TWI229010B - Photocatalyst composition - Google Patents

Abstract

Disclosed is a photocatalyst composition comprising (A) particles of a modified photocatalyst and (B) a binder component which comprises a phenyl group-containing silicone, optionally containing an alkyl group, wherein the particles of a modified photocatalyst (A) are prepared by subjecting particles of a photocatalyst to a modification treatment with at least one modifier compound selected from the group consisting of different compounds each of which independently comprises at least one structural unit selected from the group consisting of a triorganosilane unit, a monooxydiorganosilane unit, and a dioxyorganosilane unit. Also disclosed are a film formed from the photocatalyst composition; a functional composite comprising a substrate and the film formed on the substrate; and a molded article formed from the photocatalyst composition.

Description

1229010 A7 B7 V. Description of the Invention (1) Technical Field The present invention relates to a photocatalyst composition. In more detail, the present invention relates to a photocatalyst containing (A) modified photocatalyst particles and (B) binder components. The f-sign is that the modified photocatalyst particles (A) use at least one of the * A compound having at least one structural unit selected from the group consisting of a trihydrocarbyl silane unit, a monohydroxy dihydrocarbyl silane unit, and a dihydroxy hydrocarbyl silane unit as a modifier is obtained by modifying a photocatalyst particle, and the binder component (B ) System includes a phenyl-containing polysiloxane containing a desired alkyl group. Photocatalysts, represented by titanium oxide, can be used in the fields of environmental purification, anti-fouling, anti-fog, etc., because they can decompose substances by light energy and hydrophilize the surface. When the photocatalyst composition of the present invention is used to form a film containing a modified photocatalyst on the surface of a substrate, the modified photocatalyst is firmly fixed on the surface of the substrate without impairing its activity and the coating formed thereon. The film or the substrate covered with the above-mentioned film is not deteriorated by the action of the modified photocatalyst. In addition, the above-mentioned film is excellent in durability, stain resistance, hardness, and the like, and is extremely useful for preventing the adhesion of dirt on the surface of various substrates and preventing fogging. The present invention also relates to a film formed using the photocatalyst composition, a functional composite formed from the film and a substrate coated therewith, and a formed body formed using the photocatalyst composition. . Technical background Some substances should be irradiated with light having a greater energy than the energy gap (bandgap) between the conduction band and the valence electron band of the substance, that is, the irradiation is more effective on the light than the gap between the substances. For short-wavelength light (excitation light), the size of this paper applies the Chinese National Standard (CNS) A4 (210X297 mm),--= 1-m 1 ^ 1 111 (Please read the precautions on the back before filling this page ) Order

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -4- 1229010 a7 B7 V. Description of the invention (2), the electrons in the valence band are excited due to light energy (photoexcitation), and electrons are generated on the conduction band. The valence band Generate a positive point. At this time, various chemical reactions can be performed using the reducing power of the electrons generated by the conduction band and / or the oxidizing power of the positive holes generated by the valence electron band. That is, a substance as described above can be used as a catalyst under the irradiation of excitation light. Therefore, the above-mentioned substances are also called photocatalysts, and the most representative example of titanium oxide is also well known. The chemical reaction promoted by the photocatalyst can be exemplified by oxidative decomposition reactions of various organic substances. Therefore, if this photocatalyst is immobilized on the surface of various substrates, various organic substances adhering to the surface of the substrate can be oxidized and decomposed using light energy. On the other hand, when the photocatalyst is irradiated with light, it is known that the surface of the photocatalyst becomes more hydrophilic. Therefore, if the photocatalyst is immobilized on the surface of various substrates, the hydrophilicity of the surface of the substrate can be improved by light irradiation. In recent years, research has been actively conducted in order to utilize the characteristics of the above-mentioned photocatalysts in various fields starting from environmental purification, preventing the adhesion of dirt on the surface of various substrates and preventing fogging. In this case, the method of immobilizing the photocatalyst on the surface of various substrates plays a very important role. Various methods have been proposed for immobilizing photocatalysts. For example, Japanese Patent Application Laid-Open No. 6 0-0 4 0 5 3 discloses a method for immobilizing a photocatalyst on a substrate surface by a sputtering method. One of the most widely used and most useful methods of these methods is a method in which a photocatalyst-containing composition is coated on the surface of a substrate, and a photocatalyst-containing film is formed to immobilize the photocatalyst on the surface of the substrate. When using this method for photocatalyst immobilization, the necessary conditions are as follows: This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

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Printed by the Employees 'Cooperative of the Intellectual Property Bureau of the Ministry of Economics -5- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economics 1229010 A7 A7 B7 V. Description of the invention (3) (1) Without impairing the photocatalyst activity, the photocatalyst can be used It is firmly fixed on the surface of the substrate, and the film formed by (2) and the substrate covered with the film have durability that is not deteriorated by the action of the photocatalyst. There have been various proposals for a method for fixing a photocatalyst by coating. For example, Japanese Patent Laid-Open No. 6 0-1 1 8 2 3 6 discloses that a photocatalyst precursor, such as a sol containing an organic titanic acid, is applied to After the surface of the substrate, the precursor of the photocatalyst is gelatinized by sintering, and the converted photocatalyst is fixed to the surface of the substrate while being converted into the photocatalyst. However, the method includes the step of generating photocatalyst fine particle crystals on the surface of the substrate, and this step requires sintering at a high temperature. Therefore, when the surface area of the substrate is wide, it becomes difficult to fix the photocatalyst. Japanese Patent Application Laid-Open No. 6-2 7 8 2 4 1 (corresponding to USP 5, 595, 813) discloses a method of using a sol containing a photocatalyst (there is no need to generate a photocatalyst particle-like crystal), which is used to dissolve in water A method of coating a titanium oxide sol on the surface of a substrate. However, since the titanium oxide sol is not film-forming under mild conditions, this method also requires sintering at high temperatures. In addition, there are disadvantages that the resulting coating is fragile and easy to break, the photocatalyst is peeled off from the surface of the substrate, and the photocatalyst cannot exhibit the effect on the surface of the substrate. It also discloses a method for applying a resin coating material mixed with a photocatalyst to a surface of a substrate. For example, Japanese Unexamined Patent Publication No. 7 — 1 7 1 4 0 8 Gongxingg (corresponding to USP 5, 5 4 7, 8 2 3) and Japanese Unexamined Patent Application Paper Standards apply Chinese National Standard (CNS) A4 specifications (21〇 &gt); < 297 cm) ~ _ -6-(Please read the precautions on the back before filling this page)

1229010 Printed by A7 B7 of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (4) 9-1 0 0 4 3 No. 7 disclosed in fluororesin or polysilicone resin which is not easily decomposed by photocatalyst. A method of mixing a photocatalyst with a resin-containing coating material of a film-forming element and applying the resin coating material to the surface of a substrate ° However, in these methods, the photocatalyst has poor dispersibility to the resin coating material, and the resin coating material becomes cloudy. In addition, in order to obtain a good film by these methods, it is necessary to use a large amount of the above-mentioned resin, and there is a disadvantage that a photocatalyst is buried in a film formed by coating, and it is difficult to fully exhibit activity. In addition, Japanese Patent Application Laid-Open No. 9-3 4 0 5 2 discloses a method for applying a resin coating material and photocatalyst particles adjusted to wettability of a solvent constituting the resin coating material. That is, a method of coating a resin coating on the surface of a substrate and then coating photocatalyst particles on the resin coating before the resin coating is hardened. However, in addition to the complicated steps, this method has the disadvantage of not being able to obtain a uniform and transparent coating film. In addition, in this patent publication, in order to simplify the steps, a method of mixing photocatalyst particles whose wettability to a solvent has been adjusted in a resin coating and coating the resultant is also disclosed. However, merely adjusting the wettability to the solvent does not prevent the photocatalyst particles from being buried in the coating film formed by coating, and there are disadvantages that most of the photocatalyst particles are buried in the coating film and it is difficult to fully exhibit activity. In addition, if an organic substrate such as a plastic molded body, a thin film, or an organic coating film is used as a substrate for immobilizing the photocatalyst, the photocatalyst-containing film obtained by the conventional technology described above will be oxidized and decomposed by the photocatalyst. It deteriorates the interface between the organic substrate and the photocatalyst-containing film, and has the disadvantage that it cannot maintain durability for a long time. In order to overcome the various shortcomings of the above-mentioned conventional technologies, the inventors and others have adopted the paper size of China National Standard (CNS) A4 (210 X 297 mm). (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1229010 A7 B7 V. Description of the Invention (5) The photocatalyst particles have been modified by a modified photocatalyst with low surface energy polysilicon oxide, and the surface energy is A photocatalyst composition composed of a high binder (International Publication No. 2000-3 0 7 4 7 (corresponding to EP 1 1 3 6 1 2 5 A 1)). The photocatalyst composition has a concentration of photocatalyst particles that is low near the surface in contact with the organic substrate and high near the surface in contact with the film due to the coating film formed. The photocatalyst composition is anisotropic toward the film thickness, so it is not affected by the photocatalyst. The effect degrades the interface with the organic substrate, and can form a photocatalyst film with large photocatalytic activity. However, even if a polysilicone resin that is more difficult to decompose with a photocatalyst is used as a high surface energy adhesive in this method, it cannot completely prevent the adhesive itself from being degraded by a long-term photocatalyst action, and it is difficult to obtain superior long-term durability. The technical problems of the photocatalyst immobilized components. In addition, Japanese Unexamined Patent Publication No. 9-2 2 7 8 3 1 discloses that a photocatalyst particle is coated with a silane derivative containing a hydrolyzable group or a siloxane oligomer containing a hydrolyzable group, and the like on the surface of the photocatalyst particle. A photocatalytic coating composition in which the electric point is shifted to acidity (results can increase surface energy), thereby imparting excellent dispersion stability to the photocatalyst particles and maintaining the long-term stability of the coating film forming element (adhesive). . However, in this method, the photocatalyst particles do not tilt themselves (present anisotropy in the distribution) in the coating film, and it is difficult to obtain the above-mentioned photocatalyst-immobilized member having excellent long-term durability. Also, Japanese Patent Laid-Open No. 2000-1-6 4 5 8 3 discloses a photocatalyst containing a photocatalyst for forming an inclined coating film containing photocatalyst particles and a polysiloxane-free acrylic resin and an aqueous solvent as essential components. Coating composition The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

-8- 1229010 A7 B7 V. Description of the invention (6). In this case, in order to obtain the acrylic resin component of the hydrophobic portion of the polysiloxane acrylic resin, the tilted coating film is oriented like a gap between the photocatalyst particles and the substrate in a hydrophilic (higher surface energy), and it is easy to The acrylic resin decomposed by the photocatalyst becomes necessary, and as a result, the film itself becomes extremely poor in durability. That is, in the method of immobilizing the photocatalyst on the surface of the substrate by coating, there has been no one that can completely satisfy the conditions (1) and (2) described above without complicated steps. The present invention is to provide a photocatalyst immobilization technology that can completely satisfy the conditions (1) and (2) above without complicated steps. Specifically, it provides a photocatalyst composition that can obtain a functional composite with excellent properties without complicated steps. The interface between the substrate of the functional composite and the photocatalyst-containing film, and the adhesive containing the photocatalyst film. No degradation of components, and excellent balance between hardness and softness (impact resistance), the ability to control water wettability (hydrophilicity, hydrophobicity) and / or photocatalytic activity on the surface after long-term light irradiation The durability is excellent. In addition, the present invention also provides a photocatalyst molding member that can obtain a molded body that exhibits long-term control of water wettability (hydrophilicity, hydrophobicity) and / or photocatalytic activity without requiring complicated steps. SUMMARY OF THE INVENTION In view of this, the present inventors have made intensive research in order to solve the above problems. As a result, it was unexpectedly found that the photocatalyst composition containing (A) modified photocatalyst particles and (B) binder components was characterized by the modified photocatalyst particles (this paper size applies the Chinese National Standard (CNS) Λ4 specification (210X297 mm) ） I ~ ^ — · ----— (Please read the notes on the back before filling this page)

Printed by the Employees 'Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-9-Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1229010 A7 B7 V. Description of the invention (7) A) is used from the At least one compound of a monohydroxy dihydrocarbyl silane unit and a structural unit of a dihydroxy hydrocarbyl silane unit is obtained as a modifying agent compound, and the adhesive component (B) includes a phenyl group containing a desired alkyl group. The polysilicon photocatalyst composition can achieve the above object and complete the present invention. That is, when the photocatalyst composition is used to form a modified film containing a modified photocatalyst on the surface of an organic substrate, no complicated steps are required to obtain the adhesion between the organic substrate and the interface containing the photocatalyst film and the photocatalyst-containing film. The components of the agent do not deteriorate, and the balance between hardness and softness (impact resistance) is excellent. The water wettability (hydrophilicity, hydrophobicity) of the surface exposed to light for a long period of time can control the performance and / or exhibit photocatalytic activity. Functional composite with superior durability. Based on this, the present invention has been completed. Therefore, the main object of the present invention is to provide a film containing a modified photocatalyst on the surface of an organic substrate without requiring complicated steps to obtain an interface between the organic substrate and the photocatalyst-containing film without degradation, hardness, etc. A functional compound with excellent balance with softness (impact resistance), long-term light irradiation (hydrophilicity, hydrophobicity) of water surface (hydrophilicity, hydrophobicity) control performance and / or photocatalytic activity durability Of photocatalyst composition. Another object of the present invention is to provide a coating film and a molded body which can effectively prevent dirt adhesion and fogging on the surface of a substrate, and has extremely excellent durability, and a functional composite body in which the coating film is formed on a substrate. The above-mentioned and other various objects, various features, and various advantages of the present invention can be made clear by referring to the accompanying drawings and detailed description and the description of the scope of patent application. 1Paper size applies Chinese national standard (0 offenders) 8 4 specifications (210 '/ 297 mm)' -10- (Please read the precautions on the back before filling this page)

1229010 A7 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (8) A brief description of the diagram is shown in the diagram: Figure 1 shows the measurement of the modified stomach 5 M & TKS-2 5 1 (commercially available titanium oxide organosol) particle size distribution chart. FIG. 2 is a particle size distribution diagram of a modified photocatalyst organosol (A-1) obtained by subjecting the above-mentioned T K S-2 51 to a modification treatment using a wet particle size analyzer. Figure 3 (a) is a TEM photograph of a cross section of a test plate (D-1) having a photocatalyst-containing coating film obtained in Example 1. Figure 3 (b) is a diagrammatic illustration of Figure 3 (a). Figure 4 (a) is a TEM photograph of a cross section of the epoxy resin (D-2) containing the photocatalyst coating film obtained in Example 2. Figure 4 (b) is a diagrammatic illustration of Figure 4 (a). Figure 5 (a) is a partially enlarged view of the TEM photo of Figure 4 (a). Figure 5 (b) is a diagrammatic illustration of Figure 5 (a). Figure 6 (a) is a TEM photograph of a cross section of an epoxy resin (D-3) having a photocatalyst-containing coating film obtained in Comparative Example 1. Figure 6 (b) is a diagrammatic illustration of Figure 6 (a). Brief description of the number 1 Modified photocatalyst particles 2 Film containing photocatalyst The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling in this page).! ·· Order

-11-1229010 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (9 3 Acrylic urethane coating 4 Pigment titanium oxide 5 Epoxy resin 5 (. B) modified photocatalyst particle phase 1 The boundary part of the binder phase 7 without modified photocatalyst particles is shown in Figure 5 (b). Figure 6 Encapsulated epoxy resin 7 Bonded phase without modified photocatalyst particles 8 Detailed description of the polysiloxane invention According to the present invention, a photocatalyst composition containing (A) modified photocatalyst particles and (b) binder components is provided, characterized in that the modified photocatalyst particles (A) are made using at least one kind of A compound of at least one structural unit of the group consisting of a trihydrocarbylsilane unit represented by formula (1), a monohydroxydihydrocarbylsilane unit represented by formula (2), and a dihydroxyalkylsilane unit represented by formula (3) The modifier compound (b) is obtained by modifying the photocatalyst particles (a). The adhesive component (B) includes polysiloxane (BP) containing a phenyl group represented by the following formula (4), and The phenyl-containing polysiloxane (BP) Those containing an alkyl group. R 3 S i — (1) (wherein R each independently represents a linear or bi-chain alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, Straight-chain or bi-chain carbon number 1 to 30 fluoroalkyl, straight-chain or bi-chain carbon number 2 to 30 This paper size applies to China National Standard (CNS) A4 (210 X 297) Li) (Please read the notes on the back before filling this page)

-12- 1229010 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Alkenyl, phenyl, alkoxy or hydroxyl with 1 to 20 carbon atoms of the invention description (10),-(R 2 S i 0 )-(2) (where R is as defined by formula (1)), ο-R——SI19 (where R is as defined by formula (1)), RlpR qXrS 1 〇 (4- pqr) / 2 (4) (wherein each R1 represents a phenyl group, and R2 each independently represents a linear or bi-chain alkyl group having 1 to 30 carbon atoms, a cycloalkane having 5 to 20 carbon atoms or Straight-chain or bi-chain alkenyl groups having 2 to 30 carbon atoms; X each independently represents a hydrogen atom, a hydroxyl group, a hydroxy group having 1 to 20 carbon atoms, a fluorenyl group having 1 to 20 carbon atoms, and an amine Oxy, a carbon-defining group or a halogen atom having a carbon number of 1 to 2; and P, Q, and r are ... 〇 < p < 4, 〇Sq < 4, 〇gr < 4 and 0 < (ρ + Q + r) < 4, and ◦ · 05 $ ρ / (ρ + Q) S 1). In order to make the present invention easier to understand, the basic features and better aspects of the present invention are listed below. 1. A photocatalyst composition containing (A) modified photocatalyst particles and (b) binder components, characterized in that the modified photocatalyst particles (A) use at least one of Hydrocarbyl silane unit, the unit shown in formula (2) _ s2: This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm)--gMttk-Ink I 1 — Clothing II I f Please read the back Notes before filling out this page

-13- 1229010 A7 B7 V. Description of the invention (11) At least one structural unit of the group consisting of hydrocarbylsilane units and dihydroxyhydrocarbylsilane units represented by formula (3) is used as a modifier compound (b). The photocatalyst particles (a) are obtained by modifying the adhesive component (B). The adhesive component (B) includes polysiloxane (BP) containing a phenyl group represented by the following formula (4), and the polysiloxane containing phenyl ( BP) If necessary, it may further include a base: R 3 S i — (1) (where R independently represents a linear or bi-chain alkyl group having 1 to 30 carbon atoms and 5 to 2 carbon atoms) 0 cycloalkyl, linear or bi-chain carbon number 1 to 3 0 fluoroalkyl, linear or bi-chain carbon number 2 to 3 ◦ alkenyl, phenyl, carbon number 1 to 20 alkoxy or hydroxy), — (R 2 S i 〇) — (2) (where R is as defined by the general formula (1)), (Please read the precautions on the back before filling in this purchase ) ο R—S—ο— Intellectual Property Bureau of the Ministry of Economic Affairs g (printed by industrial and consumer cooperatives (where R is as defined by general formula (1)), R 1 PR 2 QX r S i 〇 (4- p-Q-r) / · 2 (4) (where Each R1 represents a phenyl group, and R2 each independently represents a straight-chain or bi-chain alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a straight-chain or bi-chain carbon number 2 Alkenyl to 30; X each independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amineoxy group, and an oxime having 1 to 20 carbon atoms This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) -14- 1229010 A7 B7 V. Description of the invention (12) group or halogen atom; 4, OSr < 4 and 〇 < (p + Q + r) < 4 and 0.05 $ ρ / (ρ + Q) S 1) 0 2. The photocatalyst composition according to the above item 1, which is characterized by In the formulae (1) to (3), R represents each independently a linear or bi-chain alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, linear or Bi-chain fluoroalkyl group with 1 to 30 carbons, straight or bi-chain alkenyl group with 2 to 30 carbons or alkoxy group with 1 to 20 carbons. The photocatalyst composition according to item 1 or 2 above, wherein the polysiloxane (BP) containing a phenyl group is represented by the following formula (5), Those of alkyl group containing phenyl polysiloxane (BP1): R 1 s X t S i 〇 (4-s-t) / 2 (5) (wherein R 1 represents a phenyl group; X each independently represents a hydrogen atom , Hydroxyl, alkoxy having 1 to 20 carbons, fluorenyloxy having 1 to 20 carbons, amineoxy, oxime group or halogen atom having 1 to 20 carbons; and s and t are: 0 < s < 4, 0St < 4, and 0 < (s + t) < 4). 4. The photocatalyst composition according to item 1 or 2 above, characterized in that the adhesive component (B) further includes a polysiloxane (BA) containing an alkyl group represented by the following formula (6): RUXVS i 0 (4-u-V) / '2 (6) (In the formula, R 2 each independently represents a linear or quasi-chain carbon number 1 to this paper size. Applicable to China National Standard (CNS) A4 specification (210X 297) Li) (Please read the notes on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -15- 1229010 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (13) A 30-based courtyard, a cycloalkyl with a carbon number of 5 to 2 or Straight-chain or bi-chain alkenyl group having 2 to 30 carbon atoms; X each independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an amine oxygen group Group, an oxime group or a halogen atom having 1 to 20 carbon atoms; and u and v are: 0 < u < 4, 0sv < 4, and 0 < (u + v) < 4) 0 5 The photocatalyst composition according to item 1 or 2, characterized in that the adhesive component (B) includes a phenyl group-containing polysiloxane (BP 1) containing no alkyl group represented by formula (5) and a compound represented by formula (6) (BAM: R 1 s X t S i 〇 (4-s-t) / 2 (5) (wherein each R1 represents a phenyl group; X each independently represents a hydrogen atom, a hydroxyl group, Alkoxy groups having 1 to 20 carbon atoms, fluorenyl groups having 1 to 20 carbon atoms, amineoxy groups, oxime groups having 1 to 20 carbon atoms or dendrimers, and s and t are: 0 < s < 4 , 〇St < 4, and 0 < (s + t) <4); R 2 u X v S 1 0 (4-u-V) / 2 (6) (wherein R 2 each independently represents a linear or bi-chain alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms or a linear or # chain-like one Alkenyl groups having 2 to 30 carbon atoms; and X each independently represent a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a fluorenyloxy group having 1 to 20 carbon atoms, an amineoxy group, and 1 to 20 carbon atoms 2 0 oxime This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

-16- 1229010 A7 B7 V. Description of the invention (14) group or halogen atom; and u and v are: 0 < u < 4 '0 $ v < 4' and 0 < (U + V) < 4) 0 6 $ 卩 ± @The photocatalyst composition of item 4, characterized in that the polysiloxane containing the radical (BA) has a single warp-based hydrocarbyl sarane unit (D) shown in formula (7) and formula (8) ) Shown in dioxo organic units (T)-(R 2 2 S i)-(7) (^? R2 each independently represents a linear or quasi-chain carbon number of 1 to 30 Alkyl, alkenyl having 2 to 30 carbons with a carbon number of 5 $ 2 0); Β2 —ji—O — (8)

I 0

I (where R2 is as defined by formula (7)). 7 · The photocatalyst composition according to item 3 or 5 above, characterized in that the weight average molecular weight of the phenyl-containing polysiloxane (Bp 1) is colloidal filtration chromatography from a calibration curve obtained using standard polystyrene The measurement value obtained by the method is 500 to 10,000. 8. The photocatalyst composition according to item 4 or 5 above, characterized in that the weight-average molecular weight of the alkyl-containing polysiloxane (BA) is determined by a calibration curve obtained by colloidal filtration chromatography using standard polystyrene Obtained determinations are 500 to 10,000. This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the precautions on the back before filling this page) * 1Τ

Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs t -17- 1229010 A7 B7 V. Description of the invention (15) Number) The average particle diameter is below 400 nm. i. The photocatalyst composition according to any one of claims 1 to 9, wherein the photocatalyst particles (a) are titanium oxide particles. 1 1. The photocatalyst composition according to item 1 or 2 above, characterized in that the modifier compound (b) is a Si-fluorenyl-containing silicon compound (b 1) represented by formula (9): Η XRVS i 0 (4-χ-y) / 2 (9) (wherein R each independently represents a linear or bi-chain alkyl group having 1 to 30 carbon atoms and a cycloalkane having 5 to 20 carbon atoms Radicals, linear or bi-chain fluoroalkyls having 1 to 30 carbons, linear or bi-chain alkenyls having 2 to 30 carbons, phenyl, alkanes having 1 to 20 carbons Oxy or hydroxy; X and y are: 0 < x < 4, 0 < y < 4, and (x + y) ^ 4). 12. The photocatalyst composition according to item 11 above, characterized in that the Si-fluorenyl group-containing silicon compound contains at least one Si-fluorenyl-containing sand compound selected from the group consisting of formula (1 0). 1. Compounds containing both terminal S i-fluorenyl groups not included in formula (1 1), and compounds consisting of polysulphur oxygen groups not included in formula (1 2): I 3 H—-Si—— R3 (10) This paper size applies to Chinese National Standard (CNS) A4 (210X 297 mm) (Please read the precautions on the back before filling this page) Order

Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -18- 1229010 A7 B7 V. Description of the invention (16) (Please read the precautions on the back before filling out this page) (where R3 each independently represents a straight chain or a Qi chain Alkyl group with 1 to 30 carbon atoms, alkenyl group with 2 to 30 carbon atoms, linear or ambivalent, cycloalkyl group with 5 to 20 carbon atoms, straight or ambivalent carbon A fluoroalkyl group, a phenyl group, or a silyloxy group represented by the formula (1 3): —〇 一 (R42Si〇) m— SiR43 (13) (wherein R4 each independently represents a linear or Bi-chain alkyl group with 1 to 30 carbons, cycloalkyl group with 5 to 20 carbons, linear or bi-chain fluoroalkyl group with 1 to 30 carbons, linear or bi-chain Alkenyl or phenyl with a carbon number of 2 to 30, and m is an integer, O ^ m ^ lOO)); H — (R32S i 〇) n — S i R32 — Η (11) (wherein, R3 is as defined in formula (10), η is an integer, 0 ^ η ^ 1 0 0 0); (R3HS i 0) a (R32S i 0) b (R33HS i Ο1 / 2) c (12) (where R3 is as defined by formula (10), a is an integer of 1 or more, b is an integer of 0 or more, (a + b) S10000, and c is 0 or 2, but (a + b ) Is an integer of 2 or more, and when c = 〇, the polysilicon of formula (1 2) is a cyclic polysiloxane, and when c = 2, the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the formula (1 2 ) The polysilicon is chain polysilicon). 1 3 · The photocatalyst composition according to any one of items 1 to 12 above, which is a resin. 1 4 · The photocatalyst composition according to any one of the above items 1 to 13 is a film-coated person. 15. The photocatalyst composition according to item 14 above, characterized in that the distribution of the modified photocatalyst particles (A) is anisotropic, and the paper size of the modified photocatalyst is applicable to the Chinese National Standard (CNS) A4 specification ( 210X297 mm) -19- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1229010 A7 B7 V. Description of the invention (17) The concentration of the media particles (A) is increased from one side of the film to the other. 16 · The photocatalyst composition according to any one of items 1 to 13 above, which is a molded body. 17 · The photocatalyst composition according to item 16 above, characterized in that the distribution of the modified photocatalyst particles (A) is anisotropic, and the concentration of the modified photocatalyst particles (A) is from the inside of the formed body Surface lifter. 18. The photocatalyst composition according to item 4 above, wherein the phenyl-containing polysiloxane (B P) and the alkyl-containing polysiloxane (BA) are film-coated with a microphase separation structure. 19. The photocatalyst composition according to item 18 above, characterized in that the distribution of the modified photocatalyst particles (A) is anisotropic, and the concentration of the modified photocatalyst particles (A) is from one face of the coating Raised on the other side. 2 0. The photocatalyst composition according to item 4 above, wherein the phenyl-containing polysiloxane (B P) and the alkyl-containing polysiloxane (B A) are formed bodies having a microphase separation structure. 2 1 · The photocatalyst composition according to item 20 above, which is an anisotropic distribution of the modified photocatalyst particles (A), and the concentration of the modified photocatalyst particles (A) increases from the inside of the formed body to the surface . 2 2 · —A functional composite obtained by forming a film containing the photocatalyst composition according to any one of the above items 1 to 13 on a substrate. 2 3. The functional complex according to item 22 above, characterized in that the distribution of the modified photocatalyst particles (A) is anisotropic, and the concentration of the modified photocatalyst particles (A) is determined by the coating The contact surface with the substrate is elevated toward the other exposed surface. This paper size applies Chinese National Standard (CNS) A4 specification (21〇297mm) '— -20- (Please read the precautions on the back before filling this page)

1229010 A7 B7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (18) 2 4-A functional compound obtained by forming a film on a substrate, characterized in that the film contains the above The photocatalyst composition of item 4, and the phenyl-containing polysiloxane (BP) and the alkyl-containing polysiloxane (BA) have a microphase separation structure. ~ 2 5 · The functional composite according to item 24 above, characterized in that the distribution of the modified photocatalyst particles (A) is anisotropic, and the concentration of the modified photocatalyst particles (A) is determined by the coating The contact surface between the film and the substrate is elevated toward the other exposed surface. Hereinafter, the present invention will be described in detail. The modified photocatalyst particles (A) used in the present invention are obtained by subjecting the photocatalyst particles (a) to a modification treatment using at least one of the following modifier compounds. The term "modification" in the present invention means the immobilization of at least one of the following modifier compounds (b) to the surface of the photocatalyst particles (a). The immobilization of the modifier compounds on the surface of the photocatalyst particles is recognized by van dei · waal's adsorption (physical adsorption) or coulomb adsorption or chemical bonding. In particular, modification using a chemical bond is preferred because the modifier compound has a strong interaction with the photocatalyst, and the modifier compound is firmly immobilized on the surface of the photocatalyst particles. Examples of the photocatalyst particles (a) that can be used in the present invention are, for example, Ti〇2, Zn〇, SrTi〇3, CdS, GaP,

InP, GaAs, BaTi〇3, BaTi〇3,

BaT i〇4, BaT i〇9, K3Nb〇3, Nb205, F e203, Ta205, K3Ta3S i202, W03, This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) (Please read the notes on the back before filling out this page)

-21-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1229010

5 11 〇 2, B 1 2 0.3, B 1 V 〇 4, Ni 〇, c u 2 〇,

SiC, MoS2, InPb, Riii02, Ce02, Ta3N5, etc., and a layered oxide containing at least one element selected from the group consisting of Ti, D and V (see Japanese Patent Laid-Open No. 6 2-7 4 No. 4 5 No. 2, Japanese Patent Laid-open No. 2-Gong 7 2 5 3 No. Japanese Laid-open Patent No. 7-2 4 3 2 9 No., Japanese Laid-open Patent No. 8-8 9 7 9 9 Japanese Patent Laid-open No. 8 — 8 9 8 00 // Japanese Patent Laid-open No. 8-8 9 8 04, Japanese Patent Laid-open No. 8 — 1 9 80Θ 1 and Japanese Patent Laid-open No. 9 — 24 8 465 Gazette, Japanese Unexamined Patent Publication No. 0 0 9 9 6 9 4, Japanese Unexamined Patent Publication No. 102 2 4 4 1 65, etc.), nitrogen-doped titanium oxide (refer to Japanese Unexamined Patent Publication No. 2 〇1-2 7 8 6 2 5 (corresponding to US20020012628A1 and EP1138634A1), Japanese Patent Laid-Open No. 2000-278627, Japanese Patent Laying-Open No. 2001-335321 (corresponding to US200001.56056037A1 and Ερ1160202A1), Japanese Patent Laid-Open No. 2 0 0 2 — 〇2 9 7 50, Japanese Patent Laid-Open No. 1-207082, etc.) or anoxic titanium oxide (refer to Japanese Patent Laid-Open No. 2 0 〇1-2 1 2 4 5 7 Message (corresponding to E p 1 1 2 5 6 3 6)), may also be used visible light response type photocatalyst of titanium oxide. In addition, T a〇N, L a T i〇2 N,

Oxygen such as CaNb〇2N, LaT a〇N2, CaTa〇2N, etc. This paper size applies Chinese National Standard (CMS) A4 specification (21〇 × 297 mm) (Please read the precautions on the back before filling this page)

-22- 1229010 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (2) Compounds or oxygen and sulfur compounds such as S m 2 T i 2 S 2 07 have high photocatalyst activity in visible light and are suitable use. In addition, p t, Rh,

Ru, Nb, Cu, Sn, Ni, Fc and other metals and / or these oxides or immobilized ones, or photocatalysts coated with porous calcium phosphate (refer to Japanese Patent Application Laid-open No. Hei 10-2 4 4 1 6 Bulletin 6 (corresponding to USP 6, 180, 648B1), etc. Among these photocatalysts, titanium oxide is preferred because it is non-toxic and has excellent chemical stability. Titanium oxide is known as three crystal types of anatase type, rutile type, and Zolucaet type, and any of them can be used. The crystal particle diameter (primary particle diameter) of the above photocatalyst is preferably from 1 to 4,000 nm, and more preferably from 1 to 50 nm. The properties of the photocatalyst used in the present invention are important factors because they can express the dispersion stability, film-forming property, and various functions of the modified photocatalyst (A). The photocatalyst used in the present invention is a photocatalyst having a number average particle diameter of a mixture of primary particles and secondary particles of 400 nm or less, and can be used effectively because of the surface characteristics of the modified photocatalyst. In particular, when a photocatalyst having a number average particle diameter of 100 nm or less is used, a photocatalyst composition formed of the modified photocatalyst (A) and the adhesive component (B) described below can be used to obtain a film with excellent transparency. So excellent. It is better to select a photocatalyst of 80 n m or more and 3 n m or more, and it is better to appropriately select a photocatalyst of 50 n m or more and 3 n m or more. For the following reasons, it is preferable to use a photocatalyst sol instead of a photocatalyst powder for these photocatalysts. This is a powder that is generally made of fine particles. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

-23- 1229010 Α7 Β7 V. Description of the invention (21) Because single crystal particles (primary particles) form strong agglomerated secondary particles, the invalid surface characteristics are very difficult to disperse into the primary particles. In contrast, when a photocatalyst sol is used, the photocatalyst particles do not dissolve but exist in a form close to the primary particles. Therefore, the surface characteristics can be effectively used. Therefore, the modified photocatalyst generated by the photocatalyst sol not only has dispersion stability, film formation properties, etc. Superior, can also effectively display various functions and is suitable for use. The photocatalyst sol used in the present invention means that the primary and / or secondary particles of the photocatalyst particles are dispersed in water at a solid content of 0.01 to 70% by weight, preferably from 0.1 to 50% by weight. And / or organic solvents. In the present invention, "wt% of solids" refers to the ratio of the weight of the remaining nonvolatile components to the weight before heating after the dispersion or turbid liquid is heated in the air at about 120 ° C for more than 2 hours. . Examples of the organic solvent used in the above photocatalyst sol include alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol, and methanol, and aromatic hydrocarbons such as toluene or xylene. , Aliphatic hydrocarbons such as hexane, cyclohexane, heptane, esters such as ethyl acetate, n-butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane Ethers such as alkane, amines such as dimethylacetamide, dimethylformamide, halides such as chloroform, dichloromethane, and carbon tetrachloride, dimethylarsox, nitrobenzene, and the like. These solvents may be used singly or in combination. The titanium oxide sol used as the photocatalyst sol may be exemplified by, for example, water as a dividing medium, in which the oxide particles are degelatinized oxyhydroxide hydrosol. (Here, when water is used as the dispersion medium, it means that the dispersion medium contains about 80% or more of water). The modulation of this sol is well known, and the paper size can be applied to the Chinese National Standard (CNS) A4 specification (21〇 × 297 mm) ~ -24- --.----------- (Please read the (Please fill in this page again)

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1229010 A7 B7 V. Description of the invention (22) Easy to make (see Japanese Patent Laid-Open No. 6 3 — 1 7 2 2 No. 1 and Japanese Patent Laid-open No. 7 — 8 1 9 Gazette (corresponding to EP581216B1), Japanese Patent Publication No. 9-165218 (corresponding to USP 5,840, 111), Japanese Patent Publication No. 1 1 4 3 3 2 7 (corresponding to USP 6,340,711B1, and EP 8 2 6 6 3 3 B 1), etc.). For example, metatitanic acid generated by heating and hydrolysis of an aqueous solution of titanium sulfate or titanium tetrachloride is neutralized with ammonia water, and the precipitated aqueous titanium oxide is filtered, washed, and dehydrated to obtain an aggregate of titanium oxide particles. This agglomerate is subjected to hydrothermal treatment such as degumming under the action of nitric acid, hydrochloric acid, ammonia or the like to obtain a titanium oxide hydrosol. In addition, titanium oxide hydrosol can be used to dissolve titanium oxide particles under the action of acid or alkali. Alternatively, dispersing stabilizers such as sodium polyacrylate can be used instead of acid or alkali if necessary. A sol dispersed in water. In addition, according to the method disclosed in Japanese Patent Application Laid-Open No. 10-6 7 5 1 6, even in an aqueous solution where p Η is approximately neutral, it is easy to obtain anatase with excellent dispersion stability and particle surface modified with peroxy groups. Ore type titanium oxide sol. The titanium oxide hydrosol may be a commercially available titanium dioxide sol. (For example, Japan's Ishihara Industry Co., Ltd. "STS-02", Japan's Tanaka Transcription Co., Ltd. "τ ◦-2 4 0", etc.). The solid matter in the titanium oxide hydrosol is 50% by weight or less, and more preferably 30% by weight or less. Further, it is preferably 30% by weight or less and 0.1 ·% by weight or more. This hydrosol has a low viscosity (20 ° C.). In the present invention, if the viscosity of the hydrosol is 0 · 5 g · cm _ 1 · The paper size applies to the Chinese National Standard (CNS) A4 specification (210x297 mm) I -r-nn--(Please read the back first (Notes to fill out this page)

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Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -25- 1229010 A7 B7 V. Description of Invention (23) Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs sec'1M2000g. 1 g · c m — 1 · s e c m-丄 s e c-1 is more preferable, and i g SOOg ^ cm-i ^ sec-1 is more preferable. Also, for example, gadolinium oxide sol (refer to Japanese Patent Application Laid-Open No. 8-5 9 2 35) or a layered oxide sol having at least one element selected from the group consisting of τ i, Nb, Ta, and V ( Refer to JP-A-Hei 9-2 5 1 2 3, JP-A 9-67124 (corresponding to USP 5, 8 63, 5 1 4), JP-A 9- 2 2 7 1 2 2, Japanese Unexamined Patent Publication No. 9-2 2 7 1 2 3 (Japanese Unexamined Patent Publication No. 10-259023, etc.), various methods for producing photocatalyst sols are known to those who use chemical solvents. In addition, organic solvents are used as dispersed particles to disperse the photocatalyst organosol. In the example, the interface between the first phase and the second phase, which has phase-shifting activity, such as polyethylene glycols, forms a third phase. Mutual dissolution and / or dilution of soluble solvents (refer to Japanese Patent Application Laid-Open No. 2010-1), adjust the mec of the sol to about 1 in a water-insoluble organic solvent with an anionic interface such as sodium dodecylbenzenesulfonate 1 To 1 0 0 0 g · • sec to Sho 5 8-2 9 8 6 3) or a method of removing water by adding a high alcohol such as butanol to the photocatalyst hydrosol. In addition, the solid medium, such as the above compound and the first compound) 6 7 7 active agent method (based on fiber solubilization, based on the quality of the photoreceptor described in it (in the 1 phase, treatment and disperse No. 2 7 Refer to "Isothermal boiling (decompression organic solvent photocatalyst of the second phase with different water solubility in organic bulletin) transfer to this special open point more water) Distillation agent (Please read the precautions on the back before filling this page)

This paper size applies Chinese National Standard (CNS) A4 (210X29 * 7mm) -26- 1229010 A7 B7 V. Description of the invention (24) Dispersion medium in which titanium oxide particles are dispersed titanium dioxide organosols are commercially available Commodities (for example, "Te 1 ^ 3-(Please read the precautions on the back before filling out this page) made by Teca Corporation" 2 5 1 "). Here, "substantially using an organic solvent as a dispersion medium" means that the dispersion medium contains about 80% or more of an organic solvent. The at least one modifier compound (b) used in the present invention has a trihydrocarbylsilane unit represented by the following formula (1), a monohydroxydihydrocarbylsilane unit represented by the following formula (· 2), and the following formula ( 3) a group of at least one structural unit of the group of the dihydroxyhydrocarbyl silane units shown in the group. R 3 S i — (1) (In the formula, R each independently represents a linear or bi-chain alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, linear or poly Chain-shaped fluoroalkyl group having 1 to 30 carbon atoms, straight chain or bi-chain alkenyl group having 2 to 30 carbon atoms, phenyl group, alkoxy group having 1 to 20 carbon atoms or hydroxyl group),-( R 2 S i 0)-(2) (where R is as defined by the general formula (1)), printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs R—silo—— (where R is as As defined by (1)). The modified photocatalyst particles (A) obtained by subjecting the surface of the photocatalyst particles to a modification treatment with the modifier compound (b) having the above-mentioned structural unit have extremely small surface energy on the surface of the particles. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -27- 1229010 A7 B7 V. Description of the invention (27) The modified photocatalyst particles (A) are not only silicon compounds containing Si-fluorene groups ( b 1) is a mixture with photocatalyst (a), and it can be speculated that there will be some kind of interaction between the two due to the accompanying chemical reaction, which is excellent. In fact, the modified photocatalyst (A) obtained in this way is excellent in dispersion stability, chemical stability, durability and the like for organic solvents. In the present invention, the photocatalyst (a) is modified by the silicon compound (b 1) containing the Si-fluorenyl group represented by the formula (9), and dehydrogenation condensation of Si-fluorenyl group may also be used. The catalyst is between 0 and χ 5. (: In the following case, in this case, the dehydrogenation condensation catalyst may be first fixed to the photocatalyst (a) by a method such as a photoreduction method, and then the Si compound (b 1) containing the Si-fluorenyl group may be applied. In the modification treatment, the photocatalyst (a) may be subjected to the modification treatment in the presence of the dehydrocondensation catalyst with the above-mentioned Si compound (b 1) -containing silicon compound (b 1). Here, the Si-fluorene group is subjected to the modification treatment. The dehydrocondensation catalyst refers to an active hydrogen group such as a S i -fluorenyl group and a hydroxyl group (τ i -〇Η group in the case of titanium oxide) or a thiol group, an amine group, and a carboxyl group, which are present on the surface of the photocatalyst. Substances that accelerate the dehydrocondensation reaction rate of water, etc., can use the dehydrocondensation catalyst to modify the surface of the photocatalyst under mild conditions. At this time, 100 parts by weight of the photocatalyst system is added 0.1 to 1 20 parts by weight, preferably 1 to 5 parts by weight of the dehydrogenation condensation catalyst. The dehydrogenation condensation catalyst can be exemplified by platinum group catalysts, that is, ruthenium, rhodium, palladium, starvation, iridium, and platinum. And its compounds or early bodies of silver, iron, copper, cobalt, nickel, and tin temples and their compounds. Among these, the plutonium catalyst is preferred, and the lead This paper size applies to China National Standard (CNS) Α4 size (210X29 * 7mm) nk I--· 1% n I ml h h (Please read the precautions on the back before filling this page)

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Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics -30-1229010 Α7 Β7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (28) Monomers and their compounds are the best. Here, as the platinum compound, for example, platinum chloride (Π), tetrachloroplatinic acid (Π), platinum (IV) chloride, hexachloroplatinic acid (IV), platinum (IV) ammonium hexachloride, Potassium chloride (IV), platinum hydroxide (Π), platinum dioxide (IV), dichloro-dicyclopentadiene-platinum (Π) 'platinum-vinylsiloxane complex, platinum-phosphine complex Compounds, platinum-olefin complexes, and the like. In the silicon compound (bl) containing a Si-fluorenyl group represented by the above formula (9), which can be suitably used as a modifier compound in the present invention, the Si-fluorene group selectively modifies the photocatalyst under relaxation conditions. Essential functional group. On the other hand, although the hydrolyzable group can also be used for the photocatalyst modification, but the side reactions are too many, which will make the stability of the obtained modified photocatalyst worse, and its content is better. In the present invention, the sand compound (b 1) containing a Si-fluorenyl group represented by the above formula (9), which can be suitably used as a modifier compound, can be exemplified by having at least one member selected from the group consisting of the formula (1 0). At least one of the group consisting of a silicon compound containing a single Si-fluorenyl group, a silicon compound containing two terminal Si-fluorenyl groups represented by formula (1 1), and a fluorene polysiloxy group represented by formula (1 2) Si-fluorenyl-containing silicon compounds containing hydrolyzable silyl groups. R3 (In the formula, R 3 each independently represents a straight-chain or bi-chain alkyl group having 1 to 30 carbon atoms, a straight-chain or bi-chain alkyl group having 2 to 30 carbon atoms, carbon paper size Applicable to China National Standard (CNS) Α4 specification (210X297 mm) .— * ----— (Please read the notes on the back before filling this page) Order

J1. -31-1229010 at Β7 V. Description of the invention (29) Cycloalkyl group having a number of 5 to 20, fluoroalkyl group having a carbon number of 1 to 30, a phenyl group, or a formula ( 13) Silaneoxy), —〇 一 (R 4 2 S i 〇) m — S i R 4 3 (13) (In the formula, R4 each independently represents a linear or ambivalent carbon number 1 Alkyl to 30, cycloalkyl with 5 to 20 carbons, linear or bi-chain fluoroalkyl with 1 to 30 carbons, linear or bi-chain carbon to 2 to 3 Alkenyl or phenyl of 0; m is an integer, O ^ m ^ lOO)); Η-(R 3 2 S i 〇) n-S i R 3 2-H (1 1) (wherein R3 Is as defined by formula (10), η is an integer, 〇 ^ η ^ 1 0 0 0); (R3H S i 0) a (R32 S i 0) b (R3sH S i 0 1/2) c (12) (In the formula, R3 is as defined by formula (10); a is an integer of 1 or more, b is an integer of 0 or more, (a + b) $ 10000, and c is 0 or 2, but (a + b) is 2 The above integer, and when c = 0, the sintered polymer sand of formula (1 2) is a spheroidal polylithic oxygen, and when c = 2, the sintered polymer shovel of formula (1 2) is a chain-shaped polysilicon. Oxygen) 0 In the present invention, the monomer S1 is represented by the formula (10). Specific examples of monofluorinated silicon compounds include bis (trimethylsilyloxy) methyl sand, bis (trimethylsilyloxy) ethylsilane, and bis (trimethylsilyloxy) n-propyl Silane, bis (trimethylsilyloxy) isopropyl sand garden, bis (trimethylsilyloxy) n-butylsilane, bis (trimethylsilyloxy) n-hexylsilane, bis (trimethyl Silane) cyclohexyl sand institute, bis (trimethylsilyloxy) phenyl silane, bis (triethylsilyloxy) methyl sand institute, this paper size applies to China National Standard (CNS) Α4 size (210x 297mm) —— · -I U ---- Φ II (Please read the notes on the back before filling this page) Order printed by the Intellectual Property Bureau's Consumer Cooperatives • J. -32- 1229010 A7 B7 Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau 5. Description of the invention (30) Bis (triethylsilyloxy) ethylsilane, ginseng (trimethylsilyloxy) silane, ginseng (triethylsilyloxy) Silane, pentamethyldisilaxane, 1, 1, 1, 3, 3, 5, 5-heptamethyltrisiloxane, 1, 1, 1, 1, 3, 3, 5, 5, 6, 6 —Ninemethyltetrasiloxane, trimethylsilane, ethyldimethylsilane, methyldiethylsilane, triethylsilane, phenyldimethylsilane , Diphenylmethylsilane, cyclohexyldimethylsilane, tertiary butyldimethylsilane, tertiary butylmethylsilane, n-octadecyldimethylsilane, tri-n-propylsilane, tri- Isopropyl silane, tri-isobutyl silane, tri-n-hexyl silane, triphenyl silane, allyl dimethyl silane, 1-allyl-1, 1, 3, 3-tetramethyl silane Oxane 1,1,3,3-tetramethyldisilaxane, chloromethyldimethylsilane, 7-octyl-methyl-Lixiyuan, etc. Among these silicon compounds containing a single Si-fluorenyl group, in order to improve the reactivity (dehydrogenation condensation reaction) and surface energy of the Si-fluorenyl group during photocatalytic modification, bis (trimethylsilyloxy) (Meth) silyl, tris (trimethylsilyloxy) silane, pentamethyldisilaxane and the like have a silyloxy group and not a phenyl group as shown in the formula (14) below. R5 Η—Si * —R5 (1 4) (wherein R5 each independently represents a linear or bi-chain alkyl group having 1 to 30 carbon atoms, a linear or bi-chain carbon number being 2 to 3 Alkenyl group of 0, cycloalkyl group with 5 to 20 carbon atoms, linear or ambivalent carbon number of 1 to 3 0 I paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) " -33-(Please read the notes on the back before filling this page)

1229010 A7 B7 V. Description of the invention (31) A fluoroalkyl group or a silyloxy group represented by the formula (i 3 b), but at least one of R 5 is a silyloxy group represented by the formula (1 3 b). —〇— (R4.2Si〇) m—SiR4 3 (13b) (wherein R4 · each independently represents a linear or bi-chain alkyl group having 1 to 30 carbon atoms and 5 to 20 carbon atoms Cycloalkyl, linear or fluorinated fluoroalkyl having 1 to 30 carbons; m is an integer and OSmS 1 0 0 0)); In the present invention, the formula (11) contains Specific examples of the Si-fluorenyl-based silicon compound at both ends can be exemplified by 1,1,3,3-tetramethyldisilaxane, 1,1,3,3,5,5-hexamethyltrisiloxane Alkane, 1, 1, 3, 3, 5, 5, 7, 7-octamethyltetrasiloxane and other terminal polydimethylsiloxanes having a number average molecular weight of 5 0 0 0 or less, or 1, 1, 3, 3-tetraethyldisilazane, 1, 1, 3, 3, 5, 5-hexaethyltrisiloxane, 1, 1, 1, 3, 3, 5, 5, 7, 7-octaethyltetrasiloxane, iso-terminated polydiethylsiloxanes with an average molecular weight below 50,000, or 1, 1, 3, 3 -tetrabenzyl radical, end, 1, 1, 3 , 3, 5, 5-hexaphenyltrisoxanes, 1, 1, 1, 3, 3, 5, 5, 7, 7-octaphenyltetrasiloxane, etc. 0 0 0 or less terminal polydiphenylsiloxanes, or 1, 3-diphenyl-1,3-dimethyl-disiloxane, 1, 3, 5-trimethyl-1, Equivalent average molecular weight of 3, 5-triphenyltrisiloxane, 1, 3, 5, 7-tetramethyl-1, 3, 5, 7-tetraphenyltetraxane is less than 5 0 0 0 0 Η terminal polyphenylmethylsiloxanes, or dimethylsilane, ethylmethylsilane, diethylsilane, this paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) ''- — -34- II 「」 *. Ί fm · 1 —ϋ —ϋ m I (Please read the notes on the back before filling this page), 11

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1229010 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (32) Phenylmethylsilane, diphenylsilane, cyclohexylmethylsilane, third butyl methyl Silyl, di-third butyl silane, n-octadecyl methyl silane, allyl methyl silane and the like. Among them, in order to improve the reactivity (dehydrocondensation reaction) of Si-fluorenyl group and low surface energy in the photocatalytic modification treatment, the number average molecular weight is 10,000 or less, preferably 2,000 or less, more preferably The fluorene-terminated polydialkylsiloxane (Formula (15)) below 1000 is preferably a silicon compound containing both terminal S i -fluorenyl groups. H- (R62SiO) d-SiR62-H (15) (wherein R6 each independently represents a linear or bi-chain alkyl group having 1 to 30 carbon atoms, a linear or bi-chain carbon number 1 Fluoroalkyl group to 30, d is an integer of 0 or more); In the present invention, the polysilicon oxide represented by the above formula (1 2) has dispersion stability during photocatalyst modification treatment (to prevent photocatalyst particle aggregation) In this respect, a polysiloxane having a number average molecular weight of 5,000 or less, preferably 2,000 or less, and more preferably 1,000 or less is preferably used. ) ° In the present invention, the modified photocatalyst particles (A) obtained by subjecting the surface of the photocatalyst particles to a modification treatment with the modifier unit (b) having the above-mentioned structural unit, have the following inclination, and are in accordance with the present invention The required component of the binder component (B) used in the photocatalyst composition is polysand oxygen (BP) containing a phenyl group having a surface energy bureau, and the modified photocatalyst particles (a) must have a lower surface energy. At this time, the modifier (b) used to obtain the modified photocatalyst particles (A) should not contain high surface energy-(Please read the precautions on the back before filling this page) • i__

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This paper size applies the Chinese National Standard (CMS) A4 specification (21〇 × 297 mm) -35- 1229010 A7 B7 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives 5. The structure of the phenyl or hydroxyl group of the invention description (33) Those are better. Therefore, the modifier compound (b) is a structural unit having the formulas (1) to (3), in which R each independently represents a linear or branched alkyl group having 1 to 30 carbon atoms. , A cycloalkyl group having 5 to 20 carbon atoms, a linear or bi-chain fluoroalkyl group having 1 to 30 carbon atoms, a linear or bi-chain alkenyl group having 2 to 30 carbon atoms, or An alkoxy group having 1 to 20 carbon atoms is preferred. In addition, the preferred form of the modified photocatalyst particles (A) of the present invention is that the number average particle diameter of the mixture of primary particles and secondary particles of the modified photocatalyst is 400 nm or less, more preferably 1 nm or more. The sol state is preferably less than 0 nm, and more preferably 5 nm to 80 nm. In particular, when a modified photocatalyst sol having a number-average particle diameter of 100 nm or less is used in the photocatalyst composition of the present invention, the concentration of the modified photocatalyst particles is lower near the contact surface with the organic substrate, and is coated on the film. The contact surface is relatively high, and it is better to form a film with anisotropic distribution in the film thickness direction, and it does not deteriorate the interface with the organic substrate due to the effect of the photocatalyst, and it can be formed. Covered and excellent. Such a modified photocatalyst sol can be obtained by using the above-mentioned photocatalyst sol as a photocatalyst subjected to the modification treatment with the above-mentioned modifier compound (b). In addition, the number expressed by the particle diameter of titanium dioxide and the like has always been a primary particle diameter (grain particle diameter), rather than considering secondary particle diameter caused by agglomeration. The photocatalyst composition of the present invention is made of the binder component (B) containing the modified photocatalyst (A) and a polysiloxane (B P) containing a phenyl group represented by the following formula (4). ----: ---- Read II (Please read the notes on the back before filling in this education) Order

ΙΊ. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297mm) -36- 1229010 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (35) R7R7-Si-0- (18 ) R7 (wherein R 7 each independently represents a phenyl group, a linear or bi-chain alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms);-Si-〇- (19) I 0 I The polysiloxane containing the above structure is, for example, a general formula R 7 si X 3 (wherein, R 7 represents a phenyl group, a linear or bi-chain alkyl group having 1 to 30 carbon atoms. Or a cycloalkyl group having 5 to 20 carbon atoms. Each X independently represents a member selected from a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an amineoxy group Reactive groups of groups consisting of oxime groups having 1 to 20 carbon atoms and halogen atoms. The same applies hereinafter) to trifunctional silane derivatives represented by the general formula R 7 2 S i X 2 The silane derivative and / or the 4-functional silane derivative represented by the general formula R'S i X 4 are partially hydrolyzed and polycondensed. If necessary, the monofunctional silane derivative represented by the general formula R 7 3 S i X can be used and / Or the alcohol stops the end and is modulated. The partial condensate of the silane derivative monomer thus obtained has a weight-average molecular weight in terms of polystyrene of 1,000 to 100,000, preferably 400 to 50,000. For the manufacturing method of the polysiloxane used as the adhesive component (B) in the present invention, for example, refer to "The Science of the Sol-Gel Method" (for a flower coward) (please read the precautions on the back before filling this page) Seeing clothes

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This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -38- 1229010 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (36); issued by Agunes Chengfeng Agency, Japan ( 1 9 8 8)). Among these, if a trapezoidal structure represented by the formula (16) containing 10 mol% or more, and preferably 40 mol% or more is selected, as the average composition formula (4), a polyphenylene oxide containing polyphenylene oxide is used. In the case of (BP), the coating film formed from the photocatalyst composition of the present invention is excellent in hardness, heat resistance, weather resistance, pollution resistance, and chemical resistance. In particular, the above-mentioned ladder structure having a phenyl ladder structure [where R7 is all phenyl in formula (16)] is preferable because the above-mentioned coating properties can be strongly enhanced. This trapezoidal structure can be identified, for example, by the existence of two siloxane-based bonds in the vicinity of 1 0 0 0 cm 1 and 1 16 0 cm 1 in the infrared absorption spectrum. (Refer to J · F · B1. 〇 w η, J1 · ·, e t a 1 ·: J · A m · C h e m · S 〇 c ·, 8 2, 6 1 9 4 (1960)). The phenyl group-containing polysiloxane (B P) used in the present invention used in the present invention must have a P h —S i bond (P h ·· phenyl). That is, in the photocatalyst composition of the present invention, a modified photocatalyst (A) to which a modification agent compound (b) having a structure (formula (1) to formula (3)) having a very small surface energy is subjected to a modification treatment. The adhesive is modified by using the adhesive component (B) containing phenyl-containing polysiloxane (BP) having a higher surface energy than the modified photocatalyst (A). The distribution of the photocatalyst (A) can be tilted. Here, "self-inclination" means that when a film or a molded body is formed from a photocatalyst composition, the modified photocatalyst (A) during the formation process corresponds to the properties of the abutment surface of the film or the molded body (especially hydrophilic / hydrophobic). ()), The structure with modified photocatalyst (A) concentration gradient is automatically formed. (Please read the notes on the back before filling this page)

-J— · This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) -39- 1229010 A7 ___B7__ V. Description of the invention (37) (Please read the precautions on the back before filling this page) This kind of poly-sand oxygen (BP) containing a high surface energy phenyl group exhibits its own tilting effect. The p-phenyl group (R 1) and R 2 (R 2 each independently represent a linear or bi-chain carbon number of 1 to Total of 30 alkyl groups, cycloalkyl groups having 5 to 20 carbon atoms, or straight-chain or bi-chain alkenyl groups having 2 to 30 carbon atoms) {In the following, (Ri + R2) 丨, 5 mol% or more is sufficient to use a phenyl-containing polysiloxane (BP) represented by the above formula (4). In addition, the above-mentioned self-inclination performance is enhanced as the ratio of phenyl (R 1) to (R 1 + R 2) increases. Therefore, the phenyl group-containing polysiloxane (BP) used as the binder component (B) in the photocatalyst composition of the present invention, more preferably, the ratio of (Ri + R2) to the phenyl group (R1) is 10. Molar% or more, more preferably 20 Molar% or more, and most preferably 50 Molar% or more. In addition, the phenyl-containing polysiloxane (BP) has good adhesion to organic substrates such as organic resins, and the silane oxide bond (-◦-S i-) that forms its skeleton does not undergo oxidative decomposition due to the action of photocatalysts. Therefore, the functional composite obtained by coating the photocatalyst composition of the present invention on a substrate or the formed body obtained by printing the photocatalyst composition of the present invention by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has excellent weather resistance 〇 In the photocatalyst composition of the present invention, the polyphenylene-containing polysand oxygen (BP) used in the adhesive component (B) can exhibit a better effect than the above, and it is not shown in the following formula (5) The alkyl group contains phenyl-containing polysiloxane (BP 1). R 1 s X t S i 〇 (4-s-t) / 2 (5) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -40- 1229010 A7 B7 V. Description of the invention (39) (Please read the precautions on the back before filling this page.) The coating film formed by Mingzhi Photocatalyst composition is based on polysiloxane containing no phenyl group (BP 1) and polysiloxane containing alkyl group (BA ) In the microphase-separated binder, the modified photocatalyst particles (A) have a dispersed structure, and are better for long-term weather resistance. In this case, if the phenyl-containing polysiloxane (BP 1) and the alkyl-containing polysiloxane (BA) are respectively used, the weight average molecular weight in terms of polystyrene measured by GPC is 100. To 10,000, preferably 500 to 6,000, more preferably 700 to 4,000, the microphase separation structure of the above-mentioned adhesive component (B) is more remarkable. Here, the "microphase separation structure of polysiloxane containing phenyl group (BP1) and polysiloxane containing alkyl group (BA)" means that each polysiloxane is formed to 1 nm 3 to 1 // m 3, compared with It is preferably 10 nm 3 to 0 · 1 // m 3, and more preferably 10 nm 3 to 0 · 0 0 1 // in 3, and the phases are separated. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In addition, the above-mentioned alkyl-containing polysiloxane (BA) mixed with the above-mentioned phenyl-containing polysiloxane (BP 1), if used, has the following formula (7) The molar ratio of the hydroxydihydrocarbylsilane unit (D) and the dioxyorganosilane unit (T) represented by formula (8) is (D) / (T) = 100/0 to 5/95, more preferably 90 For structures with a ratio of / 10 to 10/90, the stress relaxation effect of the microphase separation structure derived from polysiloxane (BP 1) containing phenyl group and polysiloxane (BA) containing alkyl group is increased. The film formed of the photocatalyst composition has improved crack resistance, and as a result, has excellent weather resistance. -(R 2 2 S i 〇)-(7) This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)-111 -42- 1229010 A7 B7 V. Description of the invention (40) (where, R2 each independently represents a linear or ambivalent carbon number of 1 to (please read the precautions on the back before filling this page) 3 alkyl groups of 3, cycloalkyl groups of 5 to 20 or linear or Alkenyl with 2 to 3 carbon atoms in a chain shape; R2 -Si—0— (8)

I 0

I (where R2 is as defined by formula (7)). The binder component (B) used in the photocatalyst composition of the present invention may be any of a form dissolved in a solvent, a form dispersed in a solvent, and a form (liquid, solid) which is not mixed with a solvent. In the photocatalyst composition of the present invention, the polysiloxane (BP) containing a phenyl group represented by the above formula (4) may or may not have a reactive group (in the formula (printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 4) Where X) has a reactive group (X in formula (4)) (that is, 0 < r in formula (4)), the film or formed body formed by the photocatalyst composition of the present invention has a hardness and It is excellent in heat resistance, chemical resistance, and durability. For the same reason, 0 < t in formula (5) and 0 < v in formula (6) are preferred. In the photocatalyst composition of the present invention, the reactive group (X in the formula (4)) contained in the polysiloxane (BP) containing a phenyl group represented by the above formula (4) is a hydroxyl group and / or has a hydrolytic property. In the case of a base, a conventional hydrolyzing catalyst or a hardening catalyst in a proportion of 0.01 to 20% by weight, preferably 0.1 to 5% by weight, may be added to a polysiloxane (BP) containing a phenyl group. The hydrolysis catalyst is based on acidic hydrogen halide, carboxylic acid, sulfonic acid, acidic or weakly acidic paper. The Chinese national standard (CNS) A4 specification (210X297 mm) -43- 1229010 A7 B7 is consumed by employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the cooperative V. Description of the invention (41) Solid salts such as inorganic salts and ion exchange resins are preferred. The amount of the hydrolytic catalyst is preferably in the range of 0.001 to 5 mol to 1 mol of the hydrolyzable group on the silicon atom. Examples of the hardening catalyst include basic compounds such as sodium hydroxide, potassium hydroxide, sodium methoxide, sodium acetate, tetramethylammonium chloride, and tetramethylammonium hydroxide; tributylamine, Azabicycloundecene, ethylenediamine, diethylenediamine, ethanolamines, 7-aminopropyltrimethoxy sand, 7- (2-aminoethyl) -aminopropyltrimethoxy Silane amine compounds; tetraisopropyl titanate, tetrabutyl titanate titanium compounds; aluminum triisopropoxide, aluminum acetoacetate, aluminum perchlorate, aluminum chloride and other aluminum compounds; acetamidine Tin acetoacetate, dibutyltin octoate, dibutyltin dilaurate; cobalt octoate, cobalt acetoacetate, iron acetoacetate metal-containing compounds; phosphoric acid, nitric acid, phthalic acid, p-toluene Sulfuric acid, trichloroacetic acid, etc. In the photocatalyst composition of the present invention, when the polysiloxane (BP) containing a phenyl group represented by the above formula (4) has a Si-fluorenyl group, a multifunctional olefin compound-based crosslinking agent is added to the Si-fluorene group. The base is added in an amount of from 0.01 to 2 equivalents, preferably from 0.1 to 1 equivalent. The polyfunctional olefin compound may be any one as long as it can promote the reaction between the olefin and the Si-fluorenyl group and harden. Generally, a polyvalent olefin compound containing a vinyl group, an allyl group, a hexenyl group, and the like having a carbon number of 2 to 30 is used. Unsaturated hydrocarbon-based olefin-based polysiloxane. In addition, for the purpose of promoting the reaction between the S i -fluorenyl group and the polyfunctional olefin compound, the total amount of polysiloxane (B P) containing a phenyl group and the polyfunctional olefin compound is 1 to 100. 〇〇ppm, preferably 1 ----.---- 噗 II (Please read the precautions on the back before filling this page) Order

• J— · This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -44-1229010 A7 B7 V. Description of the invention (43) The above synthetic resins can use thermoplastic resins and hardening resins (thermosetting resins) , Photo-curable resin, moisture-curable resin, etc.), for example, acrylic resin, methacrylic resin, fluororesin, alkyd resin, amino alkyd resin, ethylene resin, polyester resin, styrene butadiene Polyolefin resin, polyolefin resin, polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether ether ketone resin, polyphenylene ether resin, polyethylene resin, polyphenylene resin Resin, polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, phenol resin, melamine resin, epoxy resin, urethane resin, polysiloxane-acrylic resin, polysiloxane resin, etc. . Examples of the natural local molecules include cellulose resins such as nitrocellulose, isoprene resins such as natural rubber, protein resins such as casein, and starch. The resin used in the present invention has at least one polymer molecular chain end and / or side chain which can be selected from a hydroxyl group and / or an alkoxy group, an alkenyl group, and a carbon number of 1 to 20. Polymers of fluorenyloxy, amineoxy, oxime groups having 1 to 20 carbon atoms, and silicon atom-containing silane groups combined with hydrolyzable groups of halogen atoms, because they are less likely to decompose to photocatalysts. Suitable for use. In addition, in the photocatalyst composition of the present invention, in order to improve the hardness, scratch resistance, and hydrophilicity of the coating, powdery or sol-state silicon oxide, aluminum oxide, oxide pins, antimony oxide, and rare earth metal oxides can be added. And other metal oxide particles. However, these metal oxide fine particles do not have the ability of the adhesive component (B) in the present invention to act as an adhesive, and are the same as photocatalyst. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) --- -i ---- 丰 —I (Please read the notes on the back before filling this page)

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Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ¾ -46- 1229010 A7 B7 V. Description of the invention (44) (Please read the precautions on the back before filling in this page) It will reduce the flexibility (bending resistance of the film or molded body) , Impact resistance). Therefore, the amount of the metal oxide added to the film formed by the photocatalyst composition is preferably 50% by weight or less of the total weight of the modified photocatalyst (A) and the metal oxide. The photocatalyst composition may be in a solvent-free state (liquid, solid) or in a state of being dispersed or suspended in a solvent, and is not particularly limited. The solvent used to disperse or suspend the photocatalyst composition of the present invention may be exemplified by Alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol, and methanol; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane, cyclohexane, and heptane Esters such as ethyl acetate, n-butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethers such as tetrahydrofuran, dioxane, dimethylacetamide, dimethyl ether Methylamines such as methylamine, chloroform, methylene chloride Halogens such as carbon tetrachloride, dimethyl arsenic, nitrobenzene, etc. These solvents can be used alone or in combination. The employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the photocatalyst composition of the present invention as a coating When the agent is used, the photocatalyst composition is preferably dispersed or suspended in a solvent. At this time, the weight ratio of the photocatalyst composition to the solvent is based on the solid content (the photocatalyst composition in the obtained dispersion or suspension). In general, it is from 0.1 to 95% by weight, preferably from 0.1 to 70% by weight. The method for preparing the dispersion or suspension of the photocatalyst composition can be exemplified by the following methods ① to ④ ① Mix the modified photocatalyst (A) dispersed or suspended in the above-mentioned solvent with the adhesive component (B) also dispersed or suspended in the above-mentioned solvent. The paper size shall be in accordance with Chinese National Standard (CNS) A4. (2) OX297 mm) -47- 1229010 A7 B7 V. Description of the invention (46) (Please read the notes on the back before filling out this page) The photocatalyst composition of the present invention can be selected, combined and matched according to the purpose when necessary. General coating Added ingredients, such as pigments, extenders, dispersants, light stabilizers, wetting agents, tackifiers, flow control agents, defoamers, plasticizers, film-forming aids, rust inhibitors, dyes, anticorrosives The modified photocatalyst (A) of the present invention has a photocatalyst particle surface modified with a modifier compound (b) having a very low surface energy structure. Therefore, the modified photocatalyst (A) and The distribution of the modified photocatalyst (A) of the photocatalyst composition of the present invention formed by the binder component (B) of phenyl-containing polysiloxane (BP) has the possibility of self-inclination. Here, "self-inclination" When the film or formed body is formed from the photocatalyst composition, the modified photocatalyst (A) during the formation process corresponds to the properties (particularly hydrophilic / hydrophobic) of the abutting surface of the film or formed body, and is formed automatically. Modified structure of photocatalyst (A) concentration gradient. In this case, if the properties (hydrophilicity / hydrophobicity) of the adjacent surfaces are different, a concentration gradient is generated according to the difference, and a concentration gradient is also generated between the inside of the film or the molded body and the interface. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. For example, when the above-mentioned self-sloping photocatalyst composition is coated on a substrate to form a film, a modified photocatalyst (A) can be obtained toward the inner surface of the substrate (such as outside air) and Increasing the surface side of the adjacent film has an inclined composition film having a gradient concentration in the film thickness direction. At this time, the content (concentration) of the modified photocatalyst in the full coating is 100, and the relative concentration of the vicinity of the inner surface of the substrate and the vicinity of the adjacent surface side is 1 200 or more. It is confirmed that the photocatalyst and hydrophilization ability are improved. effect. The relative density in the vicinity of this (adjacent to the interface on the inside of the substrate) surface side is preferably 150 or more, more preferably 200 or more. In addition, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -49- 1229010 A7 B7 V. Description of the invention (48) For example, all substrates used in the applications disclosed in the present invention can be used. (Please read the precautions on the back before filling this page) The substrate used to obtain the functional composite of the present invention can be organic substrates such as synthetic resins, natural resins, or metals, ceramics, glass, stone, cement, Inorganic substrates such as concrete, or combinations thereof. In the functional composite of the present invention, even if an organic substrate which can be decomposed by a photocatalyst is used, it is a material having excellent durability. That is, the photocatalyst composition of the present invention can provide a functional composite having excellent durability even for an organic substrate which has not been used conventionally due to durability problems. In the present invention, a method for obtaining a functional composite or formed body obtained from the photocatalyst composition, for example, when the photocatalyst composition is used in the form of a coating agent, the coating agent may be applied to a substrate and dried. The functional composite of the present invention can be obtained by applying a heat treatment at 200 ° C, preferably 40 ° to 250 ° C, if necessary. The coating method may be, for example, a spray blow method, a fluid coating method, a roll coating method, a bristle coating method, a dip coating method, a spin coating method, a screen coating method, or a casting coating method. Method, flexographic printing method, etc. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in this case, in the functional complex of the present invention, the film thickness of the film formed by the photocatalyst composition is generally from 0.1 to 200 mm, which is better. It is 0 _ 1 — 5 0 // m, more preferably 0.5 — 1 〇 // m. The method for producing the functional composite of the present invention is not limited to the case where a film made of the photocatalyst composition of the present invention is formed on a substrate. The substrate and the photocatalyst composition of the present invention can also be molded simultaneously, for example, integrally molded. Alternatively, the photocatalyst composition of the present invention may be formed before the substrate is formed. In addition, the photocatalyst composition and the substrate of the present invention can be formed separately, and then the paper size can be adapted to the Chinese National Standard (CNS) A4 specification (210X297 male foot) ~~ '~~ -51-1229010 A7 B7 V. DESCRIPTION OF THE INVENTION (49) A functional composite is produced by bonding, welding, and the like. In the above-mentioned method, any type of base material can be used when molding is performed without being connected to the base material. The substrate in this case is not limited to a solid, and liquid and gas can be used as long as the effect of the present invention is not impaired. The formed article or functional composite of the present invention can be formed into a film-like, sheet-like, block-like, nine-like or more complicated shaped article according to the method used for resin molding. Other resins may be used in each formed body as long as the effects of the present invention are not impaired. For the above-mentioned forming and mixing of the above-mentioned applications, the formed body or functional composite of the present invention and other resins can be made into powder or firstly made into nine pellets. May also contain liquid ingredients. In addition, the mixed resin may be formed into nine pellets by the following method, and a method for forming may be provided. Nine pellets may also be a so-called masterbatch which contains the local concentration of the molded body or functional composite of the present invention in other resins. The molding method used in the present invention may be an extrusion molding method, an injection molding method, a compression molding method, or the like. In addition, a calendering method can also be used by selecting a resin such as a thermoplastic resin for concrete. In addition, it is also possible to impregnate and form the molded body or functional composite of the present invention, and these and other resin mixtures by using reinforcing materials such as organic fibers containing inorganic fibers and inorganic fibers such as glass (and fabrics including these). . The formed article or functional composite of the present invention may be formed into a fibrous form. In order to process into a fibrous form, a general spinning method can be used as long as the effect of the present invention is not affected. As this spinning method, a melt spinning method and a solution spinning method can be used. When spinning, other resins mentioned above can also be used to process into fibers. For example, this paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) I — I! ---- #! (Please read the notes on the back before filling this page)

Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives-52- 1229010 A7 B7 V. Description of the invention (50) The formed body or functional composite of the present invention can also be blended with polyester, nylon, etc., or the present invention The molded body or functional composite is spun with these resins (sheath core, side-by-side type, etc.). The fiber can be long fiber or short fiber. The length direction can be uniform or very fine. The cross-sectional shape is round, triangular, L-shaped, D-shaped, Y-shaped, W-shaped, octalobal, flat, canine. Polygonal, multi-lobal, hollow, or irregular shapes are acceptable. The formed article or functional composite of the present invention in a fibrous form can also be used in the form of a woven or non-woven fabric (short fiber or long fiber). The types of fibers that can be used include, for example, cheeses of silk threads and silk aggregates, woven fabrics, knitted fabrics, and non-woven fabrics, and they can also be mixed with fibers of other resins. The shape of the yarn can be exemplified by raw yarns, false twisted yarns (including extended false twisted yarns), first twisted false twisted yarns, air jet processing systems, ring spinning systems, and open-end spinning systems, and multifiber precursor yarns. (Including ultra-fine filaments), mixed fiber, etc. In addition, mixed fibers include polyester fibers, polyamide fibers, polypropylene fibers, polyethylene fibers, polybutylene fibers, polyurethane fibers and other elastic fibers (including the addition of magnesium oxide, Zinc oxide is the representative metal oxide, metal hydroxide and other chlorine water degradation inhibitors) and other synthetic fibers, cotton, hemp, wool, silk and other natural fibers or copper ammonia fibers, rayon, polynosic (high Cellulosic fibers such as wet modulus viscose fibers) or acetate fibers. The formed body or functional composite of the present invention processed into the fibrous form described above can be used for clothing, gas, and liquid filters for the purpose of antibacterial, antifouling, deodorizing, and decomposing toxic gases. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) I —.---- Cloth— (Please read the precautions on the back before filling this page)

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Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-53- 1229010 A7 B7 V. Description of the invention (51) The above-mentioned functional composite or formed body formed by the photocatalyst composition of the present invention passes the energy band of the photocatalyst contained therein Gap (band gap energy) Light with higher energy can show hydrophobicity or hydrophilicity and / or photocatalytic activity, and photoelectric conversion function. In the present invention, light with higher energy than the bandgap of the photocatalyst can be used as light sources in sunlight or indoor lighting, such as light in a general residential environment, as well as black light (near-ultraviolet light), xenon light, mercury light, and the like. The above-mentioned formed body or functional composite provided according to the present invention is a substance having photocatalytic activity such as decomposition of organic matter, and can exhibit various functions such as antibacterial, antifouling, deodorization, NOx decomposition, etc., and can be used in air, water, etc. Environmental purification and other uses. The above-mentioned formed article or functional composite provided according to the present invention is a substance having a hydrophilic contact angle with water of 60 ° or less (preferably 10 ° or less) at 20 ° C after light irradiation ( The hydrophilic film and the substrate covered with the hydrophilic film, etc.) can also be applied to the anti-fogging technology of mirror or glass anti-fog, the anti-fouling technology to building exterior, etc. Examples of applications of the formed body or functional composite of the present invention in the field of antifouling technology include construction equipment such as building materials, building exteriors, building interiors, window frames, window glass, structural members, houses, etc. Toilets, baths, washstands, lighting appliances, lampshades, kitchen supplies, food utensils, food washers, kitchen supplies, food utensils, food washers, food dryers, fluidizers, microwave ovens, extraction cabinets, fans, etc. In addition, the exterior and finishing of vehicles can also be used in the interior depending on the application. It is also effective for vehicles that require transparency such as lighting covers, window glass, calculators, display panels, etc. This paper is applicable to China Standard (CNS) A4 specification (210X297 mm) I ---: ---- clothing-(Please read the precautions on the back before filling this page)

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Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-54- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1229010 A7 ___B7 V. Description of the Invention (52), and the exterior of mechanical devices or articles, dust covers and finishing, display Machines, their covers, traffic signs, various display devices, advertising towers and other displays, soundproof walls for roads and railways, exterior and coating of bridges, guide rails, interior and coating of tunnels, insulators, solar cell covers, The exterior parts of electronic and electrical equipment used for external use such as solar water heaters, heat collectors, etc., especially transparent parts, polyethylene awnings, greenhouses, etc. · Exterior parts, especially transparent parts, and the possibility of pollution even indoors. Environment, for example, medical or sports facilities, devices, etc. Examples of applications of the formed article or functional composite of the present invention in the field of anti-fogging technology include mirrors (vehicle rearview mirrors, bathroom mirrors, washstand mirrors, dental mirrors, road mirrors, etc.), Lenses (eyeglass lenses, optical lenses, lenses for lighting, lenses for semiconductors, lenses for photocopiers, rear-view photography lenses for vehicles, etc.), window glass for concrete, building or surrounding towers, window glass for vehicles (cars, railways) Vehicles, airplanes, ships, submarines, snowmobiles, cable cars., Park gondola, spacecraft, etc.), windshields of vehicles (cars, motorcycles, railway vehicles, aircraft, ships, submarines, snowmobiles, snow Car, gondola gondola, park gondola, spacecraft, etc.), protective goggles, sports goggles, protective covers, sports covers, helmet covers, frozen food display cabinet glass, insulated food display Cabinet glass, outer cover for measuring equipment, outer cover for vehicle rear view photographic lens, collection lens such as laser dental treatment device, outer cover for light detection sensor such as workshop distance sensor Applications of infrared sensor covers, camera filters, etc. 〇The formed body or functional composite of the present invention is used in the field of anti-static technology. The paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) (Please read the back first) (Notes to fill out this page)

-55- 1229010 A7 B7 V. Application Note (53) (Please read the precautions on the back before filling this page) Application examples can be exemplified, for example, Braun tubes, magnetic recording media, optical recording media, magneto-optical devices Recording media, audio tapes, video tapes, analog recorders, storage or components or exterior and finishing of household electrical products, storage or components or exterior and finishing of mechanical products, exterior of machinery or articles, dust protection Covers and finishes. The above-mentioned formed body or functional composite provided by the present invention is a substance having a contact angle with water of 70 ° or more (preferably 90 ° or more) at 20 ° C after light irradiation ( Hydrophobic shaped bodies or films and substrates covered with the hydrophobic film, etc.) are drip-resistant and water-blocking, and can be applied to anti-fouling technologies that prevent the adhesion of water pollution and the use of running water cleaning, and Technology to prevent snow and ice adhesion can be used for window glass, windshield, mirrors, lenses, goggles, covers, insulators, building materials, building exteriors, building interiors, structural members, vehicle exteriors and coatings, Exterior and finishing of mechanical devices, various display devices, lighting devices, residential equipment, food wares, kitchen appliances, household electrical appliances, roof components, antennas, transmission lines, snow and ice appliances, etc. When the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the above-mentioned formed body or functional composite provided by the present invention, which has a photoelectric conversion function, it can express the function of converting solar energy into electricity and can be used in applications (wet Type) Applications of optical semiconductor electrodes such as solar cells. The component provided by the present invention that changes in light wettability with water (changes from hydrophobicity to hydrophilicity, or changes from hydrophilicity to hydrophobicity) is very useful for applications such as original plates for offset printing. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -56- 1229010 A7 B7 V. Description of the invention (54) The best form of implementing the invention is described in more detail in the following examples, reference examples and comparative examples The present invention, but the present invention is not limited to this range. Various physical properties in the examples, reference examples, and comparative examples were measured by the following methods. [1] Particle size distribution and number-average particle size Add appropriate solvents to dilute the solids content in the sample to 1 to 20% by weight. Use a wet particle size analyzer (Nitoichi Microtolaku) UPA — 9 2 3 0). [2] Weight-average molecular weight It was determined by a colloidal permeation chromatography method (GPPC) using a calibration curve made of a polystyrene standard. The conditions of G PC are as follows.

• Device: HLC-8020 LC-3A Chromatograph manufactured by Tosoh Corporation • Tubular column: TSKgel GIOOOHxl, TSKgel G2000Hn, and TSKgel G4000Hxl (all of which are manufactured by Tosoh Japan) are used in series. • Data processing device • · CR-4A type data processing device made by Shimadzu Corporation of Japan • Mobile phase: Tetrahydrofuran (for analysis of polysiloxane containing phenyl group) Chloroform (for analysis of oxygen containing polystyrene without phenyl group) • Flow rate: 1 · 0 m 1 / mi η • Sample preparation method This paper size applies Chinese National Standard (cns) Α4 specification (210 × 297 mm) — I · U 夤 -I (Please read the precautions on the back before filling this page)

， 1T Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-57- V. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs I229〇i〇A7 Invention Description (55) Dilute with the solvent used in the mobile phase (adjust the concentration appropriately to 0.5 ^ 2% by weight) for analysis. [3] Infrared absorption spectrum Measured using Japan, Japan FT / IR-5300 infrared spectrometer. [4] Measurement of 2 9 Si nuclear magnetic resonance, measured by JNM LA400 manufactured by Japan Electronics Co., Ltd. [5] Hardness of coating film According to J I S-K 5 400, the pencil hardness (scratch of coating film) was obtained. [6] The hardness of the coating film after UV irradiation The surface of the coating film was irradiated with the FL2OS BLB type black light manufactured by Toshiba Optical Technology Co., Ltd. for 7 days, and then measured in accordance with the above method [5]. At this time, the system is modulated to use u VR-2 UV intensity meter made by Japan TOP Control (T 〇pc ο η). The light receiving unit is to use Japanese TOP Control UD-3 Type 6 light receiving unit (corresponding to the wavelength of 3 1 〇). — 4 0 0 nm light)} The intensity of UV light at I ”is 1 m W / cm 2. [7] Contact angle of water on the surface of the coating film After deionized water droplets were left on the surface of the coating film at 20 t for 1 minute, they were measured with a CA A-X 150 type contact angle meter made by Kyowa Kyowa Interface Science. The smaller the contact angle of water on the coating film surface, the higher the hydrophilicity of the coating film surface. 8] Changes in the hydrophilicity (hydrophobicity) of the coating film surface before and after UV irradiation （⑽ 指 公 楚） (Please read the notes on the back before filling this page)

-58- 1229010 A7 B7 V. Description of the invention (56) After irradiating the surface of the coating film with ultraviolet rays as described in [6] above for 7 days, measure the contact angle of water according to the above method [7]. [9] Photocatalytic activity of the coating film The surface of the coating film was coated with a 5% by weight methyl blue ethanol solution, and then irradiated with ultraviolet rays for 5 days according to the method of [6] above. Then according to the degree of decomposition of methyl blue after the photocatalyst action (visually evaluate the degree of discoloration of the coating film surface), the photocatalyst activity was evaluated in the following three stages. ◎: Degree of complete decomposition of methyl blue △: Blue of methyl blue remained X: No decomposition of methyl blue was observed at all [1 0] Weather-resistant surname (gloss retention) of the coating film Use Sga DPWL — 5R type double-sided light-controlled weather-resistance tester made by a tester performs an exposure test (irradiation: 60 ° C, 4 hours, dark and moist: 40 ° C, 4 hours). The 60 °-60 ° mirror reflectance after 1000 hours of exposure is measured as the final gloss, and this is divided by the initial gloss, and the resulting gloss is the gloss retention. [1 1] Evaluation of the inclined structure of the photocatalyst After embedding the sample in epoxy resin (Quet〇1812, manufactured by Japan EM Co., Ltd.), a thin slicer was made into a thin slice with a thickness of 50-60 nm by a slicer and loaded in A sieve covered with a supporting membrane. Subsequently, R u 04 steam dyeing was performed to about 5 points, and carbon deposition was performed as a sample for inspection mirror, and the cross-section of the coating film was observed with TEM. The conditions for TEM observation are as follows.

• Installation: Japan, Hitachi made HF2000 type • Acceleration voltage: 1 2 5 k V This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) —: —.——— (Please read the precautions on the back first (Fill in this page again)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-59- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1229010 A? B7 V. Description of the Invention (57) In addition, the existence of photocatalyst titanium oxide is analyzed by EDX analysis Of it. In addition, the coating film formed on the aluminum plate having the acrylic urethane coating film was observed by rough cutting the sample with a DDAD 3 2 1 type microtome manufactured by DISCO Engineering Service. Processing was performed with FIB (Focused Ion Beam), and the cross-section of the coating film was observed with TE M. F I B processing conditions are as follows. Machine used: Japan, Hitachi FB2000 type Processing conditions: Acceleration voltage (30 k V) Ion source: G a In addition, the conditions for TEM observation are as follows. • Device: HF2000 type manufactured by Hitachi in Japan. • Acceleration voltage: 200kV [1 2] Impact resistance. According to J I S — K5400, it was evaluated by DuPont (50 g x 50 cm). Reference Example 1 Synthesis of phenyl-containing polysiloxane (BP 1-1) To 78 g of dioxane placed in a reactor equipped with a reflux cooler, a thermometer, and a stirring device, 26.O g of phenyl trichloride was added. After silane, stir at room temperature for about 10 minutes. The reaction solution was maintained at 10 to 15 ° C and the standard paper size of China National Standards (CNS) A4 i 210X was applied to the paper size of 3.2 g of water and 12.9 g of dioxane in about 30 minutes; 297 mm) " -60- (Please read the notes on the back before filling this page)

1229010 Α7 Β7 5. The mixed liquid of invention description (58) was dropped into it, and then stirred at 10 to 15 ° C for about 30 minutes, and then the reaction liquid was heated to 60 ° C and stirred for 3 hours. After the resulting reaction solution was cooled to 25 to 30 ° C, 39.2 g of toluene was dropped thereinto in about 30 minutes, and then 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 19 · 2 g of methanol was added thereto in about 30 minutes. Then, the stirring was continued at 25 to 30 ° C for about 2 hours, and then the reaction solution was warmed to 60 ° C and stirred for 2 hours. The obtained reaction solution was distilled under reduced pressure at 60 ° C to obtain a polysiloxane (B P 1-1) containing a phenyl group having a weight average molecular weight of 3600 and a trapezoidal skeleton. (The obtained polysiloxane containing phenyl group (BP 1-1), the absorption of stretching vibration derived from the trapezoid skeleton in the IR spectrum was observed (1 1 3 0 cm _ 1 and 1 0 3 7 cm-1)) . In addition, from the measurement results of 2 9 S i nuclear magnetic resonance, the general formula of the above-mentioned phenyl-containing polysiloxane (BP1-1) is (Ph) "OCHs" 0.58S i〇ι.21 (here, Ph Table is not phenyl.) Reference Example 2 Synthesis of alkyl-containing polysiloxane (BA-1) was added to 300 g of methanol placed in a reactor equipped with a reflux cooler, a thermometer, and a stirring device. After 1 3 6 g of methyltrimethoxysilane (1 mole) and 120 g of dimethyldimethoxysilane (1 mole), stir at room temperature for about 10 minutes. In about 40 minutes, 12 · 6g of a 0 · 05N hydrochloric acid aqueous solution (0.7 Moore) and the mound paper size are applied to the Chinese National Standard (CNS) M specifications (210X297 mm) '— -61-(Please read the (Please fill in this page again)

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Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1229010 A7 B7 V. Description of the Invention (59) 63 g of the mixed liquid made of methanol was dropped into the reaction solution to be hydrolyzed. After the dripping force α is completed, stir for another 20 minutes at 10 t or less, and stir for 6 hours at room temperature. Then, the obtained reaction solution was distilled under reduced pressure at 60 ° C to obtain an alkyl group-containing polysiloxane (B A-1) having a weight average molecular weight of 3 600. The structure of the obtained polysiloxane (B A-1) containing an alkyl group can be confirmed to show a signal of a T structure and a D structure by a measurement result of 2 9 S i nuclear magnetic resonance. The ratio is T structure: D structure is 1: 1. The general formula for the polysiloxane (B A-1) containing an alkyl group is (C Η 3)! · 6 (0 C Η 3) 0.2 7 S i 〇1.12. Reference Example 3 Synthesis of alkyl-containing polysiloxane (BA-2) 25.8 g of methyltrichlorosilane was added to 470 g of dioxane placed in a reactor equipped with a reflux cooler 'thermometer and stirring device. After 2 5 · 8 g, stir at room temperature for about 10 minutes. The reaction solution was maintained at 10 to 15 t, and a mixed liquid of 4 · 7 g of water and 1 8 · 7 g of dioxane was dropped into the reaction solution in about 30 minutes, and then the temperature was further reduced to 10 to 15 After stirring at ° C for about 30 minutes, the reaction solution was heated to 60 ° C and stirred for 3 hours. The resulting reaction solution was further cooled to 10 to 15 ° C, and 30 · 2 g of methanol was added over about 30 minutes. Then, the stirring was continued at 25 to 30 ° C for about 2 hours, and then the reaction solution was heated again to 60 ° C and stirred for 3 hours. The obtained reaction solution was distilled at 60 ° C under reduced pressure to obtain the weight. The paper size is in accordance with Chinese National Standard (CNS) A4 (21〇X; 297 mm). — (Please read the notes on the back before filling this page)

Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-62- Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1229010 Α7 Β7 V. Description of the Invention (60) Polysiloxanes with BASF (average molecular weight: 2 8 0) (BA) -2) 〇 From the measurement results of 2 9 S i nuclear magnetic resonance, the general formula of the above-mentioned alkyl-containing polysiloxane (BA-2) is (CH3): (〇CH3). 6 2 S i 〇1.19 0 Reference Example 4 Synthesis of polyphenylene oxide (BP 1-2) containing phenyl was added to 11.8.0 g of dioxane placed in a reactor equipped with a reflux cooler, a thermometer and a stirring device. 26. After 25. 8 g of Og phenyltrichlorosilane, the mixture was stirred at room temperature for about 10 minutes. The reaction solution was maintained at 10 to 15 ° C, and a mixed liquid of 3.2 g of water and 12 · 9 g of dioxane was dropped into the solution in about 30 minutes, and then the temperature was further reduced to 10 to 1 After stirring at 5 ° C for about 30 minutes, the reaction solution was heated to 60 t and stirred for 3 hours. After the resulting reaction solution was cooled to 25 to 30 ° C, and 3 5 3 g of toluene was added over about 30 minutes, the reaction solution was again heated to 60 ° C and stirred for 2 hours. After cooling the obtained reaction solution to 10 to 15 ° C and adding 25.1 g of dimethylchlorosilane, 1.1 g of water was added in about 30 minutes while maintaining the temperature at 10 to 15 It was mixed with 4 · 3 g of diB-oxamine. Then, the stirring was continued at 25 to 30 t for about 2 hours, and then the reaction solution was heated again to 60 ° C and stirred for 3 hours. The obtained reaction solution was distilled off the solvent at 60 ° C under reduced pressure to obtain a weight average molecular weight of 1 200 containing Si-fluorenyl-containing phenyl-containing polysiloxane (BP1). CNS) Α4 specifications (210X297 mm) I-63- (Please read the precautions on the back before filling this page)

1229010 M __ B7 V. Description of the invention fel) a 2). (It was observed that the absorption from the si-fluorenyl group in the infrared absorption spectrum (2 1 4 0 c m _ 1)). (Please read the precautions on the back before filling this page.) Also, the general formula (Ph) of the above-mentioned phenyl-containing polysiloxane (BP1-2) can be obtained from the measurement results of 2 9 S i nuclear magnetic resonance. 28 (CH3) 0.57H0.29S i Oi.44. (Here Ph stands for phenyl group) Reference Example 5 Preparation of the binder component (B-1). Polysiloxane containing phenyl group (BP 1-1) 6 g synthesized in Reference Example 1 and contained in Reference Example 2 To a mixture of alkyl polysiloxane (BA-1) 3 g, 14.7 g of toluene, 29 -8 g of isopropyl alcohol, and 15.1 g of butylcellolysin were added and stirred at room temperature to obtain a binder component ( B — 1) solution. In addition, according to the general formula of each composition, the general formula of the adhesive component (B-1) can be calculated as (Ph) 0.67 (CH3) 0.5 (〇CH3) 〇.478 丨 〇1.18 (here,? ] 1 represents phenyl). Printed in Reference Example 6 of the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The composition of the binder component (B-2) was synthesized in 2 3 5 g of dioxane placed in a reactor with a reflux cooler, thermometer and stirring device After adding 2 · 5 g of methyltrichlorosilane and 15 · 5 g of phenyltrichlorosilane, the mixture was stirred at room temperature for about 10 minutes. After maintaining the reaction solution at 10 to 15 ° C, a mixture of 6.6 g of water and 26.4 g of dioxane was dropped into the solution in about 30 minutes, and then applied to the paper standard. China National Standard (CNS) A4 specification + (2 丨 OX297 mm) " -64- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1229010 A7 _____ B7 _ — — 5. Description of the invention (62) 1 0 to 1 5 After stirring at ° C for about 30 minutes, the reaction solution was heated to 60 ° C and stirred for 3 hours. After the resulting reaction solution was further cooled to 25 to 30 ° C, and 2 3 5 g of toluene was dropped thereinto in about 30 minutes, the reaction solution was again heated to 60 ° C and stirred for 2 hours. The resulting reaction solution was cooled to 10 to 15 ° C. (:, And 42.8 g of methanol was added thereto in about 30 minutes. Then, the stirring was 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 obtained reaction solution was distilled off the solvent at 60 ° C under reduced pressure to obtain a binder component (B-2) having an average molecular weight of 3 1 0. In addition, the measurement result of 2 9 S i nuclear magnetic resonance can be obtained The general formula of the adhesive component (B-2) is (Ph) 0.26 (CH3) 0.74 (OCH3) 0.77S i〇1 · 12 (here, Ph represents phenyl). Reference Example 7 Adhesive component ( B-3) was prepared in a mixture of 6 g of alkyl-containing polysiloxane (BA-2) synthesized in Reference Example 3 and alkyl-containing polysiloxane (BA-1) 3 g synthesized in Reference Example 2, 14.7 g of toluene, 29.8 g of isopropanol, and 5-1 g of butyl glutenin were added and stirred at room temperature to obtain a binder component (B-3 without phenyl polysiloxane). In addition, according to the general formula of each composition, the general formula of the above-mentioned adhesive component (B-3) can be calculated as (CH3) (〇CH3) 0.5si This paper size applies the Chinese National Standard (CNS) A4 specification (210X 29 7 mm) (Read the precautions on the back before filling in this page)

-65- 1229010 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of Invention (63) Example 1 TKS placed in a reactor with a reflux cooler, thermometer and stirring device — 2 5 1 [Trade name of oxoorganosol (manufactured by Ben Tecka), dispersion medium: a mixed solvent of toluene and isopropanol, a titanium dioxide concentration of 20% by weight, and an average crystal grain size of 6 nm (catalog 値)] 40 g In 40 ° C, a 20% by weight toluene solution of bis (trimethylsiloxane) methylsilane was added at 50 ° C for about 5 minutes, and stirring was continued at 50 ° C for 12 hours to obtain A modified photocatalyst organosol (A-1) with excellent dispersibility. At this time, the amount of hydrogen generated with the reaction of bis (trimethylsiloxane) methylsilane was 7 1 8 m 1 at 2 3 t. In addition, the obtained modified photocatalyst organosol was coated on a KBr plate and its IR spectrum was measured. It was observed that the absorption of T i —〇Η group (3 6 3 0 — 3 6 4 0 cm −1) disappeared. Figures 1 and 2 show the particle size distributions of T K S-2 5 1 before the modification treatment and the obtained modified photocatalyst organosol (A-1), respectively. It was confirmed that the particle size distribution of the obtained modified photocatalyst organosol (A-1) was monodispersed (number average particle diameter was 25 nm), and the monodispersity of TKS-2 51 before the modification treatment (number average particle diameter was The particle size distribution of 12 nm) has completely disappeared. Next, add 20 g of the modified photocatalyst organosol (A-1) at room temperature under stirring to 68 g of the solution of the binder component (B-1) prepared in Reference Example 5, and then stir Next, 0.5 g of a hardening catalyst (dibutyl dilaurate) was added to obtain a photocatalyst composition (C-1). It is cut into 50 m x 6 0 ni m aluminum plates with a thickness of 1 m (

(Please read the notes on the back before filling out this page: J Order

LT. This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -66- Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economy 1229010 A7 ___B7_ V. Description of the invention (70) Add KF 9 9 0 1 (trade name of methyl hydrodiene siloxane-dimethyl siloxane copolymer at 40 ° C for about 5 minutes, Si monofluorene content 7, 1 4 m mo 1 / g, weight-average molecular weight 3900, manufactured by Shin-Etsu Chemical Co., Ltd.) 8 g, and then stirred at 40 t for 4 8 hours to obtain a modified photocatalyst organosol (A-3). At this time, the amount of hydrogen generated with the reaction of KF 9 9 0 1 was 9 800 m 1 at 2 3 t. In addition, the obtained modified photocatalyst organosol (A-3) was coated on a KBr plate and measured. In its IR spectrum, it was observed that the absorption of T i-10 Η group (3 6 3 0 — 3 6 4 0 cm — 1) disappeared. In addition, the particle size distribution of the obtained modified photocatalyst organosol (A-3) is a single dispersion (number average particle size is 41 nm), and the single dispersion of the titanium oxide organosol before the modification treatment (number average particle size is The particle size distribution of 12 nm) has completely disappeared. Next, the crosslinker DMS — V 〇〇 [the trade name of the terminal ethylene polydimethylsiloxane] was mixed with phenyl-containing polysiloxane (BP 1 — 2) 8 · 1 g synthesized in Reference Example 4. (Manufactured by Geso Co., Ltd.)) 0. 9 g, 14.7 g of toluene, 29. 8 g of isopropyl alcohol, and 15.1 g of butylcellolysin were added and added at room temperature with stirring. The modified photocatalyst organosol (A-3) 1 2 g was added, and the dichloro-dichlorocyclopentadienyl-platinum (Π) was added in a 0.25% dioxane solution 0.4 g under stirring. A photocatalyst composition (C-5) was obtained. The obtained photocatalyst composition (C-5) was spray-coated on the steel sheet. The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

-73- 1229010 A7 B7 V. Description of the invention (74) The angle is 4 °. In addition, the evaluation results of photocatalytic activity were also very good (◎) 〇 (Please read the precautions on the back before filling this page) In addition, the exposure test was performed with a double-sided light-controlled weather resistance tester (after 1000 hours), The gloss retention was 88%, showing very good weather resistance. ^ Example 7 TKS — 2 5 1 [Trade name of titanium dioxide organosol (manufactured by Ben Thekka Company)] placed in a reactor equipped with a reflux cooler, thermometer and stirring device, dispersion medium: toluene and Mixed solvent of isopropanol, titanium dioxide concentration of 20% by weight, average crystal grain size of 6 nm (Catalog 値) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs] in 40 g at 5 ° C for about 5 minutes Add 40 g of a 10% by weight toluene solution of ginseng (trimethylsiloxy) silane, and then continue stirring at 50 t for 12 hours to obtain a modified photocatalyst organosol (A-5 with very good dispersibility). ). At this time, the amount of hydrogen generated with the reaction of ginsyl (trimethylsiloxy) silane was 230 m 1 at 23 ° C. In addition, the obtained modified titanium oxide sol was coated on a KBr plate and its IR spectrum was measured, and it was observed that the absorption of T i Η group (3 6 3 0-3 6 4 0 cm 1) disappeared. In addition, the particle size distribution of the obtained modified photocatalyst organosol (A-5) is a single dispersion (number average particle size is 3 2 nm), and the single dispersion (number average particle size) of TKS — 2 51 before the modification treatment is The particle size distribution with a diameter of 12 nm) has completely disappeared. Next, the above-mentioned photocatalyst-reducing organosol was modified at room temperature under stirring (this paper size is in accordance with Chinese National Standard (CNS) A4 specifications (21 ×: 297 mm) -77-

Claims (1)

1229010 A8 B8 C8 D8 々, patent application scope 1 No. 91 1 12032 Chinese Patent Application Amendment (please read the precautions on the back before filling out this page) Amended on June 18, 1993 1 · A photocatalyst composition containing (A) modification The photocatalyst composition of the photocatalyst particles and the (B) binder component is characterized in that the weight ratio (A) / (B) of the component (A) to the component (B) is 0 · 1/99 · 9 ~ 99/1, where The modified photocatalyst particle (A) uses at least one kind selected from the group consisting of trihydrocarbylsilane units represented by formula (1), monohydroxydihydrocarbylsilane units represented by formula (2), and dihydroxyhydrocarbyl groups represented by formula (3) A compound of at least one structural unit of a group of silane units is obtained as a modifier compound (b), and the photocatalyst particles (a) are modified. The adhesive component (B) includes the following formula (4) Polyphenylsiloxane (BP) containing phenyl shown, and the polyphenylene oxide (BP) containing phenyl may contain additional alkyl groups as needed = R 3 S i-(1) Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed (where, R each independently represents a linear or bi-chain alkane having 1 to 30 carbon atoms , Cycloalkyl with 5 to 20 carbons, Straight-chain or bi-chain fluoroalkyl with 1 to 30 carbons, Alkenyl with linear or bi-chain 2 to 30 carbons, benzene Group, alkoxy group or hydroxy group having 1 to 20 carbon atoms), (R2Si〇)-(2) (where R is as defined by the general formula (1)) (CNS) A4 specification (210 X 297 mm) 1229010 铽 C8 D8 VI. Patent application scope 2-L-(3) I (where R is as defined by the general formula (1)) '(4) ( In the formula, each R1 represents a phenyl group, and R2 each independently represents a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms, a ring-base group having 5 to 20 carbon atoms or a straight-chain or branched chain group Alkenyl groups having 2 to 3 carbon atoms; X each independently represents a hydrogen atom, alkoxy group having 1 to 20 carbon atoms, fluorenyloxy group having 1 to 20 carbon atoms, amineoxy group, and 1 to 20 carbon atoms An oxime group or a halogen atom of 20; and?, 〇1, and 1 'are: 〇 <? ≪ 4,0 ^ q < 4, 0 ^ r < 4 and 0 < (p + Q + r) < 4 and 0 · 05Sp / (p + Q) S 1). 2. The photocatalyst composition according to item 1 of the scope of patent application, wherein in formulas (1) to (3), R is an alkyl group or a carbon number of 1 to 30, each of which represents a linear or a branched chain. 5 to 20 cycloalkyl, linear or bi-chain fluoroalkyl 1 to 30 fluoroalkyl, straight or bi-chain alkenyl or carbon 1 to 30 2 0 of the alkoxy group. 3. The photocatalyst composition according to item 1 or 2 of the scope of patent application, wherein the phenyl-containing polysiloxane (BP) is a phenyl-containing polysiloxane containing no alkyl group (BP 1 shown in the following formula (5)) ): This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) (Please read the notes on the back before filling out this page), tT Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 1229010 A8 B8 C8 D8 6. Scope of patent application 3 RlsXtS i 0 (4-st) y2 (5) (where R1 represents phenyl group; (please read the precautions on the back before filling out this page) independently represent hydrogen atom, hydroxyl group, carbon Alkoxy S of 1 to 20, fluorenyloxy of 1 to 20 carbons, amineoxy, oxime group or halogen atom of 1 to 20 carbons; and s and t are: 0 < s < 4 , 0St < 4, and 0 < (s + t) < 4). 4 · If the photocatalyst composition according to item 丨 or 2 of the scope of patent application, the Φ gastric adhesive component (B) further includes a polysiloxane (BA) containing an alkyl group represented by the following formula (6): R ^ X v S i 0 (4-u-v) / 2 (6) (where, R 2 each independently represents a linear or bi-chain alkyl group having 1 to 30 carbon atoms and a ring having 5 to 20 carbon atoms Alkyl or straight-chain or bi-chain alkenyl having 2 to 30 carbons; X each independently represents a hydrogen atom, a hydroxyl group, an alkoxy having 1 to 20 carbons, and an alkoxy having 1 to 20 carbons Group, amineoxy group, oxime group or halogen atom having 1 to 20 carbon atoms; and printed by u and v at the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are: 0 < u < 4, 0Sv < 4, and0 < ( u + v) < 4) 〇5. The photocatalyst composition according to item 1 or 2 of the scope of the patent application, wherein the adhesive component (B) comprises a phenyl-containing polymer containing no alkyl group represented by formula (5) Silicone oxide (BP 1) and alkyl-containing polysilicone (BA) shown in formula (6): This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -3- 1229010 B8 C8 D8 Consumer Cooperation of Intellectual Property Bureau, Ministry of Economic Affairs Printing VI. Application for patents 4 R, XtSi〇 (4 — s — t) / 2 (5) (where each R 1 represents a phenyl group; independently represents a hydrogen atom, a hydroxyl group, and a carbon number of 1 to 2 0 An alkoxy group having an alkoxy number of 1 to 20, an amineoxy group, an oxime group or a halogen atom having a carbon number of 1 to 20; and 3 and 7 are ·· < s < 4, 0St < 4, and 0 < ( s + t) <4); R 2 u XVS i 0 (4-U-V) / 2 (6) (where, R 2 each independently represents a linear or bi-chain carbon number of 1 to 3 〇 Alkane $ '@Cycloalkyl with 5 to 20 or alkenyl with 2 to 30 carbons, straight or ambivalent; X # independently represents hydrogen atom, hydroxyl, alkoxy with 1 to 20 carbons A radical of 1 to 20 carbon atoms, an amineoxy group, an oxime group or a halogen atom of 1 to 20 carbon atoms; and hydrazone and 1 ^ are: 〇 < u < 4, 〇Sv < 4, and 0 < (u + v) < 4). 6.% A Photocatalyst composition according to item 4 of the patent, wherein the polysiloxane containing fluorenyl group (BAA) has a monohydroxydihydrocarbon S unit (D) and formula (8) represented by formula (7) (2)-(R22Si〇)-(7) (wherein R2 each independently represents a linear or bi-chain carbon number 1 to ------- --------- IT ------ ^^ 1 (Please read the notes on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -4- 1229010 A8 B8 C8 D8 __ VI. Alkyl groups with a patent range of 5 3 0, cycloalkyls with 5 to 20 carbons or straight-chain or bi-chain alkenyls with 2 to 30 carbons); R2 -4 · 丨 一 〇—— (8) I 〇I (where R2 is as defined by formula (7)). 7 · The photocatalyst composition according to item 3 of the scope of patent application, wherein the weight average molecular weight of the phenyl-containing polysiloxane (BP1) is obtained by colloidal filtration chromatography from a calibration curve obtained using standard polystyrene The measurement 値 is from 500 to 10,000. 8. The photocatalyst composition according to item 4 of the scope of patent application, wherein the weight average molecular weight of the alkyl-containing polysiloxane (BA) is obtained by a colloidal filtration chromatography method using a calibration curve obtained using standard polystyrene. The measured value is 500 to 10,000. 9 · If the photocatalyst composition according to item 1 or 2 of the patent application scope, wherein the number average particle diameter of the modified photocatalyst particles (A) is below 400 nm. 10 · The photocatalyst composition according to item 1 or 2 of the scope of patent application, wherein the photocatalyst particles (a) are titanium oxide particles. 1 1 · If the photocatalyst composition according to item i or 2 of the scope of patent application, wherein the modifier compound (b) is a silicon compound (bl) containing a Si-fluorene group represented by formula (9): HxRyS i 0 (4-xy) / 2 (9) (where the paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm)) φ— (Please read the precautions on the back before filling this page) Ministry of Economy Printed by the Intellectual Property Bureau's Consumer Cooperatives -5- 1229010 A8 B8 C8 D8 VI. Application for Patent Scope 6 (Please read the precautions on the back before filling this page) R each independently represents a linear or quasi-chain carbon number 1 Alkyl to 30's Cycloalkyls with 5 to 20 carbons, straight or ambivalent carbons 1 to 30 Fluoroalkyls, straight or bicarbonated carbons 2 to 3 0 is an alkenyl group, a phenyl group, an alkoxy group having a carbon number of 1 to 20, or a hydroxyl group; X and y are: 0 < x < 4, 0 < y < 4, and (x + y) S 4). 12. The photocatalyst composition according to item 11 of the scope of the patent application, wherein the Si-fluorenyl group-containing silicon compound comprises at least one Si-fluorenyl group-containing silicon compound selected from the group consisting of formula (10). A silicon compound containing two terminal Si-fluorenyl groups represented by formula (1 1) and a group of compounds consisting of 聚 polysilicon oxide represented by formula (1 2): R3 Η—Si—R3 (10)丨 3 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (where R3 each independently represents a linear or bi-chain carbon number of 1 to 30, an alkyl group, a linear or bi-chain carbon number of 2 Alkenyl to 30, cycloalkyl having 5 to 20 carbons, straight-chain or bi-chain fluoroalkyl having 1 to 30 carbons, phenyl, or silyloxy represented by formula (13) Group: —〇 一 (R42Si〇) m—SiR43 (13) (wherein R4 each independently represents a linear or bi-chain alkyl group having 1 to 30 carbon atoms and a cycloalkane having 5 to 20 carbon atoms Group, linear or bi-chain fluoroalkyl group having 1 to 30 carbon atoms, linear or bi-chain alkenyl group having 2 to 30 carbon atoms, phenyl group, and m is an integer, OSmSIOOO) ); H — (R32S i Ο) n — S i R32 — Η (11) this paper ruler Applicable to China National Standard (CNS) A4 (210X29 * 7mm) -6-1229010 A8 B8 C8 D8 6. Application for patent scope 7 (where, as defined by formula (10), η is an integer, 〇 ^ η ^ 1 〇〇〇); (Read the notes on the back first and fill out this page) (R3HS i 0) a (R32S i 0) b (R33HS i 〇1 / 2) c (12) (where, R 3 is as defined by formula (10), a is an integer of 1 or more, b is an integer of 0 or more, (a + b) ^ 10000, and c is 0 or 2, but (a + b) is 2 or more Integer, and when c = 〇, the polysilicon of formula (12) is cyclic polysilicon; when c = 2, the polysilicon of formula (12) is chain polysilica) ° 1 3 · If the photocatalyst composition in the scope of patent application No. 1 or 2 is the one containing additional resin. 1 4 · If the photocatalyst composition of item 1 or 2 of the scope of patent application is for film coating. 15 · If the photocatalyst composition according to item 14 of the scope of patent application, wherein the distribution of the modified photocatalyst particles (A) is anisotropic, and the concentration of the modified photocatalyst particles (A) is faced from one of the films Raised on the other side. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 16. If the photocatalyst composition of item 1 or 2 of the patent application scope, it is the shaped body. 17 · If the photocatalyst composition according to item 16 of the patent application scope, wherein the distribution of the modified photocatalyst particles (A) is anisotropic, and the concentration of the modified photocatalyst particles (A) is from the inside of the formed body to the surface Ascendant. 1 8 · If the photocatalyst composition in item 4 of the scope of patent application, the paper size containing ^ applies to China National Standard (CNS) A4 specification (210X297 mm) Z " ~ 1229010 A8 B8 C8 D8 々, scope of patent application 8 benzene The base polysiloxane (BP) and the alkyl group-containing polysiloxane (BA) are coatings having a microphase separation structure. (Please read the notes on the back before filling this page) 1 9 · If the photocatalyst composition of item 18 of the patent application scope, the distribution of the modified photocatalyst particles (A) is anisotropic, and the modified photocatalyst particles The concentration of (A) is increased from one side of the film to the other. 20 · If the photocatalyst composition in item 4 of the scope of patent application is a molded body having a microphase separation structure between the phenyl-containing polysiloxane (BP) and the alkyl-containing polysiloxane (BA). 2 1 · If the photocatalyst composition of the 20th in the scope of the patent application, the distribution of the modified photocatalyst particles (A) is anisotropic, and the concentration of the modified photocatalyst particles (A) rises from the inside of the formed body to the surface The taller. 2 2 · —A kind of functional composite, which is obtained by forming a film containing the photocatalyst composition in the scope of patent application No. 1 or 2 on the substrate. 2 3 · If the functional composite of item 22 of the patent application scope, wherein the coating is anisotropic, the distribution of the modified photocatalyst particles (A) is anisotropic, and the concentration of the modified photocatalyst particles (A) is determined by the coating The contact surface between the film and the substrate is elevated toward the other exposed surface. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2 4-a functional complex, which is obtained by forming a film on the substrate, which is characterized in that the film contains a photocatalyst composition in the fourth scope of the patent application, In addition, the phenyl-containing polysiloxane (BP) and the alkyl-containing polysiloxane (BA) have a microphase separation structure. 2 5 · If the functional composite of the 24th scope of the application for a patent, wherein the coating is an anisotropic distribution of modified photocatalyst particles (A), this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 Mm) 1229010 A8 Β8 C8 D8 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. Application for patent scope 9 and the concentration of modified photocatalyst particles (A) is from the contact surface of the film to the substrate to the other exposed surface Ascendant. ---------------- Order (please read the notes on the back before filling in this page) t -9-This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) )