Photocatalyst

Since the present invention exhibits a substance decomposition action and a surface hydrophilic action by light energy, the surface of a photocatalyst member represented by titanium oxide, which is known to be applied to fields such as environmental purification, antifouling, and antifogging. Regarding immobilization technology to.

For some substances, light with energy greater than the energy gap (bandgap) between the conduction band and valence band of the substance, that is, light with a shorter wavelength than the light corresponding to the bandgap of the substance ( When irradiated with excitation light), electrons in the valence band are excited (photoexcitation) by light energy, and electrons are generated in the conduction band and holes are generated in the valence band. At this time, various chemical reactions can be carried out by utilizing the reducing power of electrons generated in the conduction band and / or the oxidizing power of holes generated in the valence band.

That is, the above-mentioned substance can be used like a catalyst under excitation light irradiation. Therefore, the above-mentioned substances are called photocatalysts, and titanium oxide is known as the most representative example thereof. Examples of chemical reactions promoted by this photocatalyst include oxidative decomposition reactions of various organic substances. Therefore, if this photocatalyst is immobilized on the surface of various base materials, various organic substances adhering to the surface of the base material can be oxidatively decomposed by using light energy.

On the other hand, it is known that when a certain photocatalyst is irradiated with light, the hydrophilicity of the surface of the photocatalyst increases. Therefore, if this photocatalyst is immobilized on the surface of various base materials, the hydrophilicity of the surface of the base material can be increased by irradiation with light. In recent years, research has been actively conducted to apply the above-mentioned characteristics of photocatalysts to various fields such as environmental purification, prevention of dirt adhesion to the surface of various base materials, and prevention of fogging. There is. In this case, the method for immobilizing the photocatalyst on the surface of various substrates plays a very important role.

Various proposals have been made so far for the method of immobilizing the photocatalyst, but as one of the particularly useful methods, the surface of the base material is coated with a composition containing the photocatalyst to form a film containing the photocatalyst. Attention has been paid to a method of fixing the photocatalyst to the surface of the base material by allowing the photocatalyst to be fixed. When the photocatalyst is immobilized by this method, (1) the photocatalyst can be firmly immobilized on the surface of the base material without impairing the activity of the photocatalyst, and (2) the film formed and the film are coated. It is required that the base material has durability that does not deteriorate due to the action of the photocatalyst.

Furthermore, as preferable conditions for expanding the applicable range of the substrate to be immobilized, (3) the immobilization conditions are mild (room temperature to about 150 ° C), and (4) the coating film has excellent transparency and durability. , Forming a film having excellent stain resistance, hardness and the like. Various proposals have been made so far regarding a method for immobilizing a photocatalyst by coating. For example, in Patent Document 1, a precursor of a photocatalyst, for example, a sol containing an organic titanate is applied to the surface of a substrate, and then the precursor of the photocatalyst is gelled by firing to be converted into a photocatalyst, and the produced photocatalyst is used. A method of immobilizing on the surface of the base material has been proposed. However, this method includes a step of forming fine particles of a photocatalyst on the surface of the base material, and this step requires firing at a high temperature. Therefore, when the surface area of the base material is large, it is difficult to immobilize the photocatalyst.

Patent Document 2 proposes a method of coating the surface of a base material with a titanium oxide sol deglued in water as a method of using a photocatalyst-containing sol (hence, which does not require a process of forming fine particles of a photocatalyst). Has been done. However, since titanium oxide sol does not have a film-forming property under mild conditions, it is necessary to bake at a high temperature even in this method. In addition, the resulting coating is brittle and easily broken, causing the photocatalyst to fall off the surface of the substrate, thus making it impossible for the photocatalyst to be effective on the surface of the substrate.

In addition, a method of coating the surface of the base material with a resin paint mixed with a photocatalyst has also been proposed. For example, in Patent Document 3, Patent Document 4, and Patent Document 5, a photocatalyst is mixed with a resin coating material containing a resin such as a fluororesin or a silicone resin that is not easily decomposed by the action of a photocatalyst as a coating film forming element, and this resin coating material is used. A method of coating the surface of a substrate using the method has been proposed. However, in these methods, the dispersibility of the photocatalyst with respect to the resin paint is poor, so that the resin paint becomes cloudy. Further, in order to obtain a film showing good physical properties by these methods, it is necessary to increase the amount of the above resin used, but in doing so, the photocatalyst is buried in the film formed by the coating. Therefore, there is a drawback that it does not show sufficient activity.

Further, when an organic base material such as a plastic molded body, a film, or an organic coating film is used as the base material for immobilizing the photocatalyst, the photocatalyst film obtained by the above-mentioned conventional technique can use the organic base material by photocatalytic action. It also has the drawback that it oxidizes and decomposes, causing interface deterioration between the organic substrate and the photocatalyst film, and it is not possible to maintain long-term durability. Patent Document 6 proposes a method in which a resin coating material and photocatalytic particles whose wettability with respect to a solvent constituting the resin coating material is adjusted are used in combination. That is, a method has been proposed in which a resin paint is first applied to the surface of a base material, and then photocatalytic particles are applied onto the resin paint before the resin paint is cured. However, this method has a drawback that the process is complicated and a homogeneous and transparent coating film cannot be obtained. Further, in this patent publication, for the purpose of simplifying the process, a method of coating by applying a mixture of photocatalytic particles having adjusted wettability to a solvent in a resin paint is also proposed. However, simply adjusting the wettability to the solvent cannot prevent the photocatalyst particles from being buried in the film formed by the coating, and most of the photocatalyst particles are completely buried in the film. There is no effect of preventing deterioration of the organic base material due to photocatalytic action.

As a method for overcoming various drawbacks of the above-mentioned prior art, we have prepared a photocatalyst composition consisting of a modified photocatalyst in which the surface of photocatalyst particles is modified with a silicone compound having a low surface energy and a binder having a higher surface energy. Proposed as Patent Document 7. The photocatalytic composition forms a film (self-grading film) that is heterogeneously distributed in the surface direction so that the concentration of photocatalytic particles is small near the interface in contact with the organic substrate and is large near the surface of the film. A photocatalytic film having excellent weather resistance and high photocatalytic activity is formed without deterioration of the interface with the organic substrate due to the above. However, in applications where extremely high transparency is required, further improvement in transparency has been desired while achieving both high weather resistance and development of photocatalytic activity.

<patcit num="1"><text>Japanese Unexamined Patent Publication No. 60-118236</text></patcit><patcit num="2"><text>Japanese Unexamined Patent Publication No. 6-278241</text></patcit><patcit num="3"><text>Japanese Unexamined Patent Publication No. 7-171408</text></patcit><patcit num="4"><text>Japanese Unexamined Patent Publication No. 9-100437</text></patcit><patcit num="5"><text>Japanese Unexamined Patent Publication No. 11-188271</text></patcit><patcit num="6"><text>Japanese Unexamined Patent Publication No. 9-314052</text></patcit><patcit num="7"><text>International Publication No. 00/30747 Pamphlet</text></patcit>

<p> The subject of the present invention is that the surface of the photocatalyst is exposed to photocatalytic activity for a long period of time without causing deterioration of the interface between the photocatalyst having high transparency and the organic substrate and deterioration of the binder in the photocatalyst film. / Or, a functional complex having excellent durability that develops hydrophilicity and maintains high transparency can be obtained with good reproducibility without the need for complicated steps.</p>

<p> The present inventors have arrived at the present invention as a result of diligent studies to solve the above problems. That is, the present invention is as follows. 1. A photocatalyst composed of photocatalyst particles (a), binder component (B) and ultraviolet absorber (U), and the mass ratio (a) / (B) of the photocatalyst particles (a) and binder component (B). Is 0.01 / 99.99 to 5/95, the total light transmittance is 95% or more, and the photocatalytic activity and / or hydrophilicity is increased by irradiating light with an energy higher than the band gap energy of the photocatalytic particle (a). A photocatalyst characterized by showing. 2. The photocatalyst according to 1. above, which further contains a light stabilizer (H). 3. The photocatalyst according to 1 or 2 above, wherein the surface energy of the photocatalyst particles (a) is smaller than that of the binder component (B).</p><p> 4. The photocatalyst according to 1 or 2 above, wherein the binder component (B) is a phenyl group-containing silicone (BP) represented by the formula (1). R¹_pR²_qX_rSiO_{(4-PQR) / 2} (1) (In the formula, each R¹Represents a phenyl group, R²Each independently represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched alkenyl group having 2 to 30 carbon atoms. X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an asyloxy group having 1 to 20 carbon atoms, an aminoxy group, an oxime group having 1 to 20 carbon atoms, and a halogen atom. And p, q and r are 0 &lt;p &lt;4, 0 q &lt;4, 0 r &lt;4, and 0 &lt;(p + q + r) &lt;4, and 0.05 p / (p + q). ) 1. )</p><p> 5. The photocatalyst according to 1 or 2 above, wherein the photocatalyst particles (a) are visible light responsive photocatalysts. 6. A photocatalytic composition characterized by forming the photocatalyst body according to 1 or 2 above. 7. A functional complex in which the photocatalyst according to 1 or 2 above is formed as a film on a substrate, and the film thickness is 0.1 to 100 μm. 8. The photocatalyst has anisotropy in the distribution of the photocatalyst particles (a), and the concentration of the photocatalyst particles (a) is higher on the surface than on the surface of the photocatalyst in contact with the substrate. The functional complex described in 7. above. 9. The functional composite according to 7. or 8 above, wherein the photocatalytic particles (a) form a layer having a film thickness of 0.1 μm or less on the coating surface. 10. The functional complex according to any one of 7. to 9 above, wherein the photocatalytic particles (a) are not present on the surface in contact with the substrate.</p>

<p> The photocatalyst of the present invention has excellent durability in which its surface exhibits photocatalytic activity and / or hydrophilicity for a long period of time when irradiated with light and maintains high transparency.</p>

Hereinafter, the present invention will be described in detail. The photocatalyst of the present invention comprises photocatalyst particles (a), a binder component (B) and an ultraviolet absorber (U), and the mass ratio (a) / (B) of the photocatalyst particles (a) and the binder component (B). Is 0.01 / 99.99 to 5/95. From the viewpoint of transparency, the mass ratio (a) / (B) of the photocatalyst particles (a) and the binder component (B) is preferably 5/95 or less, and from the viewpoint of photocatalytic activity and / or expression of hydrophilicity. The mass ratio (a) / (B) of the photocatalyst particles (a) is preferably 0.01 / 99.99 or more, and more preferably the mass ratio (a) / (B) is 0.1 / 99.9 to 5/95. More preferably, the mass ratio (a) / (B) is in the range of 0.3 / 99.7 to 5/95.

The total light transmittance of the photocatalyst of the present invention is 95% or more, and when used in an application requiring particularly high transparency, for example, a window film, a total light transmittance of 98% or more is preferable, and further. It is preferably 99% or more. In the present invention, the photocatalytic activity means that an oxidation or reduction reaction is caused by light irradiation. These photocatalytic activities can be determined, for example, by measuring the decomposability of organic substances such as dyes when the surface of the material is irradiated with light. A surface having photocatalytic activity exhibits excellent decomposition activity and stain resistance of contaminated organic substances.

Further, in the present invention, hydrophilicity preferably means a case where the contact angle of water at 20 ° C is 60 ° or less, but particularly on a surface having hydrophilicity with a contact angle of water of 20 ° or less, it rains. It is preferable because it exhibits stain resistance due to self-purification ability (self-cleaning) with water. From the viewpoint of exhibiting more excellent stain resistance and antifogging property, the contact angle of water on the surface is preferably 10 ° or less, more preferably 5 ° or less.

The photocatalyst of the present invention is preferably from a photocatalyst composition (C) containing photocatalyst particles (a) and a binder component (B) or a precursor (B') of the binder component (B) and an ultraviolet absorber (U). Can be formed. Here, the precursor (B') of the binder component (B) reacts with drying, heating, moisture absorption, light irradiation, etc. to form the binder component (B) contained in the photocatalyst of the present invention. Say.

In the present invention, the surface energy of the binder component (B) and / or its precursor (B') is preferably larger than that of the photocatalytic particles (a), and the relative difference in surface energy thereof is 2 mN / m or more. preferable. The larger the relative difference in surface energy, the greater the self-inclination of the distribution of the photocatalytic particles (a). Here, the self-tilt property means a structure in which the photocatalyst particles (a) have a concentration gradient of the photocatalyst particles (a) in the process of forming the photocatalyst, corresponding to the properties of the interface (interface energy, etc.) in contact with the photocatalyst. It means that it is formed autonomously, and especially when the photocatalyst is formed so as to be in contact with air, the photocatalyst particles (a) will be present in a large proportion on the surface of the photocatalyst in contact with air.

Further, since photocatalytic activity and / or hydrophilicity is expressed on the surface of the photocatalyst, it is preferable that a large amount of photocatalytic particles (a) is present on the surface of the film from the viewpoint of utilization efficiency of the photocatalyst particles (a), and a layer is formed on the surface of the film. It is more preferable to form. If the photocatalytic particles (a) are not present on the surface in contact with the base material, the base material is not violated even when the photocatalytic activity is exhibited, which is preferable.

Examples of the photocatalytic particles (a) that can be used in the present invention include, for example, TiO.₂, ZnO, SrTiO₃, CdS, GaP, InP, GaAs, BaTiO₃, BaTiO₄, BaTi₄O₉, K₂NbO₃, Nb₂O₅, Fe₂O₃, Ta₂O₅, K₃Ta₃Si₂O₃, WO₃, SnO₂, Bi₂O₃, BiVO₄, NiO, Cu₂O, SiC, MoS₂, InPb, RuO₂, CeO₂, Ta₃N₅Etc., and further, layered oxides having at least one element selected from Ti, Nb, Ta, and V (for example, JP-A-62-74452, JP-A-2-172535, JP-A-7-24329). Japanese Patent Application Laid-Open No. 8-89799, Japanese Patent Application Laid-Open No. 8-89800, Japanese Patent Application Laid-Open No. 8-89804, Japanese Patent Application Laid-Open No. 8-198061, Japanese Patent Application Laid-Open No. 9-248465, Japanese Patent Application Laid-Open No. 10-99694 , JP-A-10-244165, etc.).

Among these photocatalytic particles (a), TiO₂(Titanium oxide) is preferable because it is harmless and has excellent chemical stability. As titanium oxide, any of anatase, rutile, and brookite can be used. Further, when a visible light responsive photocatalyst capable of exhibiting photocatalytic activity and / or hydrophilicity by irradiation with visible light (for example, a wavelength of about 400 to 800 nm) is selected as the photocatalytic particle (a) used in the present invention, The photocatalyst body formed from the photocatalyst composition of the present invention is preferable because it can sufficiently exhibit antibacterial and antifouling effects even in a place such as a room where ultraviolet rays are not sufficiently irradiated.

Any of the above visible light responsive photocatalysts can be used as long as they exhibit photocatalytic activity and / or hydrophilicity with visible light. For example, TaON and LaTiO can be used.₂N, CaNbO₂N, LaTaON₂, CaTaO₂Oxynitride compounds such as N (see, for example, Japanese Patent Application Laid-Open No. 2002-66333) and Sm₂Ti₂S₂O₇Oxysulfide compounds such as (see, for example, Japanese Patent Application Laid-Open No. 2002-233770), Ta₃N₅Nitriding compounds such as CaIn₂O₄, SrIn₂O₄, ZnGa₂O₄, Na₂Sb₂O₆Titanium oxide precursors (titanium oxysulfate, titanium chloride, alkoxytitanium) in the presence of oxides containing metal ions in the d10 electronic state (see, for example, JP-A-2002-59008) and nitrogen-containing compounds such as ammonia and urea. Etc.) and nitrogen-doped titanium oxide obtained by firing high-surface titanium oxide (for example, JP-A-2002-29750, JP-A-2002-87818, JP-A-2002-154823, JP-A-2001-207082) (Refer to the publication), Sulfur-doped titanium oxide and titanium oxide obtained by firing titanium oxide precursors (titanium oxysulfate, titanium chloride, alkoxytitanium, etc.) in the presence of sulfur compounds such as thiourea are treated with hydrogen plasma or vacuum. Oxygen-deficient titanium oxide obtained by heat treatment underneath (see, for example, Japanese Patent Application Laid-Open No. 2001-98219), and photocatalyst particles are treated with a halogenated platinum compound (for example, Japanese Patent Application Laid-Open No. 2002-239353). A surface-treated photocatalyst obtained by treating with a tungsten alkoxide (see JP-A-2001-286755) and the like can be preferably mentioned. Among the above visible light responsive photocatalysts, the oxynitride compound, the oxysulfide compound, and the nitride compound have a large photocatalytic activity due to visible light and can be particularly preferably used.

Further, the above-mentioned photocatalytic particles (a) are preferably prepared by adding or immobilizing metals such as Pt, Rh, Ru, Nb, Cu, Sn, Ni, Fe and / or oxides thereof, or using porous calcium phosphate or the like. It can also be coated and used as a photocatalyst (see, for example, Japanese Patent Application Laid-Open No. 10-244166). As the form of the photocatalyst particles (a), any of powder, dispersion, and sol can be used. For the modification treatment with the modifier compound (b) in the present invention, it is preferable to use a photocatalyst sol or a photocatalyst dispersion for reasons of efficiency, uniformity and the like. Here, the photocatalyst sol and the photocatalyst dispersion used in the present invention contain photocatalyst particles in water and / or an organic solvent in an amount of 0.01 to 80% by mass, preferably 0.1 to 50% by mass as primary particles and / or secondary particles. It is distributed.

As the photocatalyst sol and the photocatalyst dispersion, the photocatalyst particles having a number average dispersion particle diameter of 400 nm or less of a mixture of primary particles and secondary particles (either primary particles or secondary particles may be used) are modified. It is desirable because the surface characteristics of the photocatalyst can be effectively used. In particular, when photocatalyst particles having a number average dispersion particle size of 100 nm or less are used, a film having excellent transparency can be obtained from the photocatalyst composition of the present invention, which is highly preferable. A photocatalyst sol and a photocatalyst dispersion liquid of 80 nm or less and 3 nm or more, more preferably 50 nm or less and 3 nm or more are preferably selected.

Here, examples of the organic solvent used in the photocatalyst sol or the photocatalyst dispersion include ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol, alcohols such as methanol, toluene, xylene and the like. Aromatic hydrocarbons, aliphatic hydrocarbons such as hexane, cyclohexane and heptane, esters such as ethyl acetate and n-butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran, dioxane and the like. Examples thereof include amides such as ethers, dimethylacetamide and dimethylformamide, halogen compounds such as chloroform, methylene chloride and carbon tetrachloride, dimethylsulfoxide, nitrobenzene and the like, and a mixture of two or more of these.

Taking a titanium oxide sol as an example of the photocatalytic sol, for example, a titanium oxide hydrosol in which water is substantially used as a dispersion medium and titanium oxide particles are deflated in the dispersion medium can be mentioned. Here, substantially using water as a dispersion medium means that the dispersion medium contains about 80% by mass or more of water. The preparation of such a sol is known and can be easily produced (see, for example, JP-A-63-17221, JP-A-7-819, JP-A-9-165218, JP-A-11-43327, etc.). ). For example, metatitanium acid produced by heating and hydrolyzing an aqueous solution of titanium sulfate or titanium tetrachloride is neutralized with aqueous ammonia, and the precipitated titanium hydroxide-containing is filtered, washed, and dehydrated to obtain aggregates of titanium oxide particles. Be done. Titanium oxide hydrosol can be obtained by degluing this agglutinate under the action of nitric acid, hydrochloric acid, ammonia or the like and performing hydrothermal treatment or the like. Further, an anatase-type titanium oxide sol having a particle surface modified with a peroxo group, which is excellent in dispersion stability even in an aqueous solution having a pH near neutral, can be easily obtained by, for example, the method proposed in JP-A-10-67516. Can be done. The titanium oxide hydrosol described above is also commercially available as a titania sol. (For example, "STS-02" manufactured by Ishihara Sangyo Co., Ltd .: product name, "TO-240" manufactured by Tanaka Transfer Co., Ltd .: product name, etc.)

Further, for example, a cerium oxide sol (see, for example, JP-A-8-59235) or a layered oxide sol having at least one element selected from the group consisting of Ti, Nb, Ta, and V (for example, JP-A-9-). Oxidation of various methods for producing photocatalytic sol such as JP-A-25123, JP-A-9-67124, JP-A-9-227122, JP-A-9-227123, JP-A-10-259023, etc.) It is known as well as titanium sol.

Further, a visible light responsive photocatalytic sol that can be suitably used in the present invention is also commercially available. (For example, "NTB-200" manufactured by Showa Denko Corporation, "TSS" manufactured by Sumitomo Chemical Co., Ltd., etc.) Further, in the photocatalyst organosol in which an organic solvent is substantially used as a dispersion medium and photocatalyst particles are dispersed therein, for example, the above-mentioned photocatalyst hydrosol is a compound having interphase transfer activity such as polyethylene glycols (different first phase and second phase). A third phase is formed at the interface with the phase, treated with a compound that dissolves and / or solubilizes the first, second, and third phases with each other) and diluted with an organic solvent (eg,). JP-A-10-167727), a method of preparing a sol by dispersing and transferring it in an organic solvent insoluble in water with an anionic surfactant such as sodium dodecylbenzenesulfonate (for example, JP-A-58-29863). It can be obtained by adding alcohols having a higher boiling point than water such as butyl cellosolve or butyl cellosolve to the photocatalyst hydrosol, and then removing the water by (reduced pressure) distillation or the like. Further, a titanium oxide organosol in which an organic solvent is substantially used as a dispersion medium and titanium oxide particles are dispersed therein is commercially available (for example, "TKS-251" manufactured by TAYCA CORPORATION: trade name). Here, substantially using an organic solvent as a dispersion medium means that the dispersion medium contains about 80% by mass or more of the organic solvent. The photocatalyst dispersion is obtained by dispersing the powder of the photocatalyst particles (a) described above in water and / or in an organic solvent under a strong shearing force by adding a dispersion stabilizer as needed. be able to.

The photocatalytic particles (a) of the present invention can be modified by using at least one modifier compound (b) described later. Since the surface energy of the photocatalytic particles (a) can be reduced by performing the modification treatment, the surface energy difference between the binder component (B) and / or its precursor (B') can be further increased. It is possible and preferable. In the present invention, the modification means that at least one modification agent compound (b), which will be described later, is immobilized on the surface of the photocatalytic particles (a). The immobilization of the above-mentioned modifier compound on the surface of the photocatalytic particles is considered to be due to physical adsorption by van der Waals force or chemical bonding. In particular, modification using a chemical bond is preferable because the interaction between the modifier compound and the photocatalyst is strong and the modifier compound is firmly immobilized on the surface of the photocatalyst particles.

In the present invention, the modifier compound (b) used for denaturing the photocatalyst particles (a) is a triorganosilane unit represented by the following formula (2) and a mono represented by the following formula (3). Oxydiorganosilane unit, dioxyorganosilane unit represented by the following formula (4), and methylene fluoride (-CF)₂-) Selected from the group consisting of units It is more preferable to be selected from the group consisting of compounds having at least one structural unit in terms of reducing surface energy. R₃Si- (2) (In the equation, R is an independently linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and a linear or branched alkyl group having 1 to 1 carbon atoms. Represents ~ 30 fluoroalkyl groups, linear or branched alkenyl groups with 2 to 30 carbon atoms, phenyl groups, alkoxy groups with 1 to 20 carbon atoms, or hydroxyl groups.)-(R₂SiO)-(3) (In the equation, R is as defined in equation (2).)

<chemistry num="1"><img file="JP2006297209A_D0001.tif" /></chemistry>(In the equation, R is as defined in equation (2).)

In the present invention, the modification treatment of the photocatalyst particles (a) with the denaturant compound (b) is carried out in the presence or absence of water and / or an organic solvent in the presence or absence of the above-mentioned photocatalyst particles (a) and the above-mentioned modifier compound. (b) is preferably mixed at a mass ratio of (a) / (b) = 1/99 to 99.99 / 0.01, more preferably (a) / (b) = 10/90 to 99.5 / 0.5, preferably. It can be obtained by heating at 0 to 200 ° C., more preferably 10 to 80 ° C., or by changing the solvent composition of the mixture by (decompression) distillation or the like.

Here, when the above modification treatment is performed, examples of the organic solvent that can be used include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane and heptane, ethyl acetate and n-butyl acetate. Esters such as ethylene glycol, butyl cellosolve, isopropanol, n-butanol, ethanol, methanol and other alcohols, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, tetrahydrofuran, dioxane and other ethers, dimethylacetamide, dimethyl Examples thereof include amides such as formamide, halogen compounds such as chloroform, methylene chloride and carbon tetrachloride, dimethylsulfoxide, nitrobenzene and the like, and mixtures of two or more of these.

Examples of the modifier compound (b) preferably used for modifying the photocatalyst particles (a) of the present invention include a SiH group, a hydrolyzable silyl group (alkoxysilyl group, hydroxysilyl group, and the like. Silicon compounds, fluoroalkyl compounds, which are reactive with photocatalyst particles (a) such as silyl halide groups, acetoxysilyl groups, aminoxysilyl groups), epoxy groups, acetoacetyl groups, thiol groups, acid anhydride groups, etc. Fluoroolefin polymers and the like can be mentioned. These compounds are more preferable because they can be chemically bonded to the photocatalytic particles (a) and are firmly immobilized on the surface of the photocatalyst particles (a).

Among the above modifiers, for example, compounds having a Si-H group include bis (trimethylsiloxy) methylsilane, bis (trimethylsiloxy) ethylsilane, bis (trimethylsiloxy) n-propylsilane, and bis (trimethylsiloxy) i-propyl. Silane, bis (trimethylsiloxy) n-butylsilane, bis (trimethylsiloxy) n-hexylsilane, bis (trimethylsiloxy) cyclohexylsilane, bis (trimethylsiloxy) phenylsilane, bis (triethylsiloxy) methylsilane, bis (triethylsiloxy) ethylsilane , Tris (trimethylsiloxy) silane, Tris (triethylsiloxy) silane, pentamethyldisiloxane, 1,1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,1,3,3,5 , 5,6,6-Nonamethyltetrasiloxane, trimethylsilane, ethyldimethylsilane, methyldiethylsilane, triethylsilane, phenyldimethylsilane, diphenylmethylsilane, cyclohexyldimethylsilane, t-butyldimethylsilane, di-t-butylmethyl Silane, n-octadecyldimethylsilane, tri-n-propylsilane, tri-i-propylsilane, tri-i-butylsilane, tri-n-hexylsilane, triphenylsilane, allyldimethylsilane, 1-allyl-1,1 , 3,3-Tetramethyldisiloxane, chloromethyldimethylsilane, 7-octenyldimethylsilane and the like.

Further, as the modifier compound (b) used in the present invention, for example, a SiH group, a hydrolyzable silyl group (alkoxysilyl group, hydroxysilyl group, halide silyl group, acetoxysilyl group, aminoxysilyl group) Etc.), reactive groups, polyoxyalkylene groups, sulfonic acid groups, carboxyl groups, phosphoric acid groups, etc. that can be expected to form chemical bonds with photocatalyst particles such as epoxy groups, acetoacetyl groups, thiol groups, acid anhydride groups, etc. A modified photocatalyst obtained by using a fluoroalkyl compound having 1 to 30 carbon atoms or a fluoroalkylene compound having a number average molecular weight of 100 to 1,000,000, which has a hydrophilic group that can be expected to have an affinity with photocatalyst particles (a). The surface energy of the above is very small, and the photocatalyst composition of the present invention is preferable because a photocatalyst having a large photocatalytic activity and excellent antibacterial and antifouling properties can be obtained.

Examples of the fluorine-based compound include a fluoroalkyl compound represented by the formula (5) and a fluoroolefin polymer represented by the formula (7). CF₃(CF₂)_g-Y- (V)_w (5) [In the formula, g represents an integer from 0 to 29. Y represents a w-valent organic group having a molecular weight of 14 to 50,000. w is an integer from 1 to 20. V consists of an epoxy group, a hydroxyl group, an acetoacetyl group, a thiol group, a cyclic acid anhydride group, a carboxyl group, a sulfonic acid group, a polyoxyalkylene group, a phosphoric acid group, and a group represented by the following formula (6). Represents at least one functional group selected from the group. -SiW_xR_y (6) (In the formula, W is an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxic group, Represents at least one group selected from the amide group. R is a linear or branched alkyl group with 1 to 30 carbon atoms, a cycloalkyl group with 5 to 20 carbon atoms, and an unsubstituted or substituted group. Represents at least one hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms substituted with an alkoxy group having 1 to 20 carbon atoms or a halogen atom. X represents 1 or more. It is an integer of 3 or less, and y is an integer of 0 or more and 2 or less. Also, x + y = 3.)]

<chemistry num="2"><img file="JP2006297209A_D0002.tif" /></chemistry>(In the formula, A¹~ A⁵May be the same or different, and indicates one selected from a fluorine atom, a hydrogen atom, a chlorine atom, an alkyl group having 1 to 6 carbon atoms, and a halo-substituted alkyl group having 1 to 6 carbon atoms, respectively. Y has a w-valent organic group having a molecular weight of 14 to 50,000 (a group having a w-valent other than the bond of the organic group Y with the main chain, preferably a group having a methylene fluoride unit, and more preferably a perfluoroalkyl group. Group). V is at least one functional group selected from the group consisting of an epoxy group, a hydroxyl group, an acetoacetyl group, a thiol group, a cyclic acid anhydride group, a carboxyl group, a sulfonic acid group, a polyoxyalkylene group and a hydrolyzable silyl group. Represents. k is an integer of 0 or more and 1000000 or less, and l is an integer of 1 or more and 100,000 or less. However, when k = 0, A is preferable.³~ A⁵At least one of the fluorine atoms, more preferably A³, A⁴Both represent a fluorine atom. w is an integer from 1 to 20. )

Specific examples of the above-mentioned fluorine-based compound include, for example, 2-perfluorooctylethyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluorooctylethylmethyldimethoxysilane, and trifluoromethylethyltrimethoxy. Fluoroalkylsilanes such as silane and trifluoromethylethyltriethoxysilane, nafion resin, fluoroolefins such as chlorotrifluoroethylene and tetrafluoroethylene, and epoxy groups, hydroxyl groups, carboxyl groups, acetoacetyl groups, thiol groups, and cyclic acids. Examples thereof include a copolymer with monomers having an anhydride group, a sulfonic acid group, a polyoxyalkylene group and the like (vinyl ether, vinyl ester, allyl compound, etc.). Further, in the present invention, as the modifier compound (b) used for denaturing the photocatalyst particles (a), the affinity between the long-chain alkyl group having 10 to 100 carbon atoms and the reactive group and / or the photocatalyst particles. A compound (b3) having a hydrophilic group that can be expected to have properties can also be used. Examples of the long-chain alkyl group-containing compound (b3) include nonionic surfactants such as alkylpolyoxyethylene ether, alkylpolyoxyethylene ether phosphate, alkylpolyoxyethylene ether sulfate, and alkylpolyoxyethylene phosphate. Examples thereof include anionic surfactants such as esters, alkylpolyoxyethylene sulfate esters, alkyl sulfates, alkylbenzene sulfonates, and alkylbenzene sulfonic acids.

Specific examples of these include sodium lauryl polyoxyethylene ether phosphate, sodium lauryl polyoxyethylene ether sulfate, lauryl polyoxyethylene phosphate ester, lauryl polyoxyethylene sulfate ester, sodium dodecyl benzene sulfonate, and sodium lauryl benzene sulfonate. Examples thereof include sodium dodecyl sulfate, sodium lauryl sulfate, dodecylbenzene sulfonic acid, and lauryl benzene sulfonic acid. These compounds can be used alone or in combination of two or more.

In the preferred form of the photocatalyst particles (a) modified with the modifier compound (b) in the present invention, the number average dispersed particle diameter of the mixture of the primary particles and the secondary particles of the modified photocatalyst is 800 nm or less, more preferably 1 nm. It is 400 nm or more, particularly preferably 5 nm or more and 100 nm or less. It is preferably in the form of a sol or dispersion. The state of the sol or the dispersion liquid can be preferably obtained by using the above-mentioned photocatalyst sol or the photocatalyst dispersion liquid as the photocatalyst particles (a) to be modified with the modifier compound (b). When the photocatalyst powder is modified with the modifier compound (b), it is preferable to disperse the photocatalyst powder in a solvent with a bead mill, a ball mill or the like after the modification treatment.

In the present invention, examples of the components that can be used for the binder component (B) and its precursor (B') include various monomers, synthetic resins, natural resins, etc., and after the formation of the photocatalyst, drying Examples thereof include those that are cured by heating, moisture absorption, light irradiation, and the like. Further, the form may be in a solvent-free state (pellets, powder, liquid, etc.) or in a form dissolved or dispersed in a solvent, and there is no particular limitation.

As the synthetic resin, all thermoplastic resins and curable resins (thermocurable resins, photocurable resins, moisture curable resins, etc.) can be used. For example, acrylic resins, methacrylic resins, alkyd resins, etc. Aminoalkyd resin, vinyl resin, polyester resin, styrene-butadiene resin, polyolefin resin, polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether ether ketone resin, polyphenylene oxide resin, polysulphon resin, polyphenylene sulfone resin , Polyether resin, Polyvinyl chloride resin, Polyvinylidene chloride resin, Urea resin, Phenolic resin, Melamine resin, Epoxy resin, Urethane resin, Silicon-acrylic resin, Silicone resin, Fluorine resin, Water glass and zirconium compound, Examples thereof include inorganic compounds such as titanium oxide. Examples of the natural polymer include cellulosic resins such as nitrocellulose, isoprene resins such as natural rubber, protein resins such as casein, and starch.

In the present invention, for the relative difference between the surface energy and the surface energy, refer to, for example, Polymer Handbook (published by A Wiley-interscience publication in the United States), the Japanese Industrial Standards wetting tension test (JIS-K-6768), and further. Can be preferably obtained by measuring by the following method or the like. For example, a base material having a film of a binder component (B) or its precursor (B') is prepared, deionized water is dropped, and the contact angle (θ) at 20 ° C is measured. The surface energy can also be obtained by the empirical formula of.

<maths num="1"><img file="JP2006297209A_D0003.tif" /></maths>[In the formula, γs represents the surface energy (mN / m) of the surface layer where the contact angle of deionized water is measured, and γl represents the surface energy of water {72.8 mN / m (20 ° C)}. ]

The binder component (B) and its precursor (B') used in the photocatalyst composition of the present invention have a surface energy of preferably 2 mN / m or more, more preferably 5 mN / m or more, as compared with the above-mentioned modified photocatalyst (a). If a larger one of 10 mN / m or more is selected, the self-tilt property becomes large, which is very preferable. Examples of the binder component (B) having a relatively large surface energy and its precursor (B') that can be used in the photocatalyst of the present invention include a phenyl group-containing silicone (BP) represented by the following formula (1). However, the siloxane bond (-O-Si-) forming its skeleton is most preferably used because it does not undergo oxidative decomposition due to photocatalytic action. R¹_pR²_qX_rSiO_{(4-pqr) / 2} (1) (In the formula, each R¹Represents a phenyl group, R²Independently represent a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched alkenyl group having 2 to 30 carbon atoms. X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an asyloxy group having 1 to 20 carbon atoms, an aminoxy group, an oxime group having 1 to 20 carbon atoms, and a halogen atom. And p, q, r and s are 0 &lt;p &lt;4, 0 q &lt;4, 0 r &lt;4 and 0 &lt;(p + q + r) &lt;4, and 0.05 p / (p + q) 1. )

Further, as the phenyl group-containing silicone (BP), the phenyl group-containing silicone (BP1) containing no alkyl group represented by the following formula (8) has a higher surface energy and is preferable. R¹_tX_uSiO_{(4-tu) / 2} (8) (In the formula, R¹Represents a phenyl group, and X independently represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an asyloxy group having 1 to 20 carbon atoms, an aminoxy group, an oxime group having 1 to 20 carbon atoms, and a halogen atom. .. And t, u are 0 &lt;t &lt;4, 0 u &lt;4, and 0 &lt;(t + u) &lt;4. )

The phenyl group-containing silicone (BP1) represented by the above formula (8), which is most preferable in terms of reactivity (good crosslinkability), is the number average obtained by polycondensing phenyltrialkoxysilane and / or phenyltrichlorosilane. It is a phenyl group-containing silicone having a number average molecular weight of 400 to 1000000 obtained by reacting an oligomer having a molecular weight of 300 to 5000 with an oligomer having a number average molecular weight of 100 to 3000 obtained by polycondensing tetraalkoxysilane and / or tetraalkoxysilane.

In the present invention, a silicone resin such as the above-mentioned phenyl group-containing silicone (BP) is contained as the binder component (B) and its precursor (B'), and the silicone resin has a hydroxysilyl group and / or hydrolysis. When it has a degradable silyl group, a conventionally known hydrolysis catalyst or curing catalyst can be added to the silicone resin at a ratio of preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass. As the hydrolysis catalyst, acidic hydrogen halide, carboxylic acid, sulfonic acid, acidic or weakly acidic inorganic salt, solid acid such as ion exchange resin and the like are preferable. The amount of the hydrolyzing catalyst is preferably in the range of 0.001 to 5 mol with respect to 1 mol of the hydrolyzable group on the silicon atom.

Examples of the curing catalyst include basic compounds such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, and tetramethylammonium hydroxide; tributylamine, diazabicycloundecene, and the like. Amine compounds such as ethylenediamine, diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane; titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate; aluminum- Aluminum compounds such as triisopropoxide, aluminum-triacetylacetonate, tris- (ethylacetoacetonato) aluminum, aluminum perchlorate, aluminum chloride; tin acetylacetonate, dibutyltin octylate, dibutyltin dilaurate, etc. Tin compounds; like zirconium-tetraacetylacetonate, tetra- (ethylacetoacetonate) zirconium, zirconium-tributoxy-acetylacetonate, zirconium-dibutoxy-diacetylacetonate, zirconium-dichloro-diacetylacetonate, tetrabutylzirconate Zirconium compounds; metal-containing compounds such as cobalt octylate, cobalt acetylacetonate, and iron acetylacetonate; acidic compounds such as phosphoric acid, nitrate, phthalic acid, p-toluenesulfonic acid, and trichloroacetic acid.

In the present invention, it is preferable to use a metal compound among the above-mentioned curing catalysts because it also exerts an effect as a reactivity improver for reactive groups as described above. Among them, it is preferable to use a zirconium compound, preferably zirconium-tetraacetylacetonate, because the hardness, chemical resistance, boiling water resistance, weather resistance and the like of the photocatalyst formed from the zirconium compound are further improved. The binder component (B) and its precursor (B') in the present invention include a hydroxyl group and / or an alkoxy group having 1 to 20 carbon atoms, an oxy group, an asyloxy group having 1 to 20 carbon atoms, an aminoxime group, and carbon. Acrylic polymers having a silyl group having a silicon atom bonded to at least one hydrolyzable group selected from the group consisting of several 1 to 20 oxime groups and halogen atoms at the end and / or side chain of the polymer molecular chain , The surface energy is relatively high and the weather resistance is excellent, so that it can be preferably used.

In the present invention, the binder component (F) selected from the silicone resin and the fluorine resin having a lower surface energy than the binder component (B) and its precursor (B') is mass ratio (F) / (B) =. Those containing in the range of 0.01 / 99.9 to 95/5, preferably (F) / (B) = 0.01 / 99.9 to 50/50, and more preferably (F) / (B) = 0.01 / 99.9 to 10/90 Since the binder component (F) has an action of promoting the self-tilt function of the photocatalyst particles (a), it becomes an excellent self-tilt type photocatalyst, which is very preferable.

Examples of the fluororesin that can be suitably used as the binder component (F) in the photocatalyst of the present invention include 2-perfluorooctylethyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, and 2-perfluorooctyl. Fluoroalkylsilanes such as ethylmethyldimethoxysilane, trifluoromethylethyltrimethoxysilane, trifluoromethylethyltriethoxysilane and their polycondensates, PTFE and polyvinylidene fluoride, as well as nafion resin, chlorotrifluoroethylene and tetrafluoro Examples thereof include a copolymer of fluoroolefins such as ethylene and monomers (vinyl ether, vinyl ester, allyl compound, etc.). These fluororesins can be used alone or in combination of two or more.

Further, in the photocatalyst of the present invention, examples of the silicone-based resin that can be suitably used as the binder component (F) include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, alkoxy group-containing silicone oil, and silanol group. Silicone oil containing silicone oil, silicone oil containing vinyl group, silicone oils such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, polyether-modified silicone, polyglycerin-modified silicone, amino-modified silicone, epoxy-modified silicone, mercapto-modified silicone, methacryl Modified silicones such as modified silicone, carboxylic acid modified silicone, fatty acid ester modified silicone, alcohol modified silicone, alkyl modified silicone, fluoroalkyl modified silicone, and (alkyl) alkoxy such as tetraethoxysilane, methyltriethoxysilane, and dimethyldiethoxysilane. Examples thereof include silane monomers, oligomers, and polymers, silane coupling agents such as vinyl trichlorosilane, vinyl trimethoxysilane, and γ-aminopropyltrimethoxysilane, reaction products thereof, and silicone surfactants. These silicones can be used alone or in combination of two or more.

When the above-mentioned phenyl group-containing silicone (BP) is used as the binder component (B) or its precursor (B') in the present invention, when phenylmethylpolysiloxane is used as the binder component (F), the film forming property is formed. , It is preferable because it is excellent in hardness, heat resistance, stain resistance, chemical resistance and the like.

The photocatalyst of the present invention is characterized by containing an ultraviolet absorber (U) in addition to the above-mentioned photocatalyst particles (a) and binder component (B). By containing the ultraviolet absorber (U), the photocatalyst of the present invention is extremely excellent in light resistance, weather resistance and the like. Further, the functional composite of the present invention in which the photocatalyst is formed as a film on the base material also has very high light resistance and weather resistance due to the effect of the ultraviolet absorber (U) contained in the photocatalyst. It will be excellent.

The effect of improving the weather resistance of the ultraviolet absorber (U) in the present invention is a structure that exhibits photocatalytic activity and / or hydrophilicity at a very small photocatalytic content in the photocatalyst of the present invention, that is, photocatalytic particles (a). Is effectively expressed by the structure that exists in a large proportion on the surface of the photocatalyst in contact with air. That is, in a photocatalyst having a high photocatalytic content, the ultraviolet absorber (U) itself is decomposed by the photocatalytic action, so that the effect of improving weather resistance cannot be effectively exhibited. The content of the ultraviolet absorber (U) in the photocatalyst of the present invention is not limited as long as it can improve the weather resistance without inhibiting the development of photocatalytic activity and / or hydrophilicity. For example, the photocatalyst. Is preferably contained in an amount of 0.001 to 10% by mass, preferably 0.01 to 5% by mass.

As the ultraviolet absorber (U) that can be used in the present invention, benzophenone-based, benzotriazole-based, and triazine-based ultraviolet absorbers can be preferably exemplified. Specific examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4. -n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2' -Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy- 4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-stearyloxybenzophenone, octabenzophenone, and 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acry Loxybenzophenone, 2-hydroxy-5-methacryloxybenzophenone, 2-hydroxy-4- (acryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-diethoxy) Examples thereof include polymerizable benzophenone-based ultraviolet absorbers such as benzophenone and 2-hydroxy-4- (acryloxy-triethoxy) benzophenone, and (co) polymers thereof.

Specifically, as the above-mentioned benzotriazole-based ultraviolet absorber, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-tert-butylphenyl) benzo Triazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy- 3,5-Di-tert-octylphenyl) benzotriazole, 2- [2'-hydroxy-3', 5'-bis (α, α'-dimethylbenzyl) phenyl] benzotriazole), methyl-3- [3 -tert-Butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] Condensate of propionate and polyethylene glycol (molecular weight 300) (manufactured by Nippon Ciba Geigy Co., Ltd., product name: TINUVIN-1130) , Isooctyl-3- [3- (2H-benzotriazole-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate (manufactured by Nippon Ciba Geigy Co., Ltd., product name: TINUVIN-384), 2-( 3-Dodecyl-5-Methyl-2-hydroxyphenyl) Bentriazole (manufactured by Nippon Ciba Geigy Co., Ltd., product name: TINUVIN-571), 2- (2'-hydroxy-3'-tert-butyl-5'-methyl Phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole , 2- [2'-Hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidemethyl) -5'-methylphenyl] benzotriazole, 2,2-methylenebis [4- (1,1, 1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by Nippon Ciba Geigy Co., Ltd., product name: TINUVIN-900), and 2- (2'-hydroxy-5'-methacryloxyethyl phenyl) -2H- Benzotriazole (manufactured by Otsuka Chemical Co., Ltd., product name: RUVA-93), 2- (2'-hydroxy-5'-methacryloxyethyl-3-tert-butylphenyl) -2H-benzotriazole, 2- (2) '-Hydroxy-5'-Methacryloxypropyl-3-tert-butylphenyl) -5-chloro-2H-benzotriazole, 3-methacryloyl-2-hydroxypropyl-3- [3'-(2 "-benzotriazole" Zoryl) -4-Hydroxy-5-tert-butyl] Phenylpropionate (manufactured by Nippon Ciba Geigy Co., Ltd., product name: CGL-104) and other polymerizable benzotriazole-based ultraviolet absorbers and their (co) polymerization In addition to products, TINUVIN-384-2 (product name, manufactured by Nippon Ciba Geigy Co., Ltd.), TINUVIN-99-2 (product name, manufactured by Nippon Ciba Geigy Co., Ltd.), TINUVIN-109 (product name, manufactured by Nippon Ciba Geigy Co., Ltd.) , TINUVIN-328 (product name, manufactured by Nippon Ciba Geigy Co., Ltd.), TINUVIN-928 (product name, manufactured by Nippon Ciba Geigy Co., Ltd.), etc.In addition to polymerizable benzotriazole-based ultraviolet absorbers such as CGL-104) and their (co) polymers, TINUVIN-384-2 (product name, manufactured by Nippon Ciba Geigy Co., Ltd.), TINUVIN-99-2 (product) Name, Nippon Ciba Geigy Co., Ltd., TINUVIN-109 (Product name, Japan Ciba Geigy Co., Ltd.), TINUVIN-328 (Product name, Japan Ciba Geigy Co., Ltd.), TINUVIN-928 (Product name, Japan Ciba Geigy Co., Ltd.) (Made by Co., Ltd.) and the like.In addition to polymerizable benzotriazole-based ultraviolet absorbers such as CGL-104) and their (co) polymers, TINUVIN-384-2 (product name, manufactured by Nippon Ciba Geigy Co., Ltd.), TINUVIN-99-2 (product) Name, Nippon Ciba Geigy Co., Ltd., TINUVIN-109 (Product name, Japan Ciba Geigy Co., Ltd.), TINUVIN-328 (Product name, Japan Ciba Geigy Co., Ltd.), TINUVIN-928 (Product name, Japan Ciba Geigy Co., Ltd.) (Made by Co., Ltd.) and the like.

Specific examples of the triazine-based ultraviolet absorber that can be used in the present invention include TINUVIN-400 (product name, manufactured by Nippon Ciba Geigy Co., Ltd.) and TINUVIN-411L (product name, manufactured by Nippon Ciba Geigy Co., Ltd.). Further, among the photocatalysts of the present invention, those further containing a photostabilizer (H) such as hindered amine type and / or hindered phenol type have the photocatalyst and function of the present invention due to the synergistic effect with the above ultraviolet absorber. The sex complex is preferable because it exhibits excellent weather resistance and light resistance.

The content of the photostabilizer (H) in the photocatalyst of the present invention is not limited as long as it can improve the weather resistance without inhibiting the development of photocatalytic activity and / or hydrophilicity, but for example, the photocatalyst. It is preferably contained in an amount of 0.001 to 10% by mass, preferably 0.01 to 5% by mass. Specific examples of hindered amine-based light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethylpiperidyl) sebacate, and bis (1, 2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, 1-[2- [3- (3,,) 5-Di-tert-butyl-4-hydroxyphenyl) propynyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxy] -2,2,6, A mixture of 6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-sevacate (Nippon Ciba Geigy) Made by Co., Ltd., Product name: TINUVIN-292), Bis (1-Octoxy-2,2,6,6-Tetramethyl-4-piperidyl) Sevacate, TINUVIN-123 (Product name, manufactured by Nippon Ciba Geigy Co., Ltd.) , TINUVIN-111FDL (product name, manufactured by Nippon Ciba Geigy Co., Ltd.), TINUVIN292 (product name, manufactured by Nippon Ciba Geigy Co., Ltd.), and 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2 , 2,6,6-Pentamethyl-4-piperidyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2, 2,6,6-Pentamethyl-4-iminopiperidyl methacrylate, 2,2,6,6,-tetramethyl-4-iminopiperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl Examples thereof include polymerizable hindered amine-based ultraviolet absorbers such as methacrylate, 4-cyano-1,2,2,6,6-pentamethyl-4-piperidyl methacrylate and their (co) polymers.

Specific examples of the hindered phenolic light stabilizer include bis (3,5-tert-butyl) -4-hydroxytoluene, TINUVIN-144 (product name, manufactured by Nippon Ciba Geigy Co., Ltd.) and the like. it can. The photocatalyst composition for obtaining the photocatalyst of the present invention may be in a solvent-free state (liquid, solid) or in a solvent-dissolved or dispersed state, and is not particularly limited, but is used as a coating agent. In this case, a state of being dissolved or dispersed in a solvent is preferable from the viewpoint of adjusting the viscosity. At this time, the total amount of the photocatalyst particles (a), the binder component (B), its precursor (B'), and the ultraviolet absorber (U) in the photocatalyst composition is preferably 0.01 to 95% by mass, more preferably. It is 0.1 to 70% by mass.

The photocatalytic composition of the present invention can contain a compound having a boiling point of 150 ° C. or higher and a molecular weight of 1000 or lower. By blending a compound having a boiling point of 150 ° C or higher and a molecular weight of 1000 or lower, the influence of the environment (temperature, humidity, coating conditions, etc.) in the photocatalytic body formation process becomes smaller, and the above-mentioned self regarding the photocatalyst particles (a) It is possible to further improve the formation reproducibility of the gradient photocatalyst. In the photocatalytic composition of the present invention, examples of the compound having a boiling point of 150 ° C. or higher and a molecular weight of 1000 or less include various solvents and plasticizers having a boiling point of 150 ° C. or higher.

Examples of the solvent include alcohols such as butyl cellosolve, butyl carbitol, propylene glycol, propylene glycol monoethyl ether and propylene glycol monobutyl ether, hydrocarbons such as decane, undecane, dodecane and sorbesso, and esters such as cellosolve acetate. Examples include ketones such as cyclohexanone, ethers such as diethyl carbitol and dibutyl carbitol, amides such as dimethylacetamide and dimethylformamide, and dimethylsulfoxide. These solvents are used alone or in combination.

Examples of the plasticizer include aliphatic dibasic acid esters such as di (2-ethylhexyl) adipate, phosphate triesters such as tri-phosphate (2-ethylhexyl), glycol esters, and dibutylphthalates. , Di-n-octylphthalate, phthalates such as dilaurylphthalate, tetraline paraffin, isoparaffin and the like.

At this time, as the solvent for adjusting the viscosity used in the photocatalyst composition of the present invention, a solvent having a boiling point of 150 ° C. or less can be mentioned in addition to the above-mentioned solvent. Examples of these include water, alcohols such as ethylene glycol, isopropanol, n-butanol, ethanol and methanol, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane and heptane, and acetic acid. Examples thereof include esters such as ethyl and n-butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane. These solvents are used alone or in combination. Further, in the photocatalyst composition of the present invention, if necessary, components usually added to and blended with paints and molding resins, such as pigments, curing catalysts, cross-linking agents, fillers, dispersants, wetting agents, thickeners, etc. Rheology control agents, antifoaming agents, plasticizers, film forming aids, rust preventives, dyes, preservatives and the like can be selected and combined according to their respective purposes.

The photocatalyst of the present invention is preferably in the form of a film or a molded product. When the photocatalyst body in the present invention is formed into a film, the above photocatalyst composition is applied to a substrate, dried, and then preferably 20 ° C to 500 ° C, more preferably 40 ° C to 250 ° C. It can be obtained by forming a film on the base material by performing heat treatment, irradiation with ultraviolet rays, or the like. Examples of the coating method include a spray spraying method, a flow coating method, a roll coating method, a brush coating method, a dip coating method, a spin coating method, a screen printing method, a casting method, a gravure printing method, a flexographic printing method and the like. ..

When the photocatalyst of the present invention is formed on a substrate as a film, the thickness of the film is preferably 0.1 to 100 μm. The thickness is preferably 100 μm or less from the aspect of transparency, and preferably 0.1 μm or more from the aspect of substrate protection. More preferably, it is 0.5 to 50 μm. Although the term film is used in the present specification, it does not necessarily have to be a continuous film, and may be in the form of a discontinuous film, an island-shaped dispersion film, or the like. The surface of the functional composite having the film of the photocatalyst of the present invention on the substrate thus obtained exhibits photocatalytic activity and / or hydrophilicity, and further has a photoelectric conversion function by light irradiation. Is possible. That is, in another aspect of the present invention, as the photocatalyst formed from the photocatalyst composition, a molded product or a functional composite having a film on a substrate is provided.

The base material used to obtain the functional composite of the present invention is not particularly limited, and for example, all the base materials used for the purposes disclosed in the present invention can be used. Examples of the base material used for obtaining the functional composite of the present invention include organic base materials such as synthetic resin and natural resin, inorganic base materials such as metal, ceramics, glass, stone, cement and concrete, and A combination thereof and the like can be mentioned. In the functional composite of the present invention, the durability is extremely excellent even when an organic base material that decomposes with a photocatalyst is used. That is, the photocatalyst of the present invention can provide a functional composite having excellent durability even for an organic base material which has not been conventionally used due to a problem of durability.

The method for producing the functional composite of the present invention is not limited to the case of forming the photocatalyst of the present invention on a substrate. The base material and the photocatalytic composition of the present invention may be molded at the same time, for example, integrally molded. Further, after molding the photocatalyst composition of the present invention, the base material may be molded. Further, the photocatalyst composition of the present invention and the base material may be individually molded and then adhered, fused, or the like to form a functional composite. When molding is performed by the above method without contacting the original base material, another base material may be used. The base material in this case is not limited to a solid, and may be a liquid or a gas as long as the effects of the present invention are not impaired. If necessary, the molded product or functional composite of the present invention can be made into a film, a sheet, a block, a pellet, or a molded product having a more complicated shape by the method used for resin molding. In molding, it can be used in combination with other resins as long as the effects of the present invention are not impaired.

The molding method for the present invention can be an extrusion molding method, an injection molding method, a press molding method, or the like. In addition, a calendar molding method is also possible depending on the selection of the resin, such as using a thermoplastic resin in combination. Further, organic fibers including natural fibers, inorganic fibers such as glass (including these woven fabrics) are used as reinforcing materials to impregnate the molded product or functional composite of the present invention, and a mixture thereof with other resins. , Laminate molding is also possible.

The molded product or functional composite of the present invention may also be fibrous. In order to process into a fibrous form, a usual spinning method can be used as long as the effect of the present invention is not impaired. As the spinning method, melt spinning and solution spinning are used. When spinning, it can be processed into a fibrous form by using it together with the other resins described above. For example, a conventional resin (thermoplastic resin is preferable for molding), for example, polyester, nylon, etc., blended with the molded product or functional composite of the present invention, or with the molded product or functional composite of the present invention. These resins may be composite-spun (sheath core, side-by-side type, etc.).

The fibers may be long fibers or short fibers, and may be uniform in the length direction or thick and thin, and the cross-sectional shape may be round, triangular, L-shaped, T-shaped, Y-shaped, W-shaped, or Yaba. It may be a polygonal type such as a type, a flat type, a dogbone type, a multi-leaf type, a hollow type, or an amorphous type. The fibrous molded product or functional composite of the present invention can also be used as a woven fabric or a non-woven fabric (short fiber or long fiber).

In addition, the morphology of the fibers that can be used includes threads, cheese-like fibers that are aggregates of threads, woven fabrics, knitted fabrics, non-woven fabrics, and the like, and may be mixed with fibers of other resins. The form of the yarn includes raw yarn, false twisted yarn (including drawn false twisted yarn), pre-twisted false twisted yarn, air injection processed yarn, ring spun yarn, spun yarn such as open end spun yarn, and multifilament yarn (ultrafine yarn). ), Mixed yarn and the like. The fibers to be mixed include elastic fibers such as polyester fibers, polyamide fibers, polyacrylic fibers, polyvinyl fibers, polypropylene fibers, and polyurethane fibers (metal oxides typified by magnesium oxide and zinc oxide, and metals). Synthetic fibers such as (including those to which a chlorine water deterioration inhibitor such as hydroxide is added), natural fibers such as cotton, linen, wool and silk, cellulose fibers such as cupra, rayon and polynosic, and acetate fibers Can be mentioned. The molded product or functional composite of the present invention processed into a fibrous form can be used for clothing, gas, and liquid filters for the purpose of antibacterial, antifouling, deodorant, and toxic gas decomposition.

The photocatalyst of the present invention, or the above-mentioned functional composite in which the photocatalyst is immobilized on a substrate, is hydrophobic or hydrophilic by irradiating light with an energy higher than the band gap energy of the photocatalyst contained therein. / Or shows photocatalytic activity and further photoelectric conversion function. Further, the photocatalyst particles (a) in the photocatalyst are represented by the above-mentioned triorganosilane unit represented by the formula (1), the monooxydiorganosilane unit represented by the formula (2), and the formula (3). Photocatalytic particles (a) are modified with at least one modifier compound (b) selected from the group consisting of compounds having at least one structural unit selected from the group consisting of dioxyorganosilane units. In some cases, at least a part of the organic group (R) bonded to the silicon atom of the modifier compound (b) existing in the vicinity of the photocatalyst particle (a) by irradiation with excitation light is replaced with a hydroxyl group by the decomposition action of the photocatalyst. To. As a result, the hydrophilicity of the surface of the photocatalyst of the present invention is increased, and when the generated hydroxyl groups undergo a dehydration condensation reaction to form a siloxane bond, the hardness of the photocatalyst becomes extremely high. Such a state is preferable in the mode of the present invention.

Similarly, when the above-mentioned silicone-based resin is used as the binder component (B), at least a part of the organic groups bonded to the silicon atoms of the silicone existing in the vicinity of the photocatalyst particles (a) by irradiation with excitation light is removed. When the photocatalyst is replaced with a hydroxyl group by the decomposition action of the photocatalyst, the hydrophilicity of the surface of the photocatalyst of the present invention is enhanced, and the dehydration condensation reaction between the generated hydroxyl groups proceeds to form a siloxane bond, the hardness of the photocatalyst is extremely high. Will be expensive. Such a state is preferable in the mode of the present invention. In the present invention, as a light source of light having an energy higher than the band gap energy of the photocatalyst particles (a), in addition to light obtained in a general residential environment such as sunlight and indoor lighting, a black light, a xenon lamp, and a mercury lamp , LED, etc. light can be used.

The photocatalyst or functional complex of the present invention having photocatalytic activity such as decomposition of organic substances exhibits various functions such as antibacterial, antifouling, deodorant, and NOx decomposition, and purifies the environment such as air and water. It can be used for such purposes. The photocatalyst or functional composite of the present invention, which is hydrophilic (hydrophilic membrane and hydrophilic film) having a contact angle with water at 20 ° C of 60 ° or less (preferably 10 ° or less) by light irradiation. The base material coated with the hydrophilic film) can be applied to antifogging technology for preventing fogging of mirrors and glass, as well as antifouling technology and antistatic technology for building exteriors and the like.

Examples of applications of the photocatalyst or functional composite of the present invention to the field of antifouling technology include building materials, building exteriors, building interiors, window frames, windowpanes, structural members, housing and other building equipment, especially toilet bowls. Bathtubs, washbasins, lighting fixtures, lighting covers, kitchen utensils, tableware, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, etc. It can be used and is effective for use in parts that require transparency such as vehicle lighting covers, windowpanes, instruments, display panels, etc., and also for exteriors of machinery and articles, dustproof covers and paintings, display equipment, etc. Its covers, traffic signs, various display devices, display objects such as advertising towers, sound insulation walls for roads and railways, bridges, guard rail exteriors and paints, tunnel interiors and paints, glass, solar cell covers, solar water heaters Exterior parts of electronic and electrical equipment used outside such as covers, especially transparent parts, vinyl houses, exteriors such as greenhouses, especially transparent parts, and environments that may be contaminated even indoors, such as for medical use Applications such as physical education facilities and equipment can be mentioned.

Examples of applications of the photocatalyst or functional composite of the present invention to the field of antifogging technology include mirrors (rear confirmation mirrors for vehicles, bathroom mirrors, washroom mirrors, dental mirrors, road mirrors, etc.) and lenses. (Eyeglass lenses, optical lenses, illumination lenses, semiconductor lenses, copying machine lenses, rearview camera lenses for vehicles, etc.), prisms, window glasses for buildings and ring-viewing towers, window glasses for vehicles (automobiles, railroad vehicles, aircraft) , Ships, submersibles, snow vehicles, ropeway gondola, amusement park gondola, spacecraft, etc.), windshields for vehicles (automobiles, motorcycles, railroad vehicles, aircraft, ships, submersibles, snow vehicles, snowmobiles, ropeways, etc. Gondolas, amusement park gondola, spacecraft, etc.), protective goggles, sports goggles, protective mask shields, sports mask shields, helmet shields, frozen food display case glass, thermal insulation food display case glass , Measuring equipment cover, Rear view camera lens cover for vehicles, Focusing lens for laser dental treatment equipment, Laser light detection sensor cover such as inter-vehicle distance sensor, Infrared sensor cover, Camera filter, etc. be able to.

Examples of applications of the photocatalyst or functional composite of the present invention to the field of antistatic technology include brown tubes, magnetic recording media, optical recording media, optical magnetic recording media, audio tapes, video tapes, analog records, and household applications. Housing, parts, exterior and painting of electrical products, housing, parts, exterior and painting of OA equipment products, building materials, building exterior, building interior, window frames, windowpanes, structural members, exterior and painting of vehicles, machinery and articles Applications such as exterior, dustproof cover and painting can be mentioned.

Examples of applications of the photocatalyst or functional complex of the present invention in the fields of antibacterial and antifungal technology include building materials, building exteriors, building interiors, window frames, structural members, and building equipment such as houses, especially toilet bowls and bathtubs. Washbasins, lighting fixtures, lighting covers, kitchen utensils, tableware, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods, ventilators, cupboards, cupboards, bathroom and washroom walls, ceilings, doorknobs, and even For hygiene management in medical and public facilities, for example, parts in hospitals, various parts of ambulances, food / pharmaceutical factories, public facilities such as schools / gymnasiums / stations, public baths, public toilets, inns, hotels, etc. Examples of applications include wall surfaces, floors and ceilings, furniture, fixtures, and door knobs in various places. In particular, it can be widely used for members in hospitals as a method for preventing nosocomial infections. The members in the hospital include floors, walls, ceilings, handrails, door handles, water faucets, etc. in places where an unspecified number of things come into contact, such as hospital rooms, examination rooms, corridors, stairs, elevators, waiting rooms, and washrooms. , Various medical equipment and the like. In addition, antibacterial and antifungal properties can be effectively imparted not only to hospitals but also to various members in places requiring hygiene such as ambulances, food storage rooms, and food cooking rooms. The photocatalyst or functional composite of the present invention having a photoelectric conversion function can exhibit functions such as power conversion of solar energy, and is an optical semiconductor electrode used for a (wet) solar cell or the like. It can be used for such purposes.

The present invention will be described in more detail with reference to the following Examples, Reference Examples and Comparative Examples, but these do not limit the scope of the present invention in any way. In Examples, Reference Examples and Comparative Examples, various physical properties were measured by the following methods. 1. Number average particle size The sample was diluted with an appropriate solvent so that the photocatalyst content in the sample was 1 to 20% by mass, and measured using a wet particle size analyzer (Microtrac UPA-9230, manufactured by Nikkiso).

2. Number average molecular weight Obtained by gel permeation chromatography (GPC) using a calibration curve prepared using a polystyrene standard. The conditions of GPC are as follows. Equipment: Tosoh HLC-8020LC-3A type chromatograph Column: TSKgel G1000H_XL, TSKgelG2000H_XLAnd TSKgel G4000_XL(Both manufactured by Tosoh) were connected in series and used.

Data processing equipment: CR-4A type data processing equipment manufactured by Shimadzu Corporation Mobile phase: tetrahydrofuran (used for analysis of phenyl group-containing silicone) Toluene (used for analysis of phenyl group-free silicone) Flow velocity: 1.0 ml / min -Sample preparation method Diluted with the solvent used for the mobile phase (concentration was adjusted appropriately in the range of 0.5 to 2% by weight) and used for analysis.

3. Infrared absorption spectrum Measured using an FT / IR-5300 infrared spectrometer manufactured by JASCO Corporation. 4. Film hardness Obtained as pencil hardness (scratch on the film) according to JIS-K-5400. 5. Film hardness after UV irradiation The film surface was irradiated with light from Toshiba Lighting &amp; Technology's FL20SBLB type black light for 7 days, and then measured by the method in 4. above. At this time, measurement was performed using a UVR-2 type UV intensity meter manufactured by Topcon, Japan {using a UD-36 type light receiving part manufactured by Topcon, Japan (corresponding to light with a wavelength of 310 to 400 nm) as a light receiving part}. UV intensity is 1mW / cm²It was adjusted to be.

6. Transparency The haze value and total light transmittance were measured according to JIS-K-7105 using a turbidity meter NDH2000 manufactured by Nippon Denshoku Kogyo. 7. Angle of contact of water with respect to the surface of the film A drop of deionized water was placed on the surface of the film, left at 20 ° C for 1 minute, and then measured using a CA-X150 contact angle meter manufactured by Kyowa Interface Science. The smaller the contact angle of water with the film, the more hydrophilic the surface of the film. 8. Changes in hydrophilicity (hydrophobicity) of the film surface before and after irradiation with ultraviolet rays After irradiating the surface of the film with ultraviolet rays by the method of 6. above for 7 days, the contact angle of water was measured by the method of 7. above. ..

9. Photocatalytic activity After applying a 5% by mass ethanol solution of methylene blue to the surface of the film, it was irradiated with ultraviolet rays for 5 days by the method of 5. above. Then, the activity of the photocatalyst was evaluated in the following three stages based on the degree of decomposition of methylene blue by the action of the photocatalyst (visually evaluated based on the degree of fading of the film surface). : Methylene blue is completely decomposed. Δ: A slight blue color of methylene blue remains. ×: Almost no decomposition of methylene blue was observed.

10. Weather resistance (transparency) An exposure test (black panel temperature 63 ° C, rainfall 18 minutes / 2 hours) was conducted using a sunshine weather meter manufactured by Suga Test Instruments. The contact angle and transparency of water after 2000 hours of exposure were evaluated. 11. Stain resistance The test board was attached to the fence facing the general road (truck traffic of about 500 to 1000 vehicles / day) for 3 months, and then the degree of pollution was visually evaluated.

[Reference example 1]

[Synthesis of phenyl group-containing silicone (BP)] After adding 26.0 g of phenyltrichlorosilane to 78 g of dioxane placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, the mixture was stirred at room temperature for about 10 minutes. A mixed solution consisting of 3.2 g of water and 12.9 g of dioxane was added dropwise over about 30 minutes while keeping the reaction solution at 10 to 15 ° C, and then stirred at 10 to 15 ° C for about 30 minutes, followed by The reaction solution was heated to 60 ° C. and stirred for 3 hours. The temperature of the obtained reaction solution was lowered to 25 to 30 ° C., 392 g of toluene was added dropwise over about 30 minutes, the temperature of the reaction solution was raised to 60 ° C. again, and the mixture was stirred for 2 hours.

The temperature of the obtained reaction solution was lowered to 10 to 15 ° C, and 19.2 g of methanol was added over about 30 minutes. After that, 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. A phenyl group-containing silicone (BP1) having a ladder-skeleton having a number average molecular weight of 1200 was obtained by distilling off the solvent from the obtained reaction solution under reduced pressure at 60 ° C. The obtained phenyl group-containing silicone (BP1) has an absorption (1130 cm) derived from the expansion and contraction vibration of the ladder-skeleton in the IR spectrum.^-1And 1037 cm^-1) Was observed.

Subsequently, 100 g of the above-mentioned phenyl group-containing silicone (BP1) was added to 100 g of toluene placed in a reactor having a reflux condenser, a thermometer and a stirrer, and the mixture was stirred at room temperature for about 10 minutes. To this, 50 g of a tetramethoxysilane oligomer (with a methoxy group content of 65% by mass) and 7.5 g of dibutyl tin dilaurate were added. Then, the reaction solution was heated to 80 ° C. and stirred for 3 hours, and then 125 g each of toluene and ethanol were added to the reaction solution to obtain a phenyl group-containing silicone (BP2) solution. The obtained phenyl group-containing silicone (BP2) had a number average molecular weight of 4300.

[Reference example 2]

[Synthesis of denaturated photocatalytic particles (a)] Number average particles by adding 4 g of sodium lauryl polyoxyethylene ether sulfate to 20 g of anatase-type titanium oxide particles obtained by hydrothermal synthesis, and adding 27 g of isopropanol and 68 g of toluene. A long-chain alkyl-modified treated titanium oxide organosol (a1) having a diameter of 12 nm was obtained.

[Reference example 3]

[Synthesis of modified photocatalyst particles (a)] 45 g of long-chain alkyl modified titanium oxide organosol (a1) prepared in Reference Example 2 was placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and screwed therein. By adding 1 g of (trimethylsiloxy) methylsilane at 40 ° C for about 5 minutes and continuing stirring at 40 ° C for 12 hours, a silicon-denatured photocatalyst organosol (a2) having a number average particle size of 17 nm was obtained. It was. At this time, the amount of hydrogen gas generated by the reaction of bis (trimethylsiloxy) methylsilane was 90 ml at 23 ° C. Moreover, when the obtained modified titanium oxide organosol was coated on a KBr plate and the IR spectrum was measured, the absorption of Ti-OH groups (3630 to 3640 cm) was observed.^-1) Disappeared.

[Example 1]

Toluene 12.55 g, isopropanol 9.5 g, and cyclohexanone 8.5 g were added to 18.1 g of the phenyl group-containing silicone (BP2) synthesized in Reference Example 1, and TINUVIN-400 {trade name (manufactured by Ciba Geigy Japan)} 0.018 g as an ultraviolet absorber. And TINUVIN-384-2 {trade name (manufactured by Japan Ciba Geigy)} After adding 0.018 g and stirring at room temperature, 1.1 g of X-1044 {tetrakis (acetylacetonato) zirconium 20% by mass solution (mass ratio is Toluene / methanol = 5/1) trade name (manufactured by Matsumoto Pharmaceutical Co., Ltd.)} was added. To this, 0.19 g of the long-chain alkyl-modified treated titanium oxide organosol (a1) prepared in Reference Example 2 was added under stirring at room temperature to obtain a photocatalyst composition (C-1). The photocatalyst composition (C-1) is spray-coated on a 10 cm × 10 cm acrylic resin plate (thickness 2 mm) so that the film thickness is 2 μm, dried at room temperature for 30 minutes, and heated at 80 ° C for 30 minutes. As a result, a test plate (G-1) having a photocatalyst-containing film was obtained.

The obtained test plate (G-1) having a photocatalyst-containing film had an average pencil hardness of 2B and an average contact angle with water of 85 °. In addition, the transparency had an average haze value of 0, a total light transmittance of 100%, and the transparency of the appearance was also good. The contact angle of water after irradiation with ultraviolet rays (black light) on the obtained test plate (G-1) having a photocatalyst-containing film was 0 °. Furthermore, the pencil hardness was F, and the result of photocatalytic activity evaluation was also very good ().

In addition, as a result of the stain resistance evaluation of the obtained test plate (G-1), no stain was found, and the stain resistance was very good. Furthermore, the transparency by the exposure test (after 2000 hours) by the Dew Panel optical control weather meter was 0.8 on average, there was almost no change in appearance, and the contact angle of water was 0 °, showing very good weather resistance. It was. As a result of observing the coating cross section of the obtained test plate (G-1) with a transmission electron microscope (TEM), almost no photocatalyst particles were present at the interface between the photocatalyst-containing coating and the acrylic resin as the base material. , It was observed that modified photocatalyst particles were present on the surface of the photocatalyst-containing film.

[Example 2]

Toluene 12.55 g, isopropanol 9.5 g, and cyclohexanone 8.5 g were added to 18.1 g of the phenyl group-containing silicone (BP2) synthesized in Reference Example 1, and TINUVIN-400 {trade name (manufactured by Ciba Geigy Japan)} 0.018 g as an ultraviolet absorber. Toluene-123 {trade name (manufactured by Ciba Geigy Japan)} 0.018 g was added as a light stabilizer, and after stirring at room temperature, 1.1 g of X-1044 {tetrakis (acetylacetonato) zirconium 20% by mass solution (mass) A trade name (manufactured by Matsumoto Pharmaceutical Co., Ltd.) with a ratio of toluene / methanol = 5/1)} was added. To this, 0.19 g of the silicon-modified photocatalyst organosol (a2) prepared in Reference Example 3 was added under stirring at room temperature to obtain a photocatalyst composition (C-2). The photocatalyst composition (C-2) is spray-coated on a 10 cm × 10 cm acrylic resin plate (thickness 2 mm) so that the film thickness is 2 μm, dried at room temperature for 30 minutes, and heated at 80 ° C for 30 minutes. As a result, a test plate (G-2) having a photocatalyst-containing film was obtained.

The average pencil hardness of the obtained test plate (G-2) having a photocatalyst-containing film was 3B, and the average contact angle with water was 92 °. In addition, the transparency had an average haze value of 0, a total light transmittance of 100%, and the transparency of the appearance was also good. The contact angle of water after irradiation with ultraviolet rays (black light) on the obtained test plate (G-2) having a photocatalyst-containing film was 0 °. Furthermore, the pencil hardness was HB, and the result of photocatalytic activity evaluation was also very good ().

In addition, as a result of the stain resistance evaluation of the obtained test plate (G-2), no stain was found, and the stain resistance was very good. Furthermore, the transparency by the exposure test (after 2000 hours) by the Dew Panel optical control weather meter was 0.4 with an average haze value, there was almost no change in appearance, and the contact angle of water was 0 °, showing very good weather resistance. It was. As a result of observing the coating cross section of the obtained test plate (G-2) by TEM, almost no photocatalyst particles were present at the interface between the photocatalyst-containing coating and the acrylic resin as the base material, and the surface of the photocatalyst-containing coating was It was observed that modified photocatalytic particles were present in.

[Comparative example 1]

The photocatalyst composition (C-3) was prepared in the same manner as in Example 1 except that no ultraviolet absorber was added. Using the obtained photocatalyst composition (C-3), the same operation as in Example 1 was carried out to obtain a test plate (G-3) having a photocatalyst-containing film. The transparency of the obtained test plate (G-3) by an exposure test (after 2000 hours) with a Dew panel optical control weather meter was an average haze value of 2.8, and whitening of the test plate (G-3) was observed. As a result of observing the cross section of the film of the obtained test plate (G-3) by TEM, although there were almost no photocatalyst particles at the interface between the photocatalyst-containing film and the acrylic resin as the base material, the cross section of the film was observed. Some photocatalytic particles were present at the interface with the substrate depending on the location, and this was presumed to be the cause of whitening in the weather resistance test. In Examples 1 and 2, even if some photocatalytic particles were present at the interface of the base material, the light did not reach the photocatalyst particles at the interface of the base material due to the presence of the ultraviolet absorber in the film, so that good weather resistance was exhibited. It is estimated to be.

The photocatalyst or functional composite provided by the photocatalyst composition of the present invention has good transparency and weather resistance, exhibits various functions such as antibacterial, antifouling, deodorant, and NOx decomposition, and is used for antifouling. It can be suitably used for applications such as environmental purification of air and water.