of an inorganic substance that is different from the
inorganic substance serving as a starting material are
obtained.
[0408] In the formulation used in the second hydrothermal
synthesis, a carbonic acid source or a hydrogen source can be
blended with the components described above.
[0409] The carbonic acid source can be, for example, carbon dioxide
(carbonic acid gas), formic acid and/or urea.
[0410] The hydrogen source can be, for example, hydrogen (hydrogen
gas), an acid such as formic acid or lactic acid, a hydrocarbon
such as methane or ethane, or the like.
[0411] The proportion of the carbonic acid source or hydrogen
source is, for example, 5 to 140 parts by mass and preferably 10 to
70 parts by mass per 100 parts by mass of the inorganic
substance.
[0412] The proportion of the carbonic acid source can be, for
example, 5 to 100 mL and preferably 10 to 50 mL per 100 g of the
inorganic substance. The number of moles of the carbonic acid
source can be, for example, 0.4 to 100 mol, preferably 1.01 to 10.0
mol and more preferably 1.05 to 1.30 mol per mol of the inorganic
substance.
[0413] The proportion of the hydrogen source can be, for example, 5
to 100 mL and preferably 10 to 50 mL per 100 g of the inorganic
substance. The number of moles of the hydrogen source can be, for
example, 0.4 to 100 mol, preferably 1.01 to 10.0 mol and more
preferably 1.05 to 2.0 mol per mol of the inorganic substance.
[0414] In the high temperature treatment in an organic compound, an
inorganic substance and an organic compound are blended and heated
under, for example, normal atmospheric pressure conditions. The
organic compound is subjected to the high-temperature treatment
while serving as an organic group-introducing compound as well as a
solvent for dispersing or dissolving the inorganic substance.
[0415] The proportion of the organic compound is, for example, 10
to 10000 parts by mass and preferably 100 to 1000 parts by mass per
100 parts by mass of the inorganic substance. The proportion of the
organic compound in terms of volume is, for example, 10 to 10000 mL
and preferably 100 to 1000 mL per 100 g of the inorganic
substance.
[0416] The heating temperature is, for example, a temperature above
100.degree. C., preferably 125.degree. C. or higher, and more
preferably 150.degree. C. or higher, and, usually for example,
300.degree. C. or lower, and preferably 275.degree. C. or lower.
The heating time is, for example, 1 to 60 minutes and preferably 3
to 30 minutes.
[0417] There is no particular limitation on the shape of the
organic-inorganic composite particles (primary particles) obtained
in the above-described manner, and for example the
organic-inorganic composite particles may be anisotropic or
isotropic, with an average particle size (maximum length in the
case where they are anisotropic) of, for example, 200 .mu.m or
less, preferably 1 nm to 200 .mu.m, more preferably 3 nm to 50
.mu.m and particularly preferably 3 nm to 10 .mu.m.
[0418] As will be described in detail in the examples given below,
the average particle size of the organic-inorganic composite
particles is determined by measurement by dynamic light scattering
(DLS) and/or calculated from a transmission electron microscopic
(TEM) or scanning electron microscopic (SEM) image analysis.
[0419] If the average particle size is below the above range, the
proportion of the volume of the organic group relative to the
surface of the organic-inorganic composite particles will be high,
and the function of the inorganic particles is unlikely to be
obtained.
[0420] If, on the other hand, the average particle size exceeds the
above range, the organic-inorganic composite particles may be
crushed when mixed with the resin or the like.
[0421] The organic-inorganic composite particles thus obtained are
unlikely to coagulate in a dry state, and even if the
organic-inorganic composite particles appear coagulated in a dry
state, the coagulation (formation of secondary particles) will be
reliably prevented in the particle-dispersed resin composition and
the particle-dispersed resin molded article, and therefore the
organic-inorganic composite particles are dispersed substantially
uniformly in the resin as primary particles.
[0422] In other words, the organic-inorganic composite particles
have at least a configuration that does not allow the inorganic
particles to contact with each other by steric hindrance of the
organic group.
[0423] In the organic-inorganic composite particles, the proportion
of the surface area of the organic group relative to the surface
area of the inorganic particles, or in other words, the surface
coverage by the organic group in the organic-inorganic composite
particles (=(surface area of organic group/surface area of
inorganic particles).times.100) is, for example, 30% or greater and
preferably 60% or greater and usually 200% or less.
[0424] To calculate the surface coverage, first, the shape of the
inorganic particles is checked with a transmission electron
microscope (TEM), the average particle size is then calculated, and
the specific surface area of the particles is calculated from the
shape of the inorganic particles and the average particle size.
Alternatively, the proportion of the organic group in the
organic-inorganic composite particles is calculated from the weight
change as a result of the organic-inorganic composite particles
being heated to 800.degree. C. with a differential thermal balance
(TG-DTA). After that, the amount of the organic group per particle
is calculated from the molecular weight of the organic group, the
particle density and the average volume. Then, the surface coverage
is determined from the calculated results.
[0425] In the case where at least the surface coverage is high and
the organic group of the organic-inorganic composite particles has
a length sufficient to cancel the electric charge of the inorganic
particles, the type of solvent (medium) for dispersing the
organic-inorganic composite particles can be controlled (designed
or managed) according to the type of organic group.
[0426] The organic-inorganic composite particles obtained in the
above-described manner can be subjected to wet classification.
[0427] That is, a solvent is added to the organic-inorganic
composite particles, and the resulting mixture is stirred and
allowed to stand still, and thereafter separated into a supernatant
and a precipitate. The solvent varies depending on the type of
organic groups, but for example, the same solvents as those listed
above can be used. Preferably, the solvent is a hydroxyl
group-containing aliphatic hydrocarbon, a carbonyl group-containing
aliphatic hydrocarbon, an aliphatic hydrocarbon, a halogenated
aliphatic hydrocarbon or an aqueous pH adjusting solution.
[0428] After that, the supernatant is recovered, and it is thereby
possible to obtain organic-inorganic composite particles having a
small particle size.
[0429] With the wet classification, the average particle size of
the resulting organic-inorganic composite particles (primary
particles) can be adjusted to, for example, 1 nm to 450 nm,
preferably 3 nm to 200 nm and more preferably 3 nm to 100 nm.
[0430] It is also possible to select the resin and the
organic-inorganic composite particles such that the solubility
parameters (SP values) thereof satisfy a predetermined
relationship.
[0431] Specifically, the resin and the organic-inorganic composite
particles are selected so as to attain a predetermined SP
difference (.DELTA.SP, specifically, the absolute value of the
difference between the solubility parameter of resin (SP.sub.RESIN
value) and the solubility parameter of organic-inorganic composite
particles (SP.sub.PARTICLE value)).
[0432] Preferable hydrophilic groups included in both the
functional group and the organic group are a carboxyl group and a
hydroxyl group, and preferable hydrophobic groups included in both
the functional group and the organic group are a hydrocarbon group
and the like. The affinity between the organic-inorganic composite
particles and the resin can be enhanced as a result of both the
functional group and the organic group having any of the above
groups having the same property (hydrophilicity or
hydrophobicity).
[0433] Specifically, in order to prepare a particle-dispersed resin
composition, for example, a solvent, organic-inorganic composite
particles and a resin are blended, and the resulting mixture is
stirred (solution preparation). The thus-prepared
particle-dispersed resin composition is a varnish (solution)
containing a solvent.
[0434] There is no particular limitation on the solvent, and the
solvent can be any of the solvents used in washing described above.
Other examples include alicyclic hydrocarbons such as cyclopentane
and cyclohexane; esters such as ethyl acetate; polyols such as
ethylene glycol and glycerol; nitrogen-containing compounds such as
N-methylpyrrolidone, pyridine, acetonitrile and dimethylformamide;
acryl-based monomers such as isostearyl acrylate, lauryl acrylate,
isoboronyl acrylate, butyl acrylate, methacrylate, acrylic acid,
tetrahydrofurfuryl acrylate, 1,6-hexanediol diacrylate,
2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxyethyl
acrylate, and acryloylmorpholine; vinyl group-containing monomers
such as styrene and ethylene; epoxy-containing monomers such as
bisphenol A epoxy; and the like.
[0435] These solvents can be used singly or in a combination of two
or more. A halogenated aliphatic hydrocarbon and an aqueous pH
adjusting solution are preferable.
[0436] Specifically, in order to prepare a particle-dispersed resin
composition, first, the above solvent and a resin are blended so as
to dissolve the resin in the solvent to prepare a resin solution.
After that, the resin solution is blended with organic-inorganic
composite particles, and the resulting mixture is stirred to
prepare a particle-dispersed resin composition (first preparation
method).
[0437] The proportion of resin per 100 parts by mass of the resin
solution is, for example, 40 parts by mass or less, preferably 35
parts by mass or less, and more preferably 30 parts by mass or
less, and usually 1 part by mass or greater. If the proportion of
resin exceeds the above range, the solubility of resin may be
low.
[0438] The proportion of the organic-inorganic composite particles
per 100 parts by mass of the solids content (resin) of the resin
solution is, for example, 1 to 1000 parts by mass, preferably 5 to
500 parts by mass and more preferably 10 to 300 parts by mass.
Also, the proportion of the organic-inorganic composite particles
per 100 parts by mass of the total amount of the resin solution
(the total amount of the resin and the solvent) is, for example,
0.1 to 300 parts by mass, preferably 1 to 200 parts by mass and
more preferably 3 to 100 parts by mass.
[0439] Also, the particle-dispersed resin composition can also be
prepared by blending a solvent and organic-inorganic composite
particles to disperse the organic-inorganic composite particles in
the solvent to prepare a particle dispersion, and then blending the
particle dispersion with a resin and stirring the resulting mixture
(second preparation method).
[0440] In the particle dispersion, the organic-inorganic composite
particles are dispersed in the solvent as primary particle.
[0441] The proportion of the organic-inorganic composite particles
per 100 parts by mass of the particle dispersion is, for example,
0.1 to 70 parts by mass, preferably 0.2 to 60 parts by mass, and
more preferably 0.5 to 50 parts by mass.
[0442] The proportion of resin per 100 parts by mass of the solids
content (organic-inorganic composite particles) of the particle
dispersion is, for example, 10 to 10000 parts by mass, preferably
20 to 2000 parts by mass and more preferably 40 to 1000 parts by
mass.
[0443] Furthermore, the particle-dispersed resin composition can
also be prepared by, for example, blending a solvent,
organic-inorganic composite particles and a resin simultaneously
and stirring the resulting mixture (third preparation method).
[0444] The proportions of respective components per 100 parts by
mass of the total amount of the particle-dispersed resin
composition are as follows: the proportion of the organic-inorganic
composite particles is, for example, 0.1 to 50 parts by mass,
preferably 1 to 40 parts by mass and more preferably 3 to 30 parts
by mass; and the proportion of resin is, 40 parts by mass or less,
preferably 35 parts by mass or less and more preferably 30 parts by
mass or less, and unusually 1 part by mass or greater. The
proportion of the solvent is the remainder obtained by excluding
the organic-inorganic composite particles and the resin from the
particle-dispersed resin composition.
[0445] The particle-dispersed resin composition can also be
prepared by, first, preparing a resin solution and a particle
dispersion in a separate manner, and then blending and stirring the
resin solution and the particle dispersion (fourth preparation
method).
[0446] The proportion of resin in the resin solution is the same as
those shown in the first preparation method described above.
[0447] The proportion of the organic-inorganic composite particles
in the particle dispersion is the same as those shown in the second
preparation method described above.
[0448] The resin solution and the particle dispersion are blended
such that the proportion of resin relative to the organic-inorganic
composite particles in terms of mass is, for example, 99:1 to
10:90, preferably 95:5 to 20:80 and more preferably 90:10 to
30:70.
[0449] Furthermore, the particle-dispersed resin composition can
also be prepared without the use of a solvent by, for example,
melting a resin by application of heat and blending the resin with
organic-inorganic composite particles (fifth preparation
method).
[0450] The thus-prepared particle-dispersed resin composition is a
melt of the particle-dispersed resin composition which does not
include a solvent.
[0451] The heating temperature is, in the case where the resin is a
thermoplastic resin, greater than or equal to the melting
temperature of the resin, specifically, 200 to 350.degree. C. In
the case where the resin is a thermosetting resin, the heating
temperature is a temperature at which the resin is B-staged, for
example, 85 to 140.degree. C.
[0452] The proportion of resin relative to the organic-inorganic
composite particles in terms of mass is, for example, 99:1 to
10:90, preferably 95:5 to 20:80 and more preferably 90:10 to
30:70.
[0453] In the particle-dispersed resin composition obtained by any
of the above-described preparation methods, the organic-inorganic
composite particles are uniformly dispersed in the resin.
Specifically, in the particle-dispersed resin composition, the
organic-inorganic composite particles are dispersed as primary
particles in the resin (without substantial coagulation).
[0454] After that, the obtained particle-dispersed resin
composition is applied to, for example, a known support plate to
form a coating, and the coating is dried, whereby a
particle-dispersed resin molded article as a film is molded.
[0455] The particle-dispersed resin composition is applied by
using, for example, a known application method such as spin coating
or bar coating. Simultaneously with or immediately after
application of the particle-dispersed resin composition, the
solvent is removed by volatilization. If necessary, the solvent can
be dried by application of heat after application of the
particle-dispersed resin composition.
[0456] The thickness of the obtained film can be set as appropriate
according to the use and purpose, and the thickness is, for
example, 0.1 to 2000 .mu.m, preferably 0.5 to 1000 .mu.m and more
preferably 1.0 to 500 .mu.m.
[0457] The particle-dispersed resin molded article as a film can
also be molded by a melt molding method in which the
particle-dispersed resin composition is extruded by an extruding
machine or the like.
[0458] The particle-dispersed resin molded article can also be
molded as a block (mass) by injecting the particle-dispersed resin
composition into a metal mold or the like and thereafter subjecting
the resultant to, for example, heat molding such as heat
pressing.
[0459] In any of the particle-dispersed resin molded articles
molded in the above-described manner, the organic-inorganic
composite particles are dispersed as primary particles in the
resin.
[0460] That is, with a simple method in which a resin and
organic-inorganic composite particles are blended such that the
organic-inorganic composite particles are dispersed as primary
particles in the resin by steric hindrance of the organic group,
the organic-inorganic composite particles can be easily and
uniformly dispersed in the resin in the particle dispersion and the
particle-dispersed resin molded article. In short, with such a very
simple operation, the organic-inorganic composite particles can be
dispersed as primary particles in the resin. Also, the
organic-inorganic composite particles can be dispersed as primary
particles in the resin regardless of the type of inorganic
particles with the above-described simple operation.
[0461] Accordingly, the particle-dispersed resin compositions and
the particle-dispersed resin molded articles obtained by the
above-described methods have excellent clarity because the
organic-inorganic composite particles are uniformly dispersed in
the resin, and therefore they can be suitably used in various
industrial applications including optical applications.
Third Embodiment
[0462] Embodiment corresponding to the inventions of catalyst
particles, a catalyst solution, a catalyst composition and a
catalyst molded article, which are included in the third group of
inventions
[0463] The catalyst particles of the present invention contain
inorganic particles with a catalytic action and an organic group
that binds to the surface of the inorganic particles.
[0464] The inorganic particles preferably have a photocatalytic
action that exerts a catalytic action for a gas and/or a liquid
(described later) by absorbing light.
[0465] Such catalyst particles can be obtained by, for example,
surface-treating an inorganic substance and/or a complex thereof
with an organic compound.
[0466] The inorganic substance include a metal composed of a metal
element such as a main group element or a transition element, a
nonmetal composed of a nonmetal element such as boron or silicon,
an inorganic compound containing a metal element and/or a nonmetal,
or the like.
[0467] Examples of the metal element and the nonmetal element
include elements that are located on the left side and the lower
side of a border line that is assumed to pass through boron (B) of
the IIIB group, silicon (Si) of the IVB group, arsenic (As) of the
VB group, tellurium (Te) of the VIB group and astatine (At) of the
VIIB group on the long-form periodic table (IUPAC, 1989), as well
as the elements that are located on the border line, and the same
elements as those listed in the second embodiment.
[0468] The inorganic compound can be, for example, a hydrogen
compound, a hydroxide, a nitride, a halide, an oxide, a carbonate,
a sulfate, a nitrate, an acetate, a formate, a sulfide, a carbide,
a phosphorus compound, or the like. The inorganic compound may be a
composite compound such as, for example, an oxynitride or a
composite oxide.
[0469] Among the inorganic substances listed above, a preferable
example is an inorganic compound, and more preferable examples are
an oxide, a sulfate, a nitrate, an acetate, a formate and a
composite oxide. An oxide is particularly preferable.
[0470] Examples of the oxide include metal oxides, and preferable
examples include titanium oxide (titanium dioxide, titanium oxide
(IV), titania: TiO.sub.2), tungsten oxide (tungsten trioxide,
tungsten oxide (VI), WO.sub.3), cerium oxide (cerium dioxide,
cerium oxide (IV), ceria: CeO.sub.2), zirconium oxide (zirconium
dioxide, zirconium oxide (IV), zirconia: ZrO.sub.2), tantalum oxide
(tantalum dioxide, tantalum oxide (IV), TaO.sub.2) and the
like.
[0471] The arrangement of atoms in an oxide is not particularly
limited, and can be, for example, either crystalline or
non-crystalline (amorphous).
[0472] The oxides can be used singly or in a combination of two or
more
[0473] The sulfate is a compound consisting of a sulfate ion
(SO.sub.4.sup.2-) and a metal cation (more specifically, a compound
formed by substitution of the hydrogen atoms of sulfuric acid
(H.sub.2SO.sub.4) with a metal), and the metal element contained in
the sulfate can be, for example, a group IVA element or a group IB
element. Ti and Cu are preferable.
[0474] Specifically, the sulfate is preferably titanium sulfate,
zirconium sulfate, hafnium sulfate, copper sulfate, silver sulfate
or the like. Titanium sulfate and copper sulfate are more
preferable.
[0475] The sulfates can be used singly or in a combination of two
or more.
[0476] The nitrate is a compound consisting of a nitrate ion
(NO.sub.3.sup.-) and a metal cation (more specifically, a compound
formed by substitution of the hydrogen atom of nitric acid
(HNO.sub.3) with a metal), and the metal element contained in the
nitrate can be, for example, a group VIII element. Pd and Pt are
preferable.
[0477] Specifically, preferable nitrates are iron nitrate, cobalt
nitrate, nickel nitrate, ruthenium nitrate, rhodium nitrate,
palladium nitrate, osmium nitrate, iridium nitrate and the like.
Palladium nitrate and platinum nitrate are more preferable.
[0478] The nitrates can be used singly or in a combination of two
or more.
[0479] The acetate is a compound consisting of an acetate ion
(CH.sub.3COO.sup.-) and a metal cation (more specifically, a
compound formed by substitution of the hydrogen atom of the
carboxyl group (--COOH) in acetic acid with a metal), and the metal
element contained in the acetate can be, for example, a group VIII
element. Ni is preferable.
[0480] Specifically, a preferable acetate is nickel acetate.
[0481] The acetates can be used singly or in a combination of two
or more.
[0482] The formate is a compound consisting of a formate ion
(HCOO.sup.-) and a metal cation (more specifically, a compound
formed by substitution of the hydrogen atom of the carboxyl group
(--COOH) in formic acid with a metal), and the metal element
contained in the formate can be, for example, a group IB element.
Cu is preferable.
[0483] Specifically, a preferable formate is copper formate.
[0484] The formates can be used singly or in a combination of two
or more.
[0485] The composite oxide is a compound consisting of oxygen and a
plurality of elements, and the plurality of elements is a
combination of at least two elements selected from the elements
other than oxygen contained in the oxides listed above, the group I
elements, and the group II elements.
[0486] Examples of the group I elements include alkali metals such
as Li, Na, K, Rb, and Cs. Examples of the group II elements include
the same alkaline earth metals as those listed in the second
embodiment.
[0487] Examples of the combination of a plurality of elements
include combinations that include at least a group II element such
as a combination of a group II element and a group IVB element, a
combination of a group II element and a group VIII element, a
combination of a group II element and a group IVA element, and a
combination of a group II element and a group VA element;
combinations that include at least a group I element such as a
combination of a group I element and a group IVA element, a
combination of a group I element, a group IVA element and a
lanthanide series element, and a combination of a group I element
and a group VA element; a combination of a group VA element and a
group JIB element; and the like.
[0488] Examples of the composite oxide containing at least a group
II element include alkaline earth metal titanates, alkaline earth
metal zirconates, alkaline earth metal ferrates, alkaline earth
metal stannates, alkaline earth metal niobates and the like.
[0489] Examples of the composite oxide containing at least a group
I element include alkali metal titanates, alkali metal zirconates,
alkali metal vanadates, alkali metal niobates and the like.
[0490] Examples of the composite oxide containing a group VA
element and a group JIB group element include metal niobates and
the like.
[0491] Preferable composite oxides are alkaline earth metal
titanates, alkali metal titanates, alkaline earth metal niobates,
alkali metal niobates and metal niobates.
[0492] Examples of alkaline earth metal titanates include beryllium
titanate (BeTiO.sub.3), magnesium titanate (MgTiO.sub.3), calcium
titanate (CaTiO.sub.3), strontium titanate (SrTiO.sub.3), barium
titanate (BaTiO.sub.3), barium tetratitinate (BaTi.sub.4O.sub.9),
radium titanate (RaTiO.sub.3) and the like.
[0493] Examples of alkali metal titanates include sodium
hexatitanate (Na.sub.2Ti.sub.6O.sub.13), potassium lanthanum
titanate (K.sub.2La.sub.2Ti.sub.3O.sub.10) and the like.
[0494] Examples of alkaline earth metal niobates include strontium
diniobate (Sr.sub.2Nb.sub.2O.sub.7) and the like.
[0495] Examples of alkali metal niobates include potassium
hexaniobate (K.sub.4Nb.sub.6O.sub.17) and the like.
[0496] Examples of metal niobates include zinc diniobate
(ZnNb.sub.2O.sub.6) and the like.
[0497] The composite oxides can be used singly or in a combination
of two or more.
[0498] The complex contains a central atom and/or a central ion and
a ligand that coordinates thereto.
[0499] Examples of the central atom include the same metal elements
as those listed above. Preferable examples include a group IVA
element, a group VIII element and a group IVB element. More
preferable examples include Ti, Zr, Fe, Ni, Ru, Sn and the
like.
[0500] Examples of the central ion include cations of the metal
elements listed above.
[0501] Examples of the ligand include coordinating compounds such
as carboxylic acid, hydroxycarboxylic acid and acetylacetone;
coordinating ions such as cations and hydroxide ions of the above
coordinating compounds; and the like.
[0502] Examples of the carboxylic acid include dicarboxylic acids
such as oxalic acid, succinic acid, phthalic acid, and the
like.
[0503] Examples of the hydroxycarboxylic acid include
monohydroxymonocarboxylic acids (specifically,
.alpha.-monohydroxycarboxylic acids) such as 2-hydroxyoctanoic
acid, lactic acid and glycolic acid; monohydroxydicarboxylic acids
such as malic acid; monohydroxytricarboxylic acids such as citric
acid; and the like.
[0504] The coordination number is, for example, 1 to 6 and
preferably 1 to 3.
[0505] The complex can be obtained by preparation from a metal
element and a ligand described above.
[0506] The inorganic substance (specifically, oxide, composite
oxide) and the complex can be formed (prepared) as salts and/or
hydrates. Examples of the salts include salts with cations such as
ammonium ions.
[0507] The inorganic substances and the complexes listed above can
be used singly or in a combination of two or more.
[0508] In the case where an inorganic substance and/or a complex
are used in combination, the combination of an inorganic substance
and/or a complex can be, for example, a combination of a plurality
of types of inorganic substances (first combination) or a
combination of an inorganic substance and a complex (second
combination).
[0509] The first combination can be, for example, a combination of
a plurality of types of inorganic substances. Specific examples
include a combination of an oxide (first inorganic substance) and
at least one inorganic substance (second inorganic substance)
selected from the group consisting of metals, sulfates, nitrates
and formates.
[0510] More specifically, examples of the first combination include
a combination of a metal oxide and a metal (group VIII element), a
combination of a metal oxide and a sulfate, and a combination of a
metal oxide and a formate. Specific examples of the first
combination include a combination of tungsten oxide and palladium,
a combination of tungsten oxide and platinum, a combination of
tungsten oxide and copper sulfate, and a combination of tungsten
oxide and copper formate.
[0511] Examples of the second combination include a combination of
a complex whose ligand is hydroxycarboxylic acid and a metal, a
combination of a complex whose ligand is hydroxycarboxylic acid, a
hydroxide and an acetate, and a combination of a complex whose
ligand is hydroxycarboxylic acid, a hydroxide and a complex whose
ligand is acetylacetone.
[0512] Specific examples of the second combination include a
combination of a titanium complex whose central atom is titanium
and whose ligand is 2-hydroxyoctanoic acid and platinum, a
combination of a titanium complex whose central atom is titanium
and whose ligand is 2-hydroxyoctanoic acid, strontium hydroxide and
nickel acetate, and a combination of a titanium complex whose
central atom is titanium and whose ligand is 2-hydroxyoctanoic
acid, strontium hydroxide and a ruthenium complex whose central
atom is ruthenium and ligand is acetylacetone.
[0513] The organic compound is, for example, an organic
group-introducing compound that introduces (disposes) an organic
group on the surface of inorganic particles. Specifically, the
organic compound contains a binding group capable of binding to the
surface of inorganic particles and an organic group. In other
words, the organic group is bound to the surface of inorganic
particles via a binding group.
[0514] The binding group is selected as appropriate according to
the type of inorganic particles and examples thereof include
functional groups such as phosphoric acid group (--PO(OH).sub.2,
phosphono group), phosphoric acid ester group (phosphonate group),
carboxyl group, carboxylic acid ester group (carboxy ester group),
amino group, sulfo group, hydroxyl group, thiol group, epoxy group,
isocyanate group, nitro group, azo group, silyloxy group, imino
group, aldehyde group (acyl group), nitrile group and vinyl group
(polymerizable group). Preferable examples include phosphoric acid
group, phosphoric acid ester group, carboxyl group, amino group,
sulfo group, hydroxyl group, thiol group, epoxy group, azo group,
vinyl group and the like. More preferable examples include
phosphoric acid group, phosphoric acid ester group, carboxyl group,
amino group and hydroxyl group.
[0515] Phosphoric acid ester groups are, for example, alkyl ester
groups of phosphoric acid (specifically, orthophosphoric acid), or
in other words, alkoxy phosphonyls, and can be represented by the
following formula (1):
--PO(OR).sub.nH.sub.2-n (1) [0516] where R is an alkyl group having
1 to 3 carbon atoms, and n is an integer of 1 or 2. In the above
formula (I), the alkyl group represented by R is preferably methyl
or ethyl. [0517] n is preferably 2.
[0518] Examples of phosphoric acid ester groups include dialkyl
phosphate esters such as dimethyl phosphate esters (dimethoxy
phosphonyl: --PO(OCH.sub.3).sub.2), diethyl phosphate esters
(diethoxy phosphonyl: --PO(OC.sub.2H.sub.5).sub.2), dipropyl
phosphate esters (dipropoxy phosphonyl:
--PO(OC.sub.3H.sub.7).sub.2); monoalkyl phosphate esters such as
monomethyl phosphate esters (monomethoxy phosphonyl:
--PO(OCH.sub.3)H), monoethyl phosphate esters (monoethoxy
phosphonyl: --PO(O.sub.2CH.sub.5)H) and monopropyl phosphate esters
(monopropoxy phosphonyl: --PO(O.sub.3CH.sub.7)H); and the like.
Dialkyl phosphate esters are preferable.
[0519] The binding group is selected as appropriate according to
the type of inorganic particles. Specifically, when the inorganic
particles contain titanium oxide, for example, a phosphoric acid
group and/or a phosphoric acid ester group are selected. When the
inorganic particles contain tungstic acid (described later), for
example, an amino group is selected. When the inorganic particles
contain strontium titanate, for example, a carboxylic acid, a
phosphoric acid group and/or a phosphoric acid ester group are
selected.
[0520] One or more of these binding groups are contained in the
organic compound. Specifically, the binding group is bound to a
terminal or a side chain of the organic group.
[0521] The organic group includes, for example, a hydrocarbon group
such as an aliphatic group, an alicyclic group, an araliphatic
group or an aromatic group, or the like. Examples of the
hydrocarbon group include the same hydrocarbon groups as those
listed in the second embodiment.
[0522] The organic group is a hydrophobic group for imparting
hydrophobicity to the surface of inorganic particles.
[0523] Accordingly, the organic compounds containing a hydrophobic
group described above are used as hydrophobic organic compounds for
hydrophobic treatment of inorganic particles.
[0524] Specific examples of such hydrophobic organic compounds in
the case where the binding group is a phosphoric acid group include
aliphatic group-containing phosphonic acids including saturated
aliphatic group-containing phosphonic acids (saturated phosphonic
acids) such as methylphosphonic acid, hexyl phosphonic acid,
octylphosphonic acid and decylphosphonic acid, and the like. Other
examples of the hydrophobic organic compounds include alicyclic
group-containing phosphonic acids (alicyclic phosphonic acids) such
as cyclohexyl phosphonic acid; araliphatic group-containing
phosphonic acids (araliphatic phosphonic acids) such as
6-phenylhexyl phosphonic acid; aromatic group-containing phosphonic
acids (aromatic phosphonic acids) such as phenyl phosphonic acid
and toluenephosphonic acid; and the like.
[0525] Specific examples of hydrophobic organic compounds in the
case where the binding group is a phosphoric acid ester group
include aliphatic group-containing phosphonate esters including
saturated aliphatic group-containing phosphonate esters (saturated
phosphonic acid dialkyl esters) such as hexyl phosphonic acid
diethyl ester, octylphosphonic acid diethyl ester and
decylphosphonic acid diethyl ester, and the like. Other examples of
the hydrophobic organic compounds include alicyclic
group-containing phosphonic acid alkyl esters (alicyclic phosphonic
acid dialkyl esters) such as cyclohexanephosphonic acid diethyl
ester; araliphatic group-containing phosphonate esters (araliphatic
phosphonic acid dialkyl esters) such as 6-phenylhexyl phosphonic
acid diethyl ester; aromatic group-containing phosphonic acid alkyl
esters (aromatic phosphonic acid dialkyl esters) such as phenyl
phosphonic acid diethyl ester and toluenephosphonic acid diethyl
ester; and the like.
[0526] Specific examples of hydrophobic organic compounds in the
case where the binding group is a carboxyl group include aliphatic
group-containing carboxylic acids (fatty acids) such as hexanoic
acid, octanoic acid and decanoic acid; araliphatic group-containing
carboxylic acids such as 6-phenylhexanoic acid; and the like.
[0527] Specific examples of hydrophobic organic compounds in the
case where the binding group is an amino group include aliphatic
group-containing amines such as hexylamine, octylamine and
decylamine; and the like.
[0528] Alternatively, the organic compound can also be used as a
hydrophilic organic compound for hydrophilic treatment of inorganic
particles. In this case, the organic group contained in the
hydrophilic organic compound includes any of the above hydrocarbon
groups and a hydrophilic group that binds to the hydrocarbon
group.
[0529] Specifically, in the hydrophilic organic compound, the
hydrophilic group is bound to a terminal (the terminal (the other
terminal) opposite the terminal that is bound to the binding group
(one terminal)) or a side chain of the hydrocarbon group.
[0530] The hydrophilic group is a functional group having a
polarity (or in other words, polar group), and examples thereof
include a phosphoric acid group, a phosphoric acid ester group, a
hydroxyl group, a carboxyl group, an amino group, a sulfo group, a
carbonyl group, a cyano group, a nitro group, an aldehyde group, a
thiol group and the like.
[0531] Preferable examples of the hydrophilic group include a
phosphoric acid group, phosphoric acid ester group, a hydroxyl
group, a carboxyl group, a carboxylic acid ester group (carboxy
ester group), an amino group, and a sulfo group. More preferable
examples include a phosphoric acid group and a phosphoric acid
ester group.
[0532] One or more of the hydrophilic groups are contained in the
hydrophilic organic compound. In the case where a plurality of
hydrophilic groups are contained in the hydrophilic organic
compound, for example, an amino group and a sulfo group are used in
combination.
[0533] Examples of the organic group containing a phosphoric acid
group (phosphoric acid group-containing organic group) include
phosphonosaturated aliphatic groups (phosphonoaliphatic groups)
such as 3-phosphonopropyl, 6-phosphonohexyl and 10-phosphonodecyl;
phosphonoaraliphatic groups such as 6-phosphonophenylhexyl; and the
like.
[0534] Examples of the organic group containing a phosphoric acid
ester group (phosphoric acid ester group-containing organic group)
include alkoxyphosphonyl hydrocarbon groups including
alkoxyphosphonyl saturated aliphatic groups (alkoxyphosphonyl
aliphatic groups) such as 3-(diethoxy-phosphonyl)propyl,
6-(diethoxy-phosphonyl)hexyl and 10-(diethoxy-phosphonyl)decyl; and
alkoxyphosphonyl araliphatic groups such as
6-(diethoxy-phosphonyl)phenylhexyl.
[0535] Examples of the organic group containing a hydroxyl group
(hydroxy group-containing organic group) include hydroxy aliphatic
groups such as 10-hydroxydecyl; and the like.
[0536] Examples of the organic group containing a carboxyl group
(carboxyl group-containing organic group) include carboxysaturated
aliphatic groups (carboxyaliphatic groups) such as 2-carboxyethyl,
3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl,
7-carboxyheptyl, 8-carboxyoctyl, 9-carboxynonyl and
10-carboxydecyl; and the like.
[0537] Examples of the organic group containing a carboxylic acid
ester group (carboxy ester group-containing organic group) include
carboxy ester aliphatic groups such as 2-(methoxy-carbonyl)ethyl,
3-(methoxy-carbonyl)propyl, 4-(methoxy-carbonyl)butyl,
5-(methoxy-carbonyl)pentyl, 6-(methoxy-carbonyl)hexyl,
7-(methoxy-carbonyl)heptyl, 8-(methoxy-carbonyl)octyl,
9-(methoxy-carbonyl)nonyl and 10-(methoxy-carbonyl)decyl.
[0538] Examples of the organic group containing an amino group and
a sulfo group (amino group- and sulfo group-containing organic
group) include amino/sulphoaliphatic groups such as
2-amino-3-sulfopropyl.
[0539] Specifically, examples of the organic compound containing a
hydrophilic group include a phosphoric acid group-containing
organic compound, a phosphoric acid ester group-containing organic
compound, a hydroxyl group-containing organic compound, a carboxyl
ester group-containing organic compound, an amino group-containing
organic compound, a sulfo group-containing organic compound, a
carbonyl group-containing organic compound, a cyano
group-containing organic compound, a nitro group-containing organic
compound, an aldehyde group-containing organic compound, a thiol
group-containing organic compound and the like.
[0540] Preferable examples include a phosphoric acid
group-containing organic compound, a phosphoric acid ester
group-containing organic compound, a hydroxyl group-containing
organic compound and a carboxy ester group-containing organic
compound.
[0541] Examples of the phosphoric acid group-containing organic
compound in the case where the binding group is a phosphoric acid
group and the polar group is a carboxyl group (more specifically,
in the case where the phosphoric acid group is bound to the
inorganic particles containing titanium oxide) include
monophosphonocarboxylic acids, and specific examples include
3-phosphono propionic acid, 6-phosphonohexanoic acid, 10-phosphono
decanoic acid, 6-phosphonophenylhexanoic acid, and the like.
[0542] Examples of the phosphoric acid ester group-containing
organic compound in the case where the binding group is a
phosphoric acid ester group and the polar group is a carboxy ester
group (more specifically, in the case where the phosphoric acid
ester group is bound to the inorganic particles containing titanium
oxide) include 3-(diethoxy-phosphonyl)ethyl propionic acid ester,
6-(diethoxy-phosphonyl)hexanoic acid ethyl ester,
10-(diethoxy-phosphonyl)decanoic acid ethyl ester and the like. The
above-listed phosphoric acid ester group-containing organic
compounds are also regarded as carboxy ester group-containing
organic compounds.
[0543] Examples of the phosphoric acid ester group-containing
organic compound in the case where the binding group is a
phosphoric acid ester group and the polar group is a hydroxyl group
(more specifically, in the case where the phosphoric acid ester
group is bound to the inorganic particles containing titanium
oxide) include phosphoric acid ester group- and hydroxyl
group-containing compounds such as 10-(diethoxy-phosphonyl)decanol;
and the like. The phosphoric acid ester group- and hydroxyl
group-containing compounds are also regarded as hydroxyl
group-containing compounds.
[0544] The same or mutually different organic groups may be
used.
[0545] In the case where mutually different organic groups are
used, or in other words, the organic group contains a plurality of
different types of organic groups, a plurality of homologous
organic groups and/or a plurality of heterologous organic groups
are contained.
[0546] Examples of the homologous organic groups include a
combination of a plurality of aliphatic groups, a combination of a
plurality of phosphonoaliphatic groups, a combination of a
plurality of alkoxyphosphonyl aliphatic groups, a combination of a
plurality of carboxyaliphatic groups, a combination of a plurality
of carboxy ester aliphatic groups, and the like.
[0547] The combination of a plurality of aliphatic groups can be,
for example, a combination of a saturated aliphatic group having
less than 10 carbon atoms and a saturated aliphatic group having 10
or more carbon atoms. Specific examples include a combination of
octyl and decyl, and a combination of methyl and decyl. Another
example of the combination of a plurality of aliphatic groups is a
combination of a saturated aliphatic group having less than 7
carbon atoms and a saturated aliphatic group having 7 or more
carbon atoms. Specific examples include a combination of methyl and
octyl, a combination of hexyl and decyl, and a combination of hexyl
and octyl. Another example is a combination of a saturated
aliphatic group having less than 5 carbon atoms and a saturated
aliphatic group having 5 or more carbon atoms. A specific example
is a combination of methyl and hexyl.
[0548] Examples of the combination of a plurality of
phosphonoaliphatic groups include a combination of a
phosphonoaliphatic group having less than 5 carbon atoms and a
phosphonoaliphatic group having 5 or more carbon atoms. A specific
example is a combination of 3-phosphonopropyl and
6-phosphonohexyl.
[0549] Examples of the combination of a plurality of
alkoxyphosphonyl aliphatic groups include a combination of an
alkoxyphosphonyl aliphatic group having less than 10 carbon atoms
and an alkoxyphosphonyl aliphatic group having 10 or more carbon
atoms. Specific examples include a combination of
3-(diethoxy-phosphonyl)propyl and 6-(diethoxy-phosphonyl)hexyl, and
a combination of 3-(diethoxy-phosphonyl)propyl and
10-(diethoxy-phosphonyl)decyl.
[0550] Examples of the combination of a plurality of
carboxyaliphatic groups include a carboxyaliphatic group having
less than 5 carbon atoms and a carboxyaliphatic group having 5 or
more carbon atoms. A specific example is a combination of
2-carboxyethyl and 5-carboxypropyl.
[0551] The combination of a plurality of carboxy ester aliphatic
groups can be, for example, a combination of a carboxy ester
aliphatic group having less than 7 carbon atoms and a carboxy ester
aliphatic group having 7 or more carbon atoms. Specific examples
include a combination of 2-(methoxy-carbonyl)ethyl and
5-(methoxy-carbonyl)heptyl, and a combination of
2-(methoxy-carbonyl)ethyl and 9-(methoxy-carbonyl)nonyl.
[0552] When the organic group contains a plurality of homologous
organic groups, a plurality of organic groups having different
sizes (lengths or/and dimensions, or in other words, the number of
carbon atoms) are contained in the organic group. Accordingly, in a
space between adjacent larger organic groups, a resin molecule
enters a gap (pocket) formed in accordance with the smaller organic
group, and the interaction between the larger organic group and the
resin molecule can be enhanced. As a result, the dispersibility of
the catalyst particles can be enhanced.
[0553] Examples of the heterologous organic groups include a
combination of two different groups selected from the group
consisting of an aliphatic group, an alicyclic group, an
araliphatic group, an aromatic group, a phosphonoaliphatic group, a
phosphonoaraliphatic group, an alkoxyphosphonyl aliphatic group, an
alkoxyphosphonyl araliphatic group, a hydroxy aliphatic group, a
carboxyaliphatic group, a carboxyaraliphatic group, a
carboxyaromatic group, a carboxy ester aliphatic group and an
amino/sulphoaliphatic group.
[0554] Preferable examples of the heterologous organic groups
include a combination of an aliphatic group and an araliphatic
group, a combination of an aliphatic group and a carboxyaliphatic
group, a combination of an aliphatic group and a carboxy ester
aliphatic group, and a combination of a carboxyaliphatic group and
a carboxy ester aliphatic group.
[0555] The combination of an aliphatic group and an araliphatic
group can be, for example, a combination of a saturated aliphatic
group having 6 to 12 carbon atoms and an araliphatic group having 7
to 15 carbon atoms, and a specific example is a combination of
octyl and phenylhexyl.
[0556] The combination of an aliphatic group and a carboxyaliphatic
group can be, for example, a combination of an aliphatic group
having less than 6 carbon atoms and a carboxyaliphatic group having
less than 6 carbon atoms. Specific examples include a combination
of methyl and 2-carboxyethyl and a combination of methyl and
5-carboxypentyl. Another example is a combination of an aliphatic
group having 6 or more carbon atoms and a carboxyaliphatic group
having less than 6 carbon atoms, and specific examples include a
combination of octyl and 2-carboxyethyl and a combination of octyl
and 5-carboxypentyl.
[0557] The combination of an aliphatic group and a carboxy ester
aliphatic group can be, for example, a combination of an aliphatic
group having less than 6 carbon atoms and a carboxy ester aliphatic
group having less than 6 carbon atoms, and a specific example is a
combination of methyl and 2-(methoxy-carbonyl)ethyl.
[0558] Also, the combination of an aliphatic group and a carboxy
ester aliphatic group can be, for example, a combination of an
aliphatic group having less than 6 carbon atoms and a carboxy ester
aliphatic group having 6 or more carbon atoms, and a specific
example is a combination of methyl and
9-(methoxy-carbonyl)nonyl.
[0559] Another example of the combination of an aliphatic group and
a carboxy ester aliphatic group is a combination of an aliphatic
group having 7 or more carbon atoms and a carboxy ester aliphatic
group having 7 or more carbon atoms, and specific examples include
a combination of octyl and 9-(methoxy-carbonyl)nonyl and a
combination of decyl and 9-(methoxy-carbonyl)nonyl.
[0560] Another example of the combination of an aliphatic group and
a carboxy ester aliphatic group is a combination of an aliphatic
group having 6 or more carbon atoms and a carboxy ester aliphatic
group having less than 6 carbon atoms, and a specific example is a
combination of decyl and 2-(methoxy-carbonyl)ethyl.
[0561] The combination of a carboxyaliphatic group and a carboxy
ester aliphatic group can be, for example, a combination of a
carboxyaliphatic group having less than 5 carbon atoms and a
carboxy ester aliphatic group having 6 or more carbon atoms, and a
specific example is a combination of 2-carboxyethyl and
9-(methoxy-carbonyl)nonyl.
[0562] As long as the organic group contains a plurality of
heterologous organic groups, when the resin is prepared as a
mixture of a plurality of resin components, the organic group can
exert excellent compatibility with the resin molecules of the
respective resin components having excellent compatibility with the
organic groups of the respective groups. Accordingly, the
interaction between the organic groups and the resin molecules of
the resin components can be enhanced. As a result, the
dispersibility of the catalyst particles can be enhanced.
[0563] The organic groups are present on the surface of inorganic
particles in the catalyst particles. Specifically, the organic
groups extend from the surface of inorganic particles toward the
outside of the inorganic particles via a binding group.
[0564] The catalyst particles are produced by subjecting an
inorganic substance and/or a complex and an organic compound to a
reaction treatment, preferably to a high temperature treatment.
[0565] The high temperature treatment is carried out in a solvent.
As the solvent, for example, water and any of the organic compounds
listed above can be used.
[0566] Specifically, the catalyst particles are obtained by
surface-treating (hydrothermal synthesis: hydrothermal reaction) an
inorganic substance and/or a complex with an organic compound in
hot high pressure water, or surface-treating an inorganic substance
and/or a complex in a hot organic compound. In other words, the
catalyst particles are obtained by surface-treating the surface of
(inorganic particles formed of) the inorganic substance and/or the
complex with any of the organic compounds containing an organic
group listed above.
[0567] In the hydrothermal synthesis, for example, the inorganic
substance and the organic compound are reacted under
high-temperature and high-pressure conditions in the presence of
water (first hydrothermal synthesis).
[0568] Preferable examples of the inorganic substance subjected to
the first hydrothermal synthesis include an oxide, a sulfate, a
nitrate, a formate, a hydroxide and a metal.
[0569] The inorganic substances subjected to the first hydrothermal
synthesis can be used singly or in combination. In the case where
the inorganic substances are used in combination, the first
combination mentioned above is used.
[0570] To carry out the first hydrothermal synthesis, first, a
reaction system is prepared under high-temperature and
high-pressure conditions by placing an inorganic substance, an
organic compound and water in a pressure-resistant airtight
container and heating them.
[0571] The proportions of respective components are the same as
those (in terms of mass, volume, mol, and the like) shown in the
second embodiment.
[0572] Particularly when the inorganic substances are used in
combination, specifically, when the first combination is used, the
amount of the first inorganic substance is greater than that of the
second inorganic substance when they are blended. Specifically, the
proportion of the second inorganic substance per 100 parts by mass
of the first inorganic substance is, for example, 20 parts by mass
or less, preferably 10 parts by mass or less, and more preferably 5
parts by mass or less, and usually 0.01 parts by mass or greater.
In other words, the proportion of the second inorganic substance
per mol of the first inorganic substance is, for example, 0.2 mol
or less, preferably 0.1 mol or less, and more preferably 0.05 mol
or less, and usually 0.0001 mol or greater.
[0573] Specific reaction conditions for the hydrothermal reaction
are as follows. The heating temperature is, for example, 100 to
600.degree. C., and preferably 200 to 500.degree. C. The pressure
is, for example, 0.2 to 50 MPa, preferably 1 to 50 MPa, and more
preferably 10 to 50 MPa. The reaction time is, for example, 1 to
2000 minutes, preferably 2 to 1000 minutes, and more preferably 3
to 500 minutes. In the case where a continuous reactor is used, the
reaction time is set to, for example, one minute or less.
[0574] The reaction product obtained by the above reaction includes
a precipitate that mostly precipitates in water and a deposit that
adheres to the inner wall of the airtight container.
[0575] The precipitate is obtained by, for example, sedimentation
separation in which the reaction product is settled by gravity or a
centrifugal field. Preferably, the precipitate is obtained as a
precipitate of the reaction product by centrifugal sedimentation
(centrifugal separation) in which the reaction product is settled
by a centrifugal field.
[0576] The deposit is recovered by, for example, a scraper
(spatula) or the like.
[0577] The reaction product can also be recovered (separated) by
adding a solvent to wash away an unreacted organic compound (or in
other words, dissolving the organic compound in the solvent) and
thereafter removing the solvent.
[0578] As the solvent, the same solvents as those listed in the
second embodiment can be used.
[0579] The washed reaction product is separated from the solvent
(supernatant liquid) by, for example, filtration, decantation or
the like, and recovered. After that, the reaction product is dried
by, for example, application of heat, an air stream or the like if
necessary.
[0580] In this manner, the catalyst particles containing inorganic
particles and an organic group that binds to the surface of the
inorganic particles are obtained.
[0581] Alternatively, unlike the first hydrothermal synthesis, by
subjecting an inorganic substance and/or a complex (starting
material) and an organic compound to a hydrothermal synthesis, it
is possible to obtain catalyst particles containing inorganic
particles formed of an inorganic substance and/or a complex that
is/are different from the starting material (second hydrothermal
synthesis).
[0582] Examples of the inorganic substance subjected to the second
hydrothermal synthesis include a hydroxide, a sulfate, an acetate,
a metal, hydrates thereof and the like.
[0583] In the hydroxide, the element (element that constitutes a
cation that combines with a hydroxyl ion (OH.sup.-)) contained in
the hydroxide can be the same as the element that combines with
oxygen in an oxide listed above.
[0584] Specifically, the hydroxide can be, for example, strontium
hydroxide (Sr(OH).sub.2) or the like.
[0585] The complex subjected to the second hydrothermal synthesis
can be, for example, titanium complex or the like.
[0586] Examples of the hydrates subjected to the second
hydrothermal synthesis include tungstic acid (WO.sub.3.H.sub.2O),
ammonium tungstate pentahydrate
((NH.sub.4).sub.2WO.sub.4.5H.sub.2O) and the like. These hydrates
produce tungsten oxide as a result of elimination of water of
hydration in the second hydrothermal synthesis.
[0587] Such inorganic substances and complexes (raw materials) can
be used singly or in a combination of two or more.
[0588] In the case where the raw materials subjected to the second
hydrothermal synthesis are used in combination, the first
combination and the second combination mentioned above are
used.
[0589] In the case where the first combination is used, and the
second inorganic substance is a metal, the second inorganic
substance does not cause a change in the chemical composition
before and after the reaction (second hydrothermal synthesis).
[0590] Specific examples of the second inorganic substance
subjected to the second hydrothermal synthesis in the first
combination include palladium, platinum and the like. These
elements do not cause a change in the chemical composition before
and after the reaction (second hydrothermal synthesis).
[0591] After the second hydrothermal synthesis, the metal or oxide
forming the second inorganic substance is supported on the first
inorganic substance.
[0592] The term "supported" as used herein is defined as the state
in which the metal or oxide is present substantially uniformly
inside of and/or on the surface of the first inorganic
substance.
[0593] Specifically, a metal (copper) forming a sulfate (copper) is
supported on an oxide (tungsten oxide) after the second
hydrothermal synthesis. Also, a group VIII element (palladium or
platinum) is supported on an oxide (tungsten oxide) after the
second hydrothermal synthesis. Furthermore, a metal (copper)
forming a formate (copper formate) is supported on tungsten oxide
after the second hydrothermal synthesis.
[0594] The proportions of respective components in the second
hydrothermal synthesis per 100 parts by mass of the inorganic
substance and the complex are as follows: the proportion of the
organic compound is, for example, 1 to 1500 parts by mass,
preferably 5 to 500 parts by mass and more preferably 5 to 250
parts by mass; and the proportion of water is, for example, 50 to
8000 parts by mass, preferably 80 to 6600 parts by mass and more
preferably 80 to 4500 parts by mass.
[0595] The proportion of the organic compound is, for example, 0.9
to 1880 mL, preferably 4.5 to 630 mL and more preferably 4.5 to 320
mL per 100 g of the inorganic substance and the complex, and the
number of moles of the organic compound may be, for example, 0.01
to 10000 mol and preferably 0.1 to 10 mol per mol of the inorganic
substance and the complex.
[0596] The proportion of water is, for example, 50 to 8000 mL,
preferably 80 to 6600 mL and more preferably 100 to 4500 mL per 100
g of the inorganic substance and the complex.
[0597] In the case where an inorganic substance and a complex are
used in combination, the second combination mentioned above is
used. More specifically, when a combination of a complex and an
inorganic substance is used, the proportion of the inorganic
substance per 100 parts by mass of the complex is, for example, 10
parts by mass or less, preferably 8 parts by mass or less and more
preferably 5 parts by mass or less, and usually 0.001 parts by mass
or greater. In other words, the proportion of the inorganic
substance per mol of the complex is, for example, 0.1 mol or less,
preferably 0.08 mol or less and more preferably 0.05 mol or less,
and usually 0.00001 mol or greater.
[0598] In the case where a plurality of complexes are used,
specifically, in the case where a combination of a titanium complex
and a ruthenium complex is used, the proportion of the ruthenium
complex per 100 parts by mass of the titanium complex is, for
example, 50 parts by mass or less, preferably 25 parts by mass or
less and usually 0.1 parts by mass or greater. In other words, the
proportion of the ruthenium complex per mol of the titanium complex
is, for example, 0.5 mol or less, preferably 0.25 mol or less, and
usually 0.0001 mol or greater.
[0599] The reaction conditions for the second hydrothermal
synthesis are the same as those for the first hydrothermal
synthesis described above.
[0600] In the case where a combination of a titanium complex and
platinum is used as the second combination, the titanium complex
produces titanium oxide as a result of the reaction (second
hydrothermal synthesis) while platinum does not cause a change in
the chemical reaction in the chemical composition before and after
the reaction. Also, in the case where a combination of a titanium
complex, strontium hydroxide and nickel acetate is used as the
second combination, the titanium complex and strontium hydroxide
produce strontium titanate (SrTiO.sub.3) as a result of the
reaction (second hydrothermal synthesis) while nickel acetate
produces nickel oxide (NiO). Furthermore, in the case where a
combination of a titanium complex, strontium hydroxide and a
ruthenium complex is used as the second combination, the titanium
complex and strontium hydroxide produce strontium titanate
(SrTiO.sub.3) as a result of the reaction (second hydrothermal
synthesis), while the ruthenium complex produces ruthenium oxide
(RuO.sub.2).
[0601] In this manner, the catalyst particles containing inorganic
particles formed of an inorganic substance that is different from
the inorganic substance serving as a starting material and a
complex, and an organic group that binds to the surface of the
inorganic particles are obtained.
[0602] In the formulations used in the first hydrothermal synthesis
and the second hydrothermal synthesis, a pH adjusting agent can be
blended with the components in an appropriate proportion.
[0603] The pH adjusting agent can be, for example, an aqueous
ammonia solution, an aqueous sodium hydroxide solution or the
like.
[0604] In the surface treatment performed in a hot organic
compound, an inorganic substance and/or a complex and an organic
compound are blended and heated, for example, under normal
atmospheric pressure conditions. The organic compound is subjected
to the high temperature treatment while serving as an organic
group-introducing compound as well as a solvent for dispersing or
dissolving the inorganic substance and/or the complex.
[0605] The proportion of the organic compound is, for example, 1 to
10000 parts by mass, preferably 10 to 5000 parts by mass, and more
preferably 20 to 1000 parts by mass per 100 parts by mass of the
inorganic substance and the complex. The proportion of the organic
compound in terms of volume is, for example, 1 to 10000 mL,
preferably 10 to 5000 mL, and more preferably 20 to 1000 mL per 100
g of the inorganic substance and the complex.
[0606] The heating temperature is, for example, a temperature above
100.degree. C., preferably 125.degree. C. or higher, and more
preferably 150.degree. C. or higher, and usually for example,
600.degree. C. or lower. The heating time is, for example, 1 to
2000 minutes, preferably 2 to 1000 minutes, and more preferably 3
to 500 minutes. In the case where a continuous reactor is used, the
reaction time is set to, for example, one minute or less.
[0607] Also, heating can be carried out under, for example, high
pressure. As for the high pressure conditions, the same pressures
as those used in the hydrothermal synthesis shown above can be
used.
[0608] Through the surface treatment in a hot organic compound, the
catalyst particles containing inorganic particles formed of a metal
oxide forming an inorganic substance and/or a complex, and an
organic group that binds to the surface of the inorganic particles
are obtained.
[0609] The high temperature treatment (surface treatment) described
above can be carried out once, or can be carried out a plurality of
times from a view point of enhancing treatment efficiency.
[0610] As the method for carrying out the high temperature
treatment a plurality of times, for example, a method in which each
of the first hydrothermal synthesis, the second hydrothermal
synthesis and the surface treatment in a hot organic compound is
repeated, or a method in which the above treatments are carried out
in combination is used. Preferably, the method in which the above
treatments are carried out in combination is used. More preferably,
a method in which the surface treatment in a hot organic compound
is performed after the second hydrothermal synthesis is used.
[0611] Specifically, organic-inorganic composite particles in which
a carboxyaliphatic group is bound to titanium oxide via a
phosphoric acid group are obtained by subjecting a titanium complex
to a high temperature treatment in any of the phosphoric acid ester
group-containing organic compounds (carboxy ester group-containing
organic compounds) listed above. After that, the obtained
organic-inorganic composite particles are subjected to a high
temperature treatment in an alcohol, whereby in the organic group,
a carboxy ester group-containing organic group is produced from the
carboxyaliphatic group. In other words, a carboxyl group binding to
a terminal of an aliphatic group is esterified by the alcohol.
[0612] There is no particular limitation on the configuration of
the catalyst particles (primary particles) obtained in the
above-described manner, and for example the catalyst particles may
be anisotropic or isotropic, with an average particle size (average
maximum length in the case where they are anisotropic) of, for
example, 450 nm or less, preferably 1 to 450 nm, more preferably 1
to 200 nm and particularly preferably 1 to 100 nm from a view point
of clarity.
[0613] As will be described in detail in the examples given below,
the average particle size of the catalyst particles is determined
by measurement by dynamic light scattering (DLS) or calculated from
a transmission electron microscopic (TEM) or scanning electron
microscopic (SEM) image analysis or with the Scherrer's equation
based on data of X-ray diffractometry (XRD).
[0614] If the average particle size exceeds the above range, the
clarity of the catalyst solution, the catalyst resin composition or
the catalyst molded article will be low, or the particles may be
crushed when mixed with a resin or the like.
[0615] If, on the other hand, the average particle size is below
the above range, the proportion of the volume of the organic group
relative to the surface of the catalyst particles will be high, and
the inorganic particles may be unlikely to exert its catalytic
action.
[0616] The catalyst particles thus obtained are unlikely to
coagulate in a dry state, and even if the catalyst particles appear
coagulated in a dry state, the coagulation (formation of secondary
particles) will be reliably prevented in a catalyst composition and
a catalyst molded article, and therefore the catalyst particles are
dispersed substantially uniformly in a resin as primary
particles.
[0617] In the catalyst particles, the proportion of the surface
area of the organic group relative to the surface area of the
inorganic particles, or in other words, the surface coverage by the
organic group in the catalyst particles (=(surface area of organic
group/surface area of inorganic particles).times.100) is, for
example, 30% or greater and preferably 60% or greater and usually
200% or less.
[0618] The surface coverage is determined by the same method as
that described in the second embodiment.
[0619] In the case where at least the surface coverage is high and
the organic group of the catalyst particles has a length sufficient
to cancel the electric charge of the inorganic particles, the type
of solvent (medium) for dispersing the catalyst particles can be
controlled (designed or managed) according to the type of organic
group.
[0620] The catalyst particles obtained in the above-described
manner can be subjected to wet classification.
[0621] Specifically, a solvent is added to the catalyst particles,
and the resulting mixture is stirred and allowed to stand still,
and thereafter separated into a supernatant and a precipitate. The
solvent varies depending on the type of organic group, but for
example, the same solvents as those listed above can be used, and
preferable examples include a hydroxyl group-containing aliphatic
hydrocarbon, a carbonyl group-containing aliphatic hydrocarbon, an
aliphatic hydrocarbon, a halogenated aliphatic hydrocarbon and an
aqueous pH adjusting solution.
[0622] After that, the supernatant is recovered, and it is thereby
possible to obtain catalyst particles having a small average
particle size.
[0623] With the wet classification, the average particle size of
the resulting catalyst particles (primary particles) can be
adjusted to, for example, 400 nm or less, 1 nm to 400 nm,
preferably 1 nm to 200 nm and more preferably 1 nm to 100 nm.
[0624] The catalyst particles obtained in the above-described
manner can be dispersed in a solvent or a resin to prepare a
catalyst solution or a catalyst composition.
[0625] The catalyst solution contains a solvent and catalyst
particles described above.
[0626] In order to prepare such a catalyst solution, a solvent and
catalyst particles are blended, and the resulting mixture is
stirred so as to disperse the catalyst particles in the
solvent.
[0627] There is no particular limitation on the solvent, and
examples thereof include solvents used in washing described above.
Other examples include alicyclic hydrocarbons such as cyclopentane
and cyclohexane; esters such as ethyl acetate; polyols such as
ethylene glycol and glycerol; nitrogen-containing compounds such as
N-methylpyrrolidone, pyridine, acetonitrile and dimethylformamide;
acrylic monomers such as isostearyl acrylate, lauryl acrylate,
isoboronyl acrylate, butyl acrylate, methacrylate, acrylic acid,
tetrahydrofurfuryl acrylate, 1,6-hexanediol diacrylate,
2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxyethyl
acrylate and acryloylmorpholine; vinyl group-containing monomers
such as styrene and ethylene; epoxy-containing monomers such as
bisphenol A epoxy; and the like.
[0628] These solvents can be used singly or in a combination of two
or more. A halogenated aliphatic hydrocarbon is preferable.
[0629] The proportion of the catalyst particles is, for example,
0.1 to 70 parts by mass, preferably 0.2 to 60 parts by mass and
more preferably 0.5 to 50 parts by mass per 100 parts by mass of
the catalyst solution.
[0630] In the catalyst solution obtained in this manner, the
catalyst particles have a configuration that does not allow the
inorganic particles to contact with each other, and therefore are
uniformly dispersed as primary particles in the solvent.
Accordingly, the clarity of the catalyst solution can be
enhanced.
[0631] Also, the catalyst composition contains a resin and catalyst
particles described above.
[0632] As the resin, the same resins as those listed in the second
embodiment can be used. These resins can be used singly or in a
combination of two or more.
[0633] It is also possible to select the catalyst particles and the
resin such that the solubility parameters (SP values) thereof
satisfy a predetermined relationship.
[0634] Specifically, the catalyst particles and the resin are
selected so as to attain a predetermined SP difference (.DELTA.SP,
specifically, the absolute value of the difference between the
solubility parameter of resin (SP.sub.RESIN value) and the
solubility parameter of catalyst particles (SP.sub.PARTICLE
value)).
[0635] Among the resins listed above, in the case where excellent
mechanical strength needs to be imparted to the catalyst molded
article molded from a catalyst composition, a highly oriented resin
having high orientation is preferable. As the highly oriented
resin, the same highly oriented resins as those listed in the
second embodiment can be used. Also, the resin has, for example, a
hydrophilic group such as a carboxyl group or a hydroxyl group, a
hydrophobic group such as a hydrocarbon group, and the like.
[0636] In order to prepare a catalyst composition, first, a solvent
and a resin described above are blended so as to dissolve the resin
in the solvent to prepare a resin solution. After that, the resin
solution is blended with catalyst particles, and the resulting
mixture is stirred to prepare a catalyst composition (first
preparation method).
[0637] The proportion of resin relative to the resin solution is
the same as those shown in the second embodiment.
[0638] The proportion of the catalyst particles is, for example, 1
to 1000 parts by mass, preferably 5 to 500 parts by mass and more
preferably 10 to 300 parts by mass per 100 parts by mass of the
solids content (resin) of the resin solution. The proportion of the
catalyst particles is also, for example, 0.1 to 300 parts by mass,
preferably 1 to 200 parts by mass and more preferably 3 to 100
parts by mass per 100 parts by mass of the total amount of the
resin solution (the total amount of the resin and the solvent).
[0639] Also, the catalyst composition can also be prepared by,
first, preparing a catalyst solution described above, and then
blending the catalyst solution with a resin and stirring the
resulting mixture (second preparation method).
[0640] In the catalyst solution, the catalyst particles are
dispersed as primary particles in the solvent.
[0641] The proportion of resin is, for example, 10 to 10000 parts
by mass, preferably 20 to 2000 parts by mass and more preferably 40
to 1000 parts by mass per 100 parts by mass of the solids content
(catalyst particle) of the catalyst solution.
[0642] Furthermore, the catalyst composition can also be prepared
by, for example, blending a solvent, catalyst particles and a resin
simultaneously and stirring the resulting mixture (third
preparation method).
[0643] The proportions of respective components per 100 parts by
mass of the total amount of the catalyst composition are as
follows: the proportion of the catalyst particles is, for example,
0.1 to 50 parts by mass, preferably 1 to 40 parts by mass and more
preferably 3 to 30 parts by mass; and the proportion of resin is,
40 parts by mass or less, preferably 35 parts by mass or less, more
preferably 30 parts by mass or less, and usually 1 part by mass or
greater. The proportion of the solvent is the remainder obtained by
excluding the catalyst particles and the resin from the catalyst
composition.
[0644] Also, the catalyst composition can also be prepared by,
first, preparing a resin solution and a catalyst solution in a
separate manner and then blending and stirring the resin solution
and the catalyst solution (fourth preparation method).
[0645] The proportion of resin in the resin solution is the same as
those shown in the first preparation method described above.
[0646] The proportion of the catalyst particles in the catalyst
solution is the same as those shown in the preparation method for a
catalyst solution described above.
[0647] The resin solution and the catalyst solution are blended
such that the proportion of resin relative to the catalyst
particles in terms of mass is, for example, 99:1 to 10:90,
preferably 95:5 to 20:80 and more preferably 90:10 to 30:70.
[0648] Furthermore, the catalyst composition can also be prepared
without the use of a solvent by, for example, melting a resin by
application of heat and blending the resin with catalyst particles
(fifth preparation method).
[0649] The thus-prepared catalyst composition is a melt of the
catalyst composition without a solvent.
[0650] The heating temperature is, in the case where the resin is a
thermoplastic resin, greater than or equal to the melting
temperature of the resin, specifically, 200 to 350.degree. C. In
the case where the resin is a thermosetting resin, the heating
temperature is a temperature at which the resin is B-staged, for
example, 85 to 140.degree. C.
[0651] The proportion of resin relative to the catalyst particles
in terms of mass is, for example, 99:1 to 10:90, preferably 95:5 to
20:80 and more preferably 90:10 to 30:70.
[0652] In the catalyst composition obtained by any of the
above-described preparation methods, the catalyst particles are
uniformly dispersed in the resin. Specifically, in the catalyst
composition, the catalyst particles are dispersed as primary
particles in the resin (without substantial coagulation).
[0653] After that, the obtained catalyst composition is applied to,
for example, a known support plate to form a coating, and the
coating is dried, whereby a catalyst molded article as a film is
molded.
[0654] The catalyst composition is applied by using, for example, a
known application method such as spin coating or bar coating.
Simultaneously with or immediately after application of the
catalyst composition, the solvent is removed by volatilization. If
necessary, the solvent can be dried by application of heat after
application of the catalyst composition.
[0655] The thickness of the obtained film can be set as appropriate
according to the use and purpose, and the thickness is, for
example, 0.1 to 2000 .mu.m, preferably 0.1 to 1000 .mu.m and more
preferably 0.1 to 500 .mu.m.
[0656] The catalyst molded article as a film can also be molded by
a melt molding method in which the catalyst composition is extruded
by an extruding machine or the like.
[0657] The catalyst molded article can also be molded as a block
(mass) by injecting the catalyst composition into a metal mold or
the like and thereafter subjecting the resultant to, for example,
heat molding such as heat pressing.
[0658] The catalyst molded article is formed of the catalyst
composition in which the catalyst particles are dispersed in the
resin, and the inorganic particles cannot easily come into direct
contact with the resin due to the configuration based on the steric
hindrance of the organic group of the catalyst particles.
Accordingly, the catalyst molded article can, while suppressing
degradation of the resin, exert a catalytic action for a gas or a
liquid.
[0659] Specifically, the catalyst molded article can exert a
detoxification action, a deodorization action, a disinfectant (or
in other words, antimicrobial or germicidal) action and a
decomposition action for toxins, odor (malodor), fungi and organic
substances contained in a gas such as the air by absorbing light,
specifically, for example, light having a wavelength of 1000 nm or
less, preferably light having a wavelength of 900 nm or less and
more preferably light having a wavelength of 800 nm or less.
Furthermore, the catalyst molded article can exert a detoxification
action, a disinfectant action, a dirt repellent action and a
decomposition action for toxins, fungi, excrements and organic
substances contained in a liquid such as water.
[0660] As a result, the catalyst molded article can be used as a
catalyst molded article having various catalytic actions
(photocatalytic actions) such as a detoxification action, a
deodorization action, a disinfectant action, a dirt repellent
action and a decomposition action while maintaining excellent
durability.
[0661] Furthermore, in the catalyst molded article, the catalyst
particles are uniformly dispersed, and thus clarity can be
enhanced.
[0662] As a result, the catalyst molded article can be used in
various optical applications and various construction material
applications where clarity is required.
[0663] Specifically, the catalyst molded article can be used as, in
the case where it is molded as a film, for example, an optical film
for use in an image display apparatus (liquid crystal display,
organic electroluminescent apparatus or the like) such as a
polarizing film, a phase diference film, a brightness enhancing
film, a viewing angle enhancing film, a high-refractive index film
or a light diffusing film.
[0664] The catalyst molded article can also be used as, in the case
where it is molded as a film, for example, a construction material
(construction) film such as an ultraviolet absorbing film, a dirt
repellent film, an antimicrobial film, a deodorizing film, a
super-hydrophilic film, a germicidal film, a detoxification film or
a chemical substance decomposing film.
Fourth Embodiment
[0665] Embodiment corresponding to the inventions of a resin molded
article and a producing method therefor, which are included in the
fourth group of inventions
[0666] The resin molded article of the present invention can be
obtained by removing organic-inorganic composite particles from a
particle-containing resin molded article containing a resin and the
organic-inorganic composite particles.
[0667] The resin is a matrix component forming the resin molded
article and can be, for example, a thermosetting resin, a
thermoplastic resin or the like. Examples of the thermosetting
resin and the thermoplastic resin include the same thermosetting
resins and thermoplastic resins as those listed in the second
embodiment. These resins can be used singly or in a combination of
two or more.
[0668] In the case where excellent mechanical strength and
excellent clarity needs to be imparted to the particle-containing
resin molded article that is molded from a particle-containing
resin composition (described later), the resin is preferably a
polyester resin, a thermoplastic polyimide resin, a polyetherimide
resin or the like.
[0669] Also, the resin preferably has a functional group. Examples
of the functional group include hydrophilic groups such as a
carboxyl group and a hydroxyl group; hydrophobic groups such as a
hydrocarbon group; and the like.
[0670] Also, the resin has a refractive index for light having a
wavelength of 633 nm of, for example, greater than 1 and 3 or less,
preferably 1.2 to 2.5, and more preferably 1.3 to 2.0. The
refractive index is measured by, for example, a refractometer.
[0671] Also, the resin has a reflectance for light having a
wavelength of 550 nm of, for example, 1 to 10%, preferably 2 to 9%
and more preferably 3 to 8%. The reflectance is measured by, for
example, a spectrophotometer.
[0672] Also, the resin has a dielectric constant of, for example,
1.5 to 1000, preferably 2 to 100 and more preferably 2 to 10. The
dielectric constant is measured by, for example, an automatic
dielectric loss measurement apparatus at a frequency of 1 MHz.
[0673] The organic-inorganic composite particles are particles that
can be dispersed as primary particles in a solvent (described
later) and/or a resin and extracted from the resin with an
extraction solvent, and contain inorganic particles and an organic
group that binds to the surface of the inorganic particles.
[0674] Specifically, the organic-inorganic composite particles are
obtained by surface-treating an inorganic material form inorganic
particles with an organic compound. The organic-inorganic composite
particles can be used singly or in a combination of two or
more.
[0675] The inorganic material form inorganic particles can be a
metal composed of a metal element such as a main group element or a
transition element, a nonmetal composed of a nonmetal element such
as boron or silicon, an inorganic compound and/or a complex
containing a metal element and/or a nonmetal.
[0676] Examples of the metal element and the nonmetal element
include elements that are located on the left side and the lower
side of a border line that is assumed to pass through boron (B) of
the IIIB group, silicon (Si) of the IVB group, arsenic (As) of the
VB group, tellurium (Te) of the VIB group and astatine (At) of the
VIIB group on the long-form periodic table (IUPAC, 1989), as well
as the elements that are located on the border line. Specific
examples thereof include the group I elements (alkali metals) such
as Li, Na, K, Rb and Cs; the group II elements (alkaline earth
metals) such as Be, Mg, Ca, Sr, Ba and Ra; and the same elements as
those listed in the second embodiment.
[0677] Examples of the inorganic compound include the same
inorganic compounds as those listed in the second embodiment.
[0678] Preferable examples of the inorganic compound include an
oxide, a carbonate, a sulfate and the like.
[0679] The oxide can be, for example, a metal oxide. Preferable
examples include titanium oxide (titanium dioxide, titanium oxide
(IV), titania: TiO.sub.2), cerium oxide (cerium dioxide, cerium
oxide (IV), ceria: CeO.sub.2), zinc oxide (zinc oxide (II), flowers
of zinc or zinc white, ZnO) and the like.
[0680] The oxides can be used singly or in a combination of two or
more.
[0681] In the carbonate, the element that combines with carbonic
acid can be, for example, an alkali metal, an alkaline earth metal
or the like. The alkali metal and the alkaline earth metal can be
the same alkali metals and alkaline earth metals as those listed
above.
[0682] The element that combines with carbonic acid is preferably
an alkaline earth metal.
[0683] Specifically, the carbonate is preferably a carbonate
containing an alkaline earth metal, and examples of such a
carbonate include beryllium carbonate, magnesium carbonate, calcium
carbonate, strontium carbonate, barium carbonate, radium carbonate
and the like. These carbonates can be used singly or in a
combination of two or more.
[0684] The sulfate is a compound consisting of a sulfate ion
(SO.sub.4.sup.2-) and a metal cation (more specifically, a compound
formed by substitution of the hydrogen atoms of sulfuric acid
(H.sub.2SO.sub.4) with a metal), and the metal contained in the
sulfate can be, for example, an alkali metal, an alkaline earth
metal or the like. The alkali metal and the alkaline earth metal
can be the same alkali metals and alkaline earth metals as those
listed above.
[0685] The metal is preferably an alkaline earth metal.
[0686] Specifically, the sulfate is preferably a sulfate containing
an alkaline earth metal, and examples of such a sulfate include
beryllium sulfate, magnesium sulfate, calcium sulfate, strontium
sulfate, barium sulfate, radium sulfate and the like. Barium
sulfate is preferable.
[0687] The sulfates can be used singly or in a combination of two
or more.
[0688] The inorganic materials listed above can be used singly or
in a combination of two or more.
[0689] The organic compound is, for example, an organic
group-introducing compound that introduces (disposes) an organic
group on the surface of inorganic particles. Specifically, the
organic compound contains a binding group capable of binding to the
surface of inorganic particles and an organic group.
[0690] The binding group may be selected as appropriate according
to the type of inorganic particles, and examples thereof include
functional groups such as carboxyl group, phosphoric acid group
(--PO(OH).sub.2, phosphono group), amino group, sulfo group,
hydroxyl group, thiol group, epoxy group, isocyanate group (cyano
group), nitro group, azo group, silyloxy group, imino group,
aldehyde group (acyl group), nitrile group, vinyl group
(polymerizable group) and the like. Preferable examples include
carboxyl group, phosphoric acid group, amino group, sulfo group,
hydroxyl group, thiol group, epoxy group, azo group, vinyl group,
and the like. More preferable examples include carboxyl group and
phosphoric acid group.
[0691] The carboxyl group includes a carboxylic acid ester group
(carboxy ester group).
[0692] The phosphoric acid group includes a phosphoric acid ester
group (phosphonate group).
[0693] One or more of these binding groups are contained in the
organic compound. Specifically, the binding group is bound to a
terminal or a side chain of the organic group.
[0694] The binding group is selected as appropriate according to
the type of inorganic particles. Specifically, when the inorganic
particles contain cerium oxide, strontium carbonate and/or barium
sulfate, for example, carboxyl group is selected. When the
inorganic particles contain titanium oxide and/or zinc oxide, for
example, a phosphoric acid group is selected.
[0695] The organic group includes, for example, a hydrocarbon group
such as an aliphatic group, an alicyclic group, an araliphatic
group or an aromatic group, or the like.
[0696] Examples of the hydrocarbon groups include the same
hydrocarbon groups as those listed in the second embodiment.
[0697] The organic group is a hydrophobic group for imparting
hydrophobicity to the surface of inorganic particles.
[0698] Accordingly, the organic compounds containing a hydrophobic
group described above are used as hydrophobic organic compounds for
hydrophobic treatment of inorganic particles. Specific examples of
such hydrophobic organic compounds include the same hydrophobic
organic compounds as those listed in the second embodiment.
[0699] Alternatively, the organic compound can also be used as a
hydrophilic organic compound for hydrophilic treatment of inorganic
particles. In this case, the organic group contained in the
hydrophilic organic compound includes any of the above hydrocarbon
groups and a hydrophilic group that binds to the hydrocarbon
group.
[0700] Specifically, in the hydrophilic organic compound, the
hydrophilic group is bound to a terminal (the terminal (the other
terminal) opposite the terminal that is bound to the binding group
(one terminal)) or a side chain of the hydrocarbon group.
[0701] The hydrophilic group is a functional group having a
polarity (or in other words, polar group), and examples thereof
include the same functional groups as those listed in the second
embodiment. One or more of the hydrophilic groups are contained in
the hydrophilic organic compound.
[0702] Specific examples of the organic compound containing a
hydrophilic group include the same carboxyl group-containing
organic compounds, hydroxyl group-containing organic compounds,
phosphoric acid group-containing organic compounds, amino
group-containing organic compounds, sulfo group-containing organic
compounds, carbonyl group-containing organic compounds, cyano
group-containing organic compounds, nitro group-containing organic
compounds, aldehyde group-containing organic compounds and thiol
group-containing organic compounds as those listed in the second
embodiment.
[0703] The same or mutually different organic groups may be
used.
[0704] In the case where mutually different organic groups are
used, or in other words, the organic group contains a plurality of
mutually different types of organic groups, a plurality of
homologous organic groups and/or a plurality of heterologous
organic groups are contained.
[0705] Examples of the homologous organic groups include the same
combinations as those listed in the second embodiment.
[0706] A preferable example of the homologous organic groups is a
combination of a plurality of aliphatic groups, a more preferable
example is a combination of a plurality of saturated aliphatic
groups, and a particularly preferable example is a combination of a
saturated aliphatic group having less than 10 carbon atoms and a
saturated aliphatic group having 10 or more carbon atoms. Specific
examples include a combination of hexyl and decyl and a combination
of octyl and decyl.
[0707] When the organic group contains a plurality of homologous
organic groups, a plurality of organic groups having different
sizes (lengths or/and dimensions, or in other words, the number of
carbon atoms) are contained in the organic group. Accordingly, in a
space between adjacent larger organic groups, a resin molecule
enters a gap (pocket) formed in accordance with the smaller organic
group, and the interaction between the larger organic group and the
resin molecule can be enhanced. As a result, the dispersibility of
the organic-inorganic composite particles can be enhanced.
[0708] Examples of the heterologous organic groups include the same
combinations as those listed in the second embodiment.
[0709] As long as the organic group contains a plurality of
heterologous organic groups, when the resin is prepared as a
mixture of a plurality of resin components, the organic group can
exert excellent compatibility with the resin molecules of the
respective resin components having excellent compatibility with the
organic groups of the respective groups. Accordingly, the
interaction between the organic groups and the resin molecules of
the resin components can be enhanced. As a result, the
dispersibility of the organic-inorganic composite particles can be
enhanced.
[0710] The organic groups are present on the surface of inorganic
particles in the organic-inorganic composite particles.
Specifically, the organic groups are bound to the surface of
inorganic particles via a binding group. Also, the organic groups
extend from the surface of inorganic particles toward the outside
of the inorganic particles via a binding group.
[0711] The organic-inorganic composite particles are prepared by
subjecting an inorganic material and an organic compound to a
reaction treatment, preferably to a high temperature treatment.
[0712] The high temperature treatment is carried out in a solvent.
As the solvent, for example, water and any above-listed organic
compounds can be used.
[0713] Specifically, the organic-inorganic composite particles are
obtained by subjecting an inorganic material and an organic
compound to a high temperature treatment in water under high
pressure conditions (hydrothermal synthesis: hydrothermal
reaction), or subjecting an inorganic material to a high
temperature treatment in an organic compound (high temperature
treatment in an organic compound). In other words, the
organic-inorganic composite particles are obtained by
surface-treating the surface of inorganic particles formed by an
inorganic material with (or in the presence of) an organic
compound.
[0714] In the hydrothermal synthesis, for example, the inorganic
material and the organic compound are reacted under
high-temperature and high-pressure conditions in the presence of
water (first hydrothermal synthesis).
[0715] The inorganic material subjected to the first hydrothermal
synthesis is preferably an inorganic compound, and more preferably
a carbonate or a sulfate.
[0716] Specifically, first, a reaction system is prepared under
high-temperature and high-pressure conditions by placing an
inorganic material, an organic compound and water in a
pressure-resistant airtight container and heating them.
[0717] The proportions of respective components per 100 parts by
mass of the inorganic material are as follows: the proportion of
the organic compound is, for example, 1 to 1500 parts by mass,
preferably 5 to 500 parts by mass and more preferably 5 to 250
parts by mass; and the proportion of water is, for example, 50 to
8000 parts by mass, preferably 80 to 6600 parts by mass and more
preferably 100 to 4500 parts by mass.
[0718] The density of the organic compound is usually 0.8 to 1.1
g/mL, and thus the proportion of the organic compound is, for
example, 1 to 1500 mL, preferably 5 to 500 mL and more preferably 5
to 250 mL per 100 g of the inorganic material.
[0719] Also, the number of moles of the organic compound can be,
for example, 0.01 to 1000 mol, preferably 0.02 to 50 mol, and more
preferably 0.1 to 10 mol per mol of the inorganic material.
[0720] In the case where the organic compound contain a plurality
of (for example, two) different types of organic groups,
specifically, the molar ratio between an organic compound
containing one type of organic group and an organic compound
containing the other type of organic group is, for example, 10:90
to 99.9:0.1, and preferably 20:80 to 99:1.
[0721] Also, the density of water is usually approximately 1 g/mL,
and thus the proportion of water is, for example, 50 to 8000 mL,
preferably 80 to 6600 mL, and more preferably 100 to 4500 mL per
100 g of the inorganic material.
[0722] The reaction conditions for the hydrothermal reaction are
the same reaction conditions as those shown in the second
embodiment.
[0723] In the above reaction, if necessary, an aqueous pH adjusting
solution such as an aqueous ammonia solution or an aqueous solution
of potassium hydroxide can be added in an appropriate
proportion.
[0724] The reaction product obtained by the above reaction includes
a precipitate that mostly precipitates in water and a deposit that
adheres to the inner wall of the airtight container.
[0725] The precipitate is obtained by, for example, sedimentation
separation in which the reaction product is settled by gravity or a
centrifugal field. Preferably, the precipitate is obtained as a
precipitate of the reaction product by centrifugal sedimentation
(centrifugal separation) in which the reaction product is settled
by a centrifugal field.
[0726] The deposit is recovered by, for example, a scraper
(spatula) or the like.
[0727] The reaction product can also be recovered (separated) by
adding a solvent to wash away an unreacted organic compound (or in
other words, dissolving the organic compound in the solvent) and
thereafter removing the solvent (recovering step).
[0728] The solvent can be, for example, an alcohol (hydroxyl
group-containing aliphatic hydrocarbon) such as methanol, ethanol,
propanol or isopropanol; a ketone (carbonyl group-containing
aliphatic hydrocarbon) such as acetone, methyl ethyl ketone,
cyclohexanone or cyclopentanone; an aliphatic hydrocarbon such as
pentane, hexane or heptane; a halogenated aliphatic hydrocarbon
such as dichloromethane, chloroform or trichloroethane; a
halogenated aromatic hydrocarbon such as chlorobenzene or
dichlorobenzene; an ether such as tetrahydrofuran; an aromatic
hydrocarbon such as benzene, toluene or xylene; an aqueous pH
adjusting solution described above; or the like.
[0729] The washed reaction product is separated from the solvent
(supernatant liquid) by, for example, filtration, decantation or
the like, and recovered. After that, the reaction product is dried
by, for example, application of heat, an air stream or the like if
necessary.
[0730] In this manner, the organic-inorganic composite particles
containing inorganic particles and an organic group that binds to
the surface of the inorganic particles are obtained.
[0731] Note that in the first hydrothermal synthesis, the inorganic
material before reaction and the inorganic particles after reaction
have the same composition.
[0732] Alternatively, the organic-inorganic composite particles
containing inorganic particles formed of an inorganic substance
that is different from the inorganic material serving as a starting
material can also be obtained by subjecting an inorganic material
(starting material) and an organic compound to a hydrothermal
synthesis (second hydrothermal synthesis).
[0733] The inorganic material subjected to the second hydrothermal
synthesis can be, for example, a hydroxide, an acetate, a complex
or the like.
[0734] In the hydroxide, the element (element that constitutes a
cation that combines with a hydroxyl ion (OH.sup.-)) contained in
the hydroxide can be the same as the element that combines with
oxygen in an oxide listed above.
[0735] Specifically, the hydroxide can be, for example, titanium
hydroxide (Ti(OH).sub.4) or cerium hydroxide (Ce(OH).sub.4).
[0736] In the acetate, the element contained in the acetate that
combine with an acetic acid ion (CH.sub.3COO.sup.-) can be a group
JIB element, preferably Zn, Cd or the like.
[0737] Specifically, the acetate is preferably an acetate
containing a group IIB element, and specific examples of such an
acetate include zinc acetate, cadmium acetate and the like. These
acetates can be used singly or in a combination of two or more.
[0738] The complex contains a central atom and/or a central ion and
a ligand that coordinates thereto.
[0739] Examples of the central atom include the same metal elements
as those listed above. A group IVA element is preferable, and Ti is
more preferable.
[0740] Examples of the central ion include cations of the metal
elements listed above.
[0741] Examples of the ligand include coordinating compounds such
as carboxylic acid, hydroxycarboxylic acid and acetylacetone;
coordinating ions such as cations and hydroxide ions in the above
coordinating compounds; and the like.
[0742] Examples of the carboxylic acid include dicarboxylic acids
such as oxalic acid, succinic acid and phthalic acid, and the
like.
[0743] Examples of the hydroxycarboxylic acid include
monohydroxymonocarboxylic acid (specifically,
.alpha.-monohydroxycarboxylic acids) such as 2-hydroxyoctanoic
acid, lactic acid and glycolic acid; monohydroxydicarboxylic acids
such as malic acid; monohydroxytricarboxylic acids such as citric
acid; and the like.
[0744] The coordination number is, for example, 1 to 6 and
preferably 1 to 3.
[0745] The complex can be obtained by preparation from a metal
element and a ligand described above.
[0746] The complex can also be formed (prepared) as a salt and/or a
hydrate. Examples of the salt include salts with cations such as
ammonium ions.
[0747] As the organic compound, for example, the same organic
compounds as those that can be used in the first hydrothermal
synthesis described above can be used.
[0748] In the second hydrothermal synthesis, the inorganic material
and the organic compound are reacted under high-temperature and
high-pressure conditions in the presence of water.
[0749] The proportions of respective components per 100 parts by
mass of the inorganic compound are as follows: the proportion of
the organic compound is, for example, 1 to 1500 parts by mass,
preferably 5 to 500 parts by mass and more preferably 5 to 250
parts by mass; and the proportion of water is, for example, 50 to
8000 parts by mass, preferably 80 to 6600 parts by mass and more
preferably 80 to 4500 parts by mass.
[0750] Also, the proportion of the organic compound is, for
example, 0.9 to 1880 mL, preferably 4.5 to 630 mL and more
preferably 4.5 to 320 mL per 100 g of the hydroxide, and the number
of moles of the organic compound can be, for example, 0.01 to 10000
mol and preferably 0.1 to 10 mol per mol of the hydroxide.
[0751] Also, the proportion of water is, for example, 50 to 8000
mL, preferably 80 to 6600 mL and more preferably 100 to 4500 mL per
100 g of the hydroxide.
[0752] The reaction conditions for the second hydrothermal
synthesis are the same as those for the first hydrothermal
synthesis described above.
[0753] In this manner, the organic-inorganic composite particles
containing inorganic particles formed of an inorganic substance
having a different composition as that of the starting inorganic
material and an organic group that binds to the surface of the
inorganic particles are obtained.
[0754] In the high temperature treatment in an organic compound, an
inorganic material and an organic compound are blended and heated,
for example, under normal atmospheric pressure conditions. The
organic compound is subjected to the high temperature treatment
while serving as an organic group-introducing compound as well as a
solvent for dispersing or dissolving the inorganic material.
[0755] The proportion of the organic compound is, for example, 10
to 10000 parts by mass and preferably 100 to 1000 parts by mass per
100 parts by mass of the inorganic material. The proportion of the
organic compound in terms of volume is, for example, 10 to 10000 mL
and preferably 100 to 1000 mL per 100 g of the inorganic
material.
[0756] The heating temperature is the same as those shown in the
second embodiment. The heating time is the same as those shown in
the second embodiment.
[0757] There is no particular limitation on the configuration of
the organic-inorganic composite particles (primary particles)
obtained in the above-described manner, and for example the
organic-inorganic composite particles may be anisotropic or
isotropic, with an average particle size (average maximum length in
the case where they are anisotropic) of, for example, 400 nm or
less, preferably 200 nm or less and more preferably 100 nm or less,
and usually for example, 1 nm or greater and preferably 3 nm or
greater.
[0758] As will be described in detail in the examples given below,
the average particle size of the organic-inorganic composite
particles is determined by measurement by dynamic light scattering
(DLS) and/or calculated from a transmission electron microscopic
(TEM) or scanning electron microscopic (SEM) image analysis.
[0759] If the average particle size of the organic-inorganic
composite particles exceeds the above range, the micropores
(described later) will be too large, and the clarity of the resin
molded article (porous film, described later) will be low. Also,
the organic-inorganic composite particles may be crushed when mixed
with the resin or the like. If the average particle size exceeds
the above range, the organic-inorganic composite particles may be
crushed when mixed with the resin or the like.
[0760] If, on the other hand, the average particle size of the
organic-inorganic composite particles is below the above range, the
proportion of the volume of the organic group relative to the
surface of the organic-inorganic composite particles will be high,
and the function of the inorganic particles is unlikely to be
obtained.
[0761] The organic-inorganic composite particles thus obtained are
unlikely to coagulate in a dry state, and even if the
organic-inorganic composite particles appear coagulated in a dry
state, the coagulation between inorganic particles is prevented in
a particle-containing resin composition and a particle-containing
resin molded article.
[0762] In other words, the organic-inorganic composite particles
have at least a configuration that does not allow the inorganic
particles to contact with each other by steric hindrance of the
organic group.
[0763] The organic-inorganic composite particles are also particles
that can be easily re-dispersed by simply adding a solvent
(described later) even if they are once dried.
[0764] In the organic-inorganic composite particles, the proportion
of the surface area of the organic group relative to the surface
area of the inorganic particles, or in other words, the surface
coverage by the organic group in the organic-inorganic composite
particles (=(surface area of organic group/surface area of
inorganic particles).times.100) is, for example, 30% or greater and
preferably 60% or greater and usually 200% or less.
[0765] The surface coverage is determined by the same method as
that described in the second embodiment.
[0766] In the case where at least the surface coverage is high and
the organic group of the organic-inorganic composite particles has
a length sufficient to cancel the electric charge of the inorganic
particles, the type of solvent (medium) for dispersing the
organic-inorganic composite particles can be controlled (designed
or managed) according to the type of organic group.
[0767] The organic-inorganic composite particles obtained in the
above-described manner can be subjected to wet classification.
[0768] As the wet classification, the same wet classification as
that shown in the second embodiment is used.
[0769] With the wet classification, organic-inorganic composite
particles having a small average particles size can be
obtained.
[0770] With the wet classification, the average particle size of
the resulting organic-inorganic composite particles can be adjusted
to, for example, 400 nm or less, preferably 200 nm or less and more
preferably 100 nm or less, and usually, for example, 0.1 nm or
greater, and preferably 0.3 nm or greater.
[0771] It is also possible to select the resin and the
organic-inorganic composite particles such that the solubility
parameters (SP values) thereof satisfy a predetermined
relationship.
[0772] Specifically, the resin and the organic-inorganic composite
particles are selected so as to attain a predetermined SP
difference (.DELTA.SP, specifically, the absolute value of the
difference between the solubility parameter of resin (SP.sub.RESIN
value) and the solubility parameter of organic-inorganic composite
particles (SP.sub.PARTICLE value)).
[0773] Preferable hydrophilic groups included in both the
functional group and the organic group are a carboxyl group and a
hydroxyl group, and preferable hydrophobic groups included in both
the functional group and the organic group are a hydrocarbon group
and the like. The affinity between the organic-inorganic composite
particles and the resin can be enhanced as a result of both the
functional group and the organic group having any of the above
groups having the same property (hydrophilicity or
hydrophobicity).
[0774] In order to obtain the resin molded article of the present
invention, first, a particle-containing resin composition is
prepared by blending a resin and organic-inorganic composite
particles described above.
[0775] In the prepared particle-containing resin composition, the
existing (dispersed) state of organic-inorganic composite particles
in the particle-containing resin composition varies depending on
the composition of organic group contained in the organic-inorganic
composite particles. Accordingly, the existing (dispersed) state of
organic-inorganic composite particles in the particle-containing
resin composition is not limited to the proportion of resin to
organic-inorganic composite particles (described later).
[0776] To prepare a particle-containing resin composition, the same
solution preparation as that described in the second embodiment is
used.
[0777] As the solvent, the same solvents as those listed in the
second embodiment can be used. These solvents can be used singly or
in a combination of two or more. The solvent is preferably a
halogenated aliphatic hydrocarbon.
[0778] Specifically, in order to prepare a particle-containing
resin composition, first, a solvent and a resin described above are
blended so as to dissolve the resin in the solvent to prepare a
resin solution. After that, the resin solution is blended with
organic-inorganic composite particles, and the resulting mixture is
stirred to prepare a particle-containing resin composition (first
preparation method).
[0779] The proportion of resin relative to the resin solution is
the same as those (in terms of mass, volume, mol, and the like)
shown in the second embodiment.
[0780] The proportion of the organic-inorganic composite particles
is, for example, 1 to 5000 parts by mass, preferably 5 to 3000
parts by mass and more preferably 10 to 300 parts by mass per 100
parts by mass of the solids content (resin) of the resin
solution.
[0781] In particular, for example, in order to disperse (described
later) the organic-inorganic composite particles as primary
particles in the resin, the proportion of the organic-inorganic
composite particles is set to be relatively low (or in other words,
the organic-inorganic composite particles are blended at a low
concentration). Specifically, the proportion of the
organic-inorganic composite particles is set to, for example, less
than 1000 parts by mass, preferably 500 parts by mass or less, and
more preferably 300 parts by mass or less, and for example, 1 part
by mass or greater per 100 parts by mass of the solids content
(resin) of the resin solution.
[0782] On the other hand, in order to cause the organic-inorganic
composite particles to phase separate (described later) from the
resin phase, the proportion of the organic-inorganic composite
particles is set to be relatively high (or in other words, the
organic-inorganic composite particles are blended at a high
concentration). In particular, in order to form the
particle-containing resin molded article so as to have a
bicontinuous structure (described later), the proportion of the
organic-inorganic composite particles is set to, for example, 5
parts by mass or greater, preferably 10 parts by mass or greater,
more preferably 20 parts by mass or greater and usually, for
example, 5000 parts by mass or less per 100 parts by mass of the
solids content (resin) of the resin solution.
[0783] Also, in order to form the particle-containing resin molded
article so as to have a two-phase separated structure (sea-island
structure, described later), the proportion of the
organic-inorganic composite particles is, for example, 50 to 500%
and preferably 80 to 400% of that when the particle-containing
resin molded article is formed so as to have a bicontinuous
structure.
[0784] Also, the particle-containing resin composition can also be
prepared by blending a solvent and organic-inorganic composite
particles to disperse the organic-inorganic composite particles in
the solvent to prepare a particle dispersion, and then blending the
particle dispersion with a resin and stirring the resulting mixture
(second preparation method).
[0785] In the particle dispersion, the organic-inorganic composite
particles are dispersed as primary particles in the solvent.
[0786] The proportion of the organic-inorganic composite particles
is, for example, 0.1 to 80 parts by mass, preferably 0.2 to 60
parts by mass and more preferably 0.5 to 50 parts by mass per 100
parts by mass of the particle dispersion.
[0787] The proportion of resin relative to the solids content
(organic-inorganic composite particles) of the particle dispersion
is the same as those (in terms of mass, volume, mol, and the like)
shown in the second embodiment.
[0788] In particular, in order to disperse (described later) the
organic-inorganic composite particles as primary particles in the
resin, the proportion of resin is set to be relatively high (or in
other words, the resin is blended at a high concentration).
Specifically, the proportion of resin is, for example, 1 part by
mass or greater, preferably 10 parts by mass or greater, more
preferably 20 parts by mass or greater, particularly preferably 40
parts by mass or greater, and for example, 10000 parts by mass or
less per 100 parts by mass of the solids content (organic-inorganic
composite particles) of the particle dispersion.
[0789] On the other hand, in order to cause the organic-inorganic
composite particles to phase separate (described later) from the
resin phase, the proportion of resin is set to be relatively low
(or in other words, the resin is blended at a low concentration).
Specifically, in order to form the particle-containing resin molded
article so as to have a bicontinuous structure (described later),
the proportion of resin is set to, for example, less than 2000
parts by mass, preferably 1000 parts by mass or less, more
preferably 500 parts by mass or less, and for example, 1 part by
mass or greater per 100 parts by mass of the solids content
(organic-inorganic composite particles) of the particle
dispersion.
[0790] Also, in order to form the particle-containing resin molded
article so as to have a two-phase separated structure (sea-island
structure), the proportion of resin is, for example, 10 to 300% and
preferably 20 to 200% of that when the particle-containing resin
molded article is formed so as to have a bicontinuous
structure.
[0791] Furthermore, the particle-containing resin composition can
also be prepared by, for example, blending a solvent,
organic-inorganic composite particles and a resin simultaneously
and stirring the resulting mixture (third preparation method).
[0792] The proportions of respective components per 100 parts by
mass of the total amount of the organic-inorganic composite
particles and the resin are as follows: the proportion of the
organic-inorganic composite particles is, for example, 0.1 to 99.9
parts by mass, preferably 1 to 99 parts by mass and more preferably
3 to 95 parts by mass; and the proportion of resin is 0.1 to 99.9
parts by mass, preferably 1 to 99 parts by mass and more preferably
5 to 97 parts by mass.
[0793] Also, the proportion of the solvent is, for example, 1 to
10000 parts by mass and preferably 10 to 5000 parts by mass per 100
parts by mass of the total amount of the organic-inorganic
composite particles and the resin.
[0794] In particular, in order to disperse (described later) the
organic-inorganic composite particles as primary particles in the
resin, the proportion of the organic-inorganic composite particles
is set to be relatively low (or in other words, the
organic-inorganic composite particles are blended at a low
concentration). Specifically, the proportion of the
organic-inorganic composite particles is set to, for example, less
than 99 parts by mass, preferably 90 parts by mass or less, more
preferably 80 parts by mass or less, particularly preferably 70
parts by mass or less and for example, 0.1 parts by mass or greater
per 100 parts by mass of the total amount of the organic-inorganic
composite particles and the resin.
[0795] On the other hand, in order to cause the organic-inorganic
composite particles to phase separate from the resin phase, the
proportion of the organic-inorganic composite particles is set to
be relatively high (or in other words, the organic-inorganic
composite particles are blended at a high concentration). In
particular, in order to form the particle-containing resin molded
article so as to have a bicontinuous structure, the proportion of
the organic-inorganic composite particles is set to, for example, 5
parts by mass or greater, preferably 10 parts by mass or greater,
more preferably 20 parts by mass or greater and for example, 99
parts by mass or less per 100 parts by mass of the total amount of
the organic-inorganic composite particles and the resin.
[0796] Also, in order to form the particle-containing resin molded
article so as to have a two-phase separated structure (sea-island
structure), the proportion of the organic-inorganic composite
particles is, for example, 50 to 500% and preferably 80 to 400% of
that when the particle-containing resin molded article is formed so
as to have a bicontinuous structure.
[0797] Also, the particle-containing resin composition can also be
prepared by, first, preparing a resin solution and a particle
dispersion in a separate manner, and then blending and stirring the
resin solution and the particle dispersion (fourth preparation
method).
[0798] The proportion of resin in the resin solution is the same as
those shown in the first preparation method described above.
[0799] The proportion of the organic-inorganic composite particles
in the particle dispersion is the same as those shown in the second
preparation method described above.
[0800] The resin solution and the particle dispersion are blended
such that the proportion of the organic-inorganic composite
particles is, for example, 0.1 to 99.9 parts by mass, preferably 1
to 99 parts by mass and more preferably 3 to 95 parts by mass per
100 parts by mass of the total amount of the organic-inorganic
composite particles and the resin.
[0801] In particular, in order to disperse (described later) the
organic-inorganic composite particles as primary particles in the
resin, the resin solution and the particle dispersion are blended
such that the proportion of the organic-inorganic composite
particles is relatively low (or in other words, the concentration
of the organic-inorganic composite particles is low). Specifically,
the resin solution and the particle dispersion are blended such
that the proportion of the organic-inorganic composite particles
is, for example, less than 99 parts by mass, preferably 90 parts by
mass or less, more preferably 80 parts by mass or less,
particularly preferably 70 parts by mass or less and for example,
0.1 parts by mass or greater per 100 parts by mass of the total
amount of the organic-inorganic composite particles and the
resin.
[0802] On the other hand, in order to cause the organic-inorganic
composite particles to phase separate (described later) from the
resin phase, the resin solution and the particle dispersion are
blended such that the proportion of the organic-inorganic composite
particles is relatively high (or in other words, the concentration
of the organic-inorganic composite particles is high). In
particular, in order to form the particle-containing resin molded
article so as to have a bicontinuous structure, the resin solution
and the particle dispersion are blended such that the proportion of
the organic-inorganic composite particles is, for example, less
than 99.9 parts by mass, preferably 99 parts by mass or less, more
preferably 95 parts by mass or less, particularly preferably 90
parts by mass or less, for example, 5 parts by mass or greater,
preferably 10 parts by mass or greater, and more preferably 20
parts by mass or greater per 100 parts by mass of the total amount
of the organic-inorganic composite particles and the resin.
[0803] Also, in order to form the particle-containing resin molded
article so as to have a two-phase separated structure (sea-island
structure), the proportion of the organic-inorganic composite
particles is, for example, 50 to 500% and preferably 80 to 400% of
that when the particle-containing resin molded article is formed so
as to have a bicontinuous structure.
[0804] Furthermore, the particle-containing resin composition can
also be prepared by without the use of a solvent by, for example,
melting a resin by application of heat and blending the resin with
organic-inorganic composite particles (fifth preparation
method).
[0805] The thus-prepared particle-containing resin composition is a
melt of the particle-containing resin composition without a
solvent.
[0806] The heating temperature is the same as those shown in the
second embodiment.
[0807] The proportion of resin is, for example, 1 to 90 parts by
mass, preferably 5 to 80 parts by mass and more preferably 10 to 70
parts by mass per 100 parts by mass of the total amount of the
resin and the organic-inorganic composite particles.
[0808] In particular, in order to disperse (described later) the
organic-inorganic composite particles as primary particles in the
resin, the proportion of the organic-inorganic composite particles
is set to be relatively low (or in other words, the
organic-inorganic composite particles are blended at a low
concentration). Specifically, the proportion of the
organic-inorganic composite particles is, for example, less than 99
parts by mass, preferably 90 parts by mass or less, more preferably
80 parts by mass or less, particularly preferably 70 parts by mass
or less, for example, 0.01 parts by mass or greater, preferably 0.1
parts by mass or greater, and more preferably 1 part by mass or
greater per 100 parts by mass of the total amount of the resin and
the organic-inorganic composite particles.
[0809] On the other hand, in order to cause the organic-inorganic
composite particles to phase separate (described later) from the
resin, the proportion of the organic-inorganic composite particles
is set to be relatively high (or in other words, the
organic-inorganic composite particles are blended at a high
concentration). In particular, in order to form the
particle-containing resin molded article so as to have a
bicontinuous structure, the proportion of the organic-inorganic
composite particles is set to, for example, 5 parts by mass or
greater, preferably 10 parts by mass or greater, more preferably 20
parts by mass or greater and for example, 99 parts by mass or less
per 100 parts by mass of the total amount of the organic-inorganic
composite particles and the resin.
[0810] Also, in order to form the particle-containing resin molded
article so as to have a two-phase separated structure (sea-island
structure), the proportion of the organic-inorganic composite
particles is, for example, 50 to 500% and preferably 80 to 400% of
that when the particle-containing resin molded article is formed so
as to have a bicontinuous structure.
[0811] The particle-containing resin composition obtained by any of
the above-described preparation methods has a configuration that
does not allow the inorganic particles to contact with each other
by steric hindrance of the organic group, and therefore coagulation
of the inorganic particles is prevented.
[0812] Next, in order to obtain the resin molded article of the
present invention, a particle-containing resin molded article is
formed from the particle-containing resin composition prepared
above.
[0813] To form a particle-containing resin molded article, the
particle-containing resin composition is applied to, for example, a
substrate to form a coating, and the coating is dried, whereby a
particle-containing resin molded article as a film
(particle-containing resin film) is molded. After that, the film is
peeled off from the substrate.
[0814] The substrate is made of a material that is not dissolved in
an extraction liquid, which will be described later. Specific
examples include polyester films such as a polyethylene
terephthalate film (PET); olefin films such as a polyethylene film
and a polypropylene film; polyvinyl chloride films; polyimide
films; polyamide films such as a nylon film; and synthetic resin
films such as a rayon film. Other examples of the substrate include
paper substrates such as fine quality paper, Japanese paper, kraft
paper, glassine paper, synthetic paper and top-coat paper.
Furthermore, other examples of the substrate include a glass plate,
a copper plate, an aluminum plate, and an inorganic substrate such
as stainless steel (SUS).
[0815] The thickness of the substrate is, for example, 2 to 1500
.mu.m.
[0816] The particle-containing resin composition is applied by
using, for example, a known application method such as spin coating
or bar coating. Simultaneously with or immediately after
application of the particle-containing resin composition, the
solvent is removed by volatilization. If necessary, the solvent can
be dried by application of heat after application of the
particle-containing resin composition.
[0817] The thickness of the obtained film can be set as appropriate
according to the use and purpose, and the thickness is, for
example, 0.1 to 2000 .mu.m, preferably 0.2 to 1000 .mu.m and more
preferably 0.3 to 500 .mu.m.
[0818] The particle-containing resin molded article as a film can
also be molded by a melt molding method in which the
particle-containing resin composition is extruded by an extruding
machine or the like.
[0819] The particle-containing resin molded article can also be
molded as a block (mass) by injecting the particle-containing resin
composition into a metal mold or the like and thereafter subjecting
the resultant to, for example, heat molding such as heat
pressing,
[0820] In any of the particle-containing resin molded articles
molded in the above-described manner, the organic-inorganic
composite particles are dispersed as primary particles in the resin
in the case where the organic-inorganic composite particles are
blended at a low concentration. In other words, in the
particle-containing resin molded article, the organic-inorganic
composite particles are prevented from coagulating and forming
secondary particles.
[0821] On the other hand, in the case where the organic-inorganic
composite particles are blended at a high concentration, the
particle-containing resin molded article has a phase separated
structure formed of a resin phase composed of resin and a particle
phase composed of organic-inorganic composite particles. The
particle phase is phase-separated from the resin phase.
[0822] The phase separated structure can be, for example, a
two-phase separated structure (sea-island structure) in which the
particle phase is dispersed in the resin phase.
[0823] Also, the phase separated structure can be, for example, a
bicontinuous phase separated structure in which the particle phase
is three-dimensionally continuous. In the bicontinuous phase
separated structure, because the particle phase is
three-dimensionally continuous, the organic-inorganic composite
particles in the particle phase can be extracted continuously
(described later).
[0824] Other examples of the phase separated structure include a
honeycomb structure, a columnar structure and the like.
[0825] After that, the organic-inorganic composite particles are
removed from the particle-containing resin molded article, whereby
the resin molded article of the present invention can be
obtained.
[0826] In order to remove the organic-inorganic composite
particles, for example, an extraction method is used in which an
extraction solvent is brought into contact with the
particle-containing resin molded article. With the extraction
method, specifically, the particle-containing resin molded article
is immersed in an extraction liquid.
[0827] The extraction liquid can be, for example, a solvent that
dissolves organic-inorganic composite particles and permeates
through resin without corroding (damaging) the resin. Examples of
such a solvent include an acid and an alkali.
[0828] Examples of the acid include inorganic acids such as nitric
acid, hydrochloric acid, sulfuric acid, carbonic acid and
phosphoric acid; organic acids such as formic acid and acetic acid;
and the like.
[0829] Examples of the alkali include inorganic alkalis such as
sodium hydroxide, potassium hydroxide; and organic alkalis such as
ammonia.
[0830] An acid is preferable, and an inorganic acid is more
preferable.
[0831] The extraction liquid can be, for example, diluted with a
diluent such as water, an alcohol (ethanol or the like), an
aliphatic hydrocarbon (hexane or the like), and the concentration
of the extraction liquid is, for example, 1 mass % or greater and
less than 100 mass % of the total mass of the extraction liquid and
the diluent.
[0832] In the case where a solvent is used as the extraction
liquid, regardless of the level of the concentration of the
organic-inorganic composite particles (or in other words, the
structure of the organic-inorganic composite particles or particle
phase in the particle-containing resin molded article), the
organic-inorganic composite particles can be dissolved. A solvent
is preferably used particularly when in the particle-containing
resin molded article, the organic-inorganic composite particles are
blended at a low concentration and the organic-inorganic composite
particles are dispersed as primary particles in the resin. In this
case, the solvent permeates through the resin and also dissolves
the organic-inorganic composite particles dispersed as primary
particles in the resin.
[0833] There is no particular limitation on the extraction liquid,
and, for example, it can be a dispersing medium that disperses
organic-inorganic composite particles, does not corrode (damage)
resin and does not permeate through resin. Examples of the
dispersing medium include the same dispersing media as the solvents
used in the washing step described above. Specific examples include
water, an aqueous pH adjusting solution, a hydroxyl
group-containing aliphatic hydrocarbon, a carbonyl group-containing
aliphatic hydrocarbon, an aliphatic hydrocarbon, a halogenated
aliphatic hydrocarbon, a halogenated aromatic hydrocarbon, an
ether, an aromatic hydrocarbon and the like. The dispersing medium
is preferably an aliphatic hydro carbon.
[0834] In the case where a dispersing medium is used as the
extraction liquid, the organic-inorganic composite particles are
blended at a high concentration in the particle-containing resin
molded article and the particle phase composed of the
organic-inorganic composite particles is three-dimensionally
continuous and exposed at the surface of the particle-containing
resin molded article, so that the organic-inorganic composite
particles can be dispersed (extracted) into the dispersing medium
by continuously withdrawing the organic-inorganic composite
particles from the exposed surface.
[0835] The extraction temperature is, for example, 0 to 150.degree.
C. and preferably 10 to 100.degree. C. If the extraction
temperature is below the above range, the extraction time exceeds
the desired limit, which will be described next, and the producing
cost may increase. If, on the other hand, the extraction
temperature exceeds the above range, the resin may be degraded or
the producing cost may increase.
[0836] The extraction time is, for example, 30 seconds to 5 hours
and preferably 1 minute to 3 hours.
[0837] If the extraction time is below the above range, the
extraction efficiency will be low. If the extraction time exceeds
the above range, the producing cost may increase.
[0838] By removing the organic-inorganic composite particles,
micropores are formed in the particle-containing resin molded
article.
[0839] The micropores are formed as openings (gaps) separated by
the resin around the organic-inorganic composite particles.
[0840] The shape and dimension (pore size) of micropores are
substantially the same outer shape and dimension as those of the
organic-inorganic composite particles that have been removed from
the resin.
[0841] Specifically, in the case where in the particle-containing
resin molded article, the organic-inorganic composite particles are
blended in the resin at a relatively low concentration and the
organic-inorganic composite particles are dispersed as primary
particles, the micropores are formed as independent pores
(closed-cells) dispersed uniformly in the resin.
[0842] As a result, a resin molded article in which micropores are
formed, or in other words, a porous molded article can be obtained.
In the case where the resin molded article is formed as a film, a
porous film is obtained.
[0843] With the above described method, in the particle-containing
resin molded article, the organic-inorganic composite particles are
dispersed as primary particles, and the resin molded article having
micropores formed by removing the organic-inorganic composite
particles has excellent clarity and excellent mechanical
strength.
[0844] Accordingly, the resin molded article can be used in, for
example, optical applications including optical films such as a
low-refractive film and an antireflective film, as well as
electrical and electronic applications including electrical and
electronic substrates such as a low-dielectric substrate.
[0845] Moreover, the resin molded article has independent pores
(micropores) formed by removing the organic-inorganic composite
particles having an average particle size within the above range,
and it is thus possible to further enhance clarity.
[0846] In the case where the resin molded article is used as a
low-refractive film, for example, the refractive index of the
low-refractive film for light having a wavelength of 633 nm is
reduced to, for example, 99% or less of the refractive index of the
resin for light having a wavelength of 633 nm, preferably reduced
to 95% or less, more preferably reduced to 90% or less.
Specifically, the refractive index is, for example, 1 to 3,
preferably 1.05 to 2.5 and more preferably 1.1 to 2.
[0847] In the case where the resin molded article is used as an
antireflective film (low-reflection film), the reflectivity of the
antireflective film for light having a wavelength of 550 nm is
reduced to, for example, 99% or less of the reflectivity of the
resin for light having a wavelength of 550 nm, and preferably
reduced to 95% or less. Specifically, the reflectivity of the
antireflective film for light having a wavelength of 550 nm is, for
example, 9% or less, preferably 1 to 8% and more preferably 1.5 to
7%.
[0848] In the case where the resin molded article is used as a
low-dielectric substrate, the dielectric constant of the
low-dielectric substrate is reduced to, for example, 99% or less of
the dielectric constant of the resin, preferably reduced to 95% or
less, and more preferably reduced to 90% or less. Specifically, the
dielectric constant of the low-dielectric substrate is, for
example, 1 to 1000, preferably 1.2 to 100, and more preferably 1.5
to 100.
[0849] On the other hand, with the particle-containing resin molded
article, in the case where the particle-containing resin molded
article has a phase separated structure formed of a particle phase
and a resin phase, more specifically, a bicontinuous phase
separated structure in which the particle phase is
three-dimensionally continuous, the micropores are formed as
communicating pores in the resin.
[0850] In this case, the resin molded article has communicating
pores (micropores) formed by removing the organic-inorganic
composite particles, and thus has excellent mechanical strength and
can be widely used as a porous film (porous molded article) having
paths (passages) formed by communicating pores extending in the
thickness direction (front-back surface direction) in various
applications such as a sizing filter, a molecular separation
membrane, an adsorptive separation filter and an electrolyte
membrane.
[0851] In the removal (extraction) of organic-inorganic composite
particles described above, the organic-inorganic composite
particles can be partially left by adjusting the conditions
therefor.
[0852] In order to partially leave the organic-inorganic composite
particles in the resin molded article, the extraction time is set
to, for example, 80% or less, preferably 65% or less and more
preferably 50% or less of the extraction time when the
organic-inorganic composite particles are fully extracted.
Specifically, the extraction time is, for example, less than 60
minutes, preferably 30 minutes or less, and for example, 1 second
or greater.
[0853] In the resin molded article obtained by extraction performed
for the extraction time, the proportion of remaining
organic-inorganic composite particles increases toward one side of
the resin molded article, specifically, increases from the surface
of the resin molded article toward the interior (inside). In other
words, the proportion of existing micropores in the resin molded
article increases from the interior to the surface of the resin
molded article.
[0854] In the resin molded article, the concentration distribution
in the thickness direction of the micropores is in a range of, for
example, 0 to 90 volume %, preferably a range of 0 to 60 volume %
and more preferably a range of 0 to 40 volume %. Specifically, for
example, the concentration of micropores in the surface of the
porous film is 90 volume % (preferably 65 volume %), the
concentration of micropores in the center portion in the thickness
direction of the porous film is 0 volume %, and a concentration
gradient is formed therebetween.
[0855] In the case where the particle-containing resin molded
article is formed as a film on the top surface of a substrate, the
substrate is laminated on one side of the film, and the resultant
(laminate) can be immersed in an extraction liquid. After that, the
laminate is removed from the extraction liquid and dried. Then, the
film is peeled off from the substrate.
[0856] In the porous film obtained by immersing a laminate of a
film and a substrate in an extraction liquid, the proportion of
remaining organic-inorganic composite particles increases toward
the back surface (one side in the thickness direction,
substrate-side surface). In other words, the proportion of existing
micropores increases toward the surface of the porous film (the
other side in the thickness direction, the exposed surface on which
the substrate is not laminated).
[0857] In the porous film in which the organic-inorganic composite
particles partially remain, the concentration distribution in the
thickness direction of micropores is in a range of, for example, 0
to 90 volume %, preferably a range of 0 to 65 volume % and more
preferably a range of 0 to 40 volume %. Specifically, for example,
the concentration of micropores in the surface of the porous film
is 90 volume % (preferably 65 volume %), the concentration of
micropores in the back surface of the porous film is 0 volume %,
and a concentration gradient is formed in the thickness
direction.
[0858] The proportion of remaining organic-inorganic composite
particles and the proportion of existing micropores are measured by
SEM or TEM.
[0859] The porous film (resin molded article) can be used as a
refractive-index distribution optical film, a dielectric
distribution substrate or the like because the organic-inorganic
composite particles are partially left and the proportion of
existing micropores varies in the thickness direction of the porous
film.
Fifth Embodiment
[0860] Embodiment corresponding to the inventions of a titanium
complex, titanium oxide particles and a producing method therefor,
which are included in the fifth group of inventions
[0861] The titanium complex of the present invention contains a
titanium atom as a central atom and a hydroxycarboxylic acid having
a total of 7 or more carbon atoms as a ligand.
[0862] The titanium atom is a transition element having an atomic
number of 22 and can be, for example, a tetravalent titanium
atom.
[0863] The hydroxycarboxylic acid is an organic compound that has a
total of 7 or more carbon atoms and contains a carboxyl group and a
hydroxyl group, and it can be, for example, a saturated or
unsaturated hydroxycarboxylic acid having a total of 7 or more
carbon atoms such as hydroxyalkanoic acid, hydroxyalkenoic acid or
hydroxyalkynoic acid.
[0864] The total number of carbon atoms of such a hydroxycarboxylic
acid is preferably 8 or greater, for example, 16 or less, and
preferably 13 or less.
[0865] The number of carboxyl groups contained in the
hydroxycarboxylic acid is, for example, 1 to 3 and preferably 1,
and the number of hydroxyl groups is, for example, 1 to 3 and
preferably 1.
[0866] Among the hydroxycarboxylic acids listed above, a
hydroxymonocarboxylic acid and a monohydroxycarboxylic acid are
preferable, and a monohydroxymonocarboxylic acid is preferable.
[0867] Also, among the hydroxycarboxylic acids listed above, a
saturated hydroxyalkanoic acid is preferable. Specific examples
include linear hydroxyalkanoic acids having 7 to 16 carbon atoms
such as hydroxyheptanoic acid, hydroxyoctanoic acid,
hydroxynonanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid,
hydroxydodecanoic acid, hydroxytridecanoic acid,
hydroxytetradecanoic acid, hydroxypentadecanoic acid and
hydroxyhexadecanoic acid; branched hydroxyalkanoic acids having 7
to 16 carbon atoms such as hydroxy 3-ethylhexanoic acid, hydroxy
4-ethylheptoic acid and hydroxy 3-ethyloctanoic acid; and the like.
Among the hydroxyalkanoic acids listed above, linear
hydroxyalkanoic acids are preferable.
[0868] That is, among the hydroxycarboxylic acids listed above,
monohydroxymonoalkanoic acids having a total of 7 to 13 carbon
atoms such as a 2-hydroxyalkanoic acid (.alpha.-hydroxyalkanoic
acid) and a 3-hydroxyalkanoic acid (.beta.-hydroxyalkanoic acid)
are particularly preferable. Specific examples include
2-hydroxyoctanoic acid and 3-hydroxydecanoic acid.
[0869] Such monohydroxymonoalkanoic acids having a total of 7 to 13
carbon atoms can be used as a ligand constituting a titanium
complex. Furthermore, titanium complexes containing such a
monohydroxymonoalkanoic acid as a ligand can enhance heat
resistance (180.degree. C. or higher) as compared to titanium
complexes containing a hydroxycarboxylic acid having a total of 6
or fewer carbon atoms as a ligand.
[0870] Such a titanium complex is prepared by reacting a
hydroxycarboxylic acid having a total of 7 or more carbon atoms
with a titanium atom.
[0871] In order to prepare such a titanium complex, first, a
substance containing a titanium atom is dissolved in a mixed
solution of a hydrogen peroxide solution and an aqueous alkali
solution so as to give an unstable aqueous solution of
peroxotitanium complex.
[0872] The substance containing a titanium atom is not particularly
limited, and can be, for example, titanium particles, titanium
powders or the like.
[0873] The size (average particle size) of titanium particles or
titanium powders is not particularly limited.
[0874] The titanium particles can be, for example, commercially
available titanium particles (available from Wako Pure Chemical
Industries, Ltd.).
[0875] The hydrogen peroxide solution is a solution in which
hydrogen peroxide (H.sub.2O.sub.2) is dissolved in water, and has a
concentration of, for example, 10 to 50 volume % and preferably 20
to 40 volume %.
[0876] The aqueous alkali solution can be, for example, aqueous
ammonia in which ammonia (NH.sub.3) is dissolved in water; an
aqueous organic base solution in which a basic organic compound
such as an amine is dissolved in water; an aqueous inorganic base
solution in which a basic inorganic compound such as sodium
hydrogencarbonate is dissolved in water; or the like.
[0877] These aqueous alkali solutions can be used singly or in
combination.
[0878] Among the aqueous alkali solutions, aqueous ammonia is
preferable. The concentration of aqueous ammonia is, for example, 1
to 45 mass %, preferably 5 to 40 mass % and more preferably 10 to
35 mass %.
[0879] The proportion (hydrogen peroxide solution:aqueous alkali
solution) of the mixed solution of a hydrogen peroxide solution and
an aqueous alkali solution is, for example, 3:7 to 9:1, preferably
5:5 to 9:1 and more preferably 6:4 to 9:1.
[0880] The pH of the mixed solution is, for example, 6 or greater,
preferably 7 to 14 and more preferably 9 to 14.
[0881] In order to dissolve the substance containing a titanium
atom in the mixed solution, for example, the substance containing a
titanium atom is added to the mixed solution and, and the resulting
mixture is stirred for a predetermined period of time.
[0882] The proportion of the substance containing a titanium atom
is, for example, 0.5 to 5 g and preferably 1 to 3 g per 100 mL of
the hydrogen peroxide solution, and is, for example, 0.5 to 5 g and
preferably 1 to 2 g per 100 mL of the mixed solution.
[0883] Stirring conditions are as follows: the temperature is, for
example, -15 to 80.degree. C., preferably -10 to 50.degree. C. and
more preferably -5 to 25.degree. C.; and the time is, for example,
0.1 to 24 hours, preferably 1 to 10 hours and more preferably 1 to
5 hours.
[0884] In the above-described manner, the substance containing a
titanium atom is dissolved in the mixed solution, and an aqueous
solution of peroxotitanium complex is prepared.
[0885] Specifically, the aqueous solution of peroxotitanium complex
contains a peroxotitanium complex formed by reaction of a titanium
atom and hydrogen peroxide (H.sub.2O.sub.2).
[0886] Next, any one of the hydroxycarboxylic acids having a total
of 7 or more carbon atoms is mixed with the aqueous solution of
peroxotitanium complex so as to prepare a titanium
complex-containing solution.
[0887] In order to mix the hydroxycarboxylic acid with the aqueous
solution of peroxotitanium complex, for example, the
hydroxycarboxylic acid is dissolved in a solvent so as to prepare a
hydroxycarboxylic acid solution, and the hydroxycarboxylic acid
solution and the aqueous solution of peroxotitanium complex are
mixed and stirred. After stirring, if necessary, the mixture is
allowed to stand still for, for example, 10 to 40 hours.
[0888] There is no particular limitation on the solvent as long as
the hydroxycarboxylic acid can be dissolved. Examples include
water, alcohols such as methanol and ethanol, ketones such as
acetone and methyl ethyl ketone, and the like.
[0889] These solvents can be used singly or in combination.
[0890] Among the solvents, alcohols are preferable.
[0891] The concentration of the hydroxycarboxylic acid solution is,
for example, 0.1 to 80 mass %, preferably 1 to 50 mass % and more
preferably 5 to 30 mass %.
[0892] The proportion of the hydroxycarboxylic acid solution is,
for example, 10 to 100 mL, preferably 20 to 80 mL and more
preferably 30 to 60 mL per 100 mL of the aqueous solution of
peroxotitanium complex.
[0893] The proportion of hydroxycarboxylic acid is, for example, 1
to 6 mol, preferably 1 to 5 mol, and more preferably 1 to 4 mol per
mol of the substance containing a titanium atom.
[0894] If the proportion of hydroxycarboxylic acid is less than 1
mol per mol of the substance containing a titanium atom, a titanium
complex cannot be formed due to the shortage of ligand, and so a
by-product containing a ligand (hydroxycarboxylic acid) and
titanium atoms that do not form the complex may be left, and the
desired titanium oxide particles may not be obtained from the
titanium complex containing the by-product. If, on the other hand,
the proportion of hydroxycarboxylic acid exceeds 6 mol per mol of
the substance containing a titanium atom, the amount of
hydroxycarboxylic acid will be excessive and wasted, and thus it
may be inappropriate in terms of cost. Also, in this case, it is
necessary to remove excessive hydroxycarboxylic acid left after the
titanium oxide particle producing step, which makes the producing
process complex. If, on the other hand, the proportion of
hydroxycarboxylic acid is within the above range, the efficiency of
titanium oxide particle producing can be enhanced.
[0895] Stirring conditions are as follows: the temperature is, for
example, 0 to 80.degree. C., preferably 5 to 70.degree. C. and more
preferably 10 to 60.degree. C.; and the time is, for example, 0.1
to 24 hours, preferably 0.5 to 10 hours and more preferably 1 to 5
hours. After stirring, if necessary, the mixture is allowed to
stand still for, for example, 10 to 40 hours.
[0896] By mixing and stirring a hydroxycarboxylic acid and an
aqueous solution of peroxotitanium complex as described above, the
hydroxycarboxylic acid is reacted with the peroxotitanium complex
contained in the aqueous solution of peroxotitanium complex, as a
result of which a titanium complex is formed. Accordingly, a
titanium complex-containing solution that contains a titanium
complex is prepared.
[0897] Next, the obtained titanium complex-containing solution is
dried to prepare a titanium complex.
[0898] There is no particular limitation on the drying method, and
known methods such as vacuum drying, spray drying and freeze drying
can be used. For example, the solvent is dried by increasing the
temperature with a drier or the like to prepare a titanium
complex.
[0899] There is no particular limitation on the drying conditions
as long as the solvent can be removed. The temperatures is, for
example, 50 to 100.degree. C. and preferably 60 to 90.degree. C.,
and the time is 0.1 to 48 hours, preferably 0.5 to 24 hours and
more preferably 1 to 10 hours.
[0900] In the above-described manner, a titanium complex is
prepared.
[0901] The coordination number of the titanium complex is, for
example, 1 to 6 preferably 2 to 4 per titanium atom. The
coordination number can be analyzed with, for example, a mass
spectrometer such as a matrix assisted laser desorption ionization
(MALDI)-- time-of-flight (TOF) mass spectrometer (MS), or the
like
[0902] The yield of the titanium complex is, for example, 60 to 100
mol % and preferably 80 to 100 mol % relative to the substance
containing a titanium atom used.
[0903] There is no limitation on the applications of the titanium
complex prepared in this manner. For example, the titanium complex
is subjected to thermal decomposition to produce titanium oxide
particles. Specifically, for example, the titanium complex is
subjected to a high-temperature and high-pressure treatment
(hydrothermal synthesis) in water to produce titanium oxide
particles.
[0904] To produce titanium oxide particles, first, the titanium
complex and water are introduced into a reactor.
[0905] The proportion of the titanium complex is, for example, 5 to
40 parts by mass, preferably 10 to 30 parts by mass per 100 parts
by mass of water.
[0906] The reactor can be a known high-pressure reactor (autoclave)
or continuous high-pressure reactor.
[0907] An example of such a high-pressure reactor (autoclave) is a
commercially available high-pressure reactor (available from AKICO
Corporation). Another example of a continuous high-pressure reactor
is a commercially available continuous high-pressure reactor
(available from ITEC Co. Ltd.).
[0908] Then, the reactor is brought to high-temperature and
high-pressure conditions, whereby titanium oxide particles are
produced (hydrothermal synthesis).
[0909] Reaction conditions for the hydrothermal synthesis are the
same as those for the hydrothermal synthesis (first hydrothermal
synthesis) illustrated in the third embodiment.
[0910] The reaction product obtained by the above hydrothermal
synthesis includes a precipitate that mostly precipitates in water
and a deposit that adheres to the inner wall of the airtight
container.
[0911] There is no particular limitation on the method for
separating and recovering a precipitate, and it is possible to use
known methods that use a separating funnel, a filter, centrifugal
separation and the like. The precipitate can be separated and
recovered by using any of the methods. The precipitate is obtained
by, for example, sedimentation separation in which the reaction
product is settled by gravity or a centrifugal field. Preferably,
the precipitate is obtained as a precipitate of the reaction
product by centrifugal sedimentation (centrifugal separation) in
which the reaction product is settled by a centrifugal field.
[0912] The deposit is recovered by, for example, a scraper
(spatula) or the like.
[0913] The reaction product can also be recovered (separated) by
adding a solvent to wash away unreacted hydroxycarboxylic acid (or
in other words, dissolving the hydroxycarboxylic acid in the
solvent) and thereafter removing the solvent.
[0914] The solvent can be, for example, any of the solvents listed
above.
[0915] These solvents can be used singly or in combination.
[0916] Among the solvents, an alcohol is preferable.
[0917] The washed reaction product is separated from the solvent
(supernatant liquid) by, for example, filtration, decantation or
the like, and recovered. After that, the reaction product is dried
by, for example, application of heat, an air stream or the like if
necessary.
[0918] In the manner described above, titanium oxide particles are
prepared from the titanium complex.
[0919] The titanium oxide particles have a crystal structure of,
for example, anatase (tetragonal crystal), rutile (tetragonal
crystal) or brookite (orthorhombic crystal). The crystal structure
can be determined by electron diffraction such as XRD (X-ray
diffraction) or TEM (transmission electron microscope).
[0920] There is no particular limitation on the crystal structure,
and the crystal structure can be selected as appropriate by
changing the type of ligand and the conditions for synthesizing
titanium oxide. For example, the crystal structure is preferably
rutile when used as an optical material having a high refractive
index, and is preferably anatase when used as a catalyst material
that exerts photocatalytic function.
[0921] As described above, the titanium oxide particles of the
present invention are prepared by treating a titanium complex
containing a hydroxyl carboxylic acid having a total of 7 or more
carbon atoms as a ligand in hot high pressure water.
[0922] At this time, because the ligand of the titanium complex is
a hydroxyl carboxylic acid having a total of 7 or more carbon
atoms, decomposition of the ligand is suppressed even in hot high
pressure water, as a result of which coloring of the resulting
titanium oxide particles can be reduced.
[0923] Therefore, according to the present invention, reduction of
coloring of the titanium oxide particles can be achieved while
achieving reduction of the environmental load.
[0924] The applications of the titanium oxide particles of the
present invention can be, for example, various industrial products,
and optical applications and the like are preferable because
coloring is reduced.
EXAMPLES
[0925] Hereinafter, examples and the like that correspond to the
first to fifth groups of inventions that are included in the
present invention and related to each other will be described in
sequence.
Examples, Comparative Examples, Preparation Examples and Producing
Examples Corresponding to the First Group of Inventions
[0926] The first group of inventions will be described in further
detail by showing Examples, Comparative Examples, Preparation
Examples and Producing Examples corresponding to the first group of
inventions, but the first group of inventions is not limited
thereto.
[0927] The following is a description of evaluation methods for
obtained particles, particle dispersions and resin molded articles
(including optical films).
(1) X-Ray Diffractometry (XRD)
[0928] Particles were loaded into a glass holder and subjected to
X-ray diffractometry under the following conditions. After that,
from the obtained peaks, the components of the primary particles
were assigned by database search. [0929] X-ray diffractometer: D8
DISCOVER with GADDS, available from Bruker AXS
(Optical System on Incident Side)
[0929] [0930] X-ray source: CuK.alpha. (.lamda.=1.542 .ANG.), 45
kV, 360 mA [0931] Spectroscope (monochromator): multilayer mirror
[0932] Collimator diameter: 300 .mu.m
(Optical System on Light-Receiving Side)
[0932] [0933] Counter: two-dimensional PSPC (Hi-STAR) [0934]
Distance between particles and counter: 15 cm 2.theta.=20, 50, 80
degrees, .omega.=10, 25, 40 degrees, Phi=0 degrees, Psi=0 degrees
[0935] Measurement time: 10 minutes [0936] Assignment
(semiquantitation software): FPM EVA, available from Bruker AXS
(2) Fourier Transform Infrared Spectrophotometry (FT-IR)
[0937] Fourier transform infrared spectrophotometry was carried out
according to the KBr method using the following apparatus.
[0938] Fourier transform infrared spectrophotometer: FT/IRplus,
available from JASCO Corporation
(3) Observation with Field Emission-Scanning Electron Microscope
(FE-SEM)
(a) Observation of Particle Surface and Measurement of Lengthwise
Length (Maximum Length) LL and Sideways Length (Minimum Length)
SL
[0939] A sample was produced by dispersing particles on a sample
stage and coating the particles with osmium. Next, the prepared
sample was photographed with the following field emission-scanning
electron microscope (FE-SEM).
[0940] In the obtained FE-SEM micrograph, the lengthwise length
(maximum length) LL and sideways length (minimum length) SL of each
particle were measured, and then the lengthwise length LL and
sideways length SL of the entire particles were calculated from the
arithmetic mean of the measured values.
[0941] FE-SEM: JSM-7500F, available from JEOL Ltd.
[0942] Acceleration voltage: 2 kV
(b) Observation of Cross-Section of Resin Molded Articles
(Including Optical Films)
[0943] A sample was produced by machining a resin molded article
(including an optical film) with a cross section polisher
(SM-08010, available from JEOL Ltd.). After that, the prepared
sample was coated with osmium, and a cross section of the sample
was observed with the following field emission-scanning electron
microscope (FE-SEM).
[0944] FE-SEM: JSM-7001F, available from JEOL Ltd.
[0945] Acceleration voltage: 5 kV
(4) Observation with Transmission Electron Microscope (TEM)
[0946] Particles were dispersed on a Cu mesh having a microgrid
support film, and the particles were observed with a transmission
electron microscope (TEM).
[0947] TEM: HF-2000, available from Hitachi High-Tech Manufacturing
& Service Corporation
[0948] Acceleration voltage: 200 kV
(5) Particle Size Distribution Measurement
[0949] A particle dispersion was placed in a quartz cell, and
particle size distribution was measured with the following particle
size distribution measuring apparatus.
[0950] Particle size distribution measuring apparatus: Zetasizer
Nano-Zs, available from Marvern Instruments
Example 1-1
[0951] Strontium hydroxide octahydrate (available from Wako Pure
Chemical Industries, Ltd.) in an amount of 0.5 g, formic acid
(available from Wako Pure Chemical Industries, Ltd.) in an amount
of 0.0896 mL, decanoic acid (available from Wako Pure Chemical
Industries, Ltd.) in an amount of 0.2332 mL and pure water in an
amount of 2.032 mL were introduced into a 5 mL high-pressure
reactor (available from AKICO Corporation).
[0952] Next, the high-pressure reactor was closed with a cover,
heated to 400.degree. C. in a shaking furnace (available from AKICO
Corporation) so as to pressurize the inside of the high-pressure
reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal
synthesis.
[0953] After that, the high-pressure reactor was plunged into cold
water for quenching.
[0954] Next, because decanoic acid dissolves in ethanol, ethanol
(available from Wako Pure Chemical Industries, Ltd.) was added, and
the mixture was stirred and subjected to centrifugal separation
performed in a centrifuge (trade name: MX-301, available from Tomy
Seiko Co., Ltd.) at 12000 G for 10 minutes to separate a
precipitate (reaction product) from a supernatant (washing step).
This washing operation was repeated 5 times so as to remove the
remaining decanoic acid, and thereby particles were obtained.
[0955] After that, the obtained particles were evaluated by (1)
XRD, (2) FT-IR and (3) FE-SEM.
[0956] The formulation of respective components and the evaluation
results in Example 1-1 are presented in Table 1, and an
image-processed FE-SEM micrograph in Example 1-1 is shown in FIG.
1.
[0957] As a result, (1) XDR confirmed that the inorganic compound
forming the inorganic particles was SrCO.sub.3.
[0958] (2) FT-IR confirmed C--H stretching vibrations from 2800 to
3000 cm.sup.-1 and the presence of C--H bonds on the surface of the
inorganic particles.
[0959] (3) FE-SEM confirmed that the primary particles had an
acicular shape with a sideways length SL of approximately 0.1 to
0.5 .mu.m and a lengthwise length LL of approximately 0.8 to 6
.mu.m with reference to FIG. 1. It was also confirmed that the
aspect ratio of the primary particles was 8 to 60 as a result of
calculation from FIG. 1.
Examples 1-2 to 1-16
[0960] Particles were obtained in the same manner as in Example 1-1
according to the formulation and treatment conditions presented in
Table 1, and then subjected to evaluation in the same manner as in
Example 1-1. The results are presented in Table 1.
Comparative Example 1-1
[0961] Strontium hydroxide octahydrate (available from Wako Pure
Chemical Industries, Ltd.) in an amount of 0.5 g and pure water in
an amount of 2.355 mL were introduced into a 5 mL high-pressure
reactor (available from AKICO Corporation).
[0962] Next, the high-pressure reactor was closed with a cover,
heated to 400.degree. C. in a shaking furnace (available from AKICO
Corporation) so as to pressurize the inside of the high-pressure
reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal
synthesis.
[0963] After that, the high-pressure reactor was plunged into cold
water for quenching.
[0964] Next, pure water was added, and the mixture was stirred and
subjected to centrifugal separation performed in a centrifuge
(trade name: MX-301, available from Tomy Seiko Co., Ltd.) at 12000
G for 10 minutes, and thereby a precipitate was separated from a
supernatant and dried to give particles.
[0965] After that, the obtained particles were evaluated by (1) XRD
described above.
[0966] The formulation of respective components and the evaluation
results in Comparative Example 1-1 are presented in Table 1.
[0967] (1) XDR confirmed that the inorganic compound forming the
inorganic particles was SrCO.sub.3.
Comparative Example 1-2
[0968] Strontium hydroxide octahydrate (available from Wako Pure
Chemical Industries, Ltd.) in an amount of 0.5 g, formic acid
(available from Wako Pure Chemical Industries, Ltd.) in an amount
of 0.0896 mL and pure water in an amount of 2.265 mL were
introduced into a 5 mL high-pressure reactor (available from AKICO
Corporation).
[0969] Next, the high-pressure reactor was closed with a cover,
heated to 400.degree. C. in a shaking furnace (available from AKICO
Corporation) so as to pressurize the inside of the high-pressure
reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal
synthesis.
[0970] After that, the high-pressure reactor was plunged into cold
water for quenching.
[0971] Next, ethanol (available from Wako Pure Chemical Industries,
Ltd.) was added, and the mixture was stirred and subjected to
centrifugal separation performed in a centrifuge (trade name:
MX-301, available from Tomy Seiko Co., Ltd.) at 12000 G for 10
minutes to separate a precipitate (reaction product) from a
supernatant (washing step). This washing operation was repeated 5
times, and thereby particles were obtained.
[0972] After that, the obtained particles were evaluated by (1)
XRD, (2) FT-IR and (3) FE-SEM.
[0973] The formulation of respective components and the evaluation
results in Comparative Example 1-2 are presented in Table 1, and an
image-processed FE-SEM micrograph in Comparative Example 1-2 is
shown in FIG. 2.
(1) XDR confirmed that the inorganic compound forming the inorganic
particles was SrCO.sub.3.
[0974] (2) FT-IR confirmed no C--H stretching vibrations from 2800
to 3000 cm.sup.-1.
[0975] (3) FE-SEM confirmed that the primary particles had an
acicular shape with a sideways length SL of approximately 200 nm to
1 .mu.m and a lengthwise length LL of approximately 0.8 to 7.5
.mu.m with reference to FIG. 2. It was also confirmed that the
aspect ratio of the primary particles was 4 to 37 as a result of
calculation from FIG. 2.
TABLE-US-00001 TABLE 1 Formulations pH adjusting Composition
Inorganic Carbonic agent Pure Ex. of compound Organic compound acid
source Type (pH water Comp. inorganic Amount Hydrophobic/ Amount
Amount of reaction Amount Amount Ex. particles *1 Type (g)
hydrophilic Type (mL) Type (mL) system) (mL) (mL) Ex. 1-1
SrCO.sub.3 Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Decanoic
acid 0.2332 Formic acid 0.0896 -- 2.032 Ex. 1-2 SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Decanoic acid 0.9326
Formic acid 0.0299 1.333 Ex. 1-3 SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.1 Hydrophobic Decanoic acid 0.259
Formic acid 0.0896 2.328 Ex. 1-4 SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Decanoic acid 0.04664
Formic acid 0.0896 2.219 Ex. 1-5 SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Decanoic acid 0.2332
Formic acid 0.1792 1.942 Ex. 1-6 SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.17 Hydrophobic Decanoic acid 0.088
Formic acid 0.0338 0.767 Ex. 1-7 SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.342 Hydrophobic Decanoic acid 0.1768
Formic acid 0.0679 1.542 Ex. 1-8 SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Decanoic acid 0.2332
Formic acid 0.0896 2.032 Ex. 1-9 SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Decanoic acid 0.2332
Formic acid 0.08955 2.032 Ex. SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 1 Hydrophobic Decanoic acid 0.2332
Formic acid 0.1592 1.962 1-10 Ex. SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Diethyldodecyl- 0.3278
Formic acid 0.0896 1.937 1-11 phosphonate Ex. SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Hexanoic acid 0.1475
Formic acid 0.0896 2.118 1-12 Ex. SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Lauric acid 0.2359
Formic acid 0.0896 2.029 1-13 Ex. SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic 6-Phenylhexanoic
0.2198 Formic acid 0.0896 2.045 1-14 acid Ex. SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Decylamine 0.1948
Formic acid 0.0896 2.07 1-15 Ex. SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Decanoic acid 0.2332
Formic acid 0.0896 1.885 1-16 Hexanoic acid 0.1475 Comp. SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 -- -- 2.355 Ex. 1-1 Comp.
SrCO.sub.3 Sr(OH).sub.2.cndot.8H.sub.2O 0.5 -- Formic acid 0.0896
2.265 Ex. 1-2 Evaluation Primary particles Particle size SL:
Sideways Dispersibility Ex. Treatment conditions length Solvent of
Comp. Temp. Pressure Time LL: Lengthwise Aspect particle dispersion
*2 Resin molded Ex. .degree. C. MPa Min. length ratio Chloroform
Cyclohexane article *3 Optical film *4 Ex. 1-1 400 40 10 SL:
0.1-0.5 .mu.m 8-60 Dispersed as -- Dispersed as Dispersed as LL:
0.8-6 .mu.m primary particles primary particles primary particles
Ex. 1-2 400 40 10 SL: 3-4 .mu.m 1.5-5 Dispersed as Dispersed as
Dispersed as LL: 4-12.5 .mu.m primary particles primary particles
primary particles Ex. 1-3 400 40 10 SL: 1-2.5 .mu.m 3-6 Dispersed
as Dispersed as Dispersed as LL: 3-6 .mu.m primary particles
primary particles primary particles Ex. 1-4 400 40 10 SL: 0.2-0.6
.mu.m 3-35 Dispersed as Dispersed as Dispersed as LL: 0.6-7 .mu.m
primary particles primary particles primary particles Ex. 1-5 400
40 10 SL: 0.2-1.8 .mu.m 3-25 Dispersed as Dispersed as Dispersed as
LL: 0.6-5 .mu.m primary particles primary particles primary
particles Ex. 1-6 500 40 10 SL: 0.2-0.75 .mu.m 3-27 Dispersed as
Dispersed as Dispersed as LL: 0.6-5.5 .mu.m primary particles
primary particles primary particles Ex. 1-7 400 30 10 SL: 0.4-0.6
.mu.m 25-15 Dispersed as Dispersed as Dispersed as LL: 1.6 .mu.m
primary particles primary particles primary particles Ex. 1-8 350
17 3 SL: 0.1-0.5 .mu.m 5-30 Dispersed as Dispersed as Dispersed as
LL: 0.5-3 .mu.m primary particles primary particles primary
particles Ex. 1-9 400 40 120 SL: 0.1-0.4 .mu.m 2-50 Dispersed as
Dispersed as Dispersed as LL: 0.2-5 .mu.m primary particles primary
particles primary particles Ex. 400 40 120 SL: 0.4-0.8 .mu.m 1-100
Dispersed as Dispersed as Dispersed as 1-10 LL: 0.3-4.0 .mu.m
primary particles primary particles primary particles Ex. 400 40 10
SL: 0.5-0.8 .mu.m 10-36 Dispersed as Dispersed as Dispersed as 1-11
LL: 5-18 .mu.m primary particles primary particles primary
particles Ex. 400 40 10 SL: 0.1-0.5 .mu.m 8-75 Dispersed as
Dispersed as Dispersed as 1-12 LL: 0.8-7.5 .mu.m primary particles
primary particles primary particles Ex. 400 40 10 SL: 0.1-0.6 .mu.m
5-20 Dispersed as Dispersed as Dispersed as 1-13 LL: 0.5-2 .mu.m
primary particles primary particles primary particles Ex. 400 40 10
SL: 0.1-0.55 .mu.m 6-55 Dispersed as Dispersed as Dispersed as 1-14
LL: 0.6-5.5 .mu.m primary particles primary particles primary
particles Ex. 400 40 10 SL: 0.2-1 .mu.m 5-20 Dispersed as Dispersed
as Dispersed as 1-15 LL: 1-4 .mu.m primary particles primary
particles primary particles Ex. 400 40 10 SL: 0.5-0.8 .mu.m 14-30
Dispersed as Dispersed as Dispersed as 1-16 LL: 7-15 .mu.m primary
particles primary particles primary particles Comp. 400 40 10 -- --
-- -- -- Ex. 1-1 Comp. 400 40 10 SL: 0.2-1 .mu.m 4-37 Coagulated
Coagulated Coagulated Ex. 1-2 LL: 0.8-7.5 .mu.m *1: Negative
birefringence *2: Preparation Example 1-1 *3: Production Example
1-1, Size: diameter of 10 mm, thickness of 5 mm *4: Production
Example 1-2, Size: thickness of 20 .mu.m
Example 1-17
[0976] Strontium hydroxide octahydrate (available from Wako Pure
Chemical Industries, Ltd.) in an amount of 0.5 g, formic acid
(available from Wako Pure Chemical Industries, Ltd.) in an amount
of 0.0896 mL, oleic acid (available from Wako Pure Chemical
Industries, Ltd.) in an amount of 0.3737 mL and aqueous ammonia in
an amount of 1.892 mL were introduced into a 5 mL high-pressure
reactor (available from AKICO Corporation). The amount of aqueous
ammonia was adjusted such that the resulting reaction system had a
pH of 10.
[0977] Next, the high-pressure reactor was closed with a cover,
heated to 400.degree. C. in a shaking furnace (available from AKICO
Corporation) so as to pressurize the inside of the high-pressure
reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal
synthesis.
[0978] After that, the high-pressure reactor was plunged into cold
water for quenching.
[0979] Next, because oleic acid dissolves in ethanol, ethanol
(available from Wako Pure Chemical Industries, Ltd.) was added, and
the mixture was stirred and subjected to centrifugal separation
performed in a centrifuge (trade name: MX-301, available from Tomy
Seiko Co., Ltd.) at 12000 G for 10 minutes to separate a
precipitate (reaction product) from a supernatant (washing step).
This washing operation was repeated 5 times so as to remove the
remaining oleic acid, and thereby particles were obtained.
[0980] After that, the obtained particles were evaluated by (1)
XRD, (2) FT-IR and (4) TEM described above.
[0981] The formulation of respective components and the evaluation
results in Example 1-17 are presented in Table 2, and an
image-processed TEM micrograph is shown in FIG. 3.
[0982] (1) XDR confirmed that the inorganic compound forming the
inorganic particles was SrCO.sub.3.
[0983] (2) FT-IR confirmed C--H stretching vibrations from 2800 to
3000 cm.sup.-1 and the presence of C--H bonds on the surface of the
inorganic particles.
[0984] (4) TEM confirmed that the primary particles had an acicular
shape with a sideways length SL of approximately 20 to 100 nm and a
lengthwise length LL of approximately 60 to 280 nm with reference
to FIG. 3. It was also confirmed that the aspect ratio of the
primary particles was 3 to 14 as a result of calculation from FIG.
3.
Examples 1-18 to 1-28
[0985] Particles were obtained in the same manner as in Example
1-17 according to the formulation and treatment conditions
presented in Table 2, and then subjected to evaluation in the same
manner as in Example 1-17. The results are presented in Table
2.
TABLE-US-00002 TABLE 2 Formulations pH adjusting agent Inorganic
Carbonic Type Composition of compound Organic compound acid source
(pH of inorganic Amount Hydrophobic/ Amount Amount reaction Amount
Ex. particles *1 Type (g) hydrophilic Type (mL) Type (mL) system)
(mL) Ex. 1-17 SrCO.sub.3 Sr(OH).sub.2.cndot.8H.sub.2O 0.5
Hydrophobic Oleic acid 0.3737 Formic acid 0.0896 Aqueous 1.89
ammonia (pH = 10) Ex. 1-18 SrCO.sub.3 Sr(OH).sub.2.cndot.8H.sub.2O
0.5 Hydrophobic Decanoic acid 0.2332 Formic acid 0.0896 Aqueous
2.03 ammonia (pH = 10) Ex. 1-19 SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Decanoic acid 0.2332
Formic acid 0.0896 Aqueous 2.03 ammonia (pH = 11) Ex. 1-20
SrCO.sub.3 Sr(OH).sub.2.cndot.8H.sub.2O 0.3 Hydrophobic Decanoic
acid 0.5181 Formic acid 0.0995 Aqueous 2 ammonia (pH = 12) Ex. 1-21
SrCO.sub.3 Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Decanoic
acid 0.5181 Formic acid 0.0995 Aqueous 2 ammonia (pH = 12) Ex. 1-22
SrCO.sub.3 Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic Decanoic
acid 0.2332 Formic acid 0.0896 Aqueous 2.03 ammonia (pH = 8) Ex.
1-23 SrCO.sub.3 Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic
Decanoic acid 0.2332 Urea 0.1414 Aqueous 1.98 ammonia (pH = 10) Ex.
1-24 SrCO.sub.3 Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophobic
Decanoic acid 0.2332 Formic acid 0.0896 Aqueous 2.03 ammonia (pH =
12) Ex. 1-25 SrCO.sub.3 Sr(OH).sub.2.cndot.8H.sub.2O 0.5
Hydrophobic Decanoic acid 0.2332 Formic acid 0.0896 Aqueous 2.03
ammonia pH = 10) Ex. 1-26 SrCO.sub.3 Sr(OH).sub.2.cndot.8H.sub.2O
0.5 Hydrophobic 6-Phenylhexanoic 0.2198 Formic acid 0.0896 Aqueous
2.05 acid ammonia (pH = 10) Ex. 1-27 SrCO.sub.3
Sr(OH).sub.2.cndot.8H.sub.2O 0.5 Hydrophilic Decylamine 0.1948
Formic acid 0.0896 Aqueous 2.07 ammonia (pH = 10) Ex. 1-28
SrCO.sub.3 Sr(OH).sub.2.cndot.8H.sub.2O 0.3 Hydrophobic Decanoic
acid 0.2591 Formic acid 0.0995 Aqueous 2.09 Hexanoic acid 0.164
ammonia (pH = 12) Evaluation Primary particles Particle size SL:
Sideways Dispersibility Treatment conditions length Solvent of
Temp. Pressure Time LL: Lengthwise Aspect particle dispersion *2
Resin molded Ex. .degree. C. MPa Min. length ratio Chloroform
Cyclohexane article *3 Optical film *4 Ex. 1-17 400 40 10 SL:
0.02-0.1 .mu.m 3-14 Dispersed as -- Dispersed as Dispersed as LL:
0.06-0.28 .mu.m primary particles primary particles primary
particles Ex. 1-18 400 40 10 SL: 0.05-0.25 .mu.m 10-40 Dispersed as
Dispersed as Dispersed as LL: 0.5-2 .mu.m primary particles primary
particles primary particles Ex. 1-19 400 40 10 SL: 0.1-0.5 .mu.m
4-50 Dispersed as Dispersed as Dispersed as LL: 0.4-5 .mu.m primary
particles primary particles primary particles Ex. 1-20 400 40 10
SL: 0.01-0.04 .mu.m 5-20 Dispersed as Dispersed as Dispersed as LL:
0.05-0.2 .mu.m primary particles primary particles primary
particles Ex. 1-21 400 40 10 SL: 0.01-0.02 .mu.m 5-20 Dispersed as
Dispersed as Dispersed as LL: 0.05-0.2 .mu.m primary particles
primary particles primary particles Ex. 1-22 400 40 10 SL:
0.04-0.25 .mu.m 13-50 Dispersed as Dispersed as Dispersed as LL:
0.05-2 .mu.m primary particles primary particles primary particles
Ex. 1-23 400 40 10 SL: 0.1-0.2 .mu.m 10-60 Dispersed as Dispersed
as Dispersed as LL: 1-6 .mu.m primary particles primary particles
primary particles Ex. 1-24 400 40 10 SL: 0.17-0.3 .mu.m 8-23
Dispersed as Dispersed as Dispersed as LL: 1.3-4 .mu.m primary
particles primary particles primary particles Ex. 1-25 400 40 3 SL:
0.075-0.2 .mu.m 4-24 Dispersed as Dispersed as Dispersed as LL:
0.3-1.8 .mu.m primary particles primary particles primary particles
Ex. 1-26 400 40 10 SL: 0.07-0.18 .mu.m 23-38 Dispersed as Dispersed
as Dispersed as LL: 0.16-2.7 .mu.m primary particles primary
particles primary particles Ex. 1-27 400 40 10 SL: 0.125-0.35 .mu.m
4-42 Dispersed as Dispersed as Dispersed as LL: 0.43-5.3 .mu.m
primary particles primary particles primary particles Ex. 1-28 400
40 10 SL: 0.01-0.04 .mu.m 2-20 Dispersed as Dispersed as Dispersed
as LL: 0.02-0.2 .mu.m primary particles primary particles primary
particles *1: Negative birefringence *2: Preparation Example 1-1
*3: Production Example 1-1, Size: diameter of 10 mm, thickness of 5
mm *4: Production Example 1-2, Size: thickness of 20 .mu.m
Example 1-29
[0986] Strontium carbonate (available from Honjo Chemical
Corporation) in an amount of 0.5 g, decanoic acid (available from
Wako Pure Chemical Industries, Ltd.) in an amount of 0.2332 mL and
pure water in an amount of 2.122 mL were introduced into a 5 mL
high-pressure reactor (available from AKICO Corporation).
[0987] Next, the high-pressure reactor was closed with a cover,
heated to 400.degree. C. in a shaking furnace (available from AKICO
Corporation) so as to pressurize the inside of the high-pressure
reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal
synthesis.
[0988] After that, the high-pressure reactor was plunged into cold
water for quenching.
[0989] Next, because decanoic acid dissolves in ethanol, ethanol
(available from Wako Pure Chemical Industries, Ltd.) was added, and
the mixture was stirred and subjected to centrifugal separation
performed in a centrifuge (trade name: MX-301, available from Tomy
Seiko Co., Ltd.) at 12000 G for 10 minutes to separate a
precipitate (reaction product) from a supernatant (washing step).
This washing operation was repeated 5 times so as to remove the
remaining decanoic acid, and thereby particles were obtained.
[0990] After that, the obtained particles were evaluated by (1)
XRD, (2) FT-IR and (3) FE-SEM described above.
[0991] The formulation of respective components and the evaluation
results in Example 1-29 are presented in Table 3, and an
image-processed FE-SEM micrograph in Example 1-29 is shown in FIG.
4.
[0992] As a result, (1) XDR confirmed that the inorganic compound
forming the inorganic particles was SrCO.sub.3.
[0993] (2) FT-IR confirmed C--H stretching vibrations from 2800 to
3000 cm.sup.-1 and the presence of C--H bonds on the surface of the
inorganic particles.
[0994] (3) FE-SEM confirmed that the primary particles had an
acicular shape with a sideways length SL of approximately 140 to
210 nm and a lengthwise length LL of approximately 400 nm to 1
.mu.m with reference to the image-processed micrograph shown in
FIG. 4. It was also confirmed that the aspect ratio of the primary
particles was 3 to 5 as a result of calculation from the
image-processed micrograph shown in FIG. 4.
Examples 1-30 to 1-46
[0995] Particles were obtained in the same manner as in Example
1-29 according to the formulation and treatment conditions
presented in Table 3, and then subjected to evaluation in the same
manner as in Example 1-29. The results are presented in Table
3.
Comparative Example 1-3
[0996] Strontium carbonate (available from Honjo Chemical
Corporation) in an amount of 0.5 g and pure water in an amount of
2.355 mL were introduced into a 5 mL high-pressure reactor
(available from AKICO Corporation).
[0997] Next, the high-pressure reactor was closed with a cover,
heated to 400.degree. C. in a shaking furnace (available from AKICO
Corporation) so as to pressurize the inside of the high-pressure
reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal
synthesis.
[0998] After that, the high-pressure reactor was plunged into cold
water for quenching.
[0999] Next, a reaction product was recovered using ethanol
(available from Wako Pure Chemical Industries, Ltd.) and subjected
to centrifugal separation performed in a centrifuge (trade name:
MX-301, available from Tomy Seiko Co., Ltd.) at 12000 G for 10
minutes, and thereafter a precipitate was separated from a
supernatant and dried to give particles.
[1000] After that, the obtained particles were evaluated by (1)
XRD, (2) FT-IR and (3) FE-SEM described above.
[1001] The formulation of respective components and the evaluation
results in Comparative Example 1-3 are presented in Table 3, and an
image-processed FE-SEM micrograph in Comparative Example 1-3 is
shown in FIG. 5.
[1002] (1) XDR confirmed that the inorganic compound forming the
inorganic particles was SrCO.sub.3.
[1003] (2) FT-IR confirmed no C--H stretching vibrations from 2800
to 3000 cm.sup.-1.
[1004] (3) FE-SEM confirmed that the primary particles had an
acicular shape with a sideways length SL of approximately 140 to
210 nm and a lengthwise length LL of approximately 400 nm to 1
.mu.m with reference to FIG. 5. It was also confirmed that the
aspect ratio of the primary particles was 3 to 5 as a result of
calculation from FIG. 5.
TABLE-US-00003 TABLE 3 Formulations pH adjusting Composition
Inorganic Carbonic agent Ex. of compound Organic compound acid
source Type (pH Pure water Comp. inorganic Amount Hydrophobic/
Amount Amount of reaction Amount Amount Ex. particles *1 Type (g)
hydrophilic Type (mL) Type (mL) system) (mL) (mL) Ex. 1-29
SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic Decanoic acid 0.2332 -- --
2.122 Ex. 1-30 SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic Decanoic acid
0.3406 3.099 Ex. 1-31 SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic
Decanoic acid 0.3716 3.382 Ex. 1-32 SrCO.sub.3 SrCO.sub.3 0.5
Hydrophobic Decylamine 0.2845 3.155 Ex. 1-33 SrCO.sub.3 SrCO.sub.3
0.5 Hydrophobic 6-Phenylhexanoic 0.3503 3.403 acid Ex. 1-34
SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic Decylphosphonic acid 0.3823
3.057 Ex. 1-35 SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic
Decylphosphonic 0.2617 3.057 acid Ex. 1-36 SrCO.sub.3 SrCO.sub.3
0.5 Hydrophobic Cyclohexanepentanoic 0.2511 2.365 acid Ex. 1-37
SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic Norbomene 0.5 3.253 decanoic
acid Ex. 1-38 SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic
Trioctylphosphin 0.7255 3.028 oxide Ex. 1-39 SrCO.sub.3 SrCO.sub.3
0.5 Hydrophobic 10-Undecenoic 0.3458 3.407 acid Ex. 1-40 SrCO.sub.3
SrCO.sub.3 0.5 Hydrophobic Decanoic acid 0.1858 3.45 SrCO.sub.3
SrCO.sub.3 Hexanoic acid 0.1176 Ex. 1-41 SrCO.sub.3 SrCO.sub.3 0.5
Hydrophobic Norbomene 0.25 3.386 decanoic acid SrCO.sub.3
SrCO.sub.3 Hexanoic acid 0.1176 Ex. 1-42 SrCO.sub.3 SrCO.sub.3 0.5
Hydrophobic Cyclopentanedecanoic 0.2255 3.41 acid SrCO.sub.3
SrCO.sub.3 Hexanoic acid 0.1176 Ex. 1-43 SrCO.sub.3 SrCO.sub.3 0.5
Hydrophilic Ethyl 0.2332 2.122 6-hydroxyhexanoate Ex. 1-44
SrCO.sub.3 SrCO.sub.3 0.5 Hydrophilic 4-Oxovaleric acid 0.2332
2.122 Ex. 1-45 SrCO.sub.3 SrCO.sub.3 0.5 Hydrophilic
4-Hydroxyphenylacetic 0.2332 2.122 acid Ex. 1-46 SrCO.sub.3
SrCO.sub.3 0.5 Hydrophilic 3-(4- 0.2332 2.122
hydroxyphenyl)propionic acid Comp. SrCO.sub.3 SrCO.sub.3 0.5 --
2.355 Ex. 1-3 Evaluation Dispersibility Ex. Treatment conditions
Solvent of Comp. Temp. Pressure Time Primary particles particle
dispersion *2 Resin molded Ex. .degree. C. MPa Min. Particle size
Aspect ratio Chloroform Cyclohexane article *3 Optical film *4 Ex.
1-29 400 40 10 SL: 0.14-0.21 .mu.m 3-5 Dispersed as -- Dispersed as
Dispersed as LL: 0.4-1 .mu.m primary particles primary particles
primary particles Ex. 1-30 300 40 10 Dispersed as Dispersed as
Dispersed as primary particles primary particles primary particles
Ex. 1-31 300 30 10 Dispersed as Dispersed as Dispersed as primary
particles primary particles primary particles Ex. 1-32 300 40 10
Dispersed as Dispersed as Dispersed as primary particles primary
particles primary particles Ex. 1-33 300 30 10 Dispersed as
Dispersed as Dispersed as primary particles primary particles
primary particles Ex. 1-34 300 40 10 Dispersed as Dispersed as
Dispersed as primary particles primary particles primary particles
Ex. 1-35 400 40 10 Dispersed as Dispersed as Dispersed as primary
particles primary particles primary particles Ex. 1-36 400 40 10
Dispersed as Dispersed as Dispersed as primary particles primary
particles primary particles Ex. 1-37 300 30 10 Dispersed as
Dispersed as Dispersed as primary particles primary particles
primary particles Ex. 1-38 300 30 10 Dispersed as Dispersed as
Dispersed as primary particles primary particles primary particles
Ex. 1-39 300 30 10 Dispersed as Dispersed as Dispersed as primary
particles primary particles primary particles Ex. 1-40 300 30 10
Dispersed as Dispersed as Dispersed as primary particles primary
particles primary particles Ex. 1-41 300 30 10 Dispersed as
Dispersed as Dispersed as primary particles primary particles
primary particles Ex. 1-42 300 30 10 Dispersed as Dispersed as
Dispersed as primary particles primary particles primary particles
Ex. 1-43 400 40 10 Dispersed as -- -- primary particles Ex. 1-44
400 40 10 Dispersed as -- -- primary particles Ex. 1-45 400 40 10
Dispersed as -- -- primary particles Ex. 1-46 400 40 10 Dispersed
as -- -- primary particles Comp. 400 40 10 Coagulated Coagulated
Coagulated Ex. 1-3 *1: Negative birefringence *2: Preparation
Example 1-1 *3: Production Example 1-1, Size: diameter of 10 mm,
thickness of 5 mm *4: Production Example 1-2, Size: thickness of 20
.mu.m
Example 1-47
[1005] Strontium carbonate (available from Honjo Chemical
Corporation) in an amount of 0.5 g and oleic acid (available from
Wako Pure Chemical Industries, Ltd.) in an amount of 3.5 mL were
introduced into a 5 mL high-pressure reactor (available from AKICO
Corporation).
[1006] Next, the high-pressure reactor was shaken for 15 minutes
while heating to 250.degree. C. in a shaking furnace (available
from AKICO Corporation), without closing the high-pressure reactor
with a cover.
[1007] After heating, the high-pressure reactor was plunged into
cold water for quenching.
[1008] Next, because oleic acid dissolves in ethanol, ethanol
(available from Wako Pure Chemical Industries, Ltd.) was added, and
the mixture was stirred and subjected to centrifugal separation
performed in a centrifuge (trade name: MX-301, available from Tomy
Seiko Co., Ltd.) at 12000 G for 10 minutes to separate a
precipitate (reaction product) from a supernatant (washing step).
By repeating this washing step 5 times, the remaining oleic acid
was removed, and thereby particles were obtained.
[1009] After that, the obtained particles were evaluated by (1)
XRD, (2) FT-IR and (3) FE-SEM described above.
[1010] The formulation of respective components and the evaluation
results in Example 1-47 are presented in Table 4, and an
image-processed FE-SEM micrograph in Example 1-47 is shown in FIG.
6.
[1011] As a result, (1) XDR confirmed that the inorganic compound
forming the inorganic particles was SrCO.sub.3.
[1012] (2) FT-IR confirmed C--H stretching vibrations from 2800 to
3000 cm.sup.-1 and the presence of C--H bonds on the surface of the
inorganic particles.
[1013] (3) FE-SEM confirmed that the primary particles had an
acicular shape with a sideways length SL of approximately 140 to
210 nm and a lengthwise length LL of approximately 400 nm to 1
.mu.m with reference to FIG. 6. It was also confirmed that the
aspect ratio of the primary particles was 3 to 5 as a result of
calculation from FIG. 6.
Examples 1-48 to 1-54
[1014] Particles were obtained in the same manner as in Example
1-47 according to the formulation and treatment conditions
presented in Table 4, and then subjected to evaluation in the same
manner as in Example 1-47. The results are presented in Table
4.
TABLE-US-00004 TABLE 4 Formulations Composition Inorganic Carbonic
pH adjusting agent Pure of compound Organic compound acid source
Type (pH water Ex. inorganic Amount Hydrophobic/ Amount Amount of
reaction Amount Amount Comp. Ex. particles *1 Type (g) hydrophilic
Type (mL) Type (mL) system) (mL) (mL) Ex. 1-47 SrCO.sub.3
SrCO.sub.3 0.5 Hydrophobic Oleic acid 3.5 -- -- -- Ex. 1-48
SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic Oleic acid 3.5 -- Ex. 1-49
SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic Oleic acid 3.5 -- Ex. 1-50
SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic Oleic acid 3.5 -- Ex. 1-51
SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic Oleic acid 3.5 -- Ex. 1-52
SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic Hexanoic acid 3.5 -- Ex. 1-53
SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic Octanoic acid 3.5 -- Ex. 1-54
SrCO.sub.3 SrCO.sub.3 0.5 Hydrophobic 3,3,5-Trimethyl- 3.5 --
hexanoic acid Evaluation Dispersibility Treatment conditions
Primary particles Solvent of particle Ex. Temp. Pressure Time
Aspect dispersion *2 Resin molded Comp. Ex. .degree. C. MPa Min.
Particle size ratio Chloroform Cyclohexane article *3 Optical film
*4 Ex. 1-47 250 0.1 15 SL: 0.14-0.21 .mu.m 3-5 -- Dispersed as
Dispersed as Dispersed as LL: 0.4-1 .mu.m primary primary primary
particles particles particles Ex. 1-48 150 15 Dispersed as
Dispersed as Dispersed as primary primary primary particles
particles particles Ex. 1-49 200 15 Dispersed as Dispersed as
Dispersed as primary primary primary particles particles particles
Ex. 1-50 250 4 Dispersed as Dispersed as Dispersed as primary
primary primary particles particles particles Ex. 1-51 250 8
Dispersed as Dispersed as Dispersed as primary primary primary
particles particles particles Ex. 1-52 150 15 Dispersed as
Dispersed as Dispersed as primary primary primary particles
particles particles Ex. 1-53 150 15 Dispersed as Dispersed as
Dispersed as primary primary primary particles particles particles
Ex. 1-54 150 15 Dispersed as Dispersed as Dispersed as primary
primary primary particles particles particles *1: Negative
birefringence *2: Preparation Example 1-1 *3: Production Example
1-1, Size: diameter of 10 mm, thickness of 5 mm *4: Production
Example 1-2, Size: thickness of 20 .mu.m
Example 1-55
Synthesis Example 1-1
Synthesis of Titanium Complex
[1015] Under ice-cold conditions, 100 mL of 30 volume % hydrogen
peroxide solution and 25 mL of 25 wt % aqueous ammonia were added
to a 500 mL beaker. Furthermore, 1.5 g of titanium powder was added
thereto and the mixture was stirred under ice-cold conditions for 3
hours until complete dissolution. Next, 15.5 g of 2-hydroxyoctanoic
acid dissolved in 25 mL of ethanol was added and the mixture was
stirred. After complete dissolution of all components, stirring was
stopped and the mixture was allowed to stand still for one day.
After that, the mixture was dried at 75.degree. C. in a drier for 3
hours so as to give a water-soluble titanium complex
(2-hydroxyoctanoic acid titanate).
[1016] (Preparation of Magnesium Titanate)
[1017] Magnesium hydroxide (available from Wako Pure Chemical
Industries, Ltd.) in an amount of 0.0612 g, a titanium complex
(Synthesis Example 1-1) in an amount of 0.5 g, decanoic acid
(available from Wako Pure Chemical Industries, Ltd.) in an amount
of 0.5181 mL and pure water in an amount of 2.098 mL were
introduced into a 5 mL high-pressure reactor (available from AKICO
Corporation).
[1018] Next, the high-pressure reactor was closed with a cover,
heated to 400.degree. C. in a shaking furnace (available from AKICO
Corporation) so as to pressurize the inside of the high-pressure
reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal
synthesis.
[1019] After that, the high-pressure reactor was plunged into cold
water for quenching.
[1020] Next, ethanol (available from Wako Pure Chemical Industries,
Ltd.) was added, and the mixture was stirred and subjected to
centrifugal separation performed in a centrifuge (trade name:
MX-301, available from Tomy Seiko Co., Ltd.) at 12000 G for 10
minutes to separate a precipitate (reaction product) from a
supernatant (washing step). By repeating this washing step 5 times,
the remaining decanoic acid was removed, and thereby particles were
obtained.
[1021] After that, the obtained particles were evaluated by (1)
XRD, (2) FT-IR and (4) TEM described above.
[1022] The formulation of respective components and the evaluation
results in Example 1-55 are presented in Table 5, and an
image-processed TEM micrograph in Example 1-55 is shown in FIG.
7.
[1023] As a result, (1) XDR confirmed that the inorganic compound
forming the inorganic particles was magnesium titanate.
[1024] (2) FT-IR confirmed C--H stretching vibrations from 2800 to
3000 cm.sup.-1 and the presence of C--H bonds on the surface of the
inorganic particles.
[1025] (4) TEM confirmed that the primary particles had an acicular
shape with a sideways length SL of approximately 10 to 30 nm and a
lengthwise length LL of approximately 20 to 200 nm with reference
to the image-processed micrograph shown in FIG. 7. It was also
confirmed that the aspect ratio of the primary particles was 2 to
20 as a result of calculation from the image-processed micrograph
shown in FIG. 7.
Comparative Example 1-4
[1026] Magnesium hydroxide (available from Wako Pure Chemical
Industries, Ltd.) in an amount of 0.0612 g, a titanium complex
(Synthesis Example 1-1) in an amount of 0.5 g and pure water in an
amount of 2.617 mL were introduced into a 5 mL high-pressure
reactor (available from AKICO Corporation).
[1027] Next, the high-pressure reactor was closed with a cover,
heated to 400.degree. C. in a shaking furnace (available from AKICO
Corporation) so as to pressurize the inside of the high-pressure
reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal
synthesis.
[1028] After that, the high-pressure reactor was plunged into cold
water for quenching.
[1029] Next, ethanol (available from Wako Pure Chemical Industries,
Ltd.) was added, and the mixture was stirred and subjected to
centrifugal separation performed in a centrifuge (trade name:
MX-301, available from Tomy Seiko Co., Ltd.) at 12000 G for 10
minutes and dried to give particles.
[1030] After that, the obtained particles were evaluated by (1)
XRD, (2) FT-IR and (4) TEM described above.
[1031] The formulation of respective components and the evaluation
results in Comparative Example 1-4 are presented in Table 5, and an
image-processed TEM micrograph in Comparative Example 1-4 is shown
in FIG. 8.
[1032] As a result, (1) XDR confirmed that the inorganic compound
forming the inorganic particles was magnesium titanate.
[1033] (2) FT-IR confirmed C--H stretching vibrations from 2800 to
3000 cm.sup.-1 but the presence of no C--H bonds on the surface of
the inorganic particles.
[1034] (4) TEM confirmed that the primary particles had an acicular
shape with a sideways length SL of approximately 20 to 30 nm and a
lengthwise length LL of approximately 30 to 200 nm. It was also
confirmed that the aspect ratio of the primary particles was 1.5 to
10.
Comparative Examples 1-5 and 1-6
[1035] Particles were obtained in the same manner as in Example 1-4
according to the formulation and treatment conditions presented in
Table 5, and then subjected to evaluation in the same manner as in
Example 1-4. The results are presented in Table 5.
Example 1-56
[1036] The particles obtained in Example 1-26 in an amount of 0.1 g
and chloroform in an amount of 30 g were introduced into a 50 mL
screw vial.
[1037] Next, the mixture was stirred with a spatula and allowed to
stand still for one day, and thereby separated into a supernatant
and a precipitate (sedimentation separation, wet
classification).
[1038] Next, the supernatant was removed therefrom and dried to
give particles having a small particle size.
[1039] After that, the obtained particles were evaluated by (1)
XRD, (2) FT-IR and (3) FE-SEM described above.
[1040] The formulation of respective components and the evaluation
results in Example 1-56 are presented in Table 5, and an
image-processed FE-SEM micrograph in Example 1-56 is shown in FIG.
9.
[1041] As a result, (1) XDR confirmed that the inorganic compound
forming the inorganic particles was SrCO.sub.3.
[1042] (2) FT-IR confirmed C--H stretching vibrations from 2800 to
3000 cm.sup.-1 and the presence of C--H bonds on the surface of the
inorganic particles.
[1043] (3) FE-SEM confirmed that the primary particles had an
acicular shape with a sideways length SL of approximately 20 to 50
nm and a lengthwise length LL of approximately 30 to 200 nm with
reference to FIG. 9 and were smaller than the particles of Example
1-26 (particles before wet classification). It was also confirmed
that the aspect ratio of the primary particles was 1.5 to 10 as a
result of calculation from FIG. 9.
TABLE-US-00005 TABLE 5 Formulations Inorganic Carbonic pH adjusting
agent Composition of compound Organic compound acid source Type (pH
Ex. inorganic Amount Hydrophobic/ Amount Amount of reaction Amount
Comp. Ex. particles *1 Type (g) hydrophilic Type (mL) Type (mL)
system) (mL) Ex. 1-55 MgTiO.sub.3 Mg(OH).sub.2 0.0612 Hydrophobic
Decanoic acid 0.5181 -- -- Ticomplex 0.5 Comp. Ex. 1-4 MgTiO.sub.3
Mg(OH).sub.2 0.0612 -- Ticomplex 0.5 Comp. Ex. 1-5 MgTiO.sub.3
Mg(OH).sub.2 0.0612 -- Ticomplex 0.55 Comp. Ex. 1-6 MgTiO.sub.3
Mg(OH).sub.2 0.0657 -- Ticomplex 0.6 Ex. 1-56 SrCO.sub.3 (From
Examples 1-26) Formu- lations Evaluation Pure Treatment
Dispersibility water conditions Primary particles Solvent of
particle Resin Ex. Amount Temp. Pressure Time Aspect dispersion *2
molded Optical Comp. Ex. (mL) .degree. C. MPa Min. Particle size
ratio Chloroform Cyclohexane article *3 film *4 Ex. 1-55 2.098 400
40 10 SL: 10-30 nm 2-20 Dispersed as -- Dispersed as Dispersed as
LL: 20-200 nm primary primary primary particles particles particles
Comp. Ex. 1-4 2.617 400 40 10 SL: 20-30 nm 15-10 Coagulated
Coagulated Coagulated LL: 30-200 nm Comp. Ex. 1-5 2.617 400 40 120
SL: 20-30 nm 15-10 Coagulated Coagulated Coagulated LL: 30-200 nm
Comp. Ex. 1-6 3.753 300 30 120 SL: 20-30 nm 15-10 Coagulated
Coagulated Coagulated LL: 30-200 nm Ex. 1-56 (Wet classification)
SL: 0.02-0.05 .mu.m 15-10 Dispersed as Uniformly Uniformly LL:
0.03-0.2 .mu.m primary dispersed dispersed particles *1: Negative
birefringence *2: Preparation Example 1-1 *3: Production Example
1-1, Size: diameter of 10 mm, thickness of 5 mm *4: Production
Example 1-2, Size: thickness of 20 .mu.m
Preparation Example 1-1
Preparation of Particle Dispersion
[1044] The particles obtained in Example 1-48 in an amount of 0.1 g
and cyclohexane in an amount of 10 g were introduced into a 50 mL
screw vial and stirred with a spatula to give a particle dispersion
in which the particles were dispersed in cyclohexane.
[1045] This particle dispersion was subjected to (5) particle size
distribution measurement.
[1046] The obtained particle size distribution is shown in FIG.
10.
[1047] It was found out that the particle size distribution in FIG.
10 matches the particle size distribution in Example 1-48 (or in
other words, the particle size calculated from the sideways length
SL and the lengthwise length LL, average particle size: 400
nm).
[1048] Accordingly, it was confirmed that in the particle
dispersion obtained in Preparation Example 1-1, the particles were
dispersed as primary particles in cyclohexane.
[1049] Also, the particles obtained in Examples 1-1 to 1-47,
Examples 1-49 to 1-56 and Comparative Examples 1-2 to 1-6 were used
to prepare particle dispersions in the same manner as described
above. Next, the particle dispersions were evaluated by (5)
particle size distribution measurement.
[1050] As a result, in the particle dispersions prepared using the
particles obtained in Examples 1-1 to 1-47 and Examples 1-49 to
1-56, the particles were dispersed as primary particles in
cyclohexane or chloroform.
[1051] On the other hand, with the particle dispersions prepared
using the particles obtained in Comparative Examples 1-2 to 1-6,
the particle size distribution measurement confirmed that the
particles coagulated together in cyclohexane or chloroform, forming
secondary particles (with an average particle size of 0.8 .mu.m or
greater).
Production Example 1-1
Production of Resin Molded Article
[1052] The particles obtained in Example 1-36 in an amount of 0.5 g
and chloroform in an amount of 4.5 g were introduced into a 100 mL
screw vial and stirred with a spatula to give a particle dispersion
A in which the particles were dispersed in chloroform.
[1053] Next, a resin solution in which polyarylate (Mw=60,000 to
80,000, softening temperature: 200.degree. C.) in an amount of 4.5
g was dissolved in 40.5 g of chloroform was mixed with the
dispersion A to give a particle-containing resin solution, and the
particle-containing resin solution was dried at 50.degree. C. in a
drier for one hour to remove chloroform, and thereby a
particle-dispersed resin composition was obtained.
[1054] After that, the obtained particle-dispersed resin
composition was injected into a metal mold having a diameter of 10
mm and a depth of 5 mm and then molded by vacuum pressing under
conditions of 200.degree. C. and 60 MPa to give a resin molded
article.
[1055] The resin molded article was subjected to cross-section
observation with the (3) field emission-scanning electron
microscope (FE-SEM).
[1056] FIG. 11 shows an image-processed FE-SEM micrograph of a
cross section of the resin molded article in which the particles of
Example 1-36 are dispersed.
[1057] As can be seen from FIG. 11, it was confirmed that the
particles were uniformly dispersed as primary particles in
polyarylate.
[1058] The particles obtained in Examples 1-1 to 1-35, Examples
1-37 to 1-42, Examples 1-47 to 1-56 and Comparative Examples 1-2 to
1-6 were also used to produce resin molded articles in the same
manner as described above. Then, the resin molded articles were
subjected to cross-section observation with the (3) field
emission-scanning electron microscope (FE-SEM).
[1059] FIG. 12 shows an image-processed FE-SEM micrograph of a
cross section of the resin molded article in which the particles of
Comparative Example 1-2 are dispersed.
[1060] The result confirmed that, in the resin molded articles
produced using the particles obtained in Examples 1-1 to 1-35,
Examples 1-37 to 1-42, Examples 1-47 to 1-56, the particles were
uniformly dispersed as primary particles in polyarylate.
[1061] On the other hand, it was confirmed that, in the resin
molded articles produced using the particles of Comparative
Examples 1-2 to 1-6, the particles coagulated in polyarylate,
forming secondary particles.
Production Example 1-2
Production of Optical Film
[1062] The particles obtained in Example 1-36 in an amount of 0.1 g
and chloroform in an amount of 0.9 g were introduced into a 100 mL
screw vial and stirred with a spatula to give a particle dispersion
B in which the particles were dispersed in chloroform.
[1063] Next, a resin solution in which polyarylate (Mw=60,000 to
80,000, softening temperature: 200.degree. C.) in an amount of 0.9
g was dissolved in 8.1 g of chloroform was mixed with the
dispersion B to give a particle-dispersed resin solution, and the
particle-dispersed resin solution was applied to a support plate by
spin coating and dried at 50.degree. C. in a drier for one hour to
remove chloroform, and thereby a coating of particle-dispersed
resin composition was obtained.
[1064] Subsequently, the obtained coating was dried at 100.degree.
C. for 10 minutes to give a 20 .mu.m thick optical film.
[1065] The optical film was subjected to cross-section observation
with the (3) field emission-scanning electron microscope
(FE-SEM).
[1066] FIG. 13 shows an image-processed FE-SEM micrograph of a
cross section of the optical film in which the particles of Example
1-36 are dispersed.
[1067] As can be seen from FIG. 13, it was confirmed that primary
particles were uniformly dispersed in polyarylate.
[1068] Also, the particles obtained in Examples 1-1 to 1-35,
Examples 1-37 to 1-42, Examples 1-47 to 1-56 and Comparative
Examples 1-2 to 1-6 were used to produce optical films in the same
manner as described above. Next, the optical films were subjected
to cross-section observation with the (3) field emission-scanning
electron microscope (FE-SEM).
[1069] FIG. 14 shows an image-processed FE-SEM micrograph of a
cross section of the optical film in which the particles of
Comparative Example 1-2 were dispersed.
[1070] The result confirmed that in the optical films produced
using the particles obtained in Examples 1-1 to 1-35, Examples 1-37
to 1-42 and Examples 1-47 to 1-56, the particles were uniformly
dispersed as primary particles in polyarylate.
[1071] On the other hand, it was confirmed that in the optical
films produced using the particles of Comparative Examples 1-2 to
1-6, the particles coagulated in polyarylate, forming secondary
particles.
Preparation Examples and Examples Corresponding to the Second Group
of Inventions
[1072] The second group of inventions will be described in further
detail by showing Preparation Examples and Examples, but the second
group of inventions is not limited thereto.
[1073] Evaluation methods performed on organic-inorganic composite
particles, resins, solvents and films (particle-dispersed resin
molded articles) will be described below.
(1) X-Ray Diffractometry (XRD)
[1074] Organic-inorganic composite particles were loaded into a
glass holder and subjected to X-ray diffractometry under the
following conditions. After that, from the obtained peaks, the
components of the inorganic substance were assigned by database
search. [1075] X-ray diffractometer: D8 DISCOVER with GADDS,
available from Bruker AXS
(Optical System on Incident Side)
[1075] [1076] X-ray source: CuK.alpha. (.lamda.=1.542 .ANG.), 45
kV, 360 mA [1077] Spectroscope (monochromator): multilayer mirror
[1078] Collimator diameter: 300 .mu.m
(Optical System on Light-Receiving Side)
[1078] [1079] Counter: two-dimensional PSPC (Hi-STAR) [1080]
Distance between organic-inorganic composite particles and counter:
15 cm 2.theta.=20, 50, 80 degrees, .omega.=10, 25, 40 degrees,
Phi=0 degrees, Psi=0 degrees [1081] Measurement time: 10 minutes
[1082] Assignment (semiquantitation software): FPM EVA, available
from Bruker AXS
(2) Fourier Transform Infrared Spectrophotometry (FT-IR)
[1083] Fourier transform infrared spectrophotometry was carried out
on organic-inorganic composite particles according to the KBr
method using the following apparatus.
[1084] Fourier transform infrared spectrophotometer: FT/IR-470Plus,
available from JASCO Corporation
(3) Average Particle Size Measurement by Dynamic Light Scattering
(DLS)
[1085] A sample (with a concentration of solids of 1 mass % or
less) was prepared by dispersing organic-inorganic composite
particles in a solvent, and the average particle size of the
organic-inorganic composite particles in the sample was measured
with a dynamic light scattering photometer (model: ZEN 3600,
available from Sysmex Corporation).
[1086] As the solvent, hexane was used in Preparation Example 2-1,
chloroform was used in Preparation Examples 2-2, 2-3 and 2-5 to
2-7, aqueous ammonia having an ammonia concentration of 1 mass %
was used in Preparation Example 2-4.
(4) Observation with Transmission Electron Microscope (TEM)
[1087] A film was cut, and its cross section was observed with a
transmission electron microscope (TEM, H-7650, available from
Hitachi High-Technologies Corporation) for the dispersed state of
organic-inorganic composite particles.
[1088] Here, for a clear view of the cut surface of the film, the
film was embedded in epoxy resin before cutting (machining)
[1089] Also, a particle dispersion (with a concentration of solids
of 1 mass % or less) obtained by diluting organic-inorganic
composite particles with a solvent was applied dropwise onto a TEM
grid (collodion film, carbon support film) and dried. Then, the
organic-inorganic composite particles were observed with a
transmission electron microscope (TEM, H-7650, available from
Hitachi High-Technologies Corporation) and the average particle
size of the organic-inorganic composite particles was calculated by
image analysis.
(5) Clarity
[1090] Clarity of a film was visually observed.
Preparation of Organic-Inorganic Composite Particles: Second
Hydrothermal Synthesis, Wet Classification
Preparation Example 2-1
[1091] Cerium hydroxide (Ce(OH).sub.4, available from Wako Pure
Chemical Industries, Ltd.) as an inorganic substance, decanoic acid
and hexanoic acid as organic compounds and water were introduced
into a 5 mL high-pressure reactor (available from AKICO
Corporation) in amounts presented in Table 6.
[1092] Next, the high-pressure reactor was closed with a cover,
heated to 400.degree. C. in a shaking furnace (available from AKICO
Corporation) so as to pressurize the inside of the high-pressure
reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal
synthesis.
[1093] After that, the high-pressure reactor was plunged into cold
water for quenching.
[1094] Next, ethanol (available from Wako Pure Chemical Industries,
Ltd.) was added, and the mixture was stirred and subjected to
centrifugal separation performed in a centrifuge (trade name:
MX-301, available from Tomy Seiko Co., Ltd.) at 12000 G for 20
minutes to separate into a precipitate (reaction product) and a
supernatant (washing step). This washing operation was repeated 5
times. After that, ethanol in the precipitate was heated and dried
at 80.degree. C. to give organic-inorganic composite particles in
which a decyl group and a hexyl group were present on the surface
of cerium oxide (CeO.sub.2).
[1095] Next, the organic-inorganic composite particles obtained
above and chloroform were introduced into a 50 mL centrifuge tube
and subjected to centrifugal separation in a centrifuge (trade
name: MX-301, available from Tomy Seiko Co., Ltd.) at 4000 G for 5
minutes to separate into a supernatant and a precipitate (wet
classification).
[1096] Next, the supernatant was removed therefrom and dried to
give organic-inorganic composite particles having a small average
particle size.
[1097] After that, the obtained organic-inorganic composite
particles were evaluated by (1) XRD, (2) FT-IR, (3) DLS and (4) TEM
described above.
[1098] As a result, (1) XDR confirmed that the inorganic substance
forming the inorganic particles was CeO.sub.2.
[1099] Also, (2) FT-IR confirmed that there were saturated
aliphatic groups (a decyl group and a hexyl group) on the surface
of the inorganic particles.
[1100] Furthermore, (3) DLS confirmed that the average particle
size of the organic-inorganic composite particles was 7 nm, and (4)
TEM confirmed that the average particle size of the
organic-inorganic composite particles was 4 to 10 nm.
[1101] The above results are presented in Table 6.
[1102] Also, an image-processed TEM micrograph obtained by (4) TEM
in Preparation Example 2-1 is shown in FIG. 15.
Preparation Examples 2-2 to 2-7
[1103] Organic-inorganic composite particles were prepared in the
same manner as in Preparation Example 2-1, except that the
formulation of the inorganic substance, the organic compound and
water was changed to the formulations presented in Table 6, and the
resulting organic-inorganic composite particles were subjected to
wet classification.
[1104] After that, the obtained organic-inorganic composite
particles were evaluated in the same manner as in Preparation
Example 2-1. The results are presented in Table 6.
TABLE-US-00006 TABLE 6 High- Formulations temperature Inorganic
treatment substance Organic compound conditions Preparation Amount
Amount Pure water Synthesis Example Type (g) Type (mL) Type Amount
Amount (mL) method Pre. Ex. 2-1 Ce(OH).sub.4 1.09 Decanoic acid
0.5181 Hexanoic acid 0.3279 (mL) 1.771 Second hydrothermal Pre. Ex.
2-2 Ce(OH).sub.4 1.09 6-Phenylhexanoic acid 0.4884 Benzoic acid;
0.3196 (g) 1.809 synthesis Pre. Ex. 2-3 Ce(OH).sub.4 1.09 Decanoic
acid 1.0362 -- 1.01 Pre. Ex. 2-4 Ticomplex 0.5 10-Carboxydecyl 0.44
-- 2.177 phosphonate Pre. Ex. 2-5 Ticomplex 0.5 Ethyl
decylphosphonate 0.182 Ethyl 0.1638 (mL) 2.453 octylphosphonate
Pre. Ex. 2-6 SrCO.sub.3 0.5 6-Phenylhexanoic acid 0.3503 -- 3.403
First Pre. Ex. 2-7 BaSO.sub.4 0.5 6-Phenylhexanoic acid 0.3503 --
3.403 hydrothermal synthesis High-temperature Organic-inorganic
composite particles treatment conditions Average Preparation Temp.
Pressure Time Composition of particle size Example .degree. C. MPa
Min. inorganic particles*1 Organic group on surface*2 (nm)*3 Pre.
Ex. 2-1 400 40 10 CeO.sub.2 Decyl group Hexyl group 4-10 [7] Pre.
Ex. 2-2 400 40 10 CeO.sub.2 6-Phenylhexyl group Phenyl group 4-8
Pre. Ex. 2-3 400 40 10 CeO.sub.2 Decyl group -- 3-8 Pre. Ex. 2-4
400 40 10 TiO.sub.2 10-Carboxydecyl group -- 4-20 Pre. Ex. 2-5 400
40 10 TiO.sub.2 Decyl group Octyl group 4-8 Pre. Ex. 2-6 300 30 10
SrCO.sub.3 6-Phenylhexyl group -- 30-80 Pre. Ex. 2-7 300 30 10
BaSO.sub.4 6-Phenylhexyl group -- 30-80 *1Confirmed by XRD
*2Confirmed by FT-IR *3Measured by TEM The value in square brackets
was measured by DLS
Preparation of Particle-Dispersed Resin Compositions (Fourth
Preparation Method) and Production of Films
Example 2-1
[1105] A resin solution having a concentration of solids of 10 mass
% was prepared by blending polyetherimide resin (model: Ultem 1000,
available from SABIC Innovative Plastics Japan LLC) and
chloroform.
[1106] Also, a particle dispersion having a concentration of solids
of 10 mass % was prepared by blending the organic-inorganic
composite particles of Preparation Example 2-1 (inorganic
substance: CeO.sub.2, binding group: carboxyl group, organic
groups: decyl group and hexyl group) and chloroform.
[1107] Next, the resin solution and the particle dispersion were
blended such that the proportion of resin relative to the
organic-inorganic composite particles in terms of mass was 90:10,
and the organic-inorganic composite particles were dispersed in the
resin solution by an ultrasonic disperser. In this manner, a clear
varnish of particle-dispersed resin composition was prepared.
[1108] Next, the obtained varnish was applied to a support plate by
spin coating. Chloroform was mostly volatilized during application
of the varnish. After that, the applied particle-dispersed resin
composition was dried at 50.degree. C. for one hour (first drying)
and then dried at 100.degree. C. for 10 minutes (second drying) to
give a 2.3 .mu.m thick film (particle-dispersed resin molded
article).
[1109] After that, the obtained film was evaluated by (4) TEM (the
dispersed state and average particle size of organic-inorganic
composite particles) and (5) clarity described above. The results
are presented in Table 6 (average particle size) and Table 7.
[1110] Also, an image-processed TEM micrograph obtained by (4) TEM
in Example 2-1 is shown in FIG. 16.
[1111] As can be seen from FIG. 16, there are gaps between
organic-inorganic composite particles, and the organic-inorganic
composite particles have a configuration that does not allow the
inorganic particles to contact with each other by steric hindrance
of the organic groups.
Examples 2-2 to 2-14
[1112] Films were produced in the same manner as in Example 2-1,
except that the formulation of the resin solution and the particle
dispersion was changed to the formulations presented in Table
7.
[1113] After that, the obtained films were evaluated in the same
manner as in Example 2-1. The results are presented in Table 7.
[1114] Also, image-processed TEM micrographs obtained by (4) TEM in
Examples 2-2 to 2-4, 2-7, 2-8, 2-11, 2-13 and 2-14 are shown in
FIGS. 17 to 24, respectively.
TABLE-US-00007 TABLE 7 Composition Example-Comparative Example
Preparation of inorganic Paricle dispersion Ex. Ex. Ex. Ex. Ex. Ex.
Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Example particles Organic group on
surface Solvent 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 2-9 2-10 2-11 2-12
2-13 2-14 Particle dispersed- Organic-inorganic Pre. Ex. 2-1
CeO.sub.2 Decyl group Hexyl group Chloroform 10 10 10 30 -- -- --
-- -- -- -- -- -- -- resin composition composite Pre. Ex. 2-2
CeO.sub.2 6-Phenylhexyl group Phenyl group Chloroform -- -- -- 10
20 10 10 -- -- -- -- -- -- -- particles*1 Pre. Ex. 2-3 CeO.sub.2
Decyl group -- Chloroform -- -- -- -- -- -- -- 10 10 10 -- -- -- --
(parts by mass) Pre. Ex. 2-4 TiO.sub.2 10-Carboxydecyl 10group --
Aqueous ammonia*3 -- -- -- -- -- -- -- -- -- -- 10 -- -- -- Pre.
Ex. 2-5 TiO.sub.2 Decyl group Octyl group Chloroform -- -- -- -- --
-- -- -- -- -- -- 10 -- -- Pre. Ex. 2-6 SrCO.sub.3 6-Phenylhexyl
group -- Chloroform -- -- -- -- -- -- -- -- -- -- -- -- 50 -- Pre.
Ex. 2-7 BaSO.sub.4 6-Phenylhexyl group -- Chloroform -- -- -- -- --
-- -- -- -- -- -- -- -- 50 Resin*2 Resin Resin solution (parts by
mass) Solvent Pre. Ex. 2-8 Polyether resin Chloroform 90 -- -- --
80 -- -- 90 -- -- -- -- -- -- Pre. Ex. 2-9 Thermoplastic
fluorine-based polyimide resin Chloroform -- 90 -- -- -- 90 -- --
90 -- -- -- -- -- Pre. Ex. 2-10 Polyarylate Chloroform -- -- 90 60
-- -- 90 -- -- 90 -- 90 50 50 Pre. Ex. 2-11 Polyvinyl alcohol resin
Aqueous ammonia*3 -- -- -- -- -- -- -- -- -- -- 90 -- -- --
Preparation method Fourth preparation method Resin molded amide
Evaluation TEM Dispersed state of Uniformly dispersed as primary
particles (film) organic-inorganic particles Visual inspection
Clarity Clear *1Blended as particle dispersion, with concentration
of solids (organic-inorganic composite particles) of 10 mass %
*2Blended as resin solution, with concentration of solids (resin)
of 10 mass % *3Ammonia concentration of 1 mass %
[1115] In Table 7, the numerical values provided in
"Organic-inorganic composite particles" and "Resin" indicate the
amounts expressed in parts by mass. Also, the following gives
detailed description of resins.
[1116] Polyetherimide resin: Ultem 1000, available from SABIC
Innovative Plastics Japan LLC
[1117] Thermoplastic fluorine-based polyimide resin: thermoplastic
fluorine-based polyimide resin used in Example 1 of Japanese
Unexamined Patent Publication No. 2003-315541
[1118] Polyarylate: polyarylate resin used in Example 4 of Japanese
Unexamined Patent Publication No. 2009-80440
[1119] Polyvinyl alcohol resin: JC-40, available from Japan VAM
& Poval Co., Ltd.
Preparation Examples, Examples, Comparative Examples and the Like
Corresponding to the Third Group of Inventions
[1120] The present invention will be described below in further
detail by showing Preparation Examples, Examples and Comparative
Examples, but the present invention is not limited thereto.
[1121] The evaluation methods for catalyst particles, catalyst
solutions and films (catalyst molded articles) will be described
below.
Evaluation Methods
(1) X-Ray Diffractometry (XRD)
[1122] Catalyst particles were loaded into a glass holder and
subjected to X-ray diffractometry under the following conditions.
After that, from the obtained peaks, the components of the
inorganic compound were assigned by database search. [1123] X-ray
diffractometer: D8 DISCOVER with GADDS, available from Bruker
AXS
(Optical System on Incident Side)
[1123] [1124] X-ray source: CuK.alpha. (.lamda.=1.542 .ANG.), 45
kV, 360 mA [1125] Spectroscope (monochromator): multilayer mirror
[1126] Collimator diameter: 300 .mu.m
(Optical System on Light-Receiving Side)
[1126] [1127] Counter: two-dimensional PSPC (Hi-STAR) [1128]
Distance between catalyst particles and counter: 15 cm 2.theta.=20,
50, 80 degrees, .omega.=10, 25, 40 degrees, Phi=0 degrees, Psi=0
degrees [1129] Measurement time: 10 minutes [1130] Assignment
(semiquantitation software): FPM EVA, available from Bruker AXS
(2) Fourier Transform Infrared Spectrophotometry (FT-IR)
[1131] Fourier transform infrared spectrophotometry was carried out
on catalyst particles according to the KBr method using the
following apparatus.
[1132] Fourier transform infrared spectrophotometer: FT/IR-470Plus,
available from JASCO Corporation
(3) Average Particle Size Measurement
A. DLS (Dynamic Light Scattering)
[1133] A sample (catalyst solution with a concentration of solids
of 1 mass % or less) was prepared by dispersing catalyst particles
in a solvent, and the average particle size of the catalyst
particles in the sample was measured with a dynamic light
scattering photometer (model: ZEN 3600, available from Sysmex
Corporation).
B. SEM (Scanning Electron Microscope)
[1134] A catalyst solution was applied dropwise onto a sample stage
and dried. Then, the average particle size of catalyst particles
was observed by observation with a scanning electron microscope
(S-4800 available from Hitachi High-Technologies Corporation or
JSM-7001F available from JEOL Ltd.).
C. TEM (Transmission Electron Microscope)
[1135] A sample (catalyst solution with a concentration of solids
of 1 mass % or less) obtained by diluting catalyst particles with a
solvent was applied dropwise onto a TEM grid (collodion film,
carbon support film) and dried. Then, the catalyst particles were
observed with a transmission electron microscope (TEM, H-7650,
available from Hitachi High-Technologies Corporation) and the
average particle size of catalyst particles was calculated by image
analysis.
D. XRD
[1136] The average particle size of catalyst particles was
calculated by substituting the data obtained in (1) XRD above into
the following Scherrer's equation (2).
D=K.lamda./(.beta. cos .theta.), (2)
[1137] where D is the average crystalline particle size, K is the
Scherrer constant, .lamda. is the wavelength of the X-ray tube,
.beta. is the half band width, and .theta. is the diffraction
angle.
(4) Evaluation of Catalytic Action
A. Examples 3-1 to 3-78 and Comparative Examples 3-1 to 3-5
[1138] An aqueous solution containing 0.01 mass % of rhodamine B
(rhodamine B with a molecular weight of 479.01) was prepared (0.02
m mol/L).
[1139] Next, 0.01 g of catalyst particles of each of Examples 3-1
to 3-78 and Comparative Examples 3-1 to 3-5 were added to a
transparent 2 mL vial and thereafter 1 g of the prepared aqueous
solution of rhodamine B was added thereto.
[1140] After that, in a dark room, the vial was irradiated with
black light (ultraviolet rays with a wavelength of 365 nm) at an
illuminance of 1 mW/cm.sup.2 for one hour.
[1141] After that, the aqueous solution of rhodamine B in the vial
was subjected to ultraviolet-visible absorption spectrometry. The
spectrometry was carried out with an ultraviolet-visible absorption
spectrometer (U-560, available from JASCO Corporation).
[1142] Then, whether the catalyst particles exerted a catalytic
action was evaluated based on the following evaluation
criteria.
[1143] A circle ".smallcircle." was given when a peak (wavelength:
550 nm) derived from rhodamine B disappeared.
[1144] A cross "x" was given when a peak (wavelength: 550 nm)
derived from rhodamine B remained.
[1145] FIGS. 25 and 26 each show UV-visible absorption spectra at
the start of irradiation and after a predetermined period of time
has passed, obtained in Examples 3-10 and 3-66.
B. Examples 3-79 to 3-83 and Comparative Examples 3-6 to 3-13
[1146] One mol/L of aqueous acetaldehyde solution was prepared.
[1147] Next, 0.1 g of catalyst particles obtained in each of
Examples 3-79 to 3-83 and Comparative Examples 3-6 to 3-13 was
added to a vial (10 mL), and then the prepared aqueous acetaldehyde
solution was added thereto in an amount of 100 .mu.L with a
syringe. After that, a septum cap was placed on the opening of the
vial and the whole was stirred well.
[1148] After that, the vial was irradiated with light for 30
minutes using a 300W xenon lamp (Cermax LX-300, available from
Perkin Elmer Inc.). A cutoff filter (HOYA L42, available from HOYA)
was attached to the xenon lamp to shield (shade) ultraviolet light
(ultraviolet light with a wavelength of 420 nm or less).
[1149] After that, the concentration of CO.sub.2 produced by
decomposition of formaldehyde in the vial was measured by gas
chromatography (HP 5890 Series II plus/HP5972, column: Ultra-1 (0.2
mm.phi..times.25 m, df=0.33 um), available from Agilent
Technologies, Inc.).
[1150] Then, whether the catalyst particles exerted a catalytic
action was evaluated based on the following evaluation
criteria.
[1151] A circle ".smallcircle." was given when the CO.sub.2
concentration was 10 ppm or greater.
[1152] A cross "x" was given when the CO.sub.2 concentration was
less than 10 ppm.
(5) Evaluation of Resin Degradation
[1153] A white film (described later) on which catalyst particles
had been dispersed was heated at 80.degree. C. in a drier for hour.
After that, the film was irradiated with black light (ultraviolet
rays with a wavelength of 365 nm) at an illuminance of 1
mW/cm.sup.2 for 24 hours.
[1154] After that, degradation of the film was visually observed
and evaluated based on the following evaluation criteria.
[1155] A circle ".smallcircle." was given when the film was
white.
[1156] A cross "x" was given when the film was yellow.
Preparation of Titanium Complex
Preparation Example 3-1
Preparation of Titanium Complex Containing 2-hydroxyoctanoic Acid
as Ligand
[1157] Under ice-cold conditions, 100 mL of 30 volume % hydrogen
peroxide solution and 25 mL of 25 wt % aqueous ammonia were added
to a 500 mL beaker. Furthermore, 1.5 g of titanium powder was added
thereto and the mixture was stirred under ice-cold conditions for 3
hours until complete dissolution. Next, 15.5 g of 2-hydroxyoctanoic
acid dissolved in 25 mL of ethanol was added and the mixture was
stirred. After complete dissolution of all components, stirring was
stopped and the mixture was allowed to stand still for one day.
After that, the mixture was dried at 75.degree. C. in a drier for 3
hours so as to give a water-soluble titanium complex.
[1158] This titanium complex was used as a complex (see Tables 8,
10 to 14 and 16) in Examples 3-8 to 3-17, 3-31 to 3-68, 3-78 and
Comparative Example 3-3, which will be described later.
Preparation Example 3-2
Preparation of Titanium Complex Containing Glycolic Acid as
Ligand
[1159] A water-soluble titanium complex was obtained through the
same treatment as in Preparation Example 3-1, except that 3.6 g of
glycolic acid was added instead of 15.5 g of 2-hydroxyoctanoic
acid.
[1160] The titanium complex was used as a complex (see Table 9) in
Example 3-21, which will be described later.
Preparation Example 3-3
Preparation of Titanium Complex Containing Citric Acid as
Ligand
[1161] A water-soluble titanium complex was obtained through the
same treatment as in Preparation Example 3-1, except that 9.1 g of
citric acid was added instead of 15.5 g of 2-hydroxyoctanoic
acid.
[1162] This titanium complex was used as a complex (see Table 9) in
Examples 3-18 to 3-20, which will be described later.
Preparation Example 3-4
Preparation of Titanium Complex Containing Malic Acid as Ligand
[1163] A water-soluble titanium complex was obtained through the
same treatment as in Preparation Example 3-1, except that 6.3 g of
malic acid was added instead of 15.5 g of 2-hydroxyoctanoic
acid.
[1164] This titanium complex was used as a complex (see Table 9) in
Example 3-22, which will be described later.
Preparation of Catalyst Particles
Examples 3-1 to 3-83 and Comparative Examples 3-1 to 3-13
[1165] Respective components (an inorganic substance and/or a
complex, an organic compound, a pH adjusting agent and water) were
introduced into a 5 mL high-pressure reactor (available from AKICO
Corporation) according to the formulation presented in Tables 8 to
16.
[1166] Next, the high-pressure reactor was closed with a cover and
treated in a shaking furnace (available from AKICO Corporation)
under the high temperature treatment conditions presented in Tables
8 to 16.
[1167] After that, the high-pressure reactor was plunged into cold
water for quenching.
[1168] Next, ethanol (available from Wako Pure Chemical Industries,
Ltd.) was added and the mixture was stirred. Subsequently, the
mixture was subjected to centrifugal separation performed in a
centrifuge (trade name: MX-301, available from Tomy Seiko Co.,
Ltd.) at 12000 G for 20 minutes to separate a precipitate (reaction
product) from a supernatant (washing step). This washing operation
was repeated 5 times.
[1169] After that, ethanol in the precipitate was heated and dried
at 80.degree. C. to give catalyst particles.
[1170] After that, the obtained catalyst particles were evaluated
by (1) XRD, (2) FT-IR, (3) average particle size and (4) catalytic
action described above.
[1171] As a result, (1) XRD confirmed that the primary components
of the inorganic particles were TiO.sub.2 (Examples 3-1 to 3-71 and
Comparative Examples 3-1 to 3-5), WO.sub.3 (Examples 3-72 to 3-75
and Comparative Examples 3-6 to 3-13) and SrTiO.sub.3 (Examples
3-76 to 3-83).
[1172] Also, (2) FT-IR confirmed that there were organic groups
that are presented in Table 8 to 16 on the surface of the inorganic
particles.
[1173] (3) Average particle size measurement showed that, as is
clear from Tables 8 to 16, the average particle size of catalyst
particles of each of Examples 3-1 to 3-83 was 450 nm or less.
[1174] Also, it was found out, from the fact that peaks derived
from rhodamine B disappeared in Examples 3-1 to 3-78 and
Comparative Examples 3-1 to 3-5, and CO.sub.2 was produced by
decomposition of formaldehyde in Examples 3-79 to 3-83 and
Comparative Examples 3-6 to 3-13, that the catalyst particles of
Examples 3-1 to 3-83 and Comparative Examples 3-1 to 3-13 exerted
an action of decomposing organic substances (photocatalytic
action).
<Production of Catalyst Molded Articles>
[1175] A resin solution having a concentration of solids of 10 mass
% was prepared by blending polyarylate (polyarylate resin used in
Example 4 of Japanese Unexamined Patent Publication No. 2009-80440)
with chloroform and uniformly mixing them.
[1176] Besides this, a catalyst solution having a concentration of
solids of 10 mass % was prepared by blending catalyst particles of
each of Examples 3-1 to 3-83 and Comparative Examples 3-1 to 3-13
with chloroform and uniformly mixing them.
[1177] Next, the resin solution and the catalyst solution were
blended such that the proportion of resin relative to catalyst
particles in terms of mass was 90:10 (the amount of resin expressed
in parts by mass: the amount of catalyst particles expressed in
parts by mass), and the catalyst particles were dispersed in the
resin solution using an ultrasonic disperser. In this manner, a
clear varnish of catalyst composition was prepared.
[1178] Next, the obtained varnish of catalyst composition was
applied to a support plate by spin coating. Chloroform was mostly
volatilized during application of the varnish. After that, the
applied catalyst composition was dried at 50.degree. C. for one
hour (first drying) and then dried at 100.degree. C. for 10 minutes
(second drying) to give a film containing catalyst particles
(catalyst molded article).
[1179] After that, the obtained films were evaluated by (5) resin
degradation evaluation.
[1180] The results are presented in Tables 8 to 16.
[1181] As can be seen from Tables 8 to 16, the evaluation of resin
degradation showed that polyarylate resin forming the films of
Comparative Examples 3-1 to 3-13 degraded because the films
yellowed.
[1182] On the other hand, in each of Examples 3-1 to 3-83,
degradation of polyarylate resin was suppressed because the films
remained white or transparent/colorless, without any
discoloration.
[1183] In the tables, each numerical value within parentheses "( )"
provided in "Formulation" indicates the volume expressed in mL, and
other numerical values, or in other words, the numerical values
without parentheses indicate the mass expressed in g.
[1184] Also, in "Average particle size" in the tables, each
numerical value within square brackets "[ ]" indicates the average
particle size calculated through TEM or SEM image analysis, each
numerical value within angle brackets "< >" indicates the
average particle size calculated with the Scherrer's equation based
on the data obtained by XRD, and other numerical values, or in
other words, the numerical values without brackets indicate the
average particle size measured by DLS.
[1185] The following gives detailed description of TiO.sub.2 used
in Examples 3-1 to 3-7 and 3-30.
[1186] TiO.sub.2 used in Examples 3-1 and 3-2: average particle
size 7 nm, trade name CSB-M, available from Sakai Chemical Industry
Co., Ltd.
[1187] TiO.sub.2 used in Examples 3-3 and 3-30: average particle
size 9 nm, trade name SSP-25, available from Sakai Chemical
Industry Co., Ltd.
[1188] TiO.sub.2 used in Examples 3-4 and 3-5: minor diameter 5 to
15 nm, major diameter 30 to 90 nm, trade name TTO-V-3, available
from Ishihara Sangyo Kaisha, Ltd.
[1189] TiO.sub.2 used in Example 3-6: average particle size 30 to
50 nm, TTO-55(A), available from Ishihara Sangyo Kaisha, Ltd.
[1190] TiO.sub.2 used in Example 3-7: average particle size 10 to
30 nm, TTO-51(A), available from Ishihara Sangyo Kaisha, Ltd.
TABLE-US-00008 TABLE 8 Formulations Inorganic substance
High-temperature and/or complex Organic compound treatment
conditions Amount Amount Water Surface g (mL) g (mL) mL treatment
method Ex. 3-1 TiO.sub.2 0.5 Decylphosphonic acid diethyl ester
0.364 2.253 First hydrothermal Ex. 3-2 0.5
10-(Diethoxy-phosphonyl)decanoic acid ethyl ester 0.440 2.177
synthesis Ex. 3-3 0.5 Decylphosphonic acid diethyl ester 0.364
2.253 Ex. 3-4 0.04 Decylphosphonic acid 0.023 2.070 Ex. 3-5 0.5
0.291 2.326 Ex. 3-6 0.5 0.291 2.326 Ex. 3-7 0.5 Octylphosphonic
acid diethyl ester 0.328 2.289 Ex. 3-8 Ticomplex 0.1
6-Phosphonohexanoic acid 0.257 2.360 Second Ex. 3-9 (ligand:2- 0.5
Decylphosphonic acid 0.197 4.226 hydrothermal Ex. 3-10
hydroxyoctanoic 0.5 0.291 2.326 synthesis Ex. 3-11 acid) 0.5
Methylphosphonic acid 0.144 2.473 Ex. 3-12 0.5 3-Phosphonopropionic
acid 0.202 1.915 Ex. 3-13 0.5 10-(Diethoxy-phosphonyl)decand 0.422
2.195 Ex. 3-14 0.5 Decylphosphonic acid diethyl ester 0.364 2.253
Ex. 3-15 0.5 10-(Diethoxy-phosphonyl)decanoic acid ethyl ester
0.440 2.177 Ex. 3-16 0.5 Octylphosphonic acid diethyl ester 0.328
2.289 Ex. 3-17 0.6 0.282 3.472 High-temperature treatment
conditions Catalyst particles Evalution Temp. Pressure Reaction
time Inorganic Organic group Average particle size Photocatalytic
Resin .degree. C. MPa Min. particles on surface nm action
degradation Ex. 3-1 400 40 10 TiO.sub.2 Decyl <7>
.largecircle. .largecircle. Ex. 3-2 400 40 10 9-Carboxynonyl
<7> .largecircle. .largecircle. Ex. 3-3 400 40 10 Decyl
<9> .largecircle. .largecircle. Ex. 3-4 400 40 10 [5 to 15]
.largecircle. .largecircle. Ex. 3-5 400 40 10 [5 to 15]
.largecircle. .largecircle. Ex. 3-6 400 40 10 [30 to 50]
.largecircle. .largecircle. Ex. 3-7 400 40 10 Octyl [10 to 30]
.largecircle. .largecircle. Ex. 3-8 400 40 10 5-Carboxypentyl --
.largecircle. .largecircle. Ex. 3-9 200 30 10 Decyl [1 to 10]
.largecircle. .largecircle. Ex. 3-10 400 40 10 [2 to 8]
.largecircle. .largecircle. Ex. 3-11 400 40 10 Methyl --
.largecircle. .largecircle. Ex. 3-12 400 40 10 2-Carboxyethyl [3 to
50] .largecircle. .largecircle. Ex. 3-13 400 40 10 10-hydroxydecyl
[3 to 7] .largecircle. .largecircle. Ex. 3-14 400 40 10 Decyl [2 to
8] .largecircle. .largecircle. Ex. 3-15 400 40 10 9-Carboxynonyl [4
to 20] .largecircle. .largecircle. Ex. 3-16 400 40 10 Octyl [2 to
8] .largecircle. .largecircle. Ex. 3-17 300 30 120 -- .largecircle.
.largecircle.
TABLE-US-00009 TABLE 9 Formulations Inorganic substance and/or
complex Organic compound pH adjusting agent Amount Amount Amount
Water g (mL) g (mL) mL mL Ex. 3-18 Ticomplex (ligand: citric acid)
0.5 Decylphosphonic acid 0.556 -- 1.944 Ex. 3-19 0.5
6-Phosphonlhexanoic acid 0.490 2.010 Ex. 3-20 0.5
10-(Diethoxy-phosphonyl)decanoic 0.841 1.659 acid ethyl ester Ex.
3-21 Ticomplex (ligand: glycolic acid) 0.5 Decylphosphonic acid
diethyl ester 0.440 2.177 Ex. 3-22 Ticomplex (ligand: malic acid)
0.1 Decylphosphonic acid 0.291 2.326 Ex. 3-23 10 wt %
aqueousamorphous TiO.sub.2 solution 2.2523 Decylphosphonic acid
diethyl ester 0.364 -- Ex. 3-24 Titanium sulfate 0.2093 0.364 0.4M
aqueous (2.044) -- KOH solution Ex. 3-25 Ammonium ocalate
monohydrate 0.5 Octylphosphonic acid diethyl ester 0.328 -- 2.289
Ex. 3-26 50 wt % aqueous titanium (IV) (1) 0.328 1.289 Ex. 3-27
bis(ammonium lactato)dihydroxide solution (1)
10-(Diethoxy-phosphonyl)decanoic 0.733 2.622 Ex. 3-28 (2) acid
ethyl ester 0.440 1.915 Ex. 3-29 (2) 0.632 0.945 High-temperature
treatment conditions Catalyst particles Reaction Average Evaluation
Surface Temp. Pressure time Inorganic Organic group particle
Photocatal- Resin treatment method .degree. C. MPa Min. particles
on surface size nm ytic action degradation Ex. 3-18 Second
hydrothermal 400 40 10 TiO.sub.2 Decyl -- .largecircle.
.largecircle. Ex. 3-19 synthesis 400 40 10 5-Carboxypentyl --
.largecircle. .largecircle. Ex. 3-20 400 40 10 9-Carboxynonyl --
.largecircle. .largecircle. Ex. 3-21 400 40 10 Decyl [2 to 8]
.largecircle. .largecircle. Ex. 3-22 400 40 10 [8 to 40]
.largecircle. .largecircle. Ex. 3-23 First hydrothermal 400 40 5 --
.largecircle. .largecircle. synthesis Ex. 3-24 Second hydrothermal
400 40 10 -- .largecircle. .largecircle. Ex. 3-25 synthesis 400 40
10 Octyl [30] .largecircle. .largecircle. Ex. 3-26 400 40 10 [5]
.largecircle. .largecircle. Ex. 3-27 200 10 10 9-Carboxynonyl [3]
.largecircle. .largecircle. Ex. 3-28 200 10 10 [3] .largecircle.
.largecircle. Ex. 3-29 300 10 10 [5] .largecircle.
.largecircle.
TABLE-US-00010 TABLE 10 Formulations Inorganic substance and/or
complex Organic compound Amount Amount Amount Amount Water g (mL) g
(mL) g (mL) g (mL) mL Ex. TiO.sub.2 0.5 Octylphosphonic acid 0.164
Decylphosphonic acid diethyl 0.182 -- 2.357 3-30 diethyl ester
ester Ex. Ticomplex 0.1 3-(Diethoxy-phosphonyl)ethyl 0.156
6-(Diethoxy-phosphonyl)hexanoic 0.176 2.284 3-31 (ligand: propionic
acid ester acid ethyl ester Ex. 2-hydro- 0.1 3-Phosphonopropionic
acid 0.020 6-Phosphonolhexanoic acid 0.026 2.571 3-32 xyoctanoic
Ex. acid) 0.1 0.031 10-(Diethoxy-phosphonyl)decanoic 0.044 2.541
3-33 acid ethyl ester Ex. 0.1 Octylphosphonic acid diethyl 0.033
10-(Diethoxy-phosphonyl)- 0.044 2.540 3-34 ester decanoic acid
ethyl ester Ex. 0.1 0.131 Decylphosphonic acid diethyl ester 0.146
10-(Diethoxy- 0.176 2.164 3-35 phosphonyl)- decanoic acid ethyl
ester Ex. 0.1 Methylphosphonicacid 0.013 10-(Diethoxy-phosphonyl)-
0.044 -- 2.560 3-36 decanoic acid ethyl ester Ex. 0.1 0.013
6-Phosphonolhexanoic acid 0.026 2.578 3-37 High-temperature
treatment conditions Catalyst particles Evaluation Reaction Average
Photo- Resin Surface treatment Temp. Pressure time Inorganic
particle catalytic deg- method .degree. C. MPa Min. particles
Organic group on surface size nm action radation Ex. First
hydrothermal 400 40 10 TiO.sub.2 Octyl Decyl -- <9>
.largecircle. .largecircle. 3-30 synthesis Ex. Second 400 40 10
2-Carboxyethyl 5-Carboxypentyl [2 to 10] .largecircle.
.largecircle. 3-31 hydrothermal Ex. synthesis 400 40 10
2-Carboxyethyl 5-Carboxypentyl [4 to 16] .largecircle.
.largecircle. 3-32 Ex. 400 40 10 9-Carboxynonyl [4 to 8]
.largecircle. .largecircle. 3-33 Ex. 400 40 10 Octyl [4 to 15]
.largecircle. .largecircle. 3-34 Ex. 400 40 10 Decyl 9-Carbo- [2 to
10] .largecircle. .largecircle. 3-35 xynonyl Ex. 400 40 10 Methyl
9-Carboxynonyl -- [4 to 24] .largecircle. .largecircle. 3-36 Ex.
400 40 10 5-Carboxypentyl [4 to 14] .largecircle. .largecircle.
3-37
TABLE-US-00011 TABLE 11 Formulations Inorganic substance and/or
complex Organic compound Amount Amount Amount Amount Water g (mL) g
(mL) g (mL) g (mL) mL Ex. Ticomplex 0.4 Octylphosphonic 0.131
Decylphosphonic acid 0.1164 10-(Diethoxy- 0.088 2.369 3-38 (ligand:
acid diethyl ester phosphonyl)decanoic Ex. 2-hydro- 0.4 0.131
0.1164 acid ethyl ester 0.176 2.193 3-39 xyoctanoic Ex. acid) 0.4
0.197 0.0582 0.176 2.617 3-40 Ex. 0.4 Methylphosphonic 0.072
Octylphosphonic acid diethyl ester 0.131 10-(Diethoxy- 0.176 2.238
3-41 acid phosphonyl)decanoic acid ethyl ester Ex. 0.4 0.115
3-Phosphonopropionic acid 0.046 -- 2.841 3-42 Ex. 0.4 0.115
6-Phosphonohexanoic acid 0.059 2.828 3-43 Ex. 0.5 Octylphosphonic
0.131 Decylphosphonic acid 0.1164 10-(Diethoxy- 0.088 2.281 3-44
acid diethyl ester phosphonyl)decanoic Ex. 0.5 0.131 0.1164 acid
ethyl ester 0.088 2.369 3-45 Ex. 0.5 0.131 0.1164 0.176 2.193 3-46
Ex. 0.5 0.164 10-(Diethoxy-phosphonyl)decanoic 0.220 -- 2.233 3-47
acid ethyl ester Ex. 0.5 0.164 Decylphosphonic acid 0.182 2.453
3-48 Ex. 0.5 0.262 10-(Diethoxy-phosphonyl)decanoic 0.088 2.267
3-49 acid ethyl ester High-temperature treatment conditions
Catalyst particles Evaluation Surface Reaction Average Photo- Resin
treatment Temp. Pressure time Inorganic particle catalytic deg-
method .degree. C. MPa Min. particles Organic group on surface size
nm action radation Ex. Second 400 40 10 TiO.sub.2 Octyl Decyl
9-Carboxynonyl 10 .largecircle. .largecircle. 3-38 hydrothermal Ex.
synthesis 400 40 10 [3 to 12] .largecircle. .largecircle. 3-39 Ex.
400 40 10 [2 to 14] .largecircle. .largecircle. 3-40 Ex. 400 40 10
Methyl Octyl 9-Carboxynonyl [3 to 40] .largecircle. .largecircle.
3-41 Ex. 300 30 10 2-Carboxyethyl -- [3 to 40] .largecircle.
.largecircle. 3-42 Ex. 300 30 10 5-Carboxypentyl [2 to 30]
.largecircle. .largecircle. 3-43 Ex. 400 40 10 Octyl Decyl
9-Carboxynonyl 20 .largecircle. .largecircle. 3-44 Ex. 400 40 10 20
.largecircle. .largecircle. 3-45 Ex. 400 40 10 [2 to 40]
.largecircle. .largecircle. 3-46 Ex. 400 40 10 9-Carboxynonyl -- --
.largecircle. .largecircle. 3-47 Ex. 400 40 10 Decyl [4 to 8]
.largecircle. .largecircle. 3-48 Ex. 400 40 10 9-Carboxynonyl [4 to
8] .largecircle. .largecircle. 3-49
TABLE-US-00012 TABLE 12 Formulations Inorganic substance and/or
complex Organic compound Amount Amount Amount Amount g (mL) g (mL)
g (mL) g (mL) Ex. Ticomplex (ligand: 0.5 -- Octylphosphonic acid
diethyl 0.262 Decylphosphonic acid 0.0582 3-50 2-hydroxy- ester Ex.
octanoic acid) 0.5 0.295 10-(Diethoxy-phosphonyl)decanoic 0.044
3-51 acid ethyl ester Ex. 0.5 Pt 0.001 0.295 -- 3-52 Ex. 0.5 --
Methylphosphonic acid 0.072 10-(Diethoxy-phosphonyl)decanoic 0.088
3-53 acid ethyl ester Ex. 0.5 0.144 0.088 3-54 Ex. 0.5 0.144
3-Phosphonopropionic acid 0.040 3-55 diethyl ester Ex. 0.5 0.144
6-Phosphonohexanoic acid 0.051 3-56 Ex. 0.1
3-(Diethoxy-phosphonyl)ethyl 0.031 6-(Diethoxy-phosphonyl)hexanoic
0.035 3-57 propionic acid ester acid ethyl ester Ex. 0.1
3-Phosphonopropionic acid 0.020 6-Phosphonohexanoic acid 0.026 3-58
Ex. 0.5 Methylphosphonic acid 0.063 Decylphosphonic acid 0.146 3-59
Formulations High-temperature treatment conditions Organic compound
Reaction Amount Water Surface treatment Temp. Pressure time g (mL)
mL method .degree. C. MPa Min. Ex. 10-(Diethoxy-phosphonyl)- 0.088
2.296 Second 400 40 10 3-50 decanoic acid ethyl ester hydrothermal
Ex. -- 2.278 synthesis 400 40 10 3-51 Ex. 2.194 400 40 10 3-52 Ex.
Decylphosphonic acid 0.1164 2.340 400 40 10 3-53 Ex. 0.0582 2.326
400 40 10 3-54 Ex. Octylphosphonic acid 0.0655 2.407 400 40 10 3-55
Ex. 0.0655 2.407 400 40 10 3-56 Ex. -- 2.550 400 400 10 3-57 Ex.
2.571 400 40 10 3-58 Ex. 2.560 400 40 10 3-59 Catalyst particles
Average Evaluation Inorganic particle size Photocatalytic Resin
particles Organic group on surface nm action degradation Ex.
TiO.sub.2 Octyl Decyl 9-Carboxynonyl [4 to 13] .largecircle.
.largecircle. 3-50 Ex. 9-Carboxynonyl -- [4 to 8] .largecircle.
.largecircle. 3-51 Ex. TiO.sub.2/Pt -- -- .largecircle.
.largecircle. 3-52 Ex. TiO.sub.2 Methyl 9-Carboxynonyl Decyl [4 to
12] .largecircle. .largecircle. 3-53 Ex. -- .largecircle.
.largecircle. 3-54 Ex. 2-Carboxyethyl Octyl -- .largecircle.
.largecircle. 3-55 Ex. 5-Carboxypentyl -- .largecircle.
.largecircle. 3-56 Ex. 2-Carboxyethyl 5-Carboxypentyl -- [2 to 10]
.largecircle. .largecircle. 3-57 Ex. 2-Carboxyethyl 5-Carboxypentyl
[2 to 10] .largecircle. .largecircle. 3-58 Ex. Methyl Decyl [4 to
18] .largecircle. .largecircle. 3-59
TABLE-US-00013 TABLE 13 Formulations Inorganic substance and/or
complex Organic compound Amount Amount Amount Amount g (mL) g (mL)
g (mL) g (mL) Ex. Ticomplex 0.5 3-(Diethoxy-phosphonyl)ethyl 0.0623
Decylphosphonic acid 0.218 10-(Diethoxy-phosphonyl)- 0.088 3-60
(ligand: propionic acid ester diethyl ester decanoic acid ethyl
ester Ex. 2-hydroxy- 0.5 3-(Diethoxy-phosphonyl)ethyl 0.125
10-(Diethoxy-phosphonyl)- 0.176 -- 3-61 octanoic propionic acid
ester decanoic acid ethyl ester Ex. acid) 0.5 Octylphosphonic acid
diethyl 0.6555 Decylphosphonic acid 0.073 10-(Diethoxy-phosphonyl)-
0.176 3-62 ester diethyl ester decanoic acid ethyl ester Ex. 0.5
0.6555 0.073 0.264 3-63 Ex. 0.5 0.131 0.146 0.176 3-64 Ex. 0.5
0.164 Decylphosphonic acid 0.146 -- 3-65 Ex. 0.5 0.164
Decylphosphonic acid 0.182 3-66 diethyl ester Ex. 0.5 0.164 0.182
3-67 Ex. 0.5 0.164 0.182 3-68 Formulations High-temperature
treatment conditions pH adjusting agent Surface Reaction Amount
Water treatment Temp. Pressure time g (mL) mL method .degree. C.
MPa Min. Ex. -- 2.248 Second 400 40 10 3-60 hydrothermal Ex. 2.316
synthesis 400 40 10 3-61 Ex. 2.302 400 40 10 3-62 Ex. 2.214 400 40
10 3-63 Ex. 2.164 400 40 10 3-64 Ex. 2.453 400 40 10 3-65 Ex. 2.453
400 40 10 3-66 Ex. 2.271 400 40 10 3-67 Ex. 1% (2.271) -- 400 40 10
3-68 Aqueous ammonia Catalyst particles Average particle Evaluation
Inorganic size Photocatalytic Resin particles Organic group on
surface nm action degradation Ex. TiO.sub.2 2-Carboxyethyl Decyl
9-Carboxynonyl [7] .smallcircle. .smallcircle. 3-60 Ex.
9-Carboxynonyl -- [14] .smallcircle. .smallcircle. 3-61 Ex. Octyl
Decyl 9-Carboxynonyl [8] .smallcircle. .smallcircle. 3-62 Ex. [8]
.smallcircle. .smallcircle. 3-63 Ex. [7] .smallcircle.
.smallcircle. 3-64 Ex. -- [5] .smallcircle. .smallcircle. 3-65 Ex.
[5] .smallcircle. .smallcircle. 3-66 Ex. [5] .smallcircle.
.smallcircle. 3-67 Ex. -- .smallcircle. .smallcircle. 3-68
TABLE-US-00014 TABLE 14 Formulations High-temperature treatment
conditions Inorganic substance and/or complex Organic compound
Reaction Amount Amount Water Temp. Pressure time g (mL) g (mL) mL
Surface treatment method .degree. C. MPa Min. Ex. 3-69 Catalyst
particles of Example 3-57 0.1 Methanol (3.170) -- High-temperature
300 40 180 Ex. 3-70 Catalyst particles of Example 3-61 0.1 (3.170)
methanol treatment 300 40 180 Ex. 3-71 Catalyst particles of
Example 3-27 0.1 (3.170) 300 40 180 Comp. Ex. 3-1 50 wt % aqueous
titanium(IV)bis- 1 -- 3.423 Hydrothermal treatment 200 30 10 Comp.
Ex. 3-2 (ammonium lactato)dihydroxide 1 1.617 400 40 10 solution
Comp. Ex. 3-3 Ti complex 0.5 2.617 400 40 10 (ligand:
2-hydroxyoctanoic acid) Comp. Ex. 3-4 Ammonium oxalate monohydrate
0.5 4.423 200 30 10 Comp. Ex. 3-5 0.5 2.617 400 40 10 Catalyst
particles Evaluation Inorganic Average particle Photocatalytic
Resin particles Organic group on surface size nm action degradation
Ex. 3-69 TiO.sub.2 2-(Methoxy-carbonyl)ethyl
5-(Methoxy-carbonyl)pentyl [2 to 10] .largecircle. .largecircle.
Ex. 3-70 9-(Methoxy-carbonyl)nonyl [14] .largecircle. .largecircle.
Ex. 3-71 9-(Methoxy-carbonyl)nonyl -- [3] .largecircle.
.largecircle. Comp. Ex. 3-1 TiO.sub.2 -- [30] .largecircle. X Comp.
Ex. 3-2 [100] .largecircle. X Comp. Ex. 3-3 [10 to 140]
.largecircle. X Comp. Ex. 3-4 [4] .largecircle. X Comp. Ex. 3-5
[50] .largecircle. X
TABLE-US-00015 TABLE 15 Formulations Inorganic substance and/or
complex Organic compound Amount Amount Amount Water g (mL) g (mL) g
(mL) mL Ex. 3-72 Tungstic acid 0.50 -- Decylamine 0.2164 4.207 Ex.
3-73 0.50 Pd 0.005 0.2164 4.207 Ex. 3-74 0.50 Pt 0.005 0.2164 4.207
Ex. 3-75 0.50 Copper formate 0.06 0.2164 4.207 Comp. Ex. 3-6
Ammonium tungstate pentahydrate 0.50 -- -- 4.423 Comp. Ex. 3-7 0.50
2.617 Comp. Ex. 3-8 Tungstic acid 0.50 4.423 Comp. Ex. 3-9 0.50
4.423 Comp. Ex. 3-10 0.50 2.617 Comp. Ex. 3-11 1.00 2.617 Comp. Ex.
3-12 0.50 Copper sulfate 0.01 2.607 Comp. Ex. 3-13 0.50 0.10 2.517
Catalyst particles High-temperature treatment conditions Average
Surface Reaction Organic particle Evaluations treatment Temp.
Pressure time Inorganic group on size Photocatalytic Resin method
.degree. C. MPa Min. particles surface nm action degradation Ex.
3-72 Second 200 30 60 WO.sub.3 Decyl [50] .largecircle.
.largecircle. Ex. 3-73 hydrothermal 200 30 60 WO.sub.3/Pd [50]
.largecircle. .largecircle. Ex. 3-74 synthesis 200 30 60
WO.sub.3/Pt [50] .largecircle. .largecircle. Ex. 3-75 200 30 60
WO.sub.3/Cu [50] .largecircle. .largecircle. Comp. Ex. 3-6 200 30
10 WO.sub.3 -- [5] .largecircle. X Comp. Ex. 3-7 400 40 10 [100]
.largecircle. X Comp. Ex. 3-8 200 30 10 [20] .largecircle. X Comp.
Ex. 3-9 200 30 60 [60] .largecircle. X Comp. Ex. 3-10 400 40 10
[100] .largecircle. X Comp. Ex. 3-11 400 40 10 [100] .largecircle.
X Comp. Ex. 3-12 400 40 10 WO.sub.3/CuO -- .largecircle. X Comp.
Ex. 3-13 400 40 10 [200] .largecircle. X
TABLE-US-00016 TABLE 16 Formulations Inorganic substance and/or
complex Amount Amount Amount g (mL) g (mL) g (mL) Ex. 50 wt %
aqueous 0.5 Sr(OH).sub.2.cndot.8H.sub.2O 0.5 -- 3-76 titanium(IV)
bis(ammonium lactato)dihydroxide solution Ex. Ammonium oxalate 0.5
0.5 3-77 monohydrate Ex. Ti complex (ligand: 0.5 0.5 3-78
2-hydoxyoctanoic acid) Ex. 50 wt % aqueous 0.5 0.5 3-79
titanium(IV) Ex. bis(ammonium 0.5 0.5 Nickel(II)acetatetetrahydrate
0.065 3-80 lactato)dihydroxide Ex. solution 0.5 0.5
Tris(acetylacetonato)ruthenium(III) 0.104 3-81 Ex. 0.5 0.5
Nickel(II)acetatetetrahydrate 0.013 3-82 Ex. 0.5 0.5
Tris(acetylacetonato)ruthenium(III) 0.021 3-83 Formulations Organic
compound Amount Amount Water g (mL) g (mL) mL Ex. Octylphosphonic
acid diethyl ester 0.328 -- 2.289 3-76 Ex. 0.328 2.289 3-77 Ex.
0.328 2.289 3-78 Ex. 6-Phosphonicexanoic acid 0.488 Octylphosphonic
acid 0.3275 1.801 3-79 diethyl ester Ex. Octylphosponic acid
diethyl ester 0.3275 -- 2.289 3-80 Ex. 0.3275 2.289 3-81 Ex. 0.3275
2.289 3-82 Ex. 0.3275 2.289 3-83 High-temperature treatment
conditions Catalyst particles Reaction Average Evaluation Surface
treatment Temp. Pressure time particle size Photocatalytic Resin
method .degree. C. MPa Min. Inorganic particles Organic group on
surface nm action degradation Ex. Second 400 40 10 SrTiO.sub.3
Octyl -- -- .largecircle. .largecircle. 3-76 synthesis hydrothermal
Ex. 400 40 10 .largecircle. .largecircle. 3-77 Ex. 400 40 10
.largecircle. .largecircle. 3-78 Ex. 400 40 10 6-Phenylhexyl Octyl
.largecircle. .largecircle. 3-79 Ex. 400 40 10 SrTiO.sub.3/NiO
Octyl -- .largecircle. .largecircle. 3-80 Ex. 400 40 10
SrTiO.sub.3/RuO.sub.2 .largecircle. .largecircle. 3-81 Ex. 400 40
10 SrTiO.sub.3/NiO .largecircle. .largecircle. 3-82 Ex. 400 40 10
SrTiO.sub.3/RuO.sub.2 .largecircle. .largecircle. 3-83
Preparation Examples, Comparative Preparation Examples, Examples
and Comparative Examples Corresponding to the Fourth Group of
Inventions
[1191] The fourth group of inventions will be described below in
further detail by showing Preparation Examples, Comparative
Preparation Examples, Examples and Comparative Examples, but the
fourth group of inventions is not limited thereto.
[1192] Evaluation methods performed on organic-inorganic composite
particles, films (films (particle-containing resin molded articles)
before extraction), and porous films (micropore resin compositions)
will be described below.
(1) X-Ray Diffractometry (XRD)
[1193] Organic-inorganic composite particles were loaded into a
glass holder and subjected to X-ray diffractometry under the
following conditions. After that, from the obtained peaks, the
components of the inorganic substance were assigned by database
search. [1194] X-ray diffractometer: D8 DISCOVER with GADDS,
available from Bruker AXS
(Optical System on Incident Side)
[1194] [1195] X-ray source: CuK.alpha. (.lamda.=1.542 .ANG.), 45
kV, 360 mA [1196] Spectroscope (monochromator): multilayer mirror
[1197] Collimator diameter: 300 .mu.m
(Optical System on Light-Receiving Side)
[1197] [1198] Counter: two-dimensional PSPC (Hi-STAR) [1199]
Distance between organic-inorganic composite particles and counter:
15 cm 2.theta.=20, 50, 80 degrees, .omega.=10, 25, 40 degrees,
Phi=0 degrees, Psi=0 degrees [1200] Measurement time: 10 minutes
[1201] Assignment (semiquantitation software): FPM EVA, available
from Bruker AXS
(2) Fourier Transform Infrared Spectrophotometry (FT-IR)
[1202] Fourier transform infrared spectrophotometry was carried out
on organic-inorganic composite particles according to the KBr
method using the following apparatus.
[1203] Fourier transform infrared spectrophotometer: FT/IR-470Plus,
available from JASCO Corporation
(3) Average Particle Size Measurement by Dynamic Light Scattering
(DLS)
[1204] A particle dispersion (with a concentration of solids of 1
mass % or less) was prepared by dispersing organic-inorganic
composite particles in a solvent, and the average particle size of
the organic-inorganic composite particles in the particle
dispersion was measured with a dynamic light scattering photometer
(model: ZEN 3600, available from Sysmex Corporation).
[1205] As the solvent, hexane was used in Preparation Example 4-1,
chloroform was used in Preparation Examples 4-2, 4-3, 4-5 and 4-6,
and aqueous ammonia having a concentration of 1 mass % was used in
Preparation Example 4-4.
(4) Observation with Transmission Electron Microscope (TEM)
[1206] A film (film (particle-containing resin molded article)
before extraction) was cut, and the cut surface was observed with a
transmission electron microscope (TEM, H-7650, available from
Hitachi High-Technologies Corporation) for the dispersed state of
organic-inorganic composite particles in the film.
[1207] Also, the concentration distribution in the thickness
direction of micropores was observed.
[1208] Here, for a clear view of the cut surface of the film, the
film was embedded in epoxy resin before cutting (machining).
[1209] Also, a particle dispersion (with a concentration of solids
of 1 mass % or less) obtained by diluting organic-inorganic
composite particles with a solvent was applied dropwise onto a TEM
grid (collodion film, carbon support film) and dried. Then, the
organic-inorganic composite particles were observed with a
transmission electron microscope (TEM, H-7650, available from
Hitachi High-Technologies Corporation) and the average particle
size of the organic-inorganic composite particles was calculated by
image analysis.
(5) Observation with Optical Microscope
[1210] The dispersed state of organic-inorganic composite particles
in a film was observed with an optical microscope in the same
manner as in the observation with TEM described above.
(6) Clarity
[1211] Clarity of a porous film was visually observed and
evaluated.
(7) Refractive Index
[1212] The refractive index of a porous film was measured using a
prism coupler (SPA-4000, available from Sairon Technology,
Inc.).
[1213] Specifically, the porous film was placed on a silicon wafer,
and measurement was carried out.
[1214] The refractive index of the film was measured using light
having a wavelength of 633 nm.
(8) Reflectance
[1215] The reflectivity (wavelength: 550 nm) of a porous film was
measured using Hitachi spectrophotometer U-4100 (available from
Hitachi High-Technologies Corporation).
(9) Dielectric Constant
[1216] The dielectric constant of a porous film was measured using
TR-100 automatic dielectric loss measurement apparatus (available
from Ando Electric Co., Ltd.). The dielectric constant was measured
at a frequency of 1 MHz.
(10) Elongation at Break
[1217] The elongation at break of a porous film was measured using
a tensile tester (trade name, STM-T-50BP, available from Toyo
Baldwin Co. Ltd.)
[1218] Specifically, a sample having a width of 5 mm and a length
of 100 mm was made from the porous film, and elongation was
measured using the above-mentioned tensile tester, with a chuck
distance of 50 mm and a pulling speed of 5 mm/min.
Preparation of Organic-Inorganic Composite Particles
Preparation Example 4-1
[1219] Cerium hydroxide (Ce(OH).sub.4, available from Wako Pure
Chemical Industries, Ltd.) as an inorganic material, decanoic acid
and hexanoic acid as organic compounds and water were introduced
into a 5 mL high-pressure reactor (available from AKICO
Corporation) in amounts presented in Table 17.
[1220] Next, the high-pressure reactor was closed with a cover,
heated to 400.degree. C. in a shaking furnace (available from AKICO
Corporation) so as to pressurize the inside of the high-pressure
reactor to 40 MPa, and then shaken for 10 minutes for hydrothermal
synthesis.
[1221] After that, the high-pressure reactor was plunged into cold
water for quenching.
[1222] Next, ethanol (available from Wako Pure Chemical Industries,
Ltd.) was added, and the mixture was stirred and subjected to
centrifugal separation performed in a centrifuge (trade name:
MX-301, available from Tomy Seiko Co., Ltd.) at 12000 G for 20
minutes to separate into a precipitate (reaction product) and a
supernatant (washing step). This washing operation was repeated 5
times. After that, ethanol in the precipitate was heated and dried
at 80.degree. C. to give organic-inorganic composite particles in
which a decyl group and a hexyl group were bound to the surface of
cerium oxide (CeO.sub.2).
[1223] Next, the organic-inorganic composite particles obtained
above and chloroform were introduced into a 50 mL centrifuge tube,
and the mixture was subjected to centrifugal separation performed
in a centrifuge (trade name: MX-301, available from Tomy Seiko Co.,
Ltd.) at 4000 G for 5 minutes to separate into a supernatant and a
precipitate (wet classification).
[1224] Next, the supernatant was removed therefrom and dried to
give organic-inorganic composite particles having a small average
particle size.
[1225] After that, the obtained organic-inorganic composite
particles were evaluated by XRD, FT-IR, DLS and TEM described
above.
[1226] As a result, XRD confirmed that the inorganic substance
forming the inorganic particles was CeO.sub.2.
[1227] Also, FT-IR confirmed that there were saturated aliphatic
groups (a decyl group and a hexyl group) on the surface of the
inorganic particles.
[1228] Furthermore, DLS showed that the organic-inorganic composite
particles had an average particle size of 7 nm.
[1229] The above results are presented in Table 17.
TABLE-US-00017 TABLE 17 Formulations Inorganic substance and/or
complex Organic compound Preparation Amount Amount Amount Pure
water Example g (mL) g (mL) g (mL) Amount (mL) Pre. Ex. 4-1
Ce(OH).sub.4 1.09 Decanoic acid 0.5181 Hexanoic acid 0.3279 1.771
Pre. Ex. 4-2 Ce(OH).sub.4 1.09 Decanoic acid 1.0362 -- 1.01 Pre.
Ex. 4-3 Zn(CH.sub.2COO).sub.2 0.5 Ethyl 0.182 Ethyl 0.1638 2453 [2
mol/L aqueous decylphosphonate octylphosphonate KOH solution] Pre.
Ex. 4-4 Ticomplex 0.5 Ethyl 0.182 Ethyl 0.1638 2.453 (ligand:
decylphosphonate octylphosphonate 2-hydroxyoctanoic acid) Pre. Ex.
4-5 SrCO.sub.3 0.5 6-Phenylhexanoic 0.3503 -- 3.403 acid Pre. Ex.
4-6 BaSO.sub.4 0.5 Decanoic acid 0.2500 Hexanoic acid 0.1000 3.403
High-temperature treatment conditions Organic-inorganic composite
particles Reaction Composition of Preparation Temp. Pressure time
inorganic Average prticle size (nm) Example .degree. C. MPa Min.
particles*1 Organic group on surface*2 *3 Pre. Ex. 4-1 400 40 10
CeO.sub.2 Decyl group Hexyl group 4 to 10 [7] Pre. Ex. 4-2 400 40
10 CeO.sub.2 Decyl group -- 3 to 8 Pre. Ex. 4-3 400 40 10 ZnO Decyl
group Octyl group 4 to 20 Pre. Ex. 4-4 400 40 10 TiO.sub.2 Decyl
group Octyl group 4 to 8 Pre. Ex. 4-5 300 30 10 SrCO.sub.3
6-Phenylhexyl group -- 30 to 80 Pre. Ex. 4-6 300 30 10 BaSO.sub.4
Decyl group Hexyl group 30 to 80
[1230] The matters specified by asterisks in Table 17 will be
described below.
[1231] *1: The composition was confirmed by XRD.
[1232] *2: The organic groups were confirmed by FT-IR.
[1233] *3: The average particle size was measured by TEM. It should
be noted that each value within parentheses "( )" indicates the
result obtained from measurement by DLS.
Preparation Examples 4-2 to 4-6
[1234] Organic-inorganic composite particles were prepared in the
same manner as in Preparation Example 4-1, except that the
formulation (amounts) of the inorganic material, the organic
compounds and water (or aqueous pH adjusting solution) was changed
to the formulations presented in Table 17, and then subjected to
washing and wet classification.
[1235] After that, the obtained organic-inorganic composite
particles were evaluated in the same manner as in Preparation
Example 4-1. The results are presented in Table 17.
Comparative Preparation Examples 4-1 to 4-6
[1236] Untreated inorganic particles (or in other words, inorganic
particles that had not been subjected to a high temperature
treatment) were prepared as inorganic particles for use in
Comparative Preparation Examples 4-1 to 4-6, and used as inorganic
particles in Comparative Examples 4-1 to 4-12, which will be
described later (see Table 20).
Preparation of Particle-Containing Resin Compositions, Production
of Films and Production of Porous Films
Example 4-1
[1237] A resin solution having a concentration of solids of 10 mass
% was prepared by blending polyetherimide resin (model: Ultem 1000,
available from SABIC Innovative Plastics Japan LLC) with
chloroform.
[1238] Also, a particle dispersion having a concentration of solids
of 10 mass % was prepared by blending the organic-inorganic
composite particles obtained in Preparation Example 4-5 (inorganic
substance: SrCO.sub.3, organic group: 6-phenylhexyl group) with
chloroform.
[1239] Next, the resin solution and the particle dispersion were
blended such that the proportion of resin relative to
organic-inorganic composite particles was those presented in Table
18, and stirred with an ultrasonic disperser. In this manner, a
clear varnish of particle-containing resin composition was
prepared.
[1240] Next, the obtained varnish was applied to a substrate (glass
substrate having a thickness of 1100 .mu.m) by spin coating.
Chloroform was mostly volatilized during application of the
varnish.
[1241] After that, the applied particle-containing resin
composition was dried at 50.degree. C. for one hour (first drying)
and then dried at 100.degree. C. for 10 minutes (second drying) to
give a 15 .mu.m thick film (particle-containing resin molded
article).
[1242] After that, the obtained film was evaluated by TEM described
above (the dispersed state and average particle size of
organic-inorganic composite particles). The results are presented
in Table 17 (average particle size) and Table 18.
[1243] After that, the obtained film was peeled off from the
substrate, and then the organic-inorganic composite particles were
extracted from the resin under the extraction conditions shown in
Table 18.
[1244] In this extraction process, a nitric acid ethanol solution
serving as an extraction solvent permeated through the resin and
dissolved the organic-inorganic composite particles.
[1245] As a result, micropores were formed in the resin, and a
porous film (resin molded article) having the micropores was
obtained.
[1246] After that, the obtained porous films were evaluated in
terms of TEM (the presence of concentration distribution in the
thickness direction), clarity, refractive index, reflectance,
dielectric constant and elongation at break described above. The
results are presented in Table 18.
Examples 4-2 to 4-15 and Comparative Examples 4-1 to 4-12
[1247] Porous films were obtained by producing films in the same
manner as in Example 4-1, except that the formulation of the resin
solution and the particle dispersion was changed to the
formulations presented in Tables 18 to 20, and then extracting
organic-inorganic composite particles under the extraction
conditions presented in Tables 18 to 20.
[1248] In Examples 4-8 and 4-9, the film was immersed in the
extraction solvent together with the substrate without the film
being peeled off from the substrate.
[1249] In Comparative Examples 4-5 to 4-12, it was not possible to
obtain self-standing porous films because the porous film was
significantly damaged when peeled from the substrate and lost
flexibility.
[1250] The obtained films (films (particle-containing resin molded
articles) before extraction) and porous films were evaluated in the
same manner described above.
[1251] Image-processed TEM micrographs obtained in Examples 4-6,
4-7 and 4-13 are shown in FIGS. 27 to 29, respectively.
TABLE-US-00018 TABLE 18 Example Compostion of inorganic Example
Preparation Example particles Organic group on surface 4-1 4-2 4-3
4-4 4-5 4-6 4-7 4-8 4-9 Particle Organic- Preparation Example 4-1
CeO.sub.2 Decyl group Hexyl group -- -- -- -- -- -- -- -- --
dispersed-resin inorganic Preparation Example 4-2 CeO.sub.2 Decyl
group -- -- -- -- -- -- -- -- -- -- composition composite
Preparation Example 4-3 ZnO Decyl group Octyl group -- -- -- -- --
-- -- -- -- particles*4 Preparation Example 4-4 TiO.sub.2 Decyl
group Octyl group -- -- -- -- -- -- -- -- -- (parts by Preparation
Example 4-5 SrCO.sub.3 6-Phenylhexyl -- 30 30 30 50 50 50 50 50 50
mass) group Preparation Example 4-6 BaSO.sub.4 Decyl group Hexyl
group -- -- -- -- -- -- -- -- -- Resin*5 Polyetherimide resin 70 --
-- -- -- -- -- -- -- (parts by Thermoplastic fluorine-based
polyimide resin -- 70 -- -- -- -- -- -- -- mass) Polyarylate -- --
70 50 50 50 50 50 50 Extraction Presence of subtstrate No No No No
No No No Yes Yes conditions Extraction liquid*6 Nitric acid ethanol
solution Extraction state Dissolved Dissolved Dissolved Dissolved
Dissolved Dissolved Dissolved Dissolved Dissolved Extraction
temperature (.degree. C.) 60 60 60 80 60 20 20 20 20 Extraction
time (hr) 1 1 1 1 1 1 0.5 0.5 3 Resin molded Evaluation TEM State
of organic-inorganic Dispersed as primary particles article (porous
composite particles in film (particle- film) containing resin
molded article)*9 Presence of micropores Yes Presence of
concentration distribution in No No No No No No Yes Yes Yes
thickness direction of micropores Visual inspection Clarity*10
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. Refractive index Wavelength 633 nm 1.56 1.46 1.44 1.4
1.4 1.4 1.39/1.49*7 1.41/1.49*8 -- Reflectance (%) Wavelength 550
nm -- -- -- -- -- 3.5 <3.5 <3.5 -- Dielectric constant
Measurement frequency 1 MHz 3.0 2.6 2.8 2.6 2.6 2.6 2.7 2.7 2.6
Mechanical strength Elongation at break*11 .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
TABLE-US-00019 TABLE 19 Example Composition of Example Preparation
Example inorganic particles Organic group on surface 4-10 4-11 4-12
4-13 4-14 4-15 Particle dispersed- Organic-inorganic Preparation
Example 4-1 CeO.sub.2 Decyl group Hexyl group 80 80 -- -- -- --
resin composition composite particles*4 Preparation Example 4-2
CeO.sub.2 Decyl group -- -- -- 70 -- -- -- (parts by mass)
Preparation Example 4-3 ZnO Decyl group Octyl group -- -- -- 70 --
-- Preparation Example 4-4 TiO.sub.2 Decyl group Octyl group -- --
-- -- 70 -- Preparation Example 4-5 SrCO.sub.3 6-Phenylhexyl group
-- -- -- -- -- -- -- Preparation Example 4-6 BaSO.sub.4 Decyl group
Hexyl group -- -- -- -- -- 80 Resin*5 Polyetherimide resin -- -- --
-- -- -- (parts by mass) Thermoplastic fluorine-based polyimide
resin -- -- -- -- -- -- Polyarylate 20 20 30 30 30 30 Extraction
conditions Presence of substrate No No No No No No Extraction
liquid*6 Hexane Extraction state Dispersed Dispersed Dispersed
Dispersed Dispersed Dispersed Extraction temperature (.degree. C.)
20 60 60 60 60 20 Extraction time (hr) 1 1 1 1 1 1 Resin molded
Evaluation TEM State of organic-inorganic composite Bicontinuous
phase separated structure article (porous film) particles in film
(particle- containing resin molded article)*9 Presence of
micropores Yes Presence of concentration distribution No No No No
No No in thickness direction of micropores Dielectric constant
Measurement frequency 1 MHz 2.5 2.5 2.5 2.5 2.5 2.5 Mechanical
strength Elongation at break*11 .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
TABLE-US-00020 TABLE 20 Comparative Example Comparative Composition
Organic Preparation of inorganic group Comparative Example Example
particles on surface 4-1 4-2 4-3 4-4 4-5 4-6 4-7 4-8 4-9 4-10 4-11
4-12 Particle Organic- Comparative CeO.sub.2 -- -- -- -- -- -- --
-- -- 80 -- -- -- dispersed- inorganic Preparation resin composite
Example 4-1 composition particles*4 Comparative ZnO -- -- -- -- --
-- -- -- 80 -- -- -- (parts by mass) Preparation Example 4-2
Comparative TiO.sub.2 -- -- -- -- -- -- -- -- -- 80 -- --
Preparation Example 4-3 Comparative SrCO.sub.3 30 -- -- -- -- -- --
-- -- -- 80 -- Preparation Example 4-4 Comparative BaSO.sub.4 -- --
-- -- -- -- -- -- -- -- -- 80 Preparation Example 4-5 Comparative
Al.sub.2O.sub.3 -- 30 30 30 80 80 80 -- -- -- -- -- Preparation
Example 4-6 Resin*5 Polyetherimide resin -- 70 -- -- 20 -- -- -- --
-- -- -- (parts by mass) Thermoplastic fluorine-based -- -- 70 --
-- 20 -- -- -- -- -- -- polyimide resin Polyarylate 70 -- -- 70 --
-- 20 20 20 20 20 20 Extraction Presence of substrate No No No No
No No No No No No No No conditions Extraction liquid*6 Nitric acid
Hexane ethanol solution Extraction state Dissolved Dispersed
Dispersed Dispersed Dispersed Dispersed Dispersed Dispersed
Dispersed Dispersed Dispersed Dispersed Extraction temperature
(.degree. C.) 20 20 20 20 20 20 20 20 20 20 20 20 Extraction time
(hr) 5 5 5 5 5 5 5 5 5 5 5 5 Resin Evaluation TEM State of organic-
Coagulated molded inorganic composite article particles in film
(porous film) (particle-containing resin molded article)*9 Presence
of micropores Yes Presence of concentration No No No No No No No No
No No No No distribution in thickness direction of micropores
Visual Clarity*10 X X X X X X X X X X X X inspection Reflectance
(%)Wavelength 550 nm 10 10 10 10 -- -- -- -- -- -- -- -- Dielectric
Measurement frequency 28 3.1 2.7 2.9 -- -- -- -- -- -- -- --
constant 1 MHz Mechanical Elongation at break*11 X X X X
Self-standing film was not obtained due to lack of flexibility
strength
[1252] In Tables 18 to 20, the numerical values provided in
"Organic-inorganic composite particles" indicate the amount of
organic-inorganic composite particles in a particle dispersion,
expressed in parts by mass, and the numerical values provided in
"Resin" indicate the amount of resin in a resin solution, expressed
in parts by mass.
[1253] The following gives detailed description of resins presented
in Tables 18 to 20 and inorganic particles of Comparative
Preparation Examples 4-1 to 4-6 presented in Table 20, as well as
description of the matters specified by asterisks.
<Resins>
[1254] Polyetherimide resin: Ultem 1000, refractive index
(wavelength: 633 nm): 1.63, reflectance (wavelength: 550 nm): 7%,
dielectric constant: 3.2, available from SABIC Innovative
Plastics Japan LLC
[1255] Thermoplastic fluorine-based polyimide resin: thermoplastic
fluorine-based polyimide resin used in Example 1 of Japanese
Unexamined Patent Publication No. 2003-315541, refractive index
(wavelength: 633 nm): 1.52, reflectance (wavelength: 550 nm): 5%,
dielectric constant: 2.8
[1256] Polyarylate: polyarylate resin used in Example 4 of Japanese
Unexamined Patent Publication No. 2009-80440, refractive index
(wavelength: 633 nm): 1.49, reflectance (wavelength: 550 nm): 5%,
dielectric constant: 3.0
Inorganic Particles
Comparative Preparation Examples 4-1 to 4-6
[1257] CeO.sub.2: Comparative Preparation Example 4-1, average
particle size 200 nm, available from Kojundo Chemical Lab. Co.,
Ltd.
[1258] ZnO: Comparative Preparation Example 4-2, average particle
size 200 nm, available from Sakai Chemical Industry Co., Ltd.
[1259] TiO.sub.2: Comparative Preparation Example 4-3, trade name
SSP-25, average particle size 9 nm, available from Sakai Chemical
Industry Co., Ltd.
[1260] SrCO.sub.3: Comparative Preparation Example 4-4, average
particle size 200 nm, available from Honjo Chemical Corporation
[1261] BaSO.sub.4: Comparative Preparation Example 4-5, trade name
BF40, average particle size 10 nm, available from Sakai Chemical
Industry Co., Ltd.
[1262] AL.sub.2O.sub.3: Comparative Preparation Example 4-6, trade
name AEROXIDO@AluC, average particle size 15 nm, available from
Nippon Aerosil Co., Ltd.
<Specified Matters (*4 to *9)>
[1263] *4: Prepared as a particle-dispersed chloroform solution
having a concentration of solids of 10 mass %. The numerical value
indicates the amount of solids expressed in parts by mass.
[1264] *5: Prepared as a resin solution having a concentration of
solids of 10 mass %. The numerical value indicates the amount of
solids expressed in parts by mass.
[1265] *6: A nitric acid ethanol solution having a concentration of
3.2 mass % prepared by mixing 50 parts by mass of 1 mol/L (6.3 wt
%) aqueous nitric acid solution and 50 parts by mass of
ethanol.
[1266] *7: Refractive indices obtained by calculation that indicate
that the surface refractive index was 1.39 and the internal
refractive index was 1.49.
[1267] *8: Refractive indices obtained by calculation that indicate
that the refractive index of the exposed surface was 1.41 and the
refractive index of the substrate-side surface was 1.49.
[1268] *9: Determined from TEM or optical micrographs.
[1269] *10: Visually determined based on the following
criteria.
[1270] A circle ".smallcircle." was given when the film was
clear.
[1271] A cross "x" was given when the film was opaque.
[1272] *11: Elongation at break was determined based on the
following criteria.
[1273] A circle ".smallcircle." was given when the elongation was
10% or greater.
[1274] A cross "x" was given when the elongation was less than
10%<
Examples and Comparative Examples Corresponding to the Fifth Group
of Inventions
[1275] The fifth group of inventions will be described below in
further detail by showing Examples and Comparative Examples, but
the fifth group of inventions is not limited thereto.
[1276] Evaluation methods performed on titanium complexes will be
described below.
<Evaluation Methods>
(1) MALDI-TOF MS Measurement
(Measurement Apparatus)
[1277] Autoflex available from Bruker Daltonics
(Measurement Conditions)
[1278] Laser light source: N.sub.2 laser (wavelength: 337 nm)
[1279] Measurement modes: reflector mode, negative ion mode
[1280] Measured mass range (m/z): 20 to 3000
[1281] Number of scans: 1500 times
[1282] Matrix: Meso-tetrakis-(pentafluorophenyl)-porphyrin
Preparation of Titanium Complexes
Example 5-1
Preparation of Titanium Complex Containing 2-hydroxyoctanoic Acid
as Ligand
[1283] Under ice-cold conditions, 100 mL of 30 volume % hydrogen
peroxide solution (available from Wako Pure Chemical Industries,
Ltd.) and 25 mL of 25 mass % aqueous ammonia (available from Wako
Pure Chemical Industries, Ltd.) were mixed in a 500 mL beaker.
Then, 1.5 g of titanium particles (available from Wako Pure
Chemical Industries, Ltd.) were added thereto and the mixture was
stirred for 3 hours under ice-cold conditions until complete
dissolution. Next, 15.5 g of 2-hydroxyoctanoic acid dissolved in 50
mL of ethanol (titanium particles:2-hydroxyoctanoic acid=1:1.5
(molar ratio)) was added and the mixture was stirred. After
complete dissolution of all components, stirring was stopped and
the mixture was allowed to stand still for one day. After that, the
mixture was dried at 75.degree. C. in a drier for 3 hours so as to
give a water-soluble titanium complex.
[1284] The obtained water-soluble titanium complex was subjected to
MALDI-TOF MS measurement. As a result, the obtained titanium
complex was identified as a mixture composed of two titanium
complexes represented by the following chemical formulas (3) and
(4).
[1285] General Formula (3):
[1286] [Chemical Formula 1]
[1287] General Formula (4):
[1288] [Chemical Formula 2]
Example 5-2
Preparation of Titanium Complex Containing 3-hydroxydecanoic Acid
as Ligand
[1289] A water-soluble titanium complex was obtained through the
same treatment as in Example 5-1, except that 18.2 g of
3-hydroxydecanoic acid (titanium particles:3-hydroxydecanoic
acid=1:1.5 (molar ratio)) was added instead of 15.5 g of
2-hydroxyoctanoic acid.
Comparative Example 5-1
Preparation of Titanium Complex Containing Malic Acid as Ligand
[1290] A water-soluble titanium complex was obtained through the
same treatment as in Example 5-1, except that 13.0 g of malic acid
(titanium particles malic acid=1:1.5 (molar ratio)) was added
instead of 15.5 g of 2-hydroxyoctanoic acid.
Comparative Example 5-2
Preparation of Titanium Complex Containing Glycolic Acid as
Ligand
[1291] A water-soluble titanium complex was obtained through the
same treatment as in Example 5-1, except that 7.2 g of glycolic
acid (titanium particles:glycolic acid=1:1.5 (molar ratio)) was
added instead of 15.5 g of 2-hydroxyoctanoic acid.
Preparation of Titanium Oxide Particles
Example 5-3
[1292] The titanium complex prepared in Example 5-1 in an amount of
0.5 g and water in an amount of 2.3 g were introduced into a 5 mL
high-pressure reactor (available from AKICO Corporation). Next, the
high-pressure reactor was closed with a cover, and the titanium
complex and water were treated in a shaking furnace (available from
AKICO Corporation) at 400.degree. C. and 40 MPa for 10 minutes.
After that, the high-pressure reactor was plunged into cold water
for quenching.
[1293] Next, ethanol (available from Wako Pure Chemical Industries,
Ltd.) was added, and the mixture was stirred and subjected to
centrifugal separation performed in a centrifuge (trade name:
MX-301, available from Tomy Seiko Co., Ltd.) at 12000 G for 20
minutes to separate a precipitate (reaction product) from a
supernatant (washing step). This washing operation was repeated 5
times.
[1294] After that, ethanol in the precipitate was heated and dried
at 80.degree. C., and thereby pale yellow white rutile titanium
oxide particles (TiO.sub.2) were obtained.
Example 5-4
[1295] Pale yellow white rutile titanium oxide particles
(TiO.sub.2) were obtained in the same manner as in Example 5-3,
except that the titanium complex prepared in Example 5-2 was used
instead of the titanium complex prepared in Example 5-1.
Comparative Example 5-3
[1296] Brown titanium oxide particles (TiO.sub.2) were obtained in
the same manner as in Example 5-3, except that the titanium complex
prepared in Comparative Example 5-1 was used instead of the
titanium complex prepared in Example 5-1.
Comparative Example 5-4
[1297] Brown titanium oxide particles (TiO.sub.2) were obtained in
the same manner as in Example 5-3, except that the titanium complex
prepared in Example 5-4 was used instead of the titanium complex
prepared in Example 5-1.
Comparative Example 5-5
[1298] Brown titanium oxide particles (TiO.sub.2) were obtained in
the same manner as in Example 5-3, except that titanium peroxo
citric acid ammonium tetrahydrate (trade name: TAS-FINE, available
from Furuuchi Chemical Corporation) was used instead of the
titanium complex prepared in Example 5-1.
[1299] While the illustrative embodiments of the present invention
are provided in the above description, they are for illustrative
purposes only and not to be construed as limiting. Modification and
variation of the present invention that will be obvious to those
skilled in the art is to be covered by the following claims.
INDUSTRIAL APPLICABILITY
[1300] The particle-containing resin molded article has various
applications including, for example, optical applications such as
flexible substrates, electronic and electrical applications,
mechanical applications and the like. When used in electronic and
electrical applications, the particle-containing resin molded
article is used as, for example, an optical fiber, an optical disc,
a light guide plate, or a flexible substrate such as an optical
film.
[1301] The particle-dispersed resin composition and the
particle-dispersed resin molded article are used in various
industrial applications including optical applications.
[1302] Also, the catalyst molded article containing catalyst
particles can be used as, for example, an optical film such as a
polarizing film, a retardance film, a brightness enhancing film, a
viewing angle enhancing film, a high-refractive index film or a
light diffusing film; or a construction material (construction)
film such as an ultraviolet absorbing film, a dirt repellent film,
an antimicrobial film, a deodorizing film, a super-hydrophilic
film, a germicidal film, a detoxification film or a chemical
substance decomposing film.
[1303] Also, the resin molded article is used as a porous film in
optical applications including optical films such as a
low-refractive film and an antireflective film, as well as
electrical and electronic applications including electrical and
electronic substrates such as a low-dielectric substrate.
Alternatively, the resin molded article is used as a film having
paths formed by communicating pores in various applications
including sizing filters, molecular separation membrane, adsorptive
separation filters and electrolyte membranes.
[1304] Also, the titanium complex is used in production of, for
example, titanium oxide particles, and the titanium oxide particles
are used in, for example, various industrial products for optical
applications or the like.
* * * * *