Dye-sensitized photocatalyst and photocatalyst composition using the same

The present invention relates to modified photocatalytic particles. More specifically, the present invention comprises spectrosensitizing the photocatalytic particles to a compound having at least one structural unit selected from the group consisting of monooxydiorganosilane units, dioxyorganosilane units, and difluoromethylene units. The present invention relates to modified photocatalytic particles obtained by modification treatment with a modifying agent compound containing a group, and a modified photocatalytic composition containing the modified photocatalytic particles. When a film containing the modified photocatalyst is formed on the surface of the substrate by using the above-mentioned modified photocatalyst particles or the modified photocatalyst composition, the modified photocatalyst does not impair its activity and the surface of the substrate is subjected to mild conditions. In addition to being firmly immobilized, the formed film and the base material coated with the above film do not deteriorate due to the action of the modified photocatalyst. Moreover, since the above-mentioned film is excellent in transparency, durability, stain resistance, hardness and the like, it is extremely useful in preventing dirt from adhering to the surface of various base materials and preventing fogging. Further, the present invention uses a film formed by using the above-mentioned modified photocatalyst particles or the above-mentioned modified photocatalyst composition, a functional composite composed of the film and a substrate coated by the film, and the above-mentioned modified photocatalyst composition. It also relates to the molded body formed in the above.

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 the 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 regarding a method for immobilizing a photocatalyst. For example, Patent Document 1 discloses a method of forming a thin film of a photocatalyst on the surface of a base material by a sputtering method and immobilizing it. As one of the particularly useful methods among these methods, a method of fixing the photocatalyst to the surface of the base material by coating the surface of the base material with a composition containing a photocatalyst and forming a film containing the photocatalyst is attracting attention. Has been done.

When immobilizing the photocatalyst 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 formed film and the base material coated by the film shall not deteriorate due to the action of the photocatalyst. Is required. Furthermore, in expanding the scope of application of this method, (3) Immobilization can be performed under mild conditions (for example, room temperature to about 100 ° C as a temperature condition). (4) It is desired that the film to be formed has excellent transparency, durability, 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 2, 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 a 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 3 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, 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 Documents 4 and 5, a photocatalyst is mixed with a resin paint 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 the base material is used using this resin paint. A method of coating the surface of the resin 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 good film by these methods, it is necessary to increase the amount of the above resin used, but if this is done, the photocatalyst will be buried in the film formed by the coating, which is sufficient. There is a drawback that it does not show any activity.

As a method for overcoming these drawbacks, Patent Document 6 proposes a method in which a resin coating material and photocatalytic particles having adjusted wettability to a solvent constituting the resin coating material 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 a drawback that the photocatalytic particles do not show sufficient activity. That is, in the method of immobilizing the photocatalyst on the surface of the base material by coating, one that satisfies all the above conditions (1) to (4) is not yet known.

<patcit num="1"><text>Japanese Patent Application Laid-Open No. 60-044053</text></patcit><patcit num="2"><text>Japanese Unexamined Patent Publication No. 60-118236</text></patcit><patcit num="3"><text>Japanese Unexamined Patent Publication No. 06-278241</text></patcit><patcit num="4"><text>Japanese Unexamined Patent Publication No. 07-171408</text></patcit><patcit num="5"><text>Japanese Unexamined Patent Publication No. 09-100437</text></patcit><patcit num="6"><text>Japanese Patent Application Laid-Open No. 09-314052</text></patcit>

<p> Under such circumstances, the present inventor conducted diligent research to develop a method for immobilizing a photocatalyst on the surface of a base material, which satisfies all the above conditions (1) to (4). As a result, surprisingly, the present inventors include at least one structural unit in which the modified photocatalytic particles are selected from the group consisting of monooxydiorganosilane units, dioxyorganosilane units and difluoromethylene units. Using a modified photocatalyst particle obtained by modification treatment with a modifier compound containing a spectrosensitizing group, which is a compound, and a modified photocatalyst composition containing the modified photocatalyst particle and a functional substance, a group is used. When a film containing a modified photocatalyst is formed on the surface of the material, all of the above conditions (1) to (4) are satisfied, the modified photocatalyst is not buried in the film, and a sufficient effect is obtained on the surface of the film. Found to show. Further, a film formed by using the above-mentioned modified photocatalyst particles or the modified photocatalyst composition, a functional composite composed of the film and a substrate coated by the film, and the above-mentioned modified photocatalyst composition are formed. It has been found that the modified photocatalyst exerts a sufficient effect on the surface of the molded product, so that the adhesion of dirt and fogging on the surface are effectively prevented.</p><p> Based on the above new findings, the present invention has been completed. Therefore, the main object of the present invention is to form a film containing a modified photocatalyst on the surface of the base material so that the modified photocatalyst is firmly attached to the surface of the base material under mild conditions without impairing its activity. It is an object of the present invention to provide a modified photocatalytic sol capable of immobilization, and a modified photocatalytic composition containing the modified photocatalytic sol and a functional substance. Another object of the present invention is a film that effectively prevents fogging and fogging on the surface, a functional composite composed of the film and a substrate coated by the film, and fogging on the surface. It is an object of the present invention to provide a molded article which effectively prevents fogging and fogging. The above and other objects, features and benefits of the present invention will become apparent from the following detailed description and claims made with reference to the accompanying drawings.</p>

<p> According to the present invention, the photocatalytic particles are represented by the monooxydiorganosilane unit represented by the formula (1).<u style="single">, And</u>And a compound having at least one structural unit selected from the group consisting of difluoromethylene units represented by the formula (3), which is obtained by a modification treatment using a modifier compound containing a spectrosensitizing group.<u style="single">The modified photocatalyst particles are dispersed in a liquid medium, and the average particle size of the modified photocatalyst particles is 800 nm or less in terms of volume average diameter.</u>Modified photocatalytic particles<u style="single">Containing</u>A sol is provided. -(R¹R²SiO)-(1) (In the formula, R¹, R²Are independently hydrogen atoms, linear or branched alkyl groups with 1 to 30 carbon atoms, cycloalkyl groups with 5 to 20 carbon atoms, or unsubstituted or 1 to 20 carbon atoms alkyl. Represents a group, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom)<u style="single">, And</u>And -(CF₂)- (3) </p><p> Next, in order to facilitate understanding of the present invention, the basic features and preferred embodiments of the present invention are listed. 1. A group of photocatalytic particles consisting of a monooxydiorganosilane unit represented by the formula (1), a dioxyorganosilane unit represented by the formula (2), and a difluoromethylene unit represented by the formula (3). A modified photocatalytic particle which is a compound having at least one structural unit selected from the above and is obtained by modification treatment with a modifier compound containing a spectrosensitizing group. -(R¹R²SiO)-(1) (In the formula, R¹, R²Are independently hydrogen atoms, linear or branched alkyl groups with 1 to 30 carbon atoms, cycloalkyl groups with 5 to 20 carbon atoms, or unsubstituted or 1 to 20 carbon atoms alkyl. Represents a group, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom),<chemistry num="2"><img file="JP4454476B2_D0001.tif" /></chemistry>[In the formula, R¹Is as defined in equation (1)], and -(CF₂)- (3) </p><p> 2. The modified photocatalyst particles according to item 1 above, wherein the spectroscopic sensitizer has absorption in a wavelength region of 400 nm or more, and the energy level of the lowest empty orbit is higher than the energy level of the conduction band of the photocatalyst. 3. The modified photocatalyst particles according to item 1 or 2 above, wherein the average particle size of the modified photocatalyst particles is 800 nm or less in volume average diameter. 4. The modifier compound is an epoxy group, acryloyl group, metaacryloyl group, acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, ester. The modified photocatalyst particle according to any one of the above items 1 to 3, which contains at least one reactive group selected from the group consisting of groups. 5. The modifier compound is a compound having at least one hydrophilic group selected from the group consisting of a carboxyl group and a salt thereof, a phosphoric acid group and a salt thereof, a sulfonic acid group and a salt thereof, and a polyoxyalkylene group. The modified photocatalyst particles according to any one of the above items 1 to 4, wherein the modified photocatalyst particles are characterized by the above.</p><p> 6. The modified photocatalyst particle according to any one of the above items 1 to 5, wherein the modifying agent compound is a compound containing at least one silicon atom to which at least one hydrogen atom is bonded. 7. The modified photocatalytic particles according to the above items 1 to 6, which are dispersed in a liquid medium. 8. A modified photocatalytic sol comprising the modified photocatalytic particles according to item 7 above. 9. A modified photocatalyst composition containing the modified photocatalyst particles according to any one of 1 to 7 above and a monomer and / or a resin. 10. The modified photocatalyst composition according to item 9 above, wherein the resin is at least one selected from the group consisting of silicone-based resins and fluorine-based resins. 11. The modification according to item 9 above, wherein the modified photocatalyst particles are the modified photocatalyst particles according to item 4 above, and the resin has reactivity with reactive groups of the modified photocatalyst particles. Photocatalytic composition. 12. The modified photocatalyst composition according to item 9 above, wherein the monomer and / or resin is a resin coating material.</p><p> 13. A modified photocatalyst composition produced by polymerizing at least one compound selected from the group consisting of a vinyl compound and a hydrolyzable silane compound in the presence of the modified photocatalyst particles according to any one of the above items 1 to 7. .. 14. A functional composite obtained by forming a film containing the modified photocatalytic particles according to any one of 1 to 7 in the preceding section on a substrate. 15. A molded product obtained by molding the modified photocatalyst composition according to any one of 9 to 13 in the preceding paragraph. 16. A functional composite obtained by forming a film containing the modified photocatalyst composition according to any one of 9 to 13 in the preceding section on a substrate. 17. The molded product according to item 15 above, which exhibits hydrophilicity or hydrophobicity and / or photocatalytic activity when irradiated with light. 18. The functional complex according to item 14 or 16 above, which exhibits hydrophilicity or hydrophobicity and / or photocatalytic activity when irradiated with light. 19. The molded article according to item 15 above, which exhibits a photoelectric conversion function. 20. The functional complex according to item 14 or 16 above, which exhibits a photoelectric conversion function.</p>

<p> When a film containing a modified photocatalyst is formed on the surface of a substrate by using the modified photocatalyst particles obtained by the modification treatment with the modifying agent compound containing the spectral sensitizing group of the present invention, the modified photocatalyst particles are formed. Under mild conditions, the film is firmly immobilized on the surface of the substrate without impairing its activity, and the formed film and the substrate coated with the above film are deteriorated by the action of the modified photocatalyst. There is no. Moreover, since the above-mentioned film is excellent in transparency, durability, stain resistance, hardness and the like, it is extremely useful in preventing dirt from adhering to the surface of various base materials and preventing fogging. Further, in the functional composite and the molded product of the present invention, the modified photocatalyst exerts a sufficient effect on the surface thereof, so that dirt adhesion and fogging on the surface are effectively prevented.</p>

Hereinafter, the present invention will be described in detail. The modified photocatalytic particles of the present invention can be obtained by modifying the photocatalytic particles with at least one modifier compound described later. In the present invention, modification means immobilization of at least one modification agent compound described later on the surface of photocatalytic particles. It is considered that the immobilization of the above modifier compound on the surface of the photocatalytic particles is due to van der Waals force (physisorption), Coulomb force or chemical bond. 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. An example of a photocatalyst that can be used in the present invention is TiO.₂ , ZnO, SrTiO₃ , CdS, GaP, InP, GaAs, BaTiO₃ , BaTiO₄ , BaTi₄ O₉ , K₂ NbO₃ , Nb₂ O₅ , Fe₂ O₃ , Ta₂ O₅ , K₃ Ta₃ Si₂ O₃ , WO₃ , SnO₂ , Bi₂ O₃ , BiVO₄ , NiO, Cu₂ O, SiC, SiO₂ , MoS₂ , InPb, RuO₂ , CeO₂ And so on.

In addition, a layered oxide having at least one element selected from Ti, Nb, Ta, and V (Japanese Patent Laid-Open No. 62-74452, JP-A-2-172535, JP-A-7-24329, Kaihei 8-89799, JP8-89800, JP8-89804, JP8-198061, JP9-248465, JP10-99694, JP10 -244 No. 165, etc.) can also be used. Further, these photocatalysts are obtained by adding or immobilizing metals such as Pt, Rh, Ru, Nb, Cu, Sn, Ni, Fe and / or oxides thereof, or photocatalysts coated with porous calcium phosphate or the like. (Refer to Japanese Patent Application Laid-Open No. 10-244166) and the like can also be used. Of these photocatalysts, TiO₂ (Titanium oxide) is preferable because it is non-toxic and has excellent chemical stability. Three crystal forms of titanium oxide, anatase type, rutile type, and brookite type, are known, and any of these may be used. The crystal particle size (primary particle size) of the photocatalyst is preferably 1 to 200 nm, more preferably 1 to 50 nm.

In the present invention, the properties of the photocatalyst particles used are important factors for the dispersion stability, film formation property, and expression of various functions of the modified photocatalyst sol. In the present invention, for the following reasons, using a photocatalyst sol instead of a photocatalyst powder as a photocatalyst is the most preferable method for obtaining a modified photocatalyst sol. In general, powder composed of fine particles forms secondary particles in which single crystal particles (primary particles) are strongly aggregated, so that there are many surface characteristics that are wasted, but it is very difficult to disperse them even in the primary particles. Is. On the other hand, in the case of the photocatalyst sol, the photocatalyst particles are not dissolved and exist in a form close to the primary particles, so that the surface characteristics can be effectively utilized, and the modified photocatalyst sol generated from the photocatalyst sol has dispersion stability and film forming property. Not only is it excellent in terms of the like, but it can also be preferably used because it effectively expresses various functions. In the photocatalyst sol used in the present invention, the photocatalyst particles may exist as primary particles or as a mixture of primary particles and secondary particles, but are usually a mixture of primary particles and secondary particles. Exists as. As the photocatalyst particles that can be suitably used in the present invention, those having an average particle size of 400 nm or less are desirable because the surface characteristics of the photocatalyst after modification can be effectively used. Further, when a photocatalyst sol having an average particle size of 200 nm or less is used, a transparent film can be obtained from the generated modified photocatalyst sol, which is very preferable. A photocatalytic sol having an average particle size of 1 to 100 nm, more preferably 3 to 20 nm, which is a volume average particle size, is more preferably used.

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% or more of water.) The preparation of such a sol is known and can be easily produced (specially, it can be easily produced. See Kaisho 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 agglomerate under the action of nitric acid, hydrochloric acid, ammonia or the like and performing hydrothermal treatment or the like. In addition, as the titanium oxide hydrosol, titanium oxide particles are deflated under the action of acid or alkali, or a dispersion stabilizer such as sodium polyacrylate is used as necessary without using acid or alkali. Sols that are used and dispersed in water under strong shearing forces can also be used. Further, an anatase-type titanium oxide sol having a particle surface modified with a peroxo group, which has excellent dispersion stability even in an aqueous solution having a pH near neutral, can be easily obtained by the method proposed in JP-A-10-67516. it can.

The titanium oxide hydrosol described above is commercially available as a titania sol. (For example, "STS-02" manufactured by Ishihara Sangyo Co., Ltd., "TO-240" manufactured by Tanaka Transfer Co., Ltd., etc.) The solid content in the titanium oxide hydrosol is 50% by weight or less, preferably 30% by weight or less. More preferably, it is 30% by weight or less and 0.1% by weight or more. The viscosity (20 ° C) of such hydrosols is relatively low. In the present invention, the viscosity of the hydrosol may be in the range of about 2000 cps to 0.5 cps. It is preferably 1000 cps to 1 cps, and more preferably 500 cps to 1 cps. Further, for example, a cerium oxide sol (see 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 (Japanese Patent Laid-Open No. 9-25123). , JP-A-9-67124, JP-A-9-227122, JP-A-9-227123, JP-A-10-259023, etc.), etc.) Known for. Further, it is preferable to use the above-mentioned photocatalyst sol because the modified photocatalyst sol of the present invention can be directly obtained by directly modifying the above-mentioned photocatalyst sol with the above-mentioned modifier compound.

At least one modifier compound used in the present invention includes a monooxydiorganosilane unit represented by the following formula (1), a dioxyorganosilane unit represented by the following formula (2), and the following formula (3). ) Is selected from the group consisting of difluoromethylene units, and selected from the group consisting of compounds having at least one structural unit. -(R¹ R² SiO)-(1) (In the formula, R¹ , R² Are independently hydrogen atoms, linear or branched alkyl groups with 1 to 30 carbon atoms, cycloalkyl groups with 5 to 20 carbon atoms, or unsubstituted or 1 to 20 carbon atoms alkyl. Represents a group, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom),<chemistry num="3"><img file="JP4454476B2_D0002.tif" /></chemistry>[In the formula, R¹ Is as defined in equation (1)], and -(CF₂ )- (3)

When a compound having a monooxydiorganosilane unit represented by the formula (1) and / or a dioxyorganosilane unit represented by the formula (2) is used as the modifier compound, the modified photocatalytic sol of the present invention or When a film is formed using the modified photocatalyst composition of the present invention described later, or a molded product is formed using the modified photocatalyst composition of the present invention, the modified photocatalyst excited by excitation light irradiation becomes a formed film or It exhibits various activities on the surface of the molded product. Further, R in the monooxydiorganosilane unit represented by the formula (1) and / or the dioxyorganosilane unit represented by the formula (2) existing in the vicinity of the modified photocatalyst particles.¹ And R² Is replaced with a hydroxyl group by the action of a modified photocatalyst. As a result, the hydrophilicity of the surface of the film or the molded body is increased, and the dehydration condensation reaction between the generated hydroxyl groups proceeds, so that the hardness of the film or the molded body becomes very high. Further, when a modifier compound having a difluoromethylene unit represented by the formula (3) is used, the modified photocatalytic sol of the present invention or the modified photocatalytic composition of the present invention described later has photocatalytic activity and is extremely hydrophobic. It is possible to obtain a highly effective film or molded body.

The denaturant compound used in the present invention preferably contains a spectroscopic sensitizing group. The spectral sensitizing group means a group derived from various metal complexes or organic dyes (that is, sensitizing dyes) having absorption in the visible light region and / or the infrared light region. When a modifier compound having a spectral sensitizing group is used, the modified photocatalytic sol of the present invention exhibits catalytic activity and photoelectric conversion function not only by irradiation with light in the ultraviolet region but also by irradiation with light in the visible light region and / or infrared light region. can do. Examples of sensitizing pigments include xanthene pigments, oxonor pigments, cyanine pigments, merocyanine pigments, rhodocyanine pigments, styryl pigments, hemicyanine pigments, phthalocyanine pigments (including metal complexes), and porphyrin pigments (including metal complexes). (Including metal complexes), triphenylmethane dyes, perylene dyes, coronine dyes, azo dyes, nitrophenol dyes, and further described in JP-A No. 1-220380 and JP-A-5-504023. Examples include complexes of ruthenium, osmium, iron and zinc, and other metal complexes such as ruthenium red.

Among these sensitizing dyes, it has absorption in the wavelength region of 400 nm or more, and has a feature that the energy level of the lowest empty orbit (oxidation-reduction potential in the excited state) is higher than the energy level of the conduction band of the photocatalyst. Those are preferable. The characteristics of such sensitizing dyes are the measurement of light absorption spectra in the infrared, visible, and ultraviolet regions, and the measurement of redox potential by electrochemical methods (T.Tani, Photogr. Sci. Eng., 14, 72). (1970); RWBerriman et al., Ibid., 17. 235 (1973); PBGilman Jr., ibid., 18, 475 (1974), etc.), Calculation of energy level using molecular orbital method (T.Tani) et al., Photogr. Sci. Eng., 11, 129 (1967); DMSturmer et al., Ibid., 17. 146 (1973); ibid., 18, 49 (1974); RGSelby et al., J. Opt. Soc. Am., 33, 1 (1970), etc.), and further, it can be confirmed by the presence or absence and efficiency of electromotive force due to light irradiation of the Gratzel type wet solar cell prepared by the photocatalyst and the sensitizing dye.

Examples of sensitizing dyes having the above characteristics include a compound having a 9-phenylxanthene skeleton, a ruthenium complex containing a 2,2'-bipyridine derivative as a ligand, a compound having a perylene skeleton, a phthalocyanine metal complex, and a porphyrin. A system metal complex and the like can be mentioned. The method for obtaining a modifier compound having a spectral sensitizing group derived from the above-mentioned sensitizing dye is not particularly limited, but a modifier compound having a reactive group described later and an increase having reactivity with this reactive group It can be obtained by reacting a sensitive pigment. The modifier compound used in the present invention includes an epoxy group, an acryloyl group, a metaacryloyl group, an acid anhydride group, a keto group, a carboxyl group, a hydrazine residue, an isocyanate group, an isothiocyanate group, a hydroxyl group, an amino group and a cyclic carbonate. It preferably contains at least one reactive group selected from the group consisting of groups and ester groups.

The modified photocatalytic sol obtained by using the modifier compound having a reactive group is preferable because it has crosslinkability and can form a film having excellent durability and the like. Further, when a modifier compound having a hydrazine residue represented by the formula (6) and / or a keto group is used as the reactive group, the modified photocatalytic sol of the present invention has both low temperature curability and storage stability. It is particularly preferable because it enables hydrazone (semicarbazone) cross-linking, which is useful for forming a film having excellent water resistance, stain resistance, hardness and the like. -NR¹²NH₂ (6) (In the formula, R¹²Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. ) Further, the denaturing agent compound used in the present invention is preferably a compound that exhibits self-emulsifying property or solubility in water. Such a metamorphic agent compound can be obtained by introducing a hydrophilic group. Examples of the hydrophilic group include a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a polyoxyalkylene group. When a modifier compound having a hydrophilic group is used, the dispersion stability of the obtained modified photocatalyst in water becomes very good. Therefore, the modified photocatalyst sol (hydrosol) having a volume average particle diameter of 800 nm or less of the present invention is used. It is preferable because it can be easily obtained.

Here, as a preferable specific example of the group containing the hydrophilic group, for example, a group containing a polyoxyethylene group represented by the formula (7), a sulfonic acid group represented by the formula (8), or a salt thereof may be used. Examples thereof include a containing group, a carboxyl group represented by the formula (9), a group containing a salt thereof, and the like. -CH₂ CH₂ CH₂ O (CH₂ CH₂ O)_mR⁷ (7) (In the formula, m represents an integer from 1 to 1000. R⁷ Represents a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms. )<chemistry num="4"><img file="JP4454476B2_D0003.tif" /></chemistry> [In the formula, n represents an integer from 1 to 100. R⁸ Represents a linear or branched alkyl group having 1 to 30 carbon atoms. B represents a hydrogen atom, an alkali metal, ammonium represented by the following formula, or substituted ammonium. HNR⁹ R¹⁰R¹¹(R⁹ , R¹⁰, R¹¹Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms which is not substituted or substituted with a hydroxyl group. )]]

<chemistry num="5"><img file="JP4454476B2_D0004.tif" /></chemistry> [In the formula, B independently represents a hydrogen atom, an alkali metal, and ammonium or substituted ammonium represented by the following formula. HNR⁹ R¹⁰R¹¹(R⁹ , R¹⁰, R¹¹Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms which is not substituted or substituted with a hydroxyl group. )]] Examples of the modifier compound having a structural unit represented by the above formula (1) and / or the above formula (2) used for obtaining the modified photocatalyst particles of the present invention include a Si-H group described later and hydrolysis. Chemical bond with photocatalyst particles such as sex silyl group (alkoxysilyl group, hydroxysilyl group, halogenated silyl group, acetoxysilyl group, aminoxysilyl group, etc.), epoxy group, acetoacetyl group, thiol group, acid anhydride group, etc. Examples thereof include a silicon compound having a reactive group that can be expected to be produced, a silicon compound having a hydrophilic group that can be expected to have an affinity with photocatalyst particles such as a polyoxyalkylene group, and the like.

Examples of these are compounds containing at least one silicon atom to which at least one hydrogen atom represented by the average composition formula (4) is bonded (hereinafter, often referred to as "Si-H group-containing silicon compound"). The product obtained by reacting the SiH group-containing silicon compound with the vinyl silicone compound represented by the following formula (5'), and the hydrolyzable silyl group-containing silicon represented by the average composition formula (10). Compounds can be mentioned. H_pR_qQ_rX_sSiO_{(4-pqrs) / 2} (Four) [In the formula, R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an alkyl group having no substitution or having 1 to 20 carbon atoms. Represents at least one hydrocarbon group selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, and Q is (1) Linear or branched alkyl group with 1 to 30 carbon atoms, cycloalkyl group with 5 to 20 carbon atoms, unsubstituted or branched alkyl group with 1 to 20 carbon atoms, carbon number 1 to 20 At least one selected from the group consisting of an aryl group having 6 to 20 carbon atoms substituted with at least one substituent selected from the group consisting of an alkoxy group and a halogen atom, and a group consisting of a fluoroalkyl group having 1 to 30 carbon atoms. Hydrophobic group,

(2) At least one hydrophilic group selected from the group consisting of a carboxyl group and a salt thereof, a phosphoric acid group and a salt thereof, a sulfonic acid group and a salt thereof, and a polyoxyalkylene group. (3) Selected from the group consisting of an epoxy group, an acryloyl group, a metaacryloyl group, an acid anhydride group, a keto group, a hydrazine residue, an isocyanate group, an isothiocyanate group, a hydroxyl group, an amino group, a cyclic carbonate group, and an ester group. At least one reactive group, and (4) At least one spectroscopic sensitizer, Represents a group containing at least one functional group selected from the group consisting of X is at least one selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a hydroxyimino group, an enoxy group, an amino group, an amide group, an asyloxy group having 1 to 20 carbon atoms, an aminoxy group, and a halogen atom. Represents one hydrolyzable group, 0 &lt;p &lt;4, 0 &lt;q &lt;4, 0 r &lt;4, 0 s &lt;2, And (p + q + r + s) &lt;4. ] CH₂= CH-(R¹R¹SiO)_e-(R¹R¹Si)-CH = CH₂ (Five' ) (In the formula, R¹ Is a linear or branched alkyl group with 1 to 30 carbon atoms, a cycloalkyl group with 5 to 20 carbon atoms, or an unsubstituted or substituted alkyl group with 1 to 20 carbon atoms or 1 to 20 carbon atoms. Represents one or more hydrocarbon groups selected from the alkoxy group of the above or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom. e represents an integer between 1 and 10000. )

R_qX'_sSiO_{(4-qs) / 2} (Ten) (In the formula, R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or branched alkyl group having 1 to 20 carbon atoms. Represents at least one hydrocarbon group selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, and X'represents an alkoxy group having 1 to 20 carbon atoms. Represents at least one hydrolyzable group selected from the group consisting of an alkoxy group, a hydroxyl group, an enoxy group, an asyloxy group having 1 to 20 carbon atoms, an aminoxy group, and an oxime group having 1 to 20 carbon atoms, and represents 0 &lt;q &lt;4, 0 &lt;s &lt;4 and 0 &lt;(q + s) 4) Examples of the compound having a structural unit represented by the above formula (3) used for obtaining the modified photocatalyst particles of the present invention include a SiH group and a hydrolyzable silyl group (alkoxysilyl group, hydroxysilyl group). Reactive groups and polyoxys that can be expected to form chemical bonds with photocatalyst particles such as groups, silyl halide groups, acetoxysilyl groups, aminoxysilyl groups), epoxy groups, acetoacetyl groups, thiol groups, acid anhydride groups, etc. Examples thereof include fluoroalkyl compounds having 1 to 30 carbon atoms and fluoroalkylene compounds having a number average molecular weight of 100 to 1,000,000, which have hydrophilic groups that can be expected to have affinity with photocatalyst particles such as alkylene groups.

Specific examples thereof include a fluoroalkyl compound represented by the formula (11) and a fluoroolefin polymer represented by the formula (12). CF₃ (CF₂ )_g-Y- (V)_w (11) [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 is at least one selected from the group consisting of an epoxy group, a hydroxyl group, an acetoacetyl group, a thiol group, an acid anhydride group, a carboxyl group, a sulfonic acid group, a polyoxyalkylene group, and a group represented by the following formula. Represents a functional group. -SiW_xR_y(In the formula, W is composed of an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an asyloxy 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, and an amide group. Represents at least one selected 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 carbon group. Represents at least one hydrocarbon group selected from an alkyl group of 1 to 20 or an alkoxy group of 1 to 20 carbons or an aryl group of 6 to 20 carbons substituted with 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="6"><img file="JP4454476B2_D0005.tif" /></chemistry>(In the formula, A¹ ~ A⁵ May 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. m is an integer between 10 and 1,000,000, and n is an integer between 0 and 1,000,000. 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 is as defined in equation (11). ) Specific examples of these include fluoroalkylsilanes such as 2-perfluorooctylethyltrimethoxysilane, nafion resin, fluoroolefins such as chlorotrifluoroethylene and tetrafluoroethylene, and epoxy groups, hydroxyl groups, and carboxyl groups. , Copolymers with monomers having an acetoacetyl group, a thiol group, a cyclic acid anhydride group, a sulfonic acid group, a polyoxyalkylene group and the like (vinyl ether, vinyl ester, allyl compound, etc.) and the like can be mentioned.

Further, examples of the modifier compound having a structural unit represented by the above formula (1) and / or the above formula (2) and the above formula (3) used for obtaining the modified photocatalyst particles of the present invention include fluoro. Alkyl group and Si-H group, hydrolyzable silyl group (alkoxysilyl group, hydroxysilyl group, halide silyl group, acetoxysilyl group, aminoxysilyl group, etc.), epoxy group, acetacetyl group, thiol group, acid anhydride Examples thereof include a silicon compound having a reactive group that can be expected to form a chemical bond with photocatalyst particles such as a physical group. In the modified photocatalyst particles of the present invention, the above-mentioned photocatalyst (A) and the above-mentioned modifier compound (B) are mixed in water and / or an organic solvent in terms of solid content weight ratio (A) / (B) = 0.001. ~ 10,000, preferably (A) / (B) = 0.1 ~ 1, It can be obtained by mixing at a ratio of 000 and heating at 0 to 200 ° C, preferably 10 to 80 ° C, or by changing the solvent composition of the mixture by (vacuum) distillation or the like. it can. When the above modification is carried out, examples of the organic solvent that can be used include hydrophilic organic solvents such as dioxane, tetrahydrofuran, dimethylacetamide, acetone, methyl ethyl ketone, ethylene glycol, butyl cellosolve, ethanol and methanol, and toluene, xylene, hexane and the like. Hydrophilic organic solvent can be mentioned.

The modified photocatalyst particles of the present invention can also be obtained by modifying the photocatalyst powder with the above-mentioned modifier compound in the absence of water and / or an organic solvent, and then dispersing the photocatalyst powder in water and / or an organic solvent. However, in this case, it is very difficult to modify the photocatalyst in the state of the primary particles, and the volume average dispersed particle size of the modified photocatalyst sol to be produced cannot be reduced and becomes unstable, which is not preferable. A preferred method for obtaining the modified photocatalyst particles of the present invention is to use a photocatalyst sol containing photocatalyst (A) particles having a volume average particle diameter of 200 nm or less, preferably a volume average particle diameter of 1 to 100 nm, and the modifier compound described above. It is a method of denatured by the above method. In such a photocatalyst sol containing photocatalyst particles having a relatively small volume average particle size, for example, taking titanium oxide as a photocatalyst, titanium hydroxide-containing titanium is deflated in the presence of hydrochloric acid, nitric acid, ammonia, or the like. When the photocatalytic sol is obtained by hydrothermal treatment, for example, it can be obtained by adjusting the time of hydrothermal treatment. At that time, the shorter the hydrothermal treatment time, the smaller the volume average particle size.

Further, when the photocatalyst sol is modified with the modifier compound, the modification in which the photocatalyst portion is less agglutinated (preferably not preferable) due to the above-mentioned modification operation is particularly preferable. Such modification can be performed, for example, by using the above-mentioned SiH group-containing compound as a modifier compound. That is, a preferable form of the modified photocatalyst particles of the present invention is that the dispersed particles having a volume average particle diameter of 800 nm or less have a photocatalyst portion and the volume average particle diameter of the photocatalyst portion is 200 nm or less. (Such a morphology can be confirmed, for example, by TEM observation of a sample prepared from a modified photocatalyst sol diluted to 0.01% by weight or less.) Further, a modified photocatalyst sol in which such a morphology persists for a long period of time (for example, 30 ° The volume average particle size is maintained at 800 nm or less even after being stored in C for 100 days), because the physical properties of the film obtained from it are stable, which is very preferable. Examples of the modifier compound useful for obtaining such a modified photocatalytic sol include the above-mentioned SiH group-containing silicon compound.

In the present invention, for example, when a SiH group-containing silicon compound represented by the above average composition formula (4) is selected as the modifier compound used for modifying the photocatalyst, hydrogen gas is released from the mixed solution by the above modification operation. As it occurs, an increase in volume average particle size due to denaturation of the photocatalyst particles (increase in volume average particle size due to immobilization of the modifier compound on the surface of the photocatalyst particles) is observed. Further, for example, when titanium oxide is used as a photocatalyst, the reduction of Ti-OH groups in the IR spectrum is 3630 to 3640 cm due to the above modification operation.^-1Observed as a decrease in absorption of. Based on these facts, when a Si-H group-containing silicon compound is selected as the modifier compound, the modified photocatalyst sol of the present invention is not a mere mixture of a photocatalyst and a Si-H group-containing silicon compound, but some chemical bond or the like. It is very preferable because it can be predicted that it has an interaction. In fact, the modified photocatalytic sol thus obtained is extremely excellent in dispersion stability, chemical stability, durability and the like.

Examples of the SiH group-containing silicon compound represented by the average composition formula (4) include a SiH group-containing compound represented by the following formula (5). (R¹ HSiO)_a(R¹₂SiO)_b(R¹ QSiO)_c(R¹₃SiO_1/2 )_d (Five) [In the formula, R¹ Is as defined in equation (1), Q is as defined in equation (4), a is an integer greater than or equal to 1, b and c are integers greater than or equal to 0 or 1 and (a + b + c) 10000, and d is 0 or 2, where (a + b + c) is an integer greater than or equal to 2 and d = 0, the compound represented by equation (5). Is a cyclic silicone compound, and when d = 2, the compound represented by the formula (5) is a chain silicone compound. ] As another example of the SiH group-containing silicon compound of the above average composition formula (4), the repeating unit represented by the following general formula (4') in the molecule is represented by the following general formula (4 ). Examples thereof include a silicone compound having a repeating unit and a terminal group A, each of which has the terminal group A bonded to a silicon atom in the repeating unit via one oxygen atom.

<chemistry num="7"><img file="JP4454476B2_D0006.tif" /></chemistry> [In equation (4') and equation (4''), R³ Is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an alkyl group having no substituted or 1 to 20 carbon atoms or a carbon number of carbon atoms. A hydrocarbon group consisting of one or more selected from 1 to 20 alkoxy groups or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, or the functions of (1) to (4) below. It is a group having a sex-imparting group.

(1) A linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an alkyl group having no substitution or 1 to 20 carbon atoms or 1 carbon atom. At least one hydrophobic group selected from the group consisting of an alkoxy group having ~ 20 or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, and a fluoroalkyl group having 1 to 30 carbon atoms. (2) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a polyoxyalkylene group. (3) From epoxy group, acryloyl group, metaacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, ester group At least one reactive group selected from the group consisting of. (4) At least one spectroscopic sensitizer.

A is-SiR⁴ R⁵ R⁶ (R⁴ , R⁵ , R⁶ May be the same or different, hydrogen atoms or linear or branched alkyl groups with 1 to 30 carbon atoms, cycloalkyl groups with 5 to 20 carbon atoms, or unsubstituted or substituted. Represents a hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom. ), Hydrogen atom, linear or branched alkyl group with 1 to 30 carbon atoms, cycloalkyl group with 5 to 20 carbon atoms, or unsubstituted or 1 to 20 carbon atoms alkyl group or carbon Represents at least one group selected from the group consisting of an alkoxy group of number 1 to 20 or an aryl group of carbon number 6 to 20 substituted with a halogen atom. In addition, the compound having a repeating unit represented by the formula (4') and the formula (4 ) has at least one SiH group. ]

The molecule has a repeating unit represented by the formula (4'), a repeating unit represented by the formula (4''), and a terminal group A, respectively, and the terminal group A is interposed via one oxygen atom. The silicone compound bonded to the silicon atom in the repeating unit is hydrolyzed by reacting trichlorosilane and / or organotrichlorosilane (and, if necessary, diorganodichlorosilane) with water in a solvent such as dioxane. It is obtained by polycondensation, then reacting with an alcohol and / or a silylating agent represented by the formula (13), and then, if necessary, introducing a functional imparting group by a hydrosilylation reaction described later. Z-SiR⁴ R⁵ R⁶ (13) (R⁴ , R⁵ , R⁶ May be the same or different, hydrogen atoms or linear or branched alkyl groups with 1 to 30 carbon atoms, cycloalkyl groups with 5 to 20 carbon atoms, or unsubstituted or substituted. Represents a hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom. Z represents a halogen atom or a hydroxyl group. )

In the Si-H group-containing silicon compound represented by the average composition formula (4) of the present invention, the Si-H group is an essential functional group for selectively modifying the photocatalyst under mild conditions. On the other hand, the hydrolyzable group X in the average composition formula (4) can also be used for modifying the photocatalyst, but it has many side reactions and deteriorates the stability of the obtained modified photocatalyst sol. It is preferable that the content is small. A more preferable form of the average composition formula (4) is a system that does not substantially contain the hydrolyzable group X. Further, when a SiH group-containing silicon compound represented by the above average composition formula (4) having a functionality-imparting group-containing group (Q) is selected, the modified photocatalytic sol obtained in the present invention has various functions. Is preferable because it can be imparted. The functional group-containing group (Q) is preferably a group represented by the following formula. -Y- (Z)_w(In the formula, Y represents a W-valent organic group having a molecular weight of 14 to 50,000, Z is at least one selected from the group consisting of the functional group (1) to (4), and W is 1 to 20. Is an integer of.)

For example, as the functional group-containing group (Q), at least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a polyoxyalkylene group ( When a group having (2)) in the formula (4) is selected, the dispersion stability of the obtained modified photocatalyst in water becomes very good, so that the modified volume average dispersed particle size of the present invention is 800 nm or less. It is preferable because a photocatalyst sol (hydrosol) can be easily obtained. Here, as preferable specific examples of the hydrophilic group, for example, a polyoxyethylene group represented by the above formula (7), a sulfonic acid group represented by the above formula (8) or a salt thereof, and further, the above formula (9). ), Such as a carboxyl group or a salt thereof. Further, for example, when a group having a fluoroalkyl group having 1 to 30 carbon atoms, which is a hydrophobic group, is selected as the functional group-containing group (Q) (in this case, the average composition formula (4) becomes the formula (1) and / (Or a compound having structural units of formulas (2) and (3)), the obtained modified photocatalyst has a very small surface energy, and the modified photocatalyst sol of the present invention has only a large self-tilt property described later. Alternatively, it is possible to obtain a film having a very high hydrophobicity.

Further, for example, as the functional group-containing group (Q), an epoxy group, an acryloyl group, a metaacryloyl group, an acid anhydride group, a keto group, a carboxyl group, a hydrazine residue, an isocyanate group, an isothiocyanate group, a hydroxyl group and an amino group. The modified photocatalytic sol of the present invention has crosslinkability when a group containing at least one reactive group ((3) in formula (4)) selected from the group consisting of a cyclic carbonate group and an ester group is selected. , It is preferable because a film having excellent durability and the like can be formed. Here, when a reactive group having a monovalent group containing a hydrazine residue represented by the above formula (6) and / or a monovalent group containing a keto group is selected, the modified photocatalyst of the present invention is selected. The sol is particularly preferable because it has both low-temperature curability and storage stability, and enables hydrazone (semicarbazone) cross-linking which is useful for forming a film having excellent water resistance, stain resistance, hardness and the like. Further, for example, as the functional group-containing group (Q), the above-mentioned spectroscopic sensitizing group ((4) in the formula (4)) ) Is selected, the modified photocatalytic sol of the present invention can exhibit catalytic activity and photoelectric conversion function not only by irradiation with light in the ultraviolet region but also by irradiation with light in the visible light region and / or infrared light region. .. As the functional group-containing group (Q), at least one or more of the above-mentioned ones can be selected and used. In particular, when a photocatalytic hydrosol is selected as the photocatalyst to be denatured, hydrophilic groups ((2) in formula (4)) and other functional groups ((1), (3), (3) in formula (4)) ( A system in which 4)) is used in combination is preferable because the stability of the modified photocatalytic sol having the functional group to be produced becomes good.

In the present invention, a SiH group-containing silicon compound represented by the above-mentioned average composition formula (4) having a functionality-imparting group-containing group (Q) (the following average composition formula (4a)) is obtained. As a method, (a) A carbon-carbon unsaturated bond compound having a Si-H group-containing compound represented by the following average composition formula (14) and a functional imparting group ((1) to (4) in the formula (4)). Hydrosilylation reaction, (b) The SiH group-containing compound represented by the following average composition formula (14) is hydrosilylated with a carbon-carbon unsaturated bond compound having a reactive group ((3) in formula (4)). After obtaining a SiH group-containing compound having a reactive group, a method of reacting the reactive group with a functional imparting group-containing compound having reactivity can be mentioned. H_pR_qQ_rX_sSiO_{(4-pqrs) / 2} (4a) (In the equation, R, Q, and X are as defined in equation (4). 0 &lt;p &lt;4, 0 &lt;q &lt;4, 0 &lt;r &lt;4, 0 s &lt;2, and (p + q + r + s) &lt;4.) H_{(p + r)}R_qX_sSiO_{(4-pqrs) / 2} (14) (In the equation, R and X are as defined in equation (4). 0 &lt;p &lt;4, 0 &lt;q &lt;4, 0 &lt;r &lt;4, 0 s &lt;2, and (p + q + r + s) &lt;4.)

First, as a method for obtaining a SiH group-containing silicon compound having a functional imparting group, the above-mentioned method (a) (hereinafter referred to as (a) -method) will be described. In the (a) -method, the SiH group-containing compound represented by the above formula (14) has a linear or branched alkyl group having 1 to 30 carbon atoms and 5 carbon atoms as a functional imparting group. Select from ~ 20 cycloalkyl groups, or unsubstituted or 1 to 20 carbon alkyl groups or 1 to 20 carbon alkoxy groups, or 6 to 20 carbon aryl groups substituted with halogen atoms. Examples of the carbon-carbon unsaturated bond compound used when introducing the above hydrophobic group include propylene, 1-butene, 1-hexene, 1-octene, isobutene, 2-methyl-1-butene, 2-hexene and cyclohexene. , Alkyl such as 5-norbornen, allyl acetate, allyl propionate, allyl 2-ethylhexanoate, benzoic acid Allyl esters such as allyl, allyl methyl ether, allyl ethyl ether, allyl-n-hexyl ether, allyl cyclohexyl ether, allyl-2-ethylhexyl ether, allyl ethers such as allyl phenyl ether, methyl (meth) acrylate, ( (Meta) acrylates such as ethyl acrylate, butyl (meth) acrylate, -2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, vinyl acetate, propion Vinyl acid vinyl esters such as vinyl acid, vinyl butyrate, vinyl stearate, vinyl benzoate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, styrene, (meth) acrylonitrile, crotonic acid ester. Examples thereof include carbon-carbon unsaturated bond compounds. Of these, terminal olefins, 5-norbornenes, allyl esters, and allyl ethers are preferable in terms of reactivity.

Examples of the carbon-carbon unsaturated bond compound used when introducing a fluoroalkyl group having 1 to 30 carbon atoms as a functional imparting group into the SiH group-containing compound represented by the above formula (14) include the formula ( Olefins, allyl ethers, allyl esters, vinyl ethers, (meth) acrylic acid esters and the like having a perfluoroalkyl group represented by 15) can be used. -(CF₂ )_gCF₃ (15) (In the formula, g represents an integer from 0 to 29.) Examples of the carbon-carbon unsaturated bond compound used for introducing a hydrophilic group into the SiH group-containing compound represented by the above formula (14) include a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid. Olefins, allyl ethers, vinyl ethers, vinyl esters, (meth) acrylic acid esters having at least one hydrophilic group selected from the group consisting of a group or a salt thereof, a polyoxyalkylene group, and a cyclic acid anhydride. , A styrene derivative and the like.

Preferred specific examples of the carbon-carbon unsaturated bond compound having a hydrophilic group include a polyoxyethylene group-containing allyl ether represented by the formula (16), a sulfonic acid group represented by the formula (17), or a salt thereof. Examples thereof include allyl ethers having a monovalent group containing, and 5-norbornene-2,3-dicarboxylic acid anhydride and the like. CH₂ = CHCH₂ O (CH₂ CH₂ O)_mR⁷ (16) (In the formula, m represents an integer from 1 to 1,000. R⁷ Represents a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms. )<chemistry num="8"><img file="JP4454476B2_D0007.tif" /></chemistry>[In the formula, n represents an integer from 1 to 100. R⁸ Represents a linear or branched alkyl group having 1 to 30 carbon atoms. B represents a hydrogen atom, an alkali metal, ammonium represented by the following formula, or substituted ammonium. HNR⁹ R¹⁰R¹¹(R⁹ , R¹⁰, R¹¹Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms which is not substituted or substituted with a hydroxyl group. )]]

The carbon-carbon unsaturated bond compound used for introducing a reactive group into the SiH group-containing compound represented by the above formula (14) includes an epoxy group, a (meth) acryloyl group, and an acid anhydride group. , Keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, ester group, olefins having at least one reactive group, allyl ether Classes, allyl esters, vinyl ethers, vinyl esters, (meth) acrylic acid esters, styrene derivatives and the like. Preferred specific examples of the carbon-carbon unsaturated bond compound having the above reactive group include, for example, allyl glycidyl ether, glycidyl (meth) acrylate, allyl (meth) acrylate, diallyl ether, diallyl phthalate, vinyl (meth) acrylate. , Vinyl crotonate, ethylene glycol di (meth) acrylic acid ester, maleic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, 5-hexen-2-one, allyl isocyanate, allyl alcohol, ethylene glycol monoallyl Examples thereof include ether, allylamine, allyl isothiocyanate, allyl semicarbazide, (meth) crotonic acid hydrazide, 4-allyloxymethyl-2-oxo-1,3-dioxolane and the like.

Further, as the carbon-carbon unsaturated bond compound used for introducing the spectral sensitizing group into the SiH group-containing compound represented by the above formula (14), the above-mentioned olefins having a spectral sensitizing group, allyl. Examples thereof include ethers, allyl esters, vinyl ethers, vinyl esters, (meth) acrylic acid esters, styrene derivatives and the like. These can be easily obtained, for example, by reacting the above-mentioned carbon-carbon unsaturated bond compound having a reactive group with a sensitizing dye having reactivity with the reactive group. For example, the reactive group of a carbon-carbon unsaturated bond compound having a reactive group is an epoxy group, a (cyclic) acid anhydride, an isocyanate group, an isothiocyanate group, a cyclic carbonate group, an ester group, a keto group, or (meth) acryloyl. In the case of a group, it is a sensitizing dye having at least one functional group selected from the group consisting of an amino group, a carboxyl group, a hydroxyl group, a hydrazine residue and a (meth) acryloyl group, and conversely, a carbon having a reactive group. -If the reactive group of the carbon unsaturated bond compound is an amino group, a carboxyl group, a hydroxyl group, a hydrazine residue, or a (meth) acryloyl group, an epoxy group, a (cyclic) acid anhydride, an isocyanate group, an isothiocyanate group, or a cyclic group. Examples thereof include sensitizing dyes having at least one functional group selected from the group consisting of a carbonate group, an ester group, a keto group and a (meth) acryloyl group. For the reaction between the carbon-carbon unsaturated bond compound having a reactive group and the sensitizing dye having a reactivity with the carbon-carbon unsaturated bond compound, reaction conditions such as reaction temperature, reaction pressure and solvent are selected according to the type of each reactive group. Can be carried out. At that time, from the viewpoint of the stability of the sensitizing dye, the reaction temperature is preferably 300 ° C. or lower, more preferably 150 ° C. or lower and 0 ° C. or higher. In the (a) -method, the hydrosilylation reaction between the carbon-carbon unsaturated bond compound and the SiH group-containing compound represented by the average composition formula (14) is preferably in the presence of a catalyst and in the presence of an organic solvent. It can be carried out by contacting a carbon-carbon unsaturated bond compound with a SiH group-containing compound represented by the average composition formula (14) at 0 to 200 ° C under or in the absence.

As the catalyst for the hydrosilylation reaction, a platinum group catalyst, that is, a compound of ruthenium, rhodium, palladium, osmium, iridium, or platinum is suitable, and a compound of platinum and a compound of palladium are particularly suitable. Examples of the platinum compound include platinum (II) chloride, tetrachloroplatinum (II) acid, platinum (IV) chloride, hexachloroplatinum (IV) acid, ammonium hexachloroplatinate (IV), potassium hexachloroplatinum (IV), and the like. Platinum hydroxide (II), platinum dioxide (IV), dichloro-dicyclopentadienyl-platinum (II), platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-olefin complex or simple platinum, alumina or silica Examples thereof include activated carbon in which solid platinum is supported. Examples of the palladium compound include palladium (II) chloride, palladium (II) oxide and the like. Examples of the organic solvent that can be used in the hydrosilylation reaction include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane and heptane, and esters such as ethyl acetate and n-butyl acetate. Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide, halogen compounds such as chloroform, methylene chloride and carbon tetrachloride, dimethylsulfoxide, nitrobenzene and the like. Examples include mixtures of two or more of these.

Next, as a method for obtaining a SiH group-containing silicon compound having a functional imparting group, the above-mentioned method (b) (hereinafter referred to as (b) -method) will be described. Examples of the carbon-carbon unsaturated bond compound having a reactive group used in the (b) -method include those described in the (a) -method. Further, the hydrosilylation reaction between the SiH group-containing compound represented by the above average composition formula (14) and the carbon-carbon unsaturated bond compound having the reactive group is the hydrosilylation described in (a) -method. It can be carried out under the same conditions as the reaction. According to the (b) -method, a SiH group-containing silicon compound having a reactive group and having an average composition represented by the following formula (18) can be obtained by the hydrosilylation reaction. H_pR_qQ³_rX_sSiO_{(4-pqrs) / 2} (18) (In the equation, R and X are as defined in equation (4), Q³ Is at least selected from the group consisting of epoxy group, acryloyl group, metaacryloyl group, acid anhydride group, keto group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group and ester group. Represents a monovalent group with one reactive group, 0 &lt;p &lt;4, 0 &lt;q &lt;4, 0 r &lt;4, 0 s &lt;2, (p + q + r + s) &lt; It is 4. )

Further, in the above (b) -method, as the functional group-containing compound having a reactivity with the SiH group-containing silicon compound having a reactive group [average composition formula (18)], for example, a reactive group is used. If the reactive group of the SiH group-containing silicon compound has an epoxy group, an acid anhydride, an isocyanate group, an isothiocyanate group, a cyclic carbonate group, an ester group, a keto group, or a (meth) acryloyl group, an amino group, It is a functional group-containing compound having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, a hydrazine residue, and a (meth) acryloyl group, and conversely, the reactive group is an amino group, a carboxyl group, In the case of a hydroxyl group, a hydrazine residue, or a (meth) acryloyl group, it is selected from the group consisting of an epoxy group, an acid anhydride, an isocyanate group, an isothiocyanate group, a cyclic carbonate group, an ester group, a keto group, and a (meth) acryloyl group. Examples thereof include functional group-containing compounds having at least one functional group. Here, the functional group-containing group is the same as the functional group-containing group (Q) in the above-mentioned average composition formula (4).

The reaction between the SiH group-containing silicon compound having a reactive group represented by the above average composition formula (18) and the functional imparting group-containing compound having reactivity thereof depends on the type of each reactive group. The reaction conditions such as reaction temperature, reaction pressure, and solvent can be selected and carried out. At that time, from the viewpoint of the stability of the SiH group, the reaction temperature is preferably 300 ° C. or lower, more preferably 150 ° C. or lower and 0 ° C. or higher. In the modified photocatalyst sol of the present invention, as a method for obtaining the modified photocatalyst sol having the above-mentioned functional imparting group, (I) A method of modifying a photocatalytic sol by the method described above using a SiH group-containing compound having a functional group represented by the above average composition formula (4a). (II) After modifying the photocatalyst sol with a SiH group-containing silicon compound having a reactive group represented by the above average composition formula (18), functionalization having reactivity with the reactive group also described above is imparted. Examples thereof include a method of reacting a group-containing compound. Here, the reaction between the photocatalyst sol modified with the SiH group-containing silicon compound having a reactive group in the method (II) and the functional imparting group-containing compound having reactivity with the reactive group is described above. (b)-The reaction can be carried out in the same manner as in the reaction between the SiH group-containing silicon compound having a reactive group and the functional imparting group-containing compound having reactivity with the reactive group in the method.

By the way, the modification of the photocatalyst with the SiH group-containing silicon compound represented by the above-mentioned average composition formula (4) is 0 to 0 when the substance acting as a dehydrogenation condensation catalyst for the SiH group is fixed to the photocatalyst. It is more preferable to carry out at 100 ° C. In this case, a substance that acts as a dehydrogenation condensation catalyst may be fixed to the photocatalyst in advance by a method such as a photoreduction method and modified with a SiH group-containing silicon compound, or in the presence of a substance that acts as a dehydrogenation condensation catalyst. The photocatalyst may be modified with a SiH group-containing silicon compound. In the latter case, the substance acting as a dehydrogenation condensation catalyst is fixed to the photocatalyst by physical adsorption or photoreduction and modified with a SiH group-containing silicon compound. Here, the substances that act as a dehydrogenation condensation catalyst for the Si-H group include the Si-H group, the hydroxyl group (Ti-OH group in the case of titanium oxide), the thiol group, the amino group, the carboxyl group, etc. existing on the surface of the photocatalyst. It means a substance that accelerates the dehydrogenation condensation reaction with active hydrogen groups and water, etc., and selectively modifies the photocatalyst surface under mild conditions by immobilizing the substance that acts as the dehydrogenation condensation catalyst on the photocatalyst. It becomes possible to do. Examples of the substance that acts as a dehydrogenation condensation catalyst for the SiH group include platinum group catalysts, that is, simple substances of ruthenium, rhodium, palladium, osmium, iridium, and platinum and their compounds, and silver, iron, copper, cobalt, and nickel. , Tin and the like, and compounds thereof. Among these, a platinum group catalyst is preferable, and a simple substance of platinum and a compound thereof are particularly preferable.

Hereinafter, a method of modifying platinum into a photocatalytic sol by a photoreduction method will be described as an example. First, 0.001 to 5% by weight of the platinum solution is added as a solid content to the photocatalytic sol solution. Here, it is preferable to maintain the monodispersity of the photocatalytic sol by making the pH of the platinum solution substantially the same as that of the photocatalytic sol solution and keeping the zeta potential in the photocatalytic sol solution as little as possible. Here, the platinum solution means a solution composed of a salt containing platinum and a solvent. Examples of the platinum-containing salt include platinum (II) chloride, tetrachloroplatinum (II) acid, platinum (IV) chloride, hexachloroplatinum (IV) acid, ammonium hexachloroplatinate (IV), and potassium hexachloroplatinum (IV). , Platinum hydroxide (II), platinum dioxide (IV), dichloro-dicyclopentadienyl-platinum (II), platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-olefin complex and the like can be used. As the solvent, water, ethanol, propanol, isopropanol, dioxane, tetrahydrofuran, toluene and the like can be used. The concentration of the salt containing platinum in the platinum solution is preferably 0.001 to 80% by weight.

Next, while stirring the mixture of the photocatalyst sol solution and the platinum salt solution, the photocatalyst is irradiated with light having a wavelength capable of generating electrons and holes (preferably light containing ultraviolet rays). Examples of the light source for irradiating light here include an ultraviolet lamp, a BLB lamp, a xenon lamp, a mercury lamp, and a fluorescent lamp. The method of irradiating light is basically not limited, but even when a transparent container is used, the wall surface of the container absorbs the light, so it is better to irradiate the light from the opening of the container. The distance between the light source and the container should be several cm to several tens of cm. This is because if it is too close, the upper surface of the sample solution may dry due to the heat generated from the light source, and if it is too far, the illuminance decreases. The irradiation time varies depending on the illuminance of the light source, but if it is irradiated for several seconds to several tens of minutes, platinum will firmly adhere to the photocatalytic particles. The modified photocatalyst sol of the present invention is one in which the modified photocatalyst is stably dispersed in water and / or an organic solvent. The average particle size of the modified photocatalyst particles in the modified photocatalyst sol of the present invention is a volume average particle size of 800 nm or less. The average particle size refers to the average particle size in the state of being dispersed in the modified photocatalyst sol of the present invention, not the average particle size in the state of being separated from the modified photocatalyst sol.

If the average particle size of the modified photocatalyst particles is larger than 800 nm, the dispersion stability of the modified photocatalyst sol is poor, and not only the modified photocatalyst sol itself but also a modified photocatalyst composition containing the modified photocatalyst sol and a resin is used as a coating agent. Can't. In the present invention, in order to further improve the dispersion stability of the modified photocatalyst sol and efficiently exhibit various functions such as film forming property, the average particle size of the modified photocatalyst particles is set to volume. The average particle size is preferably 400 nm or less, more preferably 200 nm or less, further preferably 1 nm or more and 100 nm or less, and particularly preferably 5 nm or more and 80 nm or less. It should be noted that, conventionally, the numerical value simply displayed as the particle size in titanium dioxide or the like is the primary particle size in many cases, and is not a value in consideration of the secondary particle size due to aggregation. The modified photocatalyst sol of the present invention is a sol in which the modified photocatalyst particles as described above are dispersed in a liquid medium. In the modified photocatalyst sol of the present invention, the content of the modified photocatalyst particles is preferably 0.01 to 70% by weight, more preferably 0.1 to 50% by weight, based on the weight of the modified photocatalyst sol.

The type of liquid medium is not particularly limited, but water and / or an organic solvent can be used. Examples of the organic solvent that can be used include hydrophilic organic solvents such as dioxane, tetrahydrofuran, dimethylacetamide, acetone, methyl ethyl ketone, ethylene glycol, butyl cellosolve, ethanol and methanol, and hydrophobic organic solvents such as toluene, xylene and hexane. Further, as a form of the photocatalyst to be denatured, a photocatalyst hydrosol [substantially water is used as a dispersion medium, and photocatalyst particles are deflated in the sol. It means that the medium contains about 80% or more of water)], an aqueous modified photocatalytic sol can be obtained. Further, from the aqueous modified photocatalyst sol thus obtained, the modified photocatalyst organosol by substituting the dispersion medium with an organic solvent [substantially the organic solvent is used as the dispersion medium, and the modified photocatalyst particles become stable. It also means a dispersed sol (here, substantially using an organic solvent as a dispersion medium means using a liquid containing about 80% or more of an organic solvent as a dispersion medium)]. it can.

As a method of solvent-replacement of the aqueous modified photocatalytic sol with an organic solvent, for example, (i) A method of adding an organic solvent to an aqueous modified photocatalytic sol and then heating and removing water under reduced pressure or normal pressure. (ii) A method of adding an organic solvent after removing the water of the aqueous modified photocatalyst sol by heating under reduced pressure or normal pressure. (iii) Water-based modified photocatalyst A method of solvent-extracting the modified photocatalyst in the sol with an organic solvent can be mentioned. Here, examples of the organic solvent used for solvent substitution include aromatic hydrocarbons such as toluene and xylene, alcohols such as ethanol and n-butanol, and polyhydric alcohols such as ethylene glycol and propylene glycol. Glycol derivatives such as butyl cellosolve, ethyl cellosolve, butyl cellosolve acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, aliphatic hydrocarbons such as hexane, cyclohexane and heptane, esters such as ethyl acetate and n-butyl acetate, Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide, amines such as dibutylamine and triethanolamine, chloroform, methylene chloride, carbon tetrachloride and the like. Halogen compounds, dimethylsulfoxide, nitrobenzene, acids, alkalis and the like, and mixtures of one or more of these can be mentioned. Among them, when the solvent is replaced by the method (i), it is preferable to use a hydrophilic organic solvent such as butyl cellosolve, propylene glycol monoethyl ether, dioxane, tetrahydrofuran, dimethylacetamide, methylethylketone, ethylene glycol, ethanol, etc. When the solvent is replaced with iii), it is preferable to use a hydrophobic organic solvent such as toluene, xylene, hexane and butyl acetate.

The modified photocatalyst sol containing the modified photocatalyst particles of the present invention may be used as it is as a modified photocatalyst coating agent, or may be used as a photocatalyst composition composed of a functional substance described later. The photocatalyst composition in the present invention preferably has a solid content weight ratio (C) / (D) = 0.0001 to 100 of the modified photocatalyst sol (C) and the functional substance (D). Further, it is more preferable that the ratio is (C) / (D) = 0.001 to 10. The case where a resin is used as the functional substance will be described below. As the resin that can be used in the photocatalyst composition of the present invention, all synthetic resins and natural resins can be used. Further, the form may be a pellet or a form dissolved or dispersed in a solvent, and there is no particular limitation, but the form of a resin coating material for coating is most preferable.

The resin coating material that can be used in the present invention is not particularly limited, and known ones can be used. Examples of resin paints are oil-based paints, lacquers, solvent-based synthetic resin paints (acrylic resin-based, epoxy resin-based, urethane resin-based, fluororesin-based, silicon-acrylic resin-based, alkyd resin-based, aminoalkyd resin-based, vinyl. Resin-based, unsaturated polyester resin-based, rubber chloride-based, etc.), water-based synthetic resin paint (emulsion-based, water-based resin-based, etc.), solvent-free synthetic resin paint (powder paint, etc.), inorganic paint, electrically insulating paint, etc. be able to. Among these resin paints, silicon-based resins and fluorine-based resins that are resistant to decomposition with respect to photocatalysts, and resin paints in which silicon-based resins and fluorine-based resins are used in combination are preferably used. Examples of such silicone-based resins include alkoxysilanes and / or organoalkoxysilanes, their hydrolysis products (polysiloxanes) and / or colloidal silicas, and acrylic-silicone resins having a silicon content of 1 to 80% by weight. , Epoxy-silicone resin, urethane-silicone resin, alkoxysilane and / or organoalkoxysilane and their hydrolysis products (polysiloxane) and / or resin containing 1 to 80% by weight of colloidal silica. These silicone-based resins may be any of a solvent-soluble type, a dispersion type, and a powder type, and may contain additives such as a cross-linking agent and a catalyst.

Specific examples of the above-mentioned alkoxysilane and / or organoalkoxysilane include tetramethoxysilane, tetraethoxysilane, and tetra-n-. Tetraalkoxysilanes such as propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-Propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n -Heptylrimethoxysilane, n-octylrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane , 3-Chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 2-Hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane,

2-Hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3 -Isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-) Epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acrylicoxypropyltrimethoxysilane, 3- (meth) atacryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, etc. Trialkoxysilanes; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di- i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di -n-Hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane , Dialkoxysilanes such as diphenyldimethoxysilane and diphenyldiethoxysilane; and monoalkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane.

Of these, trialkoxysilanes and dialkoxysilanes are preferable, methyltrimethoxysilane and methyltriethoxysilane are preferable as the trialkoxysilanes, and dimethyldimethoxysilane and dimethyldisilane are used as the dialkoxysilanes. Ethoxysilane is preferred. In addition, these alkoxysilanes and / or organoalkoxysilanes can be used alone or in admixture of two or more. When the above alkoxysilane and / or organoalkoxysilane is used as a hydrolysis product (polysiloxane), the polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the partial condensate is preferably 400 to 100,000. , More preferably 800 to 50,000. Examples of the fluororesin include PTFE, polyvinylidene fluoride, acrylic-fluororesin having a fluorine content of 1 to 80% by weight, epoxy-fluororesin, urethane-fluororesin, fluoroolefin, and carbon-carbon unsaturated. Examples thereof include copolymers with compounds (vinyl ethers, vinyl esters, allyl compounds, (meth) acrylic acid esters, etc.). These fluororesins may be any of a solvent-soluble type, a dispersion type, and a powder type, and may contain additives such as a cross-linking agent and a catalyst.

Further, the modified photocatalyst sol of the present invention contains an epoxy group, an acryloyl group, a metaacryloyl group, an acid anhydride group, a keto group, a carboxyl group, a hydrazine residue, an isocyanate group, an isothiocyanate group, a hydroxyl group, an amino group and a cyclic carbonate group. , A compound or resin containing a functional group reactive with the reactive group of the modified photocatalyst sol, when modified with a compound containing at least one reactive group selected from the group consisting of ester groups. It is preferable to mix with and use as a photocatalyst composition. In the obtained photocatalyst composition, the reactive group contained in the modified photocatalyst sol may partially react with the functional group of the above compound or resin (at a temperature of 40 ° C. or less and a storage period of 8 hours). (Reactivity rate is 50% or less), most of the photocatalytic composition consists of a mixture of the modified photocatalytic sol and the above compound or resin. Among these, the photocatalyst composition containing the modified photocatalyst sol of the present invention having a hydrazine residue and / or a keto group as the reactive group and a polyhydrazine compound and / or a polycarbonyl compound as a functional substance has a low temperature. It is particularly preferable because it forms a crosslinked film by a hydrazone bond or a semicarbazone bond, which has both curability and storage stability and is excellent in water resistance, stain resistance, hardness and the like. Examples of the polyhydrazine compound include polyhydrazide compounds, polysemicarbazide compounds, and carbonated polyhydrazines. Among these, preferred polyhydrazine compounds include adipic acid dihydrazide and polysemicarbazide derivatives proposed in International Application Publication No. WO 96/01252.

The polycarbonyl compound is, for example, a copolymer containing a carbonyl group, or a carbonyl made from a mono or polyalcohol having a carbonyl group such as hydroxyacetone as described in JP-A-2-238015. Examples thereof include group-containing polyurethanes, acetoacetylated polyvinyl alcohol, acetoacetylated hydroxyalkyl cellulose, and the combination thereof. Among these, the preferable polycarbonyl compound is a carbonyl group-containing ethylenically unsaturated monomer (a) and an ethylenically unsaturated monomer (b) copolymerizable with the monomer (a). It is a copolymer containing a carbonyl group obtained by polymerization, and more preferably, the polycarbonyl compound is a carbonyl group-containing ethylenically unsaturated monomer (a) 0.1 to 30% by weight, and the monomer (a). It is a copolymer containing a carbonyl group obtained by copolymerizing 70 to 99.9% by weight of an ethylenically unsaturated monomer (b) copolymerizable with (a).

Examples of the carbonyl group-containing ethylenically unsaturated monomer (a) include diacetone acrylamide, diacetone methacrylamide, acrolein, vinyl methyl ketone, acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, formylstyrene, and the like, and their combined use. Be done. Examples of the ethylenically unsaturated monomer (b) copolymerizable with the monomer (a) include acrylic acid ester, methacrylic acid ester, ethylenically unsaturated monomers having a carboxyl group, and ethylene having an epoxy group. Examples of (meth) acrylic acid esters include sex-unsaturated monomers, acrylamide-based monomers, methacrylicamide-based monomers, vinyl cyanide, etc., and examples of the (meth) acrylic acid ester have 1 to 18 carbon atoms in the alkyl portion. (Meta) acrylic acid alkyl ester, (meth) acrylic acid hydroxyalkyl ester with 1 to 18 carbon atoms in the alkyl part, (poly) oxyethylene (meth) acrylate with 1 to 100 ethylene oxide groups, propylene Examples thereof include (poly) oxypropylene (meth) acrylate having 1 to 100 oxide groups and (poly) oxyethylene di (meth) acrylate having 1 to 100 ethylene oxide groups.

Specific examples of (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and methyl (meth) acrylate. Cyclohexyl, dodecyl (meth) acrylate and the like can be mentioned. Specific examples of the (meth) acrylic acid hydroxyalkyl ester include 2-hydroxyethyl (meth) acrylic acid, 2-hydroxypropyl (meth) acrylic acid, 2-hydroxycyclohexyl (meth) acrylic acid and the like. Specific examples of (poly) oxyethylene (meth) acrylate include (meth) ethylene glycol acrylate, (meth) ethylene glycol monomethyl ether acrylate, (meth) diethylene glycol acrylate, (meth) diethylene glycol monomethyl ether acrylate, and ( Examples thereof include tetraethylene glycol acrylate (meth) and tetraethylene glycol methoxy (meth) acrylate. Specific examples of (poly) oxypropylene (meth) acrylate include (meth) propylene glycol acrylate, (meth) propylene glycol monomethyl ether, (meth) dipropylene glycol acrylate, and (meth) dipropylene glycol acrylate. Examples thereof include monomethyl ether, tetrapropylene glycol (meth) acrylate, and tetrapropylene glycol monomethyl ether (meth) acrylate.

Specific examples of the (poly) oxyethylene di (meth) acrylate include di (meth) ethylene glycol acrylate, di (meth) diethylene glycol acrylate, and di (meth) tetraethylene glycol acrylate. Specific examples of ethylenically unsaturated monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, semiesters of maleic acid, and crotonic acid, and are based on (meth) acrylamide. Examples of monomers include (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and the like, and vinyl cyanide includes, for example, (meth) acrylonitrile. Specific examples of the ethylenically unsaturated monomers having an epoxy group include glycidyl (meth) acrylate, 2,3-epoxycyclohexyl (meth) acrylate, and allyl glycidyl ether.

Specific examples other than the above include olefins such as ethylene, propylene and isobutylene, dienes such as butadiene, haloolefins such as vinyl chloride and vinylidene chloride, vinyl acetate, vinyl propionate, vinyl n-butyrate, and benzoate. Vinyl carboxylic acid esters such as vinyl oxyate, vinyl pt-butyl benzoate, vinyl pivalate, vinyl 2-ethylhexanate, vinyl versatic acid, vinyl laurate, isopropenyl carboxylate such as isopropenyl acetate and isopropenyl propionate. Esters, vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, aromatic vinyl compounds such as styrene and vinyl toluene, allyl esters such as allyl acetate and allyl benzoate, allyl ethers such as allyl ethyl ether and allyl phenyl ether Kind, and also γ- (meth) acryloyloxypropyltrimethoxysilane, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6 , 6-Pentamethylpiperidin, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoropropyromethyl (meth) acrylate, vinylpyrrolidone, trimethylpropantri (meth) acrylate, (meth) acrylic acid Examples include allyl and the like and their combined use.

The polycarbonyl compound is preferably produced by suspension polymerization, emulsion polymerization or solution polymerization, and more preferably a latex obtained by emulsion polymerization. In this case, it is preferable to use a reactive emulsifier as the emulsifier because the film formed from the obtained latex and the modified photocatalyst composition of the present invention has good water resistance. In obtaining the above polycarbonyl compound, a water-soluble or oil-soluble persulfate, which is radically decomposed by a heat or a reducing substance to cause addition polymerization of an ethylenically unsaturated monomer as a radical polymerization catalyst, is used. Peroxides, azobis compounds, etc. are used. Examples include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2'-azobisisobutyronitrile, 2,2'. There are -azobis (2-amidinopropane) hydrogen peroxide, 2,2'-azobis (2,4-dimethylvaleronitrile), etc., and the amount is usually 0.1 to 1% by weight based on the ethylenically unsaturated monomer. It is compounded.

Normally, it is preferably carried out under normal pressure at a polymerization temperature of 65 to 90 ° C. However, it can also be carried out under high pressure according to the characteristics such as vapor pressure at the polymerization temperature of the monomer. When it is desired to accelerate the polymerization rate and polymerize at a low temperature of 70 ° C. or lower, for example, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid salt, or longalite may be used in combination with a radical polymerization catalyst. It is advantageous. Further, in order to adjust the molecular weight, a chain transfer agent such as dodecyl mercaptan can be optionally added. Further, when polymerizing the polycarbonyl compound or after polymerization, 0.1 to 80 weight of the polycarbonyl compound is added to the above-mentioned alkoxysilane and / or organoalkoxysilane and their hydrolysis products (polysiloxane) and / or colloidal silica. When modified with a modification amount of%, a film having very good weather resistance can be obtained from the photocatalyst composition composed of the modified photocatalyst sol of the present invention, which is preferable. The photocatalyst composition of the present invention can be obtained by mixing the modified photocatalyst sol of the present invention with a functional substance such as the above-mentioned resin, and an ethylenically unsaturated monomer in the presence of the modified photocatalyst sol. (Ethylene unsaturated monomers exemplified for obtaining the copolymer having the above carbonyl group) and / or hydrolyzable silane compounds (the above alkoxysilane and / or the organoalkoxysilane and their hydrolyzed products, etc.) ) Can also be obtained by radical polymerization or polycondensation. At this time, the modified photocatalytic sol of the present invention contains a group that is reactive with an ethylenically unsaturated monomer such as a (meth) acryloyl group and / or a group that is reactive with a hydrolyzable silane compound such as a hydroxysilyl group. When it is contained, the obtained modified photocatalyst composition is preferable because it becomes a modified photocatalyst-resin composite composition in which the modified photocatalyst and the resin are composited via a chemical bond.

Further, in the present invention, it is preferable to use as the above-mentioned functional substance a compound having a surface energy larger than that of the modified photocatalyst particles in the modified photocatalyst sol. Photocatalytic compositions containing such compounds have self-tilt properties with respect to the distribution of modified photocatalysts (hereinafter often referred to as "self-tilt photocatalytic compositions"). Therefore, the molded product such as the base material having the film formed from the base material and the structural material formed from the base material has anisotropy with respect to the distribution of the modification catalyst. That is, the self-grading modified photocatalyst composition autonomously has a structure having a concentration gradient such that the modified photocatalyst increases from the inside of the film or the molded body toward the surface side in the process of forming the film or the molded body. It can be formed (such a function is often referred to as "self-tilting function" below). The content of the modified photocatalyst on the surface of the film or molded body obtained from the self-tilting modified photocatalyst composition is 5 to 100% by weight, preferably 50 to 100% by weight, based on the total content of the modified photocatalyst. The content is 0 to 50% by weight, preferably 0 to 10% by weight, and the content ratio between the surface and the inside (for example, the contact surface with the base material in the case of a coating film and the central portion in the case of a molded product). Is 1.5 or more.

In order to exhibit the above functions, it is important that the volume average particle size of the modified photocatalytic sol is 800 nm or less. That is, when the volume average particle size of the modified photocatalyst sol is larger than 800 nm, the self-tilt function of the modified photocatalyst in the modified photocatalyst sol becomes very small. As the modified photocatalyst sol that can be more preferably used as the self-tilting modified photocatalyst composition in the present invention, a modified photocatalyst sol having a volume average particle diameter of 200 nm or less is desirable for exhibiting the self-tilting function. More preferably 100 nm or less and 1 nm or more, still more preferably 50 nm or less and 5 nm or more. Further, in the self-tilting type modified photocatalyst composition, one of the factors for exerting the self-tilting function of the modified photocatalyst of the present invention is the low surface energy derived from the structural units of (1) to (3) above. Conceivable. Therefore, the functional substance used in the self-tilting modified photocatalyst composition of the present invention needs to be a compound having a surface energy larger than that of the modified photocatalyst, and the surface energy is 2 dyne / cm than that of the modified photocatalyst. Larger ones are preferable.

Here, the surface energy can be measured by, for example, the following method. That is, members such as a base material and a structural material having their respective films are prepared from compounds other than the modified photocatalyst sol and the modified photocatalyst constituting the self-tilting modified photocatalyst composition, and deionized water is added dropwise. The contact angle (θ) at ° C can be measured, and the surface energy of each can be obtained by the following experimental formulas of Sell and Neumann.<maths num="1"><img file="JP4454476B2_D0008.tif" /></maths>[In the formula, γs represents the surface energy (dyne / cm) of the film (or molded product) whose contact angle of deionized water was measured, and γl represents the surface energy of water {72.8 dynes / cm (20 ° C)}. Represent. ]

In the modified photocatalyst composition of the present invention, the high surface energy compound that can be used in the self-tilting modified photocatalyst composition is not particularly limited as long as it has a surface energy satisfying the above conditions, but various monomers and synthetic resins. And natural resin and the like, and those which are cured by drying, heating, moisture absorption, light irradiation and the like after the formation of the film and the molded body can also be mentioned. Further, the high surface energy compound that can be used in the self-inclining modified photocatalyst composition of the present invention is a composition itself, and is a component of the composition that is hardly decomposable to the modified photocatalyst. A silicon-based resin composition and / or a fluorine-based resin composition capable of forming an inclined structure in which the concentration increases from the inside of the film or the molded body toward the surface is preferably used. Examples of the silicon-based resin composition and / or fluorine-based resin composition include alkoxysilanes and / or organoalkoxysilanes and their hydrolysis products as proposed in JP-A-10-72569. Examples thereof include a fluororesin composition and / or an acrylic resin composition containing 0.1 to 50% by weight of polysiloxane). These resin compositions may contain additives such as a cross-linking agent and a catalyst. The form of the self-tilting modified photocatalyst composition may be pellets or a form dissolved or dispersed in a solvent, and is not particularly limited, but the form of a resin coating material for coating is most preferable. ..

The solid content weight ratio (C') / (D') of the modified photocatalyst (C') and the high surface energy compound (D') in the self-tilting modified photocatalyst composition according to the present invention. It is preferably = 0.0001 to 10. Further, it is more preferable that the ratio is (C') / (D') = 0.001 to 1. The film or molded product formed even in the range of (C') / (D') = 0.0001 to 0.2 where the content of the modified photocatalyst is very low has sufficient photocatalytic activity and / or hydrophilicity or hydrophobicity by light irradiation. Can be expressed. Further, the film having a structure having a concentration gradient such that the modified photocatalyst particles increase from the inside toward the surface side obtained from the self-tilting modified photocatalyst composition has excellent adhesion to the substrate and is extremely durable. It is possible to provide a functional complex having good photocatalytic activity. In the present invention, the modified photocatalyst obtained by removing the liquid medium from the modified photocatalyst sol and having an average particle diameter of 800 nm or less is mixed with the above-mentioned high surface energy compound. A modified photocatalyst composition having a self-inclining property may be obtained. Such a composition is easy to handle mainly in the form of pellets, and is very suitable for obtaining a molded product having a structure having a concentration gradient such that a large amount of modified photocatalyst is present on the surface.

In the present invention, a self-inclined type containing the modified photocatalyst sol, a modified photocatalyst composition composed of the modified photocatalyst sol and a functional substance, or a modified photocatalyst in the modified photocatalyst sol and a compound having a surface energy larger than that. As a method for obtaining a film or a molded product from the modified photocatalyst composition, for example, when those forms are paints, they are applied to a base material, dried, and then heat-treated as necessary to be hydrophobic by light irradiation. Alternatively, a functional complex having hydrophilicity and / or photocatalytic activity and further a photoelectric conversion function can be obtained. 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. Further, for example, when the form of the modified photocatalytic composition (including the self-inclining type) is pellets, hydrophobic or hydrophilic and / or modified photocatalytic activity by light irradiation by extrusion molding, injection molding, press molding or the like, and further photoelectric A molded product having a conversion function can be obtained.

The film or molded body obtained from the modified photocatalyst sol or modified photocatalyst composition (including the self-inclining type) of the present invention has a light energy higher than the band gap energy of the photocatalyst contained therein (the modified photocatalyst produces a sensitizing dye). When it is present, it exhibits hydrophobicity or hydrophilicity and / or photocatalytic activity and further photoelectric conversion function by irradiating it with light containing the absorption light of the sensitizing dye. At this time, the film or molded body obtained from the modified photocatalyst sol or the modified photocatalyst composition (including the self-tilting type) of the present invention has a molecular skeleton around the modified photocatalyst of the modified photocatalyst contained therein due to the decomposition action of the photocatalyst. Since there is a modifier compound having a structural unit that is not decomposed (the structural unit of the above formulas (1) to (3)), the resin as a binder or a structural material is not deteriorated by photocatalytic action. Further, when a metamorphic agent compound having a structural unit represented by the above formula (3) is used, a highly hydrophobic film or a film or a modified photocatalyst composition (including a self-inclining type) can be obtained from the modified photocatalyst sol or modified photocatalyst composition. It is also possible to obtain structural materials. In the present invention, as the light source of the light having an energy higher than the band gap energy of the photocatalyst and the absorbed light of the sensitizing dye, the light is obtained in a general residential environment such as sunlight or an indoor lamp, and black. Light such as lights, xenon lamps, and mercury lamps can be used. In addition, the modified photocatalyst sol or modified photocatalyst composition (including self-inclining type) of the present invention contains components that are usually added to and blended with paints and the like, such as pigments, fillers, dispersants, light stabilizers, and wetting agents. , Thickeners, rheology control agents, defoamers, plasticizers, film forming aids, rust preventives, dyes, preservatives and the like can be selected and combined according to their respective purposes.

In the present invention, a molded body formed from the modified photocatalyst sol and the modified photocatalyst composition (including the self-tilting type), and a film containing the modified photocatalyst sol and the modified photocatalyst composition (including the self-tilting type) are used as a base material. The functional complex formed above can exhibit hydrophobic or hydrophilic and / or photocatalytic activity and further photoelectric conversion function by light irradiation. That is, in another aspect of the present invention, a molded body formed from the modified photocatalyst sol or the modified photocatalyst composition (including the self-tilting type), the modified photocatalyst sol or the modified photocatalyst composition (including the self-tilting type) A functional complex obtained by forming a film containing) on a substrate is provided. The above-mentioned molded product or functional composite provided by the present invention, which has photocatalytic activity such as decomposition of organic substances, exhibits various functions such as antibacterial, antifouling, deodorant, and NOx decomposition, and exhibits various functions such as air and water. It can be used for purposes such as environmental purification. The molded article or functional composite provided by the present invention having a contact angle with water at 20 ° C of 60 ° or less (preferably 10) by light irradiation. Hydrophilic materials (such as hydrophilic molded bodies and hydrophilic films, and substrates coated with the hydrophilic films) are anti-fog technology that prevents fogging of mirrors and glass, as well as anti-fog technology. It can be applied to antifouling technology and antistatic technology for building exteriors, etc., and can be applied to window glass, mirrors, lenses, goggles, covers, porcelain, building materials, building exteriors, building interiors, structural members, vehicle exteriors and paintings, etc. It can be used for the exterior of mechanical devices and articles, various display devices, lighting devices, housing equipment, tableware, kitchen utensils, household electrical products, magnetic optical recording media, optical recording media, and the like.

The above-mentioned molded product or functional composite provided by the present invention, which is hydrophobic (hydrophobic) having a contact angle with water at 20 ° C of 70 ° or more (preferably 90 ° or more) by light irradiation. Sexual moldings, hydrophobic membranes, and the hydrophobicity the base material coated with the film, etc.) are provided with drip-proof property and drainage property, antifouling technology utilizing water-based dirt adhesion prevention and running water cleaning property, and further. Can be applied to ice and snow prevention technology, etc., such as window glass, windshield, mirrors, lenses, goggles, covers, porcelain, building materials, building exteriors, building interiors, structural members, vehicle exteriors and paintings, machinery and equipment. It can be used for the exterior of articles, various display devices, lighting devices, housing equipment, tableware, kitchen utensils, household electrical products, roofing materials, antennas, power transmission lines, ice and snow gliding equipment, and the like. The above-mentioned molded body or functional composite provided by the present invention having a photoelectric conversion function can exhibit functions such as power conversion of solar energy, and is used for (wet) solar cells and the like. It can be used for applications such as opto-semiconductor electrodes. Further, the member provided by the present invention whose wettability with water is changed by light irradiation (change from hydrophobicity to hydrophilicity or change from hydrophilicity to hydrophobicity) can be applied to an original plate for offset printing or the like. Very useful for applications.

The present invention will be specifically described with reference to the following Examples, Reference Examples and Comparative Examples, but these do not limit the scope of the present invention. Various physical properties were measured in Examples, Reference Examples and Comparative Examples by the following methods. (1) Average particle size (volume average particle size) The sample was diluted by adding an appropriate solvent so that the solid content in the sample was 1-20 wt%, and the measurement was performed using a wet particle size analyzer (Nikkiso Microtrac UPA-9230). (2) Weight average molecular weight It was determined by gel permeation chromatography (GPC) using a calibration curve prepared using a dimethyl silicone preparation. The conditions of GPC are as follows. Equipment: Tosoh HLC-8020LC-3A type chromatograph Column: TSKgel G1000H_XL, TSKgelG2000H_XLAnd TSKgel G4000H_XL(Both manufactured by Tosoh) were connected in series and used. Data processing device: CR-4A type data processing device manufactured by Shimadzu Corporation -Mobile phase: Chloroform Flow velocity: 1.0 ml / min. Sample preparation method It was subjected to analysis as a chloroform solution (concentration was appropriately adjusted in the range of 0.5 to 2% by weight).

(3) Infrared absorption (IR) spectrum The measurement was performed using an FT / IR-5300 type infrared spectrometer manufactured by JASCO Corporation. (4) Viscosity The measurement was performed using a Brookfield viscometer under the conditions of rotor No. 2, rotation speed 60 rpm, and 20 ° C. (5) Surface energy of film (or molded product) It was calculated from the contact angle (θ) of water with respect to the surface of the film (or molded product) measured by the method (7) below according to the following experimental formulas of Sell and Neumann.<maths num="2"><img file="JP4454476B2_D0009.tif" /></maths>[In the formula, γs represents the surface energy (dyne / cm) of the film (or molded product) whose contact angle of deionized water was measured, and γl represents the surface energy of water {72.8 dynes / cm (20 ° C)}. Represent. ]

(6) Measurement of the distribution of modified photocatalyst in the film By casting the modified photocatalyst composition on a film for overhead projectors (hereinafter referred to as "OHP film") so that the film thickness is 20 μm, drying at room temperature for 2 days, and then heating and drying at 50 ° C for 3 days. , A smooth film was formed on the surface of the OHP film. This OHP film is embedded in an epoxy resin using a Quetol 812 set manufactured by Nissin EM, then cut together with the film, and the cross section is cut with an energy dispersion type X-ray spectrophotometer (DX-4 type X manufactured by Nippon Phillips). The analysis was performed using a line spectrophotometer) and the content of the photocatalyst at each position in the film was measured. (7) Water contact angle with respect to the surface of the film (or molded product) Droplets of deionized water were placed on the surface of the film (or molded product), 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 (or molded article), the more hydrophilic the surface of the film (or molded article).

(8) Changes in hydrophilicity or hydrophobicity of the surface of the film (or molded product) before and after irradiation with ultraviolet rays After irradiating the surface of the film (or molded product) with Toshiba Lighting &amp; Technology's FL20SBLB type black light for 1 or 3 days, the contact angle of water was measured by the method (7) above and compared with that before irradiation. .. At this time, the UV intensity measured using Topcon's UVR-2 type UV intensity meter {using Topcon's UD-36 type light receiving part (corresponding to light with a wavelength of 310 to 400 nm)} is 1 mW / cm.² It was adjusted to be. (9) Changes in hydrophilicity or hydrophobicity of the film (or molded product) surface before and after sunlight irradiation After irradiating the surface of the film (or molded product) with sunlight for 3 hours, the contact angle of water was measured by the method (7) above and compared with that before irradiation. At this time, the ultraviolet intensity measured using the UVR-2 type ultraviolet intensity meter (using the UD-36 type light receiving part as the light receiving part) is 0.3 mW / cm.² , Visible light intensity measured using the same UV intensity meter {Uses Topcon's UD-40 type light receiving part (corresponding to light with a wavelength of 370 to 490 nm) as the light receiving part} is 3 mW / cm² The sunlight intensity was adjusted by passing through a glass plate so as to be.

(10) Changes in hydrophilicity or hydrophobicity of the film (or molded product) before and after irradiation with light containing almost no ultraviolet rays Light from Toshiba Lighting &amp; Technology's FL20S / N-SDLNU type fluorescent lamp on the surface of the film (or molded product) containing almost no ultraviolet light {The spectral energy distribution of this light is shown in Fig. 1. It is shown that this light contains almost no visible light and ultraviolet rays (wavelength less than 380 nm) having a wavelength of 380 to 390 nm. } Was irradiated for 24 hours, and then the contact angle of water was measured by the method of (7) above and compared with that before irradiation. At this time, the visible light intensity measured by using the UVR-2 type ultraviolet intensity meter (using the above UD-40 type light receiving part as the light receiving part) is 0.3 mW / cm.² It was adjusted to be.

(11) Photocatalytic activity on the surface of the film (or molded product) After applying a 5 wt% ethanol solution of methylene blue to the surface of the film (or molded product), it was irradiated with the above black light for 5 days. At this time, the ultraviolet intensity measured using the UVR-2 type ultraviolet intensity meter (the above UD-36 type light receiving part is used as the light receiving part) is 1 mW / cm.² It was adjusted to be. 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 surface of the film (or molded product)}. : Methylene blue is completely decomposed. Δ: A slight blue color of methylene blue remains. ×: Almost no decomposition of methylene blue was observed.

(12) Solvent resistance of the film The modified photocatalyst composition was spray-coated on a glass plate so as to have a film thickness of 30 μm, and then dried at room temperature for 1 week to form a transparent and smooth film on the surface of the glass plate. This film was peeled off from a glass plate, placed in a wire mesh (200 mesh) bag, immersed in acetone at room temperature for 24 hours, and then the retention rate of the film weight was calculated according to the following formula.<maths num="3"><img file="JP4454476B2_D0010.tif" /></maths> The higher the retention rate of the film weight, the higher the solvent resistance of the film.

[Reference Example 1] {Synthesis of water-soluble Si-H group-containing silicon compound (1)} In a reactor equipped with a reflux condenser, a thermometer and a stirrer, 500 g of dioxane, KF9901 {trade name of methylhydrogensiloxane-dimethylsiloxane copolymer (manufactured by Shin-Etsu Chemical Co., Ltd.), Si-H group content 7.14 mmol / g (catalog) (Stated value), weight average molecular weight 3900} 500 g was added, and the temperature was raised to 80 ° C with stirring. In addition to this, Uniox MUS-8 {trade name of polyoxyethylene allylmethyl ether (manufactured by Nippon Yushi), weight average molecular weight 800 (value listed in the catalog)} 1370 g and 5% by weight of platinum (IV) chloride hexahydrate. A solution prepared by dissolving 5 g of an isopropanol solution in 2310 g of dioxane was added with stirring at 80 ° C for about 1 hour, and after continuing stirring at 80 ° C for 2 hours, Si- was cooled to room temperature. A solution containing an H group-containing silicon compound (1) {hereinafter referred to as "compound (1)"} was obtained. When 100 g of water was added to 4 g of the obtained solution containing compound (1), a uniform transparent solution was obtained. Further, when 8 g of butyl cellosolve was added and mixed with 4 g of the solution containing this compound (1), and then 8 ml of a 1N sodium hydroxide aqueous solution was added, hydrogen gas was generated, and the volume was 37 ml at 23 ° C. The Si-H group content per 1 g of the solution containing compound (1), which was determined from the amount of hydrogen gas produced, was 0.36 mmol / g (Si-H group content converted per 1 g of KF9901 was about 3.5 mmol / g). there were.

[Reference Example 2] {Synthesis of Si-H group-containing silicon compound (2) having self-emulsifying property with water} In a reactor equipped with a reflux condenser, a thermometer and a stirrer, 170 g of dioxane, HMS-301-100GM {trade name of methylhydrogensiloxane-dimethylsiloxane copolymer (manufactured by Chisso), Si-H group content 4.523 mmol / g, weight average molecular weight 5400)} 100 g was added, and the temperature was raised to 80 ° C with stirring. To this, 50 g of Uniox MUS-8 (same as used in Reference Example 1), 25 g of 5-norbornene-2,3-dicarboxylic acid anhydride and 5 wt% isopropanol of platinum chloride (IV) acid hexahydrate. Si-H was added by dissolving 1.07 g of the solution in 170 g of dioxane at 80 ° C for about 1 hour under stirring, and after continuing stirring at 80 ° C for 3 hours, cooling to room temperature. A solution containing the group-containing silicon compound (2) {hereinafter referred to as "compound (2)"} was obtained. When 100 g of water was added to 4 g of the obtained solution containing compound (2), a slightly cloudy dispersion was obtained. Further, when 8 g of butyl cellosolve was added and mixed with 2.119 g of the solution containing this compound (2), and then 8 ml of a 1N sodium hydroxide aqueous solution was added, hydrogen gas was generated, and the volume was 31.0 ml at 22 ° C. It was. The Si-H group content per 1 g of the solution containing compound (2) determined from this amount of hydrogen gas produced was 0.588 mmol / g (HMS-301-100GM: Si-H group content converted per 1 g was about 2.58 mmol. It was / g).

(<u style="single">reference</u>Example 1) In a reactor equipped with a reflux condenser, a thermometer and a stirrer, Tynoc A-6 {trade name of anatase type titanium oxide sol (manufactured by Taki Chemical Co., Ltd.), ammonia defibration type, volume average particles of particles dispersed in the sol Diameter 13nm, TiO₂A concentration of 6% by weight and an average crystallite diameter of 10 nm (value described in the catalog)} 200 g were added, and 12.5 g of the solution containing the compound (1) obtained in Reference Example 1 was stirred at 30 ° C for about 30 minutes. After addition, the mixture was further stirred at 30 ° C. for 3 hours to obtain a sol containing modified titanium oxide particles having a volume average particle diameter of 20 nm, which had very good dispersibility. At this time, hydrogen gas was generated with the reaction of compound (1), and its volume was 125 ml at 23 ° C. The IR spectrum was measured by applying the obtained sol on a KRS-5 plate and then drying it at 50 ° C for 2 hours to form a film on the KRS-5 plate as a sample. 3630 ~ 3640 cm based on the hydroxyl group (hereinafter referred to as "Ti-OH group") directly connected to the titanium atom, which was observed in the IR spectrum of titanium oxide before modification.^-1Loss of absorption was observed. The volume average particle size of the obtained sol after standing at 30 ° C for 100 days was 23 nm. Using the obtained sol, the glass plate is spray-coated to a thickness of 2 μm and then dried at room temperature for 1 week to form a transparent and smooth film on the surface of the glass plate. The changes in hydrophilicity or hydrophobicity (evaluated based on the change in the contact angle of water with respect to the film surface) and the photocatalytic activity before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 1.

(<u style="single">reference</u>Example 2) A reactor equipped with a reflux condenser, a thermometer and a stirrer, nanotitania NTB-1 {trade name of brucite type titanium oxide sol (manufactured by Showa Denko), hydrochloric acid glutinous type, volume average particle diameter of particles in the sol 8 nm, TiO₂Add 70.2 g of the solution containing the compound (1) obtained in Reference Example 1 to a concentration of 15% by weight} 200 g over about 30 minutes with stirring at 30 ° C, and continue stirring at 30 ° C for 10 hours. Obtained a sol containing modified titanium oxide particles having a volume average particle diameter of 15 nm, which had very good dispersibility. At this time, hydrogen gas was generated by the reaction of compound (1), and its volume was 274 ml at 23 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption of Ti-OH groups, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. The volume average particle size of the obtained sol after standing at 30 ° C for 100 days was 21 nm. Using the obtained sol<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 1.

(<u style="single">reference</u>Example 3) A reactor equipped with a reflux condenser, a thermometer and a stirrer, TO-240 {trade name of a sol containing anatase-type titanium oxide whose particle surface is modified with a peroxo group (manufactured by Tanaka Transfer), dispersed in the sol. Volume average particle diameter of 15 nm, TiO₂Add 420 g of a concentration of 2.4% by weight}, add 23.4 g of the solution containing compound (1) obtained in Reference Example 1 at 30 ° C for about 30 minutes, and further stir at 30 ° C for 10 hours. By continuing, a sol containing modified titanium oxide particles having a volume average particle diameter of 17 nm, which had very good dispersibility, was obtained. At this time, hydrogen gas was generated by the reaction of compound (1) by the reaction of compound (1), and its volume was 67.5 ml at 23 ° C. The volume average particle size of the obtained sol after standing at 30 ° C for 100 days was 17 nm. Using the obtained sol<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 1.

(<u style="single">reference</u>Example 4) Jupiter F6-APS {Product name of sol containing anatase-type titanium oxide whose particle surface is modified with apatite (manufactured by Showa Denko) in a reactor equipped with a reflux condenser, a thermometer and a stirrer, particles in the sol Volume average particle size 36 nm, TiO₂Concentration 23.7% by weight)} 316 g was added, 78 g of the solution containing compound (1) obtained in Reference Example 1 was added at 30 ° C for about 30 minutes under stirring, and further stirred at 30 ° C for 10 hours. By continuing, a sol containing modified titanium oxide particles having a volume average particle diameter of 61 nm, which had very good dispersibility, was obtained. At this time, hydrogen gas was generated by the reaction of compound (1) by the reaction of compound (1), and its volume was 85.7 ml at 23 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption of Ti-OH groups, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. The volume average particle size of the obtained sol after standing at 30 ° C for 100 days was 80 nm. Using the obtained sol<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 1.

(<u style="single">reference</u>Example 5) STS-02 {Anatase type titanium oxide sol trade name (manufactured by Ishihara Sangyo), hydrochloric acid defibrated type, volume average particle diameter 18 nm of particles dispersed in the sol in a reactor equipped with a reflux condenser, a thermometer and a stirrer. , TiO₂A concentration of 30% by weight, an average crystallite diameter of 7 nm (value described in the catalog), a viscosity of 175 cps} 100 g and 50 g of water were added, and the temperature was raised to 50 ° C. with stirring. To this, 31 g of the solution containing the compound (1) obtained in Reference Example 1 is added under stirring at 50 ° C for about 30 minutes, and the mixture is further stirred at 50 ° C for 3 hours and then cooled to room temperature. As a result, a sol containing modified titanium oxide particles having a volume average particle diameter of 49 nm, which had very good dispersibility, was obtained. At this time, hydrogen gas was generated with the reaction of compound (1), and its volume was 200 ml at 24 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption based on the Ti-OH group, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. To 44 g of the obtained sol, 48 g of butyl cellosolve was added over about 10 minutes at room temperature (23 ° C) under stirring, water was removed under reduced pressure with an evaporator, and then an appropriate amount of butyl cellosolve was added to make the sol content a solid content. By adjusting the content to 6% by weight based on the total weight of the above, an organosol containing modified titanium oxide particles having a volume average particle diameter of 53 nm and having a very good dispersibility and using butyl cellosolve as a dispersion medium was obtained. The dispersion prepared by adding 10 g of toluene to 10 g of the obtained organosol was stable without agglutination of modified titanium oxide particles even after being left at room temperature for 6 months. Using the obtained organosol<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 1.

(<u style="single">reference</u>Example 6) In a reactor equipped with a reflux condenser, a thermometer and a stirrer, Tynoc A-6 (<u style="single">reference</u>Add 300 g (same as the one used in Example 1), add 8.8 g of the solution containing the compound (2) obtained in Reference Example 2 at 30 ° C over about 30 minutes under stirring, and add another 30 °. By continuing stirring at C for 24 hours, a sol containing modified titanium oxide particles having a volume average particle diameter of 48 nm, which had very good dispersibility, was obtained. At this time, hydrogen gas was generated with the reaction of compound (2), and its volume was 93 ml at 23 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption based on the Ti-OH group, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. Furthermore, it was also confirmed by the above IR spectrum that the cyclic acid anhydride group derived from 5-norbornene-2,3-dicarboxylic acid anhydride used in the production of compound (2) was ring-opened. The volume average particle size of the obtained sol after standing at 30 ° C for 100 days was 78 nm. Using the obtained sol<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 2.

(<u style="single">reference</u>Example 7) In a reactor equipped with a reflux condenser, a thermometer and a stirrer, Tynoc A-6 (<u style="single">reference</u>Add 300 g (same as the one used in Example 1), add 19.7 g of the solution containing the compound (2) obtained in Reference Example 2 at 30 ° C over about 30 minutes under stirring, and add another 30 °. By continuing stirring at C for 24 hours, a sol containing modified titanium oxide particles having a volume average particle diameter of 190 nm, which had very good dispersibility, was obtained. At this time, hydrogen gas was generated with the reaction of compound (2), and its volume was 72 ml at 23 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption based on the Ti-OH group, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. Furthermore, it was also confirmed by the above IR spectrum that the cyclic acid anhydride group derived from 5-norbornene-2,3-dicarboxylic acid anhydride used in the production of compound (2) was ring-opened. The volume average particle size of the obtained sol after standing at 30 ° C for 100 days was 198 nm. Using the obtained sol<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 2.

[Reference Example 3] (Production of a sol containing flaky titanium oxide particles) ST-21 {Titanium oxide powder manufactured by Ishihara Sangyo, average crystallite diameter 20 nm (value listed in the catalog)} 10 g and cesium carbonate 7.2 g were mixed in a mortar, and the obtained mixture was transferred to a platinum crucible with a lid. The carbonate was decomposed by heating and firing in an electric furnace at 800 ° C for 30 minutes. Cesium titanate (Cs) was obtained by grinding the obtained calcined product again in a mortar and calcining it at 800 ° C for 40 hours._xTi_{(2-x / 4)}O₄ ) (X = 0.68) (orthorhombic crystalline powder) was obtained. To 9 g of the obtained cesium titanate, 300 g of a 1N hydrochloric acid aqueous solution was added, the mixture was stirred at room temperature for 3 days, and the obtained reaction mixture was filtered (using a standard 5C filter paper) to obtain a residual residue. The obtained residue was washed with ion-exchanged water and dried at 100 ° C for 3 hours to replace cesium ions with hydrogen ions (H)._xTi_{(2-x / 4)}O₄ NH₂ O) (x = 0.68) (crystalline powder) 5.1 g was obtained. This is known to have a layered crystal structure. Next, 1000 g of a 0.1 mol / l tetrabutylammonium hydroxide aqueous solution was added to 5 g of this titanium acid, and the mixture was shaken at 150 rpm with a shaker to obtain titanium oxide particles (fine flakes) having a volume average particle diameter of 110 nm. A sol containing the above was obtained.

(<u style="single">reference</u>Example 8) 500 g of the sol containing the flaky titanium oxide particles obtained in Reference Example 3 was placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and 5.8 g of a solution containing the compound (1) obtained in Reference Example 1. Is added over about 30 minutes with stirring at 30 ° C, and by continuing stirring at 30 ° C for 10 hours, it contains modified titanium oxide particles with a very good dispersibility and a volume average particle diameter of 120 nm. I got a sol to do. At this time, hydrogen gas was generated with the reaction of compound (1), and its volume was 13.7 ml at 23 ° C. The volume average particle size of the obtained sol after standing at 30 ° C for 100 days was 143 nm. Using the obtained sol<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 2.

[Reference Example 4] {Synthesis of Si-H group-containing silicon compound (3) having self-emulsifying property with water and having a ladder-type skeleton} 1400 g of dioxane, 25.9 g of trichlorosilane and 51.6 g of methyltrichlorosilane were placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and the mixture was stirred at room temperature for about 10 minutes, and 14.5 g of water was added to the obtained mixture. The mixed solvent of 58 g of and dioxane was added dropwise over about 30 minutes under stirring while keeping the temperature at 25 to 30 ° C, and then further stirred at 25 to 30 ° C for about 30 minutes and then at 60 ° C for 3 hours. .. After cooling the obtained reaction mixture to 25 to 30 ° C, 65.5 g of trimethylchlorosilane was added, and a mixed solvent of 5.4 g of water and 22 g of dioxane was further stirred while keeping the temperature at 25 to 30 ° C. It was added over about 30 minutes. After that, the mixture was further stirred at 25 to 30 ° C. for about 2 hours. The obtained reaction mixture was taken out from the reactor and the solvent was distilled off under reduced pressure at about 60 ° C. to obtain a SiH group-containing silicon compound having a ladder-type skeleton and a weight average molecular weight of 3900. (Hereinafter referred to as "ladder-type silicon compound". In the IR spectrum of this compound, absorption based on the ladder-type skeleton (1130 cm)^-1And 1050 cm^-1) Was observed. ) When 0.4 g of the obtained ladder type silicon compound was dissolved in 8 g of butyl cellosolve and 8 ml of a 1N sodium hydroxide aqueous solution was added to the obtained solution, hydrogen gas was generated, and the volume was 46.2 ml at 24 ° C. .. The SiH group content of the ladder-type silicon compound determined from the amount of hydrogen gas produced was 4.52 mmol / g.

Subsequently, 10 g of the above-mentioned ladder-type silicon compound and 20 g of tetrahydrofuran were added to a reactor equipped with a reflux condenser, a thermometer and a stirrer, and the mixture was kept at 30 ° C. under stirring. After adding 0.2 g of a 2.2 wt% xylene solution of platinum-divinyltetramethyldisiloxane complex to this, Adecaria Soap SE-10N {trade name of the compound represented by the following formula (19) (manufactured by Asahi Denka)} 1.5 A solution prepared by dissolving g in 13.5 g of tetrahydrofuran is added at 30 ° C for about 2 hours under stirring, and further stirring is continued at 30 ° C for 3 hours to have self-emulsifying property with respect to water. , A solution containing a SiH group-containing silicon compound (3) having a ladder-type skeleton (hereinafter referred to as compound (3)) was obtained.<chemistry num="9"><img file="JP4454476B2_D0011.tif" /></chemistry> When 8 g of butyl cellosolve was added and mixed with 1.75 g of the obtained solution containing compound (3), and then 8 ml of a 1N sodium hydroxide aqueous solution was added, hydrogen gas was generated, and the volume was 43.4 ml at 22 ° C. .. The Si-H group content per 1 g of the solution containing compound (3) determined from this amount of hydrogen gas produced was 0.961 mmol / g (Si-H group content converted per 1 g of compound (3) was about 4.35 mmol / g. It was g).

[Reference Example 5] {Synthesis of Si-H group-containing silicon compound (4) having self-emulsifying property with water and having a ladder-type skeleton} 445 g of dioxane and 25.9 g of methyltrichlorosilane were placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and the mixture was stirred at room temperature for about 10 minutes. The mixed solvent was added dropwise over about 30 minutes under stirring while keeping the temperature at 25 to 30 ° C., and then further stirred at 25 to 30 ° C. for about 30 minutes and then at 60 ° C. for 3 hours. After cooling the obtained reaction mixture to 25 to 30 ° C, 25.1 g of dimethylchlorosilane is added, and a mixed solvent of 1.56 g of water and 6.24 g of dioxane is stirred while keeping the temperature at 25 to 30 ° C. It was added over about 30 minutes below. After that, the mixture was further stirred at 25 to 30 ° C. for about 2 hours. The obtained reaction mixture was taken out from the reactor and the solvent was distilled off under reduced pressure at about 60 ° C. to obtain a SiH group-containing silicon compound having a ladder-type skeleton and a weight average molecular weight of 3100. (Hereinafter referred to as "ladder-type silicon compound". In the IR spectrum of this compound, absorption based on the ladder-type skeleton (1130 cm)^-1And 1050 cm^-1) Was observed. ) When 0.44 g of the obtained ladder type silicon compound was dissolved in 8 g of butyl cellosolve and 8 ml of a 1N sodium hydroxide aqueous solution was added to the obtained solution, hydrogen gas was generated, and the volume was 40.9 ml at 22 ° C. .. The SiH group content of the ladder-type silicon compound determined from the amount of hydrogen gas produced was 3.75 mmol / g.

Subsequently, 10 g of the above-mentioned ladder-type silicon compound and 15 g of dioxane were added to a reactor equipped with a reflux condenser, a thermometer and a stirrer, and the temperature was raised to 80 ° C. under stirring. To this, a solution prepared by dissolving 3 g of Uniox MUS-8 (same as that used in Reference Example 1) and 0.1 g of a 5 wt% isopropanol solution of platinum chloride (IV) acid hexahydrate in 2.25 g of dioxane was added to 80 Add the mixture under stirring at ° C for about 1 hour, continue stirring at 80 ° C for 2 hours, and then cool to room temperature to make the rudder-type skeleton self-emulsifying with water. A solution containing the SiH group-containing silicon compound (4) {hereinafter referred to as compound (4)} was obtained. When 8 g of butyl cellosolve was added and mixed with 1.42 g of the obtained solution containing compound (4), and then 8 ml of a 1N sodium hydroxide aqueous solution was added, hydrogen gas was generated, and the volume was 28.0 ml at 22 ° C. .. The Si-H group content per 1 g of the solution containing compound (4) determined from this amount of hydrogen gas produced was 0.795 mmol / g (Si-H group content converted per 1 g of compound (4) was about 2.98 mmol / g. It was g).

(<u style="single">reference</u>Example 9) In a reactor equipped with a reflux condenser, a thermometer and a stirrer, Tynoc A-6 (<u style="single">reference</u>Add 500 g (same as that used in Example 1), add 15 g of the solution containing the compound (3) obtained in Reference Example 4 at 30 ° C over about 30 minutes under stirring, and further add 30 ° C. A sol containing modified titanium oxide particles having a volume average particle diameter of 53 nm, which had very good dispersibility, was obtained by continuing stirring for 24 hours. At this time, hydrogen gas was generated with the reaction of compound (3), and its volume was 40 ml at 23 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption of Ti-OH groups, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. The volume average particle size of the obtained sol after standing at 30 ° C for 100 days was 63 nm. Using the obtained sol<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 2.

(<u style="single">reference</u>Example 10) In a reactor equipped with a reflux condenser, a thermometer and a stirrer, Tynoc A-6 (<u style="single">reference</u>Add 500 g (same as the one used in Example 1), add 10.8 g of the solution containing the compound (4) obtained in Reference Example 5 at 30 ° C over about 30 minutes under stirring, and then add another 30 °. By continuing stirring at C for 8 hours, a sol containing modified titanium oxide particles having a volume average particle diameter of 29 nm, which had very good dispersibility, was obtained. At this time, hydrogen gas was generated with the reaction of compound (3), and its volume was 100 ml at 23 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption of Ti-OH groups, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. The volume average particle size of the obtained sol after standing at 30 ° C for 100 days was 30 nm. Using the obtained sol<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 2.

(<u style="single">reference</u>Example 11) In a reactor equipped with a reflux condenser, a thermometer and a stirrer, Tynoc A-6 (<u style="single">reference</u>50 g of the same as that used in Example 1 was added, and the trade name of Aciplex (-SS950 {5 wt% ethanol-water (weight ratio 1: 1) solution of fluororesin having a sulfonic acid group) was added thereto (manufactured by Asahi Kasei Kogyo Co., Ltd.). )} 6 g was added with stirring at 30 ° C for about 30 minutes, and further stirring at 30 ° C for 8 hours resulted in very good dispersibility of modified titanium oxide with a volume average particle diameter of 150 nm. A sol containing particles was obtained. The volume average particle diameter after allowing the obtained sol to stand at 30 ° C for 100 days was 147 nm. Using the obtained sol<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 3.

(<u style="single">reference</u>Example 12) Bistrator LNSC-200A {Product name of organic solvent-based silicone-acrylic coating agent (manufactured by Nippon Soda), solid content 20% by weight} (undercoat paint for conventional photocatalyst-containing coating agents) 100g,<u style="single">reference</u>150 g of the organosol obtained in Example 5 was added over about 10 minutes at room temperature with stirring to obtain a modified photocatalyst composition. Using the obtained modified photocatalyst composition, the glass plate was spray-coated to a thickness of 30 μm, dried at room temperature for 1 week, and then heated at 50 ° C for 5 days to obtain a glass plate. A transparent and smooth film was formed on the surface, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film were evaluated before and after irradiation with ultraviolet rays. The results are shown in Table 3.

[Comparative Example 1]<u style="single">reference</u>Bistrator LNSC-200A (instead of the modified photocatalytic composition obtained in Example 12)<u style="single">reference</u>Using the same as that used in Example 12)<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 12, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 3. [Comparative Example 2] Polydulex G633 {Product name of water-based acrylic-silicon emulsion (manufactured by Asahi Kasei Kogyo), solid content 46% by weight, pH 8.8} 250 g, CS-12 {2,2,4-trimethyl-1, as a film forming aid 3-Pentanediol-monoisobutyrate trade name (manufactured by Chisso)} 22.8 g was added over 20 minutes at room temperature with stirring. Next, 22.8 g of a butyl cellosolve aqueous solution (50% by weight) was added as a film-forming aid for 20 minutes under stirring at room temperature, and then the mixture was further stirred at room temperature for 3 hours to obtain an acrylic-silicon emulsion containing the film-forming aid. Obtained. The solid content of this emulsion was 38.6% by weight.<u style="single">reference</u>Using the above emulsion instead of the modified photocatalytic composition obtained in Example 12,<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 12, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 3.

(<u style="single">reference</u>Example 13) To 100 g of acrylic-silicone emulsion containing the film-forming aid obtained in Comparative Example 2,<u style="single">reference</u>75 g of the sol obtained in Example 6 was added over about 10 minutes at room temperature with stirring to obtain a modified photocatalyst composition. Using the obtained modified photocatalyst composition,<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 12, and the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. The results are shown in Table 3. [Comparative Example 3] STS-02 (<u style="single">reference</u>Using a sol obtained by diluting 100 g (same as that used in Example 5) with 50 g of water.<u style="single">reference</u>A film was formed on the surface of the glass plate by the same method as in Example 1, but since the obtained film was cracked, the change in hydrophilicity or hydrophobicity and photocatalytic activity of the surface of this film before and after irradiation with ultraviolet rays were evaluated. I couldn't. Further, 100 g of butyl cellosolve was added to 68 g of the obtained sol under stirring at room temperature for about 10 minutes, and then water was removed under reduced pressure with an evaporator to obtain an organosol, but the particles in the sol were contained in a liquid medium. It was not possible to obtain an organosol with good dispersibility because it precipitated without being held in a stably dispersed state.

[Comparative Example 4] To a reactor equipped with a reflux condenser, a thermometer and a stirrer, add 120 g of water to ST-01 {trade name of anatase-type titanium oxide powder manufactured by Ishihara Sangyo, average crystallite diameter 7 nm (value described in the catalog)} 30 g. The temperature was raised to 50 ° C with stirring. To this, 31 g of the solution containing the compound (1) obtained in Reference Example 1 was added under stirring at 50 ° C. for about 30 minutes, and the mixture was further stirred at 50 ° C. for 3 hours and then cooled to room temperature. The particles in the obtained reaction mixture were separated and settled, and the volume average particle size was 3 μm or more. Further, after adding 200 g of butyl cellosolve to this reaction mixture, water was removed under reduced pressure with an evaporator to obtain an organosol, but the particles in the sol precipitated without being held in a stably dispersed state in a liquid medium. Therefore, it was not possible to obtain an organosol with good dispersibility. Therefore, it was not possible to form a film on the surface of the glass plate using this sol.

[Comparative Example 5] STS-02 {trade name of anatase type titanium oxide sol (manufactured by Ishihara Sangyo), volume average particle size 18 nm, hydrochloric acid defibration type, TiO in a reactor equipped with a reflux condenser, a thermometer and a stirrer.₂Concentration 30% by weight, average crystallite diameter 7 nm (value listed in the catalog)} 100 g and 100 g of water were added, and a solution of 7.5 g of methyltrimethoxysilane dissolved in 7.5 g of dioxane was stirred at 30 ° C for about 30 minutes. A sol containing modified titanium oxide particles having a volume average particle diameter of 900 nm was obtained by further adding the mixture over and stirring at 30 ° C. for 3 hours.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the absorption of Ti-OH groups, which was observed in the IR spectrum of titanium oxide before modification, was small but did not disappear. From this, it was found that a considerable amount of Ti-OH groups remained. Using the obtained sol<u style="single">reference</u>A film was formed on the surface of the glass plate by the same method as in Example 1, but only a film having a cloudy, large unevenness was obtained. In addition, the obtained modified titanium oxide sol gelled after being stored at 30 ° C for 2 months, so that the coating film evaluation could not be performed.

[Comparative Example 6] In a reactor equipped with a reflux condenser, a thermometer and a stirrer, Tynoc A-6 (<u style="single">reference</u>Add 200 g (same as that used in Example 1), add a solution of 3 g of methyltrimethoxysilane in 3 g of dioxane at 30 ° C for about 30 minutes under stirring, and then add at 30 ° C. By continuing stirring for 3 hours, a sol containing modified titanium oxide particles having a volume particle diameter of 1 μm was obtained.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the absorption of Ti-OH groups, which was observed in the IR spectrum of titanium oxide before modification, was small but did not disappear. From this, it was found that a considerable amount of Ti-OH groups remained. The obtained modified titanium oxide sol was gelled by storage at 30 ° C. for 1 week, so that the coating film evaluation could not be performed. [Comparative Example 7] STS-02 (STS-02 (<u style="single">reference</u>Add 100g (same as used in Example 5) and 100g of water, and add Aciplex-SS950 (same as used in Example 5).<u style="single">reference</u>6 g (same as that used in Example 11) was added with stirring at 30 ° C for about 30 minutes, and further stirring was continued at 30 ° C for 8 hours for denatured oxidation with a volume average particle size of 3 μm or more. A sol containing titanium particles was obtained. Since the obtained modified titanium oxide sol precipitated over time, spray coating was impossible.

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[Reference Example 6] {Synthesis of Si-H group silicon-containing compound (5) having a keto group} 500 g of dioxane and 500 g of KF9901 (same as used in Reference Example 1) were placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and the temperature was raised to 60 ° C. under stirring. After adding 16.3 g of a 0.25 wt% dioxane solution of dichloro-dicyclopentadienyl-platinum (II) to this, 250 g of Uniox MUS-8 (same as that used in Reference Example 1) was dissolved in 250 g of dioxane. The solution was added at 60 ° C with stirring for about 30 minutes, and after further stirring at 60 ° C for 30 minutes, a solution prepared by dissolving 100 g of 5-hexen-2-one in 100 g of dioxane was added at 60 ° C under stirring. After about 30 minutes of addition, the mixture was further stirred at 60 ° C for 1 hour to obtain a SiH-based silicon-containing compound (5) {hereinafter referred to as compound (5)} having a keto group. A solution containing was obtained. When 100 g of water was added to 4 g of the obtained solution containing compound (5), a slightly cloudy dispersion was obtained. Further, when 8 g of butyl cellosolve was added and mixed with 0.89 g of the solution containing this compound (5), and then 8 ml of a 1N sodium hydroxide aqueous solution was added, hydrogen gas was generated, and the volume was 27.2 ml at 23 ° C. .. The Si-H group content per 1 g of the solution containing compound (5) determined from this amount of hydrogen gas produced was 1.2 mmol / g (Si-H group content converted per 1 g of KF9901 was about 4.1 mmol / g). It was.

[Reference Example 7] {Synthesis of Si-H group-containing silicon compound (6) having a methacryloyl group} 100 g of dioxane and 100 g of KF9901 (same as used in Reference Example 1) were placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and the temperature was raised to 60 ° C. under stirring. To this, 5 g of a 0.25 wt% dioxane solution of dichloro-dicyclopentadienyl-platinum (II) was added, and then 50 g of Uniox MUS-8 (same as that used in Reference Example 1) was dissolved in 50 g of dioxane. Was added over about 1 hour with stirring at 60 ° C. Subsequently, a solution prepared by dissolving 20 g of allyl methacrylate and 0.01 g of the polymerization inhibitor 4-methoxyhydroquinone in 20 g of dioxane was added at 60 ° C for about 30 minutes with stirring, and then further stirred at 60 ° C for 1 hour. A solution containing a SiH group-containing silicon compound (6) {hereinafter referred to as compound (6)} having a methacryloyl group was obtained. When 100 g of water was added to 4 g of the obtained solution containing compound (6), a slightly cloudy dispersion was obtained. Further, when 8 g of butyl cellosolve was added and mixed with 1.25 g of the solution containing this compound (6), and then 8 ml of a 1N sodium hydroxide aqueous solution was added, hydrogen gas was generated, and the volume was 42.0 ml at 23 ° C. .. The Si-H group content per 1 g of the solution containing compound (6) determined from this amount of hydrogen gas produced was 1.3 mmol / g (Si-H group content converted per 1 g of KF9901 was about 4.6 mmol / g). It was.

[Reference Example 8] {Preparation of an emulsion of a silicon-modified polymer having a keto group} 8 g of methacrylic acid, 3 g of diacetone acrylamide, 34 g of methyl methacrylate, 40 g of butyl acrylate, 15 g of cyclohexyl methacrylate, 300 g of water, Latemul S-180A in a reactor equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer. Add 20 g of a 20% aqueous solution of {trade name of ammonium sulfosuccinic acid diesterammonium salt having a double bond copolymerizable with an ethylenically unsaturated monomer (manufactured by Kao)} and raise the temperature inside the reactor to 78 ° C. After raising to C, 0.5 g of ammonium persulfate was added and stirred at 78 ° C for 1 hour to obtain the first stage seed latex. The pH of the obtained first stage seed latex was 1.8. Next, in the seed latex of the first stage, 3 g of methacrylic acid, 12 g of diacetone acrylamide, 165 g of methyl methacrylate, 160 g of butyl acrylate, 60 g of cyclohexyl methacrylate, 330 g of water, 20 g of a 20% aqueous solution of Latemul S-180A, and ammonium persulfate. A solution containing 1.0 g and a solution containing 2.5 g of γ-methacryloxypropyltrimethoxysilane, 25 g of dimethyldimethoxysilane, and 25 g of methyltrimethoxysilane were placed in separate dropping tanks at 80 ° C. for 3 hours under stirring. And dropped into the reactor. After the dropping was completed, the temperature inside the reactor was raised to 85 ° C, and the mixture was stirred for 6 hours. After that, it was cooled to room temperature, and the hydrogen ion concentration of the reactor contents was measured and found to be 2.1. An emulsion was obtained by adding a 25% aqueous ammonia solution to adjust the pH of the reactor contents to 8 and then filtering through a 100 mesh wire mesh to filter off the agglomerates. The dry weight of the agglomerates was very small, 0.02%, based on the total weight of the monomers used. The solid content of the obtained emulsion was 44.0% by weight, and the volume average particle size was 128 μm.

[Reference Example 9] (Preparation of semicarbazide derivative aqueous solution) 230 g of isopropyl alcohol and 20 g of hydrazine monohydrate at room temperature were placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and Duranate 24A {Biulet type polyisocyanate trade name (manufactured by Asahi Kasei Kogyo), NCO A solution in which 42 g of the content was 23.3% by weight was dissolved in 168 g of tetrahydrofuran was added with stirring at 40 ° C for about 1 hour, and further stirring was continued at 40 ° C for 3 hours. Tetrahydrofuran, hydrazine, water and the like in the obtained reaction mixture were distilled off under reduced pressure, and then an appropriate amount of water was added to obtain an aqueous semicarbazide derivative having a solid content of 30%.

(<u style="single">reference</u>Example 14) In a reactor equipped with a reflux condenser, a thermometer and a stirrer, Tynoc A-6 (<u style="single">reference</u>Add 300 g (same as the one used in Example 1), add 15.3 g of the solution containing the compound (5) obtained in Reference Example 6 at 30 ° C over about 30 minutes under stirring, and add another 30 °. By continuing stirring at C for 5 hours, a sol containing modified titanium oxide particles having a volume average particle diameter of 18 nm, which had very good dispersibility, was obtained. At this time, hydrogen gas was generated with the reaction of compound (5), and its volume was 122 ml at 23 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption of Ti-OH groups, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. The volume average particle size of the obtained sol after standing at 30 ° C for 100 days was 23 nm. Next, 11.3 g of the semicarbazide derivative aqueous solution obtained in Reference Example 9 was added to 200 g of the emulsion of the silicon-modified polymer having a keto group obtained in Reference Example 8 over about 20 minutes at room temperature with stirring. To the obtained mixture, 230 g of the above sol was added with stirring at room temperature for about 30 minutes, and the mixture was further stirred at room temperature for 3 hours to obtain a modified photocatalyst composition. Using the obtained modified photocatalyst composition,<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 12, and the photocatalytic activity of the surface of this film was evaluated and found to be good (). Further, the retention rate of the film weight of the obtained film by immersion in acetone was 97%, and the solvent resistance was very good.

(<u style="single">reference</u>Example 15) STS-02 (STS-02 (<u style="single">reference</u>Add 100 g (same as that used in Example 5) and 50 g of water, add 26 g of the solution containing the compound (6) obtained in Reference Example 7 to this over about 30 minutes with stirring at 30 ° C. By continuing stirring at 30 ° C. for 7 hours, a sol containing modified titanium oxide particles having a volume average particle diameter of 38 nm, which had very good dispersibility, was obtained. At this time, hydrogen gas was generated with the reaction of compound (6), and its volume was 240 ml at 24 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption of Ti-OH groups, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. Next, in a reactor equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, 100 g of the above sol, 353 g of water, Adecaria Soap SE-1025N {trade name of surfactant (manufactured by Asahi Denka), 25% Add 2 g of aqueous solution) and raise the temperature inside the reactor to 80 ° C, then 6 g of methacrylic acid, 61 g of butyl acrylate, 70 g of methyl methacrylate, 1.2 g of acrylamide, 80 g of water, and 2.7 g of adecaria soap. , 1.4 g of sodium p-styrene sulfonate and 0.5 g of ammonium persulfate were added dropwise to the reactor volume from a dropping tank at 80 ° C. over 2 hours. After completion of the dropping, the mixture was stirred at 80 ° C. for 2 hours. After that, the mixture was cooled to room temperature, a 25% aqueous ammonia solution was added to adjust the pH of the reactor contents to 8, and then the mixture was filtered through a 100-mesh wire mesh to remove agglomerates. A modified photocatalyst composition having a diameter of 95 nm (modified photocatalyst-acrylic composite emulsion) was obtained. Using the obtained modified photocatalyst composition,<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 12, and the photocatalytic activity of the surface of this film was evaluated and found to be good ().

[Reference Example 10] {Synthesis of Si-H group-containing silicon compound (7) having self-emulsifying property with water} 50 g of dioxane and 50 g of HMS-301-100GM (same as used in Reference Example 2) were placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and the temperature was raised to 80 ° C. under stirring. To this, 25 g of Uniox MUS-8 (same as that used in Reference Example 1) and 0.53 g of a 5 wt% isopropanol solution of platinum (IV) chloride hexahydrate were dissolved in 62.5 g of dioxane at 80 ° C. SiH group-containing silicon compound (7) {hereinafter Compound (7) by adding the mixture at 80 ° C for about 1 hour, continuing stirring at 80 ° C for 2 hours, and then cooling to room temperature. A solution containing} was obtained. When 100 g of water was added to 4 g of the obtained solution containing compound (7), a slightly cloudy dispersion was obtained. Further, when 8 g of butyl cellosolve was added and mixed with 2.23 g of the solution containing this compound (7), and then 8 ml of a 1N sodium hydroxide aqueous solution was added, hydrogen gas was generated, and the volume was 45.2 ml at 21 ° C. .. The Si-H group content per 1 g of the solution containing compound (7) determined from this amount of hydrogen gas produced was 0.825 mmol / g (Si-H group content converted per 1 g of HMS-301-100GM was about 3.1 mmol / g. It was g).

[Reference Example 11] {Synthesis of SiH group-containing silicon compound (8) having self-emulsifying property with water and having a fluoroalkyl group} 50 g of methyl ethyl ketone and 50 g of HMS-301-100GM (same as that used in Reference Example 2) were placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and the temperature was raised to 60 ° C. under stirring. To this, 1.6 g of a 0.25% dioxane solution of dichloro-dicyclopentadienyl-platinum (II) was added, and then 25 g of Uniox MUS-8 (same as that used in Reference Example 1) was dissolved in 25 g of methyl ethyl ketone. Was added over about 30 minutes with stirring at 60 ° C, and further stirring was continued at 60 ° C for 30 minutes. To this, a solution prepared by dissolving 10 g of perfluorooctylethylene and 1.1 g of a 0.25% dioxane solution of dichloro-dicyclopentadienyl-platinum (II) in 10 g of methyl ethyl ketone was added at 60 ° C. over about 1 hour, and further 60 By continuing stirring at ° C for 8 hours and then cooling to room temperature, a solution containing a SiH group-containing silicon compound (8) {hereinafter referred to as compound (8)} having a fluoroalkyl group is obtained. It was. When 100 g of water was added to 4 g of the obtained solution containing the compound (8), a slightly cloudy dispersion was obtained. Further, when 8 g of butyl cellosolve was added and mixed with 1.094 g of the solution containing this compound (8), and then 8 ml of a 1N sodium hydroxide aqueous solution was added, hydrogen gas was generated, and the volume was 25.5 ml at 17 ° C. .. The Si-H group content per 1 g of the solution containing the compound (8) determined from the amount of hydrogen gas produced was 0.962 mmol / g (HMS-301-100GM: the Si-H group content converted per 1 g was about 3.31 mmol / g. It was g).

[Reference Example 12] (Measurement of surface energy of organic solvent-based acrylic coating agent) Plaace {trade name of organic solvent-based acrylic coating agent (manufactured by Musashi Paint Co., Ltd.), solid content 50% by weight} is cast on a glass plate so that the film thickness is 20 μm, and then dried at room temperature for 2 days at 50 ° C. A transparent and smooth film was formed on the surface of the glass plate by heating and drying for 3 days. The contact angle of water with respect to the obtained film surface at 20 ° C was 84 °, and the surface energy of the film determined from the Sell-Neumann empirical formula was 35.5 dynes / cm (20 ° C). [Reference Example 13] (Measurement of surface energy of water-based acrylic-silicon emulsion) Using the acrylic-silicon emulsion containing the film forming aid prepared in Comparative Example 2, a transparent and smooth film was formed on the surface of the glass plate in the same manner as in Reference Example 12. The contact angle of water with respect to the obtained film surface at 20 ° C was 89 °, and the surface energy of the film determined from the Sell-Neumann empirical formula was 31.5 dynes / cm (20 ° C).

(<u style="single">reference</u>Example 17) In a reactor equipped with a reflux condenser, a thermometer and a stirrer, Tynoc A-6 (<u style="single">reference</u>Add 400 g (same as that used in Example 1) and 10.3 g of the solution containing the compound (7) obtained in Reference Example 10 at room temperature of 30 ° C for about 30 minutes under stirring, and further to 30 ° C. By continuing stirring for 3 hours, a sol containing modified titanium oxide particles having a volume average particle diameter of 17 nm, which had very good dispersibility, was obtained. At this time, hydrogen gas was generated with the reaction of compound (7), and its volume was 80 ml at 16 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption of Ti-OH groups, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. To 100 g of the obtained sol, 100 g of butyl cellosolve was added under stirring at room temperature (23 ° C) for about 10 minutes, water was removed under reduced pressure with an evaporator, and an appropriate amount of butyl cellosolve was added. By adjusting the content to 5.8% by weight based on the total weight, an organosol containing particles having a volume average particle diameter of 25 nm, which had very good dispersibility, was obtained.

(<u style="single">reference</u>Example 18) In a reactor equipped with a reflux condenser, a thermometer and a stirrer, Tynoc A-6 (<u style="single">reference</u>Add 300 g (same as the one used in Example 1) and 15.5 g of the solution containing the compound (8) obtained in Reference Example 11 at room temperature of 30 ° C for about 30 minutes under stirring, and further to 30 ° C. By continuing stirring for 5 hours, the dispersibility is very good, and the volume average particle size is 30 nm.<u style="single">Modified titanium oxide particles</u>A sol containing the above was obtained. At this time, hydrogen gas was generated with the reaction of compound (8), and its volume was 140 ml at 16 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption of Ti-OH groups, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. To 100 g of the obtained sol, 100 g of butyl cellosolve was added under stirring at room temperature (23 ° C) for about 10 minutes, water was removed under reduced pressure with an evaporator, and an appropriate amount of butyl cellosolve was added. By adjusting the content to 7.1% by weight based on the total weight, an organosol having very good dispersibility using butyl cellosolve as a dispersion medium was obtained. Using the obtained organosol<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate in the same manner as in Example 17. The contact angle of water with respect to the obtained film surface at 20 ° C was 106.0 °, and the surface energy of the above film determined from the Sell-Neumann empirical formula was 19.2 dynes / cm (20 ° C). A modified photocatalyst composition was obtained by adding 20 g of the above organosol to 100 g of Plaace (same as that used in Reference Example 12) at room temperature (23 ° C) with stirring at room temperature for about 10 minutes. The obtained modified photocatalyst composition was cast on an OHP film so as to have a film thickness of 20 μm, dried at room temperature for 2 days, and then heated and dried at 50 ° C. for 3 days to smooth the surface of the OHP film. A film was formed. Figure 3 shows the results of measuring the distribution of titanium atoms in the cross section of this film using an energy dispersive X-ray spectrometer. Titanium oxide does not exist at the interface between the OHP film, which is the base material, and the film, and the distribution is such that the titanium oxide content increases from the inside of the film toward the surface side of the film (opposite the interface). It turned out that it was. Moreover, when the photocatalytic activity was evaluated on the surface of this film, it was good ().

〔<u style="single">reference</u>Example 19] To 100 g of the acrylic-silicon emulsion containing the film-forming aid to which the film-forming aid was added, obtained in Comparative Example 2.<u style="single">reference</u>A modified photocatalyst composition was obtained by adding 19 g of the sol obtained in Example 18 at room temperature (23 ° C.) under stirring for about 10 minutes. Using the obtained modified photocatalyst composition,<u style="single">reference</u>A smooth film was formed on the surface of the OHP film in the same manner as in Example 18. As a result of measuring the distribution of titanium atoms in the cross section of this film using an energy dispersive X-ray spectroscope, the content of titanium oxide increased from the inside of the film toward the surface side of the film (opposite the interface). It was confirmed that the distribution was gradual. Moreover, when the photocatalytic activity was evaluated on the surface of this film, it was good ().

[Comparative Example 8] Using Plaace (same as used in Reference Example 12)<u style="single">reference</u>A smooth film was formed on the surface of the OHP film in the same manner as in Example 18. However, no photocatalytic activity was observed on the surface of the obtained film (×). [Comparative Example 9] Glass plate using KS-247 {trade name of anatase type titanium oxide organosol (manufactured by TAYCA), average particle size 6 nm (catalog value), micelle diameter 30-60 nm (catalog value), solid content 15% by weight} After spray coating on the glass so that the film thickness was 0.5 μm, the mixture was dried at 50 ° C. for 1 week to form a film on the surface of the glass plate. The contact angle of water with respect to the obtained film surface at 20 ° C was 69.8 °, and the surface energy of the film obtained from the Sell-Neumann empirical formula was 48.0 dynes / cm (20 ° C). Next, 8 g of the above KS-247 was added to 100 g of Plaace (same as that used in Reference Example 12) at room temperature (23 ° C) under stirring for about 10 minutes, and the obtained composition was used.<u style="single">reference</u>A smooth film was formed on the surface of the OHP film in the same manner as in Example 18. As a result of measuring the distribution of titanium atoms in the cross section of this film using an energy dispersive X-ray spectroscope, the distribution of titanium atoms was random, from the inside of the film toward the surface side of the film (opposite the above interface). No distribution was observed in which the titanium oxide content increased. Moreover, when the photocatalytic activity of the surface of this film was evaluated, it was defective (× to Δ).

[Comparative Example 10] 30 g of ST-01 (same as that used in Comparative Example 4) and 120 g of toluene were placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and the temperature was raised to 50 ° C under stirring. The particles in the contents did not disperse in the liquid medium and settled, and did not form a sol. To this, 12.9 g of the solution containing the compound (7) obtained in Reference Example 10 was added under stirring at 50 ° C for about 30 minutes, and further stirring was continued at 50 ° C for 3 hours to disperse the modified photocatalyst. Obtained liquid. At this time, hydrogen gas was generated with the reaction of compound (7), and its volume was 70 ml at 19 ° C. The obtained modified photocatalyst dispersion was an unstable dispersion in which the modified photocatalyst particles were not maintained in a dispersed state in the liquid medium and settled over time. The liquid medium was removed from the obtained modified photocatalyst dispersion under reduced pressure at 50 ° C., and the obtained modified titanium oxide powder was placed in a tablet molding machine for preparing a sample for infrared absorption spectrum measurement, and the pressure was 750 kg / cm.² Compressed with to make pellets. The contact angle of water with respect to the surface of the obtained pellet at 20 ° C was 93.0 °, and the surface energy of the pellet obtained from the Sell-Neumann empirical formula was 28.4 dynes / cm (20 ° C). Then, 1.2 g of the modified titanium oxide powder was added to 100 g of Plaace (same as that used in Reference Example 12) at room temperature (23 ° C) with stirring to obtain a composition. Using the obtained composition, a film was formed on the surface of the OHP film in the same manner as in Example 17. As a result of measuring the distribution of titanium atoms in the cross section of this film using an energy dispersive X-ray spectrometer, it was observed that the distribution of Ti was random and a considerable amount of titanium oxide was in contact with the OHP film. It was. Moreover, when the photocatalytic activity of the surface of this film was evaluated, it was defective (× to Δ).

[Reference Example 14] {Synthesis of SiH group-containing silicon compound (9) having a cyclic acid anhydride group} 168 g of dioxane and 100 g of KF9901 (same as used in Reference Example 1) were placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and the temperature was raised to 80 ° C. under stirring. To this, 50 g of Uniox MUS-8 (same as used in Reference Example 1), 28 g of 5-norbornene-2,3-dicarboxylic acid anhydride and 5 wt% isopropanol solution of platinum chloride (IV) acid hexahydrate. A solution prepared by dissolving 1.1 g in 100 g of dioxane was added at 80 ° C for about 1 hour under stirring, and the mixture was further stirred at 80 ° C for 2 hours and then cooled to room temperature to obtain cyclic acid anhydride. A solution containing a SiH group-containing silicon compound (9) {hereinafter referred to as compound (9)} having a group was obtained. When 8 g of butyl cellosolve was added and mixed with 1.4 g of the obtained solution containing compound (9), and then 8 ml of a 1N sodium hydroxide aqueous solution was added, hydrogen gas was generated, and the volume was 35.8 ml at 21 ° C. .. The Si-H group content per 1 g of the solution containing compound (9), which was determined from the amount of hydrogen gas produced, was 1.02 mmol / g (KF9901). The Si-H group content per gram was about 4.5 mmol / g).

[Reference Example 15] {Synthesis of SiH group-containing silicon compound (10) having a spectroscopic sensitizing group} 30 g of the solution containing the compound (9) obtained in Reference Example 14 was placed in a reactor equipped with a reflux cooler, a thermometer and a stirrer, and 0.23 g of 2,4-dinitrophenylhydrazine was dissolved in 22.7 g of tetrahydrofuran. The solution was added with stirring at 20 ° C for about 30 minutes, and further stirring at 20 ° C for 3 hours resulted in a SiH group-containing silicon compound having a spectral sensitizing group (10) {hereinafter A solution containing} referred to as compound (10) was obtained. (<u style="single">reference</u>Example 20) {Preparation of modified photocatalytic sol using SiH group-containing compound (9) having a cyclic acid anhydride group} STS-02 (STS-02 (<u style="single">reference</u>200 g (same as that used in Example 5) and 100 g of water were added and heated to 30 ° C with stirring. To this, 30 g of the solution containing the compound (9) obtained in Reference Example 14 was added with stirring at 30 ° C for about 30 minutes, and further stirring was continued at 30 ° C for 3 hours to obtain extremely dispersibility. A sol containing modified titanium oxide particles having a volume average particle diameter of 29 nm was obtained. At this time, hydrogen gas was generated with the reaction of compound (9), and its volume was 112 ml at 20 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption based on the Ti-OH group, which was observed in the IR spectrum of titanium oxide before denaturation, was observed.

(Example 21) STS-02 (STS-02 (<u style="single">reference</u>(Same as that used in Example 5) 100 g and 50 g of water were added and heated to 30 ° C with stirring. To this, 26 g of the solution containing the compound (10) obtained in Reference Example 15 was added with stirring at 30 ° C for about 30 minutes, and further stirring was continued at 30 ° C for 3 hours to obtain extremely dispersibility. A sol containing orange-colored modified titanium oxide particles having a volume average particle diameter of 36 nm was obtained. At this time, hydrogen gas was generated with the reaction of compound (10), and its volume was 110 ml at 20 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption based on the Ti-OH group, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. Using the obtained sol<u style="single">reference</u>A transparent (orange) smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity of the surface of this film before and after sunlight irradiation was evaluated. The results are shown in Table 4.

(<u style="single">reference</u>Example 22) In a reactor equipped with a reflux condenser, a thermometer and a stirrer,<u style="single">reference</u>100 g of the sol obtained in Example 20 was added, and a solution prepared by dissolving 0.07 g of 2,4-dinitrophenylhydrazine in 7 g of tetrahydrofuran was added to the solution at 20 ° C for about 30 minutes with stirring, and further adjusted to 20 ° C. By continuing stirring for 3 hours, a sol containing orange-colored modified titanium oxide particles having a volume average particle diameter of 33 nm, which had very good dispersibility, was obtained. Using the obtained sol<u style="single">reference</u>A transparent (orange) smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity of the surface of this film before and after sunlight irradiation was evaluated. The results are shown in Table 4.

[Reference Comparative Example 1]<u style="single">reference</u>Using the sol obtained in Example 20,<u style="single">reference</u>A transparent and smooth film was formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity of the surface of this film before and after irradiation with sunlight was evaluated. The results are shown in Table 4.<tables num="4"><img file="JP4454476B2_D0015.tif" /></tables>

[Reference Example 16] {Synthesis of SiH group-containing silicon compound (11) having a spectroscopic sensitizing group} 10 g of 4-aminofluorescein and 1400 g of dioxane were placed in a reactor equipped with a reflux condenser, a thermometer and a stirrer, and a solution of 2.4 g of allyl isocyanate dissolved in 22.6 g of dioxane was added thereto at 30 ° C. under stirring. The mixture was added over about 30 minutes and further stirred at 30 ° C. for 5 hours. To the obtained reaction mixture, 500 g of KF9901 (same as that used in Reference Example 1) was added, and the temperature was raised to 80 ° C. with stirring. A solution prepared by dissolving 1370 g of Uniox MUS-8 (same as that used in Reference Example 1) and 5 g of a 5 wt% isopropanol solution of platinum (IV) chloride hexahydrate in 1370 g of dioxane was dissolved at 80 ° C. SiH group-containing silicon compound having a spectral sensitizing group by adding over about 1 hour, continuing stirring at 80 ° C for 2 hours, and then cooling to room temperature (11) {hereinafter Compound (11) A solution containing} "is obtained. When 100 g of water was added to 4 g of the obtained solution containing the compound (11), an aqueous solution having a uniform transparency and a fluorescent color was obtained. Further, when 8 g of butyl cellosolve was added and mixed with 4 g of the solution containing this compound (11), and then 8 ml of a 1N sodium hydroxide aqueous solution was added, hydrogen gas was generated, and the volume was 33 ml at 23 ° C. The Si-H group content per 1 g of the solution containing the compound (11) determined from this amount of hydrogen gas produced was 0.32 mmol / g (Si-H group content converted per 1 g of KF9901 was about 3.1 mmol / g). It was.

[Example 23] In a reactor equipped with a reflux condenser, a thermometer and a stirrer, Tynoc A-6 (<u style="single">reference</u>200 g (same as that used in Example 1) was added, and 12.5 g of the solution containing the compound (11) obtained in Reference Example 16 was added to the solution at 30 ° C over about 30 minutes with stirring, and further 30 ° C. By continuing stirring at C for 3 hours, a sol containing modified titanium oxide particles having a fluorescent color with a volume average particle diameter of 23 nm, which had very good dispersibility, was obtained. At this time, hydrogen gas was generated with the reaction of compound (11), and its volume was 120 ml at 23 ° C.<u style="single">reference</u>When the IR spectrum was measured by the same method as in Example 1, the disappearance of absorption based on the Ti-OH group, which was observed in the IR spectrum of titanium oxide before denaturation, was observed. Using the obtained sol<u style="single">reference</u>A transparent (yellow to green) smooth film is formed on the surface of the glass plate by the same method as in Example 1, and the change in hydrophilicity or hydrophobicity of the surface of this film before and after irradiation with light containing almost no ultraviolet rays is observed. evaluated. The results are shown in Table 5. [Reference comparison example 2]<u style="single">reference</u>In Example 1, the change in hydrophilicity or hydrophobicity of the surface of the film formed on the surface of the glass plate before and after irradiation with light containing almost no ultraviolet rays was evaluated. The results are shown in Table 5.

[Comparative Example 11] Tynok A-6 (<u style="single">reference</u>The same as that used in Example 1) was spray-coated on the glass plate so that the film thickness was 0.5 μm, and then dried at room temperature for 1 week to form a transparent and smooth film on the glass plate surface. After forming, the surface of this film was evaluated for changes in hydrophilicity or hydrophobicity before and after irradiation with light containing almost no ultraviolet rays. The results are shown in Table 5.<tables num="5"><img file="JP4454476B2_D0016.tif" /></tables>

When the modified photocatalyst particles of the present invention and the modified photocatalyst composition containing the modified photocatalyst particles and the functional substance are used to form a film containing the modified photocatalyst on the surface of the substrate, the modified photocatalyst becomes active. Under mild conditions, it is firmly immobilized on the surface of the base material, and the formed film and the base material coated with the above-mentioned film do not deteriorate due to the action of the modified photocatalyst. .. Moreover, since the above-mentioned film is excellent in transparency, durability, stain resistance, hardness and the like, it is extremely useful in preventing dirt from adhering to the surface of various base materials and preventing fogging. Further, in the functional composite and the molded product of the present invention, the modified photocatalyst exerts a sufficient effect on the surface thereof, so that dirt adhesion and fogging on the surface are effectively prevented.

<figref num="1">FIG. 1 is a graph showing the spectral energy distribution of light from the FL20S / N-SDLNU type fluorescent lamp manufactured by Toshiba Lighting &amp; Technology.</figref><figref num="2">In FIG. 2, using the modified photocatalyst composition produced in Example 17, the distribution of titanium atoms in the cross section of the film formed on the surface of an OHP (overhead projector) film was measured using an energy dispersive X-ray spectrometer. It is a graph which shows the result of this.</figref><figref num="3">FIG. 3 shows the results of measuring the distribution of titanium atoms in the cross section of the film formed on the surface of the OHP film using the modified photocatalyst composition produced in Example 18 using an energy dispersive X-ray spectrometer. It is a graph.</figref>