U.S. patent application number 11/655214 was filed with the patent office on 2007-05-24 for particles, aqueous dispersion and film of titanium oxide, and preparation thereof.
This patent application is currently assigned to SHOWA DENKO K.K.. Invention is credited to Tadashi Hamanaka, Hidenori Nakamura, Masahiro Ohmori.
Application Number | 20070116954 11/655214 |
Document ID | / |
Family ID | 26470602 |
Filed Date | 2007-05-24 |
United States Patent
Application |
20070116954 |
Kind Code |
A1 |
Ohmori; Masahiro ; et
al. |
May 24, 2007 |
Particles, aqueous dispersion and film of titanium oxide, and
preparation thereof
Abstract
An aqueous titanium oxide-dispersed sol comprising titanium
oxide particles dispersed in water, said sol comprising chloride
ions in an amount of 50 to 10,000 ppm by weight as the chlorine
element. Titanium tetrachloride is hydrolyzed to form an aqueous
titanium oxide-dispersed sol and the chloride ion concentration
thereof is controlled. Another aqueous titanium oxide-dispersed sol
comprising brookite-type titanium oxide particles dispersed in
water, said titanium oxide particles having an average particle
size of not more than 0.5 .mu.m and a specific surface area of not
less than 20 m.sup.2/g. Addition of titanium tetrachloride to hot
water at 75 to 100.degree. C. followed by hydrolysis at 75.degree.
C. to the boiling point of the mixture.
Inventors: |
Ohmori; Masahiro;
(Ichihara-shi, JP) ; Hamanaka; Tadashi;
(Ichihara-shi, JP) ; Nakamura; Hidenori;
(Kawasaki-shi, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W.
SUITE 800
WASHINGTON
DC
20037
US
|
Assignee: |
SHOWA DENKO K.K.
|
Family ID: |
26470602 |
Appl. No.: |
11/655214 |
Filed: |
January 19, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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|
10753567 |
Jan 9, 2004 |
|
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11655214 |
Jan 19, 2007 |
|
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|
09758202 |
Jan 12, 2001 |
6774147 |
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10753567 |
Jan 9, 2004 |
|
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08921343 |
Aug 29, 1997 |
6340711 |
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09758202 |
Jan 12, 2001 |
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Current U.S.
Class: |
428/402 ;
423/610; 428/432; 428/537.1; 428/537.5; 428/702 |
Current CPC
Class: |
C01P 2004/64 20130101;
C03C 2218/113 20130101; C09C 1/3607 20130101; C04B 41/5041
20130101; Y10T 428/31993 20150401; C04B 2111/00827 20130101; C01G
23/0532 20130101; C03C 2217/212 20130101; C01G 23/047 20130101;
C04B 2111/0081 20130101; C01P 2006/12 20130101; C03C 2217/213
20130101; Y10T 428/2982 20150115; Y10T 428/31989 20150401; B01J
21/063 20130101; C01G 23/0536 20130101; B82Y 30/00 20130101; C03C
2217/23 20130101; C04B 41/87 20130101; C03C 17/256 20130101; C04B
41/009 20130101; C01P 2004/50 20130101; C01P 2004/62 20130101; C01P
2006/21 20130101; C03C 2217/71 20130101; C04B 41/5041 20130101;
C04B 41/4525 20130101; C04B 41/009 20130101; C04B 35/10 20130101;
C04B 41/009 20130101; C04B 35/00 20130101; C04B 41/009 20130101;
C04B 35/48 20130101 |
Class at
Publication: |
428/402 ;
423/610; 428/702; 428/537.1; 428/537.5; 428/432 |
International
Class: |
C01G 23/047 20060101
C01G023/047; B32B 18/00 20060101 B32B018/00; B32B 17/06 20060101
B32B017/06 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 30, 1996 |
JP |
8-230776 |
May 27, 1997 |
JP |
9-137192 |
Claims
1-26. (canceled)
27. An aqueous titanium oxide-dispersed sol comprising titanium
oxide particles dispersed in water, said sol comprising chloride
ions in an amount of 50 to 10,000 ppm by weight as the chlorine
element.
28. The aqueous titanium oxide-dispersed sol according to claim 27,
wherein said titanium oxide particles are crystalline and have an
average particle size of 0.01 to 0.1 .mu.m.
29. The aqueous titanium oxide-dispersed sol according to claim 27,
wherein said titanium oxide particles are contained in an amount of
0.05 to 10 mol/l.
30. The aqueous titanium oxide-dispersed sol according to any of
the claim 27, wherein said sol contains a water-soluble polymer in
an amount of 10 to 10,000 ppm by weight.
31. The aqueous titanium oxide-dispersed sol according to any of
the claims 27, wherein said sol further contains alkyl silicate as
an adhesive in an amount as silicon oxide of 1 to 50% by weight
based on the weight of titanium oxide.
32. A titanium oxide film which is formed on a substrate using the
aqueous titanium oxide-dispersed sol as set forth in claims 27 to
31.
33. The titanium oxide film according to claim 32, wherein said
substrate is of a heat resistant material such as a glass, a
ceramic and a metal or is one selected from the group consisting of
synthetic resins, paper and wood.
34. The titanium oxide film according to claim 32, wherein said
substrate is glass.
35. The titanium oxide film according to claim 32, wherein said
titanium oxide film is a sintered film.
36. A catalyst comprising titanium dioxide particles according to
claim 27 is formed on a catalyst carrier.
37. The catalyst according to claim 36, wherein said catalyst
carrier is selected from the group consisting of alumina and
zirconia.
38. A glass tube of an illuminator on which a film of said titanium
dioxide particles according to claim 27 is formed.
39. A plastic cover of an illuminator on which a film of said
titanium particles according to claim 27 is formed.
40. A window pane of a building on which a film of said titanium
dioxide particles according to claim 27 is formed.
41. A wall of a building on which a film of said titanium dioxide
particles according to claim 27 is formed.
Description
[0001] This is a divisional of application Ser. No. 10/753,567
filed Jan. 9, 2004, which is a divisional of application Ser. No.
09/758,202 filed Jan. 12, 2001, now U.S. Pat. No. 6,774,147, which
is a divisional of application Ser. No. 08/921,343 filed Aug. 29,
1997, now U.S. Pat. No. 6,340,711, the disclosures of which are
incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to an aqueous titanium
oxide-dispersed sol, a titanium oxide film formed on a substrate of
a ceramic, a synthetic resin or the like from said sol, specific
titanium oxide particles, and a process for preparing an aqueous
titanium oxide-dispersed sol. The titanium oxide film of the
present invention is transparent and is excellent in photocatalytic
activity and adhesion to a substrate.
[0004] 2. Description of the Related Art
[0005] It is known that titanium dioxide (hereinafter simply
referred to as "titanium oxide") has three crystal phases, the
anatase, the brookite and the rutile type. When titanium oxide is
formed by combustion of titanium tetrachloride with oxygen in a
vapor phase deposition process, anatase-type titanium oxide is
formed and is stable at the lowest temperature. When the thus
formed anatase-type titanium oxide is heat treated and the
temperature is raised, brookite-type titanium oxide is formed at a
temperature of 816 to 1040.degree. C. and rutile-type titanium
oxide is formed at a temperature higher than 1040.degree. C.
[0006] Concerning a liquid process, the crystal phases of titanium
oxide formed by hydrolysis of titanium tetrachloride are reported
in detail by Kouemon Funaki in "Kogyo Kagaku (Industrial
Chemistry)" Vol. 59, No. 11, p 1295. This report concluded that
rutile-type titanium oxide is formed mainly from a high
concentration solution and anatase-type titanium oxide is formed
from a low concentration solution. It was reported that formation
of fine brookite-type titanium oxide particles in an liquid phase
process was impossible.
[0007] As seen from the above, it was difficult to stably produce
brookite-type titanium oxide in a liquid phase process. If the
titanium oxide formed in a heated process is further heat treated
at a high temperature, brookite-type titanium oxide may be obtained
but the obtained titanium oxide particles have been grown by the
heat treatment. Therefore, it was difficult to obtain fine
brookite-type titanium oxide crystal particles.
[0008] As for the process for forming a titanium oxide sol, it is
generally true that crystalline or amorphous titanium oxide
particles are dispersed in a dispersing medium, or a titanium oxide
precursor such as methane alkoxide, titanium sulfate or titanium
tetrachloride is mixed into a dispersing medium, followed by
neutralization or hydrolysis of the precursor, to form a titanium
oxide sol.
[0009] A titanium oxide sol is used for producing titanium oxide
particles or for forming a titanium oxide film by coating the sol
on a glass or ceramic.
[0010] It is known that a titanium oxide sol is a
photosemiconductor and has a transparency and an increased
photocatalytic activity when its particle size is small. The
photocatalytic activity of titanium oxide has recently been
investigated throughly. The applications of the photocatalytic
activity include removing harmful materials for cleaning, removing
odor such as ammonia for deodorization, and sterilization of
microorganisms. Titanium oxide is used in various forms such as a
bulk, particles, a film and a sol, depending on the types of the
applications. When the photocatalytic activity is to be combined
with the transparency, the titanium oxide is often formed as a
film. Accordingly, the titanium oxide is often used in the form of
a sol for forming a film.
[0011] It is recognized that the photocatalytic activity of
titanium oxide is higher in the rutile-type than in the
anatase-type. The reason is a difference of energy gap of about 0.2
eV between the two types, as the energy gap of the rutile-type is
3.02 eV and that of the anatase is 3.23 eV (see Ceramics 31 (1996),
No. 10, p 817). Because of this energy gap, the anatase-type
titanium oxide is preferably used as a photosemiconductor.
[0012] As of the brookite-type titanium oxide, a pure material of
brookite-type titanium oxide has not been obtained, and it was
difficult to obtain fine particles of brookite-type titanium oxide
having such a high specific surface area that they can be used as a
photosemiconductor since the particles of brookite-type titanium
oxide are prepared at such a high temperature that they are
sintered.
[0013] It has been proposed that when a titanium oxide film is
formed on an illuminator, for example, a glass tube of a
fluorescent lump or a cover thereof, by coating it with a titanium
oxide sol, organic materials such as oil smoke, when adhered
thereto, are decomposed by the photocatalytic activity of the
titanium oxide.
[0014] However, the sols produced by the processes described before
rarely provide a titanium oxide film having a high transparency and
an illuminator having a brookite-type titanium oxide film as the
photocatalyst has not been known.
[0015] When a titanium oxide film is used as the photocatalyst by
forming it on a glass, plastic or other substrate, it is required
that the titanium oxide film has a high photocatalytic activity.
Since the photocatalyst action is a reaction on the surface of
particles, the particles should be fine particles having a high
specific surface area and have an excellent crystillinity to obtain
a high photocatalytic activity. It is also required that the film
is transparent when the film is applied to an illuminator. To
improve the transparency, it is desired that the particles are fine
and monodispersed, as in the case of improving photocatalytic
activity. Conventionally, the anatase-type titanium oxide is used
and is made fine to solve the above problems.
[0016] It is also required that the titanium oxide film have a high
adhesivity and peeling of the titanium oxide film should be
prevented when it is formed on a substrate.
[0017] In the conventional process of hydrolyzing titanium
tetrachloride, it was difficult to obtain a titanium oxide sol
having a very small particle size and an excellent crystallinity of
the titanium oxide particles in the sol and providing a high
transparency when formed into a film.
[0018] In the process of hydrolyzing titanium alkoxide, the
particles of the obtained titanium oxide sol are excellent in
powder characteristics including very fine particle size, but the
sol includes alcohol, which involves a safety problem that
explosion may be caused when the sol is heated to form a titanium
film. To prevent the explosion, a large scale apparatus for
preventing the explosion is required and it is economically
disadvantageous. Further, titanium alkoxide is much more expensive
than titanium tetrachloride.
[0019] The object of the present invention is to provide a titanium
oxide sol which can provide, on a substrate, a titanium oxide film
excellent in photocatalytic activity and transparency as well as
adhesion to the substrate, and to provide fine brookite-type
titanium oxide particles.
SUMMARY OF THE INVENTION
[0020] As the result of investigation into titanium oxide films
formed from titanium oxide sols, the present inventors have found
that chloride ions contained in a titanium oxide sol contribute to
the transparency and adhesivity to the substrate of the titanium
oxide film; a titanium oxide sol having a certain concentration of
chloride ions provides a titanium oxide film having improved
transparency and adhesivity; and the brookite-type titanium oxide
with a large energy gap is particularly excellent in the
photocatalytic activity.
[0021] In accordance with the present invention, the following is
provided.
[0022] (1) An aqueous titanium oxide-dispersed sol comprising
titanium oxide particles dispersed in water, said sol comprising
chloride ions in an amount of 50 to 10,000 ppm by weight as the
chlorine element.
[0023] (2) An aqueous titanium oxide-dispersed sol comprising
brookite-type titanium oxide particles dispersed in water, said
titanium oxide particles having an average particle size of not
more than 0.5 .mu.m and a specific surface area of not less than 20
m.sup.2/g.
[0024] (3) Brookite-type titanium oxide particles having an average
particle size of not more than 0.5 .mu.m and a specific surface
area of not less than 20 m.sup.2/g.
[0025] (4) A titanium oxide film which is formed on a substrate
using the aqueous titanium oxide-dispersed sol as set forth in the
above (1) or (2).
[0026] (5) A process for preparing an aqueous titanium
oxide-dispersed sol, comprising the steps of:
[0027] forming an aqueous titanium oxide-dispersed sol by
hydrolysis of titanium tetrachloride, and
[0028] controlling an amount of chloride ions in said aqueous
titanium oxide-dispersed sol to 50 to 10,000 ppm by weight as the
chlorine element.
[0029] (6) A process for preparing an aqueous titanium
oxide-dispersed sol, comprising the steps of:
[0030] adding titanium tetrachloride to hot water at a temperature
of 75 to 100.degree. C., and
[0031] hydrolyzing the titanium tetrachloride at a temperature in a
range of 75.degree. C. to a boiling point of the solution or sol,
to form an aqueous sol of brookite-type titanium oxide
particles.
[0032] (7) A process for preparing brookite-type titanium oxide
particles, in which the aqueous sol of brookite-type titanium oxide
particles of the above (6) is filtered and dried.
BRIEF DESCRIPTION OF THE DRAWING
[0033] The FIGURE shows a reactor equipped with a reflux cooler,
which is used for producing a titanium oxide sol in an example of
the present invention.
DESCRIPTIONS OF THE PREFERRED EMBODIMENTS
[0034] A first aqueous titanium oxide-dispersed sol of the present
invention is a sol which provides a titanium oxide film having not
only excellent photocatalytic activity but also increased adhesion
to a substrate and transparency, and is characterized by containing
chloride ions in an amount of 50 to 10,000 ppm, preferably 100 to
4,000 ppm as the chlorine element.
[0035] In the process of hydrolyzing titanium chloride to obtain an
aqueous titanium oxide-dispersed sol, hydrogen chloride is formed
by the reaction. The hydrogen chloride is almost dissociated to
chloride ion and hydrogen ion in the sol. In general, the hydrogen
chloride escapes from the reaction system during the hydrolysis
under heating. Further, when hydrogen chloride in the sol increases
to a certain level in the hydrolysis, dechlorination treatment is
usually carried out on the sol to remove hydrogen chloride, since
if the sol contains hydrogen chloride, various problems occur in
obtaining titanium oxide particles or a titanium oxide film from
the sol. The relationship between the chloride ions in the sol and
the characteristics of the titanium oxide film have not been
considered in the prior art and there is no technology which
controls the chloride ions in the sol from this viewpoint.
[0036] If the chloride ions contained in the aqueous titanium
oxide-dispersed sol are in an amount of less than 50 ppm as the
chlorine element, the titanium oxide film formed on a substrate
from the sol has poor adhesion to the substrate. Particularly when
the titanium oxide film is heat treated, a difference in the
adhesion of the film to the substrate, depending on whether or not
the chloride ions are contained in an amount of not less than 50
ppm, appears. In the present invention, the adhesion of the film to
a substrate is represented by the peeling force of the film from
the substrate and the hardness of the film. On the other hand, if
the amount of the chloride ions in the sol increases to more than
10,000 ppm as the chlorine element, the transparency of the film is
reduced. A preferable range is 100 to 4,000 ppm.
[0037] The action of the chloride ions is not clear, but it is
supposed that as the electrical repulsion between titanium oxide
particles increases in the titanium oxide sol, the dispersibility
of the particles is improved so that the transparency and peeling
strength of the film are improved.
[0038] As the titanium oxide particles in the aqueous titanium
oxide-dispersed sol are finer, the photocatalytic activity and the
transparency of the titanium oxide film are improved. It is
preferable from the photocatalytic activity that the titanium oxide
particles are crystalline. However, if the particle size of the
titanium oxide particles is too small, such particles are difficult
to produce. Accordingly, an average particle size of titanium oxide
particles in a sol is preferably in a range of 0.01 to 0.1
.mu.m.
[0039] A second aqueous titanium oxide-dispersed sol of the present
invention is a sol which provides a titanium oxide film having
improved photocatalytic activity and transparency and is
characterized in that the titanium oxide particles dispersed in
water are brookite-type titanium oxide particles having an average
particle size of not more than 0.5 .mu.m, preferably 0.01 to 0.1
.mu.m and a specific surface area of not less than 20 m.sup.2/g.
The brookite-type titanium oxide particles have an energy gap of
3.23 eV or more.
[0040] As to the particle size of the titanium oxide particles, it
is preferable for the transparency that the titanium oxide
particles are monodispersant with an average particle size of not
more than 0.5 .mu.m, preferably 0.01 to 0.1 .mu.m. Even if the
specific surface area of the particles is large, agglomerates of
primary particles do not provide a transparent film of titanium
oxide.
[0041] In the prior art, the brookite-type titanium oxide cannot be
produced except by a process in which anatase-type titanium oxide
is heat treated. If the brookite-type titanium oxide is produced by
the heat treatment, the brookite-type titanium oxide particles are
grown to a large particle size by the heat treatment, which
therefore has not been used to form a titanium oxide film.
[0042] In a sol in which the above brookite-type titanium oxide
particles are dispersed in water, the chloride ions may be
contained in an amount of 50 to 10,000 ppm as the chlorine element,
by which the titanium oxide film formed from the sol can be
excellent not only in photocatalytic activity but also in adhesion
to a substrate.
[0043] In the above first and second aqueous titanium
oxide-dispersed sols of the present invention, if the concentration
of the titanium oxide particles is too high, the particles
agglomerate and the sol becomes unstable. If the concentration of
the titanium oxide particles is too low, there are often problems.
For example, the step of forming a titanium oxide film by coating
takes a long time. Therefore, the concentration of the titanium
oxide particles is appropriate in a range of 0.05 to 10 mol/l.
[0044] By filtering, washing and drying the aqueous titanium
oxide-dispersed sol of the present invention, titanium oxide
particles can be obtained. The brookite-type titanium oxide
particles thus obtained have an average particle size of not more
than 0.5 .mu.m, preferably 0.01 to 0.1 .mu.m and a specific surface
area of not less than 20 m.sup.2/g. They have an energy gap of 3.23
eV or more.
[0045] When the aqueous titanium oxide-dispersed sol is used to
form a titanium oxide film, it is preferred that a water-soluble
polymer is added in a small amount, for example, about 10 to 10,000
ppm, to improve the film-forming capability or coatability thereof.
Preferable water-soluble polymers include polyvinylalcohol,
methylcellulose, ethylecellulose, CMC, starch, etc.
[0046] The aqueous titanium oxide-dispersed sol of the present
invention can be coated on a substrate of various materials to form
a titanium oxide film on the surface of the substrate. The
substrate is not limited and may be ceramic, metal, plastic, wood,
paper, etc.
[0047] The substrate may be a catalyst carrier of alumina,
zirconia, etc. on which the titanium oxide film be provided as a
catalyst, by which a catalyst is produced. Also, the substrate may
be a glass tube or a plastic cover of an illuminator such as a
fluorescent lamp, on which the titanium oxide film can be formed.
This titanium oxide film is transparent and has a photocatalytic
activity, so that the film can decompose organic materials such as
oil smoke without shielding the light, which is therefore useful to
prevent dirt of a glass tube or a plastic cover. If such a titanium
oxide film is formed on a window pane or wall of a building, dirt
on the pane or wall can be also prevented. If the film is provided
on a window pane or wall of a tall building, the necessity of
cleaning can be removed or reduced so that it is useful to reduce
cost for maintenance of the building.
[0048] The methods for applying an aqueous titanium oxide-dispersed
sol to a substrate include immersion of a substrate in a sol,
spraying a sol onto a substrate, brush coating a sol on a
substrate, and so on. The thickness of the applied sol is
appropriately 0.01 to 0.2 mm. After the application of the sol to a
substrate, the water content of the sol is removed by drying to
obtain a titanium oxide film. This film may be used as a catalyst,
etc., as mentioned above.
[0049] When the substrate is of a heat resistant material, for
example, glass, the titanium oxide film formed on the substrate may
be heat treated. By this heat treatment, the film may be adhered to
the substrate more strongly and have a higher hardness. The
temperature of heat treatment is preferably not less than
200.degree. C. The upper limit of the heat treatment is not
particularly set and can be determined based on the heat resistance
of the substrate. However, the hardness and the adhesive force to
the substrate of the film do not increase even if the temperature
is very high. Therefore, a temperature up to about 800.degree. C.
is appropriate. In the case of brookite-type titanium oxide, a
temperature of not higher than 700.degree. C. is appropriate to
maintain the crystal phase of brookite-type titanium oxide.
[0050] Alternatively, the adhesive force of the transparent
titanium oxide film to the substrate can be increased without heat
treatment, by adding an appropriate adhesive to an aqueous titanium
oxide-dispersed sol of the present invention. An appropriate
adhesive includes an organic silica-containing compound such as
alkylsilicate. The amount of the adhesive may be in an amount (as
SiO.sub.2) of 1 to 50% by weight of the titanium oxide of the
titanium oxide sol. If the amount of the adhesive is less than 1%
by weight, the desired effect cannot be obtained. If the amount of
the adhesive is more than 50% by weight, a very high adhesion can
be obtained but the photocatalytic activity of the film is lost as
the titanium oxide particles are covered by the adhesive, which is
not preferable. The adhesive may be added to the sol just prior to
use (application or coating) or may be previously added when the
sol is prepared, considering the nature of the adhesive.
[0051] The atmosphere of the heat treatment is not particularly
limited and may be air. The time for the heat treatment is not
particularly limited and may be, for example, 1 to 60 minutes. The
titanium oxide film obtained after the heat treatment is about 0.05
to 1.0 .mu.m in thickness when the sol is applied in an amount as
mentioned above.
[0052] The preparation of the aqueous titanium oxide-dispersed sol
of the present invention is described below.
[0053] The process for preparing the first aqueous titanium
oxide-dispersed sol of the present invention is not particularly
limited as long as the prepared sol contains chloride ions in the
above-mentioned amount. For example, titanium alkoxide can be
hydrolyzed to form an aqueous titanium oxide-dispersed sol
containing a small amount of alcohol, to which HCl or the like be
added to control the chloride ion to the above-mentioned
concentration. However, it is preferred that titanium tetrachloride
which forms hydrogen chloride by hydrolysis is used.
[0054] The second aqueous titanium oxide-dispersed sol of the
present invention is obtained by hydrolyzing titanium tetrachloride
under certain conditions.
[0055] It is preferred that hydrogen chloride produced by the above
hydrolysis be prevented from escaping from the reactor and be
maintained in the sol. When titanium tetrachloride is hydrolyzed
while the produced hydrogen chloride leaks out, it is difficult to
make the particle size of titanium oxide particles in the sol small
and the crystallinity of the titanium oxide particles obtained is
poor.
[0056] It is not necessary to completely prevent hydrogen chloride
produced by the hydrolysis escaping or leaking from the reactor and
suppression of the escape or leakage is sufficient. The method of
prevention or suppression is not limited. For example, evacuation
or pressure reduction may be adopted, but the easiest and most
effective method is hydrolysis in a reactor equipped with a reflux
cooler. The FIGURE shows such a reactor. In the FIGURE, an aqueous
solution of titanium tetrachloride 2 is charged in a reactor 1
which is equipped with a reflux cooler 3. The reactor 1 is also
equipped with a stirrer 4, a thermometer 5 and a heater 6. As
hydrolysis produces vapor of hydrogen chloride and water, most of
the vapor is condensed by the reflux cooler and returned to the
reactor, so that the hydrogen chloride hardly escapes from the
reactor.
[0057] If the concentration of the titanium tetrachloride in the
aqueous titanium tetrachloride solution to be hydrolyzed is too
low, the productivity is low and the efficiency of forming a
titanium oxide film from the obtained aqueous titanium
oxide-dispersed sol is low. If the concentration of the titanium
tetrachloride in the aqueous titanium tetrachloride solution to be
hydrolyzed is too high, the reaction becomes vigorous so that it is
difficult to make the particle size of the titanium oxide particles
small and the dispersability is lowered, which is not suitable for
a material for forming a transparent film. Accordingly, a method of
forming a sol having a high titanium oxide concentration by
hydrolysis, followed by diluting with a large amount of water to
control the concentration of titanium oxide to 0.05 to 10 mol/l, is
not preferred. It is desired that the concentration of titanium
oxide is controlled to this range when the sol is formed. To attain
this, the concentration of titanium tetrachloride in the aqueous
titanium tetrachloride solution to be hydrolyzed is controlled to
be almost equal to the concentration of the titanium oxide to be
formed, i.e., approximately 0.05 to 10 mol/l, and if necessary,
addition of a small amount of water or condensation in the
following step to control the concentration of the titanium oxide
to 0.05 to 10 mol/l is done.
[0058] The temperature of hydrolysis is preferably in a range of
not lower than 50.degree. C. to the boiling point of the aqueous
titanium tetrachloride solution. At a temperature of lower than
50.degree. C., a long time is necessary for the hydrolysis. After
the temperature is raised to the above temperature, hydrolysis is
carried out at the temperature for about 10 minutes to 12 hours.
The time for maintaining a certain temperature for hydrolysis may
be shorter as the temperature of hydrolysis is lower.
[0059] The hydrolysis may be conducted by heating a mixture of
water and titanium tetrachloride in a reactor to the predetermined
temperature, or alternatively, by previously heating water in a
reactor and adding titanium tetrachloride to the heated water to
raise it to the predetermined temperature.
[0060] By the above hydrolysis, titanium oxide of brookite-type or
a mixture of brookite-type with anatase-type and/or rutile-type is
generally obtained. To increase the content of brookite-type
titanium oxide, it is appropriate that water is previously heated
to 75 to 100.degree. C., titanium tetrachloride is added to this
water and hydrolysis is carried out at a temperature of from
75.degree. C. to the boiling point of the solution. In accordance
with this process, the content of brookite-type titanium oxide in
the produced total titanium oxide can be increased to not less than
70% by weight.
[0061] The rate of raising the temperature is preferably not less
than 0.2.degree. C./min, more preferably not less than 0.5.degree.
C./min, since the produced titanium oxide particles become finer as
the rate of raising the temperature increases.
[0062] The preparation of the aqueous titanium oxide-dispersed sol
of the present invention may be conducted in a batch system or a
continuous system in which titanium tetrachloride and water are
continuously added to a continuous-type reactor, from the opposite
end of which the reaction solution is removed and then sent to the
dechlorination treatment.
[0063] In the first aqueous titanium oxide-dispersed sol of the
present invention, the obtained aqueous titanium oxide-dispersed
sol is then, depending on necessity, subjected to dechlorination
treatment or, if acceptable, water is added or removed to control
the chloride ion concentration to 50 to 10,000 ppm.
[0064] In the second aqueous titanium oxide-dispersed sol of the
present invention, the obtained aqueous titanium oxide-dispersed
sol may be then subjected to dechlorination treatment or, if
acceptable, water is added or removed to control the chloride ion
concentration to 50 to 10,000 ppm, if desired or necessary.
[0065] The dechlorination treatment may be a known process such as
electrodialysis, treatment with an ion exchange resin, or
electrolysis. The level of the dechlorination treatment can be
detected by pH. When the chloride ion concentration is 50 to 10,000
ppm, the pH of the sol is about 5 to 0.5 and when the chloride ion
concentration is in a preferred range of 100 to 4,000 ppm, the pH
of the sol is about 4 to 1.
[0066] An organic solvent may be added to the aqueous titanium
oxide-dispersed sol of the present invention to disperse the
titanium oxide particles in a mixture of water and an organic
solvent.
[0067] When a titanium oxide film is formed from the aqueous
titanium oxide-dispersed sol of the present invention, it is
preferred that the aqueous titanium oxide-dispersed sol is directly
used to form a titanium oxide film. A process of first forming
titanium oxide particles from the aqueous titanium oxide-dispersed
sol, followed by dispersing the obtained titanium oxide particles
in water to form a titanium oxide sol, and then using the thus
obtained sol to form a titanium oxide film, is not preferred. This
is because titanium oxide particles have a higher surface activity
as the particles are finer, but the finer titanium oxide particles
are difficult to disperse in water. That is, they become
agglomerates which provides a titanium oxide film having a lowered
transparency or photocatalytic activity.
EXAMPLES
[0068] The present invention is now described with reference to
examples of the present invention, to which the present invention
is, of course, not limited.
Examples 1 to 6
[0069] Water was added to titanium tetrachloride (purity: 99.9%)
to-control the concentration of titanium tetrachloride of the
solution to 0.25 mol/l (reduced to titanium oxide: 2% by weight),
while the aqueous solution was cooled by a cooler such as ice to
prevent the temperature of the solution from exceeding 50.degree.
C. One liter of the aqueous solution was charged in a reactor
equipped with a reflux cooler as shown in the FIGURE and heated to
the boiling point (104.degree. C.) of the solution and hydrolysis
was conducted for 60 minutes by maintaining that temperature. The
obtained sol was cooled and then subjected to electrodialysis to
remove chloride produced in and remaining after the reaction to the
chloride ion concentrations as shown in Table 1. The
electrodialysis was carried out using an electrodialysis device G3,
manufactured by Asahi Kasei Kogyo K.K., while the pH of the sol was
monitored.
[0070] Observation of the particles in the sols demonstrated that
the average particle sizes of the particles were from 0.015 to
0.018 .mu.m.
[0071] X-ray diffraction of the particles revealed that the
particles were crystalline titanium oxide.
Comparative Examples 1 and 2
[0072] The procedures of Examples 1 to 6 were repeated but the
chloride ion concentrations were controlled to 30 ppm (Comparative
Example 1) and 15,000 ppm (Comparative Example 1).
[0073] To the thus produced aqueous titanium oxide-dispersed sols
with the controlled chloride ion concentrations of Examples 1 to 6
and Comparative Examples 1 and 2, a water-soluble polymer of
polyvinylalcohol as a film-forming agent was added in an amount of
1,000 ppm based on the weight of the sols. These sols with the
chloride ion concentrations of 50 to 10,000 ppm were stable and did
not show precipitation of titanium oxide particles even after one
day (Examples 1 to 6). However, the sol with the chloride ion
concentrations of 30 ppm showed agglomeration of the titanium oxide
particles in the sol and the sol with the chloride ion
concentrations of 15,000 ppm resulted in a titanium oxide film with
a light white color.
Comparative Examples 1 and 2
[0074] Using the sols of Examples 1 to 6 and Comparative Examples 1
and 2, titanium oxide films were formed on glass plates by dip
coating a sol on a glass plate followed by drying and heat treating
at 500.degree. C. for 1 hour. The obtained titanium oxide films
were 0.15 .mu.m.
[0075] Rietveld analysis of the powder X ray diffraction patterns
of the titanium oxide revealed that the titanium oxide before the
heat treatment was a mixture of about 50% by weight of anatase-type
titanium oxide and about 50% by weight of brookite-type titanium
oxide, and the titanium oxide after the heat treatment at
800.degree. C. or more was a single type of the rutile-type
titanium oxide.
[0076] (Evaluation of Film)
[0077] The light permeability, photocatalytic activity, and
adhesive force to a quartz glass plate of a titanium oxide film
obtained from each of the aqueous titanium oxide-dispersed sols of
Examples and Comparative Examples, were evaluated.
[0078] The light permeability was measured for a titanium oxide
film formed on a quartz glass plate by using a spectrophotometer,
manufactured by Nihon Bunkoh (Japan Spectroscopy) K.K., while
continuously changing the wavelength from 700 nm to 200 nm. The
light permeability of the film at 550 nm was used as the light
permeability of the film in the present invention. The results are
shown in Table 1.
[0079] The photocatalytic activity of the titanium oxide was
measured by making a reactor using a quartz glass plate coated with
a titanium oxide film, charging 5 mol/l of oxalic acid in the
reactor, irradiating the oxalic acid with a mercury lamp while
blowing oxygen into the oxalic acid, and determining the amount of
the decomposed oxalic acid by redox titrating potassium
permanganate. The results are shown in Table 1.
[0080] The adhesivity of the film to a substrate was measured by
the pencil hardness method and by the XY-matrix cut film-peeling
method (JIS K5400). The peeling strength in the XY-matrix cut
film-peeling method is represented by the rate of the non-peeled
sections to the total cut sections. TABLE-US-00001 TABLE 1 Sample
No. Chloride ion concentration in titanium oxide sol [ppm (pH)]
Light permeability (%)/ Deomposition of oxalic acid (%) Pencil
hardness Peeling .times. .times. strength .times. ( non .times. -
.times. peeled .times. .times. sections total .times. .times. of
.times. .times. 100 .times. .times. sections ) ##EQU1## Ex. 1 50
(5) 96 43 H 95 Ex. 2 100 (4) 96 44 2H 100 Ex. 3 1,000 (1.7) 96 44
4H 100 Ex. 4 4,000 (1.0) 95 45 6H 100 Ex. 5 7,000 (0.8) 94 45 6H
100 Ex. 6 10,000 (0.7) 90 45 6H 100 Com. Ex. 1 30 (5.5) 96 43 B 70
Com. Ex. 2 15,000 (0.5) 55 42 6H 95
Examples 7 and 8 and Comparative Examples 3 and 4
[0081] The procedures as in Example 1 and Comparative Example 1
were repeated, except that the titanium oxide film was formed on a
plastic substrate of polyethyleneterephtalate and the heat
treatment was not conducted and the film was dried at 100.degree.
C. The evaluations were carried out in the same manner as in
Examples and Comparative Examples.
[0082] The results are shown in Table 2. TABLE-US-00002 TABLE 2
Sample No. Chloride ion concentration in titanium oxide sol [ppm
(pH)] Light permeability (%) Decomposition of oxalic acid (%)
Pencil hardness Peeling .times. .times. strength .times. ( non
.times. - .times. peeled .times. .times. sections total .times.
.times. of .times. .times. 100 .times. .times. sections ) ##EQU2##
Ex. 7 100 (4) 96 44 HB 90 Ex. 8 4,000 (1.0) 95 43 3H 95 Com. Ex. 3
30 (5.5) 93 43 HB 70 Com. Ex. 4 15,000 (0.5) 55 42 3H 83
Example 9
[0083] 954 ml of distilled water was charged in a reactor equipped
with a reflex cooler as shown in the FIGURE and heated to
95.degree. C. While the stirring rate was kept to about 200 rpm, 46
ml of an aqueous solution of titanium tetrachloride (titanium
element content: 16.3% by weight; density: 1.59; purity: 99.9%) was
added dropwise into the reactor at a rate of about 5 ml/min. The
temperature of the reaction solution was kept constant during the
reaction. As a result, the concentration of titanium tetrachloride
was changed to 0.25 mol/l (reduced titanium oxide concentration: 2%
by weight).
[0084] In the reactor, the reaction solution became clouded soon
after starting the addition of titanium tetrachloride, but the
temperature of the reaction solution was kept constant and, after
finishing the addition, raised to near the boiling point
(104.degree. C.) and kept at this temperature for 60 minutes to
complete and finish the reaction. After cooling, produced and
remaining chlorine was removed by electrodialysis to a pH of 2
(chloride ion: 600 ppm), followed by adding a water soluble polymer
of polyvinylalcohol in an amount of 0.1% based on the weight of
titanium oxide, to obtain a titanium oxide sol.
[0085] The sol was filtered and vacuum dried at 60.degree. C. to
obtain a powder, which was analyzed by X ray diffraction to reveal
that the titanium oxide contained 96.7% by weight of brookite-type,
0.9% by weight of rutile-type, and 2.4% by weight of anatase-type
titanium oxides.
[0086] Observation of the powder by a transmission type
electromicroscope revealed that the average particle size of the
primary particle was 15 nm.
[0087] The specific surface area of the powder was 100 m.sup.2/g by
the BET method.
[0088] The above sol was spin-coated over a quartz glass plate and
dried in a drier at 100.degree. C. to obtain a transparent film.
The light permeability of the quartz glass plate with the film was
over 95% in the range of the visible light, which demonstrated that
the plate with the film was completely transparent. The plate with
the film demonstrated an absorption in an ultraviolet region, which
revealed by the absorption end of light that the energy gap was
3.75 eV. The relationship between the energy gap and the absorption
end of light is shown by the following formula (1): .lamda.=1239/Eg
(1) where .lamda. stands for the absorption end of light in the
unit of nm, and Eg stands for the energy gap in the unit of eV.
Example 10
[0089] The procedures of Example 9 were repeated but the reaction
temperature during the addition of titanium tetrachloride was
75.degree. C.
[0090] The obtained titanium oxide powder was analyzed by the X ray
diffraction to reveal that it contained 75% by weight of
brookite-type and 25% by weight of rutile-type titanium oxides.
[0091] Observation of the powder by a transmission type
electromicroscope revealed that the average particle size of the
primary particle was 10 nm.
[0092] The specific surface area of the powder was 120 m.sup.2/g by
the BET method.
[0093] The above sol having a pH of 1 (chloride ion: 3000 ppm),
obtained by the electrodalysis, was coated over a quartz glass
plate and heat treated at 500.degree. C. to obtain a transparent
film. The transparent film was also a mixture of brookite-type and
rutile-type titanium oxides, as determined by the thin film X ray
diffraction method. The light permeability of the quartz glass
plate with the film was over 95% in the range of the visible light,
which demonstrated that the plate with the film was completely
transparent. The plate with the film demonstrated an absorption in
a ultraviolet region, which revealed by the absorption end of light
that the energy gap was 3.30 eV.
Comparative Example 5
[0094] Anatase-type titanium oxide particles having a primary
particle size of 7 nm were dispersed in water with an ultrasonic
wave dispersing device to an aqueous solution of titanium oxide
having a concentration of titanium oxide of 2% by weight as in
Example 9, during which hydrochloric acid as a coagulant was added
to control the pH to 1, followed by carrying out the same
procedures as in Example 9 to obtain an aqueous titanium
oxide-dispersed sol. The sol was coated on a glass plate and dried
at 100.degree. C. to form a transparent film.
Comparative Example 6
[0095] An aqueous titanium oxide-dispersed sol was prepared in the
same procedures as in Comparative Example 5, except that
rutile-type titanium oxide particles having a primary particle size
of 50 nm were used. The sol exhibited precipitation of titanium
oxide particles as in Comparative Example 5 and the particles were
redispersed using hydrochloric acid as a coagulant. Since a
titanium oxide film formed by the supernatant after the
precipitation did not show a photocatalytic activity, the sol, soon
after it was prepared, was subjected to dispersing treatment with
an ultrasonic dispersing device, and the obtained sol was used to
form a titanium oxide film on a glass plate in the same manner as
in Example 9 and the photocatalytic activity of the film was
evaluated.
[0096] (Evaluation of Film)
[0097] The photocatalytic activities of the titanium oxide films
obtained from the sols of Examples 9 to 11 and Comparative Example
5 and 6 were evaluated by the oxalic acid decomposition method. The
results are shown in Table 3. TABLE-US-00003 TABLE 3 Rate of
decomposition (%) (after 4 hours irradiation) Example 9 55 Example
10 48 Example 11 50 Comparative Example 5 30 Comparative Example 6
not determined since the substrate was clouded
[0098] In Comparative Example 5, the surface of the glass substrate
was not uniform as agglomerates of titanium oxide were formed.
[0099] In Comparative Example 6, the photocatalytic activities of
the titanium oxide film was not determined since a transparent
titanium oxide film was not obtained.
Example 12
[0100] In the same manner as in Example 9, 0.25 mol/l (reduced to
titanium oxide: 2% by weight) of an aqueous titanium tetrachloride
solution was subjected to hydrolysis. The resultant reaction
solution was condensed to a titanium oxide concentration of 10% by
weight, electrodialysis was carried out to remove the remaining
chlorine to a pH of 2 (chloride ion concentration of about 600
ppm), and tetramethylorthosilicate Si(OCH.sub.3).sub.4 as an
adhesive was added to the sol in an amount as SiO.sub.2 of 5% by
weight, to obtain a titanium oxide sol.
Example 13
[0101] The procedures up to the condensation and electrodialysis in
the procedures in Example 12 were repeated, followed by diluting
with isopropylalcohol to 5 times and adding tetraethylorthosilicate
Si(OC.sub.2H.sub.5).sub.4 as an adhesive in an amount, as
SiO.sub.2, of 20% by weight, to obtain a titanium oxide sol.
Example 14
[0102] The procedures of Example 12 were repeated but
tetrapropylorthosilicate Si(OC.sub.3H.sub.7).sub.4 was substituted
for tetramethylorthosilicate and added in an amount, as SiO.sub.2,
of 35% by weight, to obtain a titanium oxide sol.
Comparative Example 7
[0103] The procedures of Example 14 were repeated but
tetrapropylorthoslicate was added in an amount, as SiO.sub.2, of
55% by weight, to obtain a titanium oxide sol.
[0104] (Evaluation of Film)
[0105] Each of the sols obtained in Examples 12 to 14 and
Comparative Example 7 was spin-coated over a quartz glass plate and
allowed to stand for drying to obtain a transparent film. The light
permeabilities of the quartz glass plates with the film were over
95% in the range of the visible light, which demonstrated that the
plates with the films were completely transparent.
[0106] The pencil hardness test and the adhesion test were made on
the quartz glass plates with the titanium oxide films. The results
are shown in Table 4. TABLE-US-00004 TABLE 4 Sample No. Silicon
oxide/ titanium oxide ratio (% by weight) Deomposition of oxalic
cid (%) Pencil hardness (%) Peeling .times. .times. strength
.times. ( non .times. - .times. peeled .times. .times. sections
total .times. .times. of .times. .times. 100 .times. .times.
sections ) ##EQU3## Ex. 12 5 50 5H 100 Ex. 13 20 50 5H 100 Ex. 14
35 40 6H 100 Com. Ex. 7 55 0 7H 100
* * * * *