JP2002282700A - Photocatalyst composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocatalyst composition which can obtain a functional composite or molding which is excellent in flexural resistance and impact resistance and the surface of which develops a function for controlling wettability (hydrophilicity and hydrophobicity) and/or photocatalytic activity. SOLUTION: The photocatalyst composition comprises a photocatalyst (A) and a silicone compound expressed by formula (1) R<1> p R<2> q Xr SiO(4-p-q-r) /2 of an average composition (R<1> is a phenyl group; R<2> is at least one hydrocarbon group selected from the group consisting of alkyl, cycloalkyl, alkyl, alkoxy groups, and an allyl group substituted by a halogen atom; X is at least one reactive group selected from the group consisting of a hydrogen atom, hydroxy, alkoxy, acyloxy, aminoxy, oxime groups, and a halogen atom). Oxides such as TiO2 , ZrO, and SrTiO3 can be used as the photocatalyst (A).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a titanium oxide known to be applied to fields such as environmental purification, antifouling, antifogging, etc., since it exhibits a decomposing action of substances and a hydrophilizing action of a surface by light energy. The present invention relates to a technique for fixing a typical photocatalyst to a member surface. Specifically, the present invention relates to a photocatalyst composition which can easily fix a photocatalyst to a member surface, and further has a photocatalytic activity in which the photocatalyst is immobilized and / or a controllability of water wettability (hydrophilicity, hydrophobicity). A functional complex having the same.

[0002]

2. Description of the Related Art It is known that a photocatalyst represented by titanium oxide exhibits a decomposing action of a substance and a hydrophilizing action of a surface by light energy. This photocatalyst is used for environmental purification and antifouling,
When applied to fields such as anti-fog, the photocatalyst fixing technology plays a very important role. Coating of a substrate with a photocatalyst has attracted attention as a useful means of the photocatalyst immobilization technique. Here, the following items are listed as the minimum conditions required for the technology for fixing the photocatalyst by coating. 1) Strongly immobilized without impairing photocatalytic activity. 2) Stability such that the base material and the coating itself are not deteriorated by photocatalysis. Further, preferable conditions for expanding the applicable range of the substrate to be immobilized include the following items. 3) The conditions for immobilization are mild (from room temperature to about 150 ° C.). 4) The coating film has excellent transparency, and has excellent durability, stain resistance, and hardness.

[0003] By the way, various proposals have been made on an immobilization technique by coating a photocatalyst represented by titanium oxide. For example, as a method of coating a photocatalyst on a substrate by a sputtering method or a sol-gel method, JP-A-60-044053 discloses a method in which a thin-film photocatalyst is supported on a substrate by a sputtering method.
JP 118236 discloses that after applying an organic titanate,
A firing method has been proposed. However, these methods have a disadvantage that firing at a high temperature is required for generation and crystallization of photocatalyst particles on a substrate, and it is difficult to fix a large area.

As a method of using a photocatalyst sol which does not require the process of producing and crystallizing photocatalyst particles, for example, Japanese Patent Application Laid-Open No. Hei 6-278241 discloses a method of coating a substrate with a titanium oxide sol peptized in water. Has been proposed. Also in this method, high temperature firing is necessary because the titanium oxide sol does not have a film forming property under mild conditions,
The resulting coating was brittle and had the disadvantage of easily breaking and losing its catalytic effect.

Further, a method has been proposed in which a photocatalyst is mixed into a resin paint and the resin paint is coated on a substrate. For example, JP-A-7-171408, JP-A-9-100377, JP-A-9-227831, JP-A-9-59041, JP-A-9-1888
No. 50 and JP-A-9-227829 propose a method of using a hardly decomposable substance such as a fluororesin or a silicone resin as a resin coating to be mixed with a photocatalyst. However, in these methods, it is necessary to reduce the amount of the resin coating used in order to express sufficient photocatalytic activity and hydrophilicity, and in this case, weather resistance, hardness, adhesion, bending resistance, and It is not possible to obtain a coating having good coating properties in terms of impact resistance, abrasion resistance and the like. (Conversely, if the amount of the resin coating used is increased in order to exhibit good coating film properties, the photocatalyst is buried in the resin coating and does not exhibit sufficient photocatalytic activity or hydrophilicity.) In the immobilization technology, a technology that satisfies all the conditions required for the above-described immobilization technologies 1) to 4) has not yet been developed.

[0006]

An object of the present invention is to provide not only excellent transparency and hardness, but also excellent flexibility (bending resistance and impact resistance), and the surface of water is exposed to water for a long time. An object of the present invention is to provide a photocatalyst composition capable of obtaining a functional composite or a molded article exhibiting a controllability of wettability (hydrophilicity, hydrophobicity) and / or photocatalytic activity of the polymer.

[0007]

Means for Solving the Problems The inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is,
The first aspect of the present invention is that the photocatalyst (A) and the following average composition formula (1)
And a silicone compound (B). During ^{_{R 1 p R 2 q X r}} SiO (4-pqr) / 2 (1) ( wherein, R ¹ represents a phenyl group, R ² is a linear or branched C 1-30 alkyl group , 5-20 carbon atoms
And at least one carbon atom selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms substituted with a halogen atom. Represents a hydrogen group. X
Is at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an enoxy group, 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. 0 <p <4, 0 ≦ q <4, 0 <r <4, and 0 <
(P + q + r) <4, and 0.1 ≦ p / (p +
q) The relationship of ≤1 is satisfied. )

A second aspect of the invention is characterized in that the silicone compound (B) represented by the average composition formula (1) contains a phenyl silicone compound (B1) represented by the following average composition formula (2). Is a first photocatalyst composition. R ¹ _s X _t SiO _{(4-st) / 2} (2) (wherein, R ¹ represents a phenyl group, and X is as defined in formula (1). 0 <s <4, 0 <t <4 and 0 <
(S + t) <4. )

A third aspect of the invention is that the silicone compound (B) is
The photocatalyst composition according to any one of the first and second aspects of the invention, comprising a phenyl ladder structure represented by the general formula (3).

[0010]

Embedded image

(R ¹ represents a phenyl group.)

A fourth aspect of the invention is that the silicone compound (B) represented by the average composition formula (1) is represented by the phenyl silicone compound (B1) represented by the average composition formula (2) and the phenyl silicone compound (B1) represented by the average composition formula (4). The first, second, and third aspects of the invention, characterized in that they include a mixture of the alkyl silicone compound (B2)
Any of the third photocatalyst compositions. ^{_{R 3 u X v SiO (4}} -uv) / 2 (4) ( wherein, R ³ represents a linear or branched alkyl group having 1 to 30 carbon atoms, X is defined by equation (1) 0 <u <4, 0 <v <4, and 0 <(u + v) <4
It is. )

A fifth aspect of the present invention is that an alkyl silicone compound (B2) represented by the average composition formula (4) is composed of a monooxydiorganosilane unit (T) represented by the formula (5) and a compound represented by the formula (6). A fourth photocatalyst composition according to the invention, which has a structure having both of the dioxyorganosilane units (D) represented. — (R ³ R ³ SiO) — (5)

[0014]

Embedded image

(Wherein, R ³ represents a linear or branched alkyl group having 1 to 30 carbon atoms)

According to a sixth aspect of the present invention, the photocatalyst (A) converts the photocatalyst particles to a monooxydiorganosilane unit represented by the formula (7), a dioxyorganosilane unit represented by the formula (8), and By modifying with at least one modifier compound (C) selected from the group consisting of compounds having at least one structural unit selected from the group consisting of difluoromethylene units represented by (9) The photocatalyst composition according to any one of the first to sixth aspects of the invention, which is the modified photocatalyst (A1) obtained. — (R ⁴ R ⁴ SiO) — (7)

[0017]

Embedded image

(Wherein, R ⁴ is each independently a linear or branched alkyl group having 1 to 30 carbon atoms;
20 cycloalkyl groups, or unsubstituted or C1-C20 alkyl groups, phenyl groups, C1-C1
Represents a C20 alkoxy group, or an aryl group having 6 to 20 carbon atoms with a halogen atom is _{substituted) - (CF 2) - (} 9)

A seventh aspect of the present invention is that the modifying compound (C) is
A sixth photocatalyst composition according to the invention, which is a silicon compound having an average composition represented by the formula (10). R ⁴ _x Q _y X _z SiO _{(4-xyz) / 2} (10) (where R ⁴ is as defined in the formula (7), and X is
As defined in equation (1). In the formula, R ⁴ is the formula (7)
As defined in.

In the formula, Q represents or (A) to (E)
And a group containing at least one functionality-imparting 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 An unsubstituted or C1-C20 alkyl group or C1-C20 alkoxy group, or a C6-C20 aryl group substituted with a halogen atom, and a C1-C30 fluoroalkyl At least one hydrophobic group selected from the group consisting of groups; (I) at least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphate group or a salt thereof, a sulfonic acid group or a salt thereof, and a polyoxyalkylene group; (C) 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. Also, 0 <x <
4, 0 <y <4, 0 ≦ z <4, and (x + yz) <4. )

An eighth aspect of the present invention is that the modifier compound (C) is
A sixth photocatalyst composition according to the invention, which is a compound represented by the formula (11). As _{^{(R 4 HSiO) a (R}} 4 2 SiO) b (R 4 QSiO) c (R 4 3 SiO 1/2) d ··· (11) ( wherein, R ⁴ is defined in formula (7) And Q is as defined in the formula (10), a is an integer of 1 or more, b and c are 0 or an integer of 1 or more, and (a + b +
c) ≦ 10000 and d is 0 or 2.
Here, (a + b + c) is an integer of 2 or more and d = 0.
In the case, the compound is a cyclic silicone compound, and d =
In case 2, the compound is a chain silicone compound. )

A ninth aspect of the present invention is the photocatalyst composition according to any one of the first to eighth aspects, wherein the photocatalyst (A) is a photocatalytic sol having a number average particle diameter of 200 nm or less. A tenth aspect of the present invention is the photocatalyst composition according to any one of the first to ninth aspects of the invention, which has a self-grading property. An eleventh aspect of the present invention is the photocatalyst composition according to any one of the first to tenth aspects, wherein when the photocatalyst composition is applied and formed on a substrate, the photocatalyst (A) is in contact with the outside air. A photocatalyst composition characterized by autonomously forming a gradient composition film having a concentration gradient in the film thickness direction increasing toward the surface. A twelfth aspect of the present invention is the photocatalyst composition according to any one of the first to tenth aspects of the invention, wherein, when a molded article is formed from the photocatalyst composition, the photocatalyst (A) is formed from the inside of the molded article to the surface during the formation process. A photocatalyst composition characterized by autonomously forming a structure having a concentration gradient that increases toward the side.

A thirteenth aspect of the present invention is a functional composite obtained by forming a film containing the photocatalyst composition according to any one of the first to eleventh aspects on a substrate. The fourteenth aspect of the invention is the first aspect of the invention.
A functional composite obtained by forming a film containing the photocatalyst composition on a substrate, wherein the film has anisotropy in the thickness direction distribution of the photocatalyst (A). It is a functional complex. The fifteenth aspect of the invention is the first to first aspects of the invention.
A molded article formed from the photocatalyst composition of any one of Examples 0 and 12. A sixteenth aspect of the present invention is a molded article formed from the photocatalyst composition according to the twelfth aspect of the present invention, wherein the molded article has anisotropy in distribution from the inside to the surface of the photocatalyst (A).

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The photocatalyst (A) that can be used in the present invention is 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.
Of electrons in the valence band when irradiated with light (photoexcitation)
Is a substance that can generate conduction electrons and holes by generating TiO ₂ , ZnO, SrTiO ₃ , CdS, GaP,
InP, GaAs, BaTiO ₃ , BaTiO ₄ , BaT
i 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 , BiV
O ₄ , NiO, Cu ₂ O, SiC, MoS ₂ , InPb,
A layered oxide containing at least one element selected from RuO ₂ , CeO _{2, and the} like, and Ti, Nb, Ta, and V (JP-A-62-74452, JP-A-2-1725)
No. 35, JP-A-7-24329, JP-A-8-
89799, JP-A-8-89800, JP-A-8-89804, JP-A-8-198061, JP-A-9-248465, JP-A-10-99
694, JP-A-10-244165, etc.). In addition, Pt, R
h, Ru, Nb, Cu, Sn, Ni, Fe or other metal and / or metal oxide added or fixed, or a photocatalyst coated with porous calcium phosphate or the like (JP-A-11-267519) Etc. can also be used.

The crystal particle diameter of the photocatalyst (A) (primary particle
Diameter) is 1 to 200 nm, preferably 1 to 50 nm.
The medium is suitably selected. Among these photocatalysts (A), T
iO _Two(Titanium oxide) is harmless and has chemical stability
It is preferable because it is excellent. As titanium oxide,
Any of ze, rutile and brookite can be used. Ma
Of nitrogen-doped titanium oxide and oxygen-deficient titanium oxide
Also, a visible light responsive titanium oxide photocatalyst is preferably used.
be able to.

The photocatalyst (A) may be in any of the following forms:
Powders and photocatalytic sols can be mentioned. As the photocatalyst (A) used in the present invention, a photocatalyst in which the number average dispersed particle diameter of a mixture of primary particles and secondary particles is 200 nm or less is preferable because surface characteristics 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 photocatalyst composition of the present invention, which is very preferable. More preferably, a photocatalyst of 80 nm or less and 3 nm or more, further preferably 50 nm or less and 3 nm or more is suitably selected. These photocatalysts (A) are preferably photocatalytic sols.

In general, a powder composed of fine particles forms secondary particles in which a plurality of particles are strongly aggregated, so that there are many wasteful surface characteristics, and it is not possible to disperse even individual primary particles. Very difficult. In contrast, in the case of a photocatalyst sol, the photocatalyst particles are present in a form close to the primary particles without being dissolved, so that the surface characteristics can be effectively used, the photocatalytic activity is improved, and a photocatalyst comprising a silicone compound described later is used. The appearance of the film formed from the composition is very good. Here, the photocatalyst sol means that the photocatalyst particles have a solid content of 0.01 to 70% by mass in water and / or an organic solvent,
Preferably, it is dispersed at 0.1 to 50% by mass.

Taking titanium oxide sol as an example of the photocatalytic sol, there may be mentioned, for example, a titanium oxide hydrosol in which water is substantially used as a dispersion medium and titanium oxide particles are peptized therein. (Here, “substantially using water as a dispersion medium” means that about 80% or more of water is contained in the dispersion medium.) The preparation of such a sol is known, and can be easily manufactured. JP-A-63-17221, JP-A-7-819, JP-A-9-165218,
JP-A-11-43327, etc.). For example, metatitanic acid generated by heating and 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. Can be This aggregate is peptized under the action of nitric acid, hydrochloric acid, ammonia, or the like, and is subjected to hydrothermal treatment or the like, whereby a titanium oxide hydrosol is obtained. The titanium oxide hydrosol is prepared by pulverizing titanium oxide particles under the action of an acid or alkali, or using a dispersion stabilizer as necessary without using an acid or alkali, and using a strong A sol dispersed in water under water may also be used. In addition, pH
Has excellent dispersion stability even in an aqueous solution near neutrality,
Anatase-type titanium oxide sol having a particle surface modified with a peroxo group can also be easily obtained by the method proposed in JP-A-10-67516. The above-mentioned titanium oxide hydrosol is commercially available as titania sol. (For example, trade name "STS-02" / Ishihara Sangyo Co., Ltd./Japan, trade name "TO-240" / Tanaka Transcription Co., Ltd./Japan, etc.)

The solid content in the titanium oxide hydrosol is 5
0 mass% or less, preferably 30 mass% or less. More preferably, it is 30% by mass or less and 0.1% by mass or more.
The viscosity (20 ° C.) of such hydrosols is relatively low,
For example, it may be in the range of about 2000 cps to about 0.5 cps. Preferably it is 1000 cps-1 cps, more preferably 500 cps-1 cps.

Further, for example, a cerium oxide sol (Japanese Unexamined Patent Publication No.
-59235) and a layered oxide sol containing at least one element selected from Ti, Nb, Ta, and V (JP-A-9-25123, JP-A-9-67124).
JP-A-9-227122, JP-A-9-227122
No. 27123, Japanese Patent Application Laid-Open No. 10-259023, etc.), various methods for producing a photocatalytic sol are also disclosed in the same manner as the titanium oxide sol.

A photocatalyst organosol in which an organic solvent is substantially used as a dispersion medium and photocatalyst particles are dispersed therein is as follows:
For example, the photocatalyst hydrosol is converted into a compound having a phase transfer activity such as polyethylene glycol (a third phase is formed at the interface between different first and second phases, and the first and second phases are formed).
And the third phase are treated with a compound which dissolves and / or solubilizes each other) and diluted with an organic solvent (Japanese Patent Laid-Open No. 10-16 / 1998).
No. 7727), a method of preparing a sol by dispersing and transferring in an organic solvent insoluble in water with an anionic surfactant such as sodium dodecylbenzenesulfonate (Japanese Patent Laid-Open No. 58-2).
No. 9863) and alcohols having a higher boiling point than water, such as butyl cellosolve, are added to the photocatalyst hydrosol.
It can be obtained by a method of removing water by (reduced pressure) distillation or the like. Further, substantially using an organic solvent as a dispersion medium,
Titanium oxide organosols in which titanium oxide particles are dispersed are commercially available (for example, trade name "TKS-25").
1 "/ Taika Co., Ltd.). Here, “substantially using an organic solvent as a dispersion medium” means that the dispersion medium contains about 80% or more of an organic solvent.

As the photocatalyst (A) used in the photocatalyst composition of the present invention, a photocatalyst particle is composed of a monooxydiorganosilane unit represented by the formula (7), a dioxyorganosilane unit represented by the formula (8), And a modification treatment using at least one modifier compound (C) selected from the group consisting of compounds having at least one structural unit selected from the group consisting of difluoromethylene units represented by the formula (9). By using the modified photocatalyst (A1) obtained as described above, the photocatalyst composition of the present invention is excellent in storage stability, and the film formed from the photocatalyst composition has water wettability (hydrophilicity, It is very preferable because the controllability of (hydrophobicity) and the photocatalytic activity become very large. — (R ⁴ R ⁴ SiO) — (7)

[0033]

Embedded image

Wherein R ⁴ is independently a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms,
A cycloalkyl group having 5 to 20 carbon atoms, or an unsubstituted or an alkyl group having 1 to 20 carbon atoms, a phenyl group,
An alkoxy group, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom having 1 to 20 carbon _{atoms) - (CF 2) - (} 9)

In the present invention, the term "modification" means that at least one type of modifier compound (C) described below is immobilized on the surface of the photocatalyst particles. Modifier compound (C) above
It is thought that the immobilization of the particles on the surface of the photocatalyst particles is due to van der Waals force (physical adsorption), Coulomb force or chemical bonding. In particular, modification using a chemical bond is preferable because the interaction between the modifier compound (C) and the photocatalyst (A) is strong and the modifier compound (C) is firmly fixed to the surface of the photocatalyst particles.

The modifier compound (C) having a structural unit represented by the above formula (7) and / or the above formula (8) used for obtaining the modified photocatalyst (A1) of the present invention includes, for example, S
i-H group, hydrolyzable silyl group (alkoxysilyl group,
Reactive groups that can be expected to form a chemical bond with photocatalyst particles such as hydroxysilyl group, halogenated silyl group, acetoxysilyl group, aminoxysilyl group), epoxy group, acetoacetyl group, thiol group, and acid anhydride group. And a silicon compound having a hydrophilic group which can be expected to have an affinity for photocatalyst particles such as a silicon compound having a polyoxyalkylene group. Examples of these include a silicon compound represented by the average composition formula (10). R ⁴ _x Q _y X _z SiO _{(4-xyz) / 2} (10) (where R ⁴ is as defined in the formula (7), and X is
As defined in equation (1). )

In the formula, Q represents or the following (A) to (E)
And a group containing at least one functionality-imparting 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 An unsubstituted or C1-C20 alkyl group or C1-C20 alkoxy group, or a C6-C20 aryl group substituted with a halogen atom, and a C1-C30 fluoroalkyl At least one hydrophobic group selected from the group consisting of groups; (I) at least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphate group or a salt thereof, a sulfonic acid group or a salt thereof, and a polyoxyalkylene group; (C) 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. Also, 0 <x <
4, 0 <y <4, 0 ≦ z <4, and (x + y + z) <4
It is. )

As the silicon compound represented by the above average composition formula (10), a compound having a Si—H group (formula (1)
When at least one of X in 0) is selected to be a hydrogen atom), a hydrogen gas is generated from the mixed solution by a modification operation of the photocatalyst (A) described later, and when a photocatalyst sol is used as the photocatalyst (A), An increase in the average dispersed particle size is observed. Further, for example, when titanium oxide is used as the photocatalyst (A), a decrease in the Ti—OH group is caused by the above-mentioned modification operation from 3630 to 3640 cm ⁻¹ in the IR spectrum.
Is observed as a decrease in absorption.

From these facts, when the Si—H group-containing silicon compound is selected as the modifier compound (C), the modified photocatalyst (A1) of the present invention is a simple mixture of the photocatalyst and the Si—H group-containing silicon compound. Rather, it is very preferable because it can be predicted to have some interaction such as a chemical bond. In fact, the modified photocatalyst sol obtained in this way has very excellent dispersion stability, chemical stability, durability and the like. In contrast, the average composition formula (10)
X is a hydrolyzable group (alkoxy group having 1 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms, aminoxy group, oxime group having 1 to 20 carbon atoms,
A compound containing a halogen atom) or a hydroxyl group can be used for modifying a photocatalyst similarly to a silicon compound containing a SiH group, but it has many side reactions and deteriorates storage stability.
It is preferable that the content is small. The average composition formula (1)
A more preferred embodiment of 0) is a system substantially free of the above-mentioned hydrolyzable groups and hydroxyl groups.

The Si— represented by the above average composition formula (10)
Examples of the H group-containing silicon compound include, for example, the following formula (1)
The compound represented by 1) can be mentioned. As _{^{(R 4 HSiO) a (R}} 4 2 SiO) b (R 4 QSiO) c (R 4 3 SiO 1/2) d ··· (11) ( wherein, R ⁴ is defined in formula (7) And Q is as defined in the formula (10), a is an integer of 1 or more, b and c are 0 or an integer of 1 or more, and (a + b +
c) ≦ 10000 and d is 0 or 2.
Here, (a + b + c) is an integer of 2 or more and d = 0.
In the case, the compound is a cyclic silicone compound, and d =
In case 2, the compound is a chain silicone compound. )

When a silicon compound having a functional group-containing group (Q) is selected as the silicon compound represented by the above average composition formula (10), the modified photocatalyst (A
This is preferable because various functions can be added to 1). The functional group-containing group (Q) is preferably a group represented by the following formula. Here, the functional group imparting group-containing group (Q) is represented by the following formula (1)
It is preferably a group represented by 2). -Z- (W) _h (12) (wherein, Z represents a h-valent organic group having a molecular weight of 14 to 50,000, and W comprises the above functional group (a) to (e)) At least one member selected from the group, and h is an integer of 1 to 20.)

For example, as the functional group imparting 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 phosphate group or a salt thereof, a monovalent group containing a sulfonic acid group or a salt thereof, and a polyoxyalkylene group. One hydrophilic group [formula (1
0) in (0)], the resulting modified photocatalyst (A1) has very good dispersion stability in water.

For example, as the functional group-providing 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 (10)] Is selected, the resulting modified photocatalyst (A1)
Has a very small surface energy, so that the modified photocatalyst (A1) of the present invention not only has a large self-grading property as described later, but also can obtain a coating having a very high hydrophobicity. Further, for example, as a functional group imparting group-containing group (Q),
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,
When a group containing at least one reactive group [(U) in the formula (10)] selected from the group consisting of ester groups is selected, the modified photocatalyst (A1) of the present invention has crosslinking properties and durability. It is preferable because a film excellent in the above properties can be formed. Further, for example, when a group having a spectral sensitizing group is selected as the functional group-containing group (Q), the modified photocatalyst (A1) of the present invention can be used not only in the ultraviolet region but also in the visible light region and / or the infrared light region. The catalytic activity and the photoelectric conversion function can also be exhibited by irradiating the region with light.

Here, the spectral sensitizing group means a group derived from various metal complexes or organic dyes (ie, sensitizing dyes) having absorption in a visible light region and / or an infrared light region. Examples of sensitizing dyes include xanthene dyes, oxonol dyes, cyanine dyes, merocyanine dyes, rhodocyanine 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 even Japan Examples of the complex include ruthenium, osmium, iron, and zinc complexes described in Japanese Unexamined Patent Application Publication No. 1-220380 and Japanese Patent Application Publication No. 5-504024, and other metal complexes such as ruthenium red.

Among these sensitizing dyes, it has absorption in the wavelength region of 400 nm or more, and the energy level of the lowest unoccupied orbital (redox potential in the excited state) is higher than the energy level of the conduction band of the photocatalyst. Those having features are preferred. Such sensitizing dyes are characterized by measuring light absorption spectra in the infrared, visible, and ultraviolet regions, and measuring oxidation-reduction potential by electrochemical methods (T. Tani, Photogr. Sci. En.
g., 14, 72 (1970); RWBerriman et al., ibid., 17.
235 (1973); PBGilman Jr., ibid., 18, 475 (1974)
), Calculation of energy level using molecular orbital method (T.Tani
et al., Photogr. Sci. Eng., 11, 129 (1967); DMS
turmer et al., ibid., 17.146 (1973); ibid., 18, 49
(1974); RGSelby et al., J. Opt. Soc. Am., 33, 1
(1970)), and further, it can be confirmed by the presence or absence of an electromotive force by light irradiation of a Gratzel-type wet solar cell prepared with a photocatalyst and a spectral sensitizing dye, efficiency, and the like.

Examples of sensitizing dyes having the above characteristics include compounds having a 9-phenylxanthene skeleton,
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. The method for obtaining the silicon compound having a spectral sensitizing group derived from the sensitizing dye is not particularly limited. For example, a silicon compound having the reactive group described above and a sensitizer having a reactivity with the reactive group may be used. It can be obtained by reacting a dye.

The modifier compound (C) having the structural unit represented by the above formula (9) used for obtaining the modified photocatalyst (A1) of the present invention includes, for example, a Si—H group, Functional silyl group (alkoxysilyl group, hydroxysilyl group, halogenated silyl group, acetoxysilyl group, aminoxysilyl group, etc.), epoxy group, acetoacetyl group,
Having a hydrophilic group that can be expected to have an affinity for photocatalyst particles such as a thiol group, a photocatalyst particle such as an acid anhydride group and a reactive group or a polyoxyalkylene group that can be expected to form a chemical bond,
Examples thereof include a fluoroalkyl compound having 1 to 30 carbon atoms and a fluoroalkylene compound having a number average molecular weight of 100 to 1,000,000.

Specific examples include a fluoroalkyl compound represented by the formula (13) and a fluoroolefin polymer represented by the formula (14). _{CF 3 (CF 2) g -Y-} (V) w (13) ( wherein, g is .Y represents an integer of 0 to 29 the molecular weight 14
Represents a w-valent organic group of 50,000. w is an integer of 1 to 20. V is a hydrolyzable silyl group, epoxy group, hydroxyl group, acetoacetyl group, thiol group, cyclic acid anhydride group,
It represents at least one functional group selected from the group consisting of a carboxyl group, a sulfonic acid group, and a polyoxyalkylene group. )

[0049]

Embedded image

Wherein A ^{1 to} A ⁵ may be the same or different and each represents a fluorine atom, a hydrogen atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, and a halo-substituted alkyl having 1 to 6 carbon atoms. And m represents 10 or more and 10
Is an integer of 00000 or less, and n is 0 or more and 100000
Represents the following integers. Y represents a w-valent organic group having a molecular weight of 14 to 50,000. w is an integer of 1 to 20. V is as defined in equation (13). )

As specific examples of these, for example, 2-
Fluoroalkylsilanes such as perfluorooctylethyltrimethoxysilane, Nafion resin, fluoroolefins such as chlorotrifluoroethylene and tetrafluoroethylene and epoxy groups, hydroxyl groups, carboxyl groups, acetoacetyl groups, thiol groups, and cyclic acid anhydrides Group,
Copolymers with monomers having sulfonic acid groups, polyoxyalkylene groups and the like (vinyl ethers, vinyl esters, allyl compounds, etc.) can be mentioned.

Further, a modifier compound having a structural unit represented by the above formula (7) and / or (8) and the above formula (9) used for obtaining the modified photocatalyst (A1) of the present invention. (C) includes, for example, a fluoroalkyl group and Si—H
Particles, hydrolyzable silyl groups (alkoxysilyl groups, hydroxysilyl groups, halogenated silyl groups, acetoxysilyl groups, aminoxysilyl groups, etc.), epoxy groups, acetoacetyl groups, thiol groups, acid anhydride groups, etc. And a silicon compound having a reactive group that can be expected to form a chemical bond.

The modified photocatalyst (A1) of the present invention comprises water and / or
Alternatively, in the presence or absence of an organic solvent, the above-mentioned photocatalyst (A) and the above-mentioned modifier compound (C) are mixed at a mass ratio of (A) / (C) = 1/99 to 99.
9 / 0.1, preferably (A) / (C) = 10 / 90-
It can be obtained by mixing at a ratio of 99/1 at 0 to 150 ° C., or changing the solvent composition of the mixture by (reduced pressure) distillation or the like.

Here, in the case of performing the above-mentioned modification treatment, usable organic solvents include, for example, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane and heptane, ethyl acetate and n-acetic acid. Esters 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, and halogen compounds such as chloroform, methylene chloride and carbon tetrachloride, Examples include dimethyl sulfoxide, nitrobenzene and the like, and a mixture of two or more of these.

The photocatalyst composition of the present invention comprises the photocatalyst (A) (including the modified photocatalyst (A1)) and a silicone compound (B) represented by the following average composition formula (1). During ^{_{R 1 p R 2 q X r}} SiO (4-pqr) / 2 (1) ( wherein, R ¹ represents a phenyl group, R ² is a linear or branched C 1-30 alkyl group , 5-20 carbon atoms
And at least one carbon atom selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms substituted with a halogen atom. Represents a hydrogen group. X
Is at least one reactivity selected from the group consisting of 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, an oxime group having 1 to 20 carbon atoms, and a halogen atom. Represents a group, and 0 <p <
4, 0 ≦ q <4, 0 <r <4, and 0 <(p + q + r)
<4, and further satisfies the relationship of 0.1 ≦ p / (p + q) ≦ 1. )

In the silicone compound (B) represented by the above average composition formula (1), a Ph—Si bond (Ph: phenyl group) is converted to an R—Si bond (R: hydrogen atom or carbon number of 1 to 2).
0 monovalent organic group) in a total amount of 10 mol% or more. We have found that a film formed from a photocatalyst composition comprising a silicone compound (B) having such a structure and a photocatalyst (A) has a very high ability to hydrophilize by light irradiation. Further, the hydrophilizing ability increases as the ratio of Ph-Si bond (Ph: phenyl group) to the entire R-Si bond increases. Therefore, a more preferable structure as the silicone compound (B) used in the photocatalyst composition of the present invention is a structure in which the R-Si bond (R: a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms) is based on P
20 mol% of h-Si bond (Ph: phenyl group)
Or more, more preferably 50 mol% or more, further preferably 100 mol% (phenylsilicone compound (B
1): The following average composition formula (2)). R ¹ _s X _t SiO _{(4-st) / 2} (2) (wherein, R ¹ represents a phenyl group, and X represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, and a C ¹ to 20 carbon atom.
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 <s <4, 0 <t <4, and 0 <(s + t ) <4. )

In the photocatalyst composition of the present invention, the mass ratio of the photocatalyst (A) to the silicone compound (B) is
(A) / (B) = 1 / 99-90 / 10, but (A) / (B) = 1 / 99-40 / 60,
Furthermore, even in the range of (A) / (B) = 1/99 to 30/70 where the content of the photocatalyst is very small, the formed film has a sufficient hydrophilicity by light irradiation (superhydrophilicity: 20 Water contact angle at 10 ° C or less). In addition, since a film having a small content of the photocatalyst exhibits the intrinsic film properties of the silicone compound as a binder, the film has particularly excellent flexibility (bending resistance and impact resistance).

The silicone compound (B) represented by the above average composition formula (1) in the present invention includes, for example, at least one of the bonds represented by the general formulas (15), (16), (17) and (18). Mention may be made of silicone compounds containing different structures and mixtures thereof.

[0059]

Embedded image

-(RRSiO)-... (1
6)

[0061]

Embedded image

[0062]

Embedded image

(Wherein R independently represents 1 to 3 carbon atoms)
0 represents a monovalent organic group. )

Silicone compound having the above structure
(B) is, for example, the general formula RSix_Three(Where R is the number of carbon atoms
Represents a monovalent organic group of 1 to 30; X is a hydrogen atom, hydroxyl
Group, an alkoxy group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
Acyloxy group, aminoxy group, oxy having 1 to 20 carbon atoms
At least selected from the group consisting of
Represents one reactive group. The same applies hereinafter. ) Trifunctional
Silane derivatives and / or general formula R_TwoSix_Two2 represented by
Functional silane derivative and / or general formula Six_FourRepresented by
The tetrafunctional silane derivative is partially hydrolyzed and polycondensed,
General formula R if necessary _ThreeInduction of monofunctional silane represented by SiX
Terminate with conductors and / or alcohols.
And can be prepared by (Here, the photocatalyst composition of the present invention
In the case of the silicone compound (B) to be used,
R is a phenyl group in an amount of 10% by mole or more of the total amount.
You. ) Part of the silane derivative monomer thus obtained
The polystyrene equivalent mass average molecular weight of the polycondensate is preferably
200 to 100,000, more preferably 400
~ 50,000.

In the present invention, the silicone compound (B) represented by the above average composition formula (1) contains the ladder structure represented by the above general formula (15) in an amount of 10 mol% or more, preferably 40 mol% or more. Is preferred, the film formed from the photocatalyst composition of the present invention is excellent in hardness, heat resistance, weather resistance, stain resistance, chemical resistance, and the like, which is preferable. In particular, those having a phenyl ladder structure represented by the following general formula (3) as the ladder structure are preferable because the above-mentioned properties of the film are greatly improved. Such ladder structure, for example can be identified by the presence of absorption derived from two siloxane bonds near 1040 cm ^-1 and 1160 cm ^-1 in the infrared absorption spectrum. (JFBrown.Jr., Etal.: J.Am.Chem.Soc., 82,6194 (1960)
reference. )

[0066]

Embedded image

(R ¹ represents a phenyl group.)

Further, as the silicone compound (B) represented by the above average composition formula (1), in addition to the ladder structure represented by the above formula (4), a chain structure represented by the formula (5) may be used.
If a film having a content of not more than 30% by mass, preferably not more than 30% by mass is selected, the coating film formed from the photocatalyst composition of the present invention has hardness, heat resistance, weather resistance, stain resistance, chemical resistance and the like. This is not only excellent, but also extremely excellent in film formability, substrate adhesion, flexibility and the like.

As the silicone compound (B) represented by the average composition formula (1), the phenyl silicone compound (B1) described above and the alkyl silicone compound (B2) represented by the average composition formula (4) are Mass ratio (B1) /
(B2) = 5/95 to 95/5, preferably (B1) /
When a mixture of (B2) = 30/70 to 90/10 is used, the coating film formed from the photocatalyst composition of the present invention is:
It is preferable because it is excellent in film forming property, hardness, heat resistance, stain resistance, chemical resistance and the like. ^{_{R 3 u X v SiO (4}} -uv) / 2 (4) ( wherein, R ³ represents a linear or branched alkyl group having 1 to 30 carbon atoms, X is defined by equation (1) 0 <u <4, 0 <v <4, and 0 <(u + v) <4
It is. )

Further, the alkyl silicone compound (B) mixed with the above-mentioned phenyl silicone compound (B1)
As 2), the molar ratio of the monooxydiorganosilane unit (T) represented by the formula (5) to the dioxyorganosilane unit (D) represented by the formula (6) is (T) / (D) = 80. / 2
It is very preferable to use a film having a structure having a ratio of 0 to 5/95, since a coating film formed from the photocatalyst composition of the present invention has extremely excellent weather resistance. — (R ³ R ³ SiO) — (5)

[0071]

Embedded image

(Wherein, R ³ represents a linear or branched alkyl group having 1 to 30 carbon atoms)

The silicone compound (B) which can be used in the photocatalyst composition of the present invention may be any of a solvent-soluble type, a dispersion type, a liquid type and a powder type. When the silicone compound (B) represented by the above average composition formula (1) has a hydroxyl group and / or a hydrolyzable group in the photocatalyst composition of the present invention, it is preferable to add a conventionally known hydrolysis catalyst or curing catalyst. . Preferred examples of the hydrolysis catalyst include acidic hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, and solid acids such as ion exchange resins. The amount of the hydrolysis catalyst is 0.1 to 1 mol of the hydrolyzable group on the silicon atom.
It is preferably in the range of 001 to 5 mol.

Examples of the curing catalyst include sodium hydroxide, potassium hydroxide, sodium methylate,
Basic compounds such as sodium acetate, tetramethylammonium chloride and tetramethylammonium hydroxide; tributylamine, diazabicycloundecene, ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ- (2- Amine compounds such as aminoethyl) -aminopropyltrimethoxysilane; titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate; aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate;
Aluminum compounds such as aluminum chloride; tin compounds such as tin acetylacetonate, dibutyltin octylate, dibutyltin dilaurate; metal-containing compounds such as cobalt octylate, cobalt acetylacetonate, iron acetylacetonate; phosphoric acid, nitric acid And acidic compounds such as phthalic acid, p-toluenesulfonic acid and trichloroacetic acid.

In the photocatalyst composition of the present invention, the silicone compound (B) represented by the above average composition formula (1) contains Si-
When it has an H group, it is preferable to add a crosslinking agent such as a polyfunctional vinyl compound. The polyfunctional vinyl compound is not particularly limited as long as it has a vinyl group and reacts with the Si—H group to accelerate the curing, but is preferably a monovalent unsaturated unsaturated compound having 2 to 8 carbon atoms such as a vinyl group and a hexenyl group. Vinyl silicone having a hydrocarbon group is generally used.

A catalyst may be added for the purpose of accelerating the reaction between the Si—H group and the vinyl silicone. As the catalyst, a platinum group catalyst, that is, a compound of ruthenium, rhodium, palladium, osmium, iridium, and platinum is suitable, and a compound of platinum and a compound of palladium are particularly preferable. Platinum compounds include, for example, platinum (II) chloride, tetrachloroplatinic acid (II), platinum chloride (I
V), hexachloroplatinic acid (IV), ammonium hexachloroplatinum (IV), potassium hexachloroplatinum (IV), platinum (II) hydroxide, platinum (IV) dioxide, dichloro-dicyclopentadienyl-platinum (II), Platinum-
Vinylsiloxane complex, platinum-phosphine complex, platinum-
An olefin complex, a simple substance of platinum, alumina, silica, or activated carbon carrying solid platinum may be used. Examples of palladium compounds include palladium (II) chloride,
Ammonium tetraammonium palladium (II) chloride, palladium (II) oxide and the like can be mentioned. The platinum group catalyst is usually 5 to 1000 ppm in terms of platinum group metal based on the total amount of the Si-H group-containing silicone and vinyl silicone.
Which can be increased or decreased depending on the reactivity, economy, desired curing rate and the like. If necessary, an activity inhibitor such as various organic nitrogen compounds, organic phosphorus compounds, and acetylene compounds may be added for the purpose of suppressing the activity of the platinum group catalyst and extending the pot life.

Further, the photocatalyst composition of the present invention can be used by adding a resin, if necessary. As the resin that can be used in the photocatalyst composition of the present invention, all synthetic resins and natural resins can be used, and a hydroxyl group and / or an alkoxy group having 1 to 20 carbon atoms, an enoxy group, and a 1 to 1 carbon atom are usable.
A silyl group having a silicon atom bonded to at least one hydrolyzable group selected from the group consisting of 20 acyloxy groups, aminoxy groups, oxime groups having 1 to 20 carbon atoms, and halogen atoms; Alternatively, a polymer having a side chain is preferably selected.

The photocatalyst composition of the present invention may contain powder of metal oxide such as silica, alumina, zirconium oxide, antimony oxide, rare earth oxide or the like for improving the hardness, scratch resistance and hydrophilicity of the film. It may be added in a sol state. However, these metal oxide fine particles do not have the ability as a binder like the silicone compound in the present invention, and the flexibility (flex resistance,
Impact resistance). Therefore, the addition amount of the metal oxide is preferably such that the total mass of the photocatalyst (A) and the metal oxide in the film formed from the photocatalyst composition is 50% by mass or less.

The photocatalyst composition of the present invention may further contain, if necessary, components usually added to paints and the like, for example, pigments,
Fillers, dispersants, light stabilizers, wetting agents, thickeners, rheology control agents, defoamers, plasticizers, film-forming aids, rust inhibitors, dyes, preservatives, etc. are selected according to the respective purpose. , Can be combined and combined. The photocatalyst composition of the present invention, wherein the photocatalyst composition using the modified photocatalyst (A1) which has been modified with a modifier compound (C) having a structure with a very small surface energy as the photocatalyst (A), comprises: This is very preferable because the distribution tends to have a self-gradient. Here, the self-gradient means that when a film or a molded article is formed from the photocatalyst composition, the photocatalyst corresponds to the property (particularly hydrophilic / hydrophobic) of the interface where the film or the molded article comes into contact during the formation process, This means that a structure having a concentration gradient is formed autonomously.

In this case, if there is a difference in properties (hydrophilic / hydrophobic) on the contact surfaces, a concentration gradient is generated corresponding to the difference,
Further, a concentration gradient is generated between the inside of the film or the molded body and the interface. For example, when the self-grading photocatalyst composition is applied on a substrate and formed into a film, the concentration of the photocatalyst increases in the thickness direction such that the amount of the photocatalyst increases toward the surface of the film in contact with an interface other than the substrate (eg, outside air). It becomes possible to obtain a gradient composition film having a gradient. At this time, when the relative concentration of the photocatalyst (A) content (concentration) of 100 in the entire film is 120 or more in the vicinity of the surface 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. When the relative concentration in the vicinity of the interface on the base material side is 80 or less, the effect of preventing interface deterioration is recognized. The relative concentration in the vicinity of the substrate-side interface is preferably 50 or less, more preferably 10 or less.

When the photocatalyst composition of the present invention is self-gradient, the solid content ratio of the photocatalyst (A) to the silicone compound (B) in the photocatalyst composition is (A) / (B) =
0.1 / 99.9-30 / 70, and further (A) /
(B) = 0.1 / 99.9 to 20/80, and further, (A) / (B) = 0.1 / 99.9 to 10/90, and the content of the photocatalyst (A) is very small. Even in the range, the formed film or molded body has a sufficient hydrophilicity by light irradiation (superhydrophilicity: contact angle of water at 20 ° C. of 10 ° or less) and photocatalytic activity. In addition, since a film or a molded product having a small content of the photocatalyst (A) expresses the original physical properties of the silicone compound as a binder,
It is excellent in strength, flexibility (bending resistance, impact resistance), and the like.

A molded article formed from the photocatalyst composition of the present invention and a functional complex obtained by forming a film formed from the above photocatalyst composition on a substrate are hydrophobic or hydrophilic by irradiation with light. And / or a photocatalytic activity, and a photoelectric conversion function can be exhibited. That is, in another aspect of the present invention, a molded article formed from the photocatalyst composition and a functional composite obtained by forming a film formed from the photocatalyst composition on a substrate are provided. .

In the present invention, as a method for obtaining a functional composite or a molded article from the photocatalyst composition, for example, when the form is a paint, it is applied to a substrate, dried, and then subjected to a heat treatment or the like as necessary. By doing so, the functional complex of the present invention can be obtained. As an application method, for example, a spraying method, a flow coating method, a roll coating method,
Examples 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 form of the photocatalyst composition is a pellet, the molded article of the present invention can be obtained by extrusion molding, injection molding, press molding, or the like.

The above-mentioned functional composite or molded article formed from the photocatalyst composition of the present invention is characterized by a light having an energy higher than the band gap energy of the photocatalyst (A) contained therein (the photocatalyst (A) is spectrally enhanced). In the case of the modified photocatalyst (A1) having a sensitizing dye, light or light containing absorption light of the spectral sensitizing dye) is irradiated to irradiate the compound with a hydrophobic or hydrophilic property.
Alternatively, it exhibits photocatalytic activity, and further has a photoelectric conversion function. In the present invention, light having an energy higher than the band gap energy of the photocatalyst (A) (in the case where the photocatalyst (A) is a modified photocatalyst (A1) having a spectral sensitizing dye, contains light absorbed by the spectral sensitizing dye) As a light source for light, in addition to light obtained in a general residential environment such as sunlight and indoor lighting, light such as a black light, a xenon lamp, and a mercury lamp can be used.

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 molded articles and films, and substrates coated with the hydrophilic film, etc.) are antifogging technologies for preventing fogging of mirrors and glass, and antifouling technologies for building exteriors and antistatic. It can be applied to technology, etc.
Mirrors, lenses, goggles, covers, insulators, building materials, building exteriors, building interiors, structural members, vehicle exteriors and paints, machinery and articles exteriors, various display devices, lighting devices, housing equipment,
It can be used for applications such as tableware, kitchenware, household electrical appliances, magneto-optical recording media and optical recording media.

The above-mentioned molded article or functional composite provided by the present invention, which is a hydrophobic substance whose contact angle with water at 20 ° C. becomes 70 ° or more (preferably 90 ° or more) by light irradiation. (A hydrophobic molded body or a hydrophobic film, and a substrate coated with the hydrophobic film, etc.) are provided with drip-proof property, water-repellent property, prevention of adhesion of water-based dirt, and antifouling technology utilizing running water washing property. In addition, it can be applied to icing and snow prevention technology, etc., window glass, windshield, mirror, lens, goggle, cover, insulator, building material, building exterior, building interior, structural member, vehicle exterior and painting, machinery It can be used for exteriors of devices and articles, various display devices, lighting devices, household equipment, tableware, kitchenware, household electrical appliances, roofing materials, antennas, power lines, snow and snow gliders, and the like.

The above-mentioned molded article or functional composite provided by the present invention and having a photoelectric conversion function can exhibit functions such as power conversion of solar energy, and can be used as a (wet) solar cell. It can be used for applications such as an optical semiconductor electrode used for the purpose. Further, the member provided by the present invention, whose wettability with water changes (changes from hydrophobic to hydrophilic, or changes from hydrophilic to hydrophobic) by light irradiation, can be applied to an original plate for offset printing or the like. Very useful for applications.

The present invention will be described based on examples. still,
The methods for measuring various physical properties used in the following Examples, Reference Examples and Comparative Examples are as follows. [1] Particle size distribution and number average particle size The particle size distribution and number average particle size are diluted by appropriately adding a solvent so that the solid content in the sample is 1 to 20% by mass,
Wet particle size analyzer (Micro Truck manufactured by Nikkiso Co., Ltd.)
UPA-9230).

[2] Mass average molecular weight Using gel permeation chromatography,
It was determined from a standard polystyrene calibration curve. (Equipment used) ・ Apparatus: 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 Measurement of phenyl group-containing silicone compound: Measurement of tetrahydrofuran phenyl group-free silicone compound: toluene

[3] Infrared absorption spectrum The infrared absorption spectrum was measured by JASCO FT / IR-4.
Measured at 10. [4] ²⁹ Si measuring ²⁹ Si nuclear magnetic resonance of nuclear magnetic resonance was measured with JNM-LA400 (manufactured by JEOL Ltd.). [5] Coating film hardness The hardness of the coating film was determined as pencil hardness (scratch of the coating film) according to JIS-K5400. [6] Flex resistance The flex resistance of the coating film was evaluated according to JIS-K5400. [7] Impact resistance The flex resistance of the coating film was evaluated by the Dupont method (500 g × 50 cm) according to JIS-K5400.

[8] Contact Angle of Water on Coating Surface A drop of deionized water was placed on the surface of the coating film and allowed to stand at 20 ° C. for 1 minute.
150) was used to measure the contact angle. The smaller the contact angle of water with the coating film, the higher the hydrophilicity of the coating film surface. [9] UV irradiation A black light (Toshiba Lighting & Technology Corp.)
FL20S BLB). At this time, the light intensity was measured with an ultraviolet intensity meter (UV, manufactured by Topcon Corporation).
R-2 (UD-36 type light receiving unit: wavelength 310 to 400 nm)
Ultraviolet light intensity measured using
cm ² . [10] Irradiation with light containing almost no ultraviolet light A fluorescent lamp (manufactured by Toshiba Lighting & Technology Corp.)
FL20S-N-SDL NU type). At this time, the visible light intensity (using the UD-40 type light receiving unit as the light receiving unit) measured with the UVR-2 type ultraviolet intensity meter was 0.3 mW / cm ² .

[11] Photocatalytic activity of the coating film The coating film surface was coated with a 5% by mass ethanol solution of methylene blue, and then irradiated with the above-mentioned black light for 3 days. At this time, the UV intensity was adjusted to be 1 mW / cm ² using the UVR-2 type UV intensity meter (using the UD-36 type light receiving unit as the light receiving unit). After that, the degree of decomposition of methylene blue by the action of the photocatalyst (evaluated visually based on the degree of fading of the coating film surface)
The activity of the photocatalyst was evaluated on the basis of the following three grades. A: Methylene blue was completely decomposed. Δ: Methylene blue blue slightly remained. X: Almost no decomposition of methylene blue was observed.

[12] Weather Resistance (Gloss Retention) of Coating Film The weather resistance of the coating film was measured using an exposure test (irradiation: DPWL-5R, manufactured by Suga Test Instruments Co., Ltd.). 4 hours at 60 ° C, dark / wet: 40
C. for 4 hours). 60 ° -6 hours after 1000 hours of exposure
The 0 ° specular reflectance was measured as the final gloss value, divided by the initial gloss value, and this value was calculated as the gloss retention. [13] Evaluation of inclined structure of photocatalyst To evaluate the inclined structure of photocatalyst in a member, an ultra-thin section of a member was prepared, and TEM observation (HF2, manufactured by Hitachi, Ltd.)
000).

[0094]

Reference Example 1 Synthesis of silicone compound (a). In a reactor having a reflux condenser, a thermometer and a stirrer, 78 g of dioxane was added to phenyltrichlorosilane 2.
After adding 6.0 g, the mixture was stirred at room temperature for about 10 minutes.
To this, a mixed solution composed of 3.2 g of water and 12.9 g of dioxane was added dropwise over about 30 minutes while maintaining the reaction solution at 10 to 15 ° C., and further stirred at 10 to 15 ° C. for about 30 minutes,
Subsequently, the reaction solution was heated to 60 ° C. and stirred for 3 hours. The temperature of the obtained reaction solution was lowered to 25 to 30 ° C, and 392 g of toluene was added dropwise over about 30 minutes.
And stirred for 2 hours.

The resulting reaction solution was cooled to 10 to 15 ° C., and 19.2 g of methanol was added over about 30 minutes.
Thereafter, stirring was continued at 25 to 30 ° C. for about 2 hours,
Subsequently, the reaction solution was heated to 60 ° C. and stirred for 2 hours. The solvent was distilled off from the resulting reaction solution at 60 ° C. under reduced pressure to obtain a silicone compound (a) having a ladder skeleton having a mass average molecular weight of 3,600. (The obtained silicone compound (a) has absorptions (1130 cm ^-1 and 1037 c) derived from the stretching vibration of the ladder skeleton in the IR spectrum.
m ^-1 ) was observed. )

[0096]

Reference Example 2 Synthesis of silicone compound (b). Methyltrichlorosilane 2 was added to 235 g of dioxane in a reactor having a reflux condenser, a thermometer and a stirrer.
After adding 5.6 g and 15.5 g of phenyltrichlorosilane, the mixture was stirred at room temperature for about 10 minutes. Add water 6.6
g and 26.4 g of dioxane were added dropwise over about 30 minutes while maintaining the reaction solution at 10 to 15 ° C.
The mixture was further stirred at 10 to 15 ° C. for about 30 minutes, and then heated to 60 ° C. and stirred for 3 hours. The obtained reaction solution was
After the temperature was lowered to 5 to 30 ° C and 235 g of toluene was added dropwise over about 30 minutes, the reaction solution was heated to 60 ° C again and stirred for 2 hours.

The resulting reaction solution was cooled to 10 to 15 ° C., and 42.8 g of methanol was added over about 30 minutes. Thereafter, stirring was further continued at 25 to 30 ° C. for about 2 hours, and then the reaction solution was heated to 60 ° C. and stirred for 2 hours. The solvent was distilled off from the resulting reaction solution at 60 ° C. under reduced pressure to obtain a silicone compound (b) having a mass average molecular weight of 3100 and having a ladder skeleton. (The obtained silicone compound (b) has absorptions (1134 cm ^-1 and 1044 c) derived from the stretching vibration of the ladder skeleton in the IR spectrum.
m ^-1 ) was observed. When the structure of the obtained silicone compound (b) was measured by ²⁹ Si nuclear magnetic resonance, silane (Ph-Si) bonded to a phenyl group and silane (Me
-Si), and the ratio was Ph-
Si: Me-Si = 31: 69.

[0098]

Reference Example 3 Synthesis of silicone compound (c). After adding 26.0 g of phenyltrichlorosilane to 118.0 g of dioxane in a reactor having a reflux condenser, a thermometer and a stirrer, the mixture was stirred at room temperature for about 10 minutes. A mixture of 3.2 g of water and 12.9 g of dioxane was added dropwise thereto over about 30 minutes while maintaining the reaction solution at 10 to 15 ° C., and the mixture was further stirred at 10 to 15 ° C. for about 30 minutes. The reaction solution was heated to 60 ° C. and stirred for 3 hours.
The obtained reaction solution was cooled to 25 to 30 ° C., and 353 g of toluene was added dropwise over about 30 minutes.
The temperature was raised to 0 ° C. and the mixture was stirred for 2 hours.

After the temperature of the obtained reaction solution was lowered to 10 to 15 ° C. and 25.1 g of dimethylchlorosilane was added, a mixed solution of 1.1 g of water and 4.3 g of dioxane was further added while maintaining the temperature at 10 to 15 ° C. The addition took about 30 minutes.
Subsequently, stirring was continued at 25 to 30 ° C. for about 2 hours, and then the temperature of the reaction solution was further increased to 60 ° C. and stirred for 3 hours. The solvent was distilled off from the obtained reaction solution at about 60 ° C. under reduced pressure to obtain a silicone compound having a Si—H group having a mass average molecular weight of 1200 (C). (Absorption (2140 cm ^-1 ) derived from the Si-H group was observed.)

[0100]

Reference Example 4 Synthesis of a silicone compound (d) having no phenyl group. Methyltrichlorosilane 2 was added to 470 g of dioxane in a reactor having a reflux condenser, a thermometer and a stirrer.
After adding 5.8 g, the mixture was stirred at room temperature for about 10 minutes.
A mixture of 4.7 g of water and 18.7 g of dioxane was added dropwise thereto over about 30 minutes while maintaining the reaction solution at 10 to 15 ° C., and the mixture was further stirred at 10 to 15 ° C. for about 30 minutes.
Subsequently, the temperature of the reaction solution was raised to 60 ° C. and stirred for 3 hours.

The temperature of the obtained reaction solution was lowered to 10 to 15 ° C., and 30.2 g of methanol was added over about 30 minutes. Subsequently, stirring was continued at 25 to 30 ° C. for about 2 hours, and then the temperature of the reaction solution was further increased to 60 ° C. and stirred for 3 hours. The solvent was distilled off from the obtained reaction solution at about 60 ° C. under reduced pressure to obtain a silicone compound (d) having a weight average molecular weight of 2,800 and having no phenyl group.

[0102]

Reference Example 5 Synthesis of a silicone compound (e) having no phenyl group. Methyltrimethoxysilane 1 was added to 300 g of methanol in a reactor having 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. 11. A 0.05N aqueous hydrochloric acid solution was added thereto under ice cooling.
A mixed solution consisting 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 the dropwise addition, the mixture was further stirred for about 20 minutes at 10 ° C. or lower and for 6 hours at room temperature.

Thereafter, the solvent was distilled off from the obtained reaction solution at 60 ° C. under reduced pressure to give a mass average molecular weight of 3600.
A silicone compound (e) having no phenyl group was obtained. When the structure of the obtained silicone compound (e) was measured by ²⁹ Si nuclear magnetic resonance, signals indicating a T structure and a D structure were confirmed, and the ratio was T structure: D structure =
1: 1.

[0104]

Reference Example 6 Synthesis of Modified Photocatalyst (Modified Titanium Oxide Organosol (F)) Titanium oxide organosol (trade name: TKS-25) placed in a reactor having a reflux condenser, a thermometer and a stirrer
1, manufactured by Teica Co., Ltd., dispersion medium: mixed solvent of toluene and isopropanol, TiO2 concentration of 20% by mass, average crystallite diameter of 6 nm (catalog value) 40 g of KF9901
(Methyl hydrogen siloxane-dimethyl siloxane copolymer trade name, Si-H group content 7.14 mmol
1 / g, mass average molecular weight 3900, Shin-Etsu Chemical Co., Ltd.
8 g at about 40 ° C. over about 5 minutes.
By continuing stirring at 0 ° C. for 48 hours, a modified titanium oxide organosol (F) having very good dispersibility was obtained. At this time, the amount of hydrogen gas generated by the reaction of KF9901 was 980 ml at 23 ° C.

Further, the obtained modified titanium oxide organosol (f) was coated on a KBr plate, and the IR spectrum was measured. As a result, the absorption of Ti—OH group (3630 to 3630) was measured.
640 cm ^-1 ) was observed. The particle size distribution of the resulting modified titanium oxide organosol (f) is monodisperse (number-average particle size is 21 nm), and the monodispersion (number-average particle size) of the titanium oxide organosol before the modification treatment is Is 12 nm), and the particle size distribution has completely disappeared.

[0106]

Reference Example 7 Synthesis of Modified Photocatalyst (Modified Titanium Oxide Organosol (G)) In a reactor equipped with a reflux condenser, a thermometer and a stirrer, 1 g of 4-aminofluorescein and 140 g of dioxane were added.
Then, a solution prepared by dissolving 0.24 g of allyl isocyanate in 2.3 g of dioxane was added thereto over 30 minutes at 30 ° C. with stirring, and further stirred at 30 ° C. for 5 hours. 50 g of KF9901 (same as that used in Reference Example 6) was added to the obtained reaction mixture, and the temperature was raised to 80 ° C. with stirring. To this, UNIOX MUS-8 (trade name of polyoxyethylene allyl methyl ether, mass average molecular weight 800 (listed value in catalog), manufactured by NOF Corporation) 13
A solution prepared by dissolving 7 g and 0.5 g of a 5% by mass isopropanol solution of chloroplatinic acid (IV) hexahydrate in 137 g of dioxane was added at 80 ° C. over about 1 hour.
After stirring for 2 hours, the mixture was cooled to room temperature.

In a reactor equipped with a reflux condenser, a thermometer and a stirrer, 60 g of TKS251 (same as that used in Reference Example 6) was placed, and 12.5 g of the above reaction solution was added thereto.
g at 50 ° C. with stirring over about 30 minutes.
By continuing stirring at 0 ° C. for 12 hours, a modified titanium oxide organosol (G) having a very good dispersibility and having a fluorescent color was obtained. At this time, hydrogen gas was generated with the reaction, and the volume was 120 ml at 23 ° C.

[0108]

Reference Example 8 Synthesis of Modified Photocatalyst (Modified Titanium Oxide Organosol (H)) TKS251 (same as that used in Reference Example 6) was placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer.
5 g of Aciplex-SS950 (trade name of a 5% by mass solution of a fluororesin having a sulfonic acid group in ethanol-water (mass ratio 1: 1), manufactured by Asahi Kasei Corporation)
At 30 ° C. with stirring over about 30 minutes.
By continuing stirring at 8 ° C. for 8 hours, a modified titanium oxide organosol (h) having very good dispersibility was obtained.

The particle size distribution of the resulting modified titanium oxide organosol (h) is monodisperse (number average particle size is 54 n
m), and the particle size distribution of the monodispersed titanium oxide organosol before modification (number average particle diameter: 12 nm) was completely disappeared.

[0110]

Example 1 TKS251 was added to 10 g of a 20% by mass toluene solution of the silicone compound (a) synthesized in Reference Example 1.
2.5 g (same as that used in Reference Example 6) was added under stirring at room temperature, 4 g of butyl cellosolve was added under stirring, and 0.1 g of a curing catalyst (DX175 / Shin-Etsu Chemical Co., Ltd.) was further added. It was added under stirring to obtain a photocatalyst composition (R).

The obtained photocatalyst composition (i) was spray-coated on a steel plate so as to have a thickness of 2 μm.
After drying for a week, a steel sheet having a transparent and smooth coating film was obtained. The pencil hardness of the steel sheet having the obtained coating film was 2H, and the contact angle with water was 90 °. Further, both the bending resistance test and the impact resistance test passed. The contact angle of water after irradiating the obtained steel sheet with the coating film with ultraviolet rays (black light) for 3 days was 54 °, but the contact angle of water after 1 week of irradiation was 0 °. Good photocatalytic activity evaluation (良好)
Met.

[0112]

Example 2 TKS251 was added to 10 g of a 20% by mass toluene solution of the silicone compound (a) synthesized in Reference Example 1.
2.5 g (same as used in Reference Example 6) was added at room temperature with stirring, 4 g of butyl cellosolve was added with stirring, and 0.1 g of a curing catalyst (dibutyltin dilaurate) was added with stirring. Thus, a photocatalyst composition (nu) was obtained.

The obtained photocatalyst composition (N) was spray-coated on a glass plate so as to have a thickness of 2 μm, dried at room temperature for 1 hour and heated at 150 ° C. for 30 minutes.
A glass plate having a transparent and smooth coating film was obtained. The pencil hardness of the glass plate having the obtained coating film was 4H, and the contact angle with water was 92 °. The contact angle of water after irradiating the glass plate with the obtained coating film with ultraviolet rays (black light) for 3 days was 38 °, but the contact angle of water after 1 week of irradiation was 0 °. . The result of evaluation of the photocatalytic activity was good (△).

[0114]

Example 3 TKS2 was added to 8.75 g of a 20 mass% toluene solution of the silicone compound (b) synthesized in Reference Example 2.
After adding 3.75 g of 51 (the same as that used in Reference Example 6) at room temperature with stirring, 4 g of butyl cellosolve was added with stirring, and 0.1 g of a curing catalyst (DX175 / Shin-Etsu Chemical Co., Ltd.) Was added with stirring to obtain a photocatalyst composition (R).

The obtained photocatalyst composition (ル) was spray-coated on a steel sheet so as to have a film thickness of 2 μm, and then was applied at room temperature.
After drying for a week, a steel sheet having a transparent and smooth coating film was obtained. The pencil hardness of the steel sheet having the obtained coating film was 3H, and the contact angle with water was 87 °. Further, both the bending resistance test and the impact resistance test passed. The contact angle of water after irradiating the obtained steel sheet having the coating film with ultraviolet rays (black light) for 3 days was 62 °, but the contact angle of water after 1 week of irradiation was 10 °. The result of evaluation of the photocatalytic activity was good (△).

[0116]

Example 4 TKS2 was added to 8.75 g of a 20 mass% toluene solution of the silicone compound (c) synthesized in Reference Example 3.
After adding 3.75 g of 51 (same as that used in Reference Example 6) at room temperature under stirring, vinyl-terminated polydimethylsiloxane (trade name: DMS-V00,
0.2 g of Chisso Corporation and 0.4 g of a 0.25% dioxane solution of dichloro-dicyclopentadienyl-platinum (II) were added at room temperature with stirring, and 4 g of butyl cellosolve was added with stirring. Photocatalyst composition (e)
I got

The obtained photocatalyst composition (e) was spray-coated on a steel sheet so as to have a film thickness of 2 μm, and then was applied at room temperature.
After drying for an hour and heating at 140 ° C. for 30 minutes, a steel sheet having a transparent and smooth coating film was obtained. The pencil hardness of the steel sheet having the obtained coating film was 2H, and the contact angle with water was 94 °. Further, both the bending resistance test and the impact resistance test passed. The contact angle of water after irradiating the obtained steel sheet with the coating film with ultraviolet rays (black light) for 3 days was 20 °, but the contact angle of water after 1 week of irradiation was 6 °. The result of the evaluation of the photocatalytic activity was very good (◎).

[0118]

Example 5 The modified titanium oxide organosol (f) 0.7 synthesized in Reference Example 6 was mixed with 11.25 g of a 20% by mass toluene solution of the silicone compound (A) synthesized in Reference Example 1.
After adding 5 g under stirring at room temperature, 4 g of butyl cellosolve was added under stirring, and 0.1 g of a curing catalyst (dibutyltin dilaurate) was further added under stirring to obtain a photocatalyst composition (wa).

The obtained photocatalyst composition (wa) was spray-coated on a steel sheet so as to have a film thickness of 2 μm, and then the mixture was heated at room temperature for 1 hour.
After drying for a week and heating at 150 ° C. for 30 minutes, a steel sheet having a transparent and smooth coating film was obtained. The pencil hardness of the steel sheet having the obtained coating film was H, and the contact angle with water was 97 °. Further, both the bending resistance test and the impact resistance test passed. The contact angle of water after irradiating the obtained steel sheet having the coating film with ultraviolet rays (black light) for 3 days was 0 °. The result of the evaluation of the photocatalytic activity was very good (非常).

[0120]

Example 6 17.9 g of toluene, 32.3 g of isopropanol and 14 g of butyl cellosolve 14 were mixed with 6 g of the silicone compound (a) synthesized in Reference Example 1 and 3 g of the silicone compound (E) synthesized in Reference Example 5. .5
g, and the mixture was stirred at room temperature to obtain a mixture solution of the silicone compound (a) and the silicone compound (e).
11.5 g of the modified titanium oxide organosol (f) prepared in Reference Example 6 was added to the obtained mixture solution of the silicone compound under stirring at room temperature, and 0.4 g of a curing catalyst (dibutyltin dilaurate) was further added. Was added with stirring to obtain a photocatalyst composition (f). 1 mm thick aluminum plate cut into 50 mm x 60 mm (JIS, H, 4000 (A10
Acrylic urethane resin paint (manufactured by Nippon Paint Co., Ltd., Mighty Lac White, two-pack mixed type) was spray-coated on 50P)) and dried at room temperature for 3 days. The photocatalyst composition (f) was spray-coated on the obtained acrylic urethane-coated aluminum plate so as to have a film thickness of 2 μm, and then was applied at room temperature.
After drying for an hour and heating at 150 ° C. for 30 minutes, a test plate having a photocatalytic coating film was obtained.

The pencil hardness of the test plate having the obtained coating film was HB, and the contact angle with water was 95 °. The contact angle of water after irradiating the test plate having the obtained coating film with ultraviolet rays (black light) for 3 days was 0 °. The result of the evaluation of the photocatalytic activity was very good (非常). Further, the gloss retention by an exposure test (after 1000 hours) using a Dew panel light control weather meter was 93.
%, Indicating very good weather resistance.

[0122]

Example 7 The photocatalyst composition (f) obtained in Example 6 was spray-coated on an OHP film so as to have a film thickness of 2 μm, dried at room temperature for 2 days, and then dried at 50 ° C. for 3 days.
By heating for one day, an OHP film having a smooth coating film was obtained. When the distribution of titanium oxide in the cross section of the obtained OHP film having the photocatalytic coating film was observed by TEM observation, almost no titanium oxide was present at the interface between the OHP film as the base material and the photocatalytic coating film. Were all covered with titanium oxide.

[0123]

Example 8 Reference Example 7 was added to 8.75 g of a 20% by mass toluene solution of the silicone compound (a) synthesized in Reference Example 1.
4.5 g of modified titanium oxide organosol (g) synthesized in
Was added under stirring at room temperature, 4 g of butyl cellosolve was added under stirring, and 0.1 g of a curing catalyst (dibutyltin dilaurate) was further added under stirring to obtain a photocatalyst composition (Y).

The obtained photocatalyst composition (Y) was spray-coated on a glass plate so as to have a thickness of 2 μm, dried at room temperature for 1 hour, and heated at 150 ° C. for 30 minutes.
A glass plate having a transparent and smooth coating film was obtained. The glass plate having the obtained coating film has a contact angle with water of 34 °, and when irradiated with light (fluorescent lamp) containing almost no ultraviolet rays for one day, the water has a contact angle of 104 ° with the coating film. Increased. That is, the coating film obtained from the photocatalyst composition (Y) became hydrophobic in response to visible light. When the hydrophobic coating film was irradiated with ultraviolet light (black light) for one day, the contact angle of water became 0 ° and the coating film changed to a hydrophilic coating film.

[0125]

Example 9 Reference Example 8 was added to 8.75 g of a 20% by mass toluene solution of the silicone compound (a) synthesized in Reference Example 1.
4.1g of modified titanium oxide organosol (h) synthesized in
Was added under stirring at room temperature, 4 g of butyl cellosolve was added under stirring, and 0.1 g of a curing catalyst (dibutyltin dilaurate) was further added under stirring to obtain a photocatalyst composition (TA).

The resulting photocatalyst composition (t) was spray-coated on a glass plate so as to have a thickness of 2 μm, dried at room temperature for 1 hour, and heated at 150 ° C. for 30 minutes.
A glass plate having a smooth coating film was obtained. The contact angle with water of the glass plate having the obtained coating film was 60 °. Irradiation with ultraviolet rays (black light) for 7 days did not substantially change the contact angle of water. Was very good (◎).

[0127]

Comparative Example 1 A 20% by mass toluene solution of a silicone compound having no phenyl group (d) synthesized in Reference Example 8.
To 75 g, 3.75 g of TKS251 (same as that used in Reference Example 6) was added at room temperature with stirring, then 4 g of butyl cellosolve was added with stirring, and 0.1 g of a curing catalyst (dibutyltin dilaurate) was further stirred. It was added below to obtain a photocatalyst composition (d).

The obtained photocatalyst composition (d) was spray-coated on a steel sheet so as to have a film thickness of 2 μm, and then was applied at room temperature.
After drying for an hour and heating at 140 ° C. for 30 minutes, a steel sheet having a transparent and smooth coating film was obtained. The pencil hardness of the steel sheet having the obtained coating film was 2H, and the contact angle with water was 92 °. Further, both the bending resistance test and the impact resistance test passed. After irradiating the obtained steel sheet having the coating film with ultraviolet rays (black light) for one week, the contact angle of water was 94 °, and the evaluation of photocatalytic activity was poor (×). Further, even after irradiating the obtained steel sheet having the coating film with ultraviolet rays (black light) for one month, the coating did not become hydrophilic and the contact angle of water was 88 °.

[0129]

Comparative Example 2 6 g of a 20% by mass toluene solution of the silicone compound (d) having no phenyl group synthesized in Reference Example 4
5. TKS251 (same as that used in Reference Example 6)
After 25 g was added at room temperature with stirring, 4 g of butyl cellosolve was added with stirring, and 0.1 g of a curing catalyst (dibutyltin dilaurate) was further added with stirring to obtain a photocatalyst composition (SO).

The obtained photocatalyst composition (SO) was spray-coated on a steel sheet so as to have a film thickness of 2 μm, and then was applied at room temperature.
After drying for an hour and heating at 140 ° C. for 30 minutes, a steel sheet having a slightly turbid coating film was obtained. The steel sheet having the obtained coating has hydrophilicity (ultraviolet (black light)
Although the contact angle of water after irradiation for one week was 12 °), the coating film was very brittle, and both the bending resistance test and the impact resistance test failed.

[0131]

EFFECTS OF THE INVENTION The photocatalyst composition of the present invention not only has excellent transparency and hardness, etc., but also has both flexibility (bending resistance and impact resistance) and photocatalytic activity, and furthermore has good water wettability by light irradiation. (Hydrophilic, hydrophobic) controllable coating film can be formed under mild conditions.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F071 AA67 AA81 AB18 AB23 AF13 AF23 AF57 AH19 4G069 AA02 BA04A BA04B BA17 BA21A BA21B BA22A BA48A BB02A BB04A BB06A BB09A BB13A BB15A BC03A BC13A BC31A BCBC BC BC BC BC BC BC54A BC55A BC56A BC59A BC60A BC66A BC68A BC70A BC71A BC72A BC74A BC75A BD05A BE32A BE32B BE37A BE37B CA01 CA10 CA11 CD10 EA11 EB19 EC29 ED01 ED02 ED03 4J002 CP031 CP032 CP082 DA116 DE096 DE106 GE116

Claims (16)

[Claims] 1. A photocatalyst composition comprising a photocatalyst (A) and a silicone compound (B) represented by the following average composition formula (1). During ^{_{R 1 p R 2 q X r}} SiO (4-pqr) / 2 (1) ( wherein, R ¹ represents a phenyl group, R ² is a linear or branched C 1-30 alkyl group , 5-20 carbon atoms
And at least one carbon atom selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms substituted with a halogen atom. Represents a hydrogen group. X
Is at least one reactivity selected from the group consisting of 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, an oxime group having 1 to 20 carbon atoms, and a halogen atom. Represents a group, and 0 <p <
4, 0 ≦ q <4, 0 <r <4, and 0 <(p + q + r)
<4, and further satisfies the relationship of 0.1 ≦ p / (p + q) ≦ 1. ) 2. The method according to claim 1, wherein the silicone compound (B) represented by the average composition formula (1) contains a phenyl silicone compound (B1) represented by the following average composition formula (2). Photocatalyst composition. R ¹ _s X _t SiO _{(4-st) / 2} (2) (wherein, R ¹ represents a phenyl group, and X is as defined in formula (1). 0 <s <4, 0 <t <4 and 0 <
(S + t) <4. ) 3. The photocatalyst composition according to claim 1, wherein the silicone compound (B) has a phenyl ladder structure represented by the general formula (3). Embedded image (R ¹ represents a phenyl group.) 4. A phenyl silicone compound (B1) represented by an average composition formula (2) and an alkyl silicone represented by an average composition formula (4) wherein the silicone compound (B) represented by the average composition formula (1) is The photocatalyst composition according to any one of claims 1, 2, and 3, wherein the photocatalyst composition is contained as a mixture of the compound (B2). ^{_{R 3 u X v SiO (4}} -uv) / 2 (4) ( wherein, R ³ represents a linear or branched alkyl group having 1 to 30 carbon atoms, X is defined by equation (1) 0 <u <4, 0 <v <4, and 0 <(u + v) <4
It is. ) 5. The alkyl silicone compound (B2) represented by the average composition formula (4) is composed of a monooxydiorganosilane unit (T) represented by the formula (5) and a dioxysilane compound represented by the formula (6). The photocatalyst composition according to claim 4, having a structure having both oxyorganosilane units (D). — (R ³ R ³ SiO) — (5) (In the formula, R ³ represents a linear or branched alkyl group having 1 to 30 carbon atoms.) 6. The photocatalyst (A) converts the photocatalyst particles into a monooxydiorganosilane unit represented by the formula (7), a dioxyorganosilane unit represented by the formula (8), and a compound represented by the formula (9). Modification obtained by performing a modification treatment using at least one modifier compound (C) selected from the group consisting of compounds having at least one structural unit selected from the group consisting of difluoromethylene units represented. The photocatalyst composition according to any one of claims 1 to 6, which is a photocatalyst (A1). — (R ⁴ R ⁴ SiO) — (7) (Wherein, R ⁴ is each independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or unsubstituted or 1 to 3 carbon atoms. 2
0 alkyl group, phenyl group, alkoxy group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms substituted with a halogen atom.
Represents 20 aryl groups)-(CF ₂ )-(9) 7. The photocatalyst composition according to claim 6, wherein the modifier compound (C) is a silicon compound having an average composition represented by the formula (10). R ⁴ _x Q _y X _z SiO _{(4-xyz) / 2} (10) (where R ⁴ is as defined in the formula (7), and X is
As defined in equation (1). Further, in the formula, Q is a group containing at least one functional group that is 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 An unsubstituted or C1-C20 alkyl group or C1-C20 alkoxy group, or a C6-C20 aryl group substituted with a halogen atom, and a C1-C30 fluoroalkyl At least one hydrophobic group selected from the group consisting of groups; (I) at least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphate group or a salt thereof, a sulfonic acid group or a salt thereof, and a polyoxyalkylene group; (C) 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. Also, 0 <x <4, 0 <y <4, 0 ≦ z <4, and x +
y + z) <4. ) 8. The photocatalyst composition according to claim 6, wherein the modifier compound (C) is a compound represented by the formula (11). As _{^{(R 4 HSiO) a (R}} 4 2 SiO) b (R 4 QSiO) c (R 4 3 SiO 1/2) d ··· (11) ( wherein, R ⁴ is defined in formula (7) And Q is as defined in the formula (10), a is an integer of 1 or more, b and c are 0 or an integer of 1 or more, and (a + b +
c) ≦ 10000 and d is 0 or 2.
Here, (a + b + c) is an integer of 2 or more and d = 0.
In the case, the compound is a cyclic silicone compound, and d =
In case 2, the compound is a chain silicone compound. ) 9. The photocatalyst (A) has a number average particle diameter of 200 n.
m or less of a photocatalytic sol.
The photocatalyst composition according to any one of claims 8 to 13. 10. The photocatalyst composition according to claim 1, wherein the photocatalyst composition has a self-grading property. 11. The photocatalyst composition according to claim 1, wherein the photocatalyst (A) is in contact with outside air when the photocatalyst composition is applied and formed on a substrate. A photocatalyst composition characterized by autonomously forming a gradient composition film having a concentration gradient in a film thickness direction that increases toward a surface side. 12. The photocatalyst composition according to any one of claims 1 to 10, wherein when the molded article is formed from the photocatalyst composition, the photocatalyst (A) is formed inside the molded article during the formation process. A photocatalyst composition which autonomously forms a structure having a concentration gradient that increases from the surface toward the surface. 13. A functional composite obtained by forming a film containing the photocatalyst composition according to claim 1 on a base material. 14. A functional composite obtained by forming a film containing the photocatalyst composition according to claim 11 on a substrate, wherein the film is anisotropic in the thickness direction of the photocatalyst (A). A functional complex comprising: A molded article formed from the photocatalyst composition according to any one of claims 1 to 10. 16. A molded article formed from the photocatalyst composition according to claim 12, wherein the molded article has anisotropy in distribution from the inside to the surface of the photocatalyst (A).