WO2010001949A1

WO2010001949A1 - Coating liquid, cured film, resin multilayer body, method for producing the cured film and method for producing the resin multilayer body

Info

Publication number: WO2010001949A1
Application number: PCT/JP2009/062096
Authority: WO
Inventors: 直子阿部; 和彦伊藤; 太宇都野; 一吉井上; 健治後藤; 真弘関口
Original assignee: 出光興産株式会社
Priority date: 2008-07-02
Filing date: 2009-07-02
Publication date: 2010-01-07
Also published as: KR101653417B1; TWI462979B; KR20110030493A; JPWO2010001949A1; WO2010001949A9; TW201012882A; JP5635402B2

Abstract

Disclosed is a coating liquid containing: (A) a hydrolysis-condensation product of silane compounds having an alkoxy group, namely (A-1) a tetraalkoxysilane compound, (A-2) an organoalkoxysilane compound containing no amino group, no epoxy group and no isocyanate group, (A-3) a silane compound having an amino group and an alkoxy group, (A-4) a silane compound having an epoxy group and an alkoxy group and (A-5) a blocked isocyanate silane compound having an alkoxy group; (B) organic polymer fine particles composed of a copolymer containing a monomer unit having an ultraviolet-absorbing group; (C) a colloidal silica; (D) a curing catalyst and (E) a dispersion medium. A cured film using the coating liquid, a resin multilayer body, a method for producing the cured film and a method for producing the resin multilayer body are also disclosed.

Description

Coating liquid, cured film and resin laminate, and method for producing the cured film and resin laminate

The present invention relates to a coating solution, a cured film, a resin laminate, and a method for producing the cured film and the resin laminate.

Thermoplastics, especially polycarbonate resins, are widely used as structural materials to replace glass because of their excellent transparency, light weight, and excellent impact resistance. However, since the surface properties such as abrasion resistance, scratch resistance, weather resistance, and chemical resistance are inferior, the use thereof is limited, and there is a strong demand for improving the surface properties of the polycarbonate substrate.

As a method for improving surface characteristics, there is a method of coating the surface of a polycarbonate resin molded article with a surface treatment agent. For example, a method has been proposed in which a cured layer made of a polyfunctional acrylic photocurable resin or a melamine-based or organopolysiloxane-based thermosetting resin is formed on the surface of a polycarbonate substrate.

Among these, those coated with an organosiloxane resin are considered useful because they are excellent in wear resistance, scratch resistance and chemical resistance. However, the coating with the organosiloxane resin has a problem in adhesion to the polycarbonate resin, and particularly has a problem that the coating layer is peeled off when used outdoors for a long period of time. Further, in order to improve the adhesion and wear resistance, there is a problem that even if the thickness of the organosiloxane resin is increased, there is a problem that cracking is likely to occur at the time of curing.

For improving the adhesion, Patent Document 1 proposes a method in which various polymers having good adhesion are blended into a paint or a hard coat material, but the scratch resistance is insufficient. Moreover, although patent document 2 and 3 describe providing a hardened film on the base-material surface, and also providing an inorganic hard material layer on it, sufficient adhesiveness is not acquired.
Patent Documents 4 and 5 disclose a resin laminate comprising a coating layer having a film internal structure in which polymer nanoparticles having ultraviolet absorbing ability are highly dispersed in a siloxane matrix (Si—O skeleton) and a base material. Yes. This resin laminate is excellent in abrasion resistance and initial adhesion between the substrate and the coating layer. There was room for improvement in terms of wear resistance and wear resistance. There was also room for improvement in terms of durability (boiling resistance).

Japanese Patent Laid-Open No. 11-43646 JP 58-29835 A JP-A 64-43343 WO2006 / 022347 pamphlet WO2007 / 099784 pamphlet

The present invention has been made under such circumstances, and has good adhesion to a substrate, an inorganic hard material layer, a transparent conductive film and a photocatalyst layer without using a primer, and has excellent wear resistance. Coating liquid that gives a cured film having properties such as property, scratch resistance, flex resistance, weather resistance (ultraviolet ray absorption ability), and durability (boiling resistance), and curing having the above-mentioned characteristics by curing this coating liquid It aims at providing the manufacturing method of a resin laminated body which has a film | membrane and this cured film on a base material, and this cured film and resin laminated body.

As a result of intensive studies on the coating liquid that gives a cured film having the above characteristics, the present inventors have obtained the following knowledge.
A coating liquid containing a hydrolyzed condensate of a silane compound having an alkoxy group, an organic polymer fine particle comprising a copolymer containing a monomer unit having an ultraviolet absorbing group, colloidal silica, a curing catalyst and a dispersion medium is heated. By curing, a cured film having desired characteristics can be obtained, and the cured film is formed on the substrate or between each of the inorganic hard material layer, the transparent conductive film and the photocatalyst layer and the substrate. The inventors have found that a desired resin laminate can be obtained.
The present invention has been completed based on such findings.

That is, this invention provides the following coating liquid, a cured film, a resin laminated body, and the manufacturing method of this cured film and a resin laminated body.
[1] A coating liquid comprising the following components (A) to (E):
(A) Hydrolysis condensate of silane compounds having alkoxy groups of the following components (A-1) to (A-5) (A-1) Tetraalkoxysilane compounds (A-2) Amino groups, epoxy groups and isocyanate groups (A-3) Silane compound having amino group and alkoxy group (A-4) Silane compound having epoxy group and alkoxy group (A-5) Blocked isocyanatosilane compound having alkoxy group (B) Organic polymer fine particles comprising a copolymer containing a monomer unit having an ultraviolet absorbing group (C) Colloidal silica (D) Curing catalyst (E) Dispersion medium

[2] The coating liquid according to [1], further comprising (F) cerium oxide treated with a silane compound and (G) a dispersion stabilizer.
[3] The coating liquid according to [1] or [2], wherein the component (A-1) is a tetraalkoxysilane compound represented by the following general formula (1).
Si (OR ¹ ) ₄ (1)
[Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms or an alkyl group having an ether bond. A plurality of R ¹ may be the same or different. ]

[4] The coating liquid according to [1] or [2], wherein the component (A-2) is an organoalkoxysilane compound containing no amino group, epoxy group or isocyanate group represented by the following general formula (2).
R ² _a Si (OR ³ ) _4-a (2)
Wherein, R ² is an alkyl group or a fluorinated alkyl group of 1 to 10 carbon atoms; vinyl group; a phenyl group; or methacryloxy-substituted alkyl group having 1-3 carbon atoms in the group, R ³ is a C1- 4 represents an alkyl group or an alkyl group having an ether bond, and a represents 1 or 2. When R ² are a plurality, the plurality of R ² may be the same or different, a plurality of OR ³ may be the same or different. ]
[5] The coating liquid according to [1] or [2], wherein the component (A-3) is a silane compound having an amino group and an alkoxy group represented by the following general formula (3).
R ⁴ _b Si (OR ⁵ ) _4-b (3)
[Wherein R ⁴ is an 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 group ( Wherein x is an integer of 1 to 3)]), an alkylamino group [—NHR group (where R is an alkyl group having 1 to 3 carbon atoms)], and the number of carbon atoms substituted with one or more groups 1 to 3 alkyl groups, at least one of R ⁴ represents an amino group, or an alkyl group having 1 to 3 carbon atoms substituted with either an aminoalkyl group or an alkylamino group; R ⁵ represents an alkyl group having 1 to 4 carbon atoms, and b represents 1 or 2. If R ⁴ is plural, R ⁴ may be the same or different, the plurality of OR ⁵ may be the same or different. ]

[6] The coating liquid according to [1] or [2], wherein the component (A-4) is a silane compound having an epoxy group and an alkoxy group represented by the following general formula (4).
R ⁶ _c Si (OR ⁷ ) _4-c (4)
[Wherein R ⁶ is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or a carbon substituted with one or more groups selected from a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. Represents an alkyl group having 1 to 3 carbon atoms, and at least one of R ⁶ represents an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R ⁷ represents an alkyl group having 1 to 4 carbon atoms, and c represents 1 or 2. If R ⁶ is plural, R ⁶ may be the same or different, a plurality of OR ⁷ may be different or identical. ]
[7] The coating liquid according to [1] or [2], wherein the component (A-5) is a blocked isocyanatosilane compound having an alkoxy group represented by the following general formula (5).
R ⁸ _d Si (OR ⁹ ) _4-d (5)
[Wherein R ⁸ is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from a methacryloxy group and a blocked isocyanate group. And at least one of R ⁸ represents an alkyl group having 1 to 3 carbon atoms substituted with a blocked isocyanate group. R ⁹ represents an alkyl group having 1 to 4 carbon atoms, and d represents 1 or 2. If R ⁸ is plural, R ⁸ may be the same or different, a plurality of OR ⁹ may be the same or different. ]

[8] A reaction product obtained by contacting the hydrolysis condensate of components (A-1), (A-2) and (A-4) with components (B) to (E) The coating liquid according to any one of [1] to [7], wherein the component (A-5) is added and reacted, and then the component (A-3) is added and reacted.
[9] A reaction product obtained by heating a mixture containing the component (A-1), the component (A-2), the component (A-4) and the components (B) to (E) is added to the reaction product (A -5) The coating liquid according to any one of [1] to [7], wherein the component (A-3) is added and reacted after the component is reacted.

[10] A cured film obtained by curing the coating liquid according to any one of [1] to [9].
[11] A resin laminate comprising a base material and the cured film according to [10] directly formed on the base material.
[12] A resin laminate comprising a substrate, the cured film according to [10] formed on the substrate, and an inorganic layer formed on the cured film.
[13] A resin laminate comprising a substrate, the cured film according to [10] formed on the substrate, and a transparent conductive film formed on the cured film.
[14] A resin laminate comprising a base material, the cured film according to [10] formed on the base material, and a photocatalyst layer formed on the cured film.
[15] The resin laminate according to [13], wherein the cured film has a thickness of 0.1 to 50 μm.
[16] The resin laminate according to [13], wherein the transparent conductive film has a carrier concentration of 1 × 10 ¹⁸ / cm ³ or more.
[17] The resin laminate according to [13], wherein the substrate is a resin substrate.
[18] The resin laminate according to any one of [11], [12] and [17], wherein the substrate has irregularities.
[19] The resin laminate according to any one of [11], [12], [17] and [18], wherein the base material has an elliptic cylinder shape.
[20] The resin laminate according to any one of [11], [12], [17] and [18], wherein the base material is a cylindrical shape.
[21] The resin laminate according to any one of [11], [12], and [17] to [20], wherein a resin layer is provided on a surface of the base material on which no cured film is formed.
[22] The resin laminate according to any one of [11], [12], [14], and [17] to [21], wherein the cured film has a thickness of 0.5 to 6 μm. .
[23] The resin laminate according to any one of [11], [12], [14], and [17] to [22], wherein the substrate is a polyester resin, a polycarbonate resin, or a polyolefin resin .

[24] A method for producing a cured film, comprising a step of heating and curing the coating liquid according to any one of [1] to [9].
[25] A step of applying the coating liquid according to any one of [1] to [9] on a substrate, a step of drying the coating solution, a step of thermoforming the substrate, and the coating And a step of providing a coating layer by curing the liquid.
[26] The method for producing a resin laminate according to [25], further comprising a step of providing a resin layer on a surface of the resin laminate obtained by curing the coating liquid and having no coating layer.
[27] A step of forming a cured film obtained by curing the coating liquid according to any one of [1] to [9] on a substrate, a step of forming a transparent conductive film on the cured film, The manufacturing method of the resin laminated body characterized by including.
[28] A step of forming a cured film obtained by curing the coating liquid according to any one of [1] to [9] on a substrate, and a step of forming a photocatalytic layer on the cured film. A method for producing a resin laminate, comprising:

According to the present invention, it has good adhesion to a substrate, an inorganic hard material layer, a transparent conductive film and a photocatalyst layer without using a primer, and has excellent wear resistance, scratch resistance, and bending resistance. It is possible to provide a coating liquid that gives a cured film having properties such as property, weather resistance (ultraviolet ray absorption ability), and durability (boiling resistance).
Further, according to the present invention, the cured film having the above-mentioned characteristics obtained by curing the coating liquid and the cured film on the substrate or between each of the inorganic hard material layer, the transparent conductive film and the photocatalyst layer and the substrate. And a method for producing the cured film and the resin laminate.

First, the coating liquid of the present invention will be described.
[Coating solution]
The coating liquid of the present invention comprises the following components (A) to (E).

((A) component)
The coating liquid of the present invention contains hydrolysis condensates of the following five compounds (A-1) to (A-5) as hydrolysis condensates of the silane compound having an alkoxy group as component (A). . The hydrolysis condensate may be a hydrolysis condensate of a single compound in (A-1) to (A-5), or any one of (A-1) to (A-5) It may be a hydrolysis condensate of a mixture of two or more.
In the present invention, an alkoxy group-containing silane compound is an alkoxysilane compound and / or a partial condensate thereof, and an alkoxysilane compound partial condensate is a part of an alkoxysilane compound condensed into a siloxane in the molecule. A polyalkoxysilane compound or a polyorganoalkoxysilane compound formed by forming a bond (Si—O bond).
The hydrolyzed condensate of the silane compound having an alkoxy group includes a silane compound having the alkoxy group before hydrolysis and condensation in addition to the hydrolyzed condensate of the silane compound having an alkoxy group. is there.

<(A-1) Compound>
The compound (A-1) is a tetraalkoxysilane compound. A partial condensate (polyalkoxysilane compound) bonded with a siloxane bond (Si—O bond) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
As the compound (A-1), a tetraalkoxysilane compound and a partial condensate thereof can be represented, for example, by the following general formula (1), and a compound represented by the following general formula (6) is particularly preferable.
Si (OR ¹ ) ₄ (1)
[Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms or an alkyl group having an ether bond. A plurality of R ¹ may be the same or different. ]

[Wherein R ¹ is the same as described above, and n is an integer of 1 to 15.] ]

In the general formulas (1) and (6), examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and various butyl groups. OR ¹ in which R ¹ is an alkyl group having 1 to 4 carbon atoms having an ether bond includes, for example, a 2-methoxyethoxy group, a 3-methoxypropoxy group, and the like.
Examples of the tetraalkoxysilane compound (A-1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraisobutoxysilane.
Examples of the polyalkoxysilane compound include “M silicate 51”, “silicate 40”, and “silicate 45” manufactured by Tama Chemical Industries, Ltd., and “methyl silicate 51”, “methyl silicate 53A”, and “ethyl silicate 40” manufactured by Colcoat Co., Ltd. "Ethyl silicate 48" etc. are mentioned.

<(A-2) Compound>
The compound (A-2) is an organoalkoxysilane compound containing no amino group, epoxy group or isocyanate group. Moreover, the partial condensate can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
As the compound (A-2), the organoalkoxysilane compound and the partial condensate thereof are preferably bifunctional alkoxysilane and trifunctional alkoxysilane, and can be represented by, for example, the following general formula (2). The compound represented by (7) is preferred.

R ² _a Si (OR ³ ) _4-a (2)
Wherein, R ² is an alkyl group or a fluorinated alkyl group of 1 to 10 carbon atoms; vinyl group; a phenyl group; or methacryloxy-substituted alkyl group having 1-3 carbon atoms in the group, R ³ is a C1- 4 is an alkyl group or an alkyl group having an ether bond, and a is 1 or 2. When R ² are a plurality, the plurality of R ² may be the same or different, a plurality of OR ³ may be the same or different. ]

[Wherein R ² and R ³ are the same as above, and m is an integer of 1 to 15.] ]

In the general formulas (2) and (7), the alkyl group having 1 to 10 carbon atoms may be linear or branched. For example, a methyl group, an ethyl group, an n-propyl group, Examples include isopropyl group, various butyl groups, various hexyl groups, various octyl groups, and various decyl groups. Examples of the fluorinated alkyl group include trifluoroethyl group and trifluoropropyl group. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. The alkyl group having 1 to 4 carbon atoms or the alkyl group having an ether bond is as described in the general formula (1).

Among the organoalkoxysilane compounds represented by the general formula (2), trifunctional alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyl-tris (2-methoxy). Ethoxy) silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, ethyl-tris (2-methoxyethoxy) silane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltripropoxysilane, Hexyl riboxysilane, decyltrimethoxysilane, decyltriethoxysilane, decyltripropoxysilane, decyltributoxysilane, trifluoropropoxy with fluorine atoms introduced into substituents Fluorinated alkyl (trialkoxy) silane, such as trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, etc. γ- methacryloxypropyl trimethoxysilane. Moreover, methyldimethoxy (ethoxy) silane, ethyl diethoxy (methoxy) silane, etc. which have two types of alkoxy groups are also mentioned.

Examples of the bifunctional alkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, bis (2-methoxyethoxy) dimethylsilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane.
Specific examples of the polyorganoalkoxysilane compound include “MTMS-A” manufactured by Tama Chemical Co., Ltd., “SS-101” manufactured by Colcoat Co., Ltd., “AZ-6101” and “SR2402” manufactured by Toray Dow Corning Co., Ltd. And “AY42-163”.

<(A-3) Compound>
The compound (A-3) is an silane compound having an amino group and an alkoxy group, and does not contain an epoxy group or an isocyanate group. Moreover, the partial condensate (amino group containing polyorganoalkoxysilane compound) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
As the compound (A-3), an amino group-containing organoalkoxysilane compound and a partial condensate thereof can be represented, for example, by the following general formula (3).

R ⁴ _b Si (OR ⁵ ) _4-b (3)
[Wherein R ⁴ is an 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 group ( Wherein x is an integer of 1 to 3)]), an alkylamino group [—NHR group (where R is an alkyl group having 1 to 3 carbon atoms)], and the number of carbon atoms substituted with one or more groups An alkyl group having 1 to 3 carbon atoms and at least one R ⁴ is an amino group or an alkyl group having 1 to 3 carbon atoms substituted with either an aminoalkyl group or an alkylamino group. R ⁵ is an alkyl group having 1 to 4 carbon atoms, and b is 1 or 2. If R ⁴ is plural, R ⁴ may be the same or different, the plurality of OR ⁵ may be the same or different. ]
In the general formula (3), the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as described in the general formula (1) or (2).

Specific examples of the amino group-containing organoalkoxysilane compound represented by the general formula (3) include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and N- (2-aminoethyl) -3-amino. Propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, N-methylaminopropyltrimethoxysilane, N-methylaminopropyltriethoxysilane and the like can be mentioned.
Examples of the amino group-containing polyorganoalkoxysilane compound include “KBP-90” manufactured by Shin-Etsu Silicone Co., Ltd.

<(A-4) Compound>
The compound (A-4) is an alkoxysilane compound having an epoxy group and an alkoxy group and not containing an amino group or an isocyanate group. Moreover, the partial condensate (epoxy group containing polyorganoalkoxysilane compound) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
As the compound (A-4), an epoxy group-containing organoalkoxysilane compound and a partial condensate thereof can be represented, for example, by the following general formula (4).

R ⁶ _c Si (OR ⁷ ) _4-c (4)
[Wherein R ⁶ is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or a carbon substituted with one or more groups selected from a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. An alkyl group having 1 to 3 carbon atoms, and at least one of R ⁶ is an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R ⁷ is an alkyl group having 1 to 4 carbon atoms, and c is 1 or 2. If R ⁶ is plural, R ⁶ may be the same or different, a plurality of OR ⁷ may be different or identical. ]
In the general formula (4), the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as described in the general formula (1) or (2).

Specific examples of the epoxy group-containing organoalkoxysilane compound represented by the general formula (4) include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxy. Examples thereof include silane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

<(A-5) Compound>
The compound (A-5) is a blocked isocyanatosilane compound having an alkoxy group (generally also referred to as a blocked isocyanate silane compound), which contains a blocked isocyanate group, but has an amino group and an epoxy group. It is an alkoxysilane compound not included. Moreover, the partial condensate (blocked isocyanate group containing polyorganoalkoxysilane compound) can also be used. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
The blocked isocyanatosilane compound is an isocyanatosilane 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 (general) Also referred to as an isocyanate silane compound).

As the compound (A-5), a blocked isocyanate group-containing organoalkoxysilane compound and a partial condensate thereof can be represented, for example, by the following general formula (5).
R ⁸ _d Si (OR ⁹ ) _4-d (5)
[Wherein R ⁸ is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from a methacryloxy group and a blocked isocyanate group. And at least one of R ⁸ is an alkyl group having 1 to 3 carbon atoms substituted with a blocked isocyanate group. R ⁹ is an alkyl group having 1 to 4 carbon atoms, and d is 1 or 2. If R ⁸ is plural, R ⁸ may be the same or different, a plurality of OR ⁹ may be the same or different. ]
In the general formula (5), the alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms are as described in the general formula (1) or (2).

Specific examples of the blocked isocyanate group-containing organoalkoxysilane compound represented by the general formula (5) include 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane. , 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylethyldiethoxysilane and the like in which the isocyanate group is protected with a blocking agent. Among these, a preferred compound is 3-blocked isocyanatopropyltriethoxysilane.

Examples of isocyanate group blocking agents include oxime compounds such as acetooxime, 2-butanone oxime, cyclohexanone oxime, methyl isobutyl ketoxime, lactams such as ε-caprolactam, 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, ethyl lactate Hydroxyl-containing esters such as amyl lactate, mercaptans such as butyl mercaptan and hexyl mercaptan, acid amides such as acetanilide, acrylic amide and dimer acid amide, imidazoles such as imidazole and 2-ethylimidazole, 3,5-dimethylpyrazole Pyrazoles such as 1, triazoles such as 1,2,4-triazole, 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.

((B) component)
The coating liquid of the present invention comprises, as component (B), organic polymer fine particles (hereinafter sometimes referred to as polymer UV-absorbing resin fine particles) made of a copolymer containing a monomer unit having an ultraviolet absorbing group. contains.
Examples of the polymer ultraviolet-absorbing resin fine particles include an acrylic monomer having a skeleton (benzophenone-based, benzotriazole-based, triazine-based, etc.) acting as an ultraviolet absorber in the side chain (hereinafter referred to as an ultraviolet-absorbing acrylic monomer). And those obtained by copolymerizing other ethylenically unsaturated compounds (acrylic acid, methacrylic acid and derivatives thereof, styrene, vinyl acetate, etc.). While conventional ultraviolet absorbers are generally low molecular weight molecules having a molecular weight of 200 to 700, the weight average molecular weight of the polymer ultraviolet absorbing resin fine particles usually exceeds 10,000. Disadvantages of conventional low molecular weight ultraviolet absorbers such as compatibility with plastics and heat resistance are improved, and weather resistance can be imparted over a long period of time.

The ultraviolet-absorbing group acrylic monomer is not particularly limited as long as it is a compound having at least one ultraviolet-absorbing group and acryloyl group in the molecule. Examples of such a compound include a benzotriazole compound represented by the following general formula (8) and a benzophenone compound represented by the general formula (9).

[Wherein, X is a hydrogen atom or a chlorine atom, R ¹⁰ is a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 8 carbon atoms, and R ¹¹ is a linear or branched carbon group having 2 to 10 carbon atoms. An alkylene group, R ¹² represents a hydrogen atom or a methyl group, and p represents 0 or 1. ]

[Wherein R ¹³ is a hydrogen atom or methyl group, R ¹⁴ is a substituted or unsubstituted linear or branched alkylene group having 2 to 10 carbon atoms, R ¹⁵ is a hydrogen atom or hydroxyl group, and R ¹⁶ is hydrogen. An atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms is shown. ]

Specific examples of the benzotriazole-based compound represented by the general formula (8) include 2- (2′-hydroxy-5 ′-(meth) acryloxyphenyl) -2H-benzotriazole, 2- (2 '-Hydroxy-3'-tert-butyl-5'-(meth) acryloxymethylphenyl) -2H-benzotriazole, 2- [2'-hydroxy-5 '-(2- (meth) acryloxyethyl) phenyl ] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(2- (meth) acryloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [ And 2'-hydroxy-3'-methyl-5 '-(8- (meth) acryloxyoctyl) phenyl] -2H-benzotriazole.

Specific examples of the benzophenone compounds represented by the general formula (9) include, for example, 2-hydroxy-4- (2- (meth) acryloxyethoxy) benzophenone, 2-hydroxy-4- (4- (meta ) Acryloxybutoxy) benzophenone, 2,2'-dihydroxy-4- (2- (meth) acryloxyethoxy) benzophenone, 2,4-dihydroxy-4 '-(2- (meth) acryloxyethoxy) benzophenone, 2, , 2 ′, 4-trihydroxy-4 ′-(2- (meth) acryloxyethoxy) benzophenone, 2-hydroxy-4- (3- (meth) acryloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy-4 And-(3- (meth) acryloxy-1-hydroxypropoxy) benzophenone.
These ultraviolet-absorbing acrylic monomers may be used alone or in combination of two or more.

The content of the ultraviolet-absorbing acrylic monomer unit in the polymer ultraviolet-absorbing resin fine particles as the component (B) is from the viewpoint of the ultraviolet absorption ability of the obtained cured film, other physical properties and economic balance, etc. Usually, it is about 5 to 70% by mass, preferably about 10 to 60% by mass.
In the coating liquid of the present invention, the polymer ultraviolet absorbing resin fine particles used as the component (B) are from the viewpoints of manufacturability, dispersibility in the coating liquid, coating property of the coating solution, and transparency of the cured film. The average particle diameter is preferably in the range of 1 to 200 nm, more preferably in the range of 1 to 100 nm. The average particle diameter of the polymer ultraviolet absorbing resin fine particles can be measured by a laser diffraction scattering method.

In the present invention, the polymer ultraviolet absorbing resin fine particles are preferably used in a form dispersed in a dispersion medium. Examples of the dispersion medium include water, methanol, ethanol, propanol, 1-methoxy-2-propanol, and the like. Preferred examples include lower alcohols and cellosolves such as methyl cellosolve. By using such a dispersion medium, the dispersibility of the polymer ultraviolet absorbing resin fine particles is improved, and sedimentation can be prevented. More preferably, the dispersion medium is water. When the dispersion medium is water, it can be advantageously used for the hydrolysis and condensation reaction of the silane compound required for forming the matrix having Si—O bonds derived from the component (A).

There is no restriction | limiting in particular in the manufacturing method of the polymer ultraviolet rays absorption resin fine particle used as the said (B) component, A conventionally well-known method, for example, an emulsion polymerization method, a fine suspension polymerization method, etc. are employable.
In the emulsion polymerization method, a mixture composed of an ultraviolet-absorbing acrylic monomer as a monomer and an ethylenically unsaturated monomer copolymerized therewith is obtained from an aqueous dispersion medium, an anionic or nonionic surfactant. A method for obtaining a dispersion of polymer UV-absorbing resin fine particles by proceeding polymerization in a surfactant micelle layer emulsified into fine droplets and enclosing the monomer mixture using an emulsifier and a water-soluble polymerization initiator It is.
On the other hand, the fine suspension polymerization solution is first premixed in an aqueous medium by adding the monomer mixture, oil-soluble polymerization initiator, emulsifier and other additives as necessary, and homogenized by a homogenizer. The particle size of the oil droplets is adjusted. Next, the homogenized liquid is sent to a polymerization vessel and a polymerization reaction is performed to obtain a dispersion of polymer ultraviolet absorbing resin fine particles.
In any of the above methods, the polymerization temperature is about 30 to 80 ° C.

Examples of the water-soluble polymerization initiator used in the emulsion polymerization include water-soluble peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, these initiators or cumene hydroperoxide, t-butyl hydroperoxide, and the like. Redox initiators that combine hydroperoxides with reducing agents such as acidic sodium sulfite, ammonium sulfite, and ascorbic acid; water-soluble azo compounds such as 2,2'-azobis (2-methylpropionamidine) dihydrochloride Can be mentioned.
On the other hand, examples of the oil-soluble polymerization initiator used for fine suspension polymerization include oil-soluble organic peroxides such as diacyl peroxides, ketone peroxides, peroxy esters, peroxy dicarbonates, 2, 2 Examples thereof include azo compounds such as' -azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile).

Specific examples of the polymer ultraviolet ray absorbing resin fine particles that can be used as the component (B) include coating polymer ultraviolet absorbers ULS-700, ULS-1700, ULS-383MA, ULS manufactured by Yufu Kogyo Co., Ltd. -1383MA, ULS-383MG, ULS-385MG, ULS-1383MG, ULS-1385MG, ULS-635MH, etc. NUV-905-20EM and NCI-905-20EMA Polymer ultraviolet absorber made of a copolymer of styrene monomer and benzotriazole monomer).
In the present invention, as the component (B), the polymer ultraviolet absorbing resin fine particles may be used singly or in combination of two or more.

((C) component)
The coating liquid of the present invention contains colloidal silica as the component (C).
The colloidal silica used in the present invention 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 its surface by hydration, and is 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 vapor phase method. The average particle size is preferably about 1 to 200 nm. The composition of the particles is indeterminate, and some particles are polymerized by forming siloxane bonds (—Si—O—, —Si—O—Si—). The particle surface is porous and is generally negatively charged in water. The average particle diameter can be measured by a laser diffraction scattering method.

Commercially available products include “Ultra High-Purity Colloidal Silica” Quarton PL Series (product names: PL-1, PL-3, PL-7) manufactured by Fuso Chemical Industry Co., Ltd. “Colloidal silica” (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, MA-ST-L, 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, such as PGM-ST) "can be mentioned.
In the present invention, as the component (C), the colloidal silica may be used alone or in combination of two or more.

((D) component)
The coating liquid of the present invention contains a curing catalyst as the component (D).
This curing catalyst is a catalyst for hydrolyzing and condensing (curing) the silane compounds (A-1) to (A-5) in the component (A) described above. For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, Inorganic acids such as nitrous acid, perchloric acid, sulfamic acid, organic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, citric acid, tartaric acid, succinic acid, maleic acid, glutamic acid, lactic acid, p-toluenesulfonic acid Is mentioned.

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 , like aluminum triisopropoxide, aluminum acetylacetonate, Lewis acids such as SnCl _{_{_4,}} TiCl _4, ZnCl ₄ is It is.

Among these curing catalysts, an organic acid can be preferably used because it can be highly dispersed even if the blending amount of the components (B) and (C) is increased, and the transparency of the resulting film can be improved. In particular, organic carboxylic acids, especially acetic acid can be preferably used.
In the present invention, as the component (D), the curing catalyst may be used alone or in combination of two or more.

((E) component)
The coating liquid of the present invention contains a dispersion medium as the component (E).
The coating liquid of the present invention is used in a state where the component particles are dispersed in a dispersion medium. The dispersion medium used in the present invention is not particularly limited as long as it can uniformly mix and disperse the above component particles. For example, in addition to water, alcohols, aromatic hydrocarbons, ethers, ketones And organic dispersion media such as esters and esters. Among these organic dispersion media, specific examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, 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 Examples include alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, and butyl cellosolve. Kill.

Specific examples of other dispersion media 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. Etc.
Among these dispersion media, water and alcohols are preferable from the viewpoint of performance as a dispersion medium.
In the present invention, as the component (E), one type of the dispersion medium may be used alone, or two or more types may be used in combination.

((F) component)
The coating liquid of the present invention preferably contains cerium oxide treated (pretreated) with a silane compound as the component (F).
The pretreatment here refers to changing the surface state of cerium oxide by reacting the OH group of cerium oxide with the silanol group of the silane compound to form a covalent bond. Silane-treated cerium oxide does not form aggregates or precipitates even when mixed with a sol (for example, colloidal silica) in which anionic particles are dispersed. Can do.
The cerium oxide used is not particularly limited, but is preferably in the form of particles and having an average particle diameter of 1 to 200 nm, and more preferably 1 to 100 nm from the viewpoint of transparency. From the viewpoint of improving dispersibility, when adding the component (F) to the coating liquid of the present invention, it is preferable to add the component after dispersing it in a dispersion medium such as water or alcohol.

“Dispersion” in component (F) refers to a state in which a dispersed phase (solid) is suspended and suspended in a dispersion medium (liquid). The “sol” is a colloid having a liquid as a dispersion medium and a solid as dispersed particles, and is sometimes referred to as a colloid solution. The average particle diameter of the cerium oxide fine particles can be measured by a laser diffraction scattering method.
As a dispersion medium, although it applies to the above-mentioned (E) component, water or alcohol is preferable. In particular, the alcohol refers to an alcohol generated from the silane compound described in the components (A-1) to (A-5) in the component (A) and the alcohol described in the component (E), and particularly methanol, ethanol It is preferably dispersed in a lower alcohol such as n-propyl alcohol, isopropyl alcohol or 1-methoxy-2-propanol. In addition, water and alcohol as a dispersion medium may be used individually by 1 type, and may be used in combination of 2 or more type.

The component (F) is a dispersion obtained by reacting a cerium oxide sol having a surface charge with a silane compound and modifying the surface, and can be suitably added to the coating liquid of the present invention without agglomeration, precipitation or gelation. Is. This silane compound includes all alkoxysilanes or their hydrolyzed condensates. Therefore, since the exact solid content concentration in the state of the dispersion cannot be obtained, the total amount of cerium oxide as a raw material and the total amount of the complete condensation product of alkoxysilane is divided by the total amount of charge, and expressed as a percentage. This was taken as the calculated solid content concentration.

<Method for producing component (F)>
The method for producing the raw material cerium oxide fine particles to be used is not particularly limited. However, since the reaction with the silane compound is difficult with the powder as it is, it is suitably used as a dispersion. As the stabilizer for dispersion, an acid-stable cationic cerium oxide sol using an acidic dispersion stabilizer can be preferably used from the viewpoint of promoting the hydrolysis reaction of the silane compound, and the average particle size is 1 to 200 nm. The thickness is preferably from 1 to 100 nm from the viewpoint of imparting transparency. Examples of the acidic dispersion stabilizer to be added include inorganic acids such as hydrochloric acid, nitric acid and perchloric acid, and organic carboxylic acids such as acetic acid, formic acid and lactic acid. These may be used alone or in combination. Among these, since the organic carboxylic acid has a coordination effect on the metal, the dispersion stabilizer is preferably an inorganic acid, more preferably cerium oxide sol using hydrochloric acid, from the viewpoint of further reacting cerium oxide with the silane compound.
Examples of commercially available products include “Nidoral H-15” manufactured by Taki Chemical Co., Ltd.

The raw material silane compound used can be defined in the same way as the component (A) described above, but in order to form a siloxane bond suitably with the silanol groups of the component (A) and the component (C) during the production of the cured film, (A-1) A compound is preferred. These may be used alone or in combination.

Moreover, as a silane compound in (F) component, in addition to said tetraalkoxysilane and its hydrolysis condensate or polyalkoxysilane, organoalkoxysilane or its hydrolysis condensate or polyorganoalkoxysilane is used together. You can also. Specific examples of the organoalkoxysilane are those having one or more organic substituents among the component (A), and more preferably the components (A-2) to (A-5).
The structure of the surface treatment may be a complete two-layer structure or a structure in which each alkoxysilane, its hydrolysis condensate or polyalkoxysilane is mixed.
Since the OH group on the surface layer of the cerium oxide particles has high reactivity, if only organoalkoxysilane is directly used for the surface treatment, there is a risk of promoting aggregation / gelation of only cerium oxide due to the difference in reaction rate. Therefore, as the surface treatment of cerium oxide in component (F), first, the cerium oxide surface layer is treated with highly reactive tetraalkoxysilane or its hydrolysis condensate, and secondly organoalkoxysilane or its hydrolysis condensation. It is desirable to react with the product.
In this way, the silane-treated layer of component (F) has a structure in which some organic substituents are present, so that a siloxane bond is suitably formed with the silanol groups of component (A) and component (C) during the production of the cured film. At the same time, the flexibility of the cured film can be further improved.

A general cationic cerium oxide sol must be surface-treated with a silane compound before it becomes agglomerated and gelled with an anionic component in the coating solution of the present invention, making it difficult to add. Therefore, in order to disperse stably in the coating liquid of the present invention, it is necessary to react the OH group of the cerium oxide fine particle surface layer part of the cationic cerium oxide sol with the silanol group of the silane compound and use it after surface treatment as described above. .
In the component (F), the amount of the silane compound used for the surface treatment is considered by the mass of the silane compound as a metal oxide. The metal oxide of a silane compound is defined as the following general formula, for example.
R ¹ _m R ² _n SiO _{((4-mn) / 2)}
(Wherein R ¹ and R ² are each independently an alkyl group or fluorinated alkyl group having 1 to 10 carbon atoms; vinyl group; phenyl group; or methacryloxy group, amino group, aminoalkyl group, alkylamino group, glycidoxy group) An alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from a group, 3,4-epoxycyclohexyl group and blocked isocyanate group, and m and n are each independently 0, 1 or 2 And m + n is 0, 1 or 2.)
Metal oxides total weight of the sol mass of the silane compound in (CeO ₂ and ^{_{^{_{R 1 m R 2 n SiO (}}}} (4-mn) / 2 _{^{_{^{total)) (R 1 m R 2}}}} n SiO ((4-mn) _{/ 2)} The ratio of) is preferably 50% by mass or less, more preferably 2 to 40% by mass. If it is less than this, the cerium oxide itself may aggregate and gel, and if it is more than this, the silane compound itself may react and aggregate and gel.

The following method can be adopted as a specific method for producing the component (F).
A first liquid mixture comprising a cationic cerium oxide sol and the above-mentioned component (E) is prepared, and then a second liquid is prepared by mixing one or more silane compound (A) components. After aging at room temperature, the mixture is further stirred at room temperature or heated to obtain component (F). The component (E) may be diluted by further adding the component (F) after preparation, or the dispersion medium may be replaced by adding another dispersion medium.
Furthermore, when an organoalkoxysilane is used in combination, the following method can be more preferably employed.
A first mixed liquid composed of a cationic cerium oxide sol and a component (E) described later is prepared, and then a tetraalkoxysilane (component (A)) is mixed to prepare a second liquid. After aging at room temperature, organoalkoxysilane (component (A)) is mixed to prepare a third mixed solution. Furthermore, it is set as (F) component by making it stir at room temperature or heating. The component (E) may be diluted by further adding the component (F) after preparation, or the dispersion medium may be replaced by adding another dispersion medium.
Even if the silane-treated cerium oxide sol added to the coating liquid of the present invention is allowed to stand at room temperature for 1 week after production, no aggregated sediment is visually observed at the bottom of the container. There is no restriction | limiting in particular about this sol stationary period until it adds to the coating liquid of this invention.
In the present invention, as the component (F), the cerium oxide sol may be used alone or in combination of two or more.

((G) component)
The coating liquid of the present invention preferably contains a dispersion stabilizer as the component (G).
This dispersion stabilizer stably disperses the reactants of the silane compounds (A-1) to (A-5) and the components (B), (C), and (F) in the coating liquid, It is an additive for suppressing gelation. In the coating liquid of the present invention, the fine particles of the components (B), (C), and (F) are preferably maintained in a dispersed state without causing aggregation sedimentation or gelation. It is preferable that

Since the coating liquid of the present invention uses a condensation reaction at the time of thermal curing, it is desirable to stop the metal alkoxide in the OH form before coating. Therefore, it is desirable to maintain acidic conditions that promote the hydrolysis reaction and suppress the condensation reaction. Furthermore, since the carboxylic acid itself has not only an effect as an acid but also a coordination effect on a metal and is an effective additive for stabilizing an alkoxide, an organic acid, particularly an organic carboxylic acid is used as the component (G). It can be preferably used. For example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and the like can be mentioned. In addition, since the coating liquid of the present invention forms a cured film by thermal curing, it preferably has a boiling point that does not remain in the cured film during thermal curing, and more preferably acetic acid can be used.
In the present invention, as the component (G), one type of the dispersion stabilizer may be used alone, or two or more types may be used in combination.

(Optional additive)
In addition to the components (A) [(A-1) to (A-5)] to (E), the coating liquid of the present invention appropriately contains various known additive components used in conventional coating liquids as necessary. It can be included.
Examples of the additive component that can be contained as needed include leveling agents, flexibility imparting agents, lubricity imparting agents, antioxidants, bluing agents, antistatic agents, and antifoaming agents (antifoaming agents). ), A light stabilizer, a weather resistance imparting agent, a colorant, a fine particle dispersant (anti-settling agent), and a fine particle surface activity modifier.

<Leveling agent>
A leveling agent can be added to the coating liquid of the present invention in order to improve the smoothness of the resulting cured film and the flowability during coating. Examples thereof include a leveling agent, an acrylic leveling agent, a vinyl leveling agent, and a leveling agent in which a fluorine type and an acrylic type are combined. All work on the surface of the coating and reduce the surface tension. Each has its own characteristics and can be used according to the purpose. The ability to lower the surface tension is strong in silicone and fluorine systems, but acrylic and vinyl systems are advantageous in that wetting defects are less likely to occur when recoating.

As a specific example of the silicone leveling agent, a copolymer of polyoxyalkylene and polydimethylsiloxane can be used. Commercially available silicone leveling agents include FZ-2118, FZ-77, and FZ-2161 manufactured by Toray Dow Corning Co., Ltd., KP321, KP323, KP324, KP326, KP340, KP341, manufactured by Shin-Etsu Chemical Co., Ltd., etc. -Performance Materials Japan GK TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, TSF4453, TSF4460, BYK-300, BYK-302, BYK-306, BYK-307, BYK, etc. -320, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-345, BYK-346 BYK-348, BYK-377, BYK-378, BYK-UV3500, BYK-3510, polyether-modified silicone oil, such as BYK-3570 (polyoxyalkylene-modified silicone oil), and the like.

Also, when heat resistance of 150 ° C. or higher is required, an aralkyl-modified silicone oil having a polyester modification or a benzene ring is suitable. Examples of commercially available polyester-modified silicone oils include BYK-310, BYK-315 and BYK-370 manufactured by BYK Japan, Inc., and BYK manufactured by BYK Japan Japan, such as BYK-310, BYK-315 and BYK-370. -322, BYK-323, and the like.

As the fluorine leveling agent, a copolymer of polyoxyalkylene and fluorocarbon can be used.
Examples of commercially available fluorine leveling agents include MEGAFAC series manufactured by DIC Corporation, FC series manufactured by Sumitomo 3M Corporation, and the like.
Commercially available acrylic leveling agents include BYK-350, BYK-352, BYK-354, BYK-355, BYK358N, BYK-361N, BYK-380N, BYK-381, BYK-392 manufactured by BYK Japan, Inc. And BYK-340 into which fluorine is introduced.

By blending such a leveling agent, the finished appearance of the cured film is improved and can be uniformly applied as a thin film. The amount of the leveling agent used is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, based on the total amount of the coating solution.
As a method of blending the leveling agent, it may be blended when preparing the coating liquid, or may be blended into the coating liquid immediately before forming the cured film, and further, preparation of the coating liquid and formation of the cured film. You may mix | blend in both the last steps.

<Flexibility imparting agent>
The coating liquid of the present invention can contain a flexibility imparting agent as a stress relaxation agent in order to improve the flexibility of the obtained cured film.
As the flexibility imparting agent, for example, a silicone resin can be used.
Examples of commercially available silicone resin include Wasin Resin MK series, for example, Belsil PMS MK (a polymer containing a repeating unit (unit T) of CH ₃ SiO _3/2 , up to 1% by mass (CH ₃ )). ₂ SiO _2/2 unit (including unit D) and KR-242A manufactured by Shin-Etsu Chemical Co., Ltd. (including 98% by mass of unit T and 2% by mass of dimethyl unit D and including Si—OH end groups) ), KR-251 (containing 88 mass% of unit T and 12 mass% of dimethyl unit D and containing Si—OH end groups), KR-220L (comprising unit T of formula CH ₃ SiO _3/2 , And those containing Si—OH (silanol) end groups).

(Preparation of coating solution containing components (A) to (E))
<Content of each component>
The content of each component in the coating liquid of the present invention can be selected as appropriate, but it is preferable to select the content of each component so as to fall within the following range, for example.
Excluding the dispersion medium of component (E), the content of each component is expressed in terms of mass% with respect to the total amount of components (A) [(A-1) to (A-5)] to (D). The components (B) and (C) that are preferably used as the dispersion state are calculated using only the respective solid contents, and the dispersion medium included in each component is included in the component (E).
The content of the component (A-1) is usually about 0.01 to 40% by mass, preferably 0.1 to 20% by mass. The content of the component (A-2) is usually about 0.1 to 40% by mass, preferably 1 to 30% by mass. The content of the component (A-3) is usually about 0.1 to 30% by mass, preferably 0.3 to 20% by mass. The content of the component (A-4) is usually about 0.1 to 30% by mass, preferably 0.3 to 20% by mass. The content of the component (A-5) is usually about 0.1 to 50% by mass, preferably 1 to 40% by mass.

The content of the component (B) is usually about 0.1 to 50% by mass, preferably 1 to 40% by mass. The content of the component (C) is usually about 0.1 to 70% by mass, preferably 1 to 50% by mass. The content of component (D) is usually about 0.001 to 30% by mass, preferably 0.001 to 20% by mass. The content of the component (E) is usually about 5 to 1000 parts by weight, preferably 20 with respect to the total parts by weight of the components (A) [(A-1) to (A-5)] to (D). -800 parts by mass.
The molar ratio of the component (A-3) and the component (A-5) is not particularly limited, but is preferably 1: 1 to 1: 5, more preferably 1: 2 to 1: 4. is there. When the blending molar ratio of the component (A-3) to the component (A-5) is within the above range, the durability of the resulting cured film is further improved.

<Method for preparing coating liquid containing components (A) to (E)>
The coating liquid of the present invention was obtained by contacting the hydrolysis condensate of components (A-1), (A-2) and (A-4) with components (B) to (E). The reaction product is preferably prepared by adding (A-5) component and reacting, and then adding (A-3) component and reacting. Further, the reaction product obtained by heating the mixture containing the components (A-1), (A-2), (A-4) and (B) to (E) is added to the reaction product (A- It is more preferable to add the component (5) and react, then add the component (A-3) and react.
Specifically, it is desirable to prepare a coating solution by performing the following operations.
First, a first mixed solution containing at least the components (A-1), (A-2), (A-4), (B), (D) and (E) is prepared, and then the component (C) Are mixed to prepare a second mixed liquid, and then the component (A-5) is mixed to prepare a third mixed liquid. Finally, it is preferable to prepare a coating solution by mixing the component (A-3).

Thus, it is preferable to prepare each component separately because the liquid storage stability (such as not gelation) of the coating solution is improved.
In particular, this effect is more exhibited when the amount of water in the liquid is increased by increasing the amount of the components (B) and (C). For example, the components (A-1), (A-2), (A-4), (B), (D) and (E) are mixed and then the component (C) is added. Next, the component (A-5) is mixed, and finally the component (A-3) is mixed. In addition, (E) component can dilute a coating liquid by adding, after preparing a coating liquid.

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

In addition, it is preferable that the first mixed solution, the second mixed solution, and the third mixed solution are heat-treated after mixing the respective components. The temperature is preferably 30 ° C. to 130 ° C., more preferably 50 ° C. to 90 ° C., and the heat treatment time is preferably 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 (A-1), (A-2), (A-3), (A-4) and (A-5) in the liquid proceeds, and the boiling resistance is increased. And other durability. Reactions of the components (A-1), (A-2), (A-3), (A-4) and (A-5) can be analyzed by solution Si-NMR, thereby obtaining a suitable structure. Can design. The reaction is often extremely slow at less than 30 ° C. or less than 30 minutes, and when it exceeds 130 ° C. or more than 24 hours, (A-1), (A-2), (A-3), (A -4) and (A-5) components may proceed too much, and the liquid may gel or become highly viscous, making it impossible to apply.

The final solution (coating solution) after mixing the component (A-3) is also preferably heat-treated. In the case of mixing at room temperature, it is easily affected by stirring efficiency, and due to this, when the degree of dispersion of component (A-3) is low, the transparency of the cured film (decrease in total light transmittance, increase in haze) May fall. The temperature is preferably 30 ° C. to 130 ° C., more preferably 50 ° C. to 90 ° C., and the time is preferably 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 the temperature is less than 30 ° C. or less than 5 minutes, the effect of the heat treatment is often poor, and if it exceeds 130 ° C. or more than 10 hours, the liquid may gel or become highly viscous and may not be applied.
In the examples described later, the evaluation results of the cured film produced using the coating liquid obtained after standing for 1 week are described, but there is no particular limitation on the liquid standing period until the cured film is produced.

(Preparation of coating solution containing components (A) to (G))
<Content of each component>
The content of each component in the coating solution containing the components (A) to (G) of the present invention can be appropriately selected, but the contents of the components (A) to (E) are the same as those of the component (E). (A) to (E) except that the content of each component is expressed by mass% with respect to the total amount of components (A) [(A-1) to (A-5)] to (G) excluding the dispersion medium. It can be the same as that of the coating liquid containing the component.

The content of the component (F) is usually about 0.01 to 30% by mass, preferably 0.1 to 20% by mass. The content of component (G) is usually about 1 to 60 parts by mass, preferably about 10 to 50 parts by mass.

<Method for preparing coating liquid containing components (A) to (G)>
The coating liquid is obtained by bringing the hydrolysis condensate of components (A-1), (A-2), (A-4) and (A-5) into contact with components (B) to (G). A reaction product obtained by adding the component (A-3) to the reaction product is preferable. Specifically, it is desirable to prepare a coating solution by performing the following operations.

First, a first mixed solution containing at least the components (A-1), (A-2), (A-4), (B), and (D), (E), (G) is prepared. The components (C) and (F) are mixed with the second mixture, and then the component (A-5) is mixed to prepare a third mixture. Finally, it is preferable to prepare a coating solution by mixing the component (A-3).
Thus, it is preferable to prepare each component separately because the liquid storage stability (such as not gelation) of the coating solution 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 components (B), (C), and (F) added.
For example, after the components (A-1), (A-2), (A-4), (B), and (D), (E), (G) are mixed, the components (C) and (F) Add Next, the component (A-5) is mixed, and finally the component (A-3) is mixed.
In addition, (E) component can dilute a coating liquid by adding, after preparing a coating liquid.

As a more preferable method for preparing the coating liquid, hydrolysis condensates of the components (A-1), (A-2) and (A-4), (B), (C), (D), (E) and (G) Component (F) and component (A-5) are added to the reaction product obtained by contacting with component (G) and reacted, and component (A-3) is added to the reaction product obtained. The coating liquid can be prepared by reacting.
Specifically, the mixture containing the components (A-1), (A-2), (A-4), (B), (C), (D), (E), and (G) is heated. The components (F) and (A-5) are added to the reaction product obtained and heated, and then the component (A-3) is added to the obtained reaction product and heated to obtain a coating solution. It is. By using such a preparation method, the dispersibility of the coating liquid can be further improved, and the transparency of the cured film can be improved.

Further, hydrolysis condensates of the components (A-1), (A-2), (A-4) and (A-5), and (B), (C), (D), (E) and (E (G) Component (F) is added to the reaction product obtained by contacting G) with the reaction product, and the resulting reaction product is reacted with component (A-3) to prepare a coating solution. You can also
Specifically, for example, (A-1), (A-2), (A-4), (A-5), (B), (C), (D), (E) and (G) components (F) component (F) is added to the reaction product obtained by heating the mixture containing and heated, and then (A-3) component is added to the resulting reaction product and heated to obtain a coating solution. It is. By using such a preparation method, the dispersibility of the coating liquid can be further improved, and the transparency of the cured film can be improved.

Further, the reaction product obtained by contacting the hydrolysis condensate of components (A-1), (A-2), and (A-4) with components (B) to (G) is added to (A The coating solution can also be prepared by adding the component -5) to react, and reacting the resulting reaction product by adding the component (A-3).
Specifically, for example, a reaction product obtained by heating a mixture containing the components (A-1), (A-2), (A-4) and (B) to (G) is added to (A- 5) Add component and heat, then add (A-3) component to the resulting reaction product and heat to obtain a coating solution. By using such a preparation method, the dispersibility of the coating liquid can be further improved, and the transparency of the cured film can be improved.

It is known that the liquid storage stability of a mixed material such as the coating liquid of the present invention is likely to affect the liquid pH (for example, “Application of the sol-gel method to nanotechnology / supervision: Sakuo Sakuo” MC Publishing). In the preparation of the coating liquid of the present invention, an acidic component is mixed as the components (D) and (G), and a basic component is mixed as the components (A-3) and (D). To do.
The liquid pH value, for example, the liquid pH value evaluated with a portable pH meter (trade name: Checker 1) manufactured by calibration with a pH standard solution for calibration, the first mixed liquid and the second mixed liquid are It is preferable that pH ≦ 6, the third mixed solution, and the final mixed solution have pH ≦ 7. In particular, when the pH of the third mixed solution, that is, the component (A-3) exceeds 8, the liquid stability may be lowered. It is preferable to keep the solution in an acidic state from the start of preparation of the coating solution to the end of preparation. That is, it is preferable to prepare the coating solution by a procedure that maintains such conditions.

In addition, it is preferable that the first mixed solution, the second mixed solution, and the third mixed solution are heat-treated after mixing the respective components. The temperature is preferably 30 ° C. to 130 ° C., more preferably 50 ° C. to 90 ° C., and the heat treatment time is preferably 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 (A-1), (A-2), (A-3), (A-4), and (A-5) in the liquid proceeds and durability is increased. (Boiling resistance) and other properties are improved. The reactions of the components (A-1), (A-2), (A-3), (A-4), and (A-5) can be analyzed by solution Si-NMR, and thus have a suitable structure. Can be designed. When the temperature is less than 30 ° C. or less than 30 minutes, the reaction is often extremely slow. When the temperature exceeds 130 ° C. or more than 24 hours, (A-1), (A-2), (A-3), (A -4) and (A-5) reaction is too advanced, and the liquid may gel or become highly viscous, making it impossible to apply.

Further, the final liquid (coating liquid) after mixing the component (A-3) is preferably heat-treated. In the case of mixing at room temperature, it is easily affected by stirring efficiency, and due to this, when the degree of dispersion of component (A-3) is low, the transparency of the cured film (decrease in total light transmittance, increase in haze) May fall. The temperature is preferably 30 ° C. to 130 ° C., more preferably 50 ° C. to 90 ° C., and the time is preferably 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 the temperature is less than 30 ° C. or less than 5 minutes, the effect of the heat treatment is often poor, and if it exceeds 130 ° C. or more than 10 hours, the liquid may gel or become highly viscous and may not be applied.
In the examples described later, the evaluation results of the cured film produced using the coating liquid obtained after standing for 1 week are described, but there is no particular limitation on the liquid standing period until the cured film is produced.

Furthermore, since the component (F) used in the present invention is an acid stable type, when mixed with other dispersions, it is better to mix them in acidic sols in order to prevent aggregation, precipitation and gelation during mixing. preferable. For example, when the sol of the basic stable anionic fine particles and the component (F) are directly mixed, there is a possibility that the dispersion cannot be maintained because it is out of the pH range where it can be stably dispersed.

(Application of coating solution)
The coating liquid of the present invention is excellent in transparency, adhesion to a resin, weather resistance, abrasion resistance, and scratch resistance, and is useful as a coating material for various transparent organic members. Specifically, resin automobile windows, resin windows for buildings, road sound insulation walls, large-area transparent members such as arcades, instruments such as instrument panels, resin windows for buildings, transparent plastic parts, eyeglass lenses, goggles, transfer films It can be used as a top coat or undercoat material for transparent organic members such as greenhouses.
Furthermore, since it is very transparent, it can be easily colored, and is excellent in compatibility with various colored pigments. For example, the present invention can be applied to painting of automobile interior and exterior, industrial machinery, steel furniture, architectural interior and exterior, home appliances, plastic products, and the like. In addition, the coating solution of the present invention is in close contact with metal and has high acid resistance, so that it is resistant to acid rain, which has recently been regarded as a problem. Thus, it is particularly suitable for members used outdoors such as automobile bodies and aluminum wheels. As a use similar to paint, it can be applied to various inks by taking advantage of high colorability and compatibility with pigments.

Further, the coating liquid of the present invention can be applied to precision members used in the electric and electronic fields, the optical field and the like by taking advantage of high transparency, high adhesion, excellent wear resistance and scratch resistance. For example, in various displays such as plasma displays, liquid crystal displays, and organic EL displays, there are various films that require hard coat properties as one of their functions, such as antireflection films, polarizing films, gas barrier films, retardation films, and conductive films. It can be used as these members. In addition, hard coat materials for optical disk substrates, optical fiber coating agents, touch panels, solar cell panel coating materials, etc. can also be used for high transparency, high adhesion, excellent wear resistance, and scratch resistance. Can be mentioned. Various protective films are used in color filters, hologram elements, CCD cameras, etc. These protective films have low viscosity to some extent due to manufacturing problems as well as transparency, abrasion resistance, scratch resistance and adhesion. It is also required to be. Since the coating liquid of the present invention can be controlled to a desired viscosity by adjusting the components, it is also useful as the protective film. In addition, the coating liquid of the present invention is a material that can be bent and deformed while having a hard coat performance, and can be used for a flexible display that has been actively studied recently.

The coating liquid of the present invention also transmits electromagnetic waves in the near infrared region. Therefore, the present invention can also be applied to covering materials such as antennas for radio wave transmission / reception, RFID data carriers, and vehicle radar devices.
Other applications include coating agents for various transparent ornaments, various skin materials (for automobile seats, automobile door interiors, sofas, furniture, etc.), sliding parts (brake pads, etc.), fiber convergence agents, gas barrier coating agents, etc. Can be mentioned.

Next, the cured film of the present invention will be described.
[Curing film]
The cured film of the present invention is a cured film obtained by curing the above-described coating liquid of the present invention by a conventional method.
Specifically, a coating liquid is sprayed, dipped, curtain flow, bar coater, roll coating, etc. on the base of a resin molded product (injection molded product, film, sheet, etc.) that is a target for forming a cured film. It is applied by a known method to form a coating film.
The thickness of the coating film depends on the final form of the cured film to be formed.
In the first aspect, the thickness of the coating film is adjusted so that the thickness of the cured film is preferably 0.5 to 6 μm, more preferably 0.5 to 3 μm. Thereafter, a desired cured film is obtained by heat curing at appropriate curing conditions, usually room temperature to 190 ° C., preferably 80 to 140 ° C., for about 10 minutes to 24 hours, preferably 30 minutes to 3 hours. It is done.
In the second embodiment, the thickness of the coating film is adjusted so that the thickness of the cured film is preferably 1 to 50 μm, more preferably 2 to 20 μm. Thereafter, a desired cured film can be obtained by heating and curing at appropriate curing conditions, usually 80 to 190 ° C., preferably 100 to 140 ° C. for about 10 minutes to 24 hours, preferably 30 minutes to 3 hours. .

The cured film obtained from the coating solution containing the components (A) to (E) of the present invention has organic polymer fine particles (component (B)) and colloidal silica (component (C)) dispersed in the film. .
The dispersed state is preferably an inorganic-organic hybrid sea-island structure. The particle diameters of the particle components such as the organic polymer fine particles and colloidal silica that correspond to the islands of the sea-island structure are preferably 200 nm or less, more preferably 100 nm or less, and they are uniformly dispersed without agglomeration.
The cured film of the present invention preferably has a total light transmittance of 80% or more, more preferably 85% or more, and a haze value of preferably 10% or less, more preferably 5% or less. Such a cured film has high transparency.
The matrix having Si—O bonds in which organic polymer fine particles (component (B)) and colloidal silica (component (C)) are dispersed is (A-1), (A-2), (A-3). ), (A-4) and (A-5).
The present invention also provides a method for producing a cured film, comprising the step of heating and curing the above-described coating liquid of the present invention.

The cured film obtained from the coating liquid containing the components (A) to (G) of the present invention contains organic polymer fine particles (component (B)), colloidal silica (component (C)), cerium oxide. Particles (component (F)) are dispersed.
The cured film of the present invention preferably has a haze value of 10% or less, more preferably 5% or less. Such a cured film has excellent ultraviolet resistance and high transparency.
The matrix having Si—O bonds in which organic polymer fine particles (component (B)), colloidal silica (component (C)), and cerium oxide particles (component (F)) are dispersed is added to each component (A). Derived from.
The present invention also provides a method for producing a cured film, comprising the step of heating and curing the above-described coating liquid of the present invention.

Next, the resin laminate of the present invention will be described.
[Resin laminate]
The resin laminate includes a base material and a resin layer formed on the base material.
The resin layer formed on the substrate may be a single layer or two or more layers.
Hereinafter, the resin laminate of the present invention will be described in detail.
The 1st resin laminated body of this invention is a laminated body which has the cured film of the said this invention on a base material or between an inorganic layer (inorganic hard material layer) and a base material. Moreover, the 2nd resin laminated body of this invention is a laminated body which has a base material, the cured film of this invention formed on this base material, and the transparent conductive film formed on the cured film. Furthermore, the 3rd resin laminated body of this invention is a laminated body which has a base material, the cured film of this invention formed on this base material, and the photocatalyst layer formed on the cured film. Hereinafter, the first to third resin laminates may be collectively referred to as the resin laminate of the present invention.

The method for forming the cured film using the coating liquid of the present invention is as described in the description of the cured film of the present invention. The resin laminate of the present invention has excellent wear resistance, scratch resistance, flex resistance and boiling resistance, and the use thereof is as shown in the description of the application in the coating liquid of the present invention described above. is there.

The resin laminate of the present invention is not particularly limited as long as it has the above configuration. For example, motorcycles, tricycle windshields, automobiles, railway vehicles, windows for construction machinery vehicles, roofs for construction machinery vehicles, automotive interior components, automotive exterior components, motorbike components, truck bed covers, trains, Interior and exterior components for various vehicles such as aircraft and ships, AV equipment, washing machines, rice cookers, electric pots, IH cooking heaters and other household appliances, furniture components, mobile phones, laptop computers, remote control components, furniture Exterior materials for buildings, building materials, automotive windows, building shading films for walls, wall interiors, ceilings, floors and other architectural interiors, exterior walls such as siding, fences, roofs, gates, windbreak plates, and other architectural exteriors, window frames, Doors, handrails, sills, furniture for furniture such as duck, lighting parts such as downspots, street lamps, various displays such as plasma, liquid crystal, organic EL, solar cells, antireflection Films, optical lenses, optical disks, mirrors, glasses for correction, sunglasses, sports goggles, eyeglass lenses such as safety glasses, optical members such as window glass, bottles, cosmetic containers, containers such as detergents, body soaps, hand soaps, desserts Various packaging containers such as candy, confectionery and drinks, accessory cases, packaging materials; other parts such as pachinko machines, bags such as suitcases, toilet seats, desk mats, clocks, whiteboards, protective shields and miscellaneous goods Can be used for

Examples of the automotive interior member include an instrument panel, console box, meter cover, meter panel, indicator panel, door trim, door lock bezel, steering wheel, power window switch base, center cluster, dashboard, shift lever cover, Examples include switches and ashtrays.

Examples of the automotive exterior member include a weather strip, a bumper, a bumper guard, a side mud guard, a body panel, a door panel, a spoiler, a bonnet, a side protector, a trunk lid, a front grill, a strut mount, a wheel cap, a center pillar, a door mirror, Examples include center ornaments, side moldings, door moldings, wind moldings, windows, headlamps, tail lamps, lamp reflectors, door visors, windshield parts, and the like.
Examples of the motorbike member include a cowl, a fender, a tank cover, and a carrier box cover.
Examples of AV appliances, washing machines, rice cookers, electric pots, IH cooking heaters, and other household appliances and furniture include front panels, control panels, touch panels, membrane switch panels, buttons, emblems, surface cosmetics, etc. Is mentioned.
As the building materials, for example, road translucent sound insulation boards, soundproof boards around railways and factories, arcades, windproof panels, snow shelters, carports and bicycle parking lots, bus stops, solariums, crossing corridors, etc. roofs, entrances and dome roofs, etc. Daylighting materials, windows of buildings, etc., and plastic houses.
Examples of members of the mobile phone, notebook computer, remote controller, and the like include a housing, a display window, a keypad, and a button.

(Base material)
As the base material, a material made of at least one of resin, metal, wood, rubber, concrete, stone, ceramics, leather, paper, cloth and fiber can be used, but a resin base material (resin base material) Is preferably used.

Examples of the substrate include a resin molded body, a film, and a sheet. The film and sheet are produced using a known molding method such as an extrusion molding method, an inflation method, or a solution casting method, and they may be stretched uniaxially and / or biaxially as necessary. There is no restriction | limiting in particular in the kind of resin in a base material, According to the use of the resin laminated body obtained, it can select suitably from various types of resin.
Moreover, the base material which concerns on this invention may have an unevenness | corrugation, and shapes of base materials, such as a column shape, an elliptic cylinder type, and a prism shape, are not ask | required.
Moreover, the resin laminated body which concerns on this invention may have a space inside, and when it has an internal space, another resin layer may be laminated | stacked on the inner wall part.
Therefore, the shape of the substrate according to the present invention is not particularly limited, and the resin laminate according to the present invention includes a resin laminate obtained by insert molding or insert mold molding as described below.

In the present invention, examples of resins that can be used for the substrate include polyethylene, polypropylene, cycloolefin resins (eg, “ARTON” manufactured by JSR Corporation, “ZEONOR” “ZEONEX” manufactured by Nippon Zeon Co., Ltd.), Polyolefin resins such as methylpentene, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, cellulose resins such as diacetylcellulose, triacetylcellulose, acetylcellulose butyrate, polystyrene, syndiotactic polystyrene, acrylonitrile Styrenic resin such as butadiene / styrene resin (ABS resin), imide resin such as polyimide, polyetherimide, polyamideimide, nylon, etc. Such as lyamide resins, polyether ketones, ketone ether resins such as polyether ether ketone, sulfone resins such as polysulfone and polyethersulfone, vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride, and polymethyl methacrylate An acrylic resin, polycarbonate resin, polyphenylene sulfide, polyacetal, modified polyphenylene ether, polyvinyl alcohol, epoxy resin, fluororesin and the like can be mentioned, and a polymer alloy / polymer blend in which a plurality of the above polymers are mixed may be used. Moreover, the laminated structure which laminated | stacked the said resin two or more may be sufficient. Among the above resins, polyester resins, polyolefin resins, and polycarbonate resins are preferable.

The base material made of these resins may be either transparent or translucent, may be colored, or may be uncolored, and may be appropriately selected depending on the application. When used for optical applications, it is excellent in transparency and preferably non-colored. Among the resins, polycarbonates that are excellent in transparency, mechanical properties, heat resistance, and the like are particularly suitable.
The thickness of the substrate is not particularly limited and is appropriately selected depending on the situation, but is usually about 5 μm to 30 mm, preferably 15 μm to 10 mm.

The coating liquid of the present invention can form a cured film with good adhesion on a substrate. However, in order to further improve the adhesion, at least the surface of the substrate on which the cured film is formed is optionally formed. Further, the surface treatment can be performed by an oxidation method, an unevenness method, or the like. Examples of the oxidation method include corona discharge treatment, plasma treatment such as low pressure plasma method and atmospheric pressure plasma method, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, electron beam treatment, and intro treatment. In addition, examples of the concavo-convex method include a sand blast method and a solvent treatment method. These surface treatment methods are appropriately selected depending on the type of the substrate, but in general, the corona discharge treatment method is preferably used from the viewpoints of curing and operability. Further, a surface treatment with a silane coupling agent or a primer layer can be provided.

(Inorganic hard material layer)
The inorganic hard material layer in the 1st resin laminated body can be selected according to the function to give, and there is no restriction | limiting in particular. For example, when it is desired to impart friction resistance to the inorganic hard material layer, the inorganic hard material layer is preferably a SiO _x (1.8 ≦ x ≦ 2) film, SiN _y (1.2 ≦ y ≦ 4/3). A film or an amorphous carbon film is suitable.

The SiO _x (1.8 ≦ x ≦ 2) film and SiN _y (1.2 ≦ y ≦ 4/3) film are formed, for example, by chemical vapor deposition or physical vapor deposition described later. Therefore, the reaction is not completed stoichiometrically. Therefore, the inorganic hard material layer has a defect portion in which oxygen atoms and nitrogen atoms are not introduced, and x and y have a width in the SiO _x film and the SiN _y film.
Note that a composite material in which silicon oxide and silicon nitride are mixed, which can be produced by simultaneously adding oxygen and nitrogen, is also suitable.
In addition, the hardness of the inorganic hard material layer is sufficient if the increase in haze is less than about 10% in an evaluation using a Taber abrasion tester as shown in the examples. Or what is necessary is just about 500HV or more by micro Vickers hardness.
The thickness of the inorganic hard material layer is, for example, preferably 1 μm or more, more preferably 1 to 8 μm. Moreover, in the manufacturing method of the inorganic hard material layer mentioned later, the inorganic hard material layer is preferably laminated directly on the cured film.

The inorganic hard material layer of the resin laminate of the present invention is preferably formed by chemical vapor deposition (CVD) or physical vapor deposition (PVD). Specific examples of the CVD method include a plasma CVD method and a photo CVD method. Specific examples of the PVD method include an ion plating method, a vacuum deposition method, and a sputtering method.
An inorganic hard material layer formed using a thin film forming technique performed under vacuum as described above usually has a property of being in close contact with an inorganic component but hardly adhering to an organic component. In the case of the resin laminate of the present invention, the cured film has an inorganic / organic hybrid structure in which organic fine particles are confined in the Si—O matrix, so that the adhesion between the inorganic hard material layer and the cured film is good. .

As a specific example of laminating the inorganic hard material layer by the CVD method, a case where an SiO _x (1.8 ≦ x ≦ 2) film is formed on the cured film using the plasma CVD method will be described.
The plasma CVD method is a method in which a raw material gas is introduced into a plasma state having a high energy density, decomposed, and a target material is coated on a base material by a chemical reaction. In the present invention, a laminate comprising a substrate and a cured film in the plasma CVD apparatus is arranged, after the inside of the apparatus in a _{vacuum, SiO x (1.8 ≦ x ≦} 2) plasma CVD apparatus raw material gas of the membrane When argon gas is introduced into the gas and the respective gas flow rates are stabilized, power is applied to generate plasma to form a SiO _x (1.8 ≦ x ≦ 2) film on the cured film. .

When the inorganic hard material layer is a SiO _x (1.8 ≦ x ≦ 2) film, the raw material for forming the SiO _x (1.8 ≦ x ≦ 2) film is, for example, a silicon source gas and an oxygen source gas.
Silane gas or organosilicon compound gas is preferably used as the silicon source gas for forming the SiO _x (1.8 ≦ x ≦ 2) film.
SiH ₄ gas, Si ₂ H ₆ gas, Si ₃ H ₈ gas and the like are preferably used as silane gas.
The organosilicon compound is preferably arbitrarily selected from those in which a group containing carbon is bonded to silicon. Specific examples of the organic silicon compound suitably used include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, tetramethyldisiloxane, dimethoxydimethylsilane, diethoxydimethylsilane, methyltriethoxysilane, Examples include octamethylcyclotetrasilane.
One of these organosilicon compounds may be used alone, or two or more thereof may be used in combination.

When the silicon source gas for the SiO _x (1.8 ≦ x ≦ 2) film is a silane gas, an oxygen source gas that can be suitably used includes N ₂ O gas.
Further, when the silicon source gas of the SiO _x (1.8 ≦ x ≦ 2) film is an organic silicon compound gas, the oxygen source gas preferably used includes N ₂ O gas, O ₂ gas, and O ₃ gas. .
The flow rates of the silicon source gas and the oxygen source gas are, for example, 1 to 500 cm ³ / min, and preferably 1 to 300 cm ³ / min. The flow rate of the argon gas is, for example, 20 to 400 cm ³ / min, and preferably 100 to 300 cm ³ / min.

The plasma CVD apparatus to be used is not particularly limited as long as it is a generally used apparatus. For example, a parallel plate electrode type, a capacitive coupling type, an inductive coupling type, or the like can be used. For example, the pressure in the plasma CVD apparatus is preferably about 1.33 to 133 Pa, and more preferably about 2.7 Pa.
The frequency of the power source used for power application can be widely used from the audio wave to the microwave range.

In the case where an SiO _x (1.8 ≦ x ≦ 2) film is formed on a cured film using the plasma CVD method, an organic silicon compound is used as a silicon source gas, and the organic silicon compound is liquid at room temperature. Alternatively, in the case of a solid, the entire container containing the organosilicon compound is heated and vaporized for use.
In the above case, the flow rates of the organic silicon compound gas and the oxygen source gas are controlled to 1 to 10 cm ³ / min, for example, and introduced into the plasma CVD apparatus together with the argon gas whose flow rate is controlled to 20 to 400 cm ³ / min. (Direct vaporization method).

In addition to the direct vaporization introduction method described above, when the organosilicon compound is liquid, argon gas is used as a carrier gas, and argon gas is contained in a temperature-controllable container containing the organosilicon compound, for example, 20 to 400 cm ³ / Alternatively, the organic silicon compound may be bubbled and the organic silicon compound vapor and the argon gas may be introduced together into the plasma CVD apparatus (a bubbling introduction method using a carrier gas).

In the method for manufacturing the inorganic hard material layer, when the inorganic hard material layer is a SiN _y (1.2 ≦ y ≦ 4/3) film, a SiN _y (1.2 ≦ y ≦ 4/3) film is formed. The source gas is, for example, a silicon source gas and a nitrogen source gas.
Suitable silicon source gases include silane gases such as SiH ₄ gas, Si ₂ H ₆ gas, and Si ₃ H ₈ gas.
Further, suitable nitrogen source gas to be used include N ₂ gas and NH ₃ gas.

In the method for producing an inorganic hard material layer, when the inorganic hard material layer is an amorphous carbon film, a hydrocarbon gas is suitably used as a raw material gas for forming the amorphous carbon film.
Incidentally, if the concentration of the hydrocarbon gas is high, it may be diluted by introducing H ₂ gas simultaneously.
In the manufacturing method of the inorganic hard material layer by the above-described CVD method, the raw material gas is used as the raw material of the inorganic hard material layer, but the present invention is not limited to this. For example, you may vaporize and use the vapor deposition raw material of the inorganic hard material layer mentioned later.

As a specific example of laminating the inorganic hard material layer by the PVD method, a case where the inorganic hard material layer is laminated using the ion plating method will be described.
The ion plating method introduces reactive gas into the vacuum deposition system, generates gas plasma in the system by various methods, and ionizes some of the generated deposition particles (atoms / molecules) to accelerate. In this method, the base material placed in a vacuum is irradiated with vapor deposition particles and ions thereof to form a thin film of the vapor deposition material on the base material. That is, the ion plating method is a combined technique of vacuum deposition technique and plasma technique.
The ion plating method is disclosed in, for example, Japanese Patent Application Laid-Open No. 58-29835.

In the present invention, the laminate of the base material and the cured film, and the vapor deposition raw material of the inorganic hard material layer are respectively arranged at predetermined positions in the vacuum vapor deposition apparatus, and plasma is generated, so that argon, xenon, etc. are contained in the apparatus. An inert gas and, if necessary, reactive gases such as O ₂ , N ₂ , acetylene, and air are introduced into the apparatus, a high-frequency voltage is applied in the vicinity of the vapor deposition raw material, and the vapor deposition raw material is turned into plasma to form a cured film. An inorganic hard material layer is laminated thereon.

As a vapor deposition raw material for the inorganic hard material layer, when the inorganic hard material layer is a SiO _x (1.8 ≦ x ≦ 2) film, silicon oxide or the like can be cited, and the inorganic hard material layer can be SiN _y (1.2. ≦ y ≦ 4/3) In the case of a film, silicon nitride and the like can be mentioned. In the case where the inorganic hard material layer is an amorphous carbon film, DLC (diamond-like carbon) and the like can be mentioned.
The raw material to be formed as the inorganic hard material layer may be used as the vapor deposition raw material for the inorganic hard material layer.
In addition, the vapor deposition raw material of the inorganic hard material layer in an ion plating method is not limited to solid. For example, when the vapor deposition raw material is difficult to evaporate, the inorganic hard material layer is introduced by introducing the above-mentioned inorganic hard material layer raw material gas (silicon raw material gas and oxygen raw material gas) into the vacuum vapor deposition apparatus and performing reactive vapor deposition. May be laminated.

The pressure in the vacuum evaporation apparatus is, for example, about 1.3 × 10 ⁻³ to 1.3 × 10 ⁻¹ Pa.
The device for applying the high frequency voltage is not particularly limited as long as it is a device capable of performing high frequency discharge. The high frequency voltage is, for example, about 0.5 kV to 8.0 kV.
In the above ion plating method, it is necessary to use heating means such as resistance heating, electron beam heating, high frequency induction heating, and laser beam heating so that vapor deposition on the surface layer of the cured film is performed during high frequency discharge. Accordingly, the vapor deposition material may be evaporated.

The lamination method of the inorganic hard material layer by the PVD method is not limited to the ion plating method. As described above, the inorganic hard material layer can be laminated using a vacuum deposition method, a sputtering method, or the like.
The vacuum deposition method is a method in which a raw material is thermally evaporated in a vacuum, the evaporated particles are transported to the substrate surface, and the evaporated particles are rearranged on the substrate surface to form a thin film. In the vacuum evaporation method, the degree of vacuum is usually 1.3 × 10 ⁻² Pa or less.
Sputtering is a method in which an inert gas is turned into plasma, the obtained positive ions collide with the raw material, element atoms on the surface of the raw material are knocked out, and are attached and / or deposited on a nearby substrate. It is a method of forming.

(Transparent conductive film)
The transparent conductive film in the 2nd resin laminated body of this invention can be selected according to the function to give, and there is no restriction | limiting in particular. For example, when it is desired to impart low resistance electrical characteristics to the transparent conductive film, the transparent conductive film is preferably composed mainly of zinc oxide, zinc oxide such as AZO (aluminum doped zinc oxide) or GZO (gallium doped zinc oxide). Or ITO (tin doped indium oxide), SnO ₂ (tin oxide), IZO (zinc doped indium oxide), ICO (cerium doped indium oxide), ATO (antimony doped tin oxide), FTO (fluorine doped tin oxide) And a transparent and conductive material that does not contain zinc oxide as a main component.

One of the conductivity indicators of the transparent conductive film is a carrier concentration. The higher the carrier concentration, the higher the conductivity. A carrier concentration of 1 × 10 ¹⁸ / cm ³ or more is preferable because a surface resistance value of 10000Ω / □ or less can be obtained. Further, when the carrier concentration is 1 × 10 ¹⁹ / cm ³ or more, infrared reflection occurs and it is preferable as an antireflection film. Furthermore, if it is 5 × 10 ¹⁹ / cm ³ or more, a resin laminate having a surface resistance value of 10 to 1000 Ω / □ for use as a touch panel can be produced.

It is preferable to use an amorphous thin film as the transparent conductive film because the coverage is improved and the film thickness can be further reduced. Amorphous transparent conductive film materials include IZO (zinc-doped indium oxide), ZTO (zinc oxide-tin oxide) -based thin film, IZTO (indium oxide-zinc oxide-tin oxide) -based, and tin oxide-based thin film. Moreover, the system etc. which added the oxide which provided the electrical property, the optical characteristic, and the mechanical characteristic to those thin films are mentioned.
When the surface resistance value is set to a high resistance value, the material can be selected, or can be adjusted depending on the film thickness and film forming conditions. For example, when the surface resistance value is lowered, a crystalline material having a good (low) resistivity such as ITO can be used for the transparent conductive film. Further, although the surface resistance value can be lowered by increasing the film thickness, an improvement in transmittance can be expected by reducing the film thickness of the transparent conductive film.
Further, the surface resistance value may be appropriately determined according to the purpose of use, but when used for an electro-optical element, a photoelectric conversion element, a liquid crystal, a touch panel, etc., the surface resistance value is preferably 10Ω / □ or more. 5000Ω / □ or less, more preferably 100Ω / □ or more and 2000Ω / □ or less. The thickness of the transparent conductive film is preferably, for example, 5 nm or more, more preferably 10 to 300 nm. Moreover, in the formation method of the transparent conductive film mentioned later, Preferably a transparent conductive film is laminated | stacked directly on a cured film.

Moreover, the optimal film thickness of each layer can be determined by the following method, for example.
First, the film thickness of the transparent conductive film is determined so as to obtain a necessary surface resistance value according to the application. Next, set the refractive index of the material used for the cured film to a fixed value, and change the thickness of the cured film using an optimization algorithm to obtain the highest transmittance or the lowest reflectance. Find the thickness.
The transparent conductive film provided on the cured film may be a single layer or a multilayer film having two or more layers. For example, two or more transparent conductive films may be provided in consideration of the transmittance (reflectance) of the substrate with multilayer film having conductivity, and an antireflection film having a higher refractive index may be provided. Further, even when an antireflection film is formed, it is not limited to a single layer, and a multilayer structure (for example, 2 to 6 layers, etc.) capable of obtaining a desired transmittance (reflectance) may be formed. Good.

(Method for producing resin laminate)
Next, the manufacturing method of the 2nd resin laminated body of this invention is demonstrated.
The method for producing a resin laminate of the present invention comprises a step (a) of forming a cured film formed by curing the coating liquid containing the components (A) to (E) described above on a substrate, and the cured film on the cured film. A step (b) of forming a transparent conductive film.
In addition, about the said process (a), it is as having shown in description of the above-mentioned coating liquid and cured film.

(Formation of transparent conductive film)
The second resin laminate of the present invention has a cured film formed between the transparent conductive film and the substrate, and the transparent conductive film is preferably formed on the cured film by chemical vapor deposition (CVD). Method), physical vapor deposition (PVD method) or coating method. Specific examples of the CVD method include a plasma CVD method, a photo CVD method, a mist method, and the like. Specific examples of the PVD method include an ion plating method, a vacuum deposition method, a sputtering method, and the like. Specific examples include a spray method, a spin coat method, a barcode method, a doctor blade method, and an ink jet method.
A transparent conductive film formed by using a thin film forming technique performed under vacuum usually has a property of being in close contact with an inorganic component but hardly adhering to an organic component. In the case of the resin laminate of the present invention, since the cured film has an inorganic / organic hybrid structure in which organic fine particles are confined in the Si—O matrix, the adhesion between the transparent conductive film and the cured film is good.

As a specific example of laminating a transparent conductive film by a sputtering method, a case where an ITO film is formed on a cured film using a sputtering method will be described.
Sputtering is a method in which an inert gas is turned into plasma, the obtained positive ions collide with the raw material, and element atoms on the surface of the raw material are knocked out and adhered and / or deposited on a substrate called a target placed nearby. And forming a thin film.
In this case, an ITO sintered body is used for the target. A laminate composed of a base material and a cured film is placed in a sputtering apparatus, and after the inside of the apparatus is evacuated to a pressure of 10 ⁻⁵ Pa or less, an argon gas is introduced and a vacuum of about 0.1 to 10 Pa is applied. Apply DC power of about 1 to 10 kW / cm ² to generate plasma, and form an ITO film on the cured film.
When the transparent conductive film is an ITO film, for example, an indium oxide sintered body target added with 10% by mass of SnO ₂ is used as a raw material for forming the ITO film. In some cases, oxygen gas is mixed into the argon gas in order to control conductivity and optical characteristics.

The method for laminating the transparent conductive film by the PVD method is not limited to the sputtering method, and the transparent conductive film can be laminated by using a vacuum deposition method, an ion plating method, or the like.
The vacuum deposition method is a method in which a raw material is thermally evaporated in a vacuum, the evaporated particles are transported to the substrate surface, and the evaporated particles are rearranged on the substrate surface to form a thin film. In the vacuum evaporation method, the degree of vacuum is usually 1.3 × 10 ⁻² Pa or less.
The ion plating method introduces a reactive gas into a vacuum deposition system, generates gas plasma in the system by various methods, and ionizes a part of the generated deposition particles (atoms / molecules) for acceleration. In this method, the base material placed in a vacuum is irradiated with vapor deposition particles and ions thereof to form a thin film of the vapor deposition material on the base material. That is, the ion plating method is a combined technique of vacuum deposition technique and plasma technique.

As a specific example of laminating a transparent conductive film by a CVD method, a case where a ZnO film is formed on a cured film using a plasma CVD method will be described.
The plasma CVD method is a method in which a raw material gas is introduced into a plasma state having a high energy density, decomposed, and a target material is coated on a base material by a chemical reaction.
In the second resin laminate of the present invention, a laminate consisting of a base material and a cured film is placed in a plasma CVD apparatus, and after the inside of the apparatus is evacuated, a ZnO film source gas is supplied to the plasma CVD apparatus by argon gas. When each gas flow rate is stabilized, power is applied to generate plasma to form a ZnO film on the cured film.

(Photocatalyst layer)
The photocatalyst material used for the photocatalyst layer in the third resin laminate of the present invention 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 and 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, and 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.

The method for forming the photocatalyst layer will be described later, but when a wet method is used, a silicone compound is usually used for the matrix of the 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.

(Method for producing resin laminate)
Next, the manufacturing method of the 3rd resin laminated body of this invention is demonstrated.
The manufacturing method of the resin laminated body of this invention includes the process (a) which forms the cured film of this invention mentioned above on a base material, and the process (b) of forming a photocatalyst layer on the said cured film. In addition, about the said process (a), it is as having shown in description of the above-mentioned cured film.

There is no restriction | limiting in particular as a method of forming a photocatalyst layer on a cured film, 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. It can be dried or cured to form a photocatalytic layer. The thickness of the photocatalyst layer 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.

The resin laminate of the present invention may be a molded article (molded article of a resin laminate). The molded body of the resin laminate can be manufactured by thermoforming. Examples of thermoforming include vacuum forming, vacuum / pressure forming, pressure forming, plug assist forming, and match mold forming. (Substrate used for thermoforming)
A base material used for thermoforming (hereinafter simply referred to as “base material”) will be described below.
In order to perform molding by heat, a sheet or film mainly composed of a thermoplastic resin having a base material softening point in the range of about 50 to 300 ° C. is preferable. For example, polycarbonate, polypropylene, polyethylene, polystyrene, acrylonitrile / butadiene / styrene Resin (ABS resin), acrylonitrile / styrene resin (AS resin), methyl methacrylate / styrene resin (MS resin), polyester resin, acrylic resin, vinyl chloride resin, fluorine resin, and the like. A polymer alloy / polymer blend in which a plurality of these are mixed may be used. Further, a laminated structure in which a plurality of the resins are laminated may be used.
You may provide a decoration layer in the surface in which the cured film of a base material is not formed. Examples of the decorative layer include an ink layer, a high brightness ink layer, and a metal vapor deposition layer. Further, the decoration layer may be a single layer or a laminate in which the decoration layers are combined.
Next, the thickness of the substrate will be described.
The thickness of the base sheet or film for insert molding is preferably 5 μm to 0.7 mm. When the thickness is less than 5 μm, the film strength is low, and there is a problem that the film is broken during molding. On the other hand, when the thickness exceeds 0.7 mm, it is difficult to obtain a wound insert molding sheet, resulting in poor productivity.

Hereinafter, although an example of a thermoforming method is demonstrated, this invention is not restrict | limited by the following description.
A base sheet that has not been thermoformed is set in an injection mold so that the surface of the cured film faces the movable mold, and pre-molding is performed by vacuum suction using the movable vacuum suction hole. Do. Subsequently, the injection resin and the base sheet are integrated using in-mold molding in which the injection resin is filled on the surface side on which the cured film is not formed.
Also, after setting the thermoformed base sheet in the injection mold, the injection resin and base sheet are integrated using insert mold molding that fills the injection resin on the side where the cured film is not formed. You may make it.

Thermoforming is performed to form the forming base sheet into an uneven shape, a cylindrical shape, or an elliptical shape. Examples of the thermoforming method include vacuum forming (including plug assist forming), vacuum / pressure forming, pressure forming, match mold forming, and press forming.
In order to mount the base sheet that has been thermoformed into the injection mold, trimming is performed so that unnecessary portions are cut to match the shape of the injection mold.
The trimming method is not particularly limited, and examples thereof include a die cutting method, a laser cutting method, a water jet method, a punching blade press method, and a Thomson punching method. Trimming may be performed at the same time as thermoforming.

A base sheet that has not been thermoformed is set in an injection mold so that the surface of the cured film faces the movable mold, and preliminary molding is performed by vacuum suction using the vacuum suction hole of the movable mold. Do. Subsequently, the injection resin is filled on the surface side where the cured film is not formed. There are no particular restrictions on the conditions for in-mold injection molding, and the conditions can be met within the range of normal injection molding. The injection molding machine may be either a vertical injection molding machine or a horizontal injection molding machine.

After the thermoformed substrate sheet is set in an injection mold, an injection resin is filled on the surface side where no cured film is formed.
The insert mold injection molding conditions are not particularly limited, and can be handled within the normal injection molding condition range. The injection molding machine may be either a vertical injection molding machine or a horizontal injection molding machine.

The injection mold is provided with a mechanism for setting the base resin sheet that has been thermoformed in the direction in which the injection resin is filled on the surface side where the cured film is not formed.
In the case of a vertical injection molding machine, it is fixed by gravity if it is set in the lower mold of the mold. If it is necessary to set the mold on the upper mold, the base sheet after thermoforming is fixed by vacuum suction from the mold, the method of covering using the convex part of the mold, or fixing with a pin There are ways to do it. In the case of a horizontal injection molding machine, there are a method of fixing by vacuum suction, a method of covering using a convex portion of a mold, a method of fixing with a pin, etc. when setting on either the fixed side or the movable side.

The present invention also includes a method for producing a cured film, comprising a step of heating and curing the coating liquid of the present invention, a step of applying the coating liquid of the present invention on a substrate, and the coating There is also provided a method for producing a resin laminate comprising a step of drying a liquid, a step of thermoforming the substrate, and a step of curing the coating liquid to provide a coating layer.
In addition, the manufacturing method of the said resin laminated body can further include the process of providing a resin layer in the surface which does not have a coating layer of the resin laminated body formed by hardening | curing a coating liquid.

Examples The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Unless otherwise stated, various characteristics in each example were determined according to the following procedure.

(1) Oxide equivalent content derived from inorganic components in cured film (mass%)
A sample obtained by thermosetting the coating solution on a Teflon petri dish was subjected to thermogravimetry (20 ° C./min increase under nitrogen, room temperature to 800 ° C.), and obtained from the residue at 800 ° C. It was.
(2) Organic polymer fine particle content (% by mass) in the cured film
Calculated by calculation. Specifically, the components (A-1) to (A-5) in which the hydrolysis / condensation reaction has completely proceeded (component (A)), organic polymer fine particles (component (B)), and colloidal silica ((C The mass% of organic polymer fine particles in the total mass of component)) was calculated.
(3) Liquid stability of coating liquid The container was stored tightly for 14 days at room temperature, and the presence or absence of gelation was judged visually. For those that are not gelled, the viscosity is measured with an A & D tuning fork type vibration viscometer SV-10. Exceeded “×”.
(4) Appearance of film The appearance of the cured film was visually observed to confirm foreign matters, mottled patterns, and white turbidity.
(5) Total light transmittance and haze The total light transmittance and haze of the laminate were measured with a direct reading haze computer (HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.).

(6) Abrasion resistance Using a wear wheel CS-10F and a Taber abrasion tester (rotary abrasion tester) (Toyo Seiki Co., Ltd., model: TS), a 500 rotation Taber abrasion test was performed at a load of 4.9 N, and Taber abrasion The case where the difference (ΔH) between the haze before the test and the haze after the Taber abrasion test was less than 15 was designated as “◯”, and the case where the haze was 15 or more was designated as “x”.
(7) Scratch resistance In Examples 1 to 11 and Comparative Examples 1 to 6, steel wool # 0000 (load 4.9 N) was used, and after 50 reciprocations at 2000 mm / sec, the surface damage was visually evaluated. did. “1” indicates that there is no scratch at all, “2” indicates that there is a slight scratch, and “3” indicates that scratches are present on more than half of the rubbed area.
In Examples 12 to 16 and Comparative Examples 7 to 11, steel wool # 0000 (load 9.8 N) was used, and after 50 reciprocations at 2000 mm / sec, the surface damage was visually evaluated. “1” indicates that there is no scratch at all, “2” indicates that there is a slight scratch, and “3” indicates that scratches are present on more than half of the rubbed area.
(8) Adhesiveness In accordance with JIS K 5400, a sample (cured film) 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.), and then closely peeled off at an angle of 90 ° toward the near side, and the cured film did not peel off, and the remaining number (X) remained. Displayed by X / 100, the adhesion of the cured film was evaluated.

(9) Boiling resistance (adhesion after 5 hours of boiling)
After immersing the sample of the laminate in boiling water in a stainless steel beaker for 5 hours, the adhesion was evaluated. The evaluation of adhesion was performed in the same manner as (8) above.
(10) Weather resistance A xenon weather test (Atlas Ci65, output 6.5 kW, black panel temperature 63 ° C., relative humidity 50%) was performed in 1000 hours. The weather resistance was evaluated by the change in adhesion of the cured film before and after the test.

(11) Flexibility Resin laminate samples were produced in the same manner as in each example except that a polycarbonate standard plate (trade name: ECK100) manufactured by Sumitomo Bakelite Co., Ltd. having a size of 100 mm × width 50 mm × thickness 1 mm was used as a substrate.
The sample was held at both ends with fingers and subjected to forced bending with a radius of 50 mm curve 10 times, and no crack was found on the laminated surface.
(12) Heat resistance A heat resistance test (manufactured by Tabai, PS-222) was performed at 110 ° C. for 720 hours. The heat resistance was evaluated by the change in the adhesion of the cured film before and after the test.

(13) Organic fine particle dispersion structure A cross-section of the cured film is observed with a TEM (Transmission Electron Microscope), and 10 organic fine particles present in the 1 μm square are selected. The average particle size was determined using .63. An organic fine particle having an average particle size of 200 nm or less is “◯”, an average particle size of greater than 200 nm is “X”, and a particle size of 200 nm or less is present. “Δ” indicates that there was an amoeba shape of 200 nm or more.
(14) Inorganic fine particle dispersion structure The average particle size of each colloidal silica fine particle in the cured film was determined in the same manner as in the above (13). Samples with an average particle size of 200 nm or less were marked with “◯”, and those with an average particle size larger than 200 nm were marked with “x”.

In the examples and comparative examples, the details of the raw materials described by trade names are as follows.
Component (A-1): M silicate 51 “polyalkoxysilane which is a partial condensate (average 3 to 5 mer) of tetramethoxysilane” manufactured by Tama Chemical Industry Co., Ltd. (A-2) component: MTMS-A “Methyl” Polyorganoalkoxysilane which is a partial condensate of trimethoxysilane "(Tama Chemical Industry Co., Ltd. (A-2) component: SR2402" Polyorganoalkoxysilane which is a partial condensate of methyltrimethoxysilane "Toray Dow Corning Co., Ltd.) Product (B) component: ULS-1385MG (ultraviolet ray absorbing skeleton species: benzotriazole), manufactured by Yushi Kogyo Co., Ltd. (water dispersion / solid content concentration 30% by mass)
(B) component: ULS-385MG (ultraviolet ray absorbing skeleton species: benzophenone series)
On the other hand, manufactured by Yushi Kogyo Co., Ltd.
Component (C): IPA-ST-L (Colloidal silica)
Made by Nissan Chemical Industries Ltd. (isopropanol dispersion, colloidal silica concentration 30% by mass, average particle size 40-50 nm (manufacturer's published value))

[Examples 1 to 11, Comparative Examples 1 to 6]
Example 1
(1) Manufacture of coating liquid It prepared according to the component and compounding quantity which are shown in Table 1.
In a sample tube with a volume of 50 ml, 0.80 g of organic polymer fine particles: ULS-1385MG (component (B) + component (E)) was charged, and 1-methoxy-2-propanol (component (E)) was stirred at 500 rpm. 4.25 g, water (component (E)) 0.50 g, acetic acid (component (D)) 0.50 g, M silicate 51 (component (A-1)) 0.40 g, MTMS-A ((A-2) Component) 1.10 g, dimethoxy-3-glycidoxypropylmethylsilane (component (A-4)) 0.55 g, 20 mass% p-toluenesulfonic acid methanol liquid (component (D) + component (E)) 0 In the order of 0.05 g, each was added dropwise over 1 minute. Subsequently, after stirring for 60 minutes at room temperature and 500 rpm, the mixture was allowed to stand for one day, and this was designated as solution A.
A sample tube with a volume of 20 ml was charged with 1.10 g of 3-isocyanatopropyltriethoxysilane and 0.35 g of 2-butanone oxime (isocyanate group blocking agent), stirred at room temperature at 500 rpm for 10 minutes, and then allowed to stand for one day. This was designated as solution C. The blocking of the isocyanate group was confirmed by disappearance of the isocyanate group signal by ¹³ C-NMR. The total amount of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was taken as the amount of the blocked isocyanatosilane compound: (A-5) component.

Into a 200 ml three-necked flask equipped with a condenser, put A solution and a stir bar, stir at 500 rpm, and apply 6.50 g of IPA-ST-L (component (C) + component (E)) as solution B over 5 minutes The solution was added dropwise and stirred at room temperature for 60 minutes. Then, it heated at 600 rpm and 80 degreeC under nitrogen stream for 3 hours. Then, C liquid was added, and it stirred at 80 degreeC on the same conditions for 4 hours, Then, it left still at room temperature overnight.
Further, 0.40 g of 3-aminopropyltrimethoxysilane (component (A-3)) was added dropwise thereto as a D solution over 2 minutes. After stirring at room temperature for 10 minutes, the mixture was further heated at 700 rpm and 80 ° C. for 3 hours under a nitrogen stream.
Subsequently, it was left to stand for 1 week to obtain a coating solution.

(2) Production of laminate As a substrate, polycarbonate substrate [manufactured by Idemitsu Kosan Co., Ltd., trade name: Toughlon, product number: IV2200R (anti-glare grade), thickness 3 mm (total light transmittance 90%, haze value 0.5% )] Was used.
The coating liquid obtained in the above (1) is applied to the surface of a polycarbonate molded body having a thickness of 3 mm with a bar coater so that the cured film has a thickness of 3 μm, and is thermally cured at 130 ° C. for 2 hours. A laminate composed of a substrate and a cured film was produced.
The obtained coating liquid and laminate were evaluated. The evaluation results are shown in Table 2.

Examples 2 to 11
A coating solution was produced in the same manner as in Example 1 according to the components and blending amounts shown in Table 1, and a laminate was produced. Table 2 shows the evaluation results for the obtained coating liquid and laminate.

Comparative Example 1
It prepared according to the component and compounding quantity which are shown in Table 3.
A sample tube with a volume of 50 ml was charged with 0.90 g of ULS-1385MG (component (B) + component (E)) and stirred at 500 rpm, while 2.00 g of 1-methoxy-2-propanol (component (E)), water (Component (E)) 0.09 g, acetic acid (component (D)) 3.20 g, methyltrimethoxysilane (component (A-2)) 2.00 g, dimethoxy-3-glycidoxypropylmethylsilane ((A -4) component) 0.96 g, 5 mass% p-toluenesulfonic acid methanol solution (component (D) + component (E)) 0.20 g was added dropwise over 1 minute each. Subsequently, after stirring for 60 minutes at room temperature and 500 rpm, the mixture was allowed to stand for one day, and this was designated as solution A.
A sample tube with a volume of 20 ml was charged with 1.10 g of 3-isocyanatopropyltriethoxysilane and 0.36 g of 2-butanone oxime (isocyanate group blocking agent), stirred at room temperature at 500 rpm for 10 minutes, and then allowed to stand for one day. This was designated as solution C. The blocking of the isocyanate group was confirmed by disappearance of the isocyanate group signal by ¹³ C-NMR. The total amount of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was taken as the amount of the blocked isocyanatosilane compound: (A-5) component.

Into a 200 ml three-necked flask equipped with a condenser, put A solution and a stir bar and stir at 500 rpm. And then stirred at room temperature for 10 minutes. Then, it heated at 600 rpm and 80 degreeC under nitrogen stream for 3 hours. Then, C liquid was added, and it stirred at 80 degreeC on the same conditions for 4 hours, Then, it left still at room temperature overnight.
Further, 0.40 g of 3-aminopropyltrimethoxysilane (component (A-3)) was added dropwise thereto as a D solution over 2 minutes. After stirring at room temperature for 10 minutes, the mixture was further heated at 700 rpm and 80 ° C. for 3 hours under a nitrogen stream.
Subsequently, it was left to stand for 1 week to obtain a coating solution. (Comparative Example 1 shows a coating liquid produced without using the component (A-1) in the coating liquid of Example 1, and the organic polymer fine particle content in the cured film is the same as that of Example 1. Next, using this coating solution, a laminate composed of a substrate and a cured film was produced in the same manner as in Example 1 (2).
The obtained coating liquid and laminate were evaluated. The evaluation results are shown in Table 4.

Comparative Examples 2-6
In the same manner as in Comparative Example 1, a coating liquid was produced and a laminate was produced in accordance with the components and blending amounts shown in Table 3. (Comparative Examples 2 and 3 show the coating liquids produced without using the component (A-1) in the coating liquids of Examples 2 and 3, and the organic polymer fine particle content in the cured film is shown as follows. The same amount as in Examples 2 and 3. Comparative Example 4 shows the coating liquid produced without using the component (A-5) in the coating liquid of Example 3, and its The content of the organic polymer in the cured film is the same as in Example 3. In Comparative Example 5, the components (A-5) and (C) are not used in the coating liquid of Example 3. The coating liquid produced is shown, and the organic polymer content in the cured film is the same as that in Example 3. Comparative Example 6 is a coating liquid of Example 3 (A-1 ) And C produced without using component (C) Is indicative of the coating solution is obtained by the same amount as the organic polymer content Example 3 in the cured film.)
The obtained coating liquid and laminate were evaluated. The evaluation results are shown in Table 4.

As can be seen from Tables 1 to 4, the coating liquid of the present invention, the cured films obtained from the coating liquid, and the laminates (Examples 1 to 11) all pass in almost all evaluation items.
Comparative Examples 1 to 3 and Comparative Example 6 that do not contain the component (A-1) have good liquid stability, film appearance, transparency, adhesion, and boiling resistance, but have good scratch resistance. Compared to 11. Further, Comparative Examples 4 and 5 not containing the component (A-5) have good film appearance, transparency and adhesion, but have liquid stability and boiling resistance compared to those of Examples 1 to 11. Inferior.

Examples 12 to 16
The surface of a polycarbonate (PC) molded product having a thickness of 3 mm or a corona-treated polypropylene sheet [manufactured by Idemitsu Unitech Co., Ltd., trade name: Super Pure Array, product number: SG-140TC, thickness 300 μm (total light transmission) The ratio of 94%, haze value 2.3%) is applied with a bar coater so that the cured film is 3 μm, and is thermally cured at 130 ° C. for 2 hours to form a laminate composed of the base material and the cured film. The body was made. Furthermore, the inorganic hard material layer was formed into a film by the following method on the laminated body produced above, and the laminated body was obtained.
The obtained laminate composed of the base material, the cured film and the inorganic hard material layer was evaluated. The evaluation results are shown in Table 5.

Formation of inorganic hard layer (1) SiOx
The laminated body made of the base material and the cured film is placed in a plasma CVD apparatus and evacuated until the degree of vacuum in the apparatus becomes 2.7 × 10 ⁻³ Pa to raise the temperature of the base material to 100 ° C. The substrate was degassed by holding for 5 minutes. Then, after returning to room temperature, exhausting was performed until the degree of vacuum in the apparatus reached 2.7 × 10 ⁻⁴ Pa.
After the degree of vacuum is 2.7 × 10 ⁻⁴ Pa, SiH ₄ gas, N ₂ O gas, and Ar gas are introduced into the apparatus, and the gas flow rate is SiH ₄ gas flow rate 1 cm ³ / min, N ₂ O gas. When stable at a flow rate of 200 cm ³ / min, an Ar gas flow rate of 300 cm / min, and a degree of vacuum of about 2.7 Pa, an electric power is applied to generate plasma, and a SiO _x (1.8 μm) film thickness on the cured film is 1.8 μm. ≦ x ≦ 2) (inorganic hard material layer) was formed.

(2) Amorphous carbon film A laminated body made of the base material and the cured film is placed in a plasma CVD apparatus and evacuated until the degree of vacuum in the apparatus becomes 2.7 × 10 ⁻³ Pa. The temperature was raised to 100 ° C. and held for 5 minutes to degas the substrate. Then, after returning to room temperature, exhausting was performed until the degree of vacuum in the apparatus reached 2.7 × 10 ⁻⁴ Pa.
In a plasma CVD apparatus with a vacuum degree of 2.7 × 10 ⁻⁴ Pa, CH ₄ gas, H ₂ gas and Ar gas are flowed at a CH ₄ gas flow rate of 1 cm ³ / min, and an H ₂ gas flow rate of 150 cm ³ / min. Then, when Ar gas is introduced at a flow rate of 300 cm ³ / min and stable at a vacuum degree of about 2.7 Pa, power is applied to generate plasma to form an amorphous carbon film (inorganic hard layer) having a thickness of 7 μm. Filmed.

(3) SiNy
The laminated body made of the base material and the cured film is placed in a plasma CVD apparatus and evacuated until the degree of vacuum in the apparatus becomes 2.7 × 10 ⁻³ Pa to raise the temperature of the base material to 100 ° C. The substrate was degassed by holding for 5 minutes. Then, after returning to room temperature, exhausting was performed until the degree of vacuum in the apparatus reached 2.7 × 10 ⁻⁴ Pa.
SiH ₄ gas, NH ₃ gas, and Ar gas are introduced into the plasma CVD apparatus at a SiH ₄ gas flow rate of 1 cm ³ / min, an NH ₃ gas flow rate of 200 cm ³ / min, and an Ar gas flow rate of 400 cm ³ / min. When stable at about 7 Pa, electric power was applied to generate plasma, and an SiN _y (1.2 ≦ y ≦ 4/3) film (inorganic hard layer) having a thickness of 7 μm was formed.

(4) SiO ₂
The laminate made of the prepared base material and cured film was placed in an ion plating apparatus, and the evaporation source was SiO ₂ grain. Evacuation was performed until the degree of vacuum in the apparatus reached 2.7 × 10 ⁻⁴ Pa. A high frequency voltage of 1.5 kV was applied to the high frequency coil, and argon gas and O ₂ gas were introduced. After stopping the introduction of gas, the degree of vacuum in the apparatus was 1.33 × 10 ⁻³ Pa, and SiO ₂ ion plating was performed for 1 to 2 minutes. Thereafter, the apparatus was left to cool for 20 minutes while maintaining the vacuum in the apparatus, and a SiO ₂ film (1.8 ≦ x ≦ 2) (inorganic hard material layer) having a thickness of 1.5 μm was formed on the cured film.

Comparative Examples 7-11
Using the coating liquid of Comparative Example 1, laminates were obtained in the same manner as in Examples 12-16.
Evaluation was made on a laminate composed of the obtained base material, cured film, and inorganic hard material layer. The evaluation results are shown in Table 5.

As can be seen from Table 5, the laminates (Examples 12 to 16) using the coating liquid of Example 1 passed all of the evaluation items.
Comparative Examples 7 to 11 are laminates using the coating liquid of Comparative Example 1, and the film appearance, transparency, abrasion resistance, and scratch resistance are good, but the adhesion and boiling resistance are those of Example 12. Compared to ~ 16.

[Examples 17 to 20 and Comparative Examples 12 to 14]
Various characteristics in the above examples were determined according to the following procedures.

(1) Oxide equivalent content derived from inorganic components in cured film (mass%)
A sample obtained by thermosetting the coating solution on a Teflon petri dish was subjected to thermogravimetry (20 ° C./min increase under nitrogen, room temperature to 800 ° C.), and obtained from the residue at 800 ° C. It was.
(2) Organic polymer fine particle content (% by mass) in the cured film
Calculated by calculation. Specifically, components (A-1) to (A-5) in which hydrolysis / condensation reaction has completely progressed (component (A)), organic polymer fine particles (component (B)) and colloidal silica ((C ) Component), and mass% of organic polymer fine particles in the total mass of cerium oxide (component (F)) was calculated.
(3) Cerium oxide content (% by mass) in the cured film
Calculated by calculation.
(4) Stability of coating solution The solution was stored sealed at room temperature for 14 days, and the presence or absence of gelation was determined visually. For those that are not gelled, the viscosity is measured with an A & D tuning fork type vibration viscometer SV-10. Exceeded “×”.
(5) Appearance of film The appearance of the cured film was visually observed to confirm foreign matters, mottled patterns, and white turbidity.
(6) Total light transmittance and haze The total light transmittance and haze of the laminate were measured with a direct reading haze computer (HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.).

(7) Abrasion resistance and scratch resistance The abrasion resistance was evaluated using a wear wheel CS-10F and a Taber abrasion tester (rotary abrasion tester) (made by Toyo Seiki Co., Ltd., model: TS). A 500-rotor Taber abrasion test was performed at 9N, and the difference (ΔH) between the haze before the Taber abrasion test and the haze after the Taber abrasion test was less than 15, and “x” was 15 or more.
Regarding evaluation of scratch resistance, in Examples 17 to 20 and Comparative Examples 12 to 14, steel wool # 0000 (load 4.9 N) was used, and after 50 reciprocations at 2000 mm / sec, the surface damage state was visually observed. It was evaluated by. “1” indicates that there is no scratch at all, “2” indicates that there is a slight scratch, and “3” indicates that scratches are present on more than half of the rubbed area.
(8) Adhesiveness In accordance with JIS K 5400, a sample (cured film) 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.), and then closely peeled off at an angle of 90 ° toward the near side, and the cured film did not peel off, and the remaining number (X) remained. Displayed by X / 100, the adhesion of the cured film was evaluated.

(9) Boiling resistance A sample of the laminate was immersed in boiling water in a stainless steel beaker for 5 hours, and then the adhesion was evaluated. The evaluation of adhesion was performed in the same manner as (8) above.
(10) Weather resistance A xenon weather test (Atlas Ci65, output 6.5 kW, black panel temperature 63 ° C., relative humidity 50%) was performed in 2400 hours. The weather resistance was evaluated by the change in adhesion of the cured film before and after the test.
(11) Flexural resistance Sample of resin laminate in the same manner as in each example except that a polycarbonate standard plate (trade name: Polycaace, product number: ECK100) manufactured by Sumitomo Bakelite Co., Ltd. having a size of 100 mm × width 50 mm × thickness 1 mm was used as a substrate. Manufactured.
The sample was held at both ends with fingers and subjected to forced bending with a radius of 50 mm curve 10 times, and no crack was found on the laminated surface.
(12) Heat resistance A heat resistance test (manufactured by Tabai, PS-222) was performed at 110 ° C. for 720 hours. The heat resistance was evaluated by the change in the adhesion of the cured film before and after the test.

(13) Organic fine particle dispersion structure A cross-section of the cured film is observed with a TEM (transmission electron microscope), 10 organic fine particles present in the 1 μm square are selected, and free software manufactured by NIH (National Institute of Health), USA: NIH The average particle size was determined using Image 1.63. An organic fine particle having an average particle size of 200 nm or less is “◯”, an average particle size of greater than 200 nm is “X”, and a particle size of 200 nm or less is present. “Δ” indicates that there was an amoeba shape of 200 nm or more.
(14) Inorganic fine particle dispersion structure The average particle size of each of the cerium oxide fine particles and colloidal silica fine particles in the cured film was determined in the same manner as in the above (13). Those having an average particle size of 200 nm or less were marked with “◯”, and those having an average particle size larger than 200 nm were marked with “x”.

In the examples and comparative examples, the details of the raw materials described by trade names are as follows.
Component (A): M silicate 51 “polyalkoxysilane which is a partial condensate of tetramethoxysilane (average 3 to 5 mer)” manufactured by Tama Chemical Industry Co., Ltd. (B) component: ULS-1385MG (ultraviolet absorbing skeleton species: Benzotriazole)
On the other hand, manufactured by Yushi Kogyo Co., Ltd.
(B) component: ULS-385MG (ultraviolet ray absorbing skeleton species: benzophenone series)
On the other hand, manufactured by Yushi Kogyo Co., Ltd.
Component (C): IPA-ST-L (Colloidal silica)
Made by Nissan Chemical Industries Ltd. (isopropanol dispersion, colloidal silica concentration 30% by mass, average particle size 40-50 nm (manufacturer's published value))

Component (F ′): Niedral U-15 (cationic cerium oxide aqueous dispersion)
Made by Taki Chemical Co., Ltd. (water dispersion, cerium oxide concentration 15% by mass, average particle size 8 nm or less, pH 3.5 (manufacturer catalog value))
(The zeta potential of Nidral U-15 was measured at 20 ° C. using a Zetasizer Nano Series Nano-ZS manufactured by MALVERN under the conditions of dispersion medium: water and 50 times of accumulation, and found to be +28.8 mV. The cerium oxide particles were confirmed to have cationic properties.)
Component (F ′): Niedral H-15 (acid-stable cerium oxide aqueous dispersion)
Manufactured by Taki Chemical Co., Ltd. (water dispersion, cerium oxide concentration 15-16% by mass, stabilizer: hydrochloric acid less than 1.0% by mass, pH 1-3 (published by manufacturer))
(In addition, it was +53.7 mV when the zeta potential of Nidraral H-15 was measured using the Zetasizer Nano Series Nano-ZS manufactured by MALVERN under the conditions of 20 ° C., dispersion medium: water, and 50 accumulations. The cerium oxide particles were confirmed to have cationic properties.)

(1) Preparation of component (F) (dispersion F1)
It manufactured according to the component of Table 6, and preparation amount.
A sample tube with a volume of 50 ml was charged with 10.0 g of Nidral H-15 (component (F ′)) and stirred at 500 rpm, 7.0 g of 1-methoxy-2-propanol (component (E)), tetraethoxysilane. ((A) component) It dripped over 1 minute each in order of 2.23g. Subsequently, the mixture was stirred at room temperature for 90 minutes and then allowed to stand at room temperature for 90 minutes. This and a stirring bar were charged into a 100 ml three-necked flask equipped with a condenser, and heated at 80 ° C. for 4 hours under a nitrogen stream while stirring at 500 rpm. Then, it left still at room temperature for one week, and was set as the dispersion liquid F1 ((F) component) which consists of a reaction product of a silane compound and cerium oxide.

(2) Dispersibility test of component (F) with anionic fine particle sol 1.0 g of IPA-ST-L (IPA dispersion sol in which component (C) and anionic colloidal silica are dispersed) in a 10-ml sample tube While stirring at 400 rpm, 1.0 g of dispersion F1 (component (F)) consisting of the reaction product of the silane compound and cerium oxide was added dropwise over 1 minute, followed by stirring at room temperature for 1 hour. did. It was visually confirmed that the dispersion state after stirring was dispersed without aggregation, precipitation, or gelation.

(3) Preparation of component (F) (dispersion F2)
It manufactured according to the component of Table 6, and preparation amount.
A sample tube with a volume of 50 ml was charged with 10.0 g of Nidral H-15 (component (F ′)) and stirred at 500 rpm, 7.0 g of 1-methoxy-2-propanol (component (E)), tetraethoxysilane. ((A) component) It dripped over 1 minute in order of 1.49g. Subsequently, the mixture was stirred at room temperature for 90 minutes and then allowed to stand at room temperature for 90 minutes. This and a stirring bar were charged into a 100 ml three-necked flask equipped with a condenser, and 0.30 g of 3-glycidoxypropyltrimethoxysilane (component (A)) was added dropwise over 1 minute while stirring at 500 rpm. Stir for 120 minutes. This was heated at 80 ° C. for 9 hours under a nitrogen stream while stirring at 500 rpm. Then, it left still at room temperature for 1 week, and was set as the dispersion liquid F2 ((F) component) which consists of a reaction product of a silane compound and cerium oxide.
In addition, about this dispersion liquid F2, it confirmed that it was disperse | distributing without aggregation, precipitation, and gelatinization by the method similar to the dispersibility test of said (2).

Examples 17-18
(4) Manufacture of coating liquid It prepared according to the component of Table 7, and preparation amount.
In a sample tube having a volume of 50 ml, 0.85 g of organic polymer fine particles: ULS-1385MG (Example 17) or ULS-385MG (Example 18) (component (B) + component (E)) was charged and stirred at 500 rpm. 1-methoxy-2-propanol (component (E)) 4.25 g, water (component (E)) 0.50 g, acetic acid (component (G)) 2.80 g, M silicate 51 (component (A-1)) 0.40 g, 1.51 g of methyltrimethoxysilane (component (A-2)), 0.55 g of dimethoxy-3-glycidoxypropylmethylsilane (component (A-4)), 20 mass% p-toluenesulfone Acid methanol solution (component (D) + component (E)) was added dropwise in the order of 0.05 g over 1 minute. Subsequently, after stirring for 60 minutes at room temperature and 500 rpm, the mixture was allowed to stand for one day, and this was designated as solution A.
Into a 200 ml three-necked flask equipped with a condenser, put A solution and a stir bar, stir at 500 rpm, and apply 6.50 g of IPA-ST-L (component (C) + component (E)) as solution B over 5 minutes. The solution was added dropwise and stirred at room temperature for 20 minutes. Subsequently, the mixture was heated and stirred at 500 rpm and 80 ° C. for 7 hours under a nitrogen stream, and then allowed to stand overnight at room temperature, which was designated as A ′ solution.
A sample tube with a volume of 20 ml was charged with 1.10 g of 3-isocyanatopropyltriethoxysilane and 0.35 g of 2-butanone oxime (isocyanate group blocking agent), stirred at room temperature at 500 rpm for 10 minutes, and then allowed to stand for one day. This was designated as solution C. The blocking of the isocyanate group was confirmed by disappearance of the isocyanate group signal by ¹³ C-NMR. The total amount of 3-isocyanatopropyltriethoxysilane and 2-butanone oxime was taken as the amount of the blocked isocyanatosilane compound: (A-5) component.
While stirring the A ′ liquid at 650 rpm, 3.26 g of a dispersion F1 (component (F) + component (E)) consisting of a reaction product of a silane compound and cerium oxide was added dropwise over 5 minutes, and the mixture was stirred at room temperature for 20 minutes. Stir for minutes. Then, C liquid was added over 5 minutes, and it stirred at room temperature for 10 minutes. Subsequently, the mixture was heated and stirred at 650 rpm and 80 ° C. for 4 hours under a nitrogen stream, and then allowed to stand overnight at room temperature.
Further, 0.40 g of 3-aminopropyltrimethoxysilane (component (A-3)) was added dropwise thereto as a D solution over 2 minutes. After stirring at room temperature for 10 minutes, the mixture was further heated at 450 rpm and 80 ° C. for 3 hours under a nitrogen stream.
Subsequently, it was left to stand for 1 week to obtain a coating solution.

(5) Production of Laminate As a resin base material, a polycarbonate base material [manufactured by Idemitsu Kosan Co., Ltd., trade name: Toughlon, product number: IV2200R (anti-glare grade), thickness 3 mm (total light transmittance 90%, haze value 0.5) %)] Was used.
The coating solution obtained above is applied to the surface of a polycarbonate molded body having a thickness of 3 mm with a bar coater so that the cured film has a thickness of 7 μm, and thermally cured at 130 ° C. for 2 hours to obtain a laminate. Produced.
The obtained coating liquid and laminate were evaluated. Table 8 shows the evaluation results.

Examples 19-20
In the above “(4) Production of coating liquid”, the dispersion liquid F2 was used in place of the dispersion liquid F1, and the coating liquid according to the example was prepared according to the components and preparation amounts shown in Table 7 to prepare a laminate. Table 8 shows the evaluation results for the obtained coating liquid and laminate.

Comparative Examples 12-14
In the above “(4) Production of coating solution”, instead of the dispersion F1, Niedral U-15 or Niedral H-15 shown in Table 7 was used, and coating according to the comparative example was performed according to the components and preparation amounts shown in Table 7. The liquid was prepared and the laminated body was produced. Table 8 shows the evaluation results for the obtained coating liquid and laminate.

The coating liquids of Examples 17 to 20 all had good liquid stability, and the laminates obtained therefrom had excellent results in all evaluations. On the other hand, in Comparative Example 13, the stability of the coating liquid was low and the utility was low. Further, Comparative Examples 12 and 14 had poor adhesion.

[Examples 21 to 32, Comparative Examples 15 to 26]
Examples 21-32
[Production of resin laminate]
The coating solutions produced in Examples 1, 2, 5 and 6 were applied to the surface of the substrate so that the thickness of the cured film was 2 to 3 μm, and the following <Thermal curing conditions for the substrate and the cured film> As mentioned above, the laminated body which consists of a base material and a cured film was produced by thermosetting at the temperature and time according to the used base material.
Next, a transparent conductive film was formed by the following method on the laminate composed of the prepared base material and cured film to obtain a resin laminate.
Table 9 shows the results of evaluation of the resin laminate comprising the obtained base material, cured film and transparent conductive film.

<Heat-curing conditions for substrate and cured film>
(1) Polycarbonate [thickness: 400 μm (total light transmittance: 92%, haze value: 0.4%)], 120 ° C., 2 hours (2) Polyethylene terephthalate [manufactured by Unitika Ltd., trade name: EMBLET, grade: S, thickness: 25 μm (Total light transmittance 89%, haze value 2.5%)], 100 ° C. for 2 hours (3) polypropylene [manufactured by Idemitsu Unitech Co., Ltd., trade name: Pure Thermo, thickness 250 μm (total light transmittance 94%, haze value) 8.5%)] 100 ° C. for 2 hours

<Method for forming transparent conductive film>
(1) IZO thin film A laminate comprising the prepared base material and cured film was placed in a sputtering apparatus (Shimadzu HSM-552) and evacuated until the degree of vacuum in the apparatus became 1.0 × 10 ⁻⁴ Pa. Thereafter, argon gas was introduced into the apparatus, and the pressure in the apparatus was adjusted to 0.2 Pa. An IZO (In ₂ O ₃ : ZnO = 90: 10 mass%) sintered compact target was used as the target. A transparent conductive film having a film thickness of 20 nm or 120 nm was produced at a sputtering DC output of 100 W. The substrate temperature is room temperature.
(2) IZTO thin film An IZTO target (In ₂ O ₃ : ZnO: SnO ₂ = 20: 40: 40% by mass) was used as the target and was formed by the same method as in the above (1).
(3) ZTO thin film Using a ZTO target (ZnO: SnO ₂ = 10: 90 mass%) as a target, the ZTO thin film was formed by the same method as in the above (1).
(4) a thin film of SnO ₂ target using a SnO ₂ sintered body target were formed in a similar procedure as above (1).
(5) ITO thin film Using an ITO target (In ₂ O ₃ : SnO ₂ = 90: 10% by mass) as a target, the ITO thin film was formed by the same method as in the above (1). After the formation, heat treatment was performed at 120 ° C. for 1 hour in an atmospheric oven.

Comparative Examples 15 to 26
On the base material used in Example 21, a transparent conductive film was directly formed without forming a cured film to obtain a resin laminate.
Table 10 shows the results of the evaluation of the laminate composed of the obtained base material and transparent conductive film.

Various characteristics in Examples 21 to 32 and Comparative Examples 15 to 26 were determined according to the following procedures.
(1) Film appearance The appearance of the resin laminate was visually observed to confirm the presence or absence of foreign matters, mottled patterns, and cracks, and those that were not recognized were evaluated as “◯” and those that were recognized as “×”.
(2) Total light transmittance and haze The total light transmittance and haze of the resin laminate were measured with a direct reading haze computer (HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.).
(3) Surface hardness In accordance with JIS K5600-5-4, evaluation was performed on the surface of the transparent conductive film of the resin laminate using a pencil scratch tester for coating film (manual type) (manufactured by Imoto Seisakusho Co., Ltd.). .
(4) Scratch resistance After the surface of the transparent conductive film of the resin laminate is reciprocated 10 times with steel wool # 0000, a load of 4.9 N and 2000 mm / sec, the surface of the transparent conductive film is visually checked in three stages. It was evaluated with. “1” indicates that there is no scratch at all, “2” indicates that there is a slight scratch, and “3” indicates that scratches are present on more than half of the rubbed area.
(5) Adhesiveness In accordance with JIS K 5400, the surface of the transparent conductive film of the resin laminate was cut into 11 grids at intervals of 2 mm at intervals of 2 mm with a razor blade to make 100 grids, and a commercially available cellophane tape (" After CT-24 (width 24mm), manufactured by Nichiban Co., Ltd. is closely attached to the finger pad, it is peeled off rapidly at an angle of 90 °, and the transparent conductive film does not peel off. X) was expressed as X / 100, and the adhesion of the transparent conductive film was evaluated.
(6) Moisture resistance In a moisture resistance test (small environment tester, manufactured by ESPEC Corporation, SH-221), the sample was allowed to stand in an atmosphere of 50 ° C. and 95 RH% for 100 hours, and then the adhesion was evaluated. The adhesion was evaluated in the same manner as (5) above.

(7) Bending resistance Hold both ends of the resin laminate sample with fingers, perform a forced bending of a curve with a radius of 50 mm 10 times, check the presence or absence of cracks or delamination on the laminated surface, "," Was recognized as "x".
(8) Specific Resistance Using a low resistivity meter Loresta-EP (manufactured by Mitsubishi Chemical Corporation), the specific resistance was measured on the surface of the transparent conductive film of the resin laminate by the four-probe method.
(9) Carrier concentration The carrier concentration was measured by the van der Pole method. The Hall measuring device and its measurement conditions are as follows.
・ Hall measuring device manufactured by Toyo Technica: Resi Test 8310
・ Measurement conditions Measurement temperature: Room temperature (25 ℃)
Measurement magnetic field: 0.5T
Measurement current: 10 ^-12 to 10 ^-4 A
Measurement mode: AC magnetic field

(10) Crystallinity of transparent conductive film Crystallinity was determined by X-ray diffraction measurement. The measurement conditions of X-ray diffraction measurement (XRD) are as follows. Those having no clear crystallinity peak were regarded as amorphous.
-X-ray diffraction measurement device manufactured by Rigaku Corporation: Ultimate-III
・ Measurement conditions X-ray: Cu-Kα ray (wavelength 1.5406mm, monochromatized with graphite monochromator)
Output: 50kV-120mA
2θ-θ reflection method, continuous scan (1.0 ° / min)
2θ measurement angle: 5-80 °
Sampling interval: 0.02 °
Slit DS, SS: 2/3 °, RS: 0.6 mm

As can be seen from Tables 9 and 10, the resin laminates (Examples 21 to 32) composed of the base material, the cured film, and the transparent conductive film all passed in almost all evaluation items.
Among Comparative Examples 15 to 26 in which a cured film is not sandwiched, Comparative Examples 15 to 18 and 23 to 26 using polycarbonate as a base material have good film appearance, adhesion, and bending resistance, but are transparent. The surface hardness, scratch resistance, and conductivity are inferior to those of Examples 21 to 24 and 29 to 32. Further, Comparative Examples 19 and 20 using polypropylene as the base material are inferior in film appearance, surface hardness, scratch resistance, adhesion, and flex resistance as compared with those in Examples 25 and 26. Comparative Examples 21 and 22 using polyethylene terephthalate as the substrate have good film appearance, optical properties, adhesion, and bending resistance, but surface hardness, scratch resistance, and conductivity are higher than those of Examples 27 and 28. Inferior.

[Examples 33 to 35, Comparative Examples 27 to 29]
Example 33
(Production of resin laminate)
The coating liquid obtained in Example 1 was applied to the surface of a polycarbonate molded body having a thickness of 3 mm with a bar coater so that the cured film had a thickness of 2 to 5 μm, and thermally cured at 130 ° C. for 2 hours. A laminate composed of a substrate and a cured film was produced.
Next, the photocatalyst topcoat agent “ST-K211” manufactured by Ishihara Sangyo Co., Ltd. is applied on the cured film of the laminate comprising the base material and the cured film so that the thickness after the heat treatment is about 0.5 μm. After that, heat treatment was performed at 100 ° C. for 30 minutes to produce a photocatalyst layer.
Table 11 shows the results of evaluation of the resin laminate comprising the obtained substrate, cured film and photocatalyst layer.

Example 34
A resin laminate comprising a substrate, a cured film and a photocatalyst layer was produced in the same manner as in Example 33 except that the coating liquid obtained in Example 8 was used instead of the coating liquid obtained in Example 1. . Table 11 shows the evaluation results.

Example 35
A resin laminate comprising a substrate, a cured film and a photocatalyst layer was produced in the same manner as in Example 33 except that the coating liquid obtained in Example 9 was used instead of the coating liquid obtained in Example 1. . Table 11 shows the evaluation results.

Comparative Example 27
A resin laminate comprising a substrate, a cured film and a photocatalyst layer was produced in the same manner as in Example 33 except that the coating liquid obtained in Example 1 was not used. Table 11 shows the evaluation results.

Comparative Example 28
Example except that a primer “ST-K300” manufactured by Ishihara Sangyo Co., Ltd. was used instead of the coating solution obtained in Example 1 and this was applied so that the thickness after drying was about 0.3 μm. In the same manner as in No. 33, a resin laminate comprising a substrate, a cured film and a photocatalyst layer was produced. Table 11 shows the evaluation results.

Comparative Example 29
On the primer of Comparative Example 28, an equivalent liquid mixture (ST-K102) of an undercoat agent “ST-K102a” and “ST-K102b” manufactured by Ishihara Sangyo Co., Ltd. was dried to a thickness of about 3 μm. A resin laminate composed of a substrate, a cured film and a photocatalyst layer was produced in the same manner as in Example 33 except that the coating was performed and dried at room temperature for 5 minutes and then heated at 100 ° C. for 30 minutes. Table 11 shows the evaluation results.

Various characteristics in Examples 33 to 35 and Comparative Examples 27 to 29 were determined according to the following procedures.
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 in contact angle with time was measured. The contact angle was measured by dropping 20 ml of ion-exchanged water on the photocatalyst layer surface using a microsyringe and using an image processing contact angle meter (CA-A, manufactured by Kyowa Interface Science Co., Ltd.).

(2) Total light transmittance and haze The total light transmittance and haze of the laminate were measured with a direct reading haze computer (HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.).

(3) Degree of yellowing (YI)
Measurement was performed according to JIS K7105 using SZ-optical SENSOR (manufactured by Nippon Denshoku Industries Co., Ltd.).

(4) Abrasion resistance Using a wear wheel CS-10F and a Taber abrasion tester (rotary ablation tester) (Toyo Seiki Co., Ltd., model: TS), a 500 rotation Taber abrasion test was conducted at a load of 4.9 N, and Taber abrasion The case where the difference (ΔH) between the haze before the test and the haze after the Taber abrasion test was less than 15 was designated as “◯”, and the case where the difference was 15 or more was designated as “x”.
(5) Scratch resistance The surface of the photocatalyst layer of the resin laminate was reciprocated 50 times at 2000 mm / sec using steel wool # 0000 (load 4.9 N), and then the surface damage state of the photocatalyst layer was visually evaluated. . “1” indicates that there is no scratch at all, “2” indicates that there is a slight scratch, and “3” indicates that scratches are present on more than half of the rubbed area.

(6) Adhesiveness In accordance with JIS K 5400, the surface of the photocatalyst layer of the resin laminate was cut into 11 grids at intervals of 2 mm with a razor blade to make 100 grids, and a commercially available cellophane tape (“CT -24 (width 24 mm) "(made by Nichiban Co., Ltd.) was adhered closely with the belly of the finger, then peeled off rapidly at an angle of 90 °, and the photocatalyst layer remained without peeling (X) Was expressed as X / 100, and the adhesion of the photocatalyst layer was evaluated.

(7) Weather resistance A xenon weather test (Atlas Ci65, output 6.5 kW, black panel temperature 63 ° C., humidity 50%) was conducted, and the weather resistance was determined by the degree of change in the parameters of haze, yellowing, and adhesion. evaluated.

In each of Examples 33 to 35, the abrasion resistance, scratch resistance and weather resistance were better than those of Comparative Examples 27 to 29 in all evaluations.

Examples 36 to 43, Comparative Examples 30 to 33
(Molded body of resin laminate)
Example 36
The coating liquid of Example 1 was applied to a polycarbonate (PC) sheet having a thickness of 0.5 mm (trade name: Iupilon sheet manufactured by Mitsubishi Gas Co., Ltd.) so as to have a film thickness of 2 to 3 μm. A polycarbonate sheet for molding was produced by drying at 240 ° C. for 240 minutes. The formed molding sheet is vacuum-formed, and then set in an injection mold, and an injection-molded resin made of polycarbonate (made by Idemitsu Kosan Co., Ltd., trade name: Toughlon) is used at a resin temperature of 270 ° C. and a resin pressure of 50 MPa. A molded body of the resin laminate was manufactured by injecting onto the unformed surface. Further, the molded body was post-cured at 120 ° C. for 1 minute. Table 12 shows the evaluation results concerning the following items (1) to (3) for the molded body of the resin laminate.

(1) Film appearance The appearance of the cured film surface of the molded product was visually observed to check for foreign matters, mottled patterns, and cracks.
(2) Scratch resistance After 10 reciprocations using steel wool # 0000 (load 4.9 N), the surface damage was visually evaluated. “1” indicates that there is no scratch at all, “2” indicates that there is a slight scratch, and “3” indicates that scratches are present on more than half of the rubbed area.
(3) Adhesiveness In accordance with JIS K 5400, the cured film surface of the molded product 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.) was adhered closely with the belly of the finger, and then peeled off rapidly at an angle of 90 °, and the cured film remained without peeling from the base material ( X) was expressed as X / 100, and the adhesion of the cured film was evaluated.

Examples 37-39
A molded body was produced in the same manner as in Example 36. The polycarbonate sheet for molding was prepared according to the pre-curing temperature, pre-curing time, post-curing temperature and post-curing time shown in Table 6. The evaluation results are shown in Table 12.

Example 40
The coating liquid of Example 1 was applied to a polypropylene (PP) sheet having a thickness of 0.3 mm (trade name: Wintech, manufactured by Nippon Polypro Co., Ltd.) so as to have a film thickness of 2 to 3 μm, and pre-cured at 20 ° C. And dried for 240 minutes to produce a polypropylene sheet for molding. The formed molding sheet is vacuum-formed, then set in an injection mold, and an injection-molded resin made of polypropylene (manufactured by Prime Polymer Co., Ltd., trade name: Prime Polypro) is precured at a resin temperature of 270 ° C. and a resin pressure of 40 MPa. The molded body of the resin laminate was manufactured by injecting onto the surface where no is formed. Further, the molded body was post-cured at 120 ° C. for 30 seconds. The evaluation results are shown in Table 12.

Examples 41-43
A molded body was produced in the same manner as in Example 40. The molding polypropylene sheet was prepared according to the pre-curing temperature, pre-curing time, post-curing temperature and post-curing time shown in Table 12. The evaluation results are shown in Table 12.

Comparative Examples 30 to 33
Using the coating liquid of Comparative Example 1, molded articles were produced in the same manner as in Example 36, Example 39, Example 40, and Example 43. The evaluation results are shown in Table 12.

As can be seen from Table 12, Examples 36 to 43 are molded products of the resin laminate using the coating liquid of Example 1, and all pass in almost all evaluation items.
Comparative Examples 30 to 33 are molded products of the resin laminate using the coating liquid of Comparative Example 1, and the film appearance and adhesion are good, but the scratch resistance is inferior to those of Examples 36 to 43. .

By using the coating liquid of the present invention, automobile interior parts such as meter covers, motorcycle and tricycle windshields, resin automobile windows (various vehicle windows), resin construction material windows, roofs for construction machinery, road translucent plates (Sound insulation board), for correction, eyeglass lenses such as sunglasses, sports, safety glasses, displays such as plasma, liquid crystal, organic EL, optical discs, mobile phone parts, touch panel, solar cell and other electronic equipment parts, town It can be used for lighting parts such as road lamps, windproof plates, various resin materials for protective shields, especially polycarbonate materials, and can be suitably used as a glass substitute member.

Claims

A coating liquid comprising the following components (A) to (E):
(A) Hydrolysis condensate of silane compounds having alkoxy groups of the following components (A-1) to (A-5) (A-1) Tetraalkoxysilane compounds (A-2) Amino groups, epoxy groups and isocyanate groups (A-3) Silane compound having amino group and alkoxy group (A-4) Silane compound having epoxy group and alkoxy group (A-5) Blocked isocyanatosilane compound having alkoxy group (B) Organic polymer fine particles comprising a copolymer containing a monomer unit having an ultraviolet absorbing group (C) Colloidal silica (D) Curing catalyst (E) Dispersion medium
The coating liquid according to claim 1, further comprising (F) cerium oxide treated with a silane compound and (G) a dispersion stabilizer.
The coating liquid according to claim 1 or 2, wherein the component (A-1) is a tetraalkoxysilane compound represented by the following general formula (1).
Si (OR 1 ) 4 (1)
[Wherein R 1 represents an alkyl group having 1 to 4 carbon atoms or an alkyl group having an ether bond. A plurality of R 1 may be the same or different. ]
The coating liquid according to claim 1 or 2, wherein the component (A-2) is an organoalkoxysilane compound containing no amino group, epoxy group or isocyanate group represented by the following general formula (2).
R 2 a Si (OR 3 ) 4-a (2)
Wherein, R 2 is an alkyl group or a fluorinated alkyl group of 1 to 10 carbon atoms; vinyl group; a phenyl group; or methacryloxy-substituted alkyl group having 1-3 carbon atoms in the group, R 3 is a C1- 4 represents an alkyl group or an alkyl group having an ether bond, and a represents 1 or 2. When R 2 are a plurality, the plurality of R 2 may be the same or different, a plurality of OR 3 may be the same or different. ]
The coating liquid according to claim 1 or 2, wherein the component (A-3) is a silane compound having an amino group and an alkoxy group represented by the following general formula (3).
R 4 b Si (OR 5 ) 4-b (3)
[Wherein R 4 is an 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 group ( Wherein x is an integer of 1 to 3)]), an alkylamino group [—NHR group (where R is an alkyl group having 1 to 3 carbon atoms)], and the number of carbon atoms substituted with one or more groups 1 to 3 alkyl groups, at least one of R 4 represents an amino group, or an alkyl group having 1 to 3 carbon atoms substituted with either an aminoalkyl group or an alkylamino group; R 5 represents an alkyl group having 1 to 4 carbon atoms, and b represents 1 or 2. If R 4 is plural, R 4 may be the same or different, the plurality of OR 5 may be the same or different. ]
The coating liquid according to claim 1 or 2, wherein the component (A-4) is a silane compound having an epoxy group and an alkoxy group represented by the following general formula (4).
R 6 c Si (OR 7 ) 4-c (4)
[Wherein R 6 is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or a carbon substituted with one or more groups selected from a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. Represents an alkyl group having 1 to 3 carbon atoms, and at least one of R 6 represents an alkyl group having 1 to 3 carbon atoms substituted with a glycidoxy group or a 3,4-epoxycyclohexyl group. R 7 represents an alkyl group having 1 to 4 carbon atoms, and c represents 1 or 2. If R 6 is plural, R 6 may be the same or different, a plurality of OR 7 may be different or identical. ]
The coating liquid according to claim 1 or 2, wherein the component (A-5) is a blocked isocyanatosilane compound having an alkoxy group represented by the following general formula (5).
R 8 d Si (OR 9 ) 4-d (5)
[Wherein R 8 is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted with one or more groups selected from a methacryloxy group and a blocked isocyanate group. And at least one of R 8 represents an alkyl group having 1 to 3 carbon atoms substituted with a blocked isocyanate group. R 9 represents an alkyl group having 1 to 4 carbon atoms, and d represents 1 or 2. If R 8 is plural, R 8 may be the same or different, a plurality of OR 9 may be the same or different. ]
The reaction product obtained by bringing the hydrolysis condensate of the components (A-1), (A-2) and (A-4) and the components (B) to (E) into contact with (A) The coating liquid according to any one of claims 1 to 7, which is prepared by adding and reacting the component -5) and further reacting by adding the component (A-3).
The reaction product obtained by heating the mixture containing the component (A-1), the component (A-2), the component (A-4) and the components (B) to (E) is added to the reaction product (A-5). The coating liquid according to any one of claims 1 to 7, wherein the component (A-3) is further reacted after the component is reacted.
A cured film obtained by curing the coating liquid according to any one of claims 1 to 9.
A resin laminate comprising a substrate and the cured film according to claim 10 formed directly on the substrate.
A resin laminate comprising a substrate, the cured film according to claim 10 formed on the substrate, and an inorganic layer formed on the cured film.
A resin laminate comprising a base material, the cured film according to claim 10 formed on the base material, and a transparent conductive film formed on the cured film.
A resin laminate comprising a substrate, the cured film according to claim 10 formed on the substrate, and a photocatalyst layer formed on the cured film.
The resin laminate according to claim 13, wherein the thickness of the cured film is 0.1 to 50 µm.
Resin laminate according to claim 13 a carrier concentration of the transparent conductive film is 1 × 10 18 / cm 3 or more.
The resin laminate according to claim 13, wherein the substrate is a resin substrate.
The resin laminate according to any one of claims 11, 12, and 17, wherein the substrate has irregularities.
The resin laminate according to any one of claims 11, 12, 17 and 18, wherein the base material is an elliptic cylinder.
The resin laminate according to any one of claims 11, 12, 17 and 18, wherein the base material is a column type.
The resin laminate according to any one of claims 11, 12, and 17 to 20, further comprising a resin layer on a surface of the substrate on which no cured film is formed.
The resin laminate according to any one of claims 11, 12, 14, and 17 to 21, wherein the cured film has a thickness of 0.5 to 6 µm.
23. The resin laminate according to claim 11, wherein the substrate is a polyester resin, a polycarbonate resin or a polyolefin resin.
A method for producing a cured film, comprising a step of heating and curing the coating liquid according to any one of claims 1 to 9.
A step of applying the coating liquid according to any one of claims 1 to 9 on a substrate, a step of drying the coating solution, a step of thermoforming the substrate, and curing the coating solution to coat the substrate. And a step of providing a layer.
Furthermore, the manufacturing method of the resin laminated body of Claim 25 including the process of providing a resin layer in the surface which does not have the coating layer of the resin laminated body formed by hardening | curing the said coating liquid.
Forming a cured film formed by curing the coating liquid according to any one of claims 1 to 9 on a substrate;
Forming a transparent conductive film on the cured film,
The manufacturing method of the resin laminated body characterized by the above-mentioned.
Forming a cured film formed by curing the coating liquid according to any one of claims 1 to 9 on a substrate;
Forming a photocatalytic layer on the cured film,
The manufacturing method of the resin laminated body characterized by the above-mentioned.