JP2003275597A - Modified photocatalyst and photocatalyst composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photocatalytic material capable of forming a coating film or a formed body having excellent transparency, durability or the like under a mild condition and to provide a photocatalytic material capable of obtaining a functional composite body or a formed body having a surface exhibiting the controllability for wettability (hydrophilicity or hydrophobicity) and/or photocatalytic activity. <P>SOLUTION: The photocatalyst is a modified photocatalyst treated to be modified with a specific Si-H-containing compound. A photocatalyst composition is composed of the modified photocatalyst and a resin. The functional composite body or the formed body is formed using the photocatalyst composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to titanium oxide, which is known to be applied to the fields of environmental purification, antifouling, antifogging and the like, because it exhibits a substance decomposing action and a surface hydrophilicizing action by light energy. The present invention relates to a technique for immobilizing a representative photocatalyst on a member surface. Specifically, it relates to a modified photocatalyst that can be easily immobilized on the member surface of the photocatalyst and a photocatalyst composition using the same, and further has photocatalytic activity and / or water wettability (hydrophilicity, hydrophilicity, It relates to a member having a controllability of (hydrophobicity).

[0002]

2. Description of the Related Art It is known that a photocatalyst typified by titanium oxide exhibits a substance decomposing action and a surface hydrophilizing action by light energy. This photocatalyst is used for environmental purification and antifouling,
When applied to fields such as anti-fog, the photocatalyst immobilization technology plays a very important role. As a useful means of the photocatalyst immobilization technique, the coating of the substrate with the photocatalyst has attracted attention. Here, the following items are listed as the minimum conditions required for the technique of fixing the photocatalyst by coating. (A) Firmly fixed without impairing photocatalytic activity. (B) Stability in which the substrate and the coating itself are not deteriorated by the photocatalytic action. Furthermore, the following items are mentioned as preferable conditions for expanding the applicable range of the substrate to be immobilized. (C) The fixing conditions are mild (room temperature to about 150 ° C.). (D) The coating film has excellent transparency and forms a skin with excellent durability, stain resistance and hardness.

By the way, various proposals have been made for the immobilization technique by coating a photocatalyst represented by titanium oxide. For example, as a method of coating a substrate with a photocatalyst by a sputtering method or a sol-gel method, Japanese Patent Laid-Open No. 04404053 discloses a method of supporting a thin film photocatalyst on a substrate by a sputtering method, and Japanese Patent Laid-Open No. 60-1.
Japanese Patent No. 18236 proposes a method of applying an organic titanate and then baking it. However, these methods have a drawback that it is difficult to immobilize a large area because it is necessary to perform baking at a high temperature in order to generate and crystallize photocatalyst particles on a substrate.

Further, as a method of using a photocatalyst sol which does not require a process of producing and crystallization of photocatalyst particles, for example, in JP-A-6-278241, a method of coating a substrate with a titanium oxide sol peptized in water is disclosed. Is proposed. Even in this method, since the titanium oxide sol does not have a film forming property under mild conditions, it is necessary to perform firing at a high temperature.
The resulting coating was brittle and had the drawback of being easily broken and losing its catalytic effect.

Further, a method has been proposed in which a photocatalyst is mixed in a resin coating material and the resin coating material is coated on a substrate. For example, JP-A-7-171408, JP-A-9-100437, JP-A-9-227831, JP-A-9-59041 and JP-A-9-1888.
No. 50 and Japanese Unexamined Patent Publication No. 9-227829 propose a method of using a hardly decomposable substance such as a fluororesin or a silicone resin as a resin coating in which a photocatalyst is mixed. However, in these methods, it is necessary to reduce the amount of resin coating used in order to exhibit sufficient photocatalytic activity and hydrophilicity, and in this case, weather resistance, hardness, adhesion, flex resistance, It is not possible to obtain a coating having good coating physical properties such as impact resistance and abrasion resistance. (Conversely, if the amount of the resin coating used is increased in order to exhibit good coating film physical properties, the photocatalyst is buried in the resin coating and does not exhibit sufficient photocatalytic activity or hydrophilization ability.) In the immobilization technique, a technique satisfying all the conditions required for the immobilization techniques (a) to (d) has not yet been developed.

[0006]

[Patent Document 1] JP-A-60-040553

[Patent Document 2] Japanese Patent Laid-Open No. 60-118236

[Patent Document 3] JP-A-6-278241

[Patent Document 4] JP-A-7-171408

[Patent Document 5] Japanese Patent Laid-Open No. 9-100437

[Patent Document 6] Japanese Patent Laid-Open No. 9-227831

[Patent Document 7] Japanese Patent Laid-Open No. 9-59041

[Patent Document 8] Japanese Unexamined Patent Publication No. 9-188850

[Patent Document 9] JP-A-9-227829

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photocatalyst material which can form a film or a molded article having excellent transparency and durability under mild conditions. Further, the present invention provides a photocatalyst material capable of obtaining a functional composite or a molded product, the surface of which exhibits wettability (hydrophilicity, hydrophobicity) controllability and / or photocatalytic activity over a long period of time by light irradiation. That is.

[0008]

Means for Solving the Problems The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is,
The first aspect of the present invention is that the photocatalyst (A) has the formula (1) and the formula (2).
A modified photocatalyst obtained by modification treatment with at least one or more Si—H group-containing compound (B) selected from ^{_{H- (R 1 2 SiO) a}} -SiR 1 2 -H ··· (1) ( In the formula, ^{R 1} each independently represents a linear or branched alkyl group having 1 to 30 carbon atoms, A cycloalkyl group having 5 to 20 carbon atoms, a linear or branched fluoroalkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, A hydroxyl group or a group consisting of one or more selected from the siloxy group represented by the formula (3) is represented by: —O— (R ³ ₂ SiO) _c —SiR ³ ₃ (3) (wherein R ³ is Each independently from at least one selected from a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a phenyl group. And the group c.
Is an integer and 0 ≦ c ≦ 1000. )) A is an integer and 0 ≦ a ≦ 1000. ^{_{) H- (R 2 2 SiO)}} b -SiR 2 2 -Q ··· (2) ( wherein, ^{R 2} is each independently a linear or branched having 1 to 30 carbon atoms, alkyl groups A cycloalkyl group having 5 to 20 carbon atoms, a linear or branched fluoroalkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms , A hydroxyl group, or a group consisting of at least one selected from the siloxy groups represented by the formula (3): —O— (R ³ ₂ SiO) _c —SiR ³ ₃ (3) (in the formula, R ³ Are each independently one or more selected from a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a phenyl group. Represents a group consisting of, and c
Is an integer and 0 ≦ c ≦ 1000. )

Further, in the formula, Q is the following (A) to (E)
It is a group containing at least one functionalizing group selected from the group consisting of: (A) a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or Unsubstituted or C1-C20 alkyl group or C1-C20 alkoxy group, or C6-C20 aryl group substituted with a halogen atom, and C1-C30 fluoroalkyl At least one hydrophobic group selected from the group consisting of groups. (Ii) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a polyoxyalkylene group. (U) epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, At least one reactive group selected from the group consisting of ester groups. (E) At least one spectral sensitizing group. Further, b is an integer, and 0 ≦ b ≦ 1000. )

A second aspect of the invention is the first modified photocatalyst of the invention, wherein the photocatalyst (A) is a photocatalytic sol having a number average particle diameter of 200 nm or less. A third aspect of the invention is the modified photocatalyst according to the first or second aspect of the invention, wherein the photocatalyst (A) is titanium oxide. Fourth of invention
Is a modified photocatalyst according to any one of 1 and 2 of the invention, wherein the photocatalyst (A) is a visible light responsive photocatalyst. The fifth aspect of the invention is a photocatalyst composition comprising the modified photocatalyst according to any one of the first to fourth aspects of the invention and a resin (E). A sixth aspect of the invention is the fifth photocatalyst composition of the invention, wherein the resin (E) is a silicon-based resin. A seventh aspect of the invention is the sixth photocatalyst composition of the invention, wherein the silicon-based resin contains a ladder structure represented by the formula (4).

[0011]

[Chemical 3]

(R independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.) In the eighth aspect of the invention, the silicone resin contains a phenyl group represented by the formula (5). The sixth or seventh photocatalyst composition of the invention is characterized by containing silicone. R ⁵ _p X _r SiO _{(4-p-r) / 2} (5) (In the formula, R ⁵ represents a phenyl group, and X represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or 1 carbon atom. ~ 20
Represents at least one reactive group selected from the group consisting of an acyloxy group, an aminoxy group, an oxime group having 1 to 20 carbon atoms, and a halogen atom, and 0 <p <4, 0 <r <4,
And 0 <(p + r) <4. )

A ninth aspect of the invention is the photocatalyst composition according to any of the sixth to eighth aspects of the invention, wherein the silicone resin contains an alkyl group-containing silicone represented by the formula (6). ^{_{R 6 q X s SiO (4}} -q-s) / 2 (6) ( wherein, ^{R 6} are each independently a linear or branched alkyl group having 1 to 30 carbon atoms, 5 to 20 carbon atoms Represents a cycloalkyl group or a linear or branched alkenyl group having 2 to 30 carbon atoms, X represents a hydrogen atom, a hydroxyl group, or 1 carbon atom
To at least one reactive group selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an aminoxy group, an oxime group having 1 to 20 carbon atoms, and a halogen atom, and 0 <q <4, 0 <s <4, and 0 <(q +
s) <4. )

In a tenth aspect of the invention, the silicone resin is a phenyl group-containing silicone represented by the formula (5) and a formula (6).
The eighth photocatalyst composition of the invention is characterized by comprising a mixture of the alkyl group-containing silicone represented by The eleventh aspect of the invention is that the alkyl group-containing silicone represented by the formula (6) is a monooxydiorganosilane unit (D) represented by the formula (7) and a dioxyorganosilane represented by the formula (8). The photocatalyst composition according to any one of the seventh to ninth aspects of the invention, which is a structure having both units (T). _{^{- (R 6 2 SiO) -}} (7) ( wherein, ^{R 6} are each independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear Represents a straight or branched alkenyl group having 2 to 30 carbon atoms.)

[0015]

[Chemical 4]

(In the formula, R ⁶ is as defined in the formula (7).) The twelfth aspect of the invention is the photocatalytic composition according to any one of the fifth to eleventh aspects of the invention, which has a self-grading property. It is a photocatalyst composition characterized by having. The thirteenth invention is the fifth invention.
The photocatalyst composition according to any one of the twelfth aspects, wherein when the photocatalyst composition is applied to a substrate to form a film, the concentration of the modified photocatalyst increases in the film thickness direction toward the surface of the film in contact with outside air. It is a photocatalyst composition characterized by autonomously forming a gradient composition film having a gradient. A fourteenth invention is a photocatalyst composition according to any one of the fifth to twelfth inventions,
A photocatalyst which, when forming a molded body from the photocatalyst composition, autonomously forms a structure having a concentration gradient such that the modified photocatalyst increases from the inside of the molded body toward the surface side in the formation process. It is a composition.

The fifteenth aspect of the invention is a functional composite obtained by forming a film containing the photocatalyst composition according to any one of the fifth to thirteenth aspects of the invention on a substrate. A sixteenth invention is a functional composite obtained by forming a film containing the photocatalyst composition of the thirteenth invention on a substrate, wherein the film is anisotropic with respect to the distribution of the modified photocatalyst in the film thickness direction. It is a functional complex characterized by having. The seventeenth aspect of the invention is the functional composite according to the fifteenth or sixteenth aspect of the invention, wherein the resin (E) contained in the coating forms a phase-separated structure. The eighteenth invention is characterized by exhibiting photocatalytic activity and / or hydrophilicity by irradiating with light having an energy higher than the bandgap energy of the photocatalyst (A) contained in the film. Is a functional complex of. The nineteenth aspect of the invention is directed to irradiating with light having an energy higher than the bandgap energy of the photocatalyst (A) contained in the film, thereby forming an organic group bonded to a silicon atom existing in the vicinity of the photocatalyst (A) particles. At least a part thereof is substituted with a hydroxyl group and / or a siloxane bond, which is a functional composite according to the 15th or 16th aspect of the invention.

The twentieth aspect of the invention is a molded article formed from the photocatalyst composition of any of the fifth to twelfth aspects of the invention. The twenty-first aspect of the invention is a shaped article formed from the photocatalyst composition of the fourteenth aspect of the invention, which is characterized in that it has anisotropy in the distribution of the modified photocatalyst from the inside to the surface. The 22nd invention of the present invention is the 20th or 21st molded article of the invention, wherein the resin (E) contained in the molded article forms a phase-separated structure. 23rd invention
Is a photocatalyst (A) contained in the molded body, and exhibits photocatalytic activity and / or hydrophilicity by irradiating with light having an energy higher than the bandgap energy of the molded body. Is. Second invention
4 is at least one of organic groups bonded to silicon atoms existing in the vicinity of the photocatalyst (A) particles by irradiating with light having an energy higher than the bandgap energy of the photocatalyst (A) contained in the molded body. The molded body according to the 20th or 21th aspect of the present invention is characterized in that a part is substituted with a hydroxyl group and / or a siloxane bond.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The photocatalyst that can be used as the modified photocatalyst in the present invention is a valence electron when irradiated with light (excitation light) having an energy (that is, a short wavelength) larger than the energy gap between the conduction band and the valence band of the crystal. A substance that is capable of generating conduction electrons and holes by the excitation (photoexcitation) of electrons in the band, such as TiO ₂ , ZnO, SrTiO ₃ , CdS,
GaP, InP, GaAs, BaTiO ₃ , BaTiO _3
4 , BaTi ₄ O ₉ , K ₂ NbO ₃ , Nb ₂ O ₅ , Fe
₂ O ₃ , Ta ₂ O ₅ , K ₃ Ta ₃ Si ₂ O ₃ , WO ₃ ,
SnO ₂ , Bi ₂ O ₃ , BiVO ₄ , NiO, Cu
₂ O, SiC, MoS ₂ , InPb, RuO ₂ , CeO
_2, etc., and further a layered oxide containing at least one element selected from Ti, Nb, Ta, and V (see, for example, Japanese Patent Laid-Open No.
JP-A-2-74452, JP-A-2-172535, JP-A-7-24329, and JP-A-8-8979.
No. 9, JP-A-8-89800, and JP-A-8-8.
9804, JP-A-8-198061, JP-A-9-248465, JP-A-10-99694, JP-A-10-244165 and the like).

Among these photocatalysts (A), TiO ₂ (titanium oxide) is preferable because it is harmless and has excellent chemical stability. As titanium oxide, anatase, rutile,
Any of brookite can be used. Further, as the photocatalyst (A) used in the present invention, visible light (for example, about 400 to
When a visible-light-responsive photocatalyst capable of exhibiting photocatalytic activity and / or hydrophilicity is selected by irradiation with (800 nm wavelength), the functional composite or molded article formed from the photocatalyst composition of the present invention is exposed to ultraviolet rays. It is preferable because the antifouling property and the action of decomposing organic matter can be exhibited even in a place where the irradiation is not sufficiently performed.

Any of the above visible light responsive photocatalysts can be used as long as it exhibits photocatalytic activity and / or hydrophilicity with visible light. For example, titanium oxidation in the presence of a nitrogen-containing compound such as ammonia or urea. Nitrogen-doped titanium oxide obtained by firing a material precursor (titanium oxysulfate, titanium chloride, alkoxytitanium, etc.) or high-surface titanium oxide (for example, JP-A-2002-29750, JP-A-2002-2002).
No. 87818, JP-A No. 2002-154823, and JP-A No. 2001-207082), a titanium oxide precursor (titanium oxysulfate, titanium chloride, alkoxytitanium, etc.) is fired in the presence of a sulfur compound such as thiourea. Oxygen-deficient titanium oxide obtained by subjecting the sulfur-doped titanium oxide and the titanium oxide obtained as described above to hydrogen plasma treatment or heat treatment under vacuum (for example, Japanese Patent Application Laid-Open No. 2-212058).
No. 001-98219), and further, the photocatalyst particles are treated with a halogenated platinum compound (see, for example, JP 20
No. 02-239353) and a surface-treated photocatalyst obtained by treatment with a tungsten alkoxide (see Japanese Patent Laid-Open No. 2001-286755).

Further, the above-mentioned photocatalyst (a) is preferably P
Metals such as t, Rh, Ru, Nb, Cu, Sn, Ni, and Fe and / or oxides thereof are added or immobilized, or coated with porous calcium phosphate or the like, or as a photocatalyst (for example, JP-A-10-244166). It can also be used. The crystal particle size (primary particle size) of the photocatalyst (a) is preferably 1 to 10 μm,
More preferably 1 to 400 nm, further preferably 1 to
A photocatalyst of 200 nm, more preferably 1 to 50 nm is suitably selected.

In general, a powder composed of fine particles forms secondary particles in which a plurality of particles are strongly aggregated, and therefore has many surface properties to be wasted, and it is not possible to disperse each primary particle. Very difficult. On the other hand, in the case of the photocatalyst sol, the photocatalyst particles do not dissolve and exist in a form close to the primary particles, so that the surface characteristics can be effectively utilized, and the modified photocatalyst produced from it has dispersion stability, film-forming properties, etc. Not only is it excellent in use, but also various functions are effectively expressed, so it can be preferably used. Here, the photocatalyst sol is one in which photocatalyst particles are dispersed in water and / or an organic solvent at a solid content of 0.01 to 70% by mass, preferably 0.1 to 50% by mass.

As the photocatalyst used in the present invention, a photocatalyst having a number average dispersed particle diameter of 200 nm or less of a mixture of primary particles and secondary particles (either primary particles or secondary particles may be used) is modified. It is preferable because the surface characteristics of the photocatalyst can be effectively used. In particular, when a photocatalyst having a number average dispersed particle diameter of 100 nm or less is used, a film having excellent transparency can be obtained from the resulting modified photocatalyst, which is very preferable. A photocatalyst of 80 nm or less and 3 nm or more, and more preferably 50 nm or less and 3 nm or more is suitably selected. These photocatalysts are preferably photocatalyst sols.

Taking the sol of titanium oxide as an example of the photocatalytic sol, for example, a titanium oxide hydrosol in which water is substantially used as a dispersion medium and titanium oxide particles are deflocculated can be mentioned. (Here, substantially using water as a dispersion medium means that water is contained in the dispersion medium in an amount of about 80% by mass or more.) The preparation of such a sol is known and can be easily produced ( JP-A-63-17221, JP-A-7-819, and JP-A-9-165218.
JP-A-11-43327, etc.). For example,
Metatitanic acid produced by hydrolyzing an aqueous solution of titanium sulfate or titanium tetrachloride is neutralized with aqueous ammonia, and the precipitated hydrous titanium oxide is filtered, washed and dehydrated to obtain an aggregate of titanium oxide particles. A titanium oxide hydrosol can be obtained by deflocculating this aggregate under the action of nitric acid, hydrochloric acid, ammonia or the like and performing hydrothermal treatment or the like. Further, as the titanium oxide hydrosol, titanium oxide particles are deflocculated under the action of an acid or an alkali, or a dispersion stabilizer is used as needed without using an acid or an alkali, and a strong shear strength is obtained. Sols dispersed in water underneath can also be used. Furthermore, an anatase type titanium oxide sol in which the particle surface is modified with a peroxo group, which is excellent in dispersion stability even in an aqueous solution having a pH of around neutral, can be easily obtained by the method proposed in JP-A-10-67516. it can.

The titanium oxide hydrosol described above is also commercially available as a titania sol. (For example, the product name "ST
S-02 "/ Ishihara Sangyo Co., Ltd., trade name" TO-240 "
/ Tanaka Transfer Co., Ltd.) The solid content in the titanium oxide hydrosol is 50% by mass or less, preferably 30% by mass or less. More preferably, it is 30 mass% or less and 0.1 mass% or more. The viscosity of such hydrosols (20 ° C.) is relatively low, eg 2
The range of about 000 mPa · s to 0.5 mPa · s is preferable, and more preferably 1000 mPa · s to 1 mPa · s.
s, more preferably 500 mPa · s to 1 mPa · s
Is. Further, for example, cerium oxide sol (Japanese Patent Laid-Open No. 8-5
9235) and sol of layered oxide containing at least one element selected from Ti, Nb, Ta and V (JP-A-9-25123, JP-A-9-67124, JP-A-9-). No. 227122, JP-A-9-227.
No. 123, Japanese Patent Laid-Open No. 10-259023, etc.)
Various photocatalyst sol manufacturing methods such as the above are also disclosed in the same manner as the titanium oxide sol.

Further, a visible light responsive photocatalytic sol which can be preferably used in the present invention is commercially available. (For example, "NTB-200" manufactured by Showa Denko KK, Sumitomo Chemical Co., Ltd.)
Also, a photocatalyst organosol in which photocatalyst particles are dispersed in an organic solvent as a dispersion medium is, for example, a photocatalyst organosol prepared by converting the photocatalyst hydrosol into a compound having a phase transfer activity such as polyethylene glycol. Organic solvent, which is treated with a compound that forms a third phase at the interface between the first phase and the second phase and dissolves and / or solubilizes the first phase, the second phase, and the third phase with each other) Method (Japanese Patent Laid-Open No. 10-167727, etc.) or a sol is prepared by dispersing and transferring it in an organic solvent insoluble in water with an anionic surfactant such as sodium dodecylbenzenesulfonate (Japanese Patent Laid-Open No. Sho 58-58). No. 29863, etc.) or butyl cellosolve and the like, which have a boiling point higher than that of water, are added to the photocatalytic hydrosol, and then water is removed by (reduced pressure) distillation or the like. Wear. Further, a titanium oxide organosol in which an organic solvent is substantially used as a dispersion medium and titanium oxide particles are dispersed therein is also commercially available (for example, trade name "TKS-251" /
Teika Corporation. Here, when the organic solvent is substantially used as the dispersion medium, it is preferable that the dispersion medium contains 20% by mass of the organic solvent.
As described above, it means that the content is more preferably 80% by mass or more.

The modified photocatalyst of the present invention is obtained by modifying the above-mentioned photocatalyst with at least one Si—H group-containing compound selected from the formulas (1) and (2). ^{_{H- (R 1 2 SiO) a}} -SiR 1 2 -H ··· (1) ( In the formula, ^{R 1} each independently represents a linear or branched alkyl group having 1 to 30 carbon atoms, A cycloalkyl group having 5 to 20 carbon atoms, a linear or branched fluoroalkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, A hydroxyl group or a group consisting of one or more selected from the siloxy group represented by the formula (3) is represented by: —O— (R ³ ₂ SiO) _c —SiR ³ ₃ (3) (wherein R ³ is Each independently from at least one selected from a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a phenyl group. And the group c.
Is an integer and 0 ≦ c ≦ 1000. ) A is an integer and 0 ≦ a ≦ 1000. ^{_{) H- (R 2 2 SiO)}} b -SiR 2 2 -Q ··· (2) ( wherein, ^{R 2} is each independently a linear or branched having 1 to 30 carbon atoms, alkyl groups A cycloalkyl group having 5 to 20 carbon atoms, a linear or branched fluoroalkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms , A hydroxyl group, or a group consisting of at least one selected from the siloxy groups represented by the formula (3): —O— (R ³ ₂ SiO) _c —SiR ³ ₃ (3) (in the formula, R ³ Are each independently one or more selected from a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a phenyl group. Represents a group consisting of, and c
Is an integer and 0 ≦ c ≦ 1000. )

Further, in the formula, Q is the following (A) to (E)
It is a group containing at least one functionalizing group selected from the group consisting of: (A) a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or Unsubstituted or C1-C20 alkyl group or C1-C20 alkoxy group, or C6-C20 aryl group substituted with a halogen atom, and C1-C30 fluoroalkyl At least one hydrophobic group selected from the group consisting of groups. (Ii) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a polyoxyalkylene group. (U) epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, At least one reactive group selected from the group consisting of ester groups. (E) At least one spectral sensitizing group. Further, b is an integer, and 0 ≦ b ≦ 1000. )

In the present invention, the above formula (1) of the photocatalyst,
The modification treatment with at least one Si—H group-containing compound (B) selected from the formula (2) is carried out, for example, with water and / or
Alternatively, in the presence or absence of an organic solvent, the photocatalyst (A) and the Si—H group-containing compound (B) are preferably in a mass ratio (A) / (B) = 1/99 to 99.9 / 0.0. 1,
More preferably (A) / (B) = 10/90 to 99/1
Can be carried out by mixing at a ratio of 0 to 150 ° C. By this modification operation, hydrogen gas is generated from the mixed liquid, and when a photocatalytic sol is used as the photocatalyst, an increase in the average dispersed particle diameter is observed. Further, for example, when titanium oxide is used as a photocatalyst, the Ti—OH group is reduced by 3 in the IR spectrum by the above modification operation.
Observed as a decrease in absorption between 630 and 3640 cm ^-1 .

From the above, the modified photocatalyst of the present invention is
It is not a mere mixture of the Si-H group-containing compound and the photocatalyst described above, but it can be predicted that some interaction due to a chemical reaction occurs between them. In fact, the modified photocatalyst thus obtained is very excellent in dispersion stability, chemical stability, durability and the like in an organic solvent.

When the above modification treatment is carried out, examples of usable organic solvents include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane and heptane, ethyl acetate and n-acetate. Ester such as butyl, ethylene glycol, butyl cellosolve, isopropanol, n-butanol, ethanol,
Alcohols such as methanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide, halogen compounds such as chloroform, methylene chloride and carbon tetrachloride, Examples thereof include dimethyl sulfoxide, nitrobenzene and the like, and mixtures of two or more thereof.

In the present invention, the above formula (1) of the photocatalyst,
The modification treatment with at least one or more Si—H group-containing compounds selected from the formula (2) is performed at 0 to 100 ° C. in a state where a substance acting as a dehydrogenative condensation catalyst for Si—H groups is fixed to the photocatalyst. You can also do it. In this case, a substance acting as a dehydrogenative condensation catalyst is previously fixed to the photocatalyst by a method such as a photoreduction method, and the above formula (1) and formula (2)
The compound may be modified with at least one Si—H group-containing compound selected from the above, or at least selected from the above formulas (1) and (2) in the presence of a substance acting as a dehydrogenative condensation catalyst. The photocatalyst may be modified with one or more Si-H group-containing compounds. In the latter case, the substance acting as a dehydrogenative condensation catalyst is modified with at least one Si—H group-containing compound selected from the above formulas (1) and (2) while being fixed to the photocatalyst by physical adsorption or photoreduction. Will be done.

Here, the substance acting as a dehydrogenative condensation catalyst for the Si—H group means a Si—H group and a hydroxyl group (Ti—OH group in the case of titanium oxide) existing on the surface of the photocatalyst, a thiol group, an amino group, A photocatalyst that selectively accelerates a dehydrogenative condensation reaction with an active hydrogen group such as a carboxyl group or water and the like, and by immobilizing the substance acting as the dehydrogenative condensation catalyst on the photocatalyst under mild conditions It is possible to modify the surface. Examples of the substance acting as a dehydrogenative condensation catalyst for the Si—H group include platinum group catalysts, that is, ruthenium, rhodium, palladium, osmium, iridium, simple substances of platinum and compounds thereof, silver, iron, copper, cobalt, nickel. Examples thereof include simple substances such as tin and tin, and compounds thereof. Among these, platinum group catalysts are preferable, and simple substance of platinum and its compound are particularly preferable.

In the present invention, a photocatalyst composition comprising a modified photocatalyst modified by the Si-H group-containing compound represented by the above formula (1) and a resin described later has excellent storage stability and the photocatalyst is excellent. The film formed from the composition has extremely high wettability (hydrophilicity, hydrophobicity) controllability by light irradiation and photocatalytic activity. In the present invention,
Examples of the Si-H group-containing compound represented by the above formula (1) include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1 , 1,3,3,5,5,7,7-octamethyltetrasiloxane, etc. having a number average molecular weight of 50,000 or less
Terminal polydimethylsiloxanes, 1,1,3,3-tetraethyldisiloxane, 1,1,3,3,5,5-hexaethyltrisiloxane, 1,1,3,3,5,5,
H-terminated polydiethylsiloxanes having a number average molecular weight of 50,000 or less, such as 7,7-octaethyltetrasiloxane, 1,1,3,3-tetraphenyldisiloxane,
H having a number average molecular weight of 50,000 or less, such as 1,1,3,3,5,5-hexaphenyltrisiloxane and 1,1,3,3,5,5,7,7-octaphenyltetrasiloxane.
Terminal polydiphenylsiloxanes, 1,3-diphenyl-1,3-dimethyl-disiloxane, 1,3,5-trimethyl-1,3,5-triphenyl-trisiloxane, 1,3,5,7- Tetramethyl-1,3,5,7-
Number average molecular weight 5 such as tetraphenyl-tetrasiloxane
H-terminated polyphenylmethylsiloxanes of 0000 or less, dimethylsilane, ethylmethylsilane, diethylsilane, phenylmethylsilane, diphenylsilane, cyclohexylmethylsilane, t-butylmethylsilane, di-t-butylsilane, n-octadecylmethylsilane ,
Allylmethylsilane etc. can be illustrated.

S represented by the above formula (1) used in the present invention
The i-H group-containing compound has a number average molecular weight of 10,000 or less, preferably 200, because of the good reactivity of the Si-H group (dehydrogenative condensation reaction) during the modification treatment of the photocatalyst.
An H-terminated polydialkylsiloxane (formula (9)) of 0 or less, and more preferably 1000 or less can be preferably used. ^{_{H- (R 7 2 SiO) d}} -SiR 7 2 -H ··· (9) ( wherein, ^{R 7} linear or branched carbon atoms are each independently represent 1-30 alkyl group , D is an integer of 0 or more.) Further, in the present invention, modification obtained by modification treatment with a Si-H group-containing compound having the functionalizing group-containing group (Q) represented by the above formula (2). Photocatalysts are preferable because they can have various functions. Here, the functional group-containing group (Q) is preferably a group represented by the following formula (10). -Y- (Z) _w ... (10) (In the formula, Y represents a W-valent organic group having a molecular weight of 14 to 50,000, and Z is composed of the above-mentioned functionalization groups (a) to (e)). It is at least one selected from the group and W is an integer of 1 to 20.)

For example, as the functional group-containing group (Q),
At least one selected from the group consisting of a monovalent group containing a carboxyl group or a salt thereof, a monovalent group containing a phosphoric acid group or a salt thereof, a monovalent group containing a sulfonic acid group or a salt thereof, and a polyoxyalkylene group. When one having one hydrophilic group [(i) in formula (2)] is selected, the resulting modified photocatalyst has very good dispersion stability in water.

Further, for example, as the function-adding group-containing group (Q), a monovalent hydrophobic group containing a fluoroalkyl group having 1 to 30 carbon atoms which is a hydrophobic group [(A) in the formula (2)] When the modified photocatalyst having the above is selected, the resulting modified photocatalyst has a very small surface energy, and the modified photocatalyst of the present invention not only has a large self-grading property described later, but also can obtain a film having a very high hydrophobicity. Becomes Further, for example, as the functional group-containing group (Q), an epoxy group, an acryloyl group, a methacryloyl group, a (cyclic) acid anhydride group,
At least one reactive group selected from the group consisting of keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group and ester group [in formula (2) (U)]-containing groups are preferable because the modified photocatalyst of the present invention has crosslinkability and can form a coating film excellent in durability and the like.

Here, when the one having a monovalent group containing a hydrazine residue and / or a monovalent group containing a keto group is selected as the reactive group, the modified photocatalyst of the present invention has low-temperature curability and storage. It is particularly preferable because it enables hydrazone (semicarbazone) cross-linking which is useful for forming a film having stability and excellent water resistance, stain resistance, hardness and the like. In addition, for example, when a group having a spectral sensitizing group is selected as the functional group-containing group (Q), the modified photocatalyst of the present invention is
The catalytic activity and the photoelectric conversion function can be exhibited not only by the ultraviolet region but also by irradiation with light in the visible light region and / or the infrared light region.

Here, the spectral sensitizing group means a group derived from various metal complexes or organic dyes (that is, sensitizing dyes) having absorption in the visible light region and / or the infrared light region. Examples of sensitizing dyes include xanthene dyes, oxonol dyes, cyanine dyes, merocyanine dyes, rhodacyanine dyes, styryl dyes, hemicyanine dyes,
Merocyanine dyes, phthalocyanine dyes (including metal complexes), porphyrin dyes (including metal complexes), triphenylmethane dyes, perylene dyes, coronene dyes, azo dyes, nitrophenol dyes, and ruthenium. , Osmium, iron, zinc complexes, and other metal complexes such as ruthenium red (for example, JP-A 1-2203).
No. 80 and Japanese Patent Application Publication No. 5-504023).

Among these sensitizing dyes, they have absorption in the wavelength region of 400 nm or more, and the energy level of the lowest unoccupied orbital (redox potential of excited state) is higher than the energy level of the conduction band of the photocatalyst. Those having characteristics are preferable. The characteristics of such sensitizing dyes are that the absorption spectrum of light in the infrared, visible, and ultraviolet regions is measured, and the redox potential is measured by an electrochemical method (for example, T. Tani, Photogr.
i. Eng., 14, 72 (1970); RWBerriman et al., ibi
d., 17. 235 (1973); PBGilman Jr., ibid., 18, 475
(1974, etc.), calculation of energy levels using the molecular orbital method (for example, T. Tani et al., Photogr. Sci. Eng., 11, 1
29 (1967); DMSturmer et al., Ibid., 17.146 (197
3); ibid., 18, 49 (1974); RGSelby et al., J. Opt.
Soc. Am., 33, 1 (1970), etc.), and the presence or absence of electromotive force due to photoirradiation and efficiency of a Gratzel-type wet solar cell prepared with a photocatalyst and a spectral sensitizing dye.

As examples of the sensitizing dye having the above characteristics, compounds having a 9-phenylxanthene skeleton, 2,
Examples thereof include a ruthenium complex containing a 2-bipyridine derivative as a ligand, a compound having a perylene skeleton, a phthalocyanine-based metal complex, and a porphyrin-based metal complex. Si having a spectral sensitizing group derived from the above sensitizing dye
The method for obtaining the —H group-containing compound is not particularly limited, but, for example, by reacting the reactive group-containing Si—H group-containing compound with a sensitizing dye having reactivity with the reactive group. Obtainable. At least one selected from the above-mentioned functional group-containing groups (Q) can be used. In particular, when a photocatalytic hydrosol is selected as the photocatalyst to be modified, a hydrophilic group [(i) in the formula (2)] and another functional group ([a], (u) in the formula (2), ( E)] is also preferable because the modified photocatalyst hydrosol having a functional-imparting group to be produced has good stability. In the present invention, S having the function-imparting group-containing group (Q) represented by the above formula (2)
As a method for obtaining the i-H group-containing compound, (a) the Si-H group-containing compound represented by the above-mentioned formula (1) and the functionalization group [(a) to (e in the formula (2) )] Is used for the hydrosilylation reaction of the carbon-carbon unsaturated bond compound.

(B) Si-represented by the above formula (1)
After the H-group-containing compound and the carbon-carbon unsaturated bond compound having a reactive group [(U) in the formula (2)] are hydrosilylated to obtain a Si-H group-containing compound having a reactive group And a method of reacting a functional group-containing compound having reactivity with the reactive group. First, as a method of obtaining a Si—H group-containing compound [formula (2)] having a function-imparting group, the above-mentioned method (a) [hereinafter (a) -method] will be described. (A) -in the method, Si-represented by the above formula (1)-
In the H group-containing compound, a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number of 5 to 2 as a function imparting group.
0 cycloalkyl group, or an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom. As the carbon-carbon unsaturated bond compound used when introducing a hydrophobic group,
Olefin such as propylene, 1-butene, 1-hexene, 1-octene, isobutene, 2-methyl-1-butene, 2-hexene, cyclohexene, 5-norbornene, allyl acetate, allyl propionate, 2-ethylhexanoic acid Allyl esters such as allyl and allyl benzoate, allyl ethers such as allyl methyl ether, allyl ethyl ether, allyl-n-hexyl ether, allyl cyclohexyl ether, allyl-2-ethylhexyl ether, allyl phenyl ether, and (meth) acryl. (Meth) acrylic acid esters such as methyl acidate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and phenyl (meth) acrylate;
Vinyl acetates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, styrene, (meth) acrylonitrile And carbon-carbon unsaturated bond compounds such as crotonic acid esters. Of these, terminal olefins, 5-norbornenes, allyl esters, and allyl ethers are preferable in terms of reactivity.

The carbon-carbon unsaturated bond compound used when introducing a fluoroalkyl group having 1 to 30 carbon atoms as a function-imparting group into the Si-H group-containing compound represented by the above formula (1) is For example, olefins having a perfluoroalkyl group represented by the formula (11), allyl ethers, allyl esters, vinyl ethers, (meth)
Acrylic acid esters and the like can be used. _{- (CF 2) g CF 3} (11) ( wherein, g represents an integer of 0 to 29.) For introducing a hydrophilic group to the Si-H group-containing compound represented by the above formula (1) The carbon-carbon unsaturated bond compound used is at least one selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, a polyoxyalkylene group, and a cyclic acid anhydride. Olefins having hydrophilic groups, allyl ethers, vinyl ethers, vinyl esters,
Examples thereof include (meth) acrylic acid esters and styrene derivatives.

As a preferred specific example of the carbon-carbon unsaturated bond compound having a hydrophilic group, for example, an allyl ether formula (13) having a monovalent group containing a sulfonic acid group represented by the formula (12) or a salt thereof. ) Polyoxyethylene group-containing allyl ether represented by), and 5-norbornene-2,3-dicarboxylic acid anhydride.

[0046]

[Chemical 5]

(In the formula, n represents an integer of 1 to 100. R
⁸ represents a linear or branched alkyl group having 1 to 30 carbon atoms. B represents a hydrogen atom, an alkali metal, ammonium or a substituted ammonium represented by the following formula. HNR ⁹ R ¹⁰ R ¹¹ (R ⁹ , R ¹⁰ , and R ¹¹ are each independently a hydrogen atom, or a straight-chain or branched C1-C20 unsubstituted or substituted with a hydroxyl group. represents an alkyl _{group.)) CH 2 = CHCH 2} O (CH 2 CH 2 O) m R 12 (13) ( wherein, ^{.R 12} m is an integer of 1 to 1000 represents a hydrogen atom or a linear Represents a branched or branched alkyl group having 1 to 30 carbon atoms.)

The carbon-carbon unsaturated bond compound used for introducing a reactive group into the Si-H group-containing compound represented by the above formula (1) is an epoxy group, a (meth) acryloyl group, or ( (Cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group,
Olefins having at least one reactive group selected from the group consisting of ester groups, allyl ethers, allyl esters, vinyl ethers, vinyl esters,
Examples thereof include (meth) acrylic acid esters and styrene derivatives.

Preferred specific examples of the carbon-carbon unsaturated bond compound having the above reactive group include allyl glycidyl ether, glycidyl (meth) acrylate, allyl (meth) acrylate, diallyl ether, diallyl phthalate and (meth). Vinyl acrylate, vinyl crotonate, ethylene glycol di (meth) acrylic acid maleic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 5-hexen-2-one, allyl isocyanate, allyl alcohol, ethylene glycol Monoallyl ether, allyl amine, allyl isothiocyanate, allyl semicarbazide, (meth) acrylic acid hydrazide, 4-allyloxymethyl-2-oxo-1,3-
Dioxolane etc. can be mentioned.

The carbon-carbon unsaturated bond compound used for introducing the spectral sensitizing group into the Si-H group-containing compound represented by the above formula (1) is an olefin having the above-mentioned spectral sensitizing dye. , Allyl ethers, allyl esters, vinyl ethers, vinyl esters, (meth)
Examples thereof include acrylic acid esters and styrene derivatives. These include, for example, carbon-containing a reactive group as described above.
It can be easily obtained by reacting a carbon unsaturated bond compound with a spectral sensitizing dye having reactivity with the reactive group.

For example, the reactive group of the carbon-carbon unsaturated bond compound having a reactive group is an epoxy group, a (cyclic) acid anhydride, an isocyanate group, an isothiocyanate group, a cyclic carbonate group, an ester group, a keto group, ( In the case of (meth) acryloyl group, amino group, carboxyl group, hydroxyl group,
A spectral sensitizing dye having at least one functional group selected from the group consisting of a hydrazine residue and a (meth) acryloyl group, and conversely a reactive group of a carbon-carbon unsaturated bond compound having a reactive group is an amino group. Group, carboxyl group, hydroxyl group, hydrazine residue, (meth) acryloyl group, epoxy group, (cyclic) acid anhydride, isocyanate group, isothiocyanate group, cyclic carbonate group, ester group, keto group, (meth) Examples thereof include spectral sensitizing dyes having at least one functional group selected from the group consisting of acryloyl groups.

The reaction between the carbon-carbon unsaturated bond compound having a reactive group and the spectral sensitizing dye having a reactivity with the compound is carried out in accordance with the reaction temperature, reaction pressure, solvent, etc. depending on the kind of each reactive group. It can be carried out by selecting reaction conditions. that time,
From the viewpoint of the stability of the spectral sensitizing dye, the reaction temperature is 30.
It is preferably 0 ° C or lower, more preferably 150 ° C or lower and 0 ° C or higher. (A) -In the method, the hydrosilylation reaction of the carbon-carbon unsaturated bond compound and the Si-H group-containing compound represented by the formula (1) is preferably carried out in the presence of a catalyst, an organic solvent or 0-2 in the absence
Carbon-carbon unsaturated bond compound (H) and formula (1) at 00 ° C.
In the Si-H group-containing compound (B ') represented by, the mass ratio (H) / (B') = 0.01 or more, more preferably (H) / (B ') = 0.01 to 2, More preferably, it can be carried out by contacting with (H) / (B ′) = 0.01 to 1. At this time, the reaction product of the hydrosilylation reaction is Si-represented by the above formula (1).
It is obtained as a mixture containing the H group-containing compound and the Si—H group-containing compound represented by the formula (2). The obtained reaction product may be used as it is for modification of the photocatalyst, or may be separated and purified and used for modification of the photocatalyst.

As the catalyst for the hydrosilylation reaction, platinum group catalysts, that is, ruthenium, rhodium, palladium,
Compounds of osmium, iridium and platinum are suitable, but compounds of platinum and palladium are particularly suitable. Examples of the platinum compound include platinum (II) chloride,
Tetrachloroplatinic acid (II), platinum (IV) chloride, hexachloroplatinic acid (IV), hexachloroplatinum (IV) ammonium, hexachloroplatinum (IV) potassium, platinum (II) hydroxide, platinum (IV) dioxide, dichloro- Examples thereof include dicyclopentadienyl-platinum (II), platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-olefin complex and platinum simple substance, and alumina, silica or activated carbon on which solid platinum is supported. Examples of the palladium compound include palladium (II) chloride, ammonium tetraamminepalladium (II) chloride chloride, and palladium (II) oxide.

Examples of the organic solvent that can be used in the hydrosilylation reaction include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane and heptane, ethyl acetate, n-butyl acetate and the like. Esters, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide, halogen compounds such as chloroform, methylene chloride and carbon tetrachloride, dimethyl sulfoxide, Examples include nitrobenzene and the like, and mixtures of two or more thereof.

Next, as a method for obtaining a Si-H group-containing compound having a function-imparting group, the above-mentioned method (b) [hereinafter (b) -method] will be described. As the carbon-carbon unsaturated bond compound having a reactive group used in the (b) -method, those mentioned in the (a) -method can be mentioned. Further, the hydrosilylation reaction between the Si-H group-containing compound represented by the above formula (1) and the carbon-carbon unsaturated bond compound having the reactive group is carried out by the hydrosilylation reaction described in (a) -method. Can be carried out under the same conditions.

According to the (b) -method, a Si-H group-containing silicon compound having a reactive group having an average composition represented by the following formula (14) can be obtained by the above hydrosilylation reaction. ^{_{H- (R 2 2 SiO) b}} -SiR 2 2 -Q '··· (14) ( wherein, ^{R 2} and b are as defined in formula (2).
Q'is an epoxy group, an acryloyl group, a methacryloyl group, a (cyclic) acid anhydride group, a keto group, a carboxyl group,
At least one selected from the group consisting of hydrazine residues, isocyanate groups, isothiocyanate groups, hydroxyl groups, amino groups, cyclic carbonate groups, thiol groups, and ester groups.
It represents a monovalent group having two reactive groups. )

In the above (b) -method, the functional group-containing compound having reactivity with the Si-H group-containing compound [formula (14)] having a reactive group is, for example, the reactive group. Is an epoxy group, a (cyclic) acid anhydride, an isocyanate group, an isothiocyanate group, a cyclic carbonate group,
In the case of an ester group, a keto group, and a (meth) acryloyl group, a functionalizing group having at least one functional group selected from the group consisting of an amino group, a carboxyl group, a hydroxyl group, a hydrazine residue, and a (meth) acryloyl group. The compound is a containing compound, conversely the reactive group is an amino group, a carboxyl group,
In the case of a hydroxyl group, a hydrazine residue, a (meth) acryloyl group, a group consisting of an epoxy group, a (cyclic) acid anhydride, an isocyanate group, an isothiocyanate group, a cyclic carbonate group, an ester group, a keto group, and a (meth) acryloyl group. Examples thereof include a functional group-containing compound having at least one functional group selected from Here, the functional group-containing group is the same as the functional group-containing group (Q) in the above formula (2).

The reaction between the Si-H group-containing compound having a reactive group represented by the above formula (14) and the functional group-containing compound having a reactivity therewith depends on the kind of each reactive group. It can be carried out by selecting reaction conditions such as reaction temperature, reaction pressure, solvent and the like. At that time, from the viewpoint of the stability of the Si-H group,
The reaction temperature is preferably 300 ° C or lower, more preferably 150 ° C or lower and 0 ° C or higher. In addition, a preferred form of the modified photocatalyst of the present invention is a mixture of primary particles and secondary particles of the modified photocatalyst (either primary particles or secondary particles may be used).
Has a number average dispersed particle size of preferably 800 nm or less, more preferably 200 nm or less, and further preferably 100 n.
m or less. Further, it is preferably in a sol state. In particular, a modified photocatalyst sol having a number average dispersed particle size of 100 nm or less is extremely useful because a photocatalyst composition comprising a resin (E) described below can form a film having excellent transparency and a very large photocatalytic activity. Is preferred. Such a modified photocatalyst sol is obtained by using the above-mentioned photocatalyst sol as a photocatalyst that is modified with at least one Si—H group-containing compound selected from the above formulas (1) and (2). You can

The Si—H group-containing compound represented by the above formulas (1) and (2) used for obtaining the modified photocatalyst of the present invention has the following characteristics. 1) Having one or two Si-H groups in one molecule. 2) It has no easily hydrolyzable group (alkoxysilyl group, halogenated silyl group, etc.). 3) It is possible to efficiently introduce the functional group into the photocatalyst.

We have found that a modified photocatalyst modified with a Si-H group-containing compound having such a structure has excellent storage stability and is formed from a photocatalyst composition comprising the photocatalyst and a resin described later. It has been found that the film has various functions, and the controllability of water wettability (hydrophilicity, hydrophobicity) by photoirradiation and the photocatalytic activity become very large.
The modified photocatalyst of the present invention can be used as a photocatalyst composition comprising a resin. At this time, the solid content mass ratio of the modified photocatalyst (C) and the resin (E) in the photocatalyst composition is
Preferably (C) / (E) = 0.1 / 99.9 to 99 /
1, more preferably (C) / (E) = 1/99 to 90 /
It is 10.

As the resin usable in the photocatalyst composition of the present invention, all synthetic resins and natural resins can be used. The form thereof may be pellets or a form dissolved or dispersed in a solvent and is not particularly limited, but a form of a resin coating material for coating is most preferable. The resin paint that can be used in the present invention is not particularly limited, and known ones can be used. Examples of resin paints are oil-based paints, lacquers, solvent-based synthetic resin paints, water-based synthetic resin paints (emulsion-based, water-based resin-based, etc.), solvent-free synthetic resin paints (powder paints, etc.), inorganic paints, electrically insulating paints. Etc. can be mentioned.

The synthetic resin used in the synthetic resin coating material is acrylic resin, epoxy resin, urethane resin, silicone resin, fluororesin, alkyd resin, aminoalkyd resin, vinyl resin, unsaturated polyester resin, chlorinated rubber resin. Etc. and those obtained by mixing them or compositing them by copolymerization and the like can be mentioned. Among these resin coatings, a silicon-based resin or a fluorine-based resin which is hardly decomposed with respect to a photocatalyst, and a resin coating of a combination type of a silicon-based resin and a fluorine-based resin is preferably used.

Examples of the above-mentioned silicon-based resin include silicon-containing resins such as silicone resins, for example, silicon compounds represented by the following formula (15), and silicon compounds represented by the formula (15) and silica (colloidal silica, fumed). A mixture of silica and the like, and further a silicon compound represented by the formula (15) and / or silica (colloidal silica,
Fumed silica, etc.) Resin containing 1 to 90% by mass by mixing and / or copolymerization (for example, acrylic resin, epoxy resin, urethane resin, fluororesin or resin obtained by mixing or compositing them). Etc. can be mentioned. R _t X _u SiO _{(4-t-u) / 2} (15) (In the formula, R represents a functional group composed of one or more monovalent organic groups having 1 to 30 carbon atoms. X Is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or 1 carbon atom
~ 20 acyloxy group, aminoxy group, 1 to 20 carbon atoms
And at least one reactive group selected from the group consisting of halogen atoms. 0 ≦ t <4, 0 ≦ u <
4 and 0 <(t + u) ≦ 4. ) Examples of the silicon compound represented by the above formula (15) include silicon compounds containing at least one structure of silicon bonds represented by the formulas (4), (16), (17) and (18). You can

[0064]

[Chemical 6]

-(R ₂ SiO)-(16)

[0066]

[Chemical 7]

[0067]

[Chemical 8]

(In the formula, each R independently has 1 to 3 carbon atoms.
0 represents a monovalent organic group. ) A silicon compound containing the above-mentioned structure is, for example, represented by the formula RSi
X ₃ (In the formula, R represents a monovalent organic group having 1 to 30 carbon atoms. X represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an aminoxy group. Represents a trifunctional silane derivative represented by at least one reactive group selected from the group consisting of an oxime group having 1 to 20 carbon atoms and a halogen atom, and the same shall apply hereinafter) and / or represented by the formula R ₂ SiX _2. By partially hydrolyzing and polycondensing a bifunctional silane derivative represented by the formula SiX ₄ and / or a tetrafunctional silane derivative represented by the formula SiX ₄ , and optionally a monofunctional silane derivative represented by the formula R ₃ SiX and / or an alcohol. It can be prepared by termination. The polystyrene-converted weight average molecular weight of the partial condensate of the silane derivative monomer thus obtained is preferably 200 to 100,
000, and more preferably 400 to 50,000.

Of these, when the silicon compound represented by the above formula (15) contains 10 mol% or more, preferably 40 mol% or more of the ladder structure represented by the above formula (3), the present invention is selected. A coating film formed from the photocatalyst composition is preferable because it is very excellent in hardness, heat resistance, weather resistance, stain resistance, chemical resistance and the like. Further, as the silicon compound represented by the above formula (15), Ph-
When a phenyl group-containing silicone having 10 mol% or more of Si bonds (Ph: phenyl group) with respect to the entire R-Si bonds (R: monovalent organic group having 1 to 30 carbon atoms) is selected, the phenyl group-containing silicone is obtained. A film formed from the photocatalyst composition comprising the modified photocatalyst of the present invention is very preferable because it has a very large hydrophilicity by light irradiation. Further, the hydrophilicity and the adhesiveness to an organic resin have the above-mentioned R-Si.
It increases as the ratio of Ph-Si bonds to the total bonds increases. Therefore, a more preferable structure as the phenyl group-containing silicone used in the photocatalyst composition of the present invention is R
The ratio of Ph-Si bonds to the entire —Si bonds is 20 mol% or more, more preferably 50 mol% or more, and further preferably 100 mol% (the following formula (5)). ^{_{R 5 p X r SiO (4}} -p-r) / 2 (5) ( wherein, ^{R 5} represents a phenyl group, X represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, 1 to 4 carbon atoms ~ 20
Represents at least one reactive group selected from the group consisting of an acyloxy group, an aminoxy group, an oxime group having 1 to 20 carbon atoms, and a halogen atom, and 0 <p <4, 0 <r <4, and 0 <(p + r ) <4. )

As the silicon compound represented by the above formula (15), the phenyl group-containing silicone (F) described above and the alkyl group-containing silicone (G) represented by the following formula (6) are preferably used in a mass ratio. (F) / (G) = 5
/ 95 to 95/5, more preferably (F) / (G) = 3
When the mixture of 0/70 to 90/10 is used, the coating film formed from the photocatalyst composition of the present invention is excellent in film formability, hardness, heat resistance, stain resistance, chemical resistance and the like. It is preferable because it can be obtained. ^{_{R 6 q X s SiO (4}} -q-s) / 2 (6) ( wherein, ^{R 6} represents a linear or branched alkyl group having 1 to 30 carbon atoms, X is a hydrogen atom, a hydroxyl group , Carbon number 1
To at least one reactive group selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an aminoxy group, an oxime group having 1 to 20 carbon atoms, and a halogen atom, and 0 <q <4, 0 <s <4, and 0 <(q +
s) <4. )

Further, as the alkyl silico compound (G) to be mixed with the above-mentioned phenyl group-containing silicone (F), a monooxydiorganosilane unit (D) represented by the formula (7) and a formula (8) are represented. The molar ratio (D) / (T) of dioxyorganosilane units (T) is 80/20 to 5 /.
When a structure having a ratio of 95 is used, the stress relaxation effect of the alkyl group-containing silicone is increased, and the crack resistance of the film or molded product produced from the photocatalyst composition of the present invention is improved, resulting in extremely high weather resistance. It is preferable because it becomes excellent.

[0072] _{^{- (R 6 2 SiO) -}} (7)

[0073]

[Chemical 9]

(In the formula, R ⁶ represents a linear or branched alkyl group having 1 to 30 carbon atoms.) The above-mentioned silicone resin which can be used in the photocatalyst composition of the present invention is of a type dissolved in a solvent. It may be a dispersion type or a powder type, and may contain additives such as a crosslinking agent and a catalyst. Examples of the fluorine-based resin that can be used in the photocatalyst composition of the present invention include PTFE and polyvinylidene fluoride, and further an acrylic-fluorine resin having a fluorine content of 1 to 80% by mass, an epoxy-fluorine resin,
Urethane-fluorine resins and fluoroolefins and carbon-carbon unsaturated compounds (vinyl ethers, vinyl esters, allyl compounds, (meth) acrylic acid esters, etc.)
And the like. These fluorine-based resins may be of any type dissolved in a solvent, dispersion type or powder type, and may contain additives such as a crosslinking agent and a catalyst.

In the photocatalyst composition of the present invention, if necessary, components which are usually added to and mixed with paints such as pigments, fillers, dispersants, light stabilizers, wetting agents, thickeners, rheology control agents, Defoaming agent, plasticizer, film forming aid, rust inhibitor,
Dyes, preservatives and the like can be selected and combined in combination according to each purpose. The modified photocatalyst of the present invention, which has a structure having a very small surface energy
-H group-containing compound [preferably one in which the functional group (Q) in formula (1) and / or formula (2) is a hydrophobic group (a)]
The photocatalyst composition of the present invention composed of the modified photocatalyst modified by the method (1) and the resin (E) can have a self-grading property with respect to the distribution of the modified photocatalyst.

The term "self-gradient" as used herein means the property of the interface (particularly hydrophilic / hydrophilic) where the modified photocatalyst is in contact with the film or molded product when the film or molded product is formed from the photocatalyst composition.
(Hydrophobicity) means autonomously forming a structure having a concentration gradient of the modified photocatalyst. In this case, if there is a difference in properties (hydrophilicity / hydrophobicity) between the surfaces in contact with each other, a concentration gradient occurs corresponding to the difference, and a concentration gradient occurs between the inside of the film or molded article and the interface. ..

For example, when the above-mentioned self-grading photocatalyst composition is applied on a substrate to form a film, the amount of the modified photocatalyst increases toward the surface of the film in contact with another interface (for example, outside air) which is not the substrate. It is possible to obtain a graded composition film having a concentration gradient in the thickness direction. At this time, when the relative concentration of the modified photocatalyst content (concentration) in the entire film is 100 or more in the vicinity of the surface side in contact with another interface, the effect of improving the photocatalytic ability and the hydrophilizing ability is recognized. The relative concentration near the surface side is preferably 150 or more, more preferably 200 or more. In addition, the relative concentration near the interface on the substrate side is 80
The effect of preventing interfacial deterioration is recognized when it is below. The relative concentration near the substrate-side interface is preferably 50 or less, more preferably 10 or less. At this time, the concentration of the modified photocatalyst in the film may gradually increase from the surface in contact with the base material to the other exposed surface, or the concentration of the modified photocatalyst in the surface in contact with the base material may be low, and The concentration of the modified photocatalyst on the exposed surface of is high, and the change during that may be discontinuous.

When the photocatalyst composition of the present invention is self-grading, the solid content mass ratio of the modified photocatalyst (C) and the resin (E) in the photocatalyst composition is (C) / (E) = 0.1. / 9
9.9-40 / 60, and further (C) / (E) = 0.1
Even if the content of the modified photocatalyst is very low, ie, 99.9 to 30/70, the formed film or molded article has a sufficient hydrophilizing ability (superhydrophilizing ability:
It has a contact angle of water at 20 ° C. of 10 ° or less) and photocatalytic activity. In addition, the film or molded product having such a small photocatalyst content exhibits the original physical properties of the resin as a binder, and thus has excellent strength and flexibility (bending resistance, impact resistance) and the like.

The molded article formed from the photocatalyst composition of the present invention and the functional composite obtained by forming a film formed from the above photocatalyst composition on a substrate are hydrophobic or hydrophilic when exposed to light. It is possible to exhibit a photocatalytic activity and / or a photoelectric conversion function. That is, in another aspect of the present invention, there is provided a molded body formed from the above photocatalyst composition, and a functional composite obtained by forming a film formed from the above photocatalyst composition on a substrate. .

In the present invention, in order to improve the long-term weather resistance of the above-mentioned functional composite or molded article, the resin (E) contained therein is used.
Preferably has a phase-separated structure, and particularly preferably has a microphase-separated structure. For example, as the resin (E), a resin (E ′) having a surface energy higher than that of the modified photocatalyst (C) described above and an alkyl group-containing silicone (G) represented by the above formula (6) are preferably used in a mass ratio ( E ′) / (G) = 5/95 to 95/5, more preferably (E ′) / (G) = 30/70 to 90/10
When a mixture of the above is used, the film or molded product formed from the photocatalyst composition of the present invention is a modified photocatalyst in a binder in which a resin (E ′) having high surface energy and an alkyl group-containing silicone (G) are phase-separated. (A) has a dispersed structure and is excellent in long-term weather resistance, which is preferable.

In the phase separation of the resin (E ') having a high surface energy and the alkyl group-containing silicone (G), the phase which is not a continuous layer is preferably 1 nm ³ to 1 μm ³ ,
More preferably 10nm ³ ~0.1μm ^3, when more preferably separated micro phase by forming domains with sizes of 10nm ³ ~0.001μm ^3, exhibited more effectively. In addition, the modified photocatalyst (C) is present in the alkyl group-containing silicone (G) phase that is in a phase-separated state with the resin (E ′) having a high surface energy, because the modified photocatalyst (C) is more likely to be present on the surface of the formed film or molded article. A modified photocatalyst (C) can be present, which is preferred.

Resin (E ') having a high surface energy which is phase-separated from the alkyl group-containing silicone (G) in the present invention.
As the above-mentioned phenyl group-containing silicone (F)
However, the siloxane bond (—O—Si—) forming the skeleton is preferable because oxidative decomposition due to photocatalytic action does not occur,
Phenyl group-containing silicones containing no alkyl groups are particularly preferred. At this time, the polystyrene-converted weight average molecular weight of each of the phenyl group-containing silicone (F) and the alkyl group-containing silicone (G) measured by GPC is preferably 100 to 10,000, more preferably 500 to 6, 000, more preferably 700 to 4,0
It is preferable to use those of No. 00 because they easily form a microphase-separated structure.

In the present invention, as a method for obtaining a functional composite or a molded product from the above-mentioned photocatalyst composition, for example, when the form is a paint, it is applied to a base material, dried, and then subjected to a heat treatment or the like if necessary. By doing so, the functional complex of the present invention can be obtained. As a coating method, for example, a spraying method, a flow coating method, a roll coating method,
Examples thereof include a brush coating method, a dip coating method, a spin coating method, a screen printing method, a casting method, a gravure printing method, and a flexographic printing method.

Further, for example, when the photocatalyst composition is in the form of pellets, the molded product of the present invention can be obtained by extrusion molding, injection molding, press molding or the like. The above-mentioned functional composite or molded body formed from the photocatalyst composition of the present invention has a higher energy than the bandgap energy of the photocatalyst contained therein (in the case where the modified photocatalyst has a spectral sensitizing dye, By irradiating with light including the absorption light of the spectral sensitizing dye)
Alternatively, it exhibits a photocatalytic activity and further a photoelectric conversion function.

At this time, in the functional composite or molded product obtained from the photocatalyst composition of the present invention, the photocatalyst is provided around the photocatalyst of the modified photocatalyst contained therein, and the photocatalyst is represented by the formula (1) or (2) of the present invention. Since there is a compound which is not decomposed in the molecular skeleton due to the decomposition action of the photocatalyst, which is generated by the modification treatment with at least one or more Si-H group-containing compounds selected from the above, the resin as the binder or the structural material has a photocatalytic action. Hard to be deteriorated by. In addition, the photocatalyst existing around the photocatalyst of the modified photocatalyst by light irradiation is converted into a silicon atom of a compound produced by modifying the photocatalyst with the above Si—H group-containing compound (formula (1) and / or formula (2)). The bound organic group is replaced by a hydroxyl group by photocatalytic action to hydrophilize the surface of the coating film and the structural material, and further generate Si.
An extremely high hardness film or molded product can be obtained by the progress of the dehydration condensation reaction between —OH groups. Furthermore, the functional composite or molded product having a film thus obtained can exhibit various photocatalytic activities.

In the present invention, as a light source of light having an energy higher than the band gap energy of the photocatalyst (when the modified photocatalyst has a spectral sensitizing dye, light containing absorbed light of the spectral sensitizing dye), the solar light is used. In addition to light obtained in a general residential environment such as light and indoor lighting, light such as black light, xenon lamp, and mercury lamp can be used. The above-mentioned molded article or functional composite provided by the present invention, which has photocatalytic activity such as decomposition of organic matter, is antibacterial, antifouling,
It exhibits various functions such as deodorization and NOx decomposition, and can be used for applications such as environmental purification of the atmosphere and water.

The above-mentioned molded article or functional composite provided by the present invention, which is hydrophilic and has a contact angle with water at 20 ° C. of 60 ° or less (preferably 10 ° or less) by light irradiation. (Hydrophilic hydrophilic film, substrate coated with the hydrophilic film, etc.) is applied to antifogging technology for preventing fogging of mirrors and glass, and also for antifouling technology and antistatic technology for building exteriors, etc. Can be applied.

Examples of application of the molded product or functional composite of the present invention to the field of antifouling technology include, for example, building materials, building exteriors, building interiors, window frames, window glasses, structural members, building equipment such as houses,
In particular, toilet bowls, bathtubs, washbasins, lighting fixtures, lighting covers, kitchen utensils, dishes, dishwashers, tableware dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, etc. It can also be used for interiors, and is effective for use in parts that require transparency such as vehicle lighting covers, window glasses, measuring instruments, and display panels.In addition, the exterior of machinery and equipment, dust-proof covers and painting, Display equipment, its covers, traffic signs, various display devices, display objects such as advertising towers, sound insulation walls for roads, railways, exterior and painting of bridges, guardrails, tunnel interior and painting, insulators, solar cell covers, solar hot water Exterior parts of electronic and electric devices used outside such as heat collection covers, especially transparent members, vinyl house, greenhouses, etc., especially transparent members, and there is a risk of contamination even in the room Border, for example, facilities for medical and physical education, mention may be made of the use of the device, and the like.

Examples of application of the molded product or functional composite of the present invention to the field of antifogging technology include, for example, mirrors (rear confirmation mirrors for vehicles, mirrors for bathrooms, mirrors for washrooms, dental mirrors, road mirrors, etc.). , Lenses (eyeglass lenses, optical lenses, illumination lenses, semiconductor lenses, copier lenses, rear view camera lenses for vehicles, etc.), prisms, window glass for buildings and observation towers, vehicle window glasses (automobiles, railway vehicles) , Aircraft, ships, submersibles, snowmobiles, ropeway gondola, amusement park gondola, spacecraft, etc.), vehicle windshield (automobile,
Motorcycles, railway vehicles, aircraft, ships, submersibles, snowmobiles, snowmobiles, ropeway gondola, amusement park gondola, spaceship, etc.), protective goggles, sports goggles, protective mask shield, sports mask Shield, helmet shield, frozen food display case glass, warm food display case glass, measuring instrument cover, vehicle rear confirmation camera lens cover, focusing lens for laser dental treatment equipment, laser for inter-vehicle distance sensor, etc. Examples thereof include a cover for a light detection sensor, a cover for an infrared sensor, a filter for a camera, and the like. Examples of applications of the molded product or functional composite of the present invention to the field of anti-fog technology include, for example, cathode ray tubes, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, household electric appliances. Product housings, parts, exteriors and coatings, OA equipment Product housings, parts, exteriors and coatings, building materials, building exteriors, building interiors, window frames, window glasses, structural members, vehicle exteriors and coatings, machinery and equipment Applications include exteriors, dust-proof covers and coatings.

The above-mentioned molded article or functional composite provided by the present invention, which is hydrophilic and has a contact angle with water at 20 ° C. of 60 ° or less (preferably 10 ° or less) by light irradiation. (Hydrophilic hydrophilic film, substrate coated with the hydrophilic film, etc.) is applied to antifogging technology to prevent fogging of mirrors and glass, and also to antifouling technology and antistatic technology for building exteriors, etc. Can be applied to: window glass, mirrors, lenses, goggles, covers, insulators, building materials, building exteriors, building interiors, structural members, vehicle exteriors and paintings, machine and article exteriors, various display devices, lighting devices. , Home appliances, tableware, kitchen utensils, household appliances, magneto-optical recording media, optical recording media, etc.

The above-mentioned molded article or functional composite provided by the present invention, which is hydrophobic and has a contact angle with water at 20 ° C. of 70 ° or more (preferably 90 ° or more) by light irradiation. (Hydrophobic moldings, hydrophobic films, substrates coated with the hydrophobic film, etc.) is an antifouling technology that uses drip-proof properties and water-drainage properties, prevents the attachment of water-based stains, and cleans with running water. Moreover, it can be applied to frost and snow prevention technology, etc., such as window glass, windshield, mirror, lens, goggles, cover, insulator, building material, building exterior, building interior, structural member, vehicle exterior and painting, machinery. It can be used for applications such as exteriors of devices and articles, various display devices, lighting devices, housing equipment, tableware, kitchen appliances, household electric appliances, roofing materials, antennas, power lines, snow and snow runners, and the like.

The above-mentioned molded body or functional composite provided by the present invention, which has a photoelectric conversion function, can exhibit functions such as power conversion of solar energy, and is a (wet) solar cell. It can be used for applications such as optical semiconductor electrodes used for the above. Further, the member provided with the present invention whose wettability with water is changed by light irradiation (change from hydrophobicity to hydrophilicity or from hydrophilicity to hydrophobicity) can be used for offset printing original plates and the like. Very useful for applications.

[0093]

The present invention will be described in detail with reference to the following examples, reference examples and comparative examples, but these do not limit the scope of the present invention. In Examples, Reference Examples and Comparative Examples, various physical properties were measured by the following methods. 1. Particle size distribution and number average particle size The particle size distribution and number average particle size are appropriately diluted by adding a solvent so that the solid content in the sample is 1 to 20 mass%,
Wet particle size analyzer (Nikkiso Co., Ltd. Microtrac
UPA-9230).

2. Using weight average molecular weight gel permeation chromatography,
It was determined from a polystyrene standard calibration curve. (Devices used) -Device: Tosoh Corporation HLC-8020 LC-3A-Column: Tosoh Corporation TSKgel G-1000 HXL TSKgel G-2000 HXL TSKgel G-4000 HXL-Data processing: Shimadzu Corporation CR- 4A ・ Carrier: Tetrahydrofuran

3. Infrared absorption spectrum Infrared absorption spectrum is JASCO FT / IR-4
It was measured at 10. 4. ²⁹ Si measuring ²⁹ Si nuclear magnetic resonance of nuclear magnetic resonance, was measured by JNM-LA400 (JEOL Co., Ltd.). 5. The hardness of the hardness sample was determined as a pencil hardness (scratch of the coating film) according to JIS-K5400. The hardness of the coating film after UV irradiation is measured by UV intensity meter (U made by Topcon Corp.)
VR-2 (light receiving part: UD-36 (310-400n
m)) adjusted to have an ultraviolet intensity of 1 mW / cm ² (Toshiba Lightec Co., Ltd.)
FL20S BLB (manufactured by FL20S) was irradiated for 3 days and then measured by the above method.

6. Contact angle of water with respect to sample surface After placing a drop of deionized water on the surface of the sample and leaving it at 20 ° C. for 1 minute, a contact angle meter (CA-X manufactured by Kyowa Interface Science Co., Ltd.)
150) was used to measure the contact angle. The smaller the contact angle of water with respect to the coating film, the more hydrophilic the coating surface. 7. Measurement of water contact angle of sample surface after UV irradiation After irradiating the surface of the coating film with light of black light (FL20S BLB manufactured by Toshiba Lighting & Technology Co., Ltd.) for 3 days, the contact angle of water was measured by the method 6 above. did. At this time, the intensity of light was measured by an ultraviolet intensity meter (UVR-2 (U manufactured by Topcon Corporation).
D-36 type light receiving part: corresponding to light having a wavelength of 310 to 400 nm)) was adjusted so that the ultraviolet intensity was 1 mW / cm ² .

8. Measurement of water contact angle of sample surface after sunlight irradiation After irradiating the sample surface with sunlight for a total of 50 hours, the contact angle of water was measured by the above method 6. At this time, the ultraviolet intensity (using the UD-36 type light receiving unit described above as a light receiving unit) measured with a UVR-2 type UV intensity meter manufactured by Topcon was 0.1 to 0.3 mW / cm ² , and the same ultraviolet intensity. Visible light intensity measured using a meter (as a light receiving part, Topcon UD-
The sunlight intensity was adjusted using a glass plate so that the 40-type light receiving part (corresponding to light having a wavelength of 370 to 490 nm) was ² to 3 mW / cm ² .

9. Evaluation of Photocatalytic Activity by UV Irradiation of Sample After coating a 5% by mass solution of methylene blue in ethanol on the surface of the sample, the above black light was irradiated for 5 days. At this time, the UV intensity measured using the UVR-2 type UV intensity meter (using the UD-36 type light receiving unit as the light receiving unit) was adjusted to be 1 mW / cm ² . Then, the degree of decomposition of methylene blue due to the action of the photocatalyst (visually evaluated based on the degree of fading of the coating film surface)
Based on the above, the activity of the photocatalyst was evaluated in the following three stages. ⊚: Methylene blue is completely decomposed. Δ: A slight blue color of methylene blue remains. X: Almost no decomposition of methylene blue was observed.

10. Evaluation of photocatalytic activity of sample by sunlight irradiation After irradiating the sample surface with sunlight for 5 hours according to the above method 5, a 1% by mass aqueous solution of methylene blue was applied, and further sunlight was irradiated for 50 hours according to the above method 8. Irradiated. afterwards,
Based on the degree of decomposition of methylene blue due to the action of the photocatalyst (based on the degree of fading of the sample surface and visually evaluated), the activity of the photocatalyst was evaluated in the following three stages. ○: Methylene blue was completely decomposed. Δ: A slight blue color of methylene blue remains. X: Almost no decomposition of methylene blue was observed. 11. Weather resistance of coating film (gloss retention) The weather resistance of the coating film is an exposure test (irradiation: 60 ° C. for 4 hours, darkness) using a due panel light control weather meter (DPWL-5R manufactured by Suga Test Instruments Co., Ltd.).・ Jun: 40 ℃
4 hours). 60 ° -60 after 1000 hours of exposure
The specular reflectance was measured as the final gloss value, this was divided by the initial gloss value, and this value was calculated as the gloss retention rate. 12. Evaluation of Graded Structure of Photocatalyst The graded structure of photocatalyst in a member was evaluated by making an ultrathin section of the cross section of the member and TEM observation (HF2 manufactured by Hitachi Ltd.).
000).

Reference Example 1 Synthesis of silicon resin (1). Phenyltrichlorosilane 2 was added to 780 g of dioxane placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer.
After adding 60 g, the mixture was stirred at room temperature for about 10 minutes. To this, a mixed liquid consisting of 32 g of water and 129 g of dioxane,
After the reaction solution was added dropwise over about 30 minutes while maintaining it at 10 to 15 ° C, the reaction solution was further stirred at 10 to 15 ° C for about 30 minutes, and subsequently the reaction solution was heated to 60 ° C and stirred for 3 hours. The temperature of the obtained reaction liquid was lowered to 25 to 30 ° C., 3920 g of toluene was added dropwise over about 30 minutes, and then the reaction liquid was heated to 60 ° C. again and stirred for 2 hours.

The obtained reaction liquid was cooled to 10 to 15 ° C., and 192 g of methanol was added over about 30 minutes. After that, stirring was further continued at 25 to 30 ° C for about 2 hours, and then the reaction liquid was heated to 60 ° C and stirred for 2 hours. The solvent was distilled off from the obtained reaction solution at 60 ° C. under reduced pressure to obtain a silicon-based resin (1) having a ladder skeleton having a weight average molecular weight of 3600. (The obtained silicon-based resin (1) has absorptions (1130 cm ^-1 and 1037 cm) derived from stretching vibration of the ladder skeleton in the IR spectrum.
^-1 ) was observed. ) Further, the formula of the phenyl group-containing silicone (BP1-1) obtained from the measurement result of ²⁹ Si nuclear magnetic resonance is (P
h) ₁ (OCH ₃ ) _0.58 SiO _1.21 .
(Here, Ph represents a phenyl group.)

Reference Example 2 Synthesis of Silicon Resin (2). 1 Methyltrimethoxysilane was added to 300 g of methanol placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer.
36 g (1 mol) and dimethyldimethoxysilane 12
After adding 0 g (1 mol), the mixture was stirred at room temperature for about 10 minutes. Under this, under ice cooling, 0.05N hydrochloric acid aqueous solution 12.
A mixed solution of 6 g (0.7 mol) and 63 g of methanol was added dropwise over about 40 minutes to carry out hydrolysis. After completion of dropping, the mixture was further stirred at 10 ° C. or lower for about 20 minutes and at room temperature for 6 hours.

Thereafter, the reaction solution obtained was depressurized at 60 ° C.
Weight average molecular weight of 3600 by distilling off the solvent under
To obtain a silicone resin (2). The obtained silicon tree
The structure of fat (2)²⁹Measured by Si nuclear magnetic resonance
Around the time, signals indicating T structure and D structure were confirmed.
The ratio was T structure: D structure = 1: 1. Also,²⁹S
i Containing the above alkyl group obtained from the measurement result of nuclear magnetic resonance
The average composition formula of silicone (BA-1) is (CH_Three)
_1.5(OCH_Three)_0.27SiO _1.12.Met.

Reference Example 3 Synthesis of Si-H Group-Containing Compound Having Reactive Group In a reactor equipped with a reflux condenser, a thermometer and a stirrer, 200 g of dioxane and 1,1,3,3-tetra 200 g of methyldisiloxane (trade name: LS-7040, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the temperature was raised to 80 ° C. with stirring. To this, 20 g of 5-norbornene-2,3-dicarboxylic anhydride and dichloro-dicyclopentadienyl-
A solution of 10 g of a 0.25 mass% platinum (II) in dioxane dissolved in 70 g of dioxane was added with stirring at 80 ° C. over about 30 minutes, and the mixture was further stirred at 80 ° C. for 3 hours and then allowed to reach room temperature. By cooling, a solution containing a Si-H group-containing compound having a state-like acid anhydride as a reactive group was obtained.

To 0.488 g of the obtained solution containing the Si-H group-containing compound having a reactive group was added butyl cellosolve 8
After adding and mixing g, 1N sodium hydroxide aqueous solution 8
When ml is added, hydrogen gas is generated and its volume is 25
It was 68.0 ml at ° C. The Si-H group content per 1 g of the solution containing the Si-H group-containing compound having a reactive group was 5.525 mmo, which was determined from the amount of hydrogen gas produced.
It was 1 / g.

Reference Example 4 Synthesis of Si-H Group-Containing Compound Having Hydrophilic Group Solution containing Si-H group-containing compound having reactive group obtained in Reference Example 3 in a reactor equipped with a stirring device. 125 g was added, 3 g of triethylamine and 0.54 g of water were added thereto, and stirring was continued at 10 ° C. for 3 hours to obtain a solution containing a Si—H group-containing compound having a carboxyl group as a hydrophilic group. The obtained reaction liquid had good dispersibility in water.

[Reference Example 5] Synthesis of Si-H group-containing compound having spectral sensitizing group Si containing the reactive group obtained in Reference Example 3 in a reactor equipped with a reflux condenser, a thermometer and a stirrer. 125 g of a solution containing a compound containing an H group was added, and a solution of 1.1 g of 4-aminofluorescein dissolved in 75 g of dioxane was added thereto at 20 ° C. over about 30 minutes with stirring, and a further 50
A solution containing a Si—H group-containing compound having a yellow spectral sensitizing group was obtained by continuing stirring at 3 ° C. for 3 hours.

Example 1 Titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd., dispersion medium: charged in a reactor having a reflux condenser, a thermometer and a stirrer).
Mixed solvent of toluene and isopropanol, TiO ₂ concentration 20% by mass, average crystallite size 6 nm (catalog value) 40
4 g of 1,1,3,3-tetramethyldisiloxane (trade name: LS-7040, manufactured by Shin-Etsu Chemical Co., Ltd.)
Addition was carried out at 0 ° C. for about 5 minutes, and stirring was continued at 40 ° C. for 48 hours to obtain a modified titanium oxide organosol (1) having excellent dispersibility. At this time, 1, 1,
The amount of hydrogen gas generated by the reaction of 3,3-tetramethyldisiloxane was 2570 ml at 23 ° C.
Further, the obtained modified titanium oxide organosol (1) was added to K
When it was coated on a Br plate and the IR spectrum was measured, absorption of Ti—OH groups (3630 to 3640c
The disappearance of m ⁻¹ ) was observed.

1 and 2, titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd.) and modified titanium oxide organosol (1) before modification treatment, respectively.
The particle size distribution of is measured by using a wet particle size analyzer (Microtrac UPA-9230 manufactured by Nikkiso Co., Ltd.). Obtained modified titanium oxide organosol (1)
Has a monodispersed particle size distribution (number average particle size is 22 nm), and the monodispersed particle size distribution (number average particle size is 12 nm) of the titanium oxide organosol before modification has completely disappeared. I know that

[Example 2] Titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd., dispersion medium: charged in a reactor having a reflux condenser, a thermometer and a stirrer)
Mixed solvent of toluene and isopropanol, TiO ₂ concentration 20% by mass, average crystallite size 6 nm (catalog value) 40
8 g of DMS-H03 (trade name of H-terminated polydimethylsiloxane, Si-H group content 3.35 mmol / g, weight average molecular weight 600, manufactured by Chisso Corporation) was added to g at 40 ° C. over about 5 minutes. Then, by continuing stirring at 40 ° C. for 48 hours, a modified titanium oxide organosol (2) having very good dispersibility was obtained. At this time, the amount of hydrogen gas generated by the reaction of DMS-H03 was 500 at 23 ° C.
It was ml. Moreover, when the obtained modified titanium oxide organosol (2) was coated on a KBr plate and the IR spectrum was measured, absorption of Ti—OH groups (3630-
The disappearance of 3640 cm ^-1 was observed.

The particle size distribution of the obtained modified titanium oxide organosol (2) was a single dispersion (the number average particle size was 18 n).
m), and the particle size distribution of the monodispersed titanium oxide organosol (having a number average particle size of 12 nm) before the modification treatment completely disappeared.

Example 3 Titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd., dispersion medium: charged in a reactor having a reflux condenser, a thermometer and a stirrer)
Mixed solvent of toluene and isopropanol, TiO ₂ concentration 20% by mass, average crystallite size 6 nm (catalog value) 40
20 g of the solution containing the Si-H group-containing compound having the reactive group obtained in Reference Example 3 was added to g at 40 ° C. over about 5 minutes, and the mixture was further stirred at 40 ° C. for 12 hours,
A modified titanium oxide organosol (3) having very good dispersibility was obtained. At this time, the amount of hydrogen gas produced by the reaction was 1920 ml at 23 ° C.

Further, the obtained modified titanium oxide organosol (3) was coated on a KBr plate, and the IR spectrum was measured. As a result, absorption of Ti--OH groups (3630-3
The disappearance of 640 cm ⁻¹ was observed. In addition, 1780
absorption by cm ^-1 and 1861cm ^-1 cyclic acid anhydride group was observed. The particle size distribution of the obtained modified titanium oxide organosol (3) was a single dispersion (the number average particle size was 27 n
m), and the particle size distribution of the monodispersed titanium oxide organosol (having a number average particle size of 12 nm) before the modification treatment completely disappeared.

Example 4 Titanium oxide hydrosol (trade name: TKS-203, manufactured by Teika Co., Ltd., neutral, T) placed in a reactor having a reflux condenser, a thermometer and a stirring device.
A solution containing the Si—H group-containing compound having a hydrophilic group obtained in Reference Example 4 after adding 29.1 g of water to 10.9 g of an iO ₂ concentration of 22 mass% and an average crystallite size of 6 nm (catalog value) Add 3 g at 40 ° C over about 5 minutes and add 40 more
By continuing stirring at 12 ° C. for 12 hours, a modified titanium oxide hydrosol (4) having very good dispersibility was obtained. At this time, the amount of hydrogen gas generated by the reaction was 2 at 23 ° C.
It was 52 ml.

Further, the obtained modified titanium oxide hydrosol (4) was coated on a KBr plate and the IR spectrum was measured. As a result, absorption of Ti--OH groups (3630 to 36) was observed.
Disappearance of 40 cm ^-1 ) was observed. The particle size distribution of the obtained modified titanium oxide hydrosol (4) was a single dispersion (the number average particle size was 19 nm), and the titanium oxide organosol before the modification treatment was a single dispersion (the number average particle size). Is 12
(nm) particle size distribution has completely disappeared.

Example 5 Titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd., dispersion medium: charged in a reactor having a reflux condenser, a thermometer and a stirrer)
Mixed solvent of toluene and isopropanol, TiO ₂ concentration 20% by mass, average crystallite size 6 nm (catalog value) 40
16 g of a solution containing the Si—H group-containing compound having the spectral sensitizing group obtained in Reference Example 5 was added to g at 40 ° C. over about 5 minutes, and the mixture was further stirred at 40 ° C. for 12 hours,
A modified titanium oxide organosol (5) having very good dispersibility was obtained. At this time, the amount of hydrogen gas generated by the reaction was 1040 ml at 23 ° C.

Further, the obtained modified titanium oxide organosol (5) was coated on a KBr plate and the IR spectrum was measured.
The disappearance of 640 cm ⁻¹ was observed. The particle size distribution of the obtained modified titanium oxide organosol (5) was a single dispersion (the number average particle size was 27 nm), and the single dispersion of the titanium oxide organosol before the modification treatment (the number average particle size was a number average particle size). Particle size distribution of 12 nm) has completely disappeared.

Example 6 Visible light responsive titanium oxide hydrosol (trade name: NTB-200, Showa Denko KK) placed in a reactor having a reflux condenser, a thermometer and a stirrer.
Made, TiO2 concentration 2.5 mass%, average crystallite diameter 10 nm
(Catalog value) 40 g of 96 g, 3 g of the solution containing the Si-H group-containing compound having a hydrophilic group obtained in Reference Example 4
The mixture was added at about 5 ° C. over about 5 minutes, and the mixture was further stirred at 40 ° C. for 12 hours to obtain a visible light responsive modified titanium oxide hydrosol (6) having excellent dispersibility. At this time, the amount of hydrogen gas generated by the reaction was 2 at 23 ° C.
It was 02 ml.

Example 7 12 g of the modified titanium oxide organosol (1) prepared in Example 1 was added to 80 g of a 20 mass% toluene solution of the silicon resin (1) synthesized in Reference Example 1.
Was added under stirring at room temperature, 20 g of isopropanol and 22 g of butyl cellosolve were added with stirring, and 0.5 g of a curing catalyst (dibutyltin dilaurate) was added with stirring to obtain a photocatalyst composition (1). It was
The photocatalyst composition (1) thus obtained was coated on a glass plate to give a film thickness of 2 μm.
After spray coating so as to have a thickness of m, it was dried at room temperature for 1 hour and heated at 150 ° C. for 30 minutes to obtain a glass plate having a transparent and smooth photocatalytic coating film. The pencil hardness of the obtained glass plate having the photocatalyst coating film was H, and the contact angle with water was 93 °. The glass plate having the obtained photocatalytic coating film had a pencil hardness of 5 H or more after irradiation with ultraviolet light (black light) and a water contact angle of 0 °. Furthermore, the result of photocatalytic activity evaluation by ultraviolet irradiation was also very good (⊚).

[Embodiment 8] Polydurex G633
(Aqueous acrylic-silicone emulsion trade name, manufactured by Asahi Kasei Corporation, solid content 46 mass%, pH 8.8) 250 g
In addition, 22.8 g of CS-12 (trade name of 2,2,4-trimethyl-1,3-pentanediol-monoisobutyrate, manufactured by Chisso Corporation) as a film forming aid was stirred at room temperature for 20 hours. Added over minutes. Next, similarly, 22.8 g of a butyl cellosolve aqueous solution (50% by mass) as a film formation aid was added at room temperature with stirring over 20 minutes, and then at room temperature, 3
After stirring for an hour, an acrylic-silicone emulsion containing a film forming aid was obtained.

A photocatalyst composition (2) was obtained by adding 35 g of the modified titanium oxide hydrosol (4) prepared in Example 4 with stirring to 50 g of the obtained acrylic-silicone emulsion containing the film-forming aid. . The photocatalyst composition (2) thus obtained was cast on a glass plate so that the film thickness was 30 μm, and then dried at room temperature for 1 week, and subsequently at 50 ° C. for 5 days.
By heating for a day, a glass plate having a transparent and smooth photocatalytic coating film was obtained. The contact angle with water of the obtained glass plate having the photocatalyst coating film was 90 °. The contact angle of water on the glass plate having the obtained photocatalytic coating film after irradiation with ultraviolet rays (black light) was 10 °. Furthermore, the result of photocatalytic activity evaluation by ultraviolet irradiation is also very good (◎)
Met.

[Example 9] Acrylic-silicone emulsion 5 containing a film-forming assistant obtained by the same method as in Example 8
Photocatalyst composition (3) was obtained by adding 78 g of modified titanium oxide hydrosol (6) prepared in Example 6 to 0 g under stirring. The photocatalyst composition (3) thus obtained was cast on a glass plate so that the film thickness was 10 μm, dried at room temperature for 1 week, and then heated at 50 ° C. for 5 days to give a transparent and smooth film. A glass plate having a photocatalytic coating film was obtained. The contact angle with water of the obtained glass plate having the photocatalyst coating film was 91 °. Further, the water contact angle of the glass plate having the obtained photocatalytic coating film after irradiation with sunlight was 12 °. Furthermore, the result of photocatalytic activity evaluation by sunlight irradiation was also very good (⊚).

[Example 10] The modified titanium oxide organosol (5) 19 prepared in Example 5 was added to 80 g of a 20 mass% toluene solution of the silicon resin (1) synthesized in Reference Example 1.
g under stirring at room temperature, then 20 g of isopropanol and 22 g of butyl cellosolve are added under stirring,
Further, 0.5 g of a curing catalyst (tetrakis (acetylacetonato) zirconium) was added with stirring to obtain a photocatalyst composition (4). Obtained photocatalyst composition (4)
Was spray-coated on a glass plate to a film thickness of 2 μm, dried at room temperature for 1 hour, and heated at 150 ° C. for 30 minutes to obtain a glass plate having a transparent and smooth photocatalytic coating film. The glass plate having the obtained photocatalytic coating film had a pencil hardness of HB and a contact angle with water of 90 °. The glass plate having the obtained photocatalytic coating had a pencil hardness of 2H after irradiation with sunlight and a water contact angle of 20 °. Furthermore, the result of photocatalytic activity evaluation by sunlight irradiation was also very good (⊚).

Example 11 A mixture of 6 g of the silicone resin (1) synthesized in Reference Example 1 and 3 g of the silicone resin (2) synthesized in Reference Example 2 was mixed with 17.9 g of toluene.
Isopropanol 32.3 g, butyl cellosolve 14.
5 g was added, and the mixture was stirred at room temperature to obtain a mixed solution of the silicone resin (1) and the silicone resin (2). 11.5 g of the modified titanium oxide organosol (2) prepared in Example 2 was added to the obtained mixture solution of the silicon-based resin under stirring at room temperature, and 0.4 g of a curing catalyst (dibutyltin dilaurate) was further added. Photocatalyst composition (5) was obtained by adding under stirring.

Thickness 1 mm cut into 50 mm × 60 mm
Aluminum plate (JIS, H, 4000 (A1050P))
Acrylic urethane resin paint (manufactured by Nippon Paint Co., Ltd., Mightylac white, 2 liquid mixture type) was spray-applied to it and dried at room temperature for 3 days. The photocatalyst composition (5) was applied to the obtained acrylic urethane-coated aluminum plate to a film thickness of 2 μm.
After spray-coating so as to obtain, a test plate having a photocatalytic coating film was obtained by drying at room temperature for 1 hour and heating at 150 ° C. for 30 minutes.

The test plate having the photocatalyst coating film obtained had a pencil hardness of HB and a contact angle with water of 95 °. The test plate having the photocatalyst coating film obtained had a pencil hardness of 5 H or higher after irradiation with ultraviolet light (black light) and a water contact angle of 0 °. Furthermore, the result of photocatalytic activity evaluation was also very good (⊚). Furthermore, an exposure test (1000
The gloss retention according to (after time) was 93%, indicating a very good weather resistance.

[Example 12] The photocatalyst composition (5) obtained in Example 11 was spray-coated on an OHP film so that the film thickness was 2 µm, and then dried at room temperature for 2 days, and subsequently at 50 ° C. By heating for 3 days, an OHP film having a smooth photocatalytic coating film was obtained. When the distribution of titanium oxide in the cross section of the OHP film having the obtained photocatalytic coating film was observed by TEM observation, almost no titanium oxide was present at the interface between the OHP film of the base material and the photocatalytic coating film, and the photocatalytic coating surface It was observed that all were covered with titanium oxide.

[Comparative Example 1] Instead of 12 g of modified titanium oxide organosol (1), 8.9 g of unmodified titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd.) was used. Except for the above, the same operation as in Example 7 was carried out to obtain a glass plate having a transparent and smooth photocatalytic coating film (titanium oxide content was the same as in Example 7). The pencil hardness of the glass plate having the obtained photocatalytic coating film was H, and the contact angle with water was 86 °. The glass plate having the obtained photocatalytic coating film was irradiated with ultraviolet rays (black light),
The contact angle of water hardly changed (81 °) and the pencil hardness was 2H. Further, the photocatalytic activity evaluation by ultraviolet irradiation was also a bad result (x).

Comparative Example 2 50 g of a 20% by mass toluene solution of the silicon resin (1) synthesized in Reference Example 1 was treated with a titanium oxide organosol (trade name: TK).
After adding 50 g of S-251 (Taika Co., Ltd.) at room temperature under stirring, butyl cellosolve was stirred at 33%.
g, and curing catalyst (dibutyltin dilaurate)
0.5 g was added with stirring to obtain a photocatalyst composition (6). The photocatalyst composition (6) thus obtained was spray-coated on a glass plate to a film thickness of 2 μm, dried at room temperature for 1 hour, and then heated at 150 ° C. for 30 minutes to give a transparent and smooth photocatalyst coating. A glass plate having a film (titanium oxide content 5 times that of Example 7) was obtained. The pencil hardness of the obtained glass plate having the photocatalyst coating film was 3H, and the contact angle with water was 83 °. When the glass plate having the obtained photocatalyst coating film was irradiated with ultraviolet rays (black light), the photocatalyst coating film had cracks, and the evaluation of physical properties was impossible.

Comparative Example 3 Instead of 11.5 g of modified titanium oxide organosol (1), 8 g of unmodified titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd.) was used. Except for the above, the same operations as in Example 11 were carried out to obtain a test plate having a photocatalytic coating film (titanium oxide content was the same as in Example 11). The obtained photocatalytic coating film had a pencil hardness of H and a contact angle with water of 97 °. The test plate having the obtained photocatalytic coating film had a pencil hardness of 3H after irradiation with ultraviolet light (black light) and a water contact angle of 83 °. Further, the photocatalytic activity evaluation by ultraviolet irradiation was a bad result (x). In addition, an exposure test (1
After 000 hours), the gloss retention rate is 10% or less,
A choking phenomenon was observed.

[Comparative Example 4] Instead of 11.5 g of modified titanium oxide organosol (2), 8 g of titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd.) which had not been modified was used. Except for this, the same operation as in Example 11 was performed to obtain a photocatalyst composition (7). The photocatalyst composition (5) thus obtained was spray-coated on an OHP film so that the film thickness was 2 μm, dried at room temperature for 2 days, and then heated at 50 ° C. for 3 days to obtain a smooth photocatalyst coating. An OHP film with a membrane was obtained. The distribution of titanium oxide in the cross section of the OHP film having the obtained photocatalyst coating film was observed by TEM observation. It was observed that there was no difference in the amount of titanium.

[Comparative Example 5] The photocatalyst composition (2) obtained in Example 8 was cast on a glass plate to a thickness of 30 µm, dried at room temperature for 1 week, and then at 50 ° C. By heating for 5 days, a glass plate having a transparent and smooth photocatalytic coating film was obtained. The contact angle with water of the obtained glass plate having the photocatalyst coating film was 90 °. The glass plate having the obtained photocatalytic coating film had a water contact angle of 70 ° after irradiation with sunlight. Furthermore, the result of the photocatalytic activity evaluation by sunlight irradiation is the photocatalytic activity by ultraviolet irradiation (Example 8).
It was inferior to (△).

[0133]

The photocatalyst composition using the modified photocatalyst of the present invention has excellent transparency, durability, hardness, etc., and can control the wettability (hydrophilicity, hydrophobicity) of water, and has a photocatalytic activity. It is possible to form a photocatalyst coating film having:

[Brief description of drawings]

FIG. 1 shows a particle size distribution of titanium oxide organosol (trade name: TKS-251, manufactured by Teika Co., Ltd.) before modification treatment by a wet particle size analyzer (Microtrack U manufactured by Nikkiso Co., Ltd.).
It is a figure which shows the result measured using PA-9230).

FIG. 2 is a diagram showing the results of measuring the particle size distribution of the modified titanium oxide organosol (1) obtained in Example 1 using a wet particle size analyzer (Microtrac UPA-9230 manufactured by Nikkiso Co., Ltd.). Is.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 101/00 C08L 101/00 C09D 183/04 C09D 183/04 183/07 183/07 183/08 183 / 08 F-term (reference) 4G069 AA02 AA03 BA04A BA04B BA14B BA22A BA22B BA37 BA48A BE32A BE32B CA01 CA10 CA11 EA07 EA11 EB15Y EB19 EC27 EC29 ED01 ED02 ED86 DF03 DE0 DF03 DE0 DK03 DE01 DK01 DE01 DK001 CD01 CF01 FB096 FB266 FD206 GH00 4J035 BA12 BA14 CA022 CA052 CA062 CA152 CA19K CA192 EA01 LA03 LB01 4J038 DL031 DL071 DL081 DL111 HA216 KA08 NA06 NA07

Claims (24)

[Claims] 1. A modified photocatalyst obtained by modifying the photocatalyst (A) with at least one Si—H group-containing compound (B) selected from the formulas (1) and (2). ^{_{H- (R 1 2 SiO) a}} -SiR 1 2 -H ··· (1) ( In the formula, ^{R 1} each independently represents a linear or branched alkyl group having 1 to 30 carbon atoms, A cycloalkyl group having 5 to 20 carbon atoms, a linear or branched fluoroalkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms, A hydroxyl group or a group consisting of one or more selected from the siloxy group represented by the formula (3) is represented by: —O— (R ³ ₂ SiO) _c —SiR ³ ₃ (3) (wherein R ³ is Each independently from at least one selected from a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a phenyl group. And the group c.
Is an integer and 0 ≦ c ≦ 1000. ) A is an integer and 0 ≦ a ≦ 1000. ^{_{) H- (R 2 2 SiO)}} b -SiR 2 2 -Q ··· (2) ( wherein, ^{R 2} is each independently a linear or branched having 1 to 30 carbon atoms, alkyl groups , A cycloalkyl group having 5 to 20 carbon atoms, a linear or branched fluoroalkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a phenyl group, an alkoxy group having 1 to 20 carbon atoms , A hydroxyl group, or a group consisting of at least one selected from the siloxy groups represented by the formula (3): —O— (R ³ ₂ SiO) _c —SiR ³ ₃ (3) (in the formula, R ³ Are each independently one or more selected from a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and a phenyl group. Represents a group consisting of, and c
Is an integer and 0 ≦ c ≦ 1000. In addition, Q in the formula is a group containing at least one function-imparting group selected from the group consisting of the following (A) to (E). (A) a linear or branched alkyl group having 1 to 30 carbon atoms, a linear or branched alkenyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or Unsubstituted or C1-C20 alkyl group or C1-C20 alkoxy group, or C6-C20 aryl group substituted with a halogen atom, and C1-C30 fluoroalkyl At least one hydrophobic group selected from the group consisting of groups. (Ii) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a polyoxyalkylene group. (U) epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, At least one reactive group selected from the group consisting of ester groups. (E) At least one spectral sensitizing group. Further, b is an integer, and 0 ≦ b ≦ 1000. ) 2. The photocatalyst (A) has a number average particle diameter of 200 n.
The modified photocatalyst according to claim 1, which is a photocatalytic sol having a particle size of m or less. 3. The modified photocatalyst according to claim 1, wherein the photocatalyst (A) is titanium oxide. 4. The modified photocatalyst according to claim 1, wherein the photocatalyst (A) is a visible light responsive photocatalyst. 5. A photocatalyst composition comprising the modified photocatalyst according to claim 1 and a resin (E). 6. The photocatalyst composition according to claim 5, wherein the resin (E) is a silicone resin. 7. The photocatalyst composition according to claim 6, wherein the silicon-based resin contains a ladder structure represented by the formula (4). [Chemical 1] (R is independently a hydrogen atom or a carbon number of 1-2.
0 represents a monovalent organic group. ) 8. The photocatalyst composition according to claim 6, wherein the silicone resin contains a phenyl group-containing silicone represented by the formula (5). ^{_{R 5 p X r SiO (4}} -p-r) / 2 (5) ( wherein, ^{R 5} represents a phenyl group, X represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, 1 to 4 carbon atoms ~ 20
Represents at least one reactive group selected from the group consisting of an acyloxy group, an aminoxy group, an oxime group having 1 to 20 carbon atoms, and a halogen atom, and 0 <p <4, 0 <r <4, and 0 <(p + r ) <4. ) 9. The photocatalyst composition according to claim 6, wherein the silicone resin contains an alkyl group-containing silicone represented by the formula (6). ^{_{R 6 q X s SiO (4}} -q-s) / 2 (6) ( wherein, ^{R 6} are each independently a linear or branched alkyl group having 1 to 30 carbon atoms, 5 to 20 carbon atoms Represents a cycloalkyl group or a linear or branched alkenyl group having 2 to 30 carbon atoms, X represents a hydrogen atom, a hydroxyl group, or 1 carbon atom
To at least one reactive group selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an aminoxy group, an oxime group having 1 to 20 carbon atoms, and a halogen atom, and 0 <q <4, 0 <s <4, and 0 <(q +
s) <4. ) 10. The photocatalyst according to claim 6, wherein the silicone resin is contained as a mixture of the phenyl group-containing silicone represented by the formula (5) and the alkyl group-containing silicone represented by the formula (6). Composition. 11. An alkyl group-containing silicone represented by the formula (6) is a monooxydiorganosilane unit (D) represented by the formula (7) and a dioxyorganosilane unit represented by the formula (8). The photocatalyst composition according to claim 9 or 10, which has a structure having both (T). _{^{- (R 6 2 SiO) -}} (7) ( wherein, ^{R 6} are each independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear Represents a straight or branched alkenyl group having 2 to 30 carbon atoms. (In the formula, R ⁶ is as defined in the formula (7).) 12. The photocatalyst composition according to claim 5, wherein the photocatalyst composition has a self-grading property. 13. The photocatalyst composition according to claim 5, wherein the modified photocatalyst is in contact with the outside air when the photocatalyst composition is applied and formed on a substrate. A photocatalyst composition, which autonomously forms a graded composition film having a concentration gradient in the film thickness direction that increases toward the bottom. 14. The photocatalyst composition according to any one of claims 5 to 12, wherein a modified photocatalyst is formed on the surface of the molded body when the molded body is formed from the photocatalyst composition. A photocatalyst composition, which autonomously forms a structure having a concentration gradient that increases toward the side. 15. A functional composite obtained by forming a film containing the photocatalyst composition according to any one of claims 5 to 13 on a substrate. 16. A functional composite obtained by forming a film containing the photocatalyst composition of claim 13 on a substrate, wherein the film has anisotropy in the distribution of the modified photocatalyst in the film thickness direction. A functional complex characterized by the following. 17. The functional composite according to claim 15 or 16, wherein the resin (E) contained in the film forms a phase separation structure. 18. The photocatalytic activity and / or hydrophilicity is exhibited by irradiating with light having an energy higher than the bandgap energy of the photocatalyst (A) contained in the coating, according to claim 15 or 16. Functional complex of. 19. At least an organic group bonded to a silicon atom existing in the vicinity of the photocatalyst (A) particles by irradiating with light having an energy higher than the bandgap energy of the photocatalyst (A) contained in the film. The functional composite according to claim 15 or 16, wherein a part thereof is substituted with a hydroxyl group and / or a siloxane bond. 20. A molded product formed from the photocatalyst composition according to claim 5. 21. A molded product formed from the photocatalyst composition according to claim 14, wherein the modified photocatalyst has anisotropy in distribution from the inside to the surface. 22. The resin (E) contained in the molded article,
21. A phase-separated structure is formed.
Or the molded article according to 21. 23. The photocatalytic activity and / or hydrophilicity is exhibited by irradiating with light having an energy higher than the bandgap energy of the photocatalyst (A) contained in the molded body, according to claim 20 or 21. The molded article described. 24. By irradiating with light having an energy higher than the bandgap energy of the photocatalyst (A) contained in the molded article, the organic group bonded to the silicon atom existing in the vicinity of the photocatalyst (A) particles is formed. 22. The molded product according to claim 20, wherein at least a part of the molded product is substituted with a hydroxyl group and / or a siloxane bond.