Organic-inorganic multilayered 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 multilayer material comprising a material exhibiting a photocatalytic action as a surface layer and a method for producing the same. Such an organic-inorganic multilayer 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 exhibiting 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 exhibits a very strong photocatalytic action as described above, and thus causes various inconveniences. 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 problems of the conventional method, and to provide an organic-inorganic multilayer material which is provided with a material exhibiting a photocatalytic action as a surface layer but does not deteriorate the substrate supporting the material, and a method for producing the same. That is.

【0007】

[Means for solving problems]

The present invention relates to an organic-inorganic multilayer material having a base material and an intermediate layer and a photocatalytic layer sequentially formed on the surface of the base material, wherein the intermediate layer is an organic polymer having a metal alkoxide group as a functional group. Alternatively, the photocatalytic layer is made of an organic-inorganic hybrid material obtained by cross-linking a mixture of an organic polymer having a functional group capable of reacting with a metal alkoxide compound and a metal alkoxide compound by hydrolysis and polycondensation. Provided is an organic-inorganic multilayer material made of a material containing a metal oxide exhibiting a photocatalytic action, whereby the above 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.

【0009】

Organic polymer having a functional group capable of reacting with a metal alkoxide compound The organic polymer (A) having a functional group capable of reacting with a metal alkoxide compound means a compound having an organic chain portion as a main skeleton and having a functional group capable of reacting with a metal alkoxide compound as a functional group. This organic polymer (A) may be synthesized by any method.

【0010】

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.

【0011】

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.

【0012】

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.

【0013】

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. Be done. Particularly, a metal alkoxide group is 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.

【0014】

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.

【0015】

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.

【0016】

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.

【0017】

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.

【0018】

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.

【0019】

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, or oligomer-type metals having two or more repeating units in one molecule, such as tetramethoxysilane oligomers and tetraethoxysilane oligomers. An alkoxide compound may be used. Further, the alkoxy group may be an acetoxy group or an acetyl acetoxy group.

【0020】

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.

【0021】

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.

【0022】

The preferred material for the intermediate layer is 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, which is hydrolyzed and polycondensed. It is an organic-inorganic hybrid material obtained by cross-linking with.

【0023】

The content of the organic polymer component in the organic-inorganic hybrid material is not particularly limited, but when coating the base material of the organic material as a coating film, the base material is used in order to further improve the adhesion to the base material. It is preferable that the contact surface portion of the above is 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 with the material exhibiting photocatalytic action, in other words, the content of the metal oxide component is close to 100%. good. The content of the photocatalytic material is preferably 50% by weight or more in the highest region in order to further develop the characteristics.

【0024】

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 an organic polymer having a metal alkoxide group as a functional group or a metal. The second intermediate layer is composed of an organic-inorganic hybrid material obtained by cross-linking a mixture of an organic polymer having a functional group capable of reacting with an alkoxide compound and a metal alkoxide compound by hydrolysis and polycondensation. It may be composed of an inorganic material obtained by cross-linking an alkoxide compound by hydrolysis and polycondensation.

【0025】

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 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 material by the photocatalytic layer is prevented. As a result, the service life of the organic-inorganic multilayer material is further extended.

【0026】

Hydrolysis and polycondensation by the Sol-Gel method are performed by reacting a metal alkoxide compound or a polymer having a metal alkoxy group with water to convert an alkoxy group into a hydroxyl group, and then simultaneously polycondensing this hydroxyl group. 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.

【0027】

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 in the reaction system may be used, or the water in the atmosphere may be absorbed. You may.

【0028】

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.

【0029】

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.

【0030】

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, labor is required to form the layer, and a large amount of material is required, which is costly. Further, if it is less than 0.01 μm, pinholes are likely to occur in the layer, and there is a risk that the desired performance cannot be obtained.

【0031】

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 0.1 to the same reason as described above. It shall be 100 μm. 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, there is a risk that the layer will crack or peel off. Further, if it is less than 0.01 μm, pinholes are likely to occur in the layer, and there is a risk that the desired performance cannot be obtained.

【0032】

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 exhibiting photocatalytic action is not particularly limited, but it is preferable that the surface area is large in order to enhance the photocatalytic action. For example, when the material exhibiting photocatalytic action is in the form of particles, it is desirable that the particle size is 100 μm or less because the appearance and tactile sensation of the base material are impaired if the particle size is too large. In addition, it is desirable to reduce the particle size because the photocatalytic action tends to be more active as the particles are finer.

【0033】

An example of a material exhibiting a photocatalytic action is a material containing a metal oxide (C) exhibiting 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.

【0034】

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.

【0035】

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.

【0036】

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

【0037】

The metal oxide (C) may be an inorganic material obtained by hydrolyzing and polycondensing a 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. .. As the metal alkoxide compound exhibiting 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).

【0038】

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.

【0039】

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.

【0040】

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.

【0041】

The dry thickness of the photocatalytic layer is generally 0.01 to 100 μm, preferably 0.1 to 10 μm. If the layer thickness exceeds 100 μm, the layer may crack or peel off. Further, if it is less than 0.01 μm, pinholes are likely to occur in the layer, and there is a risk that the desired performance cannot be obtained.

【0042】

Manufacture of organic-inorganic multilayer materials The organic-inorganic multilayer 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. ..

【0043】

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. Next, a base material having a surface is provided, and after applying the obtained solution or wet gel on the surface of the base material, an intermediate layer is formed by evaporating a part of the solvent.

【0044】

In order to enhance the adhesion with the layer (second intermediate layer or photocatalytic layer) formed on this, 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.

【0045】

A second intermediate layer may be formed on this layer. In that case, a solution containing a metal alkoxide compound or a wet gel is further applied on the surface of this layer.

【0046】

Next, a photocatalytic layer made of a material exhibiting photocatalytic action is formed on the surface of the intermediate layer. As the material exhibiting photocatalytic action, it is preferable to use a material containing a metal oxide (C) exhibiting 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. The method may be carried out by directly applying a metal oxide powder (particles) containing the metal oxide (C) to the surface of the intermediate layer in the state of a wet gel. Alternatively, a method may be carried out in which a metal alkoxide compound of a metal that exhibits a photocatalytic action when formed as a metal oxide, or a mixture of metal alkoxides containing the same is prepared as a solution or a wet gel, and this is applied to the surface of the intermediate layer. ..

【0047】

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.

【0048】

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.

【0049】

The organic-inorganic multilayer material produced by such a method can be obtained in which the organic polymer component and the metal oxide component are microscopically homogeneous and covalently bonded, and the organic polymer component and the metal oxide component can be obtained. As the interfacial strength increases, the material is less likely to be deformed such as cracks and peeling of only the surface layer surface. Further, the surface layer portion is provided with a material exhibiting a photocatalytic action, which makes the material even more highly functional.

【0050】

In the organic-inorganic multilayer 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.

【0051】

Moreover, by using a metal oxide as a material exhibiting 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. ..

【0052】

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.

【0053】

[Effect of the invention]

The organic-inorganic multilayer material provided in 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 multilayer 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 Provided are organic-inorganic multilayer materials suitable for use in electronic materials, medical materials, and the like.

【0054】

[Example]

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

【0055】

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%).

【0056】

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.

【0057】

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%).

【0058】

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.

【0059】

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%).

【0060】

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.

【0061】

Example 1 5.0 g of PCS having a number average molecular weight of 4400 prepared in Synthesis Example 1 was dissolved in 50 ml of tetrahydrofuran (THF), hydrolyzed with 0.15 g of 1N-hydrochloric acid solution at room temperature, and then coated on a polycarbonate substrate using a spin coater. did. On this wet gel, 5.0 g of tetraethoxysilane (TEOS) was dissolved in 25 ml of THF, and the solution obtained by hydrolysis with 2.0 g of 1N-hydrochloric acid solution at room temperature was coated with a spin coater. Further, on this wet gel, a dispersion liquid in which 5.0 g of anatase-type titanium oxide having an average particle size of 5 μm was well dispersed in 25 ml of THF was coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heated at 100 ° C. for 10 hours.

【0062】

By such an operation, as shown in FIG. 1, the polycarbonate substrate (101) has the crosslinked PCS (102) as the first intermediate layer and the crosslinked silica (103) as the second intermediate layer, and has a photocatalytic action. An organic-inorganic multilayer material (100) having titanium oxide particles (104) as a layer was obtained.

【0063】

Example 2 5.0 g of PCS having a number average molecular weight of 4400 prepared in Synthesis Example 1 was dissolved in 50 ml of THF, hydrolyzed at room temperature using 0.15 g of 1N-hydrochloric acid solution, and then coated on a polycarbonate substrate using a spin coater. On this wet gel, 5.0 g of TEOS was dissolved in 25 ml of THF, and the solution obtained by hydrolyzing with 2.0 g of 1N-hydrochloric acid solution at room temperature was coated with a spin coater. Further, on this wet gel, 5.0 g of tetrabutoxytitanium was dissolved in 25 ml of THF, and the solution obtained by hydrolysis with 1.0 g of 1N-hydrochloric acid solution at room temperature was coated with a spin coater. Then, it was left at room temperature for 1 day and heated at 100 ° C. for 10 hours.

【0064】

By such an operation, an organic-inorganic multilayer material having crosslinked PCS as a first intermediate layer, crosslinked silica as a second intermediate layer, and crosslinked titanium oxide as a photocatalytic layer was obtained on a polycarbonate base material.

【0065】

Example 3 2.5 g of PCS and 2.5 g of TEOS having a number average molecular weight of 4400 prepared in Synthesis Example 1 are dissolved in 40 ml of THF, hydrolyzed at room temperature using 1.0 g of 1N-hydrochloric acid solution, and then coated on a polycarbonate substrate using a spin coater. did. On this wet gel, a dispersion prepared by treating 2.5 g of TEOS and 2.5 g of anatase-type titanium oxide having an average particle size of 5 μm with 1.0 g of 1N-hydrochloric acid solution in 25 ml of THF was coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heated at 100 ° C. for 10 hours.

【0066】

By such an operation, as shown in FIG. 2, an organic substance having crosslinked silica / PCS (202) as an intermediate layer and crosslinked silica / titanium oxide (203) as a photocatalytic layer on a polycarbonate base material (201). An inorganic multilayer material (200) was obtained.

【0067】

Example 4 2.5 g of PCS and 2.5 g of TEOS having a number average molecular weight of 4400 prepared in Synthesis Example 1 are dissolved in 40 ml of THF, hydrolyzed at room temperature using 1.0 g of 1N-hydrochloric acid solution, and then coated on a polycarbonate substrate using a spin coater. did. On this wet gel, a dispersion prepared by treating 2.5 g of TEOS and 2.5 g of copper (I) oxide in 25 ml of THF with 1.0 g of 1N-hydrochloric acid solution was coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heated at 100 ° C. for 10 hours.

【0068】

By such an operation, an organic-inorganic multilayer material having crosslinked silica / PCS as an intermediate layer and crosslinked silica / copper (I) oxide as a photocatalytic layer was obtained on a polycarbonate base material.

【0069】

Example 5 5.0 g of PSS having a number average molecular weight of 6000 prepared in Synthesis Example 2 was dissolved in 50 ml of THF, hydrolyzed at room temperature using 0.10 g of 1N-hydrochloric acid solution, and then coated on a polycarbonate substrate using a spin coater. On this wet gel, 5.0 g of tetramethoxysilane oligomer MKC silicate MS-56 (TMOS) manufactured by Mitsubishi Chemical Corporation with a number average molecular weight of 1000 is dissolved in 25 ml of THF, and water is added at room temperature using 2.0 g of 1N-hydrochloric acid solution. The solution obtained by decomposition was coated with a spin coater. Further, on this wet gel, a dispersion liquid in which 5.0 g of anatase-type titanium oxide having an average particle size of 5 μm was well dispersed in 25 ml of THF was coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heated at 100 ° C. for 10 hours.

【0070】

By such an operation, an organic-inorganic multilayer material having crosslinked PSS as a first intermediate layer, crosslinked silica as a second intermediate layer, and titanium oxide particles as a photocatalytic layer was obtained on a polycarbonate base material.

【0071】

Example 6 5.0 g of PSS having a number average molecular weight of 6000 prepared in Synthesis Example 2 was dissolved in 50 ml of THF, hydrolyzed at room temperature using 0.10 g of 1N-hydrochloric acid solution, and then coated on a polycarbonate substrate using a spin coater. On this wet gel, 5.0 g of TMOS was dissolved in 25 ml of THF, and the solution obtained by hydrolyzing with 2.0 g of 1N-hydrochloric acid solution at room temperature was coated with a spin coater. Further, on this wet gel, 5.0 g of a tetrabutoxytitanium oligomer having a number average molecular weight of 970 was dissolved in 25 ml of THF, and a solution hydrolyzed at room temperature with 0.90 g of 1N-hydrochloric acid solution was coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heated at 100 ° C. for 10 hours.

【0072】

By such an operation, an organic-inorganic multilayer material having crosslinked PSS as a first intermediate layer, crosslinked silica as a second intermediate layer, and crosslinked titanium oxide as a photocatalytic layer was obtained on a polycarbonate base material.

【0073】

Example 7 2.5 g of PSS and 2.5 g of TMOS having a number average molecular weight of 6000 prepared in Synthesis Example 2 are dissolved in 40 ml of THF, hydrolyzed at room temperature using 1.0 g of 1N-hydrochloric acid solution, and then coated on a polycarbonate substrate using a spin coater. did. On this wet gel, a dispersion prepared by treating 2.5 g of TMOS and 2.5 g of anatase-type titanium oxide having an average particle size of 5 μm with 1.0 g of 1N-hydrochloric acid solution in 25 ml of THF was coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heated at 100 ° C. for 10 hours.

【0074】

By such an operation, an organic-inorganic multilayer material having crosslinked silica / PSS as an intermediate layer and crosslinked silica / titanium oxide as a photocatalytic layer was obtained on a polycarbonate base material.

【0075】

Example 8 2.5 g of PSS and 2.5 g of TMOS having a number average molecular weight of 6000 prepared in Synthesis Example 2 are dissolved in 40 ml of THF, hydrolyzed at room temperature using 1.0 g of 1N-hydrochloric acid solution, and then coated on a polycarbonate substrate using a spin coater. did. On this wet gel, a dispersion prepared by treating 2.5 g of TMOS and 2.5 g of copper (I) oxide in 25 ml of THF with 1.0 g of 1N-hydrochloric acid solution was coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heated at 100 ° C. for 10 hours.

【0076】

By such an operation, an organic-inorganic multilayer material having crosslinked silica / PSS as an intermediate layer and crosslinked silica / copper (I) oxide as a photocatalytic layer was obtained on a polycarbonate base material.

【0077】

Example 9 5.0 g of PAS having a number average molecular weight of 6700 prepared in Synthesis Example 3 was dissolved in 50 ml of THF, hydrolyzed at room temperature using 0.10 g of 1N-hydrochloric acid solution, and then coated on a polycarbonate substrate using a spin coater. On this wet gel, 5.0 g of TMOS was dissolved in 25 ml of THF, and a solution hydrolyzed at room temperature with 2.0 g of 1N-hydrochloric acid solution was coated with a spin coater. Further, on this wet gel, a dispersion liquid in which 5.0 g of copper (I) oxide was well dispersed in 25 ml of THF was coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heated at 100 ° C. for 10 hours.

【0078】

By such an operation, an organic-inorganic multilayer material having crosslinked PAS as a first intermediate layer, crosslinked silica as a second intermediate layer, and copper (I) oxide particles as a photocatalytic layer is formed on a polycarbonate base material. Obtained.

【0079】

Example 10 5.0 g of PAS having a number average molecular weight of 6700 prepared in Synthesis Example 3 was dissolved in 50 ml of THF, hydrolyzed at room temperature using 0.10 g of 1N-hydrochloric acid solution, and then coated on a polycarbonate substrate using a spin coater. On this wet gel, 5.0 g of TMOS was dissolved in 25 ml of THF, and a solution hydrolyzed at room temperature with 2.0 g of 1N-hydrochloric acid solution was coated with a spin coater. Further, on this wet gel, 5.0 g of tetraisopropoxytitanium was dissolved in 25 ml of THF, and a solution hydrolyzed at room temperature with 1.2 g of 1N-hydrochloric acid solution was coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heated at 100 ° C. for 10 hours.

【0080】

By such an operation, an organic-inorganic multilayer material having crosslinked PAS as a first intermediate layer, crosslinked silica as a second intermediate layer, and crosslinked titanium oxide as a photocatalytic layer was obtained on a polycarbonate base material.

【0081】

Example 11 2.5 g of PAS and 2.5 g of TMOS having a number average molecular weight of 6700 prepared in Synthesis Example 3 are dissolved in 40 ml of THF, hydrolyzed at room temperature using 1.0 g of 1N-hydrochloric acid solution, and then coated on a polycarbonate substrate using a spin coater. did. On this wet gel, a dispersion prepared by treating 2.5 g of TMOS and 2.5 g of anatase-type titanium oxide having an average particle size of 5 μm with 1.0 g of 1N-hydrochloric acid solution in 25 ml of THF was coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heated at 100 ° C. for 10 hours.

【0082】

By such an operation, an organic-inorganic multilayer material having crosslinked silica / PAS as an intermediate layer and crosslinked silica / titanium oxide as a photocatalytic layer was obtained on a polycarbonate base material.

【0083】

Example 12 2.5 g of PAS and 2.5 g of TMOS having a number average molecular weight of 6700 prepared in Synthesis Example 3 are dissolved in 40 ml of THF, hydrolyzed at room temperature using 1.0 g of 1N-hydrochloric acid solution, and then coated on a polycarbonate substrate using a spin coater. did. On this wet gel, a dispersion prepared by treating 2.5 g of TMOS and 2.5 g of copper (I) oxide in 25 ml of THF with 1.0 g of 1N-hydrochloric acid solution was coated with a spin coater. Then, after leaving it at room temperature for 1 day, it was heated at 100 ° C. for 10 hours.

【0084】

By such an operation, an organic-inorganic multilayer material having crosslinked silica / PAS as an intermediate layer and crosslinked silica / copper (I) oxide as a photocatalytic layer was obtained on a polycarbonate base material.

【0085】

Comparative example 1 A dispersion of 2.5 g of TEOS and 2.5 g of anatase-type titanium oxide having an average particle size of 5 μm treated with 1.0 g of 1N-hydrochloric acid solution in 25 ml of THF was coated on a polycarbonate substrate using a spin coater.

【0086】

Comparative example 2 A dispersion liquid obtained by treating 2.5 g of TMOS and 2.5 g of copper (I) oxide in 25 ml of THF with 1.0 g of 1N-hydrochloric acid solution was coated on a polycarbonate substrate using a spin coater.

【0087】

Comparative example 3 5.0 g of tetrabutoxytitanium was dissolved in 25 ml of THF, and a solution hydrolyzed at room temperature with 1.0 g of 1N-hydrochloric acid solution was coated on a polycarbonate substrate using a spin coater.

【0088】

Comparative example 4 A dispersion of 2.5 g of PCS having a number average molecular weight of 4400 and 2.5 g of anatase-type titanium oxide having an average particle size of 5 μm treated with 0.10 g of 1N-hydrochloric acid solution in 40 ml of THF was coated on a polycarbonate substrate using a spin coater.

【0089】

Comparative example 5 A dispersion prepared by treating 2.5 g of PCS having a number average molecular weight of 4400 and 2.5 g of copper (I) oxide in 40 ml of THF with 0.10 g of 1N-hydrochloric acid solution was coated on a polycarbonate substrate using a spin coater.

【0090】

Go board and peeling test The grid and peeling tests were performed using the organic-inorganic multilayer materials obtained in Examples 1 to 12 and Comparative Examples 1 to 3. JIS K 5400 was used as a reference as the test method.

【0091】

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. ..

【0092】

As a result, in the test pieces of Comparative Examples 1 to 3, most of the eyes were peeled off. On the other hand, in the test pieces of Examples 1 to 12, no peeling of the metal oxide layer was observed.

【0093】

From these results, it was confirmed that the organic-inorganic multilayer material of the present invention has excellent interfacial strength.

【0094】

[table 1]

<img file="JP2000190415A_D0001.tif" />【0095】

Accelerated weathering test using weather meter The accelerated weather resistance test of the organic-inorganic multilayer materials obtained in Examples 1 to 12 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.

【0096】

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 200 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.

【0097】

As a result, although the substrates of the test pieces of Comparative Examples 4 and 5 were discolored, the substrates of the test pieces of Examples 1 to 12 were almost the same as those before the test. 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 12, it is considered that the organic material was not oxidized because the titanium oxide and copper (I) oxide and the polycarbonate substrate were separated by the silica phase.

【0098】

From these results, the organic-inorganic multilayer 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.

【0099】

[Table 2]

<img file="JP2000190415A_D0002.tif" />【0100】

Tobacco deodorant test The deodorant test of tobacco odor was carried out using the organic-inorganic multilayer material and the polycarbonate substrate obtained in Examples 1 to 12. 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 3.

【0101】

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 multilayer materials of Examples 1 to 12.

【0102】

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

【0103】

[Table 3]

<img file="JP2000190415A_D0003.tif" />【0104】

Ammonia deodorant test The deodorant property test of ammonia was carried out using the organic-inorganic multilayer material and the polycarbonate substrate obtained in Examples 1 to 12. 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 4.

【0105】

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

【0106】

[Table 4]

<img file="JP2000190415A_D0004.tif" />【0107】

Methyl mercaptan deodorant test The deodorant property test of methyl mercaptan was carried out using the organic-inorganic multilayer material and the polycarbonate substrate obtained in Examples 1 to 12. 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 5.

【0108】

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

【0109】

[Table 5]

<img file="JP2000190415A_D0005.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 multilayer material of this invention.

[Figure 2]

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