U.S. patent application number 14/122928 was filed with the patent office on 2014-07-17 for metal oxide particles containing titanium oxide coated with silicon dioxide-stannic oxide complex oxide.
This patent application is currently assigned to NISSAN CHEMICAL INDUSTRIES, LTD.. The applicant listed for this patent is Motoko Asada, Tomoki Furukawa, Yoshinari Koyama. Invention is credited to Motoko Asada, Tomoki Furukawa, Yoshinari Koyama.
Application Number | 20140199554 14/122928 |
Document ID | / |
Family ID | 47259471 |
Filed Date | 2014-07-17 |
United States Patent
Application |
20140199554 |
Kind Code |
A1 |
Koyama; Yoshinari ; et
al. |
July 17, 2014 |
METAL OXIDE PARTICLES CONTAINING TITANIUM OXIDE COATED WITH SILICON
DIOXIDE-STANNIC OXIDE COMPLEX OXIDE
Abstract
A metal oxide particle containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide including: a titanium
oxide-containing core particle (A); and a coating layer with which
the titanium oxide-containing core particle (A) is coated and that
is made of silicon dioxide-stannic oxide complex oxide colloidal
particles (B) having a mass ratio of silicon dioxide/stannic oxide
of 0.1 to 5.0, wherein one or more intermediate thin film layers
that are made of any one of an oxide; a complex oxide of at least
one element selected from the group consisting of Si, Al, Sn, Zr,
Zn, Sb, Nb, Ta, and W; and a mixture of the oxide and the complex
oxide are interposed between the titanium oxide-containing core
particle (A) and the coating layer made of the silicon
dioxide-stannic oxide complex oxide colloidal particles (B).
Inventors: |
Koyama; Yoshinari;
(Sodegaura-shi, JP) ; Furukawa; Tomoki;
(Sodegaura-shi, JP) ; Asada; Motoko;
(Sodegaura-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Koyama; Yoshinari
Furukawa; Tomoki
Asada; Motoko |
Sodegaura-shi
Sodegaura-shi
Sodegaura-shi |
|
JP
JP
JP |
|
|
Assignee: |
NISSAN CHEMICAL INDUSTRIES,
LTD.
Tokyo
JP
|
Family ID: |
47259471 |
Appl. No.: |
14/122928 |
Filed: |
June 1, 2012 |
PCT Filed: |
June 1, 2012 |
PCT NO: |
PCT/JP2012/064296 |
371 Date: |
March 7, 2014 |
Current U.S.
Class: |
428/447 ;
106/287.14; 106/287.19; 106/441; 524/430 |
Current CPC
Class: |
C09C 1/3661 20130101;
C09D 7/62 20180101; C09D 7/67 20180101; C01G 23/053 20130101; C01P
2004/64 20130101; C01G 23/047 20130101; B82Y 30/00 20130101; C08G
18/0866 20130101; Y10T 428/31663 20150401; C01P 2004/84 20130101;
C09D 5/00 20130101; C01P 2006/22 20130101; C09D 175/04
20130101 |
Class at
Publication: |
428/447 ;
106/441; 106/287.19; 106/287.14; 524/430 |
International
Class: |
C09D 5/00 20060101
C09D005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 3, 2011 |
JP |
2011-125259 |
Claims
1. A metal oxide particle containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide comprising: a titanium
oxide-containing core particle (A); and a coating layer with which
the titanium oxide-containing core particle (A) is coated and that
is made of silicon dioxide-stannic oxide complex oxide colloidal
particles (B) having a mass ratio of silicon dioxide/stannic oxide
of 0.1 to 5.0, wherein one or more intermediate thin film layers
that are made of any one of an oxide; a complex oxide of at least
one element selected from the group consisting of Si, Al, Sn, Zr,
Zn, Sb, Nb, Ta, and W; and a mixture of the oxide and the complex
oxide are interposed between the titanium oxide-containing core
particle (A) and the coating layer made of the silicon
dioxide-stannic oxide complex oxide colloidal particles (B).
2. The metal oxide particle containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide according to claim 1,
wherein a titanium oxide content in the titanium oxide-containing
core particle (A) is 5% by mass to 100% by mass in terms of
TiO.sub.2, and an amount of the coating layer made of the silicon
dioxide-stannic oxide complex oxide colloidal particles (B) to a
mass of the titanium oxide-containing core particle (A) is in a
range of 0.01 to 1.0.
3. The metal oxide particle containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide according to claim 1,
wherein the titanium oxide-containing core particle (A) includes at
least one element selected from the group consisting of Si, Al, Sn,
Zr, Zn, Sb, Nb, Ta, and W.
4. The metal oxide particle containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide according to claim 1,
wherein a crystal type of the titanium oxide-containing core
particle (A) is a rutile type.
5. The metal oxide particle containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide according to claim 1,
wherein an organic silicon compound or an amine-based compound is
bonded to a surface of the metal oxide particle.
6. A dispersion sol of metal oxide particles containing titanium
oxide coated with silicon dioxide-stannic oxide complex oxide
comprising: a dispersion medium; and metal oxide particles
dispersed in the dispersion medium, wherein the metal oxide
particles are each the metal oxide particle containing titanium
oxide coated with silicon dioxide-stannic oxide complex oxide as
claimed in claim 1, and the dispersion medium is water, an organic
solvent, or a mixed solvent of water and the organic solvent.
7. A coating liquid for forming a transparent coating film
comprising: metal oxide particles; and a matrix formation
component, wherein the metal oxide particles each include the metal
oxide particle containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide as claimed in claim 1, and the
matrix formation component includes at least one selected from the
group consisting of an organic silicon compound of Formula (I):
R.sup.1.sub.aR.sup.2.sub.bSi(OR.sup.3).sub.4-(a+b) (I) (where
R.sup.1 is a C.sub.1-10 hydrocarbon group, a vinyl group, a
methacryloxy group, or an organic group containing a mercapto
group, an amino group, or an epoxy group; R.sup.2 is a C.sub.1-4
hydrocarbon group; R.sup.3 is a C.sub.1-8 hydrocarbon group or an
acyl group; and a and b are each 0 or 1), a hydrolysate of the
organic silicon compound, and a partial condensate of the
hydrolysate.
8. A coating liquid for forming a transparent coating film
comprising: metal oxide particles; and a matrix formation
component, wherein the metal oxide particles each include the metal
oxide particle containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide as claimed in claim 1, and the
matrix formation component includes at least one resin selected
from the group consisting of a thermosetting resin, a thermoplastic
resin, and an ultraviolet curing resin.
9. The coating liquid for forming a transparent coating film
according to claim 8, wherein the matrix formation component is a
polyester-based resin or a urethane-based resin.
10. A substrate coated with a transparent coating film comprising:
a transparent coating film formed on a surface of the substrate by
using the coating liquid for forming a transparent coating film as
claimed in claim 7.
11. A substrate coated with a transparent coating film comprising:
a primer film formed on a surface of the substrate by using the
coating liquid for forming a transparent coating film as claimed in
claim 8; and a hard coating film formed on the primer film by using
the coating liquid for forming a transparent coating film
comprising: metal oxide particles; and a matrix formation
component, wherein the metal oxide particles each include the metal
oxide particle containing titanium oxide coated with, silicon
dioxide-stannic oxide complex oxide, comprising: a titanium
oxide-containing core particle (A); and a coating layer with which
the titanium oxide-containing core particle (A) is coated and that
is made of silicon dioxide-stannic oxide complex oxide colloidal
particles (B) having a mass ratio of silicon dioxide/stannic oxide
of 0.1 to 5.0, wherein one or more intermediate thin film layers
that are made of any one of an oxide: a complex oxide of at least
one element selected from the group consisting of Si, Al, Sn, Zr,
Zn, Sb, Nb, Ta, and W; and a mixture of the oxide and the complex
oxide are interposed between the titanium oxide-containing core
particle (A) and the coating layer made of the silicon
dioxide-stannic oxide complex oxide colloidal particles (B), and
the matrix formation component includes at least one selected from
the group consisting of an organic silicon compound of formula (1):
R.sup.1.sub.aR.sup.2.sub.bSi(OR.sup.3).sub.4-(a+b) (I) (where
R.sup.1 is a C.sub.1-10 hydrocarbon group, a vinyl group, a
methacryloxy group, or an organic group containing a mercapto
group, an amino group, or an epoxy group; R.sup.2 is a C.sub.1-4
hydrocarbon group; R.sup.3 is a C.sub.1-8 hydrocarbon group or an
acyl group; and a and b are each 0 or 1), a hydrolysate of the
organic silicon compound, and a partial condensate of the
hydrolysate.
12. The substrate coated with a transparent coating film according
to claim 10, further comprising: an anti-reflective coating on the
transparent coating film or the hard coating film.
Description
TECHNICAL FIELD
[0001] The present invention relates to a metal oxide particle
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide comprising: a titanium oxide-containing core particle
(A); and a coating layer with which the titanium oxide-containing
core particle (A) is coated and that is made of silicon
dioxide-stannic oxide complex oxide colloidal particles (B) having
a mass ratio of silicon dioxide/stannic oxide of 0.1-5.0, in which
one or more intermediate thin film layers that are made of any one
of an oxide; a complex oxide of at least one element selected from
the group consisting of Si, Al, Sn, Zf, Zn, Sb, Nb, Ta, and W; and
a mixture of the oxide and the complex oxide are interposed between
the titanium oxide-containing core particle (A) and the coating
layer made of the silicon dioxide-stannic oxide complex oxide
colloidal particles (B). The present Invention also relates to a
water dispersion sol, organic solvent dispersion sol, or mixed
solvent of water and organic solvent dispersion sol of the
particles, a coating liquid for forming a transparent coating film
containing the particles; and a substrate coated with a transparent
coating film formed using the coating liquid.
BACKGROUND ART
[0002] Plastic molded articles are used in a large quantity,
utilizing the advantages such as light weight, easy formability,
and impact resistance. On the other hand, the plastic molded
articles have practical disadvantages when used for lenses for
glasses, window materials, and the like because the plastic molded
articles are easily scratched due to insufficient hardness, are
easily affected by solvents, are charged to attach dusts, and have
insufficient heat resistance. Consequently, a technique to apply
protection coating film to a plastic molded article has been
developed. A large number of various kinds of coating liquids have
been developed as a coating liquid for forming a coating film used
for the protection coating film.
[0003] As a coating liquid for forming a coating film that provides
a hard coating film having hardness close to those of inorganic
substances, a coating solution for forming a coating film in which
an organic silicon compound or a hydrolysate thereof is a main
component (a resin component or a coating film forming component)
is used for lenses for glasses (see Patent Document 1).
[0004] The coating solution for forming a coating film has still
insufficient scratch resistance, so that a coating liquid made by
further adding a silicon dioxide sol that is colloidally dispersed
to the coating liquid for forming a coating film has been developed
and used for lenses for glasses (see Patent Document 2).
[0005] Most of plastic lenses for glasses have been produced by
east polymerization of a diethylene glycol bis(allyl carbonate)
monomer. Such a lens has a refractive index of about 1.50 that is
lower than a refractive index of a glass lens of about 1.52, and
the lens thus has a disadvantage that a thickness of the edge of
the lens is made thick when the lens is used as a lens for
nearsightedness. Consequently, recently, a monomer having higher
refractive index than the refractive index of diethylene glycol
bis(allyl carbonate) has been developed and a high refractive index
resin material having a refractive index in a range of 1.54 to 1.76
has been developed (see Patent Documents 3 and 4).
[0006] A method for using a colloidal dispersion of metal oxide
fine particles of Sb and Ti as a coating material applied to the
high refractive index resin lens has been also developed (see
Patent Documents 5 and 6).
[0007] A coating composition is disclosed which includes a silane
coupling agent and particles (c) obtained by coating a surface of
colloidal particles (a) of a metal oxide having a primary particle
diameter of 2 nm to 60 nm acting as cores with a coating material
(b) made of colloidal particles of an acidic oxide, contains (c) in
a ratio of 2% by mass to 50 % by mass in terms of the metal oxide,
and includes a stable modified metal oxide sol having a primary
particle diameter of 2 nm to 1.00 nm. As a specific example of the
used colloidal particles, a modified titanium oxide-stannic
oxide-zirconium oxide complex colloid coated with antimony
pentoxide containing an alkyl amine is disclosed (see Patent
Document 7). A titanium oxide-stannic oxide zirconium oxide complex
colloid stabilized with an alkyl amine or an oxycarboxylic acid is
disclosed (see to Patent Document 8).
PRIOR ART DOCUMENTS
Patent Documents
[0008] Patent Document 1: Japanese Patent Application Publication
No. S52-11261 (JP S52-11261 A)
[0009] Patent Document 2: Japanese Patent Application Publication
No. S53-111336 (JP S53-111336A)
[0010] Patent Document 3: Japanese Patent Application Publication
No. S55-13747 (JP S55-13747A)
[0011] Patent Document 4: Japanese Patent Application Publication
No. S64-54021 (JP S64-54021 A)
[0012] Patent Document 5: Japanese Patent Application Publication
No. S62-151801 (JP S62-151801 A)
[0013] Patent Document 6: Japanese Patent Application. Publication
No. S63-275682 (JP S63-2756S2 A)
[0014] Patent Document 7: Japanese Patent Application Publication
No. 2001-123115 (JP 2001-123115 A)
[0015] Patent Document 8: Japanese Patent Application Publication
No. H10-306258 (JP H10-306258 A)
SUMMARY OF THE INVENTION
Problem to be Solved by the Invention
[0016] In a high refractive index resin lens, however, a coating
film using a silicon dioxide sol generates an interference pattern,
resulting in poor lens appearance. In a coating film using a
titanium oxide sol, the lens is disadvantageously colored in blue
due to excitation of the titanium oxide by ultraviolet rays. When
an anti-reflective coating is not applied on the coating film,
excitation of the titanium oxide caused by ultraviolet rays cannot
be suppressed, and thus, cracks are prone to generate.
[0017] An object of the present invention is to provide metal oxide
particles that can adjust a refractive index to be high so as to be
used with medium and high refractive index plastic substrates
having a refractive n.sub.D of 1.54 to 1.76, has a microscopic
particle diameter in order to ensure high transparency, and can
almost suppress excitation caused by ultraviolet rays. Another
object of the present invention is to provide a coating liquid for
forming a transparent coating film including such particles and a
substrate coated with a transparent coating film.
Means for Solving the Problem
[0018] The present invention provides, as a first aspect, a metal
oxide particle containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide comprising:
[0019] a titanium oxide-containing core particle (A); and
[0020] a coating layer with which the titanium oxide-containing
core particle (A) is coated and that is made of silicon
dioxide-stannic oxide complex oxide colloidal particles (B) having
a mass ratio of silicon dioxide/stannic oxide of 0.1 to 5.0, in
which one or more intermediate thin film layers that are made of
anyone of an oxide; a complex oxide of at least one element
selected from the group consisting of Si, Al, Sn, Zr, Zn, Sb, Nb,
Ta, and W; and a mixture of the oxide and the complex oxide are
interposed between the titanium oxide-containing core particle (A)
and the coating layer made of the silicon dioxide-stannic oxide
complex oxide colloidal particles (B);
[0021] as a second aspect, the metal oxide particle containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide according to the first aspect, in which a titanium oxide
content in the titanium oxide-containing core particle (A) is 5% by
mass to 100% by mass in terms of TiO.sub.2, and an amount of the
coating layer made of the silicon dioxide-stannic oxide complex
oxide colloidal particles (B) to a mass of the titanium
oxide-containing core-particle (A) is in a range of 0.01 to
1.0;
[0022] as a third aspect, the metal oxide particle containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide according to the first aspect or the second aspect, in which
the titanium oxide-containing core particle (A) includes at least
one element selected from the group consisting of Si, Al, Sn, Zr,
Zn, Sb, Nb, Ta, and W;
[0023] as a fourth aspect, the metal oxide particle containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide according to any one of the first aspect to the third aspect,
in which a crystal type of the titanium oxide-containing core
particle (A) is a rutile type;
[0024] as a fifth aspect, the metal oxide particle containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide according to any one of the first aspect to the fourth
aspect, in which an organic silicon compound or an amine-based
compound is bonded to a surface of the metal oxide particle;
[0025] as a sixth aspect, a dispersion sol of metal oxide particles
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide comprising:
[0026] a dispersion medium; and
[0027] metal oxide particles dispersed in the dispersion medium, in
which the metal oxide particles are each the metal oxide particle
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide as described in any one of the first aspect to the
fifth aspect, and the dispersion medium is water, an organic
solvent, or a mixed solvent of water and the organic solvent;
[0028] as a seventh aspect, a coating liquid for forming a
transparent coating film comprising;
[0029] metal oxide particles; and
[0030] a matrix formation component, in which
[0031] the metal oxide particles each include such metal oxide
particle containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide as described in any one of the
first aspect to the fifth aspect, and
[0032] the matrix formation component includes at least one
selected from the group consisting of an organic silicon compound
of Formula (I):
R.sup.1.sub.aR.sup.2.sub.bSi(OR.sup.3).sub.4-(a+b) (I)
[0033] (where R.sup.1 is a C.sub.1-10 hydrocarbon group, a vinyl
group, a methacryloxy group, or an organic group containing a
mercapto group, an amino group, or an epoxy group; R.sup.2 is a
C.sub.1-4 hydrocarbon group; R.sup.3 is a C.sub.1-8 hydrocarbon
group or an acyl group; and a and b are each 0 or 1), a hydrolysate
of the organic silicon compound, and a partial condensate of the
hydrolysate;
[0034] as an eighth aspect, a coating liquid for forming a
transparent coating film comprising;
[0035] metal oxide particles; and
[0036] a matrix formation component, in which
[0037] the metal oxide particles each include the metal oxide
particle containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide as described in any one of the
first aspect to the fifth aspect, and
[0038] the matrix formation component includes-at least one resin
selected from the group consisting of a thermosetting resin, a
thermoplastic resin, and an ultraviolet curing resin;
[0039] as a ninth aspect, the coating liquid for forming a
transparent coating film according to the eighth aspect, in which
the matrix formation component is a polyester-based resin or a
urethane-based resin;
[0040] as a tenth aspect, a substrate coated with a transparent
coating film comprising:
[0041] a transparent coating film formed on a surface of the
substrate by using the coating liquid for forming a transparent
coating film as described in any one of the seventh aspect to the
ninth aspect;
[0042] as an eleventh aspect, a substrate coated with a transparent
coating film comprising:
[0043] a primer film formed on a surface of the substrate by using
the coating liquid for forming a transparent coating film as
described in the eighth aspect or the ninth aspect, and a hard
coating film formed on the primer film by using the coating liquid
for forming a transparent coating film as described in the seventh
aspect; and
[0044] as a twelfth aspect, the substrate coated with a transparent
coating film according to the tenth aspect or the eleventh aspect,
further comprising:
[0045] an anti-reflective coating on the transparent coating Rim or
the hard coating film.
EFFECTS OF THE INVENTION
[0046] When a metal oxide particle containing titanium oxide coated
with silicon dioxide-stannic oxide complex oxide of the present
invention comprising: a titanium oxide-containing core particle
(A); and a coating layer with which the titanium oxide-containing
core particle is coated and that is made of silicon dioxide-stannic
oxide complex oxide colloidal particles (B) having a mass ratio of
silicon dioxide/stannic oxide of 0.1-5.0, in which one or more
intermediate thin film layers that are-made of any one of an oxide;
a complex oxide of at least one element selected from the group
consisting of Si, Al, Sn, Zr, Zn, Sb, Nb, Ta, and W; and a mixture
of the oxide and the complex oxide are interposed between the
titanium oxide-containing core particle (A) and the coating layer
made of the silicon dioxide-stannic oxide complex oxide colloidal
particles (B) is formulated in a coating liquid for forming a
transparent coating film that forms a transparent coating film on a
substrate such as synthetic resin lenses, the transparent coating
film has no change in color or color deterioration even when the
transparent coating film is irradiated with ultraviolet rays. In
other words, the metal oxide particle of the present invention is a
metal oxide particle having excellent weatherability and light
stability.
[0047] The metal oxide particles of the present invention also have
high transparency because a particle diameter of the metal oxide
particles is microscopic.
[0048] According to the present invention, a refractive index of
the transparent coating film formed on a substrate can be easily
adjusted by changing a mass ratio of the matrix formation component
and the metal oxide particles containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide colloidal particles in
the coating liquid or a composition of the metal oxide particles
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide colloidal particles. Consequently, when the coating
liquid for forming a transparent coating film of the present
invention is used, the refractive index of the transparent coating
film formed from the coating liquid can be equalized to the
refractive index of the substrate and an interference pattern
caused by difference in refractive indices of the transparent
coating film and the substrate can be eliminated. The coating
liquid for forming a transparent coating film of the present
invention can thus be suitably used for a coating liquid for
forming a transparent coating film for medium and high refractive
index lenses. When the refractive index of the coating film is set
significantly higher than the refractive index of the substrate,
glaze of the substrate surface can be made significantly high.
[0049] The coating film formed on the substrate using the coating
liquid for forming a transparent coating film according to the
present invention contains titanium oxide as the main component in
the metal oxide particles in the coating film, and therefore, the
coating film has an excellent shielding effect to ultraviolet rays
and is suitable for a surface coating film, a topcoat film, or both
for automobiles and the like.
[0050] The coating film formed on the substrate using the coating
liquid for forming a transparent coating film according to the
present invention is colorless and transparent, has excellent
adhesion to the substrate, weatherability, light stability,
chemical resistance, flexibility, and dyeing affinity, and has high
surface hardness. As a result the coating film according to the
present invention has excellent scratch resistance and abrasion
resistance. Consequently, the coating liquid for forming a
transparent coating film according to the present invention is
suitable for providing lenses for glasses, various kinds of optical
lenses for cameras and the like, various kinds of display element
filters, looking glass, and the like. When the coating liquid for
forming a transparent coating film according to the present
invention is formed into a high refractive index layer at the time
of forming a multilayer anti-reflective coating on the substrate
surface of the looking glass, window glass, the various kinds of
display element filters, and the like, a content can be clearly
seen.
[0051] When the and-reflective coating described above is formed on
surfaces of various display elements, fluorescent light and the
like are not reflected on these display elements, and therefore,
images are clear and eyestrain can be prevented.
MODES FOR CARRYING OUT THE INVENTION
[0052] The metal oxide particles containing titanium oxide coated
with silicon dioxide-stannic oxide complex oxide colloidal
particles of the present invention is characterized by including:
titanium oxide-containing core particles (A); and coating layers
with which the titanium oxide-Containing core particles are coated
and that are made of silicon dioxide-stannic oxide complex oxide
colloidal particles, in which one or more intermediate thin film
layers that are made of any one of an oxide; a complex oxide of at
least one element selected from the group consisting of Si, Al, Sn,
Zr, Zn, Sb, Nb, Ta, and W; and a mixture of the-oxide and the
complex oxide are interposed between the titanium oxide-containing
core particles (A) and the coating layers made of the silicon
dioxide-stannic oxide complex oxide colloidal particles (B).
[0053] A primary particle diameter of the complex metal oxide
particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide is not particularly limited,
and the diameter is in a range of 1 nm to 100 nm, and preferably in
a range of 2 nm to 60 nm. Here, the primary particle diameter
refers to a diameter measured by transmission electron microscope
observation.
[0054] When the primary particle diameter is less than 1 nm, a
coating film obtained by using a coating liquid containing these
particles has insufficient hardness and poor scratch resistance and
abrasion resistance. The refractive index of the coating film may
not be sufficiently high. When the primary particle diameter
exceeds 100 nm, an obtained coating film may be clouded and
opaque.
[0055] The primary particle diameter of the titanium
oxide-containing core particles (A) is not particularly limited,
and it is desirable that the primary particle diameter be
approximately in a range of 1 nm to 100 nm, and preferably in a
range of 2 nm to 50 nm.
[0056] A content of titanium oxide in the titanium oxide-containing
core particles (A) is 5% by mass to 100% by mass, preferably 10% by
mass or more, and more preferably 20% by mass or more in terms of
TiO.sub.2. When the content of titanium oxide is less than 10% by
mass, a refractive index of a transparent coating film obtained by
using a coating liquid containing these particles is not high, and
an interference pattern may be generated depending on the
refractive index of the substrate.
[0057] The titanium oxide-containing core particles (A) may be made
of only titanium oxide or may be made of titanium oxide and a
component or components other than titanium oxide. The titanium
oxide-containing core particles (A) preferably include at least one
element selected from the group consisting of Si, Al, Sn, Zr, Zn,
Sb, Nb, Ta, and W. Titanium oxide and the component other than
titanium oxide described above may be a mixture or a solid solution
state.
[0058] Specific examples of the case that the component(s) other
than titanium oxide is(are) included in the titanium
oxide-containing core particles (A) include particles made of
titanium oxide and stannic oxide or particles made of titanium
oxide and stannic oxide and zirconium oxide.
[0059] The titanium oxide-containing core particles (A) may be
amorphous, or crystals such as anatase type crystal, rutile type
crystal, or brookite type crystal. The titanium oxide-containing
core particles (A) may also be a perovskite type titanium compound
such as barium titanate (BaTiO.sub.3 or BaOTiO.sub.2). Among them,
a crystal type of the titanium oxide-containing core particles (A)
is preferably the rutile type crystal
[0060] An amount of the coating layers made of the silicon
dioxide-stannic oxide complex oxide colloidal particles (B) in the
metal oxide particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide colloidal particles of the
present invention is in a range of 0.01 to 1.0 to a mass of the
titanium oxide-containing core particles (A).
[0061] In the metal oxide particles containing titanium oxide
coated with silicon dioxide-stannic oxide complex oxide colloidal
particles of the present invention, one or more intermediate thin
film layers that are made of any one of an oxide; a complex oxide
of at least one element selected from the group consisting of Si,
Al, Sn, Zr, Zn, Sb, Nb, Ta, and W; and a mixture of the oxide and
the complex oxide are interposed between the titanium
oxide-containing core particles (A) and the coating layers made of
the silicon dioxide-stannic oxide complex oxide colloidal particles
(B). The intermediate thin film layer may be one layer or two or
more layers.
[0062] By interposing at least one intermediate thin film layer
between the titanium oxide-containing core particles (A) and the
coating layers made of the silicon dioxide-stannic oxide complex
oxide colloidal particles (B), the refractive index of the metal
oxide particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide colloidal particles can be
adjusted and it is possible to improve various properties, such as
light stability, weatherability, adhesion between the coating film
and the substrate, of a coating film obtained by using a coating
liquid containing these particles. Furthermore, coloring of the
metal oxide particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide colloidal particles can be
suppressed and the transparency of the coating film can be
improved.
[0063] The number of the intermediate thin film layers that are
provided at least one layer and the thickness of the layer are not
particularly limited as long as a ratio of the titanium
oxide-containing core particles (A.) and the coating layers made of
the silicon dioxide-stannic oxide complex oxide colloidal particles
(B) in the metal oxide particles containing titanium oxide coated
with silicon dioxide-stannic oxide complex oxide colloidal
particles is in a range of 0.01 to 1.0 as an amount of the coating
layers made of the silicon dioxide-stannic oxide complex oxide
colloidal particles (B) to a mass of the titanium oxide-containing
core particles (A) as a standard.
[0064] As the intermediate thin film layer, silicon dioxide,
antimony oxide, aluminum oxide, or zirconium oxide is particularly
suitable. As forms, silicon dioxide, antimony oxide, aluminum oxide
or zirconium oxide may be stacked for each component to form a thin
film layer, or complex compound such as antimony oxide-silicon
dioxide complex is formed to form a thin film layer.
[0065] In this case, when silicon oxide and zirconium oxide and/or
aluminum oxide are used as materials for the intermediate thin film
layer, complex oxide particles containing titanium oxide coated
with antimony oxide that can form a transparent coating film having
excellent weatherability, light stability, adhesion to the
substrate, film hardness, scratch resistance, and flexibility can
be obtained. When silicon oxide is contained in the thin film
layer, stability of a complex oxide fine particle dispersion water
sol is improved; a pot life of a coating liquid described below
becomes longer, and increase in hardness of an obtained transparent
coating film and improvement of adhesion between the transparent
coating film and an anti-reflective coating that is formed on the
transparent coating can be achieved. In this case as well,
weatherability, light stability, adhesion to the substrate, film
hardness, scratch resistance, flexibility, and the like are
improved.
[0066] In the metal oxide particles containing titanium oxide
coated with silicon dioxide-stannic oxide complex oxide of the
present invention, an organic silicon compound or an amine-based
compound is preferably bonded to the surface of the metal oxide
particles.
[0067] As the organic silicon compound used, a known organic
silicon compound known as silane coupling agent can be used. A Type
of the organic silicon compound is adequately selected depending on
applications and the type of solvent.
[0068] As the organic silicon compound, specifically, the compounds
of General Formulae (1) to (4) below are used.
Monofunctional silanes of General Formula (1): R.sub.3SiX (1)
(in General Formula (1), R is an organic group having a C.sub.1-8
alkyl group, a phenyl group, a vinyl group, a methacryloxy group, a
mercapto group, an amino group, and an epoxy group, and X is a
hydrolyzable group). Examples of the monofunctional silanes may
include trimethylsilane, dimethylphenylsilane, and
dimethylvinylsilane.
Bifunctional Silanes of General Formula (2): R.sub.2SiX.sub.2
(2)
(in General Formula (2), R is an organic group having a C.sub.1-8
alkyl group, a phenyl group, a vinyl group, a methacryloxy group, a
mercapto group, an amino group, and an epoxy group, and X is a
hydrolyzable group). Examples of the bifunctional silanes may
include dimethyl silane and diphenyl silane.
Trifunctional silanes of General Formula (3): RSiX.sub.3 (3)
(in General Formula (3), R is an organic group having a C.sub.1-8
alkyl group, a phenyl group, a vinyl group, a methacryloxy group, a
mercapto group, an amino group, and an epoxy group, and X is a
hydrolyzable group). Examples of the trifunctional silanes may
include methylsilane and phenylsilane.
Tetrafunctional Silanes of General Formula (4): SiX.sub.4 (4)
(in General Formula (4), X is a hydrolyzable group). Examples of
the tetrafunctional silanes may include tetraalkoxysilanes such as
tetraethoxysilane.
[0069] These organic silicon compounds may be used singly or in
combination of two or more of them. When surface modification
treatment is carried out in which the organic silicon compound is
bonded to the surface of the metal oxide particles containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide, the organic silicon compound may be partially hydrolyzed or
the surface modification treatment may be carried out without
hydrolysis. A preferable state after the surface modification
treatment is a state in which the hydrolyzable groups are reacted
with hydroxy groups on the surface of the metal oxide particles
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide. However, a state in which a part of the hydroxy
groups remains untreated does not cause any problems.
[0070] Examples of the amine-based compounds used may include
alkylamines such as ethylamine, triethylamine, isopropylamine and
n-propylamine, aralkylamines such as benzyl amine, alicyclic amines
such as piperidine, alkanolamines such as monoethanolamine and
triethanolamine, quaternary ammonium salts and quaternary ammonium
hydroxides such as tetramethylammonium hydroxide.
[0071] These amine-based compounds may be used singly or in
combination of two or more of them.
[0072] These amine-based compounds may be bonded to the surface of
the particles by, for example, reacting with hydroxy groups on the
surface of the metal oxide particles containing titanium oxide
coated with silicon dioxide-stannic oxide complex oxide or by
coordination bonds to the surface of the particles.
[0073] For bonding the organic silicon compound or the amine-based
compound to the surface of the complex metal oxide particles
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide colloidal particles, for example, the complex metal
oxide particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide colloidal particles are mixed
in an alcohol solution of the organic silicon compound or the
amine-based compound and then a predetermined amount of water and,
if necessary, a hydrolysis catalyst are added, and thereafter, the
mixture may be left to stand for a predetermined period at room
temperature or may be subjected to heat treatment.
[0074] This process can be also carried out by adding the
hydrolysate of the organic silicon compound and the complex metal
oxide particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide colloidal particles to a mixed
liquid of water and alcohol and subjecting the mixture to heat
treatment.
[0075] The organic silicon compound or the amine-based compound
used can be added in an amount of 0.1% by mass to 40% by mass to a
mass of the metal oxide particles in the complex metal oxide
particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide colloidal particles.
[0076] The metal oxide particles containing titanium oxide coated
with silicon dioxide-stannic oxide complex oxide of the present
invention can be treated as a metal oxide dispersion sol in which
the metal oxide particles are dispersed in water, an organic
solvent, or a mixed solvent of water and the organic solvent.
[0077] A complex metal oxide particle containing titanium oxide
coated with silicon dioxide-stannic oxide complex oxide dispersion
sol of the present invention is a sol in the which the complex
metal oxide particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide are dispersed in water, an
organic solvent, or a mixed solvent of water and the organic
solvent.
[0078] The intermediate thin film layer is provided in the complex
metal oxide particle containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide dispersion sol of the present
invention, and therefore, the sol has excellent dispersion
stability compared with the conventionally known titanium oxide sol
and titanium oxide-based complex oxide sol.
[0079] A total metal oxide concentration in the water dispersion
sol of the complex metal oxide particles containing titanium oxide
coated with silicon dioxide-stannic oxide complex oxide colloidal
particles is in a range of 0.01% by mass to 40% by mass, and
preferably in a range of 0.5% by mass to 20% by mass. When the
total metal oxide concentration is less than 0.01% by mass, a
concentration of a coating liquid obtained by formulating other
components is too low, so that a desired thickness of an obtained
coating film may not be acquired. When the total metal oxide
concentration exceeds 40% by mass, stability of the sol maybe
insufficient.
[0080] In the case of an organic solvent dispersion sol of the
complex metal oxide particles containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide, the organic silicon
compound or the amine-based compound is preferably bonded to the
surface of the complex metal oxide particles containing titanium
oxide coated with silicon dioxide-stannic oxide complex oxide to
carry out the surface modification treatment. The particles to
which the surface modification treatment is carried out have
excellent dispersibility to an organic solvent because the surface
of the particles is hydrophobic.
[0081] A total metal oxide concentration of the organic solvent
dispersion sol of the complex metal oxide particles containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide is in a range of 1% by mass to 60% by mass, and preferably in
a range of 2% by mass to 30% by mass. When the total metal oxide
concentration is less than 1% by mass, a concentration of a coating
liquid obtained by formulating other components is too low, so that
a desired thickness of an obtained coating film may not be
acquired. When a solid content concentration exceeds 60% by mass,
stability of the sol is insufficient.
[0082] Specific examples of the organic solvent used in the organic
solvent dispersion sol of the complex metal oxide particles
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide of the present invention include alcohols such as
methanol, ethanol, isopropyl alcohol; cellosolves such as methyl
cellosolve and ethyl cellosolve; glycols such as ethylene glycol;
esters such as methyl acetate and ethyl acetate; ethers such as
diethyl ether and tetrahydrofuran; ketones such as acetone and
methyl ethyl ketone; halogenated hydrocarbons such as
dichloroethane; aromatic hydrocarbons such toluene and xylene; and
N-dimethylformamide. These solvents may be used in combination of
two or more of them.
[0083] A first coating liquid for forming a transparent coating
film according to the present invention is characterized by
including the metal oxide particles containing titanium oxide
coated with silicon dioxide-stannic oxide complex oxide and one or
more of an organic silicon compound of General Formula (I), a
hydrolysate of the organic silicon compound, and a partial
condensate of the hydrolysate as a matrix formation component.
R.sup.1.sub.aR.sup.2.sub.bSi(OR.sup.3).sub.4-(a+b) (I)
(where R.sup.1 is a C.sub.1-10 hydrocarbon group, a vinyl group, a
methacryloxy group, or an organic group containing a mercapto
group, an amino group, or an epoxy group; R.sup.2 is a C.sub.1-4
hydrocarbon group; R.sup.3 is a C.sub.1-8 hydrocarbon group or an
acyl group; and a and b are each 0 or 1).
[0084] Specific example of the organic silicon compound of General
Formula (I) may include tetramethoxysilane, tetraethoxysilane,
methyltrimethoxysilane, ethyltriethoxysilane,
methyltriethoxysilane, phenyltriethoxysilane,
dimethyldimethoxysilane, phenylnrethyldimethoxysilane,
vinyltrimethoxysilane, vinyltriethoxysilane,
vinyltris(.beta.-methoxyethoxy)silane,
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-glycidoxypropyltriethoxysilane,
.gamma.-glycidoxypropylmethyldimethoxysilane,
.gamma.-glycidoxypropylmethyldiethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
N-.beta.(aminoethyl).gamma.-aminopropyltrimethoxysilane,
N-.beta.(aminoethyl).gamma.-aminopropylmethyldimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
N-phenyl-.gamma.-aminopropyltrimethoxysilane, and
.gamma.-mercaptopropyltrimethoxysilane. These compounds may be used
singly or by mixing two or more of them.
[0085] These organic silicon compounds are preferably hydrolyzed
and used in the presence of acid under a non-solvent condition or
in a polar organic solvent such as alcohol.
[0086] The organic silicon compound of General Formula (I) and the
complex metal oxide particles containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide may be mixed after
hydrolysis of the organic silicon compound of Formula (I) or the
organic silicon compound of General Formula (I) may be hydrolyzed
after mixing with the complex metal oxide particles containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide. In the hydrolysis, the organic silicon compound of General
Formula (I) may be fully hydrolyzed or may be partially
hydrolyzed.
[0087] A ratio of the matrix formation component in the coating
liquid for forming a transparent coating film is adequately in a
range of 10% by mass to 90% by mass and preferably in a range of
20% by mass to 80% by mass. When the ratio is less than 10% by
mass, adhesion between a substrate and a coating film may be
deteriorated, and when exceeding 90% by mass, a coating film having
a high refractive index may not be obtained.
[0088] A second coating liquid for forming a transparent coating
film of the present invention is characterized by including the
metal oxide particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide and at least one resin selected
from the group consisting of a thermosetting resin, a thermoplastic
resin, and an ultraviolet curing resin as a matrix formation
component.
[0089] As the matrix formation component, an acrylic resin, a
melamine-based resin, a urethane based resin, a polyester resin, a
phosphagen-based resin, or the like is used. Among them, the
polyester-based resin and the urethane based resin are
preferable.
[0090] In the coating liquid for forming a transparent coating film
of the present invention, the complex metal oxide particles
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide are 5 parts by mass to 1000 parts by mass and
preferably 10 parts by mass to 600 parts by mass to 100 parts by
mass of a solid content of the matrix formation component dried at
110.degree. C.
[0091] In the coating liquid for forming a transparent coating film
of the present invention, the following components (C) to (F) may
he optionally included other than the complex metal oxide particles
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide and the matrix formation component.
[0092] Component (C):
[0093] The component (C) is one or more hydrolysate or partial
condensate of the tetrafunctional organic silicon compound of
General formula (5): Si(OR.sup.4).sub.4 (5) (in General Formula
(5), R.sup.4 is a C.sub.1-8 hydrocarbon group, an alkoxyalkyl group
or an acyl group).
[0094] The organic silicon compound of General Formula (5) is used
for the purpose of adjusting a refractive index of a transparent
coating film to be formed, and also for accelerating a curing rate
of the coated transparent coating film and improving a hardness of
the transparent coating film. By using the component (C), the
refractive index of the transparent coating film alter coring can
be adequately adjusted depending on the refractive index of the
substrate and adhesion of the anti-reflective coating can be
ensured even if the content of the complex metal oxide particles
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide is decreased to some extent.
[0095] Specific examples of the tetrafunctional organic silicon
compound of General formula (5) may include tetramethoxysilane,
tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane,
tetrabutoxysilane, tetraphenoxysilane silane, tetraacetoxysilane,
tetraallyloxysilane, tetrakis(2-methoxyethoxy)silane,
tetrakis(2-ethylbutoxysilane), and tetrakis(2-ethylhexyloxy)
silane. These compounds may be used singly or in combination of two
or more of them. These compounds are preferably hydrolyzed and used
in the presence of acid under a non-solvent condition or in an
organic solvent such as alcohol.
[0096] A content ratio of the component (C) in the coating liquid
for forming a transparent coating film is adequately 0% by mass to
50% by mass to the mass of the coating liquid for forming a
transparent coating film as a standard. This is because the
transparent coating film after curing is easily cracked when the
content ratio exceeds 50% by mass.
[0097] Component (D):
[0098] The component (D) is metal oxide fine particles of at least
one element selected from the group consisting of Si, Al, Sn, Sb,
Ta, Ce, La, Zn, W, Nb, Zr, and In or a complex metal oxide of one
or more elements selected from the group, and a primary particle
diameter of the component (D) is 1 nm to 50 nm. Specifically, metal
oxide fine particles such as SiO.sub.2, Al.sub.2O.sub.3, SnO.sub.2,
Sb.sub.2O.sub.5, Ta.sub.2O.sub.5, CeO.sub.2, La.sub.2O.sub.3, ZnO,
WO.sub.3, ZrO.sub.2, In.sub.2O.sub.3, and Nb.sub.2O.sub.5, complex
oxide fine particles such as ZnSbO.sub.6 and ZnSnO.sub.3, or both
of the metal oxide fine particles and the complex oxide fine
particles are dispersed in water or an organic solvent in a
colloidal state.
[0099] The component (D) to the surface of which the organic
silicon compound of General Formulae (1) to (4) or the amine-based
compound is bonded also can be used.
[0100] Component (E):
[0101] The component (E) is at least one selected from the group
consisting of a polyfunctional epoxy compound, a polyvalent
carboxylic acid, and a polyvalent carboxylic acid anhydride. These
compounds are used for the purpose of Improvement of hardness of
the transparent coating film to be formed.
[0102] The polyfunctional epoxy compound means an epoxy resin
having two or more epoxy groups in one molecule, and examples of
the polyfunctional epoxy compound include ethylene glycol
diglycidyl ether, diethylene glycol diglycidyl ether, and
1,4-cyclohexanedimethanol diglycidyl ether, which have been
known.
[0103] Examples of the polyvalent carboxylic acid and the
polyvalent carboxylic acid anhydride include malonic acid, succinic
acid, adipic acid, azelaic acid, maleic acid, orthophthalic acid,
terephthalic acid, fumaric acid, itaconic acid, oxaloacetic acid,
succinic anhydride, maleic anhydride, itaconic anhydride,
2,3-dimethylmaleic anhydride, and phthalic anhydride.
[0104] A content ratio of the component (E) in the coating liquid
for forming a transparent coating film is adequately 0% by mass to
40% by mass to the mass of the coating liquid for forming a
transparent coating film as a standard. This is because when the
content ratio exceeds 40% by mass, adhesion between the transparent
coating film after curing and the anti-reflective coating formed
thereon is deteriorated.
[0105] Component (F):
[0106] The component (F) is at least one curing catalyst selected
from amines, amino acids, metal acetylacetonates, organic acid
metal salts, perchloric acids, salts of perchloric acids, acids,
and metal chlorides. The component (F) is used for accelerating
curing of silanol groups or epoxy groups that the organic
silicon-based matrix formation component contained in the coating
liquid for forming a transparent coating film. By using these
curing catalysts, a coating film formation reaction can be
accelerated.
[0107] Specific examples of the curing catalyst include amines such
as n-butylamine, triethylamine, guanidine, and biguanidide; amino
acids such as glycine; metal acetylacetonates such as aluminum
acetylacetonate, chromium acetylacetonate, titanyl acetylacetonate,
and cobalt acetylacetonate; organic acid metal salts such as sodium
acetate, zinc naphthenate, cobalt naphthenate, zinc octoate, and
tin octoate; perchloric acid and salts thereof such as perchloric
acid, ammonium perchlorate, and magnesium perchlorate; acids such
as hydrochloric acid, phosphoric acid, nitric acid, and
p-toluenesulfonic acid; and metal salts being Lewis acids such as
SnCl.sub.2, AlCl.sub.3, FeCl.sub.3, TiCl.sub.4, ZnCl.sub.2, and
SbCl.sub.3.
[0108] Types and a used amount of these curing catalysts can be
adjusted and used depending on the composition of the coating
liquid for forming a transparent coating film. An upper limit of
the used amount is desirably 5% by mass or less to the total solid
content in the coating liquid.
[0109] In order to improve performance of the transparent film
formed on the substrate using the coating liquid for forming a
transparent coating film of the present invention, a small amount
of a surfactant an antistatic agent, an ultraviolet absorber, an
oxidation inhibitor, a disperse dye, an oil soluble dye, a
fluorescent, dye, a pigment, a photochromic compound, and a
thixotropic agent may be added, if necessary.
[0110] For the coating liquid for forming a transparent coating
film of the present invention, a solvent is used for the purpose of
providing flowability, adjusting solid content concentration, and
adjusting surface tension, viscosity, and evaporation rate. The
solvent used is water or an organic solvent.
[0111] Examples of the organic solvent used include alcohols such
as methanol, ethanol, isopropyl alcohol; cellosolves such as methyl
cellosolve and ethyl cellosolve; glycols such as ethylene glycol;
esters such as methyl acetate and ethyl acetate; ethers such as
diethyl ether and tetrahydrofuran; ketones such as acetone and
methyl ethyl ketone; halogenated hydrocarbons such as
dichloroethane; aromatic hydrocarbons such toluene and xylene; and
N-dimethylformamide.
[0112] As a method for producing the metal oxide particles
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide of the present invention, a conventionally known
method can be employed.
[0113] The titanium oxide-containing core particles (A) can be
produced by, for example, a method for producing complex oxide
particles disclosed in Japanese Patent Application Publication No.
H10-306258 (JP H10-306258 A) applied by the applicant of the
present invention. A solid content concentration of the water
dispersion sol of the titanium oxide-containing core particles (A)
is 0.1% by mass to 30% by mass and preferably 0.5% by mass to 20%
by mass as the total metal oxide. When the concentration of the
water dispersion sol is less than 0.1% by mass, the productivity is
low, which is industrially disadvantageous. When the solid content
concentration exceeds 30% by mass, the obtained particles tend to
form agglomerate, and therefore, it is difficult to obtain an
excellent transparent coating film, which is not preferable.
[0114] A method for forming the intermediate thin film layer made
of any one of the oxide; the complex oxide of at least one element
selected from the group consisting of Si, Al, Sn, Zr, Zn, Sb, Nb,
Ta, and W; and the mixture of the oxide and the complex oxide
includes firstly providing an aqueous solution or a colloidal
particle dispersion liquid of an element that is a constituent of
the intermediate thin film, charging the titanium oxide-containing
core particles (A) in the solution or the dispersion liquid, and
forming the intermediate thin film on the surface of the titanium
oxide-containing core particles (A). At the time of forming the
intermediate thin film layer, heating is preferably performed at
40.degree. C. or more or 200.degree. C. or less.
[0115] Subsequently, a water dispersion sol of the silicon
dioxide-stannic oxide complex oxide colloidal particles (B) is
added to the water dispersion sol of the titanium oxide-containing
core particles (A) on which the intermediate thin film layer is
formed to form a coating layer. An amount of the added silicon
dioxide-stannic oxide complex oxide colloidal particles (B) is in a
range of 0.01 to 1.0 to the titanium oxide-containing core
particles (A).
[0116] For the water dispersion sol of the metal oxide particles
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide obtained by the method described above, pH and
temperature of the dispersion sol may be adequately adjusted, if
necessary, and the water dispersion sol may be heated, if
necessary. Heating is preferably performed at 40.degree. C. or more
or 200.degree. C. or less. After forming the coating layer,
impurity may be removed by rinsing treatment, if necessary. The
total metal oxide concentration can be adjusted by a method such as
ultrafiltration or evaporative concentration.
[0117] The dispersion sol of the metal oxide particles containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide of the present invention is a sol in which water, an organic
solvent, or a mixed solvent of water and the organic solvent is
used as a dispersion medium. The organic solvent dispersion sol can
be produced by solvent replacement of water, which is the
dispersion medium of the water dispersion sol, by a commonly used
method such as a distillation method or an ultrafiltration
method.
[0118] The coating liquid for forming a transparent coating film of
the present invention can be obtained by mixing the metal oxide
particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide obtained by the method
described above with the matrix formation component and, if
necessary, other components.
[0119] At the time of producing the coating liquid for forming a
transparent coating film of the present invention, the dispersion
sol of the metal oxide particles containing titanium oxide coated
with silicon dioxide-stannic oxide complex oxide can be suitably
used.
[0120] A solid content concentration of the coating liquid for
forming a transparent coating film is 1% by mass to 70% by mass and
preferably 2% by mass to 50% by mass as a total concentration that
includes a solid content originated from other components used as
necessary by mixing.
[0121] At the time of producing the coating liquid for forming a
transparent coating film of the present invention, when the metal
oxide particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide can be easily dispersed in the
coating liquid, the metal oxide particles may be used in the form
of a line powder, in addition to in the form of the dispersion sol,
and further the dried dispersion sol may be used.
[0122] Subsequently, a substrate coated with a transparent coating
film of the present invention will be described. The substrate
coated with a transparent coating film of the present invention has
a substrate and a high refractive index transparent coating film
formed on the substrate, and the transparent coating film is formed
from the coating liquid for forming a transparent coating film.
[0123] The substrate coated with a transparent coating film of the
present invention is characterized by including the transparent
coating film formed by using the first or the second coating liquid
for forming a transparent coating film on the surface of the
substrate.
[0124] The substrate coated with a transparent coating film of the
present invention is also characterized by including a primer film
formed by using the second coating liquid for forming a transparent
coating film on the surface of the substrate and a hard coating
film formed by using the first coating liquid for forming a
transparent coating film on the primer film. The substrate coated
with a transparent coating film may further include an
anti-reflective coating on the transparent coating film or the hard
coating film.
[0125] Various substrates made of glass, a plastic, and other
materials are employed for the substrate used. Specific examples of
the substrate include lenses for glasses, various optical lenses
for a camera and the like, various display element filters, looking
glass, wind glass, coating films for automobiles, and lamp covers
used for automobiles. On the surface of the substrate, a
transparent coating film is formed as a hard coating film. Other
than the hard coating film, a transparent coating film used as a
primer film for a plastic lens may be formed.
[0126] The thickness of the coating film formed on these substrate
surfaces varies depending on applications for the substrate coated
with a coating film, and is preferably 0.05 .mu.m to 30 .mu.m.
[0127] The substrate coated with a transparent coating film of the
present invention can be produced by applying the coating liquid
for forming a transparent coating film to the surface of the
substrate by the conventionally known methods such as a dipping
method, a spin coating method, a spraying method, a roll coater
method, and a flowing method and drying the substrate to form the
coating film, and subsequently heating the coating film at a
temperature lower than a heat resistance temperature of the
substrate. For a lens substrate having a heat distortion
temperature of less than 100.degree. C., the spin coating method in
which the lens substrate does not have to be fixed with a jig, is
particularly preferable. When a substrate for forming a coating
film is a resin lens, the coating film is desirably formed by
applying the coating liquid onto the substrate, and thereafter,
heating and drying the substrate at a temperature of 40.degree. C.
to 200.degree. C. for several hours.
[0128] When an ultraviolet curing resin is used as the matrix
formation component of the coating liquid for forming a transparent
coating film, the substrate coated with a coating film according to
the present invention can be produced by a method in which, after
the coating liquid is applied to the surface of the substrate, the
coated film is dried, and cured by irradiating the surface of the
substrate on which the coating liquid is applied with ultraviolet
rays having a predetermined wavelength.
[0129] Furthermore, at the time of producing the substrate coated
with a coating film of the present invention, for the purpose of
improving adhesion between a substrate. for example, a lens
substrate and the coating film, the surface of the substrate may be
previously treated with an alkali, an acid, or a surfactant, or may
be treated by grinding with inorganic or organic fine particles, or
may be treated with a primer or plasma.
[0130] The substrate coated with a coating film of the present
invention may be a substrate having a primer film between the
substrate and the hard coating layer. In this case, the primer film
may be formed by using the second coating liquid for forming a
transparent coating film and the hard coating film may be formed by
using the first coating liquid for forming a transparent coating
film.
[0131] In a plastic lens using a high refractive index optical
material, a hard coating film is formed on the surface and a
multi-coating layer is further formed on the hard coating film for
the purpose of antireflection. In a process for forming the
multi-coating layer, distortion is generated in the plastic lens
substrate, and therefore, the lens may easily be broken by impact
caused by failing and the like. Consequently, a soft primer film
that absorbs impact is provided between, the plastic lens and the
hard coating film.
[0132] An interference pattern may be generated when the refractive
index of the primer film is not equal to that of the substrate.
However, when the second coating liquid for forming a transparent
coating film is used, which includes the resin such as the acrylic
resin, the melamine-based resin, the urethane based resin, the
polyester resin, and the phosphagen-based resin as the matrix
component among the coating liquids for forming a transparent
coating film of the present invention, a primer film having an
almost equal refractive index to the refractive index of the
substrate can be formed.
[0133] In the case of forming the primer film described above, the
coating film is cured after the coating liquid is applied by the
method described above.
[0134] The coating liquid for forming a transparent coating film of
the present invention can contain: a curing agent for accelerating
the reaction; metal oxide fine particles for adjusting the
refractive index to the refractive index of the substrate; and
further various types of surfactants for improving wettability at
the time of application and improving smoothness of the cured
coating film can be added. Additives such as an ultraviolet
absorber and an antioxidant can be further added as long as the
additives do not affect physical property of the cured film.
[0135] The anti-reflective coating that is provided on the coating
film obtained from the coating liquid for forming a transparent
coating film of the present invention and made of a vapor-deposited
film of an inorganic oxide is not particularly limited, and a
single layer or a multi-layer anti-reflective coating made of the
vapor-deposited film of the inorganic oxide that has been known may
be used. Examples of the anti-reflective coating include
anti-reflective coatings disclosed in Japanese Patent Application
Publication No. H2-262104 (JP H2-262104 A) and Japanese Patent
Application Publication No. S56-116003 (JP S56-116003 A).
[0136] An impact absorption film improves impact resistance. The
impact absorption film is configured of a polyacrylic acid-based
resin, a polyvinyl acetate-based resin, a polyvinyl alcohol-based
resin, and the like.
[0137] The coating film obtained from the coating liquid for
forming a transparent coating film of the present invention can be
used for a reflection film as a high refractive index film, and
further can be used for a multi-functional film by adding
functional components such as antifogging, photochromic, and
antifouling components.
[0138] Optical members having the coating film made of the coating
composition of the present invention can be used for lenses for
cameras, window glass for automobiles, optical filters attached to
liquid crystal displays or plasma displays, other than the lenses
for glasses.
EXAMPLES
[0139] The present invention will be further described in detail
with reference to the following examples. The present invention,
however, is not limited to the examples
Preparation Examples
Preparation Example 1
[0140] A water dispersion sol of titanium oxide-containing core
particles (A1) was prepared based on Example 2 in Japanese Patent
Application Publication No. H10-245224 (JP H10-245224 A).
[0141] Process (a): Into a 3-liter separable flask made of glass
with a jacket, 293.8 g (79.8 g in terms of TiO.sub.2) of titanium
tetrachloride (manufacture by Sumitomo Sitix Co., Ltd., a
concentration of 27.2% by mass in terms of TiO.sub.2, Cl 32.0% by
mass) and 371.6 g of water were poured to prepare 665 g of titanium
chloride aqueous solution (12.0% by mass in terms of TiO.sub.2).
Stirred with a stirring bar made of glass, the aqueous solution was
heated to 50.degree. C. and thereafter, 950.8 g of 35% by mass
hydrogen peroxide aqueous solution and 566.4 g of metal tin powder
(manufactured by Yamaishi Metal Co., Ltd., trade name AT-Sn, No.
200) were added with cooling. The addition of the hydrogen peroxide
aqueous solution and the metal tin powder was performed such that
first 31.5 g (0.265 mol) of the metal tin, and then 53.8 g (0.554
mol) of the hydrogen peroxide aqueous solution were gradually
added. After the reaction was completed, 31.5 g (0.265 mol) of the
metal tin, and then 53.8 g (0.554 mol) of the hydrogen peroxide
aqueous solution were gradually added. As described above, by
repeating the addition of the metal tin and the successive addition
of the hydrogen peroxide aqueous solution 17 times in total at 5 to
10-minute intervals, separation addition (31.5 of the metal tin and
53.8 g of the hydrogen peroxide aqueous solution were added 17
times) was carried out, and thereafter, finally 30.9 g of the metal
tin and then 36.2 g of the hydrogen peroxide aqueous solution were
added to carry out 18 times in total of the separation addition.
The reaction was an exothermal reaction, and therefore, a
temperature of the aqueous solution rose to 70% to 75% by the
addition of the metal tin. After the reaction was completed, the
aqueous solution was cooled to 50% to 60%. The reaction was carried
out at 50% to 75%. An addition ratio of the hydrogen peroxide and
the metal tin in one time was 2.09 in the molar ratio of
H.sub.2O.sub.2/Sn. A required time for the addition of the hydrogen
peroxide aqueous solution and the metal tin was 3.0 hours. After
the reaction, was completed, 3195.6 g of a basic titanium
chloride-tin complex salt aqueous solution was obtained. At this
time, a concentration of the aqueous solution was 25% by mass as a
total concentration in terms of TiO.sub.2+SnO.sub.2.
[0142] Process (b): 11269 g of water and 211 g of 28% by mass
aqueous ammonia were added to 2870 g of the basic titanium
chloride-tin complex salt aqueous solution and the aqueous solution
was diluted to a concentration of 5% by mass in terms of
TiO.sub.2+SnO.sub.2. This aqueous solution was hydrolyzed at
95.degree. C. for 10 hours to obtain agglomerate slurry of a
titanium oxide-stannic oxide complex colloid.
[0143] Process (c): Excessive electrolyte was removed from the
agglomerate slurry of the titanium oxide-stannic oxide complex
colloid obtained in the process (b) by repeating operations of
concentration and water pouring using about 15 liters of water in
an ultrafiltration device, and thereafter, the slurry was
deflocculated to obtain 14350 g of an acidic titanium,
oxide-stannic oxide complex water dispersion sol. A primary
particle diameter of the titanium oxide-stannic oxide complex
colloidal particles measured by transmission electron, microscope
observation was 4 nm to 8 nm.
[0144] Process (d): 14350 g of the acidic titanium oxide-stannic
oxide complex sol obtained in the process (c) was alkalified by
adding 137 g of isopropylamine, and thereafter, excessive
electrolyte was removed from the sol by repeating operations of
concentration and water pouring using about 24 liter of water in an
ultrafiltration device to obtain 14600 g of an alkaline titanium
oxide-stannic oxide complex water dispersion sol. The alkaline
water dispersion sol further was passed through a column packed
with 200 milliliters of an anion-exchange resin (manufactured by
ORGANO CORPORATION: Amberlite (.RTM.) IRA-410) to obtain 15500 g of
an alkaline titanium oxide-stannic oxide complex water dispersion
sol from which almost all anions were removed. The sol was
concentrated with a rotary evaporator under reduced pressure to
obtain 7 kg of a water dispersion sot of the titanium
oxide-containing core particles (A1). At this time, a concentration
was 10% by mass in terms of (TiO.sub.2+SnO.sub.2). A primary
particle diameter of the titanium oxide-containing core particles
(A1) measured by transmission electron microscope observation was 4
nm to 8 nm. The powder of the obtained sol dried at 110.degree. C.
was analyzed by X-ray diffraction analysis and was determined to be
rutile type crystal.
Preparation Example 2
[0145] A water dispersion sol of titanium oxide-containing core
particles (A2) was prepared based on Example 2 in Japanese Patent
Application Publication No. H10-310429 (JP H10-310429 A).
[0146] Process (a): Into a 3-liter separable flask made of glass
with a jacket, 587.5 g (159.8 g in terms of TiO.sub.2) of titanium
tetrachloride (27.2% by mass in terms of TiO.sub.2, Cl 32.0% by
mass, manufacture by Sumitomo Sitix Co., Ltd.), 114.6 g (49.2 g in
terms of ZrO.sub.2) of zirconium oxycarbonate and (43.0% by mass in
terms of ZrO.sub.2), manufactured by Daiichi Kigenso Kagaku Kogyo
Co., Ltd), and 629.6 g of water were poured to prepare 1331.7 g of
a mixed aqueous solution of titanium chloride and zirconium
oxychloride (12.0% by mass in terms of TiO.sub.2, 3.7% by mass in
terms of ZrO.sub.2). Stirred with a stirring bar made of glass, the
aqueous solution was heated to 60.degree. C., and thereafter, 358.0
g of 35% by mass hydrogen, peroxide aqueous solution and 190.0 g of
metal tin powder (manufactured by Yamaishi Metal Co., Ltd., trade
name AT-Sn, No. 200) was added with cooling. The addition of the
hydrogen peroxide aqueous solution and the metal tin powder was
performed such that first 35.8 g (0.37 mol) of the hydrogen
peroxide aqueous solution, and then 19.0 g (0.16 mol) of the metal
tin were gradually added. After completion of the reaction that was
waited for about 5 minutes to about 1.0 minutes, 35.8 g (0.37 mol)
of the hydrogen peroxide, and then 19.0 g. (0.16 mol) of the metal
tin were gradually added. As described above, by repeating the
addition of the hydrogen peroxide and the successive addition of
the metal tin 10 times in total at 5 to 10-minute intervals,
separation addition (35.8 of the hydrogen peroxide and 19.0 g of
the metal tin were added 10 times) was carried out. The reaction
was an exothermal reaction, and therefore, a temperature of the
aqueous solution rose to 80.degree. C. to 85.degree. C. by the
addition of the metal tin. After the reaction was completed, the
aqueous solution was cooled to 60.degree. C. to 70.degree. C. The
reaction was carried out at a temperature of 60.degree. C. to
85.degree. C. An addition ratio of the hydrogen peroxide and the
metal tin was 2.31 in the molar ratio of H.sub.2O.sub.2/Sn. A
required time for the addition of the hydrogen peroxide aqueous
solution and the metal tin was 2.5 hours. Here, an adequate amount
of water was added because water was evaporated by the reaction.
After the reaction was completed, 1780 g of a basic titanium
chloride-zirconium-tin complex salt aqueous solution which was
clear light yellow was obtained. In the obtained basic titanium
chloride-zirconium-tin complex salt aqueous solution, a titanium
component was 8.98% by mass in terms of TiO.sub.2, a zirconium
component was 2.76% by mass in terms of ZrO.sub.2, a tin component
was 13.55% by mass in terms of SnO.sub.2, the molar ratio of
ZrO.sub.2/TiO.sub.2 was 0.2, and the molar ratio of
TiO.sub.2/(ZrO.sub.2+SnO.sub.2) was 1.0. The molar ratio of
(Ti+Zr+Sn)/Cl was 0.76.
[0147] Process (b): 259 g of 28% by mass aqueous ammonia and 6964 g
of water were added to 1780 g of the basic titanium
chloride-zirconium-tin complex salt aqueous solution obtained in
the process (a) and the aqueous solution was diluted to a
concentration of 5% by mass in terms of
TiO.sub.2+ZrO.sub.2+SnO.sub.2. This aqueous solution was hydrolyzed
at 95.degree. C. to 98.degree. C. for 12 hours to obtain
agglomerate slurry of titanium oxide-zirconium oxide-stannic oxide
complex colloidal particles.
[0148] Process (c): Excessive electrolyte was removed from the
agglomerate slurry of the titanium oxide-zirconium oxide-stannic
oxide complex colloidal particles obtained in the process (b) by
repeating operations of concentration and water pouring using about
20 liter of water in an ultrafiltration device, and thereafter, the
slurry was deflocculated to obtain 8400 g of an acidic titanium
oxide-zirconium oxide-stannic oxide complex colloidal particle
water dispersion sol. A primary particle diameter of the titanium
oxide-stannic oxide complex colloidal particles measured by
transmission electron microscope observation was 4 nm to 8 nm.
[0149] Process (d): 9000 g of the acidic complex sol of the
titanium oxide-zirconium oxide-stannic oxide colloidal particles
obtained in the process (c) was alkalified by adding 27.0 g of
isopropylamine, and thereafter, excessive electrolyte was removed
from the complex sol by repeating operations of concentration and
water pouring using about 20 liters of water in an ultrafiltration
device to obtain 8000 g of an alkaline water dispersion sol of the
titanium oxide-zirconium oxide-stannic oxide complex colloidal
particles, This sol was passed through a column packed with 500
milliliters of an anion-exchange resin (manufactured by ORGANO
CORPORATION: Amberlite (.RTM.) IRA-410) to obtain 9050 g of an
alkaline water dispersion sol of the titanium oxide-zirconium
oxide-stannic oxide complex colloidal particles from which almost
all anions were removed. The sol was concentrated with an
ultrafiltration device to obtain 3100 g of a concentrated water
dispersion sol of the titanium oxide-zirconium oxide-stannic oxide
complex colloidal particles. The obtained sol had a specific
gravity of 1.140, a viscosity of 10.3 mPas, a pH of 10.31, a
conductivity of 1105 .mu.s/cm, a concentration of 5.18% by mass in
terms of TiO.sub.2, a concentration of 1.58% by mass in terms of
ZrO.sub.2, a concentration of 7.7% by mass in terms of SnO.sub.2,
and a primary particle diameter determined with a transmission
electron microscope of 4 nm to 8 nm. The obtained titanium
oxide-zirconium oxide-stannic oxide complex colloidal particles
were defined as titanium oxide-containing core particles (A2). The
powder of the obtained sol dried at 110.degree. C. was analyzed by
X-ray diffraction analysts and was determined to be a mixture of
rattle type crystal and anatase type crystal.
Preparation Example 3
[0150] 1169 g of pure water was poured into a 3-liter container and
151 g of oxalic acid dihydrate (manufactured by Ube industries,
Ltd.), 227 g of titanium tetraisopropoxide (a content of 64 g in
terms of TiO.sub.2, manufactured by KANTO CHEMICAL CO., INC.), and
582 g of 25% by mass tetramethylammonium hydroxide aqueous solution
(manufactured by TAMA CHEMICALS CO., LTD.) were added with
stirring. In the obtained mixed solution, the molar ratio of oxalic
acid/titanium atom was 1.5 and the molar ratio of
tetramethylammonium hydroxide/oxalic acid was 1.33. 2131 g of the
mixed solution was maintained at 88.degree. C. to 92.degree. C. for
3 hours under atmospheric pressure in an open system and generated
isopropanol as by-product was removed by distillation to prepare
1937 g of titanium containing aqueous solution. To the obtained
titanium containing aqueous solution, 194 g of pure water was added
to adjust a concentration of the titanium containing aqueous
solution in terms of TiO.sub.2 to 3.0% by mass. The titanium
containing aqueous solution after adjusting the concentration had a
pH of 4.7 and a conductivity of 31.4 mS/cm. To 3 L stainless
autoclave container, 2131 g of the titanium containing aqueous
solution was charged and hydrothermally treated at 140.degree. C.
for 5 hours. After the solution was cooled to room temperature, the
taken out solution after the hydrothermal treatment was a highly
transparent water dispersion sol of titanium oxide colloidal
particles. The obtained sol had a specific gravity of 1.037, a pH
of 3.8, a conductivity of 35.7 mS/cm, a concentration of TiO.sub.2
of 3.0% by mass, a concentration of tetramethylammonium hydroxide
of 6.8% by mass, a concentration of oxalic acid of 5.1% by mass, a
particle diameter determined by a dynamic light scattering method
(measured by N5 manufactured by Coulter Inc.) of 12 nm, and a
viscosity of 3.2 mPas (measured by a B-type viscometer). In
transmission electron microscope observation, substantially
spherical particles having a primary particle diameter of 5 nm to 8
nm were observed. The powder of the obtained sol dried at
110.degree. C. was analyzed by X-ray diffraction analysis and was
determined to be anatase type crystal. The obtained titanium oxide
colloidal particles were defined as titanium oxide-containing core
particles (A3).
Preparation Example 4
[0151] A titanium oxide-containing core particle (A4) dispersion
sol was prepared as follows. 197 g of pure water was poured into
2-liter container, and 269 g of a tin oxalate solution (a content
of 75 g in terms of SnO.sub.2 and 67 g in terms of oxalic acid),
142 g of titanium tetraisopropoxide (a content of 40 g in terms of
TiO.sub.2), 73 g of oxalic acid dihydrate (52 g in terms of oxalic
acid), and 319 g of 25% by mass tetramethylammonium hydroxide
aqueous solution were added with stirring. In the obtained mixed
solution, the molar ratio of oxalic acid/titanium atom was 1.3 and
the molar ratio of tetramethylammonium hydroxide/titanium atom was
1.75. 1000 g of the mixed solution was maintained at 80.degree. C.
for 2 hours and further maintained under reduced pressure of 580
Torr for 2 hours to prepare a titanium mixed solution. The titanium
mixed solution after preparation had a pH of 5.1, a conductivity of
30.9 mS/cm, and a concentration of TiO.sub.2 of 4.0% by mass. Into
a 3-liter autoclave container having a glass lining, 1000 g of the
titanium mixed solution was charged and hydrothermally treated at
140.degree. C. for 5 hours. After the solution was cooled to room
temperature, the taken out solution after the hydrothermal
treatment was a light opaque white water dispersion sol of titanium
oxide colloidal particles. The obtained sol had a pH of 3.9, a
conductivity of 32.6 mS/cm, a concentration of TiO.sub.2 of 4.0% by
mass, a concentration of tetramethylammonium hydroxide of 8.0% by
mass, a concentration of oxalic acid of 5.9% by mass, and a
particle diameter determined by the dynamic light scattering method
of 16 nm. In transmission electron microscope observation,
elliptical particles having a primary particle diameter of 5 nm to
15 nm were observed. The powder of the obtained sol dried at
110.degree. C. was analyzed by X-ray diffraction analysis and was
determined to be rutile type crystal. The obtained titanium oxide
colloidal particles were defined as titanium oxide-containing core
particles (A4).
Preparation Example 5
[0152] 35.6 kg of a potassium silicate aqueous solution (a content
of 19.9% by mass as SiO.sub.2, manufactured by Nissan Chemical
Industries, Ltd.) was diluted with 330.0 kg of pure water, and
thereafter, 18.1 kg of 48% by mass potassium hydroxide aqueous
solution and 3.2 kg of antimony trioxide (a content of 99% by mass
as Sb.sub.2O.sub.3, manufactured by Mikuni Seiren K.K.) were added
and subsequently 2.2 kg of 35% by mass of hydrogen peroxide aqueous
solution wad added with stirring, and the mixture was reacted at
93.degree. C. for 1 hour to obtain a potassium silicate antimonate
aqueous solution. 427.5 g of the obtained potassium silicate
antimonate aqueous solution was diluted with 1 kg of pure water and
the diluted solution was passed through a column packed with a
hydrogen type cation exchange resin (Amberlite (.RTM.) 01-120B) to
obtain 2703 g of a water dispersion sol of silicon dioxide-antimony
pentoxide complex oxide colloidal particles (pH 2.1, 0.64% by mass
as Sb.sub.2O.sub.5 and 1.26% by mass as SiO.sub.2, a mass ratio of
SiO.sub.2/Sb.sub.2O.sub.5 of 2.0). Subsequently, 10.2 g of
diisopropylamine was added to the obtained water dispersion sol.
The obtained sol was an alkaline water dispersion sol of the
silicon dioxide-antimony pentoxide complex oxide colloidal
particles and a pH thereof was 8.2. In the obtained water
dispersion sol, colloidal particles having a primary particle
diameter of 5 nm or less was observed.
Preparation Example 6
[0153] 77.2 g of JIS No. 3 sodium silicate (a content of 29.8% by
mass as SiO.sub.2, manufactured by Fuji Kagaku CORP.) was dissolved
in 1282 g of pure water, and subsequently 20.9 g of sodium stannate
NaSnO.sub.3H.sub.2O (a content of 55.1% by mass as SnO.sub.2,
manufactured by Showa Kako Corporation) was dissolved. The obtained
aqueous solution was passed through a column packed with a hydrogen
type cation exchange resin (Amberlite (.RTM.) IR-120B) to obtain
2634 g of an acidic water dispersion sol of silicon dioxide-stannic
oxide complex colloidal particles (B1) (pH 2.4, a content of 0.44%
by mass as Sn.sub.2O and 0.87% by mass as SiO.sub.2, a mass ratio
of SiO.sub.2/SnO.sub.2 2.0). Subsequently, 6.9 g of
diisopropylamine was added to the obtained water dispersion sol.
The obtained sol was an alkaline water dispersion sol of the
silicon dioxide-stannic oxide complex colloidal particles (B1) and
a pH thereof was 8.0. In the water dispersion sol, colloidal
particles having a primary particle diameter of 5 nm or less were
observed by a transmission electron microscope.
Example 1
[0154] 70.8 g of zirconium oxychloride (a content of 21.19% by mass
as ZrO.sub.2, manufactured by Daiichi Kigenso Kagaku Kogyo Co.,
Ltd.) was diluted with 429.2 g of pure water to prepare 500 g of a
zirconium oxychloride aqueous solution (a content of 3.0% by mass
as ZrO.sub.2), and 1000 g of the water dispersion sol of the
titanium oxide-containing core particles (A1) prepared in
Preparation Example 1 was added with stirring. Subsequently, the
water dispersion sol was hydrolyzed by heating to 95.degree. C. to
obtain a water dispersion sol of the titanium oxide-containing core
particles (A1) on the surface of which a thin film of zirconium
oxide was formed. The obtained water dispersion sol had a pH of 1.2
and a total metal oxide concentration of 20% by mass. In
transmission electron microscope observation, colloidal particles
having a primary particle diameter of 4 nm to 8 nm were observed.
1455 g of the obtained water dispersion sol was added to 2634 g of
the alkaline water dispersion sol of the silicon dioxide-stannic
oxide complex colloidal particles (B1) prepared in Preparation
Example 6 with stirring. Subsequently, the sol was passed through a
column packed with 500 milliliters of an anion-exchange resin
(Amberlite (.RTM.) IRA-410, manufactured by ORGANO CORPORATION).
Subsequently, the water dispersion sol after passing through the
column was heated at 95.degree. C. for 3 hours and concentrated by
an ultrafiltration membrane method to obtain a water dispersion sol
of metal oxide particles containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide in which an
intermediate thin film layer made of zirconium oxide was formed
between the titanium oxide-containing core particles (A1) and the
silicon dioxide-stannic oxide complex colloidal particles (B1). The
obtained water dispersion sol had a total metal oxide concentration
of 20% by mass. In transmission electron microscope observation of
the sol, a primary particle diameter was 4 nm to 10 nm.
Subsequently, the dispersion medium of the obtained water
dispersion sol was replaced with methanol by using a rotary
evaporator to obtain a methanol dispersion sol of the metal oxide
particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide in which an intermediate thin
film layer made of zirconium oxide was formed between the titanium
oxide-containing core particles (A1) and the silicon
dioxide-stannic oxide complex colloidal particles (B1). This
methanol dispersion sol had a total metal oxide concentration of
30% by mass, a viscosity of 3.2 mPas, a particle diameter
determined by a dynamic light scattering method (DLS particle
diameter, measured by N4PULS manufactured by BECKMAN COULTER Inc.)
of 32 nm, and a moisture content of 1.2% by mass.
Example 2
[0155] 70.8 g of zirconium oxychloride (a content of 21.19% by mass
as ZrO.sub.2, manufactured by Daiichi Kigenso Kagaku Kogyo Co.,
Ltd.) was diluted with 429.2 g of pure water to prepare 500 g of a
zirconium oxychloride aqueous solution (a content of 3.0% by mass
as ZrO.sub.2), and 1298.7 g of the water dispersion sol of the
titanium oxide-containing core particles (A2) prepared in
Preparation Example 2 was added with stirring. Subsequently, the
water dispersion sol was hydrolyzed by heating to 95.degree. C. to
obtain a water dispersion sol of the titanium oxide-containing core
particles (A2) on the surface of which a thin film of zirconium
oxide was formed. The obtained water dispersion sol had a pH of 1.2
and a total metal oxide concentration of 20% by mass. In
transmission electron microscope observation of this sol, colloidal
particles having a primary particle diameter of 4 nm to 8 nm were
observed. 1764 g of the obtained water dispersion sol was added to
2634 g of the alkaline water dispersion sol of the silicon
dioxide-stannic oxide complex colloidal particles (B1) prepared in
Preparation Example 6 with stirring. Subsequently, the sol was
passed through a column packed with 500 milliliters of an
anion-exchange resin (Amberlite (.RTM.) IRA-410, manufactured by
ORGANO CORPORATION). Subsequently, the water dispersion sol after
passing through the column was heated at 95.degree. C. for 3 hours
and concentrated by an ultrafiltration membrane method to obtain a
water dispersion sol of metal oxide particles containing titanium
oxide coated with silicon dioxide-stannic oxide complex oxide in
which an intermediate thin film layer made of zirconium oxide was
formed between the titanium oxide-containing core particles (A2)
and the silicon dioxide-stannic oxide complex-colloidal particles
(B1). The obtained water dispersion sol had a total metal oxide
concentration of 20% by mass. In transmission, electron microscope
observation of the sol, a primary particle diameter was 4 nm to 10
nm. Subsequently, the dispersion medium of the obtained water
dispersion sol was replaced with methanol by using a rotary
evaporator to obtain a methanol dispersion sol of the metal oxide
particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide in which an intermediate thin
film layer made of zirconium oxide was formed between the titanium
oxide-containing core particles (A2) and the silicon
dioxide-stannic oxide complex colloidal panicles (B1). This
methanol dispersion sol had as total metal oxide concentration of
30% by mass, a viscosity of 3.2 mPas, a DLS particle diameter of 36
nm, and a moisture content of 1.5% by mass.
Example 3
[0156] 35.8 g of zirconium oxychloride (a content of 21.19% by mass
as ZrO.sub.2, manufactured by Daiichi Kigenso Kagaku Kogyo Co.,
Ltd.) was diluted with 217 g of pure water to prepare 253 g of a
zirconium oxychloride aqueous solution (a content of 3.0% by mass
as ZrO.sub.2), and 1.331 g of the water dispersion sol of the
titanium oxide-containing core particles (A3) prepared in
Preparation Example 3 was added with stirring. Subsequently, the
water dispersion sol was hydrolyzed by heating to 95.degree. C. to
obtain a water dispersion sol of the titanium oxide-containing core
particles (A3) on the surface of which a thin film of zirconium
oxide was formed. The obtained water dispersion sol had a pH of 1.2
and a total metal oxide concentration of 20% by mass. In
transmission electron microscope observation of this sol, colloidal
particles having a primary particle diameter of 4 nm to 8 nm were
observed. The obtained water dispersion sol was added to 1090 g of
the alkaline water dispersion sol of the silicon dioxide-stannic
oxide complex colloidal particles (B1) prepared in Preparation
Example 6 with stirring. Subsequently, the sol was passed through a
column packed with 500 milliliters of an anion-exchange resin
(Amberlite (.RTM.) IRA-410, manufactured by ORGANO CORPORATION).
Subsequently, the water dispersion sol after passing through the
column was heated at 150.degree. C. for 3 hours and concentrated by
an ultrafiltration membrane method to obtain a water dispersion sol
of metal oxide particles containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide in which an
intermediate thin film layer made of zirconium oxide was formed
between the titanium oxide-containing core particles (A3) and the
silicon dioxide-stannic oxide complex colloidal particles (B1). The
obtained water dispersion sol had a total metal oxide concentration
of 20% by mass. In transmission electron microscope observation of
the sol, a primary particle diameter was 5 nm to 10 nm.
Subsequently, the dispersion medium of the obtained water
dispersion sol was replaced with methanol by using a rotary
evaporator to obtain a methanol dispersion sol of the metal oxide
particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide in which an intermediate thin
film layer made of zirconium oxide was formed between the titanium
oxide-containing core particles (A3) and the silicon
dioxide-stannic oxide complex colloidal particles (B1). This
methanol dispersion sol had a total metal oxide concentration of
30% by mass, a viscosity of 2.2 mPas, a DLS particle diameter of 22
nm, and a moisture content of 1.0% by mass.
Example 4
[0157] 35.9 g of zirconium oxychloride (a content of 21.19% by mass
as ZrO.sub.2, manufactured by Daiichi Kigenso Kagaku Kogyo Co.,
Ltd.) was diluted with 217 g of pure water to prepare 253 g of a
zirconium oxychloride aqueous solution (a content of 3.0% by mass
as ZrO.sub.2), and 1000 g of the water dispersion sol of the
titanium oxide-containing core particles (A4) prepared in
Preparation Example 4 was added with stirring. Subsequently, the
water dispersion sol was hydrolyzed by heating to 95.degree. C. to
obtain a water dispersion sol of the titanium oxide-containing core
particles (A4) on the surface of which a thin film of zirconium
oxide was formed. The obtained water dispersion sol had a pH of 1.2
and a total metal oxide concentration of 20% by mass. In
transmission electron microscope observation of this sol, colloidal
particles having a primary particle diameter of 5 nm to 15 nm were
observed. 1231 g of the obtained water dispersion sol was added to
1090 g of the alkaline water dispersion sol of the silicon
dioxide-stannic oxide complex colloidal particles (B1) prepared in
Preparation Example 6 with stirring. Subsequently, the sol was
passed through a column packed with 500 milliliters of an
anion-exchange resin (Amberlite (.RTM.) IRA-410, manufactured by
ORGANO CORPORATION). Subsequently, the water dispersion sol after
passing through the column was heated at 150.degree. C. for 3 hours
to obtain a water dispersion sol of metal oxide particles
containing titanium oxide coated with silicon dioxide-stannic oxide
complex oxide in which an intermediate thin film layer made of
zirconium oxide was formed between the titanium oxide-containing
core particles (A4) and the silicon dioxide-stannic oxide complex
colloidal particles (B1). The obtained water dispersion sol was
2877 g and had a total metal oxide concentration of 2.1% by mass.
In transmission, electron microscope observation of the sol, a
primary particle diameter was 5 nm to 18 nm. Further, the
dispersion medium of the obtained water dispersion sol was replaced
with methanol by using a rotary evaporator to obtain a methanol
dispersion sol of the metal oxide particles containing titanium
oxide coated with silicon dioxide-stannic oxide complex oxide in
which an intermediate thin film layer made of zirconium oxide was
formed between the titanium oxide-containing core particles (A1)
and the silicon dioxide-stannic oxide complex colloidal particles
(B1). This methanol dispersion sol had a concentration of 30% by
mass, a viscosity of 2.0 mPas, a DLS particle diameter of 24 nm,
and a moisture content of 0.9% by mass.
Example 5
[0158] A water dispersion sol of metal oxide particles containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide in which an intermediate thin film layer made of silicon
dioxide-antimony pentoxide complex oxide was formed between she
titanium oxide-containing core particles (A1) and the silicon
dioxide-stannic oxide complex colloidal particles (B1) was obtained
in a similar manner to Example 1, except that 1211 g of the water
dispersion sol of the silicon dioxide-antimony pentoxide complex
oxide colloidal particles prepared in Preparation Example 5 was
used instead of 500 g of the zirconium oxychloride aqueous
solution. Further, the dispersion medium of the obtained water
dispersion sol was replaced with methanol by using a rotary
evaporator to obtain a methanol dispersion sol of the metal oxide
particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide in which an intermediate thin
film layer made of silicon dioxide-antimony pentoxide complex oxide
was formed between the titanium oxide-containing core particles
(A1) and the silicon dioxide-stannic oxide complex colloidal
particles (B1). The obtained methanol dispersion sol had a
concentration of 30% by mass, a viscosity of 3.1 mPas, a DLS
particle diameter of 32 nm, and a moisture content of 1.1 % by
mass.
Example 6
[0159] A water dispersion sol of metal oxide particles containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide in which an intermediate thin film layer made of silicon
dioxide-antimony pentoxide complex oxide was formed between the
titanium oxide-containing core particles (A2) and the silicon
dioxide-stannic oxide complex colloidal particles (B1) was obtained
in a similar manner to Example 2, except that 1211 g of the water
dispersion sol of the silicon dioxide-antimony pentoxide complex
oxide colloidal particles prepared in Preparation Example 5 was
used instead of 500 g of the zirconium oxychloride aqueous
solution. Further, the dispersion medium of the obtained water
dispersion sol was replaced with methanol by using a rotary
evaporator to obtain a methanol dispersion sol of the metal oxide
particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide in which an intermediate thin
film layer made of silicon dioxide-antimony pentoxide complex oxide
was formed between the titanium oxide-containing core particles
(A2) and the silicon dioxide-stannic oxide complex colloidal
particles (B1). The obtained methanol dispersion sol had a
concentration of 30% by mass, a viscosity of 3.3 mPas, a DLS
particle diameter of 35 nm, and a moisture content of 2.0% by
mass.
Example 7
[0160] A water dispersion sol of metal oxide particles containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide in which an intermediate thin film layer made of silicon
dioxide-antimony pentoxide complex oxide was formed between the
titanium oxide-containing core particles (A3) and the silicon
dioxide-stannic oxide complex colloidal particles (B1) was obtained
in a similar manner to Example 3, except that 653 g of the water
dispersion sol of the silicon dioxide-antimony pentoxide complex
oxide colloidal particles prepared in Preparation Example 5 was
used instead of 253 g of the zirconium oxychloride aqueous
solution. Further, the dispersion medium of the obtained water
dispersion sol was replaced with methanol by using a rotary
evaporator to obtain a methanol dispersion sol of the metal oxide
particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide in which an intermediate thin
film layer made of silicon dioxide-antimony pentoxide complex oxide
was formed between the titanium oxide-containing core particles
(A3) and the silicon dioxide-stannic oxide complex colloidal
particles (B1). The obtained methanol dispersion sol had a
concentration of 30% by mass, a viscosity of 1.6 mPas, a DLS
particle diameter of 18 nm, and a moisture content of 1.1 % by
mass.
Example 8
[0161] A water dispersion sol of metal oxide particles containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide in which an intermediate thin film layer made of silicon
dioxide-antimony pentoxide complex oxide was formed between the
titanium oxide-containing core particles (A4) and the silicon
dioxide-stannic oxide complex colloidal particles (B1) was obtained
in a similar manner to Example 3, except that 653 g of the water
dispersion sol of the silicon dioxide-antimony pentoxide complex
oxide colloidal particles prepared in Preparation Example 5 was
used instead of 253 g of the zirconium oxychloride aqueous
solution. Further, the dispersion medium of the obtained water
dispersion sol was replaced with methanol by using a rotary
evaporator to obtain a methanol dispersion sol of the metal oxide
particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide in which an intermediate thin
film layer made of silicon dioxide-antimony pentoxide complex oxide
was formed between the titanium oxide-containing core particles
(A4) and the silicon dioxide-stannic oxide complex colloidal
particles (B1). The obtained methanol dispersion sol had a
concentration of 30% by mass, a viscosity of 2.4 mPas, a DLS
particle diameter of 21 nm, and a moisture content of 1.3% by
mass.
Comparative Example 1
[0162] 1150 g of the water dispersion sol of the titanium
oxide-containing core particles (A1) prepared in Preparation
Example 1 was added to 2634 g of the alkaline water dispersion sol
of the silicon dioxide-stannic oxide complex colloidal particles
(B1) prepared in Preparation Example 6 with stirring. Subsequently,
the sol was passed through a column packed with 500 milliliters of
an anion-exchange resin (Amberlite (.RTM.) IRA-410, manufactured by
ORGANO CORPORATION). Subsequently, the water dispersion sol after
passing through the column was heated at 95.degree. C. for 3 hours
and concentrated by an ultrafiltration membrane method to obtain a
water dispersion sol of metal oxide particles containing titanium
oxide coated with silicon dioxide-stannic oxide complex oxide made
of the titanium oxide-containing core particles (A1) and a coating
layer made of the silicon dioxide-stannic oxide complex colloidal
particles (B1). The obtained water dispersion sol had a total metal
oxide concentration of 16.5% by mass. In transmission electron
microscope observation of the sol, a primary particle diameter was
4 nm to 10 nm. Further, the dispersion medium of the obtained water
dispersion sol was replaced with methanol by using a rotary
evaporator to obtain a methanol dispersion sol of the metal oxide
particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide made of the titanium
oxide-containing core particles (A1) and a coating layer made of
the silicon dioxide-stannic oxide complex colloidal particles (B1).
The obtained methanol dispersion sol had a concentration of 30% by
mass, a viscosity of 3.8 mPas, a DLS particle diameter of 41 nm,
and a moisture content of 0.9% by mass.
Comparative Example 2
[0163] A water dispersion sol of metal oxide particles containing
titanium oxide coated with silicon dioxide-antimony pentoxide
complex oxide in which an intermediate thin film layer made of
zirconium oxide was formed between the titanium oxide-containing
core particles (A2) and the silicon dioxide-antimony pentoxide
complex oxide colloidal particles was obtained in a similar manner
to Example 2, except that 747 g of the alkaline water dispersion
sol of the silicon dioxide-antimony pentoxide complex oxide
colloidal particles prepared in Preparation Example 5 was used
instead of 1090 g of the alkaline water dispersion sol of the
silicon dioxide-stannic oxide complex colloidal particles (B1)
prepared in Preparation Example 6. In transmission electron
microscope observation of the sol, a primary particle diameter was
4 nm to 10 nm. Further, the dispersion medium of the obtained water
dispersion sol was replaced with methanol by using a rotary
evaporator to obtain a methanol dispersion sol of the metal oxide
particles containing titanium oxide coated with silicon
dioxide-antimony pentoxide complex oxide in which an intermediate
thin film layer made of zirconium oxide was formed between the
titanium oxide-containing core particles (A2) and the silicon
dioxide-antimony pentoxide complex oxide colloidal particles. The
obtained methanol dispersion sol had a concentration of 30% by
mass, a viscosity of 3.4 mPas, a DLS particle diameter of 44 nm,
and a moisture content of 0.7% by mass.
Comparative Example 3
[0164] 1666 g of the water dispersion sol of the titanium
oxide-containing core particles (A3) prepared in Preparation
Example 3 was added to 1317 g of the alkaline water dispersion sol
of the silicon dioxide-stannic oxide complex colloidal particles
(B1) prepared in Preparation Example 6 with stirring. Subsequently,
the sol was passed through a column packed with 500 milliliters of
an anion-exchange resin (Amberlite (.RTM.) IRA-410, manufactured by
ORGANO CORPORATION). Subsequently, the water dispersion sol after
passing through the column was heated at 95.degree. C. for 3 hours
and concentrated by an ultrafiltration membrane method to obtain a
water dispersion sol of metal oxide particles containing titanium
oxide coated with silicon dioxide-stannic oxide complex oxide made
of the titanium oxide-containing core particles (A3) and a coating
layer made of the silicon dioxide-stannic oxide complex colloidal
particles (B1). The obtained water dispersion sol had a total metal
oxide concentration of 16.8% by mass. In transmission electron
microscope observation of the sol a primary particle diameter was 5
nm to 10 nm. Further, the dispersion medium of the obtained water
dispersion sol was replaced with methanol by using a rotary
evaporator to obtain a methanol dispersion sol of the metal oxide
particles containing titanium oxide coated with silicon
dioxide-stannic oxide complex oxide made of the titanium
oxide-containing core particles (A3) and a coating layer made of
the silicon dioxide-stannic oxide complex colloidal particles (B1).
The obtained methanol dispersion sol had a concentration of 30% by
mass, a viscosity of 1.6 mPas, a DLS particle diameter of 13 nm,
and a moisture content of 2.5% by mass.
Comparative Example 4
[0165] A water dispersion sol of metal oxide particles containing
titanium oxide coated with silicon dioxide-antimony pentoxide
complex oxide in which an intermediate thin film layer made of
zirconium oxide was formed between the titanium oxide-containing
core particles (A4) and the silicon dioxide-antimony pentoxide
complex oxide colloidal particles was obtained in a similar manner
to Example 4, except that 747 g of the alkaline water dispersion
sol of the silicon dioxide-antimony pentoxide complex oxide
colloidal particles prepared in Preparation Example 5 was used
instead of 1090 g of the alkaline water dispersion sol of the
silicon dioxide-stannic oxide complex colloidal particles (B1)
prepared in Preparation Example 6. In transmission electron
microscope observation of the sol, a primary particle diameter was
5 nm to 18 nm. Further, the dispersion medium of the obtained water
dispersion sol was replaced with methanol by using a rotary
evaporator to obtain a methanol dispersion sol of the metal oxide
particles containing titanium oxide coated with silicon
dioxide-antimony pentoxide complex oxide in which an intermediate
thin film layer made of zirconium oxide was formed between the
titanium oxide-containing core particles (A4) and the silicon
dioxide-antimony pentoxide complex oxide colloidal particles. The
obtained methanol dispersion sol had a concentration of 30% by
mass, a viscosity of 2.1 mPas, a DLS particle diameter of 1.8 nm,
and a moisture content of 1.7% by mass.
Example 9
[0166] To a container made of glass and equipped with a magnetic
stirrer, 55.8 parts by mass of
.gamma.-glycidoxypropyltrimethoxysilane was added, and then 19.5
parts by mass of 0.01 N hydrochloric acid was added dropwise over 3
hours with stirring. After the dropwise addition, the mixture was
stirred for 0.5 hours to obtain a partially hydrolysate of
.gamma.-glycidoxypropyltrimethoxysilane. Subsequently, to 75.3
parts by mass of the partially hydrolysate of
.gamma.-glycidoxypropyltrimethoxysilane, 151.0 parts by mass of the
methanol dispersion sol of the metal oxide particles containing
titanium oxide coated with silicon dioxide-stannic oxide complex
oxide in which the intermediate thin film layer made of zirconium
oxide was formed between the titanium oxide-containing core
particles (A1) and the silicon dioxide-stannic oxide complex
colloidal particles (B1) (a content of 30% by mass in terms of the
total metal oxide) obtained in Example 1, 65 parts by mass of butyl
cellosolve, and further 0.9 parts by mass of aluminum
acetylacetonate as a curing agent were added and the mixture was
sufficiently stirred. Thereafter, the mixture was filtered to
prepare a coating liquid for forming a transparent coating film.
151.0 parts by mass of a commercially available water dispersed
emulsion polyurethane (SUPERFLEX (.RTM.) 170, manufactured by
Dai-ichi Kogyo Seiyaku Co., Ltd., a solid content concentration of
30% by mass) and 74 parts by mass of pore water were mixed to
prepare a coating liquid for a foundation layer.
[0167] (Formation of Cured Film)
[0168] A commercially available polycarbonate plate having a
refractive index of n.sub.D=1.59 was prepared, and first the
coating composition for a foundation layer was applied by a spin
coating method and the applied composition was treated by heating
at 100.degree. C. for 30 minutes to form a coating film. Further,
the coating liquid for forming a transparent coating film was
applied and the applied coating liquid was subjected to heat
treatment at 120.degree. C. for 2 hours to cure the coating film.
Evaluation results are shown in Table 1.
Example 10
[0169] Preparation was carried out in a similar manner to Example
10, except that 151.5 parts by mass of the methanol dispersion sol
of the metal oxide particles containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide (a content of 30% by
mass in terms of the total metal oxide) in which the intermediate
thin film layer made of zirconium oxide was formed between the
titanium oxide-containing core particles (A2) and the silicon
dioxide-stannic oxide complex colloidal particles (B1) obtained In
Example 2 was used. Evaluation results are shown in Table 1.
Example 11
[0170] Preparation was carried out in a similar manner to Example
10, except that 151 parts by mass of the methanol dispersion sol of
the metal oxide particles containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide (a content of 30% by
mass in terms of the total metal oxide) in which the intermediate
thin film layer made of zirconium oxide was formed between the
titanium oxide-containing core particles (A3) and the silicon
dioxide-stannic oxide complex colloidal particles (B1) obtained in
Example 3 was used. Evaluation results are shown in Table 1.
Example 12
[0171] A water dispersion sol of the metal oxide particles
containing titanium oxide coated with silicon, dioxide-stannic
oxide complex oxide in which the intermediate thin film layer made
of zirconium oxide was formed between the titanium oxide-containing
core particles (A4) and the silicon dioxide-stannic oxide complex
colloidal particles (B1) was obtained. Preparation was carried out
in a similar manner to Example 10, except that 151 parts by mass of
the obtained dispersion sol (a content of 30% by mass in terms of
the total metal oxide) was used. Evaluation results are shown in
Table 1.
Example 13
[0172] Preparation was carried out in a similar manner to Example
10. except that 151 parts by mass of the water dispersion sol of
the metal oxide particles containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide in which the
intermediate thin film layer made of silicon dioxide-antimony
pentoxide complex oxide was formed between the titanium
oxide-containing core particles (A1) and the silicon
dioxide-stannic oxide complex colloidal particles (B1) (a content
of 30% by mass in terms of the total metal oxide) obtained in
Example 5 was used. Evaluation results are shown in Table 1.
Example 14
[0173] Preparation was carried out in a similar manner to Example
10, except that 151 parts by mass of the water dispersion sol of
the metal oxide particles containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide in which the
intermediate thin film layer made of silicon dioxide-antimony
pentoxide complex oxide was formed between the titanium
oxide-containing core particles (A2) and the silicon
dioxide-stannic oxide complex colloidal particles (B1) (a content
of 30% by mass in terms of the total metal oxide) obtained in
Example 6 was used.
Example 15
[0174] Preparation was carried out in a similar manner to Example
10, except that 151 parts by mass of the water dispersion sol of
the metal oxide particles containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide in which the
intermediate thin film layer made of silicon dioxide-antimony
pentoxide complex oxide was formed between the titanium
oxide-containing core particles (A3) and the silicon
dioxide-stannic oxide complex colloidal particles (B1) (a content
of 30% by mass in terms of the total metal oxide) obtained in
Example 7 was used. Evaluation results are shown in Table 1.
Example 16
[0175] Preparation was carried out in a similar manner to Example
10, except that 151 parts by mass of the water dispersion sol of
the metal oxide particles containing titanium oxide coated with
silicon dioxide-stannic oxide complex oxide in which the
intermediate thin film layer made of silicon dioxide-antimony
pentoxide complex oxide was formed between the titanium
oxide-containing core particles (A4) and the silicon
dioxide-stannic oxide complex colloidal particles (B1) (a content
of 30% by mass in terms of the total metal oxide) obtained in
Example 8 was used. Evaluation results are shown in Table 1.
Comparative Example 5
[0176] Preparation was carried out using the sol prepared in
Comparative Example 1 instead of the sol used in Example 10.
Evaluation results are shown in Table 1.
Comparative Example 6
[0177] Preparation was carried out using the sol prepared in
Comparative Example 2 instead of the sol used in Example 10.
Evaluation results are shown in Table 1.
Comparative Example 7
[0178] Preparation was carried out using the sol prepared in
Comparative Example 3 instead of the sol used in Example 10.
Evaluation results are shown in Table 1.
Comparative Example 8
[0179] Preparation was carried out using the sol prepared in
Comparative Example 4 instead of the sol used in Example 10.
Evaluation results are shown in Table 1.
[0180] Various properties of optical members having a cured film
obtained in Examples and Comparative Examples were measured by the
following measurement methods.
[0181] (1) Weatherability Test
[0182] Exposure to the obtained optical members was carried out
under a high-pressure mercury lamp (manufactured by ORC
MANUFACTURING CO., LTD., UV-800) for 100 hours. Change in
appearance of the optical members after exposure was visually
determined.
A: No change in color at all B: Almost no change in color C:
Extreme change in color (2) Crack resistance test
[0183] Appearance of the test specimens used in the light stability
test (1) was visually observed and determined.
A: No crack generation B: Almost no crack generation C: Slight
crack generation D: Crack generation in entire surface
(3) Scratch Resistance Test
[0184] The surface of the cured film was scratched with a steel
wool No. 0000 and difficulty of scratch generation was visually
determined. Criteria are as follows.
A: No scratches are observed B: Slight scratches are observed C:
Many of remarkable scratches are observed
(4) Transparency Test
[0185] In a dark room, whether cloudiness in the cured film exists
or not was visually determined under fluorescent light. Criteria
are as follows.
A: Almost no cloudiness is generated B: Cloudiness is generated but
does not cause problem as the transparent cured film C: Remarkable
whitening is generated. (5) Long term Stability Test
[0186] Each coating liquid for forming a transparent coating film
prepared in Examples 9 to 16 and Comparative Examples 5 to 8 was
stored at 10.degree. C. for 60 days, and thereafter, transparent
coating films were formed in similar manners to Examples 9 to 16
and Comparative Examples 5 to 8 and the weatherability test (1) of
the transparent coating films was carried out. Deference between
the transparent coating film formed just after preparing the
coating liquid for forming a transparent coating film and the
transparent coating film formed from the coating liquid after
storing at 10.degree. C. at 60 days was evaluated in three steps of
A, B, and C.
A: No difference is observed B: Slight decrease in performance is
observed C: Obvious decrease in performance is observed
TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3 Example 4
Example 5 Example 6 Core particles (A) TiO.sub.2--SnO.sub.2
TiO.sub.2--ZrO.sub.2--SnO.sub.2 TiO.sub.2 TiO.sub.2
TiO.sub.2--SnO.sub.2 TiO.sub.2--ZrO.sub.2--SnO.sub.2 Intermediate
layer ZrO.sub.2 ZrO.sub.2 ZrO.sub.2 ZrO.sub.2
Sb.sub.2O.sub.2--SiO.sub.2 Sb.sub.2O.sub.2--SiO.sub.2 Coating layer
(D) SnO.sub.2--SiO.sub.2 SnO.sub.2--SiO.sub.2 SnO.sub.2--SiO.sub.2
SnO.sub.2--SiO.sub.2 SnO.sub.2--SiO.sub.2 SnO.sub.2--SiO.sub.2
TiO.sub.2 in core particles (A) (% 10.5 39.9 100 100 10.5 39.9 by
mass) (B)/(A) (% by mass) 34.5 34.5 35.8 35.7 34.5 34.5 Crystal
type of core particles Rutile Rutile/ Anatase Rutile Rutile Rutile/
(A) Anatase Anatase Primary particle diameter (nm) 4-10 4-10 5-10
5-18 4-10 4-10 Comparative Comparative Comparative Comparative
Example 7 Example 8 Example 1 Example 2 Example 3 Example 4 Core
particles (A) TiO.sub.2 TiO.sub.2 TiO.sub.2--SnO.sub.2
TiO.sub.2--ZrO.sub.2--SnO.sub.2 TiO.sub.2 TiO.sub.2 Intermediate
layer Sb.sub.2O.sub.2--SiO.sub.2 Sb.sub.2O.sub.2--SiO.sub.2 None
ZrO.sub.2 None ZrO.sub.2 Coating layer (D) SnO.sub.2--SiO.sub.2
SnO.sub.2--SiO.sub.2 SnO.sub.2--SiO.sub.2
Sb.sub.2O.sub.2--SiO.sub.2 SnO.sub.2--SiO.sub.2
Sb.sub.2O.sub.2--SiO.sub.2 TiO.sub.2 in core particles (A) (% 100
100 10.5 39.9 100 100 by mass) (B)/(A) (% by mass) 35.8 35.7 34.5
34.5 35.8 35.7 Crystal type of core particles Anatase Rutile Rutile
Rutile/ Anatase Rutile (A) Anatase Primary particle diameter (nm)
5-10 5-18 4-10 4-10 5-10 5-18 Example Example Example Evaluation
result Example 9 10 11 12 Example 13 Example 14 Weatherability A A
A A A A Crack resistance A A A A A A Scratch resistance A A A A A A
Transparency A A A A A A Long term stability A A A A A A Example
Example Comparative Comparative Comparative Comparative Evaluation
result 15 16 Example 5 Example 6 Example 7 Example 8 Weatherability
A A B A C B Crack resistance A A B C C A Scratch resistance A A A C
A C Transparency A A A A A A Long term stability A A B A B A
[0187] Examples of 1 to 8 of the present invention showed excellent
scratch resistance, adhesion, transparency, and weatherability.
Comparative Examples 1 to 4 showed insufficient scratch resistance,
transparency, and weatherability.
* * * * *