JP5351378B2 - Organic-inorganic composite and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic/inorganic composite that has on the surface thereof a photocatalyst layer having both a desired degree of hardness and excellent adhesion to a substrate and to provide a process for producing the organic/inorganic composite. <P>SOLUTION: The organic/inorganic composite is provided, which has a photocatalyst layer on the surface of a polysiloxane-based composite comprising as the main component a condensation product of an organic silicon compound represented by formula (I): R<SB>n</SB>SiX<SB>4-n</SB>(wherein R denotes an organic group which is such that the carbon atom of the organic group can form a direct bond to Si in the formula; X denotes a hydroxy group or a hydrolyzable group; and n denotes 1 or 2), at least one kind of photosensitive compound sensitive to a light having a wavelength of 350 nm or less which is selected from the group consisting of a metal chelate compound, a compound of a metal organic acid salt, a metal compound having two or more hydroxy groups or hydrolyzable groups, a hydrolyzate of each of theses compounds and a condensation product of each of these compounds and/or a compound derived from the photosensitive compound. The process for producing the organic/inorganic composite is provided. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to an organic-inorganic composite and a method for producing the same, and more particularly to an organic-inorganic composite having a photocatalyst layer on the surface and a method for producing the same.

  Currently, trifunctional silanes are mainly used as raw materials for commercially available silane-based coating agents, and polysiloxanes having appropriate hardness and flexibility are formed by such trifunctional silanes. However, the film of trifunctional silane still lacks hard coat properties. To compensate for this, it is compensated by mixing tetrafunctional silane or colloidal silica with trifunctional silane, but the film is hardened. In this case, there is a problem that cracking is likely to occur and adhesion is deteriorated. For example, an antifouling film-forming composition containing a trifunctional alkoxysilane compound having an epoxy group has been proposed as a silane-based coating agent (see, for example, Patent Document 1).

  Examples of the silane coating agent include a composition for forming an antifouling film containing a trifunctional alkoxysilane compound having an epoxy group (see Patent Document 1). A silane-based coating agent containing a photocatalyst has also been proposed, and a film is cured using a photoacid generator, a crosslinking agent, a curing catalyst, or the like (see, for example, Patent Documents 2 and 3). Furthermore, a silane-based organic-inorganic composite gradient material having a component gradient structure in which the content of the metal compound in the material continuously changes in the depth direction from the surface of the material has also been proposed (for example, Patent Documents). 4).

Japanese Patent Laid-Open No. 10-195417 JP 2002-363494 A JP 2000-169755 A JP 2000-336281 A

  An object of the present invention is to provide a novel organic-inorganic composite having a photocatalyst layer, in particular, an organic-inorganic composite having a photocatalyst layer having a desired hardness on the surface and excellent adhesion to a substrate, and the organic-inorganic composite It is in providing the manufacturing method of a body.

  The inventors of the present invention have been working on the development of a novel organic-inorganic composite, and by first thermosetting a composition containing a specific organosilicon compound and a photosensitive compound, the surface has a higher hardness than the inside, It has been found that an organic-inorganic composite having excellent adhesion to the substrate can be produced, and furthermore, by irradiating with light, the surface has a very high hardness, and the inside and the back side have an appropriate hardness. In addition, it has been found that an organic-inorganic composite having excellent adhesion to the substrate can be produced (Japanese Patent Application No. 2006-013933). As a result of further research, the present inventors have found a highly useful organic-inorganic composite that effectively exhibits the photocatalytic function while maintaining the above effects, and has completed the present invention.

That is, the present invention
[1] Formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si in the formula, X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and n is 2. , R may be the same or different, and when (4-n) is 2 or more, X may be the same or different.) At least one 350 nm selected from the group consisting of a metal chelate compound, a metal organic acid salt compound, a metal compound having two or more hydroxyl groups or hydrolyzable groups, a hydrolyzate thereof, and a condensate thereof as a main component An organic-inorganic composite comprising a photocatalyst layer on the surface of a polysiloxane-based composite containing a light-sensitive compound and / or a compound derived therefrom that is sensitive to light having the following wavelengths; ] The metal chelate compound is hydroxy Alternatively, the organic-inorganic composite as described in [1] above having a hydrolyzable group, or [3] the metal organic acid salt compound having a hydroxyl group or a hydrolyzable group [1] or [2], or [4] a hydrolyzate and / or condensate of a metal compound having two or more hydroxyl groups or hydrolyzable groups. The organic-inorganic composite as described in any one of [1] to [3] above, which is a product hydrolyzed with 0.5 mol or more of water with respect to 1 mol of the metal compound having a group The hydrolyzate and / or condensate of [5] metal chelate compound is a product hydrolyzed using 5 to 100 mol of water with respect to 1 mol of metal chelate compound. Any of the above [1] to [4] An organic inorganic composite according to.

  In addition, the present invention provides a product obtained by hydrolyzing the hydrolyzate and / or condensate of [6] metal organic acid salt compound with 5 to 100 mol of water with respect to 1 mol of metal organic acid salt compound. The organic-inorganic composite according to any one of [1] to [5] above, or [7] a metal chelate compound is a β-ketocarbonyl compound, β-ketoester compound, or α-hydroxy The organic-inorganic composite according to any one of [1] to [6] above, which is an ester compound, or [8] a hydrolyzable group is an alkoxy group having 1 to 4 carbon atoms or 1 carbon atom. Or an organic-inorganic composite according to any one of [1] to [7] above, or [9] a metal in a metal compound, a metal chelate compound or a metal organic acid salt compound, , Titanium, zirconium, al The organic-inorganic composite as described in any one of [1] to [8] above, which is at least one selected from the group consisting of nickel, silicon, germanium, indium, tin, tantalum, zinc, tungsten, and lead Or [10] R in formula (I) is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an epoxyalkyl group having 1 to 10 carbon atoms. [1] to [10], wherein the organic-inorganic composite according to any one of [1] to [9] or a thin film having a photocatalyst layer on the surface of a [11] polysiloxane composite layer The carbon content of the layer surface portion in the depth direction 10 nm from the surface of the layer of the [12] polysiloxane-based composite layer is a layer in the depth direction of 10 nm from the back surface of the polysiloxane-based composite layer. back An organic-inorganic composite according to [11], wherein the 80% or less of a thin film of carbon content parts.

[13] The organic-inorganic composite as described in [11] or [12] above, wherein the carbon content is gradually increased from the surface of the [13] polysiloxane composite layer to a predetermined depth. [14] The organic-inorganic composite as described in [13] above, wherein the depth at which the carbon content gradually increases is 5 to 80% of the layer thickness, and [15] carbon content The organic-inorganic composite as described in [13] or [14] above, wherein the depth in which the amount gradually increases is 50 to 2000 nm, and [16] JIS when formed on a glass substrate The organic-inorganic composite according to any one of [11] to [15] above, wherein the pencil hardness specified in the K 5600-5-4 pencil method is a thin film of 5H or more, and the formula [17] (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si in the formula, X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and n is 2. , R may be the same or different, and when (4-n) is 2 or more, X may be the same or different.) A photocatalyst is formed on the polysiloxane layer as a main component, and the carbon content of the layer surface portion in the depth direction 10 nm from the layer surface is 80% or less of the carbon content of the layer back surface portion in the depth direction 10 nm from the layer back surface. A polysiloxane thin film characterized by comprising a layer; and [18] a polysiloxane as described in [17] above, wherein the carbon content is gradually increased from the surface of the polysiloxane layer to a predetermined depth. Siloxane-based thin films and [19] carbon content gradually increased Depth there are concerns polysiloxane-based thin film according to [18] above, wherein the 5 to 80% of the layer thickness.

  Further, the present invention provides [20] a polysiloxane thin film as described in [18] or [19] above, wherein the depth at which the carbon content gradually increases is 50 to 2000 nm, 21] The polycrystal as described in any one of [17] to [20] above, wherein the pencil hardness specified in the JIS K 5600-5-4 pencil method is 5H or more when formed on a glass substrate. A siloxane-based thin film or [22] polysiloxane-based layer is composed of a metal chelate compound, a metal organic acid salt compound, a metal compound having two or more hydroxyl groups or hydrolyzable groups, a hydrolyzate thereof, and a condensate thereof. [17] to [17], comprising at least one photosensitive compound selected from the group consisting of a photosensitive compound sensitive to light having a wavelength of 350 nm or less, and / or a compound derived therefrom. The polysiloxane thin film according to any one of [21], the [23] metal chelate compound having a hydroxyl group or a hydrolyzable group, and the polysiloxane thin film according to the above [22], wherein [24] The metal organic acid salt compound has a hydroxyl group or a hydrolyzable group, and the polysiloxane thin film according to the above [22] or [23], or [25] two or more hydroxyl groups or hydrolyzable groups A hydrolyzate and / or condensate of a metal compound having a hydrolyzate is a product hydrolyzed with 0.5 mol or more of water with respect to 1 mol of a metal compound having two or more hydroxyl groups or hydrolyzable groups. The polysiloxane thin film according to any one of the above [22] to [24], or the hydrolyzate and / or condensate of [26] metal chelate compound, Per mole of the compound relates to polysiloxane-based thin film according to any one of [22] - [25] which is a product was hydrolyzed using 5 to 100 moles of water.

In addition, the present invention provides a product obtained by hydrolyzing [27] hydrolyzate and / or condensate of metal organic acid salt compound with 5 to 100 mol of water with respect to 1 mol of metal organic acid salt compound. The polysiloxane-based thin film according to any one of the above [22] to [26] or the [28] metal chelate compound is a β-ketocarbonyl compound, β-ketoester compound, or α-hydroxy The polysiloxane thin film according to any one of the above [22] to [27], which is an ester compound, or [29] a hydrolyzable group is an alkoxy group having 1 to 4 carbon atoms or 1 carbon atom To the polysiloxane thin film according to any one of the above [22] to [28], [30] a metal compound, a metal chelate compound, or a metal organic acid salt compound, [22]-[29], wherein the metal is at least one selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, lead The polysiloxane thin film according to any one of the above and [31] R in formula (I) is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an epoxyalkyl group having 1 to 10 carbon atoms. The polysiloxane thin film according to any one of the above [17] to [30], or [32] the formula (I)
R _n SiX _4-n (I)
(In the formula, R represents an organic group in which a carbon atom is directly bonded to Si in the formula, X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and n is 2. , R may be the same or different, and when (4-n) is 2 or more, X may be the same or different.) At least one light selected from the group consisting of condensates, metal chelate compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, their hydrolysates, and their condensates A composition for forming a polysiloxane complex containing a sensitive compound is dried to form a polysiloxane complex to form a polysiloxane complex, and a photocatalyst is contained on the surface of the polysiloxane complex. Composition for photocatalyst layer formation And a photocatalyst layer forming step of forming a photocatalyst layer by drying and a UV light irradiation step of irradiating the polysiloxane complex with light having a wavelength of 350 nm or less. The method for producing a composite or [33] The organic-inorganic composite according to [32], wherein the UV irradiation step is performed after the polysiloxane-based composite formation step and before the photocatalyst layer formation step. It relates to a manufacturing method.

  [34] The method for producing an organic-inorganic composite according to [32] above, wherein the [34] UV irradiation step is performed after the polysiloxane-based composite formation step and the photocatalyst layer formation step. [35] In any one of the above [32] to [34], in the UV irradiation step, the light to be irradiated is light mainly composed of light having any wavelength in the range of 150 to 350 nm. In the method for producing an organic-inorganic composite according to [36] or [36] UV irradiation step, the light to be irradiated is light mainly composed of light of any wavelength in the range of 250 to 310 nm. Any of the above [32] to [36], wherein the method for producing an organic-inorganic composite according to [35] above, or [37] the condensate of the organosilicon compound has an average particle size of 10 nm or less Organic-inorganic composite Or [38] The method for producing an organic-inorganic composite according to any one of [32] to [37] above, wherein the average particle size of the photosensitive compound is 10 nm or less, [39] The metal atom of the photosensitive compound is contained in an amount of 0.01 to 0.5 molar equivalents relative to the silicon atom in the organosilicon compound represented by formula (I) and / or its condensate. The present invention relates to the method for producing an organic-inorganic composite according to any one of [32] to [38].

  The organic-inorganic composite of the present invention is mainly composed of a condensate of an organosilicon compound represented by the formula (I), and has a metal chelate compound, a metal organic acid salt compound, two or more hydroxyl groups, or a hydrolyzable group. Poly compounds containing at least one photosensitive compound sensitive to light having a wavelength of 350 nm or less and / or a compound derived therefrom, selected from the group consisting of metal compounds, hydrolysates thereof, and condensates thereof There is no particular limitation as long as it is an organic-inorganic composite having a photocatalyst layer on the surface of the siloxane-based composite. However, it is preferable to provide a photocatalyst layer directly on the surface of the polysiloxane-based composite, so that there is no binder made of organic matter. Chinihikari catalyst it becomes possible to effectively exhibit photocatalytic activity. Also, the adhesion between the polysiloxane complex and the photocatalyst particles is high, and the photocatalyst particles can be reliably held on the surface of the polysiloxane complex.

  First, the polysiloxane complex will be described. Polysiloxane-based composites are, for example, those obtained by dispersing a photosensitive compound and / or a derivative thereof in a non-bonded state in a condensate of an organosilicon compound, or in a condensate of an organosilicon compound. And / or derivatives thereof (for example, those having a Si-OM bond (M represents a metal atom in a photosensitive compound)) and those having a mixed state thereof. It can be manufactured using a composition for forming a polysiloxane complex, which will be described later.

  In formula (I), R represents an organic group in which a carbon atom is directly bonded to Si in the formula. Examples of the organic group include a hydrocarbon group, a group made of a polymer, etc., a hydrocarbon group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. Or an epoxyalkyl group having 1 to 10 carbon atoms is more preferred. Moreover, the C1-C10 alkyl group which has a methacryloxy group as a substituent is preferable. Further, the hydrocarbon group may have a halogen such as fluorine as a substituent. The organic group may contain a silicon atom or a group containing a polymer such as polysiloxane, polyvinylsilane, or polyacrylsilane. N represents 1 or 2, and n = 1 is particularly preferable. When n is 2, R may be the same or different.

  X represents a hydroxyl group or a hydrolyzable group. When (4-n) of formula (I) is 2 or more, X may be the same or different. A hydrolyzable group is, for example, a group that can be hydrolyzed to form a silanol group or a siloxane condensate by heating at 25 ° C. to 100 ° C. in the presence of no catalyst and excess water. Specifically, an alkoxy group, an acyloxy group, a halogen group, an isocyanate group and the like can be mentioned, and an alkoxy group having 1 to 4 carbon atoms or an acyloxy group having 1 to 4 carbon atoms can be exemplified. preferable.

  Specifically, as the organosilicon compound, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, Pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxy Silane, trimethylchlorosilane, vinyltrimethoxysilane, (meth) acryloxypropyltrimethoxysilane, glycidyloxy Trimethoxysilane, 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane, oxacyclohexyltrimethoxysilane, methyltri (meth) acryloxysilane, methyl [2- (meth) acryloxyethoxy] silane, methyl- Triglycidyloxysilane, methyltris (3-methyl-3-oxetanemethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, octyltrimethoxy Examples thereof include silane and octadecylmethoxysilane. These can be used alone or in combination of two or more. Among these organosilicon compounds represented by the formula (I), an alkyl group (R) having 6 or more carbon atoms such as hexyltrimethoxysilane, decyltrimethoxysilane, octyltrimethoxysilane, octadecylmethoxysilane, etc. Since the organosilicon compound having two alkyl groups (R) such as dimethyldimethoxysilane and the like has relatively little decomposition of the R component by UV irradiation, the film can be obtained by using a part or all of them. It becomes possible to improve the water repellency.

  Examples of the polymer-based organosilicon compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate. (Meth) acrylic acid ester; (meth) acrylic acid, itaconic acid, fumaric acid and other carboxylic acids and maleic anhydride and other acid anhydrides; glycidyl (meth) acrylate and other epoxy compounds; diethylaminoethyl (meth) acrylate, amino Amino compounds such as ethyl vinyl ether; amide compounds such as (meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl (meth) acrylamide; acrylonitrile , Styrene, alpha-methyl styrene, vinyl chloride, vinyl acetate, a vinyl polymer obtained by copolymerizing a vinyl compound selected from vinyl propionate may be mentioned those the R component of the Formula (I).

  The light-sensitive compound in the polysiloxane complex of the present invention is a compound sensitive to light having a wavelength of 350 nm or less. Regardless of the mechanism, the light-sensitive compound having a wavelength of 350 nm or less irradiated from the surface side is used. It is a compound that can remove the carbon component on the surface side by the action, and preferably, the carbon content of the surface portion in the depth direction 10 nm from the surface is a portion where the carbon amount is not reduced (in the case of a film, for example, , 80% or less, more preferably 2 to 60%, still more preferably 2 to 40% of the carbon content of the back surface in the depth direction 10 nm from the film back surface, particularly preferably carbon. A compound that can remove components to a predetermined depth so that the removal amount gradually decreases from the surface side, that is, the carbon content gradually decreases from the surface to a predetermined depth. It refers to a compound capable of forming a film of pressurized. Specifically, for example, a compound that absorbs light having a wavelength of 350 nm or less and excites it. In addition, light having a wavelength of 350 nm or less is light using a light source having light of any wavelength of 350 nm or less as a component, preferably a light source mainly having light of any wavelength of 350 nm or less. It means light used, that is, light using a light source having a wavelength of 350 nm or less with the largest component amount. In addition, the organosilicon compound condensate as the main component in the polysiloxane composite of the present invention is further condensed with the organosilicon compound and / or the condensate thereof in the polysiloxane composite forming composition of the present invention described later. Means something.

  Examples of the photosensitive compound in the polysiloxane complex of the present invention include metal chelate compounds, metal organic acid salt compounds, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensation thereof. It is at least one compound selected from the group consisting of products, preferably a hydrolyzate and / or a condensate, and particularly preferably a hydrolyzate and / or a condensate of a metal chelate compound. Examples of the compound derived therefrom include those obtained by further condensing a condensate of a metal chelate compound. As described above, the photosensitive compound and / or derivative thereof may be chemically bonded to the organosilicon compound, dispersed in a non-bonded state, or in a mixed state thereof. .

  The metal chelate compound is preferably a metal chelate compound having a hydroxyl group or a hydrolyzable group, and more preferably a metal chelate compound having two or more hydroxyl groups or hydrolyzable groups. In addition, having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more. Further, as the metal chelate compound, β-ketocarbonyl compounds, β-ketoester compounds, and α-hydroxyester compounds are preferable. Specifically, methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, acetoacetic acid β-ketoesters such as n-butyl, sec-butyl acetoacetate, t-butyl acetoacetate; acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane Β-diketones such as -2,4-dione, nonane-2,4-dione and 5-methyl-hexane-2,4-dione; hydroxycarboxylic acids such as glycolic acid and lactic acid; Is mentioned.

  The metal organic acid salt compound is a compound composed of a salt obtained from a metal ion and an organic acid. Examples of the organic acid include carboxylic acids such as acetic acid, oxalic acid, tartaric acid, benzoic acid; sulfonic acid, sulfinic acid, thiophenol. Organic compounds exhibiting acidity such as sulfur-containing organic acids such as phenol compounds, enol compounds, oxime compounds, imide compounds, aromatic sulfonamides, and the like.

  In addition, the metal compound having two or more hydroxyl groups or hydrolyzable groups excludes the metal chelate compound and the metal organic acid salt compound, and examples thereof include metal hydroxides and metal alcoholates. .

  Examples of the hydrolyzable group in the metal compound, metal chelate compound or metal organic acid salt compound include an alkoxy group, an acyloxy group, a halogen group, and an isocyanate group, and an alkoxy group having 1 to 4 carbon atoms and 1 to 1 carbon atoms. An acyloxy group of 4 is preferred. In addition, having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more.

  Such a hydrolyzate and / or condensate of a metal compound is obtained by hydrolyzing 0.5 mol or more of water with respect to 1 mol of a metal compound having two or more hydroxyl groups or hydrolyzable groups. It is preferable that it is a thing hydrolyzed using 0.5-2 mol water.

  The hydrolyzate and / or condensate of the metal chelate compound is more preferably hydrolyzed using 5 to 100 mol of water with respect to 1 mol of the metal chelate compound, and 5 to 20 mol. More preferably, it is hydrolyzed with water.

  In addition, the hydrolyzate and / or condensate of the metal organic acid salt compound is more preferably hydrolyzed using 5 to 100 mol of water with respect to 1 mol of the metal organic acid salt compound, More preferably, it is hydrolyzed with 5 to 20 moles of water.

  Examples of the metal in the metal compound, metal chelate compound or metal organic acid salt compound include titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, lead, etc. Among these, titanium Zirconium and aluminum are preferable, and titanium is particularly preferable. Two or more of these may be used.

  Specific examples of the polysiloxane-based composite include a molded body cast and molded into a mold, and a thin film (polysiloxane-based composite layer) formed by coating on a substrate. In the case of forming a polysiloxane-based composite layer, it is not particularly limited as long as it is applied on a substrate and then thermally cured (dried), but after thermosetting, light having a wavelength of 350 nm or less was irradiated. In this case, a harder thin film (polysiloxane composite layer) can be obtained, and the adhesion between the polysiloxane composite layer and the photocatalyst layer is improved. This light irradiation can be performed before and / or after the formation of the photocatalyst layer.

  When the polysiloxane composite of the present invention is a layer (polysiloxane composite layer), the polysiloxane composite layer has a structure in which the carbon content on the surface of the layer is less than the carbon content on the back of the layer. Preferably, the carbon content of the layer surface portion (position at a depth of 10 nm) in the depth direction 10 nm from the layer surface is 80% or less of the carbon content of the layer back surface portion in the depth direction 10 nm from the layer back surface. More preferably, it is more preferably 2 to 60%. Here, the carbon content of the layer surface portion is lower than the carbon content of the layer back surface portion. The total carbon content from the layer surface to the layer center portion is the total carbon content from the layer back surface to the layer center portion. Means less than the amount.

  In addition, the polysiloxane composite layer preferably has a gradual increase in carbon content from the surface of the layer to a predetermined depth. The depth at which such a carbon content gradually increases may be a layer thickness of 5 It is preferably ˜80%, more preferably 10˜50%. Specifically, for example, when the layer thickness is about 1 to 2.5 μm, the depth at which the carbon content gradually increases is 50 to 2000 nm.

Next, the photocatalyst layer will be described. The photocatalyst in the photocatalyst layer is sensitive to a wavelength of light exceeding 350 nm, unlike the photosensitive compound, and examples thereof include metal oxides. Specifically, titanium oxide (TiO ₂ ), Zinc oxide (ZnO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi ₂ O ₃ ), iron oxide (Fe ₂ O ₃ ) and the like. These may be used alone or in combination of two or more. Among these, titanium oxide is preferable, and either anatase type or rutile type may be used, but anatase type titanium oxide is preferable. Specific examples include Vistraiter NDC-137C (manufactured by Nippon Soda Co., Ltd.), titanium oxide fine particles ST, STS series (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

  The polysiloxane thin film of the present invention is mainly composed of a condensate of an organosilicon compound represented by the formula (I), and the carbon content of the layer surface portion in the depth direction 10 nm from the layer surface is There is no particular limitation as long as a photocatalyst layer is provided on a polysiloxane layer that is 80% or less of the carbon content of the back surface of the layer in the depth direction of 10 nm. It is preferably 2 to 60% of the carbon content of the layer back surface portion in the depth direction 10 nm from the back surface, and it is preferable to contain a photosensitive compound sensitive to light having a wavelength of 350 nm or less. In the present invention, a photocatalyst layer can be provided on the polysiloxane layer via an intermediate layer, but it is preferable to provide a photocatalyst layer directly on the polysiloxane layer, so that there is no organic binder. Therefore, immediately after production, the photocatalyst can effectively exhibit the photocatalytic activity. In addition, the adhesion between the polysiloxane layer and the photocatalyst particles is high, and the photocatalyst particles can be reliably held on the polysiloxane layer. The polysiloxane-based layer preferably has a gradual increase in carbon content from the surface of the layer to a predetermined depth. The depth at which such a carbon content gradually increases may be 5 to 5 times the layer thickness. It is preferably 80%, more preferably 10 to 50%. Specifically, for example, when the layer thickness is about 1 to 2.5 μm, the depth at which the carbon content gradually increases is It is about 50 to 2000 nm. In addition, about the detail of the polysiloxane type layer of the polysiloxane type thin film of this invention, it is the same as that of the above-mentioned polysiloxane type composite layer, and is the same also about a photocatalyst layer.

  The organic-inorganic composite as the thin film of the present invention and the polysiloxane thin film of the present invention have a pencil hardness specified in the JIS K 5600-5-4 pencil method when formed on a glass substrate of a thin film after heat curing. It is about 1H-4H, and it is preferable that it is 2H-4H from the point of adhesiveness with a board | substrate, and hardness. Moreover, as pencil hardness prescribed | regulated to JISK5600-5-4 pencil method when it forms in the glass substrate of the thin film after light irradiation, it is preferable that it is 5H or more, and it is preferable that it is 7H or more.

  The thin film of the present invention can be used as, for example, a hard coat film, a gas barrier film, an antistatic film, a UV cut film, an antireflection film and the like, and is extremely useful as a hard coat film because of its high surface hardness. . Application examples of the hard coat film include, for example, automobile glass, headlights, exterior parts, interior parts, electrical parts, sunroofs; mobile phone front cases, rear cases, battery cases; spectacle lenses; optical discs; Film, television front panel, CRT cover, video reflector, and the like.

  In addition, as a method for producing the organic-inorganic composite of the present invention, an organosilicon compound represented by the formula (I) and / or a condensate thereof, a metal chelate compound, a metal organic acid salt compound, two or more hydroxyl groups or hydrolysates Drying a composition for forming a polysiloxane complex containing a metal compound having a decomposable group, a hydrolyzate thereof, and at least one photosensitive compound selected from the group consisting of condensates thereof; A polysiloxane complex forming step for forming a polysiloxane complex, and a photocatalyst layer formation in which a photocatalyst layer forming composition containing a photocatalyst is applied to the surface of the polysiloxane complex and dried to form a photocatalyst layer The method is not particularly limited as long as the method includes a step and a UV light irradiation step of irradiating the polysiloxane-based composite with light having a wavelength of 350 nm or less. , UV irradiation step, after the polysiloxane complex formation step may be performed before the photocatalyst layer forming step or may be performed after the polysiloxane complex formation step and a photocatalytic layer forming step. The polysiloxane-based composite forming step is a step of casting a composition for forming a polysiloxane-based composite into a mold and drying it when molding a molded body, and when forming a thin film, In this step, the composition for forming a siloxane-based composite is applied and dried. The organic-inorganic composite produced by the production method of the present invention has a very high hardness and a very high adhesion of the photocatalyst layer.

  The composition for forming a polysiloxane complex includes an organosilicon compound represented by formula (I) and / or a condensate thereof, a metal chelate compound, a metal organic acid salt compound, two or more hydroxyl groups, or a hydrolyzable group. Is not particularly limited as long as it is a composition containing at least one photosensitive compound selected from the group consisting of a metal compound having a hydrogen atom, a hydrolyzate thereof, and a condensate thereof. And a solvent.

  The organosilicon compound represented by the formula (I) in the composition for forming a polysiloxane complex of the present invention is the same as described above, and is preferably a condensate, and the average particle size thereof is 10 nm or less. It is preferable that it is 4 nm or less. The photosensitive compound in the composition for forming a polysiloxane complex of the present invention is the same as described above, and is preferably a hydrolyzate and / or a condensate. Decomposed products and / or condensates are preferable, and the average particle size is preferably 10 nm or less, more preferably 7 nm or less. Thereby, the transparency of the organic-inorganic composite (thin film) can be improved. These average particle diameters can be measured using, for example, HPPS manufactured by Malvern Instruments Ltd.

  The solvent to be used is not particularly limited. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and octane; alicyclic hydrocarbons such as cyclohexane and cyclopentane. Ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; dimethyl sulfoxide And the like; alcohols such as methanol and ethanol; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate; and the like. These solvents can be used alone or in combination of two or more.

  The solid content (organosilicon component, photosensitive compound component) in the composition for forming a polysiloxane complex of the present invention is preferably 1 to 75% by weight, and preferably 10 to 60% by weight. More preferred. Further, the content of the photosensitive compound is generally 0.01 to 0.5 mol of metal atoms in the photosensitive compound with respect to Si in the organosilicon compound, although it depends on the type. An equivalent, preferably 0.05 to 0.2 molar equivalent.

  Moreover, tetrafunctional silane and colloidal silica can also be added to the composition for forming a polysiloxane complex of the present invention for the purpose of improving the hardness of the resulting coating film. Examples of the tetrafunctional silane include tetraaminosilane, tetrachlorosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrabenzyloxysilane, tetraphenoxysilane, tetra (meth) acryloxysilane, tetrakis [2 -(Meth) acryloxyethoxy] silane, tetrakis (2-vinyloxyethoxy) silane, tetraglycidyloxysilane, tetrakis (2-vinyloxybutoxy) silane, tetrakis (3-methyl-3-oxetanemethoxy) silane be able to. Examples of the colloidal silica include water-dispersed colloidal silica and organic solvent-dispersed colloidal silica such as methanol or isopropyl alcohol.

  In addition, the composition for forming a polysiloxane-based composite is separately provided to develop various properties such as coloring of the obtained coating film, thickening of the coating film, prevention of UV transmission to the base, provision of corrosion resistance, and heat resistance. It is also possible to add and disperse the filler. Examples of the filler include water-insoluble pigments such as organic pigments and inorganic pigments, and particulate and fibrous or scale-like metals and alloys other than pigments, and oxides, hydroxides, carbides, nitrides thereof, and the like. Examples thereof include sulfides. Specific examples of this filler include particulate, fibrous or scale-like iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, Manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, carbonic acid Magnesium, Barium sulfate, Bentonite, Mica, Zinc green, Chrome green, Cobalt green, Viridian, Guinea green, Cobalt chromium green, Shale green, Green earth, Manganese green, Pigment green, Ultramarine, Bituminous, Rock ultramarine, Cobalt blue, Cerulean Blue, copper borate, molybdenum blue, copper sulfide, koval Purple, Mars Purple, Manganese Purple, Pigment Violet, Lead Oxide, Calcium Leadate, Zinc Yellow, Lead Sulfide, Chrome Yellow, Ocher, Cadmium Yellow, Strontium Yellow, Titanium Yellow, Resurge, Pigment Yellow, Cuprous Oxide, Cadmium Red, Selenium red, chrome vermilion, bengara, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead zinc white, bunchison white, lead phthalate, manganese white, sulfuric acid Examples thereof include lead, graphite, bone black, diamond black, thermostatic black, vegetable black, potassium titanate whisker, and molybdenum disulfide.

  The composition for forming a polysiloxane complex of the present invention includes other known dehydrating agents such as methyl orthoformate, methyl orthoacetate, and tetraethoxysilane, various surfactants, silane coupling agents other than the above, Additives such as titanium coupling agents, dyes, dispersants, thickeners and leveling agents can also be added.

  Examples of the method for preparing the composition for forming a polysiloxane complex of the present invention include a method of adding water and a solvent as necessary, and mixing an organosilicon compound and a photosensitive compound, specifically, The photosensitive compound is mixed with a solvent, a predetermined amount of water is added, and then an organosilicon compound is added and mixed, or after mixing the organosilicon compound and the photosensitive compound, water is added ( Examples thereof include a method of partially) hydrolyzing, and a method of mixing separately (partially) hydrolyzed organosilicon compounds and photosensitive compounds. It is not always necessary to add water or a solvent, but it is preferable to add (partly) a hydrolyzate by adding water. The amount of the predetermined amount of water depends on the type of the photosensitive compound. For example, when the photosensitive compound is a metal compound having two or more hydroxyl groups or hydrolyzable groups, the amount of water is 1 mol of the metal compound. It is preferable to use 0.5 mol or more of water, and more preferably 0.5 to 2 mol of water. In the case where the photosensitive compound is a metal chelate compound having one or more hydroxyl groups or hydrolyzable groups, it is preferable to use 5 to 100 mol of water with respect to 1 mol of the metal chelate compound, More preferably, water is used.

  Moreover, as a composition for photocatalyst layer formation, if it is a composition containing a photocatalyst, it will not restrict | limit in particular, It is preferable to contain water and a solvent further. The solvent to be used is the same as that in the composition for forming a polysiloxane complex. Moreover, as solid content (photocatalyst component) of the composition for photocatalyst layer formation, it is preferable that it is 0.1-20 weight%, and it is more preferable that it is 0.5-10 weight%.

  Examples of the substrate on which the thin film of the present invention can be formed include metals, ceramics, glass, and plastics. Conventionally, it has been difficult to form a thin film on a plastic substrate, and it has been limited to inorganic substrates such as glass. However, the thin film of the present invention can easily form a film even if it is difficult to form a plastic substrate. Suitable for optical components. Examples of such plastic include polycarbonate resin, acrylic resin, polyimide resin, polyester resin, epoxy resin, liquid crystal polymer resin, and polyether sulfone.

  As a coating method of the composition for forming a polysiloxane complex and the composition for forming a photocatalyst layer, a known coating method can be used, for example, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method. Method, curtain coating method, gravure printing method, silk screen method, ink jet method and the like. Moreover, it does not restrict | limit especially as a film thickness to form, For example, it is about 0.05-200 micrometers.

  The thermosetting treatment (drying treatment) of the composition for forming a polysiloxane complex and the composition for forming a photocatalyst layer is preferably performed at 40 to 200 ° C. for about 1 to 120 minutes, for example, at 60 to 120 ° C. More preferably, it is performed for about 10 to 60 minutes.

The irradiation with light having a wavelength of 350 nm or less performed on the polysiloxane-based composite can be performed using a known apparatus such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an excimer lamp. The light to be used may be light having any wavelength of 350 nm or less as a component, preferably light having any wavelength in the range of 150 to 350 nm, preferably 250 to More preferably, the light is mainly composed of light of any wavelength in the range of 310 nm. As long as it is sensitive to wavelengths in this range and is not sensitive to light exceeding 350 nm, preferably 310 nm, it is hardly affected by sunlight. Further it, as the irradiation light amount of irradiated light, for example, about 1~100J / cm ^2, in consideration of the film curing efficiency (radiation energy and film curing degree relationship) is about 3~20J / cm ² Is preferable, and about 3-10 J / cm ² is more preferable. Note that irradiation with light having a wavelength of 350 nm or less is irradiation using a light source having light of any wavelength of 350 nm or less, preferably a light source having light of any wavelength of 350 nm or less as a main component. Irradiation used, that is, irradiation using a light source having a wavelength of 350 nm or less with the largest component amount. Note that since the photocatalyst layer exhibits its function by sunlight or the like, the photocatalyst layer may not be irradiated with light having a wavelength of 350 nm or less.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.

<Preparation of TiO ₂ nanoparticle liquid (photosensitive compound)>
After dissolving 89.7 g of diisopropoxybisacetylacetonate titanium (manufactured by Nippon Soda Co., Ltd., T-50 titanium oxide equivalent solid content 16.5 wt%) in 172.9 g of industrial ethanol, 33.3 g of ion-exchanged water ( 10 times mol / mol of TiO ₂ ) was slowly added dropwise with stirring to cause hydrolysis. One day later, the solution was filtered to obtain a yellow transparent TiO2 nanoparticle liquid (A-1) having a solid content of 5.0% by weight in terms of titanium oxide. The average particle size was 4.1 nm and was monodispersed.

<Preparation of polysiloxane-based layer coating solution (organosilicon compound + photosensitive compound)>
A solution obtained by stirring 300 g of a 5.0 wt% TiO ₂ nanoparticle solution (A-1) and 250.4 g of vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1003) for 30 minutes at room temperature; , 300 wt% of TiO ₂ nanoparticle solution (A-1) of 5.0 wt% and 399.26 g of 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) are stirred at room temperature for 30 minutes. A solution was prepared by mixing the obtained solution at a predetermined ratio (B-1 solution). Vinyltrimethoxysilane: 3-glycidoxypropyltrimethoxysilane = 7: 3 (molar ratio), element ratio (Ti: Si) is (1: 9), solid content (RSiO _1.5 (R is The vinyl group or 3-glycidoxypropyl group) + TiO ₂ ) was 32.5 wt%.

<Photocatalyst layer coating solution>
As the photocatalyst layer coating solution, Vistraiter NDC-137C (manufactured by Nippon Soda Co., Ltd., SiO ₂ and photocatalyst TiO ₂ containing product, solid content 8 wt%) was diluted with ethanol to a solid content of 1 wt%. (C-1 solution).

[Example 1]
The coating solution (B-1) was applied to a UV / ozone-cleaned polycarbonate (PC) substrate with a bar coater (Rod No. 12) and dried at 120 ° C. for 30 minutes in a hot air circulating dryer (D-1). film). Subsequently, UV light was irradiated using a conveyor type high-pressure mercury lamp (manufactured by Eye Graphics, 160 W / cm, lamp height 10 cm, irradiation time 5 seconds) to obtain a silane hard coat film (E-1 film). In FIG. 1, the figure showing the film | membrane component by ESCA about an E-1 film | membrane is shown. The film thickness is 3 to 4 μm, and in the elemental analysis of carbon in the depth direction by ESCA, the carbon content on the film surface (exactly, 10 nm depth from the surface) is the film back surface (exactly from the back surface). The thickness of the surface layer with a low carbon content was about 300 nm when the carbon content at 10 nm depth) was 100%.

  A coating liquid (C-1) is applied onto this E-1 film with a bar coater (Rod No. 5), and dried at 120 ° C. for 30 minutes in a hot air circulating drier. A two-layer film (F-1 film) of the hard coat layer was obtained. The film thickness of the photocatalyst layer was 0.08 μm. When this F-1 film was subjected to a pencil hardness test according to the JIS K 5600-5-4 pencil method, the pencil hardness was F. In addition, the pencil hardness at the time of forming the same film | membrane on a glass substrate (soda-lime glass substrate) was 8H.

[Example 2]
A D-1 film was produced in the same manner as in Example 1. Before UV irradiation, the coating liquid (C-1) was applied on this film with a bar coater (Rod No. 5) and dried in a hot air circulating dryer at 120 ° C. for 30 minutes. Thereafter, in the same manner as in Example 1, UV light was irradiated using a conveyor type high-pressure mercury lamp (manufactured by Eye Graphics, 160 W / cm, lamp height 10 cm, irradiation time 5 seconds), photocatalyst layer + polysiloxane hard coat layer A two-layer film (F-2 film) was obtained.

Example 3
The dried film produced in Example 2 was irradiated with UV light (ultraviolet intensity 90 mW / cm ² ) of an eye super super weather resistance tester (SUV manufactured by Eye Graphics) for 8 hours, and a photocatalyst layer + polysiloxane hard coat A two-layer film (F-3 film) was obtained.

<Membrane evaluation method>
1. Cross cut tape peeling test In accordance with JIS K5600, incisions of 1 mm intervals were made into the coating film 11 by 10 in length and breadth to create 100 cross cuts. Cellotape (registered trademark) was affixed to each sample, and the tape was peeled off after being rubbed multiple times with the belly of the finger and evaluated by the number of grids remaining without peeling off the coating film.

2. Taber-type abrasion test Haze after a wearer wheel (CS-10F) is attached to a Taber-type abrasion tester (Toyo Tester Kogyo Co., Ltd., TABER'S Ablation Tester) and subjected to a 500-rotation test under a load of 500 g. The rate was measured.

3. Steel Wool Test Steel wool # 0000 was attached to a rubbing tester (Rubbing Tester manufactured by Taihei Rika Kogyo Co., Ltd.), and the haze ratio after 30 reciprocations under a load of 500 g was measured.

4). Measurement of Contact Angle Using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., Drop Master 700 and slide-down method kit DM-SA), the contact angle of ion-exchanged water immediately after membrane production was measured. The film after the steel wool test was irradiated with 365 nm UV light with black light (FL15BLB, manufactured by Toshiba, intensity 1 mW / cm ² ) for 5 hours, and then the contact angle of ion-exchanged water was measured. The measured value was an average value of 5 measurement points.

  The results are shown in Table 1.

  As shown in Table 1, the photocatalyst layer formed on the silane-based hard coat film (polysiloxane-based layer) having a smaller amount of carbon on the front surface than the back surface has good adhesion, and the contact angle of water is 10 immediately after production. The superhydrophilic property was shown below ° C. In addition, the abrasion resistance was also good, and the superhydrophilicity was restored by irradiating BLB even after the steel wool test. It has also been clarified that an excellent film can be obtained in the same manner whether UV is irradiated before coating the photocatalyst layer or UV light is irradiated after coating the photocatalyst layer.

It is a figure which shows the film | membrane component by ESCA of the polysiloxane type layer (E-1 film | membrane) of the organic inorganic composite which concerns on Example 1 of this invention.

Claims (3)

Formula (I)
RnSiX4-n (I)
(In the formula, R may have a halogen atom, a methacryloxy group, an epoxy group or a glycidoxy group as a substituent, or a C1-C10 alkyl group which may have a halogen atom as a substituent. Represents an alkenyl group having 2 to 10 carbon atoms , X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and when n is 2, R may be the same or different; When (4-n) is 2 or more, X may be the same or different.) The main component is a condensate of an organosilicon compound represented by
Hydrolyzate and condensate of metal chelate compound, hydrolyzate and condensate of metal organic acid salt compound, hydrolyzate of metal compound having two or more hydroxyl groups or hydrolyzable groups, and condensate A polysiloxane containing at least one selected from the group, wherein the metal element of the compound is titanium, zirconium or aluminum, and is a photosensitive compound sensitive to light having a wavelength of 350 nm or less, and / or a compound derived therefrom. An organic-inorganic composite comprising a photocatalyst layer on the surface of a system composite. Formula (I)
RnSiX4-n (I)
(In the formula, R may have a halogen atom, a methacryloxy group, an epoxy group or a glycidoxy group as a substituent, or a C1-C10 alkyl group which may have a halogen atom as a substituent. Represents an alkenyl group having 2 to 10 carbon atoms , X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and when n is 2, R may be the same or different; When (4-n) is 2 or more, X may be the same or different.) The main component is a condensate of an organosilicon compound represented by
Hydrolyzate and condensate of metal chelate compound, hydrolyzate and condensate of metal organic acid salt compound, hydrolyzate of metal compound having two or more hydroxyl groups or hydrolyzable groups, and condensate Containing at least one selected from the group consisting of titanium, zirconium, and aluminum, a photosensitive compound that is sensitive to light having a wavelength of 350 nm or less, and / or a compound derived therefrom.
The photocatalyst layer was provided on the polysiloxane-based layer in which the carbon content of the layer surface portion in the depth direction 10 nm from the layer surface was 80% or less of the carbon content of the layer back surface portion in the depth direction 10 nm from the layer back surface. A polysiloxane thin film characterized by the above. Formula (I)
RnSiX4-n (I)
(In the formula, R may have a halogen atom, a methacryloxy group, an epoxy group or a glycidoxy group as a substituent, or a C1-C10 alkyl group which may have a halogen atom as a substituent. Represents an alkenyl group having 2 to 10 carbon atoms , X represents a hydroxyl group or a hydrolyzable group, n represents 1 or 2, and when n is 2, R may be the same or different; When (4-n) is 2 or more, X may be the same or different.), And / or a condensate thereof,
Hydrolyzate and condensate of metal chelate compound, hydrolyzate and condensate of metal organic acid salt compound, hydrolyzate of metal compound having two or more hydroxyl groups or hydrolyzable groups, and condensate A composition for forming a polysiloxane complex comprising at least one selected from the group, wherein the metal element of the compound is titanium, zirconium or aluminum, and a photosensitive compound sensitive to light having a wavelength of 350 nm or less. A polysiloxane complex forming step of drying to form a polysiloxane complex;
A photocatalyst layer forming step of applying a photocatalyst layer-forming composition containing a photocatalyst to the polysiloxane-based composite surface and drying to form a photocatalyst layer; and
A method for producing an organic-inorganic composite, comprising: a UV light irradiation step of irradiating the polysiloxane-based composite with light having a wavelength of 350 nm or less.

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