JP4943883B2 - Resin laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin laminate having a photocatalytic function and excels in weatherability and durability. <P>SOLUTION: The resin laminate 1 includes a photocatalytic function layer 10, a middle layer 20 and a resin base layer 30. The middle layer 20 is a layer wherein organic polymer type particles including an ultraviolet-absorbing group and having an average particle diameter of 1 to 200 nm are dispersed in a matrix having an Si-O bond. The middle layer 20 is, for example, formed of a coating composition including (1) an alkoxysilane compound, (2) the organic polymer type particles including the ultraviolet-absorbing group and having an average particle diameter of 1 to 200 nm, (3) a curing catalyst, (4) a solvent, (5) an aminosilane compound and (6) an epxoysilane compound. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a resin laminate having a photocatalytic function.

  In recent years, a laminated body in which a photocatalytic layer is formed on the surface of a synthetic resin and a photocatalytic function is provided has been developed. This laminated body decomposes organic substances that cause bad odors by using photocatalyst particles exposed on the surface, provides antifouling and antibacterial effects, and exhibits hydrophilicity. It is being used for building materials such as roofing materials and road materials such as soundproof walls of highways (for example, Patent Document 1). However, when used mainly outdoors as described above, it is necessary to provide weather resistance in order to prevent the decrease in transparency, yellowing, and delamination due to sunlight.

  In a resin laminate including a layer having a photocatalytic function, in order to prevent the resin layer from being decomposed by the photocatalyst, an intermediate layer containing an inorganic material as a matrix component is usually disposed in a layer in direct contact with the photocatalytic layer. Further, in order to impart weather resistance, for example, a weather resistant layer is formed between the intermediate layer and the resin base material layer.

As the weathering layer, an acrylic resin or the like having a low molecular weight weathering agent (ultraviolet absorber, light stabilizer, etc.) added in a few percent is often used (Patent Document 2), but the weathering effect is not sufficient. .
Attempts have been made to add 30% or more of a weathering agent in order to improve the weather resistance (Patent Document 3). However, the weathering agent migrates to the interface with the resin base material during use, and aggregates there to form a resin laminate. Haze sometimes worsened.

In order to solve these problems, a technique has been proposed in which a polymer type weathering agent in which a weathering component is bonded to an acrylic polymer is used as a film to form a weathering layer (Patent Document 4). However, such a polymer-type weathering agent has a glass transition point lower than that of a normal acrylic polymer.
For this reason, when a photocatalyst laminate is used in an environment that exceeds the glass transition point of the polymer-type weathering agent, the polymer-type weathering agent expands greatly and a large stress is generated at the interface with the resin substrate (for example, polycarbonate). To do. As a result, there was a problem that the weather resistant layer and the resin base material layer were peeled off.
JP 2000-17619 A JP 2005-14350 A JP 2001-47584 A JP 2002-361807 A

  An object of the present invention is to provide a resin laminate having a photocatalytic function and excellent weather resistance and durability.

According to the present invention, the following resin laminate is provided.
1. Including a photocatalyst layer, an intermediate layer, and a resin base material layer,
A resin laminate in which the intermediate layer is a layer in which organic polymer fine particles containing an ultraviolet absorbing group and having an average particle size of 1 to 200 nm are dispersed in a matrix having Si-O bonds.
2. 2. The resin laminate according to 1, wherein the intermediate layer is formed from a coating composition (I) containing the following components (1) to (6).
(1) Alkoxysilane compound (2) Organic polymer type fine particles having an ultraviolet absorbing group and an average particle size of 1 to 200 nm (3) Curing catalyst (4) Solvent (5) Aminosilane compound (6) Epoxysilane compound 2. The resin laminate according to 1, wherein the intermediate layer is formed from a coating composition (II) containing the following components (2) to (8).
(2) Organic polymer type fine particles having an average particle diameter of 1 to 200 nm containing an ultraviolet absorbing group (3) Curing catalyst (4) Solvent (5) Aminosilane compound (6) Epoxysilane compound (7) Organoalkoxysilane compound or 3. Polyorganoalkoxysilane compound (8) Blocked isocyanate silane compound The intermediate layer contains an organic polymer type fine particle having an average particle size of 1 to 200 nm and an ultraviolet ray absorbing particle having an average particle size of 1 to 200 nm and / or colloidal silica containing an ultraviolet absorbing group, and an Si—O bond. 2. The resin laminate according to 1, which is a layer dispersed in a matrix having
5. 5. The resin laminate according to 4, wherein the intermediate layer is formed from a coating composition (III) containing the following components (2) to (9).
(2) Organic polymer type fine particles having an average particle diameter of 1 to 200 nm containing an ultraviolet absorbing group (3) Curing catalyst (4) Solvent (5) Aminosilane compound (6) Epoxysilane compound (7) Organoalkoxysilane compound or 5. Polyorganoalkoxysilane compound (8) Blocked isocyanate silane compound (9) Inorganic ultraviolet absorbing particles and / or colloidal silica Including a photocatalyst layer, an inorganic layer, an intermediate layer, and a resin base material layer,
A resin laminate in which the intermediate layer is formed from a coating composition (A) containing the following components (a) to (d).
(A) Acrylic compound (b) Organic polymer type fine particles containing ultraviolet absorbing groups and having an average particle diameter of 1 to 200 nm (c) Radical initiator (d) Solvent 7. The resin laminate according to any one of 1 to 6, wherein the organic polymer fine particles contain an acrylic resin and / or a styrene resin.
8). The resin laminate according to any one of 1 to 7, wherein the visible light transmittance of the resin laminate is 80% or more.

  ADVANTAGE OF THE INVENTION According to this invention, while having a photocatalyst function, the resin laminated body excellent in the weather resistance and durability can be provided.

[First resin laminate]
The first resin laminate of the present invention includes a photocatalyst layer, an intermediate layer, and a resin base material layer, and the intermediate layer contains organic polymer type fine particles having an average particle diameter of 1 to 200 nm containing an ultraviolet absorbing group, It is a layer dispersed in a matrix having Si—O bonds.
One embodiment of this resin laminate is shown in FIG. As shown in this figure, the resin laminate 1 includes a photocatalyst layer 10, a first intermediate layer 20, and a resin base layer 30.

The organic polymer type fine particles contained in the intermediate layer are preferably a polymer compound having a skeleton having the function of an ultraviolet absorber in the molecule.
The organic polymer type fine particles preferably contain an acrylic resin and / or a styrene resin. For example, an acrylic monomer and / or a styrene monomer and other ethylenically unsaturated compounds (acrylic acid, methacrylic acid and those having a skeleton (benzophenone, benzotriazole, triazine)) acting as an ultraviolet absorber in the side chain And derivatives thereof, styrene, vinyl acetate, etc.). Conventional organic fine particles containing an ultraviolet absorbing group are generally low molecular weight molecules having a molecular weight of 200 to 700, whereas the organic polymer type fine particles containing an ultraviolet absorbing group of the present invention usually have a weight average molecular weight exceeding 10,000. Disadvantages of conventional organic fine particles containing ultraviolet absorbing groups, such as compatibility with plastic and heat resistance, are improved, and weather resistance performance can be imparted over a long period of time.

  Furthermore, the organic polymer type fine particles are required to have an average particle diameter of 1 to 200 nm. If it exceeds 200 nm, the transparency of the resin laminate with a photocatalytic function may be lowered. A preferable average particle diameter is 100 nm or less.

Examples of the use form include a powder or a dispersion system dispersed in an organic solvent such as ethyl acetate, and an emulsion system dispersed in water.
As specific examples, coating ultraviolet light absorbers ULS-700, ULS-1700, ULS-383MA, ULS-1383MA, ULS-383MG, ULS-385MG, ULS-1383MG, and ULS manufactured by Yushi Co., Ltd. -1385MG, ULS-635MH, ULS-933LP, ULS-935LH, ULS-1935LH, HC-935UE, XL-504, XL-524, XL-547, XL-729, XL-730, Nikko Chemical Laboratory NCI-905-20EM, NCI-905-20EMA, and the like. Preferably, the solubilizing solvent is water, lower alcohols such as methanol, ethanol, propanol and methoxypropanol, and cellosolves such as methyl cellosolve and ethyl cellosolve. By using such a solvent, the dispersibility of the polymer ultraviolet absorber is improved, and sedimentation can be prevented. More preferably, the solubilizing solvent is water. When the solubilizing solvent is water, it is advantageous because it can also be used for hydrolysis and condensation reactions of silane compounds, which are necessary for forming a matrix having Si—O bonds.

  As the matrix having an Si—O bond, a silicone compound or the like can be used. As an example, a hydrolyzed alkoxysilane such as polyorganoalkoxysilane, tetraethoxysilane, or ethyltriethoxysilane, and then condensed to form a matrix as it is.

The intermediate layer is preferably formed from a coating composition (I) containing the following components (1) to (6).
(1) Alkoxysilane compound (2) Organic polymer type fine particle containing ultraviolet absorbing group (3) Curing catalyst (4) Solvent (5) Aminosilane compound (6) Epoxysilane compound

In another embodiment, the intermediate layer is preferably formed from a coating composition (II) comprising the following components (2) to (8).
(2) Organic polymer type fine particles having an average particle diameter of 1 to 200 nm containing an ultraviolet absorbing group (3) Curing catalyst (4) Solvent (5) Aminosilane compound (6) Epoxysilane compound (7) Organoalkoxysilane compound or Polyorganoalkoxysilane compound (8) Blocked isocyanate silane compound

  The alkoxysilane compound (1) is preferably a bifunctional alkoxysilane, a trifunctional alkoxysilane or a tetrafunctional alkoxysilane, more preferably a trifunctional alkoxysilane or a tetrafunctional alkoxysilane. A condensate (polyalkoxysilane compound) linked by a -O bond can also be used. In addition, these may be used alone or in combination.

  Trifunctional alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and γ-methacrylic. Examples thereof include loxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and blocked isocyanate trimethoxysilane in which an isocyanate group is blocked with 2-butanooxime or the like.

Examples of the tetrafunctional alkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraisobutoxysilane.
Specific examples of the polyalkoxysilane compound include polyalkoxysilanes such as “silicate 40”, “silicate 45”, “silicate 48”, “M silicate 51”, and “MTMS-silicate A” manufactured by Tama Chemical Industry Co., Ltd. Examples include compounds (alkoxysilicate compounds).

The curing catalyst (3) is a catalyst for hydrolysis and condensation (curing) of the silane compounds (1), (5), (6), (7) and (8). Examples thereof include hydrochloric acid, sulfuric acid, nitric acid , Inorganic acids such as phosphoric acid, nitrous acid, perchloric acid, sulfamic acid, organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, tartaric acid, succinic acid, maleic acid, glutamic acid, lactic acid, p-toluenesulfonic acid Examples include acids.
Lithium hydroxide, sodium hydroxide, potassium hydroxide, n-hexylamine, dimethylamine, tributylamine, diazabicycloundecene, ethanolamine acetate, dimethylaniline formate, tetraethylammonium benzoate, sodium acetate, potassium acetate Organic metal salts such as sodium propionate, sodium glutamate, potassium propionate, sodium formate, potassium formate, benzoyltrimethylammonium acetate, tetramethylammonium acetate, tin octylate, tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide , aluminum triisopropoxide, aluminum _{acetylacetonate,} SnCl _4, TiCl 4, etc. Lewis acids ZnCl ₄ and the like can be mentioned, et al That.

  Among these curing catalysts (3), the organic polymer type fine particles (2) containing an ultraviolet absorbing group can be highly dispersed even when the blending amount is increased, and the transparency of the resulting film can be improved. Is preferred. In particular, organic carboxylic acids, especially acetic acid can be preferably used. These may be used alone or in combination.

  The aminosilane compound (amino group-containing silane compound) (5) is an alkoxysilane compound containing an amino group but not containing an epoxy group and an isocyanate group. Specific examples include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3- Aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N -Methylaminopropyltriethoxysilane and the like.

A suitable aminosilane compound (5) can be represented by the following formula (2).
(R ¹¹ ) _n Si (OR ² ) _4-n (2)
(In the formula, R ¹¹ may be the same or different, and the alkyl group having 1 to 4 carbon atoms; vinyl group; phenyl group; or methacryloxy group, amino group (—NH ₂ group), aminoalkyl group (— (CH ₂ )) _x— NH ₂ ), an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from the group consisting of alkylamino groups (—NHR groups), and at least one of R ¹¹ is an amino group, An alkyl group having 1 to 3 carbon atoms substituted with either an aminoalkyl group or an alkylamino group, wherein x in the aminoalkyl group is an integer of 1 to 3, and R in the alkylamino group is a carbon number. 1 to 3 alkyl groups, R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)

  The epoxy silane compound (epoxy group-containing silane compound) (6) is an alkoxy silane compound containing an epoxy group but not an amino group or an isocyanate group. Specific examples include 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like.

A suitable epoxysilane compound (6) can be represented by the following formula (3).
(R ²¹ ) _n Si (OR ² ) _4-n (3)
Wherein R ²¹ may be the same or different and is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or one or more selected from the group consisting of a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group And at least one of R ²¹ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 or 2.)

The organoalkoxysilane compound (7) is an organoalkoxysilane compound containing no amino group, epoxy group, or isocyanate group. Bifunctional alkoxysilane and trifunctional alkoxysilane are preferred. Furthermore, a partial condensate (that is, a polyorganoalkoxysilane compound) in which these compounds are bonded by a siloxane bond (Si—O bond) can also be used. In addition, these compounds may be used independently and may be used in combination of multiple.
Trifunctional alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyl-tris (2-methoxyethoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyl Tripropoxysilane, ethyltributoxysilane, ethyl-tris (2-methoxyethoxy) silane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane, hexylriboxysilane, decyltrimethoxysilane, decyltriethoxysilane Fluorinated alkyl (trialkoxy) silanes such as decyltripropoxysilane, decyltributoxysilane, and trifluoropropyltrimethoxysilane in which a fluorine atom is introduced into the substituent. Emissions, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, .gamma.-methacryloxypropyltrimethoxysilane, and the like. Moreover, methyldimethoxy (ethoxy) silane, ethyl diethoxy (methoxy) silane, etc. which have two types of alkoxy groups are mentioned.
Examples of the bifunctional alkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, bis (2-methoxyethoxy) dimethylsilane, diethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, and the like.

A suitable organoalkoxysilane compound (7) can be represented by the following formula (1).
(R ¹ ) _m Si (OR ² ) _4-m (1)
(In the formula, R ¹ may be the same or different and is an alkyl group having 1 to 10 carbon atoms; a fluorinated alkyl group; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with a methacryloxy group. R ² is an alkyl group having 1 to 4 carbon atoms or an ether group, and m is an integer of 1 or 2.)

The polyorganoalkoxysilane compound (7) is preferably an alkoxysilane compound having a molecular weight of 200 to 6000. For example, it can be expressed by the following formula.
A suitable polyorganoalkoxysilane compound (7) can be represented by the following formula (1 ′).
(R ¹ ) _m Si _n O _n-1 (OR ² ) _{2n + 2-m} (1 ′)
(In the formula, R ¹ may be the same or different and is an alkyl group having 1 to 10 carbon atoms; a fluorinated alkyl group; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with a methacryloxy group. R ² is an alkyl group having 1 to 4 carbon atoms or an alkyl group having an ether group, m is an integer of n to 2n, and n is an integer of 2 to 15.)
The polyorganoalkoxysilane compound (7) may be a mixture of a plurality of compounds having different n. In the above formula (1 ′), specific examples of the alkyl group include the alkyl group in the trifunctional alkoxysilane.
As the polyorganoalkoxysilane compound, specifically, polymethylmethoxysiloxane formed by partial condensation of methyltrimethoxysilane or phenyltrimethoxysilane which are trifunctional alkoxysilanes (MTMS-A used in the examples corresponds). In some cases, it may be expressed as methylmethoxysiloxane.) And polyphenylmethoxysiloxane, and diethyldiethoxysilane, which is a bifunctional alkoxysilane, are partially condensed to form polydiethylethoxysiloxane.

  Specific examples of the polyorganoalkoxysilane compound (7) include “MTMS-A” manufactured by Tama Chemical Industry Co., Ltd., “SS-101” manufactured by Colcoat Co., Ltd., and “AZ-” manufactured by Toray Dow Corning Co., Ltd. 6101 "," SR2402 "," AY42-163 ", and the like.

The blocked isocyanate silane compound (8) is an isocyanate silane compound in which an isocyanate group is protected by a blocking agent such as oxime to be inactive and is deblocked by heating to activate (regenerate) the isocyanate group.
An isocyanate silane compound (isocyanate group-containing silane compound) is an alkoxysilane compound that contains an isocyanate group but does not contain an amino group or an epoxy group. Specific examples include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, isocyanate silane compounds, and the like. In the present invention, compounds in which isocyanate groups of these isocyanate silane compounds are blocked are used. The blocked isocyanate silane compound is preferably blocked isocyanate propyltriethoxysilane.

  Examples of isocyanate group blocking agents include oxime compounds such as acetooxime, 2-butanone oxime, cyclohexanone oxime, methyl isobutyl ketoxime, lactams such as ε-caprolaclam, alkylphenols such as monoalkylphenol (cresol, nonylphenol, etc.), Active methylene compounds such as 3,5-xylenol, dialkylphenols such as di-t-butylphenol, trialkylphenols such as trimethylphenol, malonic acid diesters such as diethyl malonate, acetoacetates such as acetylacetone and ethyl acetoacetate , Alcohols such as methanol, ethanol and n-butanol, hydroxyl group-containing ethers such as methyl cellosolve and butyl cellosolve, hydroxyl group such as ethyl lactate and amyl lactate Stealtes, mercaptans such as butyl mercaptan, hexyl mercaptan, acid amides such as acetanilide, acrylic amide, and timer acid amide, imidazoles such as imidazole and 2-ethylimidazole, pyrazoles such as 3,5-dimethylpyrazole, 1 , 2,4-triazole and the like, and acid imides such as succinimide and phthalic imide can be used. In order to control the dissociation temperature of the blocking agent, a catalyst such as dibutyltin dilaurate may be used in combination.

The said coating composition (I) and coating composition (II) are used in the state mixed with solvent (4), such as water and / or an organic solvent. The solvent (4) is not particularly limited as long as the above components can be mixed uniformly. For example, in addition to water, organic solvents such as alcohols, aromatic hydrocarbons, ethers, ketones, esters, etc. Can be mentioned. Among these organic solvents, specific examples of alcohol include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, and n-octyl. Alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, 1-methoxy-2-propanol (propylene glycol monomethyl ether), propylene monomethyl ether acetate, diacetone alcohol , Methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve and the like.
Specific examples of other solvents include cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, xylene, dichloroethane, toluene, methyl acetate, ethyl acetate, ethoxyethyl acetate, and the like. Is mentioned.
These may be used singly or in combination of two or more.

  In coating composition (I), the compounding quantity of each component (1)-(6) is as follows. First, the blending amount of the solvent (4) is preferably 10 to 1000 parts by mass, more preferably 10 to 100 parts by mass in total of the blending amounts of the components (1) to (3), (5) and (6). It is -800 mass parts, Most preferably, it is 50-600 mass parts.

  Component (1) is preferably 5 to 90 parts by mass, more preferably 10 to 90 parts by mass, and more preferably 15 to 75 parts by mass. If it is less than 5 mass parts, there exists a possibility that adhesiveness with an inorganic layer (a matrix is an inorganic substance) may be insufficient. If the blending amount exceeds 90 parts by mass, the adhesion with the organic layer (a layer whose matrix is an organic substance, such as a resin base material layer) may be insufficient.

  The blending amount of the organic polymer type fine particles (2) containing an ultraviolet absorbing group is preferably 1 to 95 parts by mass, more preferably 3 to 85 parts by mass, and still more preferably 5 to 75 parts by mass. When the amount is less than 1 part by mass, sufficient weather resistance may not be exhibited. If it exceeds 95 parts by mass, the film forming property may be deteriorated (cracked).

  The amount of the curing catalyst (3) is preferably 0.1 to 30 parts by mass. If the amount is less than 0.1 parts by mass, curing may be caused. If the amount exceeds 30 parts by mass, curing may be too fast and the intermediate layer film may be non-uniform.

The aminosilane compound (5) is preferably 3-55 parts by mass, more preferably 5-45 parts by mass. If it exceeds 55 parts by mass, the film forming property may be deteriorated (cracked).
The epoxysilane compound (6) is preferably 3 to 60 parts by mass, more preferably 5 to 45 parts by mass. If it exceeds 60 parts by mass, the transparency of the film (intermediate layer) may be inferior.

  The coating composition (I) is prepared by mixing the components (1) to (6). A first mixed solution containing at least component (1) and component (2) is prepared, a second mixed solution containing at least components (1), (5), and (6) is prepared, and then both are mixed. Is preferred. By doing so, the storage stability (such as not gelling) of the coating composition is improved. In addition, Preferably, component (3), (4) is mixed with a 1st liquid mixture.

In the coating composition (II), the blending amounts of the components (2) to (8) can be set as appropriate, and are as follows, for example.
(2) Organic polymer type fine particles containing ultraviolet absorbing groups and having an average particle size of 1 to 200 nm: 0.1 to 50% by weight (more preferably 5 to 50% by weight)
(3) Curing catalyst: 0.1 to 40% by weight (more preferably 0.1 to 30% by weight)
(5) Aminosilane compound: 1 to 60% by weight (more preferably 3 to 40% by weight)
(6) Epoxysilane compound: 1 to 60% by weight (more preferably 5 to 50% by weight)
(7) Organoalkoxysilane compound or polyorganoalkoxysilane compound: preferably 10 to 80% by weight (more preferably 15 to 75% by weight)
(8) Blocked isocyanate silane compound: 1 to 60% by weight (more preferably 5 to 60% by weight)
(4) Solvent: When the total of components (2), (3), (5), (6), (7) and (8) is 100 parts by weight, 5-1000 parts by weight (more preferably 20- 800 parts by weight)

  When the organic polymer type fine particles (2) containing an ultraviolet absorbing group and having an average particle size of 1 to 200 nm are mixed in an amount exceeding 50% by weight, the scratch resistance and film forming property may be deteriorated (cracked). is there. If it is less than 0.1% by weight, sufficient weather resistance may not be exhibited.

  When the curing catalyst (3) exceeds 40% by weight, the stability of the coating solution may be reduced. When the curing catalyst (3) is less than 0.1% by weight, it may cause poor curing.

  When the aminosilane compound (5) is mixed in an amount exceeding 60% by weight, the film-forming property is deteriorated (cracked), and when it is less than 1% by weight, the adhesion and scratch resistance may be significantly decreased. Furthermore, about the minimum of compounding quantity, as shown in an Example, using 3 weight% or more is preferable for abrasion-resistant expression.

  When the epoxysilane compound (6) exceeds 60% by weight, the transparency, adhesion, scratch resistance, and coating solution stability of the film are deteriorated. May decrease (crack). Furthermore, about the minimum of compounding quantity, using 5 weight% or more is preferable for film forming property expression. More preferably, it is 10% by weight or more.

When the organoalkoxysilane compound or the polyorganoalkoxysilane compound (7) is mixed in an amount exceeding 80% by weight, the adhesion may be lowered. When the amount is less than 10% by weight, the scratch resistance and film-forming property are decreased. May decrease (crack, etc.).

When the blocked isocyanate silane compound (8) is mixed in an amount exceeding 60% by weight, the film forming property is lowered, and when it is less than 1% by weight, the coating liquid stability may be lowered. Furthermore, with respect to the lower limit of the blending amount, it is preferable to use 5% by weight or more in order to develop durability (moisture resistance). More preferably, it is 10% by weight or more.
The amount of the blocked isocyanate silane compound (8) is the total amount of the isocyanate silane compound and the blocking agent.
The compounding molar ratio of the isocyanate silane compound and the blocking agent is usually 0.9 to 1.1: 0.9 to 1.1, preferably 0.95 to 1.05: 0.95 to 1.05. It is.

  The amount of the solvent (4) is preferably 5 to 1000 parts by weight when the total of the components (2), (3), (5), (6), (7) and (8) is 100 parts by weight. More preferably, it is used in the range of 20 to 800 parts by weight, particularly preferably 50 to 600 parts by weight.

The coating composition (II) is prepared by mixing the components (2) to (8).
Preferably, a first mixed solution containing at least component (7) and component (8) is prepared, and finally component (5) is mixed.
Thus, when prepared separately, the liquid storage stability of the coating composition (such as non-gelling) is improved, which is preferable.
For example, the components (7), (6), (2) to (4) are mixed, the component (8) is added, and finally the component (5) is mixed.
Component (4) can be added to the coating composition to further dilute the coating composition.

  The intermediate layer of the resin laminate of the present invention is preferably an organic polymer type fine particle having an average particle diameter of 1 to 200 nm and an inorganic ultraviolet absorbing particle having an average particle diameter of 1 to 200 nm and / or containing an ultraviolet absorbing group and / or This is a layer in which colloidal silica is dispersed in a matrix having Si—O bonds. In order to obtain such an intermediate layer, a coating obtained by further adding inorganic ultraviolet absorbing particles and / or colloidal silica (9) to the coating composition (II) containing the components (2) to (8) described above. Composition (III) may be used. The average particle diameter of the inorganic ultraviolet absorber and / or colloidal silica is preferably 1 to 100 nm.

  A semiconductor can be illustrated as an inorganic type ultraviolet absorptive particle (9). A semiconductor absorbs light having energy greater than the band gap, that is, ultraviolet light, and generates electrons in the conduction band and holes in the valence band. It is thought that the energy release process is converted into energy such as heat by these recombination. Titanium oxide, zinc oxide, cerium oxide, iron oxide, zirconium oxide, tungsten trioxide, strontium titanate, and the like are generally known inorganic ultraviolet absorbing particles. For example, the band gap energy of titanium oxide is 3 eV for the rutile type and 3.2 eV for the anatase type, which corresponds to light energy having wavelengths of about 410 nm and 390 nm, respectively. Light of a shorter wavelength than that, that is, ultraviolet rays can be absorbed. A rutile type is often used because it can cut longer wavelength ultraviolet rays. Conversely, light having a wavelength longer than that, that is, visible light is not essentially absorbed.

  Commercially available products can be used according to the application and production method, but as titanium oxide, "Neutral titania sol TSK-5" manufactured by Ishihara Sangyo Co., Ltd., cerium oxide is a cerium oxide-based ultraviolet ray manufactured by Taki Chemical. As the zinc oxide, such as the absorbent “Nidoral”, the aqueous dispersion type anionic emulsion Niedral P-10, the water dispersion type cationic emulsion Niedral U-15, the powder type, etc., “ZS-” manufactured by Sumitomo Osaka Cement Co., Ltd. 303 ”,“ ultrafine zinc oxide FZO ”manufactured by Ishihara Sangyo Co., Ltd., and the like. The inorganic ultraviolet absorbing particles convert ultraviolet energy into weak energy by the action of the electrons and release it. At this time, since the inorganic ultraviolet absorbing particles themselves do not cause a substance change, the effect is maintained for a long time.

  Colloidal silica (9) is also called colloidal silica or colloidal silicic acid. In water, it refers to a colloidal suspension of silicon oxide having Si—OH groups on the surface by hydration. Formed when hydrochloric acid is added to an aqueous solution of sodium silicate. Recently, new preparation methods have been developed one after another, and there are those dispersed in a non-aqueous solution and fine powders made by a gas phase method, and the particle diameters are various from several nm to several μm. In the present invention, those having an average particle diameter of 1 to 200 nm are used. In some cases, the composition of the particles is indefinite, and a siloxane bond (—Si—O—, —Si—O—Si—) is formed to form a polymer. The particle surface is porous and is generally negatively charged in water.

  Commercially available products include “Ultra High-Purity Colloidal Silica” Quartron PL Series (product names: PL-1, PL-3, PL-7) manufactured by Fuso Chemical Industry Co., Ltd. "Aqueous silica sol" (Product name: Snowtex 20, Snowtex 30, Snowtex 40, Snowtex O, Snowtex O-40, Snowtex C, Snowtex N, Snowtex S, Snowtex 20L, Snowtex OL) Etc. "or" organosilica sol (product names: methanol silica sol, MA-ST-MS, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-MS, MIBK-ST, XBA-ST PMA-ST, DMAC-ST) or the like "are mentioned.

  Although only organic polymer type fine particles are excellent in UV resistance, there is a method of increasing the content of organic polymer type fine particles in the intermediate layer when durability is further required. However, it is expected that the abrasion resistance will decrease significantly. In addition, it is possible to produce an intermediate layer only with inorganic ultraviolet absorbing particles and / or colloidal silica, but since the flexibility of the intermediate layer is reduced and it becomes difficult to prevent cracks during thermosetting, It becomes difficult to increase the thickness of the layer. As a result, sufficient ultraviolet absorbing ability cannot be exhibited. In the present invention, by using the organic polymer type fine particles together with the inorganic ultraviolet absorbent and / or colloidal silica, excellent ultraviolet absorption can be obtained without deteriorating other characteristics.

In the coating composition (III), the amount of each of the components (2) to (9) can be set as appropriate, and is as follows, for example.
(2) Organic polymer type fine particles containing ultraviolet absorbing groups and having an average particle size of 1 to 200 nm: 0.1 to 50% by weight (more preferably 5 to 50% by weight)
(3) Curing catalyst: 0.1 to 40% by weight (more preferably 0.1 to 30% by weight)
(5) Aminosilane compound: 1 to 60% by weight (more preferably 3 to 40% by weight)
(6) Epoxysilane compound: 1 to 60% by weight (more preferably 5 to 50% by weight)
(7) Organoalkoxysilane compound or polyorganoalkoxysilane compound: preferably 10 to 80% by weight (more preferably 15 to 75% by weight)
(8) Blocked isocyanate silane compound: 1 to 60% by weight (more preferably 5 to 60% by weight)
(9) Inorganic ultraviolet absorbing particles and / or colloidal silica:
When component (9) is only inorganic UV-absorbing particles, preferably 0.1 to 50% by weight (more preferably 0.1 to 30% by weight)
When component (9) is only colloidal silica, preferably 0.1 to 80% by weight (more preferably 0.1 to 50% by weight)
When component (9) is inorganic ultraviolet absorbing particles and colloidal silica, preferably, the inorganic ultraviolet absorbing particles are 0.1 to 50% by weight (more preferably 0.1 to 30% by weight), and colloidal silica is 0.1 to 80% by weight (more preferably 0.1 to 50% by weight)
(4) Solvent: 5 to 1000 parts by weight (more preferably 20 to 800 parts by weight) when the total of components (2), (3) and (5) to (9) is 100 parts by weight
In addition, the compounding quantity of said (2), (3) and (5)-(9) is weight% with respect to the total amount of (2), (3) and (5)-(9).

  If the inorganic ultraviolet absorbing particles (9) are mixed in an amount exceeding 50% by weight, the film forming property may be deteriorated. If the amount is less than 0.1% by weight, sufficient weather resistance may not be exhibited. There is.

  If the colloidal silica (9) is mixed in an amount exceeding 80% by weight, the film-forming property may be deteriorated or uniform dispersion may be difficult. If the amount is less than 0.1% by weight, sufficient scratch resistance is obtained. There is a possibility that the effect of imparting sex may not be obtained.

The coating composition (III) is prepared by mixing the components (2) to (9).
Preferably, a first mixed liquid containing at least component (7) and component (8) is prepared, component (5) is subsequently mixed, and finally component (9) is mixed. More preferably, a first mixed solution containing at least components (7), (6), (2), (3) is prepared, and then component (8) is mixed to form a second mixed solution, and further A component (5) is mixed and a 3rd liquid mixture is produced. Finally, component (9) is mixed to form a coating composition.
Thus, it is preferable to prepare each component separately because the liquid storage stability (such as non-gelling) of the coating composition is improved. In particular, this effect is more exhibited when the amount of water in the liquid increases due to an increase in the amount of component (2) or component (9) added.
For example, the components (7), (6), (2), (3) and (4) are mixed and then the component (8) is added. Next, component (5) is mixed, and finally component (9) is mixed.
Component (4) can be added to the coating composition to further dilute the coating composition.

It is known that the liquid storage stability of a mixed material such as the coating composition of the present invention is likely to affect the liquid pH (for example, “application / supervision of sol-gel method to nanotechnology: Sakuo Sakuo”). CMC Publishing). In the production of the coating composition of the present invention, since the acidic component is mixed as the component (3) and the basic component is mixed as the components (5) and (3), the liquid pH changes depending on the mixing order.
As the liquid pH value, for example, the liquid pH value evaluated with a portable pH meter (trade name: Checker 1) manufactured by a calibration pH standard solution, the above first mixed liquid and second mixed liquid are It is preferable that pH ≦ 6, the third mixed solution, and the final mixed solution have pH ≦ 7. In particular, if the pH of the third mixed solution, that is, the component (5), exceeds 8, the liquid stability may be lowered. The liquid is preferably kept in an acidic state from the start of the production of the coating composition to the end of the production. That is, it is preferable to produce the coating composition by a procedure in which such conditions are maintained.

  Moreover, it is preferable to heat-process said 1st liquid mixture, 2nd liquid mixture, and 3rd liquid mixture after mixing of each component. The temperature is 30 ° C. to 130 ° C., more preferably 50 ° C. to 90 ° C., and the heat treatment time is 30 minutes to 24 hours, more preferably 1 hour to 8 hours. The mixing and heating means is not particularly limited as long as it can uniformly mix and heat. By heating in this way, the condensation reaction of the components (7), (5), (6) and (8) in the liquid proceeds, and the boiling resistance and other durability are improved. The reactions of components (7), (5), (6), and (8) can be analyzed by solution Si-NMR, and can be designed to have a suitable structure. The reaction is often extremely slow at less than 30 ° C. or less than 1 hour, and the reaction of components (7), (5), (6), (8) proceeds when it is at 130 ° C. or more or 24 hours or more. Too much, the liquid may gel or become highly viscous, and may not be applied.

  Moreover, it is preferable to heat-process the last liquid (coating composition) after mixing a component (9). In the case of mixing at room temperature, it is easily affected by the stirring efficiency. If the degree of dispersion of the component (9) is low due to this, the transparency of the cured film (decrease in total light transmittance, increase in haze) decreases. There is a fear. The temperature is 30 ° C. to 130 ° C., more preferably 50 ° C. to 90 ° C., and the time is 5 minutes to 10 hours, more preferably 15 minutes to 6 hours. The mixing and heating means is not particularly limited as long as it can uniformly mix and heat. If it is less than 30 ° C. or less than 5 minutes, the effect of the heat treatment is often poor, and if it is 130 ° C. or more or 10 hours or more, the liquid may gel or become highly viscous and may not be applied.

The coating composition (I), the coating composition (II) and the coating composition (III) can be added with a leveling agent and a lubricant for the cured film in addition to the above-described components. For example, a copolymer of polyoxyalkylene and polydimethylsiloxane, a copolymer of polyoxyalkylene and fluorocarbon, and the like can be used.
In addition, a light stabilizer (hindered amine type, Ni type, benzoate type), a weather resistance imparting agent, a colorant, or an antistatic agent can be added depending on the application.

  Although there is no restriction | limiting in the kind of resin base material, The material with high transparency whose visible light transmittance is 80% or more is preferable. In particular, a polycarbonate resin, an acrylic resin, or a polyester resin is preferable, and among them, the polycarbonate resin is particularly preferable because it is excellent not only in transparency but also in mechanical properties. Also, other resin materials can be used with a visible light transmittance of 80% or more depending on the thickness of the substrate. When the visible light transmittance is less than 80%, it is difficult to use for applications such as carports and highway soundproof walls. For the purpose of improving the adhesion of the laminate, the resin substrate may be subjected to a surface treatment. Examples of the surface treatment method include corona discharge treatment, oxygen plasma treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, sand blast treatment, solvent treatment and the like.

The photocatalyst material used for the photocatalyst layer is not particularly limited, and conventionally known materials such as titanium dioxide, strontium titanate, barium titanate, sodium titanate, zirconium dioxide, α-Fe ₂ O ₃ , tungsten oxide, cadmium sulfide. Zinc sulfide or the like can be used. These may be used alone or in combination. Among these, titanium dioxide, particularly anatase-type titanium dioxide, is useful as a practical photocatalyst. Moreover, you may add a conventionally well-known photocatalyst promoter for the purpose of promoting the activity of these photocatalysts. Preferred examples of the photocatalyst promoter include platinum group metals such as platinum, palladium, rhodium, and ruthenium. These may be used alone or in combination. The addition amount of the photocatalyst promoter is usually selected in the range of 1 to 20% by mass with respect to the photocatalyst from the viewpoint of photocatalytic activity.

  Although the formation method of a photocatalyst layer is mentioned later, when using a wet method, a silicone type compound is normally used for the matrix of a photocatalyst layer. For example, as an example, a product obtained by hydrolyzing an alkoxysilane such as polyorganosiloxane or tetraethoxysilane and then condensing it becomes a matrix as it is.

  As shown in FIG. 1, the laminate of the present invention may be formed from three layers of a photocatalyst layer 10, an intermediate layer 20, and a resin base material 30, or between the photocatalyst layer 10 and the intermediate layer 20 and / or an intermediate. Another layer may be interposed between the layer 20 and the resin base material 30. For example, as shown in FIG. 2, an organic layer 40 may be formed between the resin base material 30 and the intermediate layer 20. In addition, as shown in FIG. 3, an inorganic layer 50 may be provided between the intermediate layer 20 and the photocatalyst layer 10. Moreover, you may provide combining an organic layer and an inorganic layer. The layer structure between the photocatalyst layer 10 and the resin substrate 30 often affects the adhesion of the laminate.

  When it is predicted that the adhesion between the resin base material 30 and the intermediate layer 20 is not sufficient, it is preferable to provide the organic layer 40. As the organic layer 40, a conventionally known material having a matrix of an organic component and having a certain degree of adhesion with an inorganic material can be used. For example, acrylic silicone paints, acrylic adhesives, urethane adhesives, various commercially available primers (urethane, acrylic, epoxy, chlorinated polyethylene, ethylene-vinyl acetate copolymer, etc.) can be used. It is.

  Similarly, when it is expected that the adhesion between the photocatalyst layer 10 and the intermediate layer 20 is not sufficient, the inorganic layer 50 is preferably provided. As the inorganic layer 50, a conventionally known material having an inorganic component as a matrix and having a certain degree of adhesion with an organic material can be used. For example, a silicone-based paint, a silicone-modified product, a mixture of polydimethylsiloxane and silica, a mixture of polydimethylsiloxane and an acrylic resin, various commercially available photocatalyst undercoat agents, and the like can be used.

  The layers 20, 40 and 50 are usually formed by applying a liquid material (for example, the above-described coating composition) which is a raw material of these layers, and then drying or curing.

  As the coating method, conventionally known methods such as dip coating, spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating are used. Drying or curing conditions vary depending on various materials. In particular, if the intermediate layer 20 is mentioned, the appropriate curing conditions are usually 70 to 150 ° C., preferably 80 to 140 ° C., and 30 to 120 minutes to obtain a cured film. The thickness of the intermediate layer 20 is preferably 1 to 20 μm, more preferably 2 to 15 μm. If it is less than 1 μm, the weather resistance may be insufficient, and if it exceeds 20 μm, the film forming property may be deteriorated (cracked). On the other hand, the thicknesses of the layers 40 and 50 may be such that adhesion is exhibited, but is usually selected in the range of 0.05 to 10 μm, preferably 0.1 to 5 μm. If it is less than 0.05 μm, the adhesion may be insufficient, and if it exceeds 10 μm, the film forming property may be deteriorated (cracked). Considering the ease of production of the laminate, a laminate comprising only the layers 10, 20, and 30 is preferable if a certain level of adhesion can be secured. From this point of view, the coating composition exhibits relatively good adhesion to both the organic layer and the inorganic layer, and therefore can be suitably used as a single intermediate layer.

There is no restriction | limiting in particular as a method of forming the photocatalyst layer 10 in the intermediate | middle layer 20 or the inorganic layer 50, Various methods can be used. For example, a PVD method such as a vacuum deposition method and a sputtering method, a dry method such as a metal spraying method, a wet method using a coating liquid, and the like can be given. As the coating liquid used in the wet method, a solution obtained by dispersing photocatalyst particles and the like in a suitable inorganic binder (for example, a silicone compound) is preferably used.
The coating liquid is applied by a known method such as dip coating, spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, gravure coating, etc. The photocatalyst layer 10 can be formed by drying or curing. The thickness of the photocatalyst layer 10 is usually 5 nm to 2 μm, preferably 10 nm to 2 μm, and particularly preferably 20 nm to 1 μm. If it is less than 5 nm, the photocatalytic function may not be sufficiently exhibited. If it exceeds 2 μm, the photocatalytic function is not improved so much even if it is thicker.

[Second resin laminate]
The 2nd resin laminated body of this invention contains a photocatalyst layer, an inorganic layer, an intermediate | middle layer, and a resin base material layer, and an intermediate | middle layer is formed from the coating composition (A) mentioned later. In this resin laminate, since an organic intermediate layer is used, decomposition by the photocatalyst is prevented by using an inorganic layer between the photocatalyst layer and the intermediate layer.
One embodiment of this resin laminate is shown in FIG. As shown in this figure, the resin laminate 2 includes a photocatalyst layer 10, an inorganic layer 50, an intermediate layer 22, and a resin base material layer 30.

The intermediate layer 22 of this resin laminate is formed from a coating composition (A) containing the following components (a) to (d).
(A) Acrylic compound (b) Organic polymer type fine particle containing ultraviolet absorbing group (c) Radical initiator (d) Solvent

  The organic polymer type fine particles (b) and the solvent (d) are the same as the organic polymer type fine particles (2) and the solvent (4) described in the coating composition (I), respectively.

  The acrylic compound (a) is (meth) acrylic acid esters obtained by reacting (meth) acrylic acids with various alcohols. For example, methyl (meth) acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, t-butyl acrylate, t-butyl methacrylate, fluoromethyl acrylate, 2,2,2-fluoroethyl methacrylate, 1,2, Halogenated alkyl (meth) acrylates such as 2,2-tetrachloroethyl acrylate, hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-methoxyethyl acrylate , Alkoxy (meth) acrylates such as 2-ethoxyethyl methacrylate, aryl (meth) acrylates such as phenyl acrylate and phenyl methacrylate, etc. It is. A plurality of these (meth) acrylic acid esters may be used. Further, other ethylenically unsaturated compounds (acrylic acid, methacrylic acid and derivatives thereof, styrene, vinyl acetate, etc.) may be used in combination. Furthermore, commercially available acrylic adhesives (for example, Konishi Co., Ltd. VP-2000) can also be used.

  The radical initiator (c) serves to increase the molecular weight of the acrylic compound (a). For example, as radical polymerization initiators, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, and methylcyclohexanone peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide Hydroperoxides such as oxide, cumene hydroperoxide, t-butyl hydroperoxide, diisobutyryl peroxide, bis-3,5,5-trimethylhexanol peroxide, lauroyl peroxide, benzoyl peroxide, m-toluylbenzoyl Diacyl peroxides such as peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) Sun, 1,3-bis (t-butylperoxyisopropyl) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene, etc. Dialkyl peroxides, 1,1-di (t-butylperoxy-3,5,5-trimethyl) cyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di (t-butylperoxy) Peroxyketals such as butane, 1,1,3,3-tetramethylbutylperoxyneodicarbonate, α-cumylperoxyneodicarbonate, t-butylperoxyneodicarbonate, t-hexylperoxypivalate, t-butylperoxypi Valate, 1,1,3,3-tetramethylbutylperoxy-2- Ethyl hexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyhexahydroterephthalate, 1,1 , 3,3-tetramethylbutylperoxy-3,5,5-trimethylhexanoate, t-amylperoxy 3,5,5-trimethylhexanoate, t-butylperoxy 3,5,5-trimethylhexanoate, alkyl peresters such as t-butylperoxyacetate, t-butylperoxybenzoate, dibutylperoxytrimethyladipate, di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (1,1-butylcyclohexyl) Sao Peroxy such as sidicarbonate), diisopropyloxydicarbonate, t-amylperoxyisopropylcarbonate, t-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexylcarbonate, 1,6-bis (t-butylperoxycarboxy) hexane And carbonates.

  The above radical initiators may be used alone or in combination.

  The coating composition (A) is used in a state of being mixed with water and / or an organic solvent (solvent (d)).

  Moreover, you may further add the aminosilane compound (5) used by coating composition (I), and an epoxysilane compound (6). Thereby, the adhesiveness with the inorganic layer 50 may be greatly improved.

  The compounding quantity of each component (a)-(d) is as follows. First, the compounding amount of the solvent (d) is preferably 10 to 1000 parts by mass, more preferably 10 to 800 parts by mass, particularly preferably 100 parts by mass of the total amount of components (a) to (c). 50 to 600 parts by mass.

  Component (a) is preferably 5 to 90 parts by mass, more preferably 10 to 90 parts by mass, and particularly preferably 15 to 75 parts by mass. If it is less than 5 mass parts, there exists a possibility that adhesiveness with the resin base material layer 30 may be insufficient. If the blending amount exceeds 90 parts by mass, the adhesion with the inorganic layer 50 may be insufficient.

  The blending amount of the organic polymer type fine particles (b) containing an ultraviolet absorbing group is preferably 1 to 95 parts by mass, more preferably 3 to 85 parts by mass, and still more preferably 5 to 75 parts by mass. When the amount is less than 1 part by mass, sufficient weather resistance may not be exhibited. If it exceeds 95 parts by mass, the film forming property may be deteriorated (cracked).

  The amount of the radical initiator (c) is preferably 0.005 to 5 parts by mass. If it is less than 0.005 parts by mass, it will cause curing failure, and if it exceeds 5 parts by mass, curing may be too fast and the intermediate layer film may become non-uniform.

When adding an aminosilane compound (5), the compounding quantity becomes like this. Preferably it is 3-55 mass parts, More preferably, it is 3-45 mass parts. If it exceeds 55 parts by mass, the film forming property may be deteriorated (cracked). When adding an epoxysilane compound (6), the compounding quantity becomes like this. Preferably it is 3-60 mass parts, More preferably, it is 3-45 mass parts. If it exceeds 60 parts by mass, the transparency of the film (intermediate layer) may be inferior.

  The coating composition (A) is prepared by mixing the components (a) to (d). When the aminosilane compound (5) and the epoxysilane compound (6) are added, a first mixed liquid containing at least the component (a) and the component (b) is prepared, and at least the components (a), (5), ( It is preferable to prepare the 2nd liquid mixture containing 6), and to mix both after that. By doing so, the storage stability (such as not gelling) of the coating composition is improved. Preferably, components (c) and (d) are mixed in the first mixed solution.

The coating composition (A) can contain the same additives as the coating composition (I).
The intermediate layer of the second resin laminate can be produced in the same manner as the intermediate layer of the first resin laminate.

The photocatalyst layer, inorganic layer, and resin base material layer of the second resin laminate are as described in the first resin laminate.
Furthermore, the second resin laminate can also have other layers interposed between the layers, like the first resin laminate. For example, an organic layer 40 as shown in FIG. 2 can be provided between the resin base layer 30 and the intermediate layer 22 as necessary. Further, the organic layer 40 can be provided between the inorganic layer 50 and the intermediate layer 22.

  The second resin laminate can be produced in the same manner as the first resin laminate.

  Both the first and second resin laminates preferably have a visible light transmittance of 80% or more. When the transmittance is high, it can be suitably used for applications such as carports and sound barriers.

[First resin laminate]
Example 1
In the sample tube, an aqueous dispersion “ULS-1385MG” of benzotriazole-based UV-absorbing group-bonded acrylic fine particles (manufactured by Yushi Kogyo Co., Ltd .; solid content 30%, of which 50% is UV absorber framework) 2 8 g and 10 g of 1-methoxy-2-propanol were charged, and 2 g of tetramethoxysilane was added dropwise with stirring. Subsequently, 0.1 g of a 20% p-toluenesulfonic acid methanol solution and 1.5 g of acetic acid were added dropwise and stirred for 30 minutes. This was designated as A-1. A mixed liquid of 2 g of methyltrimethoxysilane, 2 g of 3-aminopropyltrimethoxysilane and 2 g of 3-glycidoxypropyltrimethoxysilane was prepared, and this was designated as A-2 liquid. The A-1 solution was slowly dropped into the A-2 solution and stirred for 2 hours. Subsequently, the mixture was allowed to stand at 25 ° C. for 1 week. This was designated as solution A (coating composition (I)).

  A cured film is formed on the surface of a 100 mm × 100 mm × 3 mm polycarbonate (PC) molded body (visible light transmittance 90%) prepared from “IV2200R” manufactured by Idemitsu Kosan Co., Ltd. It was applied to a thickness of about 5 μm, naturally dried at room temperature for 5 minutes, and then cured at 120 ° C. for 1 hour. This laminated intermediate was evaluated according to the evaluation method described later. The results are shown in Table 1.

  After applying the photocatalyst topcoat agent “STK-211” manufactured by Ishihara Sangyo Co., Ltd. to the surface of the above-mentioned laminated intermediate on the cured film side so as to have a thickness of about 0.5 μm after heat treatment, at 100 ° C. for 30 minutes. Heat treatment was performed to form a photocatalyst film, and a resin laminate was produced. The contact angle and light transmittance of this resin laminate were evaluated according to the evaluation method described later. The results are shown in Table 1.

Example 2
Instead of “ULS-1385MG”, an aqueous dispersion of benzophenone-based UV-absorbing group-bonded acrylic fine particles “ULS-385MG” (manufactured by Yushi Kogyo Co., Ltd .; solid content 30%, of which 50% is UV absorber) A laminated intermediate and a resin laminated body were produced in the same manner as in Example 1 except that the skeleton was used, and physical properties were evaluated. The results are shown in Table 1.

Example 3
1.2 g of “ULS-1385MG”, 3.8 g of tetramethoxysilane, 3.8 g of methyltrimethoxysilane, 1.0 g of 3-aminopropyltrimethoxysilane, and 1.3 of 3-glycidoxypropyltrimethoxysilane. A coating composition was produced in the same manner as in Example 1 except that the amount was 0 g. Using this coating composition, a laminated intermediate and a resin laminated body were produced in the same manner as in Example 1, and physical properties were evaluated. The results are shown in Table 1.

Example 4
8.7 g of “ULS-1385MG”, 16 g of 1-methoxy-2-propanol, 1.0 g of tetramethoxysilane, 0.05 g of 20% p-toluenesulfonic acid methanol solution, 0.75 g of acetic acid, A coating composition was produced in the same manner as in Example 1 except that 1.0 g of methoxysilane, 0.4 g of 3-aminopropyltrimethoxysilane and 0.4 g of 3-glycidoxypropyltrimethoxysilane were used. Using this, in the same manner as in Example 1, a laminate intermediate and a resin laminate were prepared, and physical properties were evaluated. The results are shown in Table 1.

Example 5
The solution A used in Example 1 was applied to the surface of an acrylic (PMMA) plate (color: clear, 100 mm × 100 mm × 3 mm, visible light transmittance 93%) manufactured by Sampratec Co., Ltd. so that the cured film was about 5 μm. After being naturally dried at room temperature for 5 minutes, it was cured at 80 ° C. for 2 hours. This laminated intermediate was evaluated in the same manner as in Example 1. The results are shown in Table 1.
After applying the photocatalyst topcoat agent “STK-211” produced by Ishihara Sangyo Co., Ltd. to the surface of the laminated intermediate on the cured film side so as to have a thickness of about 0.5 μm after heating, it is heated at 80 ° C. for 1 hour It processed, the photocatalyst film | membrane was formed and the resin laminated body was produced. The contact angle and light transmittance of this resin laminate were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 6
An organic primer “ST-K300” manufactured by Ishihara Sangyo Co., Ltd. was applied to the surface of the polycarbonate plate so that the thickness after drying was about 0.3 μm, and then dried at room temperature for 30 minutes. On this primer layer, the liquid A of Example 1 was applied and cured in the same manner as in Example 1. This laminated intermediate was evaluated in the same manner as in Example 1. The results are shown in Table 1.
Next, a photocatalytic film was formed on the surface of the laminated intermediate on the cured film side in the same manner as in Example 1. The contact angle and light transmittance of this resin laminate were evaluated according to the evaluation method described later. The results are shown in Table 1.

Example 7
A sample tube having a volume of 50 g was charged with ULS-1385MG: 8.4 g, 1-methoxy-2-propanol: 10 g, and ion-exchanged water: 1 g, and stirred at 700 ppm while acetic acid: 1.0 g, methyltrimethoxysilane: 4 g, dimethoxy-3-glycidoxypropylmethylsilane: 1.9 g, 20% p-toluenesulfonic acid methanol solution: 0.1 g were added dropwise in this order over 1 minute. Subsequently, after stirring at room temperature for 10 minutes, the mixture was allowed to stand for 1 day, which was designated as A′-1 solution.
A sample tube with a capacity of 20 g was charged with 3-isocyanatopropyltriethoxysilane: 2.2 g and 2-butanooxime: 0.7 g, stirred at 500 ppm for 10 minutes, and allowed to stand for 1 day. It was.

A 200-ml three-necked flask equipped with a condenser was charged with the A′-1 solution and a stirrer, and heated at 80 ° C. for 3 hours at 600 rpm under a nitrogen stream. Subsequently, A′-2 solution was added, and the mixture was heated at 80 ° C. for 4 hours under the same conditions. Furthermore, after adding 0.8 g of 3-aminopropyltrimethoxysilane to this over 2 minutes, it heated at 600 rpm for 6 hours at 80 degreeC.
Subsequently, the mixture was allowed to stand for 1 week, and this was used as A ′ solution (coating composition (II)).
Using the A ′ liquid (coating composition (II)) instead of the A liquid, a laminated intermediate and a resin laminated body were produced in the same manner as in Example 1, and physical properties were evaluated. The results are shown in Table 1.

Example 8
12 g of “ULS-1385MG”, 1.3 g of dimethoxy-3-glycidoxypropylmethylsilane, 2.1 g of 3-isocyanatopropyltriethoxysilane, and 3 g of MTMS-A instead of methyltrimethoxysilane In the same manner as in Example 7, a coating composition was produced. Using this, a laminated intermediate and a resin laminated body were produced in the same manner as in Example 1, and physical properties were evaluated. The results are shown in Table 1.

Example 9
A sample tube having a volume of 50 g was charged with ULS-1385MG: 8.4 g, 1-methoxy-2-propanol: 10 g, and ion-exchanged water: 1 g, while stirring at 700 ppm, acetic acid: 1.0 g, MTMS-A: 3 g , Dimethoxy-3-glycidoxypropylmethylsilane: 1.9 g, 20% p-toluenesulfonic acid methanol solution: 0.1 g, each in the order of dropwise addition over 1 minute. Subsequently, after stirring at room temperature for 10 minutes, the mixture was allowed to stand for 1 day, and this was designated as A ″ -1 solution.
A sample tube having a volume of 20 g was charged with 3-isocyanatopropyltriethoxysilane: 2.2 g and 2-butanooxime: 0.7 g, stirred at 500 ppm for 10 minutes, and allowed to stand for 1 day. Liquid.

A ″ -1 liquid and a stirrer were placed in a 200 ml three-necked flask equipped with a condenser, and heated at 80 ° C. for 3 hours at 600 rpm under a nitrogen stream. Subsequently, A ″ -2 solution was added and heated at 80 ° C. for 4 hours under the same conditions. Furthermore, after adding 0.8 g of 3-aminopropyltrimethoxysilane to this over 2 minutes, it heated at 600 rpm for 6 hours at 80 degreeC.
Subsequently, after standing at 25 ° C. in a dark place for 1 day, while stirring at 650 rpm, IPA-ST (manufactured by Nissan Chemical Industries, Ltd., isopropanol dispersion, colloidal silica concentration 30% by weight, particle system 10-20 nm ( (Manufacturer published value)): 5.7 g was dropped over 2 minutes. After stirring at room temperature for 30 minutes, the mixture was further heated at 80 ° C. for 60 minutes.
Subsequently, the mixture was allowed to stand for 1 week, and this was designated as A ″ solution (coating composition (III)).
Using the A ″ liquid (coating composition (III)) instead of the A liquid, a laminated intermediate and a resin laminated body were produced in the same manner as in Example 1, and physical properties were evaluated. The results are shown in Table 1.

Example 10
No ion-exchanged water was added, 4 g of methyltrimethoxysilane was used instead of MTMS-A, Snowtex O-40 (manufactured by Nissan Chemical Industries, Ltd., water dispersion, colloidal silica concentration 20 wt. %, Particle diameter 10-20 nm (manufacturer published value) 2.5 g and Niedral U-15 (manufactured by Taki Chemical Co., Ltd., water dispersion, cerium oxide concentration 15% by weight, particle diameter 8 nm or less (manufacturer catalog value) ) Was used in the same manner as in Example 9 except that 4.7 g was used, and a laminated intermediate and a resin laminate were prepared in the same manner as in Example 1 and evaluated for physical properties. It was. The results are shown in Table 1.

[Second resin laminate]
Reference example 1
A sample tube was charged with 6.2 g of “ULS-1385MG” and 10 g of 1-methoxy-2-propanol, and with stirring, 6.2 g of 1-methyl methacrylate and 0.062 g of 2,2′-azobisisobutyronitrile. Was added dropwise and stirred for 30 minutes. Subsequently, the mixture was allowed to stand at 25 ° C. for 1 week. This was designated as B liquid (coating composition (A)).
The liquid B was applied to the surface of the same polycarbonate molded body as in Example 1 so that the cured film had a thickness of about 5 μm, allowed to dry naturally at room temperature for 5 minutes, and then cured at 120 ° C. for 1 hour. This laminated intermediate (1) was evaluated according to the evaluation method described later. The results are shown in Table 2.

Next, an equivalent mixed solution of inorganic undercoat agents “ST-K102a” and “ST-K102b” manufactured by Ishihara Sangyo Co., Ltd. is dried and heated on the surface of the laminated intermediate (1) on the cured film side. Was applied to a thickness of about 3 μm, dried at room temperature for 5 minutes, and then heated at 100 ° C. for 30 minutes. This was designated as laminated intermediate (2).
Next, a photocatalyst film was formed on the surface of the undercoat layer of the laminate (2) in the same manner as in Example 1. The contact angle and light transmittance of this resin laminate were evaluated according to the evaluation method described later. The results are shown in Table 2.

Reference example 2
A sample tube was charged with 5.0 g of “ULS-1385MG” and 10 g of 1-methoxy-2-propanol, and with stirring, 2.3 g of 1-methyl methacrylate and 0.043 g of 2,2′-azobisisobutyronitrile. Was added dropwise and stirred for 30 minutes. This was designated as C-1 solution. A liquid mixture of 2.0 g of 1-methyl methacrylate, 1.6 g of 3-aminopropyltrimethoxysilane and 1.6 g of 3-glycidoxypropyltrimethoxysilane was prepared, and this was designated as C-2 liquid. C-1 liquid was slowly dripped at C-2 liquid, and it stirred for 2 hours. Subsequently, the mixture was allowed to stand at 25 ° C. for 1 week. This was designated as solution C (coating composition (A)).
The liquid C obtained above was applied to the surface of the polycarbonate plate so that the cured film had a thickness of about 5 μm, allowed to dry naturally at room temperature for 5 minutes, and then cured at 120 ° C. for 1 hour. This laminated intermediate (1) was evaluated according to the evaluation method described later. The results are shown in Table 2.

Next, an organic primer “ST-K300” manufactured by Ishihara Sangyo Co., Ltd. was applied to the surface of the laminated intermediate (1) on the cured film side so that the thickness after drying was about 0.3 μm. For 30 minutes, and further, an equivalent mixture of inorganic undercoat agents “ST-K102a” and “ST-K102b” manufactured by Ishihara Sangyo Co., Ltd. is dried to a thickness of about 3 μm. And dried at room temperature for 5 minutes and then heated at 100 ° C. for 30 minutes. This was designated as laminated intermediate (2).
Next, a photocatalytic film was formed on the surface of the undercoat layer of the laminate intermediate (2) in the same manner as in Example 1. The contact angle and light transmittance of this resin laminate were evaluated according to the evaluation method described later. The results are shown in Table 2.

Comparative Example 1
4 g of 1-methyl methacrylate, 0.15 g of an ultraviolet absorber 2,4-dihydroxybenzophenone, and 0.042 g of 2,2′-azobisisobutyronitrile were added to 8 g of isopropanol and sufficiently stirred. This solution was applied to the surface of the polycarbonate plate so that the cured film had a thickness of about 5 μm, naturally dried at room temperature for 5 minutes, and then cured at 80 ° C. for 1 hour. This laminated intermediate was evaluated according to the evaluation method described later. The results are shown in Table 2.
On the cured product side surface of the laminated intermediate obtained here, an equivalent mixed liquid of undercoat agents “ST-K102a” and “ST-K102b” manufactured by Ishihara Sangyo Co., Ltd. was dried to a thickness of about 3 μm. After being coated and dried at room temperature for 5 minutes, it was heated at 100 ° C. for 30 minutes. Further thereon, a photocatalytic film was formed in the same manner as in Example 1. The contact angle and light transmittance of this resin laminate were evaluated according to the evaluation method described later. The results are shown in Table 2.

Comparative Example 2
Sample preparation was performed in the same manner as in Comparative Example 1 except that the amount of the ultraviolet absorber 2,4-dihydroxybenzophenone was changed to 2 g and 2,2′-azobisisobutyronitrile 0.06 g, and the physical properties were evaluated. The results are shown in Table 2.

Comparative Example 3
Nippon Catalyst Co., Ltd. UV-absorbing film coating agent “UV-G101” 5 g and Sumika Bayer Urethane Co., Ltd. isocyanate curing agent “Desmodur N3200” 0.05 g are uniformly mixed and dried after heating. Was applied to the surface of the polycarbonate plate so as to be about 5 μm, and then dried at 100 ° C. for 3 minutes and at 40 ° C. for 24 hours. This laminated intermediate was evaluated according to the evaluation method described later. The results are shown in Table 2.
On the cured product side surface of the above-mentioned laminated intermediate, an equivalent mixed liquid of the undercoat agents “ST-K102a” and “ST-K102b” manufactured by Ishihara Sangyo Co., Ltd. is dried to be about 3 μm in thickness. After applying and drying at room temperature for 5 minutes, it was heated at 100 ° C. for 30 minutes. Further thereon, a photocatalytic film was formed in the same manner as in Example 1. The contact angle and light transmittance of this resin laminate were evaluated according to the evaluation method described later. The results are shown in Table 2.

[Evaluation methods]
1. Evaluation of resin laminate (1) Photocatalytic function As an index of whether or not the photocatalytic function is manifested, the degree of hydrophilicity can be mentioned (in general, if the contact angle with water has a hydrophilicity of 40 ° or less, antifouling It is said to have sex). As an index of how much photocatalytic function is expressed, the contact angle was measured by the following method.
The photocatalyst layer was irradiated with 1 mW / cm ² of ultraviolet light with a black light blue lamp, and the change with time in contact angle was measured. The contact angle was measured by dropping 20 ml of ion-exchanged water on the surface of the photocatalyst layer using a microsyringe and using an image processing contact angle meter (Kyowa Interface Science Co., Ltd., CA-A).

(2) Visible light transmittance It measured using the direct reading haze computer (Suga Test Instruments Co., Ltd. product, HGM-2DP).

2. Evaluation of Laminated Intermediate (1) Haze Measurement was performed using a direct reading haze computer (HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.).

(2) Degree of yellowing (YI)
It measured based on JISK7105 using SZ-optical SENSOR (Nippon Denshoku Industries Co., Ltd. product).

(3) Adhesion In accordance with JIS K5400, a sample was cut into 11 grids at 2 mm intervals with a razor blade to make 100 grids, and a commercially available cellophane tape (“CT-24 (width 24 mm)”). , Manufactured by Nichiban Co., Ltd.) with the abdomen of the finger well, and then peeled off rapidly at an angle of 90 °, and the remaining number (X) of the film without peeling was displayed as X / 100. .

(4) Weather resistance A xenon weather test (Atlas Ci165, output 6.5 kW, black panel temperature 63 ° C., humidity 50%) was performed, and weather resistance was evaluated based on the degree of change in the parameters (1) to (3) above. did.

(5) Cold-heat shock resistance A cold-heat shock test (manufactured by ESPEC, TSA-200D-W, -30 ° C for 1 hour, 110 ° C for 1 hour for 100 cycles) was performed. The heat resistance test property was evaluated by the change in adhesion (see (3) above) before and after the heat shock test.

(6) Average particle diameter of organic polymer type fine particles Cross-sectional observation of the intermediate layer was performed with a TEM (transmission electron microscope), and 10 particles existing in the 1 μm square were selected and manufactured by NIH (National Institute of Health) in the United States. Average particle size was determined using free software: NIH Image 1.63. In addition, the average particle diameter in Example 1-8 was 40-60 micrometers. Moreover, the cross-sectional photograph (magnification: 100,000 times) of the intermediate layer produced in Example 1 is shown in FIG. The gray portion (or black portion) in the photograph is a matrix having Si—O bonds, and the white portion (or white point) is organic polymer fine particles containing an ultraviolet ray absorbing group. This was confirmed by an elemental analyzer incorporated in the TEM.

The total of the calculated amount of non-volatile content when the components (1), (5), and (6) are completely hydrolyzed / condensed and the amount remaining after removing the solvent in the component (2) is 100% by mass, Table 1 shows values obtained by calculating the content (wt%) of the ultraviolet absorbing unit in the intermediate layer. Further, assuming that the density d of the intermediate layer is 1 g / cm ³ (approximate organic substance density) and 2.5 g / cm ³ (approximate SiO ₂ density), for each assumption, the intermediate layer (volume = 100 mm × 100 mm) The amount of ultraviolet absorbing unit (mg) in × 5 × 10 ⁻³ mm) was determined.

Since the intermediate layer of Example 1 includes Si—O units, the density d is between 1 g / cm ³ and 2.5 g / cm ³ . Therefore, the maximum UV absorption unit in the intermediate layer is 11.9 mg. On the other hand, since the intermediate layer of Comparative Example 2 contains only organic components, it may be considered that d to 1 g / cm ^3, and the inherent ultraviolet absorption unit is approximately 17 mg. It can be seen from Tables 1 and 2 that Comparative Example 2 is superior in weather resistance to the intermediate layer of Example 1 although the amount of the ultraviolet absorbing unit is larger. This is because the organic fine particles exist stably in the intermediate layer. Similarly, the intermediate layers of Examples 2 to 8 are also excellent in weather resistance. The low weather resistance of the intermediate layer of Comparative Example 1 is due to the use of a low molecular weight UV absorber. With respect to the intermediate layer of Comparative Example 3 in which the polymer ultraviolet absorber was used as a film as it was, the thermal shock resistance was inferior.

  From Tables 1 and 2, it can be seen that in the resin laminates of the examples, the photocatalytic function is exhibited and the transparency of the resin laminate is maintained. Furthermore, the resin laminates of the examples were excellent in weather resistance and heat resistance, such as hardly yellowing, haze did not deteriorate, and interface peeling did not easily occur under the usage environment.

  The resin laminate of the present invention can be used for road-related materials (such as soundproof walls) and building materials (such as arcade skylights and carports).

It is a figure which shows one Embodiment of the 1st resin laminated body of this invention. It is a figure which shows other embodiment of the 1st resin laminated body of this invention. It is a figure which shows other embodiment of the 1st resin laminated body of this invention. It is a figure which shows other embodiment of the 2nd resin laminated body of this invention. 2 is a cross-sectional photograph (magnification: 100,000 times) of an intermediate layer produced in Example 1. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 1st resin laminated body 2 2nd resin laminated body 10 Photocatalyst layer 20 Intermediate layer of 1st resin laminated body 22 Intermediate layer of 2nd resin laminated body 30 Resin base material layer 40 Organic layer 50 Inorganic layer

Claims (9)

On the resin base material layer, an intermediate layer is formed using the coating composition (I) containing the following components (1) to (6),
The manufacturing method of the resin laminated body which forms a photocatalyst layer on the said intermediate | middle layer.
(1) Alkoxysilane compound (2) Organic polymer type fine particles having an average particle diameter of 1 to 200 nm containing an ultraviolet absorbing group (3) Curing catalyst (4) Solvent (5) Aminosilane compound (6) Epoxysilane compound On the resin base material layer, an intermediate layer is formed using a coating composition (II) containing the following components (2) to (8),
The manufacturing method of the resin laminated body which forms a photocatalyst layer on the said intermediate | middle layer.
(2) Organic polymer type fine particles having an average particle diameter of 1 to 200 nm containing an ultraviolet absorbing group (3) Curing catalyst (4) Solvent (5) Aminosilane compound (6) Epoxysilane compound (7) Organoalkoxysilane compound or Polyorganoalkoxysilane compound (8) Blocked isocyanate silane compound On the resin base material layer, an intermediate layer is formed using a coating composition (III) containing the following components (2) to (9),
The manufacturing method of the resin laminated body which forms a photocatalyst layer on the said intermediate | middle layer.
(2) Organic polymer type fine particles having an average particle diameter of 1 to 200 nm containing an ultraviolet absorbing group (3) Curing catalyst (4) Solvent (5) Aminosilane compound (6) Epoxysilane compound (7) Organoalkoxysilane compound or Polyorganoalkoxysilane compound (8) Blocked isocyanate silane compound (9) Inorganic ultraviolet absorbing particles and / or colloidal silica A coating composition is produced using the following compounds (1) to (6),
An intermediate layer is formed on the resin base layer using the coating composition,
The manufacturing method of the resin laminated body which forms a photocatalyst layer on the said intermediate | middle layer.
(1) Alkoxysilane compound (2) Organic polymer type fine particles having an average particle diameter of 1 to 200 nm containing an ultraviolet absorbing group (3) Curing catalyst (4) Solvent (5) Aminosilane compound (6) Epoxysilane compound A coating composition is produced using the following compounds (2) to (8),
An intermediate layer is formed on the resin base layer using the coating composition,
The manufacturing method of the resin laminated body which forms a photocatalyst layer on the said intermediate | middle layer.
(2) Organic polymer type fine particles having an average particle diameter of 1 to 200 nm containing an ultraviolet absorbing group (3) Curing catalyst (4) Solvent (5) Aminosilane compound (6) Epoxysilane compound (7) Organoalkoxysilane compound or Polyorganoalkoxysilane compound (8) Blocked isocyanate silane compound A coating composition is produced using the following compounds (2) to (9),
An intermediate layer is formed on the resin base layer using the coating composition,
The manufacturing method of the resin laminated body which forms a photocatalyst layer on the said intermediate | middle layer.
(2) Organic polymer type fine particles having an average particle diameter of 1 to 200 nm containing an ultraviolet absorbing group (3) Curing catalyst (4) Solvent (5) Aminosilane compound (6) Epoxysilane compound (7) Organoalkoxysilane compound or Polyorganoalkoxysilane compound (8) Blocked isocyanate silane compound (9) Inorganic ultraviolet absorbing particles and / or colloidal silica The method for producing a resin laminate according to any one of claims 1 to 6 , wherein the organic polymer-type fine particles contain an acrylic resin and / or a styrene resin. The resin laminated body manufactured by the manufacturing method of any one of Claims 1-7 . The resin laminate according to claim 8, wherein the resin laminate has a visible light transmittance of 80% or more.