Organic-inorganic hybrid material and its production

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to an organic-inorganic hybrid material comprising a material exhibiting a photocatalytic action as a surface layer and a method for producing the same. Such an organic-inorganic hybrid material is a functional material useful for applications that require removal of various odors and stains, sterilization, and the like.

【0002】

[Conventional technology]

Recently, titanium oxide, which is a material having a photocatalytic action, has been used as a deodorant, antifouling, antibacterial, and sterilizing material. This means that when titanium oxide is exposed to light, active oxygen species such as OH radicals are generated on the surface, and most of the organic substances attached to the surface are finally decomposed into carbon dioxide and water. We are using. Since the photocatalytic action of titanium oxide is very strong, titanium oxide has often been supported on the surface of an inorganic material such as ceramics such as tiles.

【0003】

However, in the future, it will be more necessary to support it on other materials, for example, organic materials such as plastics and fibers having excellent moldability. However, titanium oxide has a very strong photocatalytic action as described above, so that various inconveniences occur. That is, the base material portion in contact with titanium oxide undergoes significant deterioration due to its strong oxidizing action. In the case of organic materials, unlike inorganic materials, this deterioration leads to a shorter service life.

【0004】

In order to prevent this, when titanium oxide is supported on a base material, a method of using a persistent resin such as a fluororesin or a silicon-based resin as an adhesive (Japanese Patent Laid-Open No. 7-171408, JP-A-7-265714) has been used so far. And a method of supporting titanium oxide fine particles on a porous body (Japanese Patent Laid-Open No. 3-157125, Japanese Patent Application Laid-Open No. 7-213913) have been proposed. However, even if these methods are adopted, the deterioration of these materials cannot be sufficiently prevented due to the contact between titanium oxide and the resin or the base material as the adhesive.

【0005】

In addition, a method of partially coating titanium oxide particles with alkyl silicate (Japanese Patent Laid-Open No. 10-33988) has also been proposed, but if the amount of alkyl silicate added is small, the contact area between titanium oxide and the base material becomes large, and the contact area becomes large. After all, deterioration of the base material cannot be prevented. On the contrary, if the amount of alkyl silicate added is increased, the relative amount of titanium oxide in the material decreases, so that the photocatalytic action is not sufficiently exhibited.

【0006】

[Problems to be Solved by the Invention]

An object of the present invention is to solve the above-mentioned conventional problems and to provide an organic-inorganic hybrid material which is provided with a material exhibiting a photocatalytic action as a surface layer but does not deteriorate the base material supporting the material, and a method for producing the same. is there.

【0007】

[Means for solving problems]

According to the present invention, in an organic-inorganic hybrid material having an intermediate layer and a photocatalytic layer sequentially formed on a base material and the surface of the base material, the intermediate layer is shared by an organic polymer component and a metal oxide component. An organic-inorganic hybrid polymer material formed by bonding and having a component gradient structure in which the concentration of a metal oxide component increases in the surface direction, and the photocatalytic layer is a metal oxidation exhibiting a photocatalytic action. It is intended to provide an organic-inorganic hybrid material composed of a material containing a substance, whereby the above-mentioned object is achieved.

【0008】

BEST MODE FOR CARRYING OUT THE INVENTION

Base material As the base material, an inorganic material such as ceramics such as tile can be used as in the conventional case, but an organic material can also be used. For example, general-purpose plastics materials such as thermoplastic resins and thermosetting resins, and polymer materials such as engineering plastics materials can be used. The shape of the base material includes not only a plate shape but also a molded body having various shapes such as a thread, a film, a spherical shape, and a block. It is preferable to use an organic material that is lightweight and easy to mold.

【0009】

Middle layer The intermediate layer means a layer that prevents the photocatalytic layer from coming into contact with the base material by being located between the base material and the photocatalytic layer. The intermediate layer does not exhibit photocatalytic action, and even if it comes into contact with a base material made of an organic material, the contacted portion of the base material is not deteriorated, and the intermediate layer is formed of a material having good adhesion to the base material and the photocatalytic action layer. Is preferable. A preferable material for forming the intermediate layer is an organic-inorganic hybrid polymer material formed by covalently bonding an organic polymer component and a metal oxide component.

【0010】

The content of the organic polymer component in the organic-inorganic hybrid polymer material is not particularly limited, but when coating the base material of the organic material as a coating film, the base is used to further improve the adhesion to the base material. The contact surface portion with the material is preferably 50% by weight or more. Further, in order to prevent deterioration of the base material, it is desirable that the content of the organic polymer component is close to 0% at the interface portion with the material having a photocatalytic action. In other words, the closer the content of the metal oxide component is to 100% at this interface, the better.

【0011】

In order to realize such a preferable composition distribution of the organic polymer component and the metal oxide component, in the present invention, the composition of the organic-inorganic hybrid polymer material forming the intermediate layer is set to the metal oxide component in the surface direction. Adjust to increase the concentration of. In the present specification, such a structure in which the concentration of the component in the thickness direction increases or decreases is referred to as a component inclined structure.

【0012】

As the component inclined structure, the content of the organic polymer component or the metal oxide component changes continuously in the thickness direction of the material while the finally obtained organic-inorganic hybrid polymer material is micro-homogeneous. It may have a region, and is not particularly limited by the manufacturing method.

【0013】

That is, in the present invention, the composition ratio of the organic polymer and the metal oxide continuously changes in the thickness direction in the organic-inorganic hybrid polymer material except in the thickness direction, and is directed toward the surface. Basically, the concentration of metal oxides is increasing. Therefore, the organic-inorganic hybrid material of the present invention is based on a material having regions having different component concentrations discontinuously due to irregular aggregation or phase separation, or a uniform coating film having a constant component concentration formed by coating. It is different from the one on the surface of.

【0014】

The organic-inorganic hybrid polymer material is obtained by hydrolyzing and hydrolyzing, for example, an organic polymer having a metal alkoxide group as a functional group, or a mixture of an organic polymer having a functional group capable of reacting with a metal alkoxide compound and a metal alkoxide compound. Obtained by polycondensation.

【0015】

In the present invention, the organic polymer (A) having a functional group capable of reacting with the metal alkoxide compound (B) may be synthesized by any method.

【0016】

The organic polymer (A) has an organic chain portion as a main skeleton. Examples of such main skeletons are polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate; polyamide, polyacetal, polycarbonate, polyester, polyphenylene ether; polymethylpentene, polysulfone, polyether sulfone, polyphthalamide; polyphenylene. Sulfide, Polyarylate, Polyester, Polyetherimide; Thermoplastic resin such as polyether ketone and skeleton of thermoplastic elastomer; Heat of phenol resin, epoxy resin, acrylic resin, melamine resin, alkyd resin, urea resin, silicone resin, etc. Examples include the skeleton of a curable resin.

【0017】

The organic polymer (A) may have one component of the polymer or precursor as described above as the main skeleton, or may be a copolymer skeleton of these multiple components. Further, a mixture of a plurality of types may be used, and either a branched shape or a linear shape may be used. Further, it is desirable to dissolve or swell in a solvent such as a halogenated hydrocarbon-based solvent, an ether-based solvent, an alcohol-based solvent, or an aprotic polar solvent, and the number average molecular weight is 500 to 50000, preferably 1000 to 15000.

【0018】

Among these, a thermoplastic resin is preferable as the organic polymer (A), and engineering plastics such as polyamide, polyacetal, polycarbonate, polysulfone, and polyarylate are more preferable in terms of high performance.

【0019】

The functional group of the organic polymer (A) may be any as long as it can react with the metal alkoxide compound (B), and is not particularly limited, and specific examples thereof include a metal alkoxide group, a hydroxyl group, an amino group, and a carboxyl group. The metal alkoxide group is particularly preferable. The functional group equivalent of the organic polymer (A) is 1 to 100, preferably 1 to 50, and more preferably 2 to 10. If the functional group equivalent of the organic polymer (A) is less than 1, the performance of the material may deteriorate, and if it exceeds 100, the material may become brittle. The functional groups of one molecule of the organic polymer (A) may be all the same, or may be a plurality of types.

【0020】

As the metal alkoxide compound (B), any type of compound can be used as long as it does not show a photocatalytic action when it is made into a metal oxide and the contacted portion is not deteriorated even if it comes into contact with a base material made of an organic material. Can be used. Among them, the preferable one is the equation (1). A_pM formula (1) [In the formula, A is an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and M is Si, Zr, Fe, Sn, B, Al, Ge, Ce, Ta, Ba, Ga, Pb and W. It is a metal element selected from the group consisting of the above, preferably the group consisting of Si and Zr, and p is an integer of 2 to 6. ] Is a compound represented by.

【0021】

Specifically, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane, tetraalkoxyzirconiums such as tetran-propoxyzylene, tetraisopropoxyzylene, and tetrabutoxyzinezyl, and Examples thereof include metal alkoxides such as diethoxyvalium, trimethoxyboron, triethoxygallium, tributoxyaluminum, tetraethoxygermanium, tetrabutoxylead, pentan-propoxytantal, and hexaethoxytungsten.

【0022】

Another example of the metal alkoxide compound (B) is in formula (2). R_kA_lM (R'_mX)_n Equation (2) [In the formula, R is hydrogen, an alkyl group or phenyl group having 1 to 12 carbon atoms, preferably 1 to 5, A is an alkoxy group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and M is Si. , Zr, Fe, Sn, B, Al, Ge, Ce, Ta and W, etc., preferably a metal element selected from the group consisting of Si and Zr, and R'has 1 to 4 carbon atoms, preferably Is an alkylene group or an alkylidene group of 2 to 4, and X is an isocyanate group, an epoxy group, a carboxyl group, an acid halide group, an acid anhydride group, an amino group, a thiol group, a vinyl group, a methacryl group, a halogen group, etc. A general functional group, k is an integer from 0 to 5, l is an integer from 1 to 5, m is an integer from 0 or 1, and n is an integer from 0 to 5. ] Is a compound represented by.

【0023】

Taking Si as an example, to give specific examples, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, dimethoxysilane, diethoxysilane, diisopropoxysilane, monomethoxysilane, monoethoxysilane, monobutoxysilane. , Methyldimethoxysilane, ethyldiethoxysilane, dimethylmethoxysilane, diisopropylisopropoxysilane, methyltrimethoxysilane, ethyltriethoxysilane, n-propyltri n-propoxysilane, butyltributoxysilane, dimethyldimethoxysilane, diethyldiethoxy Silane, diisopropyldiisopropoxysilane, dibutyldibutoxysilane, trimethylmethoxysilane, triethylethoxylan, tri-n-propyl n-propoxysilane, tributylbutoxysilane, phenyltrimethoxylan, diphenyldiethoxysilane, triphenylmethoxysilane, etc. (Alkyl) Alkoxysilane; 3-Isocyanuspropyltriethoxysilane, 2-Isocyanateethyltri n-propoxysilane, 3-Ixanopropylmethyldimethoxysilane, 2-Ixocyanateethylethyldibutoxysilane, 3-Ixionpropyldimethylisopropoxysilane, 2-Ixocyanate ethyl diethylbutoxysilane, di (3-isocyanpropyl) diethoxysilane, di (3-isocyanpropyl) methylethoxysilane, ethoxysilane triisocyanate (alkyl) alkoxysilane; 3-glycid Xipropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3,4-epoxybutyltrimethoxysilane (Alkyl) alkoxysilane having an epoxy group such as;(Alkoxy) alkoxysilane having a carboxyl group such as carboxymethyltriethoxysilane, carboxymethylethyldiethoxysilane, carboxyethyldimethylmethoxysilane; Acid anhydride such as 3- (triethoxysilyl) -2-methylpropylsuccinate anhydride Alkoxysilane having a physical group; Alkoxysilane having an acid halide group such as 2- (4-chlorosulfonylphenyl) ethyltriethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 It has an amino group such as-(aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane (alkyl). ) Alkoxysilane; (alkyl) alkoxysilane having a thiol group such as 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Alkoxysilane having a vinyl group such as methyldiethoxysilane; having a methacryl group such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypyrropyrmethyldimethylsilane ( Alkoxy (alkyl) alkoxysilanes; (alkyl) alkoxysilanes having halogen groups such as triethoxyfluorosilane, 3-chloropropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 2-chloroethylmethyldimethoxysilane; ..3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl)-3-aminopropylmethyldimethoxysilane, (Alkoxy) alkoxysilane having an amino group such as N-phenyl-3-aminopropyltrimethoxysilane; thiol group such as 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane (Alkoxy) alkoxysilane having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltri (Alkoxy) alkoxysilane having a methacryl group such as ethoxysilane, 3-methacryloxypyrropyrmethyldimethylsilane; triethoxyfluorosilane, 3-chloropropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 2-chloroethylmethyl (Alkoxy) alkoxysilane having a halogen group such as dimethoxysilane; can be mentioned.3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl)-3-aminopropylmethyldimethoxysilane, (Alkoxy) alkoxysilane having an amino group such as N-phenyl-3-aminopropyltrimethoxysilane; thiol group such as 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane (Alkoxy) alkoxysilane having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltri (Alkoxy) alkoxysilane having a methacryl group such as ethoxysilane, 3-methacryloxypyrropyrmethyldimethylsilane; triethoxyfluorosilane, 3-chloropropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 2-chloroethylmethyl (Alkoxy) alkoxysilane having a halogen group such as dimethoxysilane; can be mentioned.(Alkoxy) alkoxysilane having a methacryl group such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypyrropyrmethyldimethylsilane; triethoxyfluorosilane, 3-chloropropyltrimethoxy (Alkoxy) alkoxysilane having a halogen group such as silane, 3-bromopropyltriethoxysilane, 2-chloroethylmethyldimethoxysilane; can be mentioned.(Alkoxy) alkoxysilane having a methacryl group such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypyrropyrmethyldimethylsilane; triethoxyfluorosilane, 3-chloropropyltrimethoxy (Alkoxy) alkoxysilane having a halogen group such as silane, 3-bromopropyltriethoxysilane, 2-chloroethylmethyldimethoxysilane; can be mentioned.

【0024】

Of course, not only Si but also metals such as Zr, Fe, Sn, B, Al, Ge, Ce, Ta and W can be exemplified by similar compounds that do not show photocatalytic action when they are used as metal oxides. it can.

【0025】

Only one kind of these metal alkoxide compounds (B) may be used, or two or more kinds thereof may be used in combination. Also, Mg [Al (iso-OC)₃H₇)₄]₂, Ba [Zr₂(OC₂H₅)₉]₂, (C₃H₇O)₂Zr [Al (OC₃H₇)₄]₂Metal alkoxide compounds containing two or more kinds of metal elements in one molecule, tetramethoxysilane oligomers, tetraethoxysilane oligomers, etc., oligomer-type metals having two or more repeating units in one molecule. An alkoxide compound may be used. Further, the alkoxy group may be an acetoxy group or an acetyl acetoxy group.

【0026】

Among the organic polymers (A), those having a hydroxyl group, an amino group, a carboxyl group or the like as functional groups can be reacted with the metal alkoxide (B) by a conventional method. As a result, an organic polymer having a metal alkoxide group having a higher reactivity as a functional group can be obtained. The reaction method between the organic polymer (A) and the metal alkoxide (B) is described in detail in, for example, paragraphs 0039 to 0054 of Japanese Patent Application No. 9-327842.

【0027】

The intermediate layer has a double structure consisting of a first intermediate layer and a second intermediate layer sequentially formed on the surface of the base material, and the first intermediate layer is a covalent bond between an organic polymer component and a metal oxide component. The organic-inorganic hybrid polymer material formed in the above, which has a component inclined structure in which the concentration of the metal oxide component increases in the surface direction, and the second intermediate layer is crosslinked with the metal oxide. It may be composed of an inorganic material formed in the above.

【0028】

In this case, the photocatalytic layer is in contact with the second intermediate layer made of metal oxide and not in contact with the organic-inorganic hybrid polymer material. Therefore, not only the deterioration of the base material is prevented, but also the deterioration of the organic chain portion contained in the organic-inorganic hybrid polymer material by the photocatalytic layer is prevented. As a result, the service life of the organic-inorganic hybrid material is further extended.

【0029】

Hydrolysis and polycondensation by the sol-gel method are to convert an alkoxy group into a hydroxyl group by reacting a metal alkoxide compound or a polymer having a metal alkoxy group with water, and then polycondensate this hydroxyl group simultaneously. This refers to a reaction in which a compound or polymer having a hydroxy metal group (for example, -SiOH) undergoes a dehydration reaction or a dealcohol reaction with an adjacent molecule, and is three-dimensionally crosslinked via an inorganic covalent bond. At this time, the polycondensation reaction is most likely to cause a dehydration reaction of two hydroxymetal groups, but it can also occur with other functional groups having active hydrogen such as a hydroxyl group, an amino group, and a carboxyl group.

【0030】

The water used in the hydrolysis reaction may be added in an amount necessary for converting all the alkoxy groups into hydroxyl groups, the water content in the reaction system may be used, or the water content in the atmosphere may be absorbed. You may.

【0031】

The reaction conditions are preferably about 0.5 to 24 hours at room temperature to 100 ° C. At that time, acidic catalysts such as hydrochloric acid, sulfuric acid, acetic acid, benzenesulfonic acid and p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, ammonia, triethylamine, piperidine, 1,8-diazabicyclo [5,4,0] -7-A basic catalyst such as undecene (DBU) may be used.

【0032】

In all the hydrolysis processes in the present invention, the content of inorganic substances and the crosslink density between polymers are adjusted for the purpose of improving or newly imparting functions such as strength, hardness, weather resistance, chemical resistance, flame retardancy, and antistatic property. Metals such as Si, Ti, Zr, Fe, Cu, Sn, B, Al, Ge, Ce, Ta, and W, metal oxides, metal complexes, inorganic salts, and the like may coexist for adjustment. Further, formamide, dimethylformamide, dioxane, oxalic acid and the like may be added as a drying inhibitor in order to suppress cracks that may occur during gelation, drying and heat treatment, and acetylacetone and the like may be added as additives. You may.

【0033】

The dry thickness of the intermediate layer is generally 0.01 to 1000 μm, preferably 0.1 to 100 μm. If this layer thickness exceeds 1000 μm, not only does it take time to form the layer, but it also requires a large amount of raw materials, which is disadvantageous in terms of cost. If it is less than 0.01 μm, pinholes are likely to occur, and the expected functions are sufficient. May not be expressed in.

【0034】

When the intermediate layer has a two-layer structure consisting of a first intermediate layer and a second intermediate layer, the dry thickness of the first intermediate layer is generally 0.01 to 1000 μm, preferably 0.1 to 100 μm. If this layer thickness exceeds 1000 μm, not only does it take time to form the layer, but it also requires a large amount of raw materials, which is disadvantageous in terms of cost. If it is less than 0.01 μm, pinholes are likely to occur, and the expected functions are sufficient. May not be expressed in. The dry thickness of the second intermediate layer is generally 0.01 to 100 μm, preferably 0.1 to 10 μm. If this layer thickness exceeds 100 μm, the layer may crack or peel off. If it is less than 0.01 μm, pinholes are likely to occur, and the expected function may not be fully exhibited.

【0035】

Photocatalytic layer The photocatalytic layer is a layer made of a material exhibiting photocatalytic action. The stronger the photocatalytic property, the better. The shape of the material having a photocatalytic action is not particularly limited, but a large surface area is preferable in order to enhance the photocatalytic action. For example, when the material having a photocatalytic action is in the form of particles, if the particle size is too large, the appearance and tactile sensation of the base material may be impaired, so it is desirable to make the material 100 μm or less. In addition, it is desirable to reduce the particle size because the photocatalytic action tends to be more active as the particles are finer.

【0036】

An example of a material exhibiting a photocatalytic action is a material containing a metal oxide (C) having a photocatalytic action. Only one type of metal oxide (C) may be used, two or more types may be used in combination, or two or more metal elements may be contained in one molecule. Further, other inorganic substances may be contained for the purpose of enhancing photocatalytic property, increasing mechanical strength, imparting flexibility, and the like.

【0037】

The content of (C) of the metal oxide in the photocatalytic layer is generally about 10 to 100% by weight, preferably about 20 to 100% by weight. As the metal oxide (C), it is preferable to use titanium oxide, copper (I) or the like.

【0038】

The titanium oxide may be obtained by a known method such as a method of neutralizing or hydrolyzing titanium sulfate, titanium tetrachloride or a titanium acid ester, or a method of vapor phase oxidation of titanium tetrachloride. Examples thereof include anatase-type titanium oxide, rutile-type titanium oxide, amorphous titanium oxide, hydrated titanium oxide, and the like, and mixtures thereof.

【0039】

Copper (I) oxide can be obtained by hydrolysis of copper (I) chloride or reduction of copper (II) oxide or copper (II) hydroxide.

【0040】

The metal oxide (C) is an inorganic polymer material obtained by hydrolyzing and polycondensing a metal metal alkoxide compound of a metal that exhibits a photocatalytic action when it is made into a metal oxide, or a metal alkoxide mixture containing the same. May be good. As the metal alkoxide compound having a photocatalytic action, it is preferable to use a metal alkoxide compound represented by the formula (1) having a metal element such as Ti or Cu as the central metal (M).

【0041】

Further, as another example, a metal alkoxide compound represented by the formula (2) having a metal element such as Ti or Cu as the central metal (M) may be used.

【0042】

Specifically, tetraalkoxytitaniums such as tetramethoxytitanium, tetraethoxytitanium, tetran-propoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium; and dimethoxycopper, diethoxycopper, din-propoxycopper, diisopropoxy. Examples thereof include dialkoxy coppers such as copper and dibutoxy copper.

【0043】

Only one kind of these metal alkoxide compounds may be used, or two or more kinds thereof may be used in combination. Further, a metal alkoxide compound in which two or more kinds of metal elements are contained in one molecule or an oligomer-type metal alkoxide compound having two or more repeating units in one molecule may be used. Further, the alkoxy group may be an acetoxy group or an acetyl acetoxy group.

【0044】

The photocatalytic layer may have a component gradient structure of a material exhibiting photocatalyst action such that the concentration of the metal oxide (C) increases toward the surface in the thickness direction. In that case, the content of the metal oxide exhibiting photocatalytic action is preferably 10 to 100% by weight, and 50 to 100% by weight in the highest region.

【0045】

The dry thickness of the photocatalytic layer is generally 0.01 to 100 μm, preferably 0.1 to 10 μm. If this layer thickness exceeds 100 μm, the layer may crack or peel off. If it is less than 0.01 μm, pinholes are likely to occur, and the expected function may not be fully exhibited.

【0046】

Manufacture of organic-inorganic hybrid materials The organic-inorganic hybrid material of the present invention is formed by utilizing a sol-gel reaction using an organic polymer having a functional group capable of reacting with a metal alkoxide compound, a metal alkoxide compound, and a material exhibiting a photocatalytic action as main raw materials. ..

【0047】

First, an organic polymer having a metal alkoxide group as a functional group, or a mixture of an organic polymer having a functional group capable of reacting with a metal alkoxide compound and a metal alkoxide compound is dissolved in an appropriate solvent, and in some cases, an acid or a base. Is added as a catalyst and hydrolyzed. A substrate having a surface is then provided, the resulting solution or wet gel is applied onto the surface of the substrate, and then an intermediate layer is formed by evaporating a portion of the solvent. As described above, it is preferable to adjust the composition of this intermediate layer so that the organic polymer component is contained in an amount of 50% by weight or more based on the solid content.

【0048】

Then, another solution or wet gel is prepared in the same manner as in the above step except that the composition ratio is changed so as to increase the concentration of the metal alkoxide compound. Then, this solution or a wet gel is applied onto the coating layer formed in the above step. Further, this step is repeated to superimpose the coating layers to form an intermediate layer. Ultimately, the content of the wet gel, i.e. the organic polymer component in the coating layer, is reduced to 30% by weight or less, preferably 10% by weight or less on a solid content basis.

【0049】

Each of the above-mentioned coating layers and each layer formed by coating a solution or a wet gel in this production step may or may not be dried before coating the next layer. In order to improve the adhesion with the layer formed on the layer, it is preferable to keep the drying to the minimum necessary. When it is dried, it may be left at room temperature to be dried, or it may be heated and dried.

【0050】

If it is desired to prevent contact between the photocatalytic layer and the organic-inorganic hybrid polymer material and further extend the service life of the organic-inorganic hybrid material, a metal oxide is formed by cross-linking on the intermediate layer. A second intermediate layer made of an inorganic polymer material may be further formed. In that case, a solution or a wet gel containing a metal alkoxide compound that does not exhibit a photocatalytic action when formed as a metal oxide is further applied on the surface of this intermediate layer.

【0051】

Next, a photocatalytic layer made of a material exhibiting photocatalysis is formed on the surface of the intermediate layer (or the second intermediate layer). As the material exhibiting a photocatalytic action, it is preferable to use a material containing a metal oxide (C) having a photocatalytic action. The photocatalytic layer can be formed, for example, by dispersing a metal oxide powder (particles) containing a metal oxide (C) in a volatile solvent and applying the obtained dispersion to the surface of the intermediate layer. Further, the powder (particles) of the metal oxide containing the metal oxide (C) may be directly applied to the surface of the intermediate layer in the state of a wet gel. A metal alkoxide compound of a metal that exhibits a photocatalytic action when it is a metal oxide, or a mixture of a metal alkoxide containing the same may be prepared as a solution or a wet gel, and this may be applied to the surface of the intermediate layer.

【0052】

This step may be repeated a plurality of times to form the photocatalytic layer into a multi-layer structure, and at that time, the composition of the material exhibiting the photocatalytic action may be changed, for example, by increasing the content of the metal oxide (C). Good. In that case, it can be a photocatalytic layer having a component gradient structure of a material exhibiting a photocatalytic action such that the concentration of the metal oxide (C) increases toward the surface in the thickness direction.

【0053】

Further, as another method for forming the component inclined structure in the intermediate layer or the photocatalytic layer, the solution diffusion method described in the specification of the agent reference number 164605, which is filed on the same day by the same applicant, can also be used. Good. By using this method, a component inclined structure can be produced in a simpler process. Then, the formed layer is dried. Drying may be carried out by leaving it at room temperature, but if it is desired to further promote the condensation reaction and strengthen the cross-linking, heat treatment is carried out at 50 to 500 ° C. for about 5 minutes to 48 hours.

【0054】

[Effect of the invention]

In the organic-inorganic hybrid material of the present invention, the organic polymer component and the metal oxide component are microscopically homogeneous, and the content of the organic polymer component or the metal oxide component continuously changes in the thickness direction of the material. In addition, the two components are covalently bonded. Therefore, it is a material having excellent chemical resistance that does not cause deformation such as cracks, peeling or warping of only the surface layer surface, or strain due to heating, thermal shock, or aging. Further, the surface layer portion is provided with a material having a photocatalytic action, which makes the material even more highly functional.

【0055】

In the organic-inorganic hybrid material of the present invention, the characteristics of the inorganic material such as heat resistance, weather resistance, surface hardness, rigidity, water resistance, chemical resistance, stain resistance, mechanical strength, and flame retardancy are given to the organic polymer. It is given well. Conversely, the characteristics such as impact resistance, flexibility, processability, and lightness of the organic polymer are satisfactorily imparted to the inorganic material.

【0056】

Moreover, by using a metal oxide as a material having a photocatalytic action, the photocatalytic properties can be maximized without deteriorating the base material by containing the material in the surface layer portion in a form that is extremely difficult to contact with the organic material. ..

【0057】

In addition, by using an organic polymer that can be covalently bonded to the metal oxide contained in the surface layer and has extremely good adhesiveness to the base material due to the interaction between the surface layer and the base material, It is possible to use a material that is unlikely to be deformed such as cracks or peeling of only the surface layer surface.

【0058】

The organic-inorganic hybrid material of the present invention is provided with a material exhibiting a photocatalytic action as a surface layer, and deterioration of the base material supporting the material is effectively prevented. Therefore, even when an organic material is used as the carrier, the service life of the organic-inorganic hybrid material is extended. That is, high-performance and high-performance plastic materials, plastic molded products or films, structural materials, optical materials, surface modifiers, hard coat agents, electricity or Suitable for use in electronic materials, medical materials, etc.

【0059】

[Example]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

【0060】

Synthesis example 1 Dissolve 70.0 g of polycarbonate diol with a number average molecular weight of 3900 and a hydroxyl group equivalent of 1.8 in 500 mL of chloroform, then add 13.3 g of 3-isocyanatepropyltriethoxysilane to this solution, heat it under reflux for 10 hours, and then cool it to room temperature. did. This reaction solution was added dropwise to 7 L of methanol to precipitate a product. The precipitate was filtered off, washed with methanol, and dried under reduced pressure (yield 97%).

【0061】

¹By H-NMR measurement, it was confirmed that the obtained product was a double-ended triethoxysilylated polycarbonate (PCS) having an alkoxysilyl group introduced at both ends. The alkoxysilyl group equivalent of this product was 1.8. As a result of GPC analysis, the number average molecular weight of this product was 4400.

【0062】

Synthesis example 2 26.0 g of polysulfone diol having a number average molecular weight of 5200 and a hydroxyl equivalent of 1.7 is dissolved in 300 mL of chloroform, then 3.5 g of 3-isocyanate propyltriethoxysilane is added to this solution, heated under reflux for 11 hours, and then cooled to room temperature. did. This reaction solution was added dropwise to 3 L of methanol to precipitate a product. The precipitate was filtered off, washed with methanol, and dried under reduced pressure (yield 96%).

【0063】

¹From H-NMR measurement, it was confirmed that the obtained product was bi-terminal triethoxysilylated polysulfone (PSS) in which an alkoxysilyl group was introduced at both ends. The alkoxysilyl group equivalent of this product was 1.7. As a result of GPC analysis, the number average molecular weight of this product was 6000.

【0064】

Synthesis example 3 30.5 g of polyallylate diol having a number average molecular weight of 6100 and a hydroxyl equivalent of 1.6 is dissolved in 300 mL of chloroform, 3.2 g of 3-isocyanatepropyltriethoxysilane is added to this solution, and the mixture is heated under reflux for 15 hours and then at room temperature. Cooled to. This reaction solution was added dropwise to 3 L of methanol to precipitate a product. The precipitate was filtered off, washed with methanol, and dried under reduced pressure (yield 96%).

【0065】

¹It was confirmed that the product obtained by H-NMR measurement was a bi-terminal triethoxysilylated polyarylate (PAS) in which an alkoxysilyl group was introduced at both ends. The alkoxysilyl group equivalent of this product was 1.6. As a result of GPC analysis, the number average molecular weight of this product was 6700.

【0066】

Example 1 A mixed composition containing PCS having a number average molecular weight of 4400 and tetraethoxysilane (TEOS) prepared in Synthesis Example 1 in the ratio shown in Table 1 was hydrolyzed in tetrahydrofuran (THF) using 1N-hydrochloric acid solution at room temperature. No. 1 to 4 solutions were obtained.

【0067】

In addition, TEOS and Ishihara Techno's titanium oxide ST-21 for photocatalyst (average particle size 0.02 μm, TiO)₂) Was treated in THF with 1N-hydrochloric acid solution at room temperature to obtain dispersions of Nos. 5 to 7.

【0068】

[table 1]

<img file="JP2000246114A_D0001.tif" />【0069】

The solutions in Table 1 were coated on a polycarbonate substrate using a spin coater in the order of Nos. 1 to 7. At this time, after applying one solution, the next solution was applied after waiting for 1 minute at room temperature. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours (film thickness 80 μm).

【0070】

By such an operation, as shown in FIG. 1, the component inclined crosslinked silica / PCS (102) is provided as the first intermediate layer and the crosslinked silica (103) is provided as the second intermediate layer on the polycarbonate base material (101). Then, an organic-inorganic hybrid material (100) having a component gradient crosslinked silica / titanium oxide (104) as a photocatalytic layer was obtained.

【0071】

Example 2 The solutions in Table 1 were coated on a polycarbonate substrate using a spin coater in the order of Nos. 1 to 4. At this time, after applying one solution, the next solution was applied after waiting for 1 minute at room temperature.

【0072】

After applying the No. 4 solution, Ishihara Techno's titanium oxide for photocatalyst ST-21 (average particle size 0.02 μm, TiO)₂) A dispersion in which 4.0 g was well dispersed in 20 ml of THF was immediately coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours.

【0073】

By such an operation, as shown in FIG. 2, the component gradient crosslinked silica / PCS (202) is provided as the first intermediate layer and the crosslinked silica (203) is provided as the second intermediate layer on the polycarbonate base material (201). Then, an organic-inorganic hybrid material (200) having titanium oxide particles (204) as a photocatalytic layer was obtained.

【0074】

Example 3 A mixed composition containing PSS having a number average molecular weight of 6000 and tetramethoxysilane oligomer MKC silicate MS-56 (TMOS) manufactured by Mitsubishi Chemical Corporation with a number average molecular weight of 1000 prepared in Synthesis Example 2 in the ratio shown in Table 2 is contained in THF. Hydrolysis was carried out at room temperature using 1N-hydrochloric acid solution to obtain No. 1 to 4 solutions.

【0075】

In addition, TMOS and Ishihara Techno's titanium oxide ST-21 for photocatalyst (average particle size 0.02 μm, TiO)₂) Was treated in THF with 1N-hydrochloric acid solution at room temperature to obtain dispersions of Nos. 5 to 7.

【0076】

[Table 2]

<img file="JP2000246114A_D0002.tif" />【0077】

The solutions in Table 2 were coated on a polycarbonate substrate using a spin coater in the order of Nos. 1 to 7. At this time, after applying one solution, the next solution was applied after waiting for 10 minutes at 50 ° C. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours (film thickness 90 μm).

【0078】

By such an operation, an organic having a component gradient crosslinked silica / PSS as a first intermediate layer, a crosslinked silica as a second intermediate layer, and a component gradient crosslinked silica / titanium oxide as a photocatalytic layer on a polycarbonate base material. -Obtained an inorganic hybrid material.

【0079】

Example 4 The mixed composition prepared in Synthesis Example 3 containing PAS having a number average molecular weight of 6700 and TMOS in the ratio shown in Table 3 was hydrolyzed in THF using 1N-hydrochloric acid solution at room temperature, and Nos. 1 to 4 Solution was obtained.

【0080】

In addition, TMOS and Ishihara Techno's titanium oxide ST-21 for photocatalyst (average particle size 0.02 μm, TiO)₂) Was treated in THF with 1N-hydrochloric acid solution at room temperature to obtain a No. 5 dispersion.

【0081】

[Table 3]

<img file="JP2000246114A_D0003.tif" />【0082】

The solutions in Table 3 were coated on a polycarbonate substrate using a spin coater in the order of Nos. 1 to 5. At this time, after applying one solution, the next solution was applied after waiting for 30 minutes at room temperature. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours.

【0083】

By such an operation, an organic-inorganic substance having a component gradient crosslinked silica / PAS as a first intermediate layer, a crosslinked silica as a second intermediate layer, and a crosslinked silica / titanium oxide as a photocatalytic layer on a polycarbonate base material. Obtained a hybrid material.

【0084】

Example 5 The solutions in Table 3 were coated on a polycarbonate substrate using a spin coater in the order of Nos. 1 to 4. At this time, after applying one solution, the next solution was applied after waiting for 30 minutes at room temperature.

【0085】

After applying the No. 4 solution, Ishihara Techno's titanium oxide for photocatalyst ST-21 (average particle size 0.02 μm, TiO)₂) A dispersion in which 4.0 g was well dispersed in 20 ml of THF was immediately coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours.

【0086】

By such an operation, an organic-inorganic hybrid material having component gradient crosslinked silica / PAS as a first intermediate layer, crosslinked silica as a second intermediate layer, and titanium oxide particles as a photocatalytic layer on a polycarbonate base material. Got

【0087】

Example 6 After coating the solutions in Table 1 on a polycarbonate substrate using a spin coater in the order of Nos. 1 to 4, a mixed composition of 2.0 g of TEOS and 2.0 g of copper (I) oxide was mixed in 20 ml of THF with 800 mg of 1N-hydrochloric acid solution. , The dispersion treated at room temperature was similarly coated with a spin coater. At this time, after applying one solution, the next solution was applied after waiting for 1 minute at room temperature. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours.

【0088】

By such an operation, the component gradient crosslinked silica / PCS is provided as the first intermediate layer, the crosslinked silica is provided as the second intermediate layer, and the crosslinked silica / copper oxide (I) is provided as the photocatalytic layer on the polycarbonate substrate. An organic-inorganic hybrid material was obtained.

【0089】

Example 7 After coating the solutions in Table 2 on a polycarbonate substrate using a spin coater in the order of Nos. 1 to 4, a mixed composition of 1.0 g of TMOS and 3.0 g of copper (I) oxide was mixed in 20 ml of THF with 400 mg of 1N-hydrochloric acid solution. , The dispersion treated at room temperature was similarly coated with a spin coater. At this time, after applying one solution, the next solution was applied after waiting for 10 minutes at 50 ° C. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours.

【0090】

By such an operation, the component gradient crosslinked silica / PSS is provided as the first intermediate layer, the crosslinked silica is provided as the second intermediate layer, and the crosslinked silica / copper oxide (I) is provided as the photocatalytic layer on the polycarbonate substrate. An organic-inorganic hybrid material was obtained.

【0091】

Example 8 The solutions in Table 3 were coated on a polycarbonate substrate using a spin coater in the order of Nos. 1 to 4. At this time, after applying one solution, the next solution was applied after waiting for 30 minutes at room temperature. After applying the solution of No. 4, a dispersion in which 4.0 g of copper (I) oxide was well dispersed in 20 ml of THF was immediately coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours.

【0092】

By such an operation, the organic-having the component gradient crosslinked silica / PAS as the first intermediate layer, the crosslinked silica as the second intermediate layer, and the copper (I) oxide particles as the photocatalytic layer on the polycarbonate base material. An inorganic hybrid material was obtained.

【0093】

Example 9 A mixed composition containing PCS having a number average molecular weight of 4400 and TEOS prepared in Synthesis Example 1 at the ratios shown in Table 4 was hydrolyzed in THF using 1N-hydrochloric acid solution at room temperature, and Nos. 1 to 4 Solution was obtained. In addition, TEOS and tetrabutoxytitanium (TBOT) were treated in THF with 1N-hydrochloric acid solution at room temperature to obtain solutions No. 5 to 8 containing these in the proportions shown in Table 4.

【0094】

[Table 4]

<img file="JP2000246114A_D0004.tif" />【0095】

The solutions in Table 4 were coated on a polycarbonate substrate using a spin coater in the order of Nos. 1 to 8. At this time, after applying one solution, the next solution was applied after waiting for 1 minute at room temperature. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours.

【0096】

By such an operation, an organic having a component gradient crosslinked silica / PCS as a first intermediate layer, a crosslinked silica as a second intermediate layer, and a component gradient crosslinked silica / titanium oxide as a photocatalytic layer on a polycarbonate base material. -Obtained an inorganic hybrid material.

【0097】

Example 10 The solution of Table 4 was coated on the polycarbonate substrate in the order of Nos. 1 to 4 using a spin coater, and then the solution of No. 6 was similarly coated with a spin coater. At this time, after applying one solution, the next solution was applied after waiting for 1 minute at room temperature. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours.

【0098】

By such an operation, an organic-inorganic substance having a component gradient crosslinked silica / PCS as a first intermediate layer, a crosslinked silica as a second intermediate layer, and a crosslinked silica / titanium oxide as a photocatalytic layer on a polycarbonate base material. Obtained a hybrid material.

【0099】

Example 11 The mixed composition prepared in Synthesis Example 2 containing PSS having a number average molecular weight of 6000 and TMOS in the ratio shown in Table 5 was hydrolyzed in THF using 1N-hydrochloric acid solution at room temperature, and Nos. 1 to 4 Solution was obtained.

【0100】

In addition, TMOS and tetrabutoxytitanium and tetramer (TBOTT) having a number average molecular weight of 970 were treated in THF with 1N-hydrochloric acid solution at room temperature, and the solutions of Nos. 5 to 8 containing these in the ratios shown in Table 5 Got

【0101】

[Table 5]

<img file="JP2000246114A_D0005.tif" />【0102】

The solutions in Table 5 were coated on a polycarbonate substrate using a spin coater in the order of Nos. 1 to 8. At this time, after applying one solution, the next solution was applied after waiting for 10 minutes at 50 ° C. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours.

【0103】

By such an operation, an organic having a component gradient crosslinked silica / PSS as a first intermediate layer, a crosslinked silica as a second intermediate layer, and a component gradient crosslinked silica / titanium oxide as a photocatalytic layer on a polycarbonate base material. -Obtained an inorganic hybrid material.

【0104】

Example 12 The solution of Table 5 was coated on the polycarbonate substrate in the order of Nos. 1 to 4 using a spin coater, and then the solution of No. 7 was similarly coated with a spin coater. At this time, after applying one solution, the next solution was applied after waiting for 10 minutes at 50 ° C. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours.

【0105】

By such an operation, an organic-inorganic substance having a component gradient crosslinked silica / PSS as a first intermediate layer, a crosslinked silica as a second intermediate layer, and a crosslinked silica / titanium oxide as a photocatalytic layer on a polycarbonate base material. Obtained a hybrid material.

【0106】

Example 13 The mixed composition prepared in Synthesis Example 3 containing PAS having a number average molecular weight of 6700 and TMOS in the ratio shown in Table 6 was hydrolyzed in THF using 1N-hydrochloric acid solution at room temperature, and Nos. 1 to 4 Solution was obtained. In addition, TMOS and tetraisopropoxytitanium (TIPOT) were treated in THF with 1N-hydrochloric acid solution at room temperature to obtain solutions No. 5 to 8 containing these in the proportions shown in Table 6.

【0107】

[Table 6]

<img file="JP2000246114A_D0006.tif" />【0108】

The solutions in Table 6 were coated on a polycarbonate substrate using a spin coater in the order of Nos. 1 to 8. At this time, after applying one solution, the next solution was applied after waiting for 30 minutes at room temperature. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours.

【0109】

By such an operation, an organic having a component gradient crosslinked silica / PAS as a first intermediate layer, a crosslinked silica as a second intermediate layer, and a component gradient crosslinked silica / titanium oxide as a photocatalytic layer on a polycarbonate base material. -Obtained an inorganic hybrid material.

【0110】

Example 14 The solution of Table 6 was coated on the polycarbonate substrate in the order of Nos. 1 to 4 using a spin coater, and then the solution of No. 8 was similarly coated with a spin coater. At this time, after applying one solution, the next solution was applied after waiting for 30 minutes at room temperature. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours.

【0111】

By such an operation, an organic-inorganic hybrid material having component gradient crosslinked silica / PAS as a first intermediate layer, crosslinked silica as a second intermediate layer, and crosslinked titanium oxide as a photocatalytic layer on a polycarbonate base material. Got

【0112】

Example 15 The solutions in Table 4 were coated on a polycarbonate substrate using a spin coater in the order of Nos. 1 to 4. At this time, after applying one solution, the next solution was applied after waiting for 1 minute at room temperature. Next, the above-mentioned wetting of titanium oxide ST-21 for photocatalyst (average particle size 0.02 μm) manufactured by Ishihara Techno using a 3500 mesh filter wire mesh (passing grain sphere reference value 4 μm) manufactured by Manabe Kogyo Co., Ltd. It was applied on the gel. Then, after leaving it at room temperature for 1 day, it was heat-treated at 100 ° C. for 10 hours. By such an operation, an organic-inorganic hybrid material having a component gradient crosslinked silica / PCS as a first intermediate layer, crosslinked silica as a second intermediate layer, and titanium oxide as a photocatalytic layer is obtained on a polycarbonate base material. It was.

【0113】

Comparative example 1 A mixed composition of 2.0 g of TEOS and 2.0 g of anatase-type titanium oxide having an average particle size of 5 μm was treated with 750 mg of 1N-hydrochloric acid solution in 20 ml of THF, and the dispersion liquid treated at room temperature was coated on a polycarbonate substrate with a spin coater.

【0114】

Comparative example 2 A mixed composition of 2.0 g of TMOS and 2.0 g of copper (I) oxide was treated in 20 ml of THF with 800 mg of 1N-hydrochloric acid solution at room temperature, and the dispersion was coated on a polycarbonate substrate with a spin coater.

【0115】

Comparative example 3 A solution obtained by hydrolyzing 4.0 g of tetrabutoxytitanium in 20 ml of THF with 850 mg of 1N-hydrochloric acid solution at room temperature was coated on a polycarbonate substrate with a spin coater.

【0116】

Comparative example 4 A mixed composition of 2.0 g of PCS having a number average molecular weight of 4400 and 2.0 g of anatase-type titanium oxide having an average particle size of 5 μm was treated with 50 mg of 1N-hydrochloric acid in 30 ml of THF, and the dispersion was treated at room temperature on a polycarbonate substrate by a spin coater. Coated.

【0117】

Comparative example 5 A mixed composition of 2.0 g of PCS having a number average molecular weight of 4400 and 2.0 g of copper (I) oxide was treated with 50 mg of 1N-hydrochloric acid solution in 30 ml of THF, and a dispersion liquid treated at room temperature was coated on a polycarbonate substrate with a spin coater.

【0118】

Thermal shock test A thermal shock test was performed using the organic-inorganic hybrid materials obtained in Examples 1 to 14 and Comparative Examples 1 to 3. The test method is to heat the test piece (30 x 30 mm) in a hot air dryer at 120 ° C for 30 minutes, immediately move it to a freezer at -20 ° C and cool it for 30 minutes, and then repeat the operation three times. The state of the film was observed.

【0119】

As a result, although the test pieces of Comparative Examples 1 to 3 cracked and peeled off from the substrate, the test pieces of Examples 1 to 14 were in good condition without any change from those before the test. The test results are shown in Table 4.

【0120】

From these results, it was confirmed that the functionally graded material of the present invention has good thermal shock resistance.

【0121】

[Table 7]

<img file="JP2000246114A_D0007.tif" />【0122】

Go board and peeling test Using the organic-inorganic hybrid materials obtained in Examples 1 to 14 and Comparative Examples 1 to 3, a grid and peeling test were performed before and after the thermal shock test. JIS K 5400 was used as a reference as the test method.

【0123】

First, a cutter knife was used to draw 11 parallel lines in each of the vertical and horizontal directions on the test piece (30 x 30 mm) at 1 mm intervals to prepare 100 grid-shaped grids. Next, an adhesive tape (cellophane tape manufactured by Nichiban Co., Ltd.) was attached on these squares to make them adhere to each other, and then the adhesive tape was instantly peeled off to observe the peeled state of the metal oxide layer of the test piece. ..

【0124】

Then, a thermal shock test was performed under the above-mentioned conditions. Then, the adhesive tape was attached to the surface of the test piece again to bring it into close contact with the test piece, and then the adhesive tape was instantly peeled off to observe the peeled state of the metal oxide layer of the test piece.

【0125】

Its binding result, most of the squares is peeled off at a stage prior to the thermal shock test in the test piece of Comparative Example 1-3. On the other hand, in the test pieces of Examples 1 to 14, no peeling of the metal oxide layer was observed even in the peeling test after the thermal shock test.

【0126】

From these results, the organic-inorganic hybrid material of the present invention adhered well to the substrate not only under mild conditions at room temperature but also after thermal shock at 140 ° C. This indicates that the organic-inorganic hybrid material of the present invention has very excellent interfacial strength.

【0127】

[Table 8]

<img file="JP2000246114A_D0008.tif" />【0128】

Accelerated weathering test using weather meter The accelerated weather resistance test of the organic-inorganic hybrid materials obtained in Examples 1 to 14 and Comparative Examples 4 and 5 was performed using a weather meter. In the test, the test piece (150 × 70 mm) was treated with a weather meter, and then the state of the substrate was visually observed.

【0129】

The test conditions are set according to JIS D 0205, and the average discharge power is 390 W / m.²And said. In addition, the injection pressure of fresh water is 1.0kgf / cm.²The water volume was 2000 ml / min, the injection time of fresh water was 12 minutes out of 60 minutes, and the test time was 400 hours in total. The device used was a WEL-75XS-HC-BEC type xenon sunshine long life weather meter manufactured by Sugai Testing Machine Co., Ltd.

【0130】

As a result, although discoloration was observed in the substrates of the test pieces of Comparative Examples 4 and 5, the substrates of the test pieces of Examples 1 to 14 were almost the same as those before the test. This difference is considered to be due to whether or not the photocatalytic material and the organic material are in contact with each other.

【0131】

In the test pieces of Comparative Examples 4 and 5, it is probable that the organic material of the substrate was oxidized and discolored because the titanium oxide and copper (I) oxide were in contact with the PCS and the polycarbonate substrate. On the other hand, in the test pieces of Examples 1 to 14, it is considered that the organic material was not oxidized because the titanium oxide and copper (I) oxide and the PCS and the polycarbonate substrate were separated by the silica layer.

【0132】

From these results, the organic-inorganic hybrid material of the present invention overcomes the conventional problem that an organic material such as a base material, an adhesive, and a binder is oxidized by a photocatalytic material and deteriorates. It can be said that.

【0133】

[Table 9]

<img file="JP2000246114A_D0009.tif" />【0134】

Tobacco deodorant test The deodorant test of tobacco odor was carried out using the organic-inorganic hybrid material and the polycarbonate substrate obtained in Examples 1 to 15. As a method, a 900 ml glass mayonnaise bottle was placed with the entrance facing down, a smoking cigarette was placed directly under the entrance for 5 seconds, and then a test piece (30 x 30 mm) was quickly put in and sealed. Then, after leaving it in the sunlight outdoors for 1 hour, it was opened and the odor inside was evaluated. The results are shown in Table 10.

【0135】

As a result, although the residual odor of tobacco was confirmed on the untreated polycarbonate substrate, the residual odor was not felt on the organic-inorganic hybrid materials of Examples 1 to 15.

【0136】

From these results, it was confirmed that the organic-inorganic hybrid material of the present invention is effective in deodorizing tobacco odor.

【0137】

[Table 10]

<img file="JP2000246114A_D0010.tif" />【0138】

Ammonia deodorant test The deodorant property test of ammonia was carried out using the organic-inorganic hybrid material and the polycarbonate substrate obtained in Examples 1 to 15. As a method, ammonia gas was introduced into a glass desiccator in which a test piece (30 × 30 mm) and a gas detector tube were set, and the gas concentration was measured over time under an indoor fluorescent lamp. The results are shown in Table 11.

【0139】

As a result, the organic-inorganic hybrid material of the present invention showed good ammonia deodorant property.

【0140】

[Table 11]

<img file="JP2000246114A_D0011.tif" />【0141】

Methyl mercaptan deodorant test The deodorant property test of methyl mercaptan was carried out using the organic-inorganic hybrid material and the polycarbonate substrate obtained in Examples 1 to 15. As a method, methyl mercaptan gas was introduced into a glass desiccator in which a test piece (30 × 30 mm) and a gas detector tube were set, and the gas concentration was measured over time under an indoor fluorescent lamp. The results are shown in Table 12.

【0142】

As a result, the organic-inorganic hybrid material of the present invention showed good deodorant properties of methyl mercaptan.

【0143】

[Table 12]

<img file="JP2000246114A_D0012.tif" />

[Simple explanation of drawings]

[Figure 1]

It is a schematic cross-sectional view which shows an example of the structure of the organic-inorganic hybrid material of this invention.

[Figure 2]

It is a schematic cross-sectional view which shows an example of the structure of the organic-inorganic hybrid material of this invention. 100, 200 ... Organic-Inorganic Hybrid Material, 101, 201 ... base material, 102, 202 ... 1st middle layer, 103, 203 ... 2nd middle layer, 104, 204 ... Photocatalytic layer.