TWI462979B - A coating liquid, a hardened film and a resin laminate, and a method for producing the hardened film and the resin laminate - Google Patents

Description

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

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

Thermoplastic plastics, especially polycarbonate resins, are widely used as structural materials instead of glass because of their excellent transparency, light weight, and excellent impact resistance. However, since surface properties such as abrasion resistance, scratch resistance, weather resistance, and chemical resistance are poor, the use thereof is limited, and it is highly desired to improve the surface properties of the polycarbonate substrate.

As a method of improving the 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 of forming a cured layer containing a polyfunctional acrylic photocurable resin, a melamine-based or an organopolyoxyalkylene-based thermosetting resin on the surface of a polycarbonate substrate has been proposed.

Among these, those covered with an organic siloxane-based resin are considered to be useful because they are excellent in abrasion resistance, scratch resistance, and chemical resistance. However, the coating of the organic siloxane-based resin has a problem in adhesion to the polycarbonate resin, and in particular, when it is used outdoors for a long period of time, there is a problem that the coating layer is peeled off. In addition, even if the film thickness of the organic siloxane oxide resin is increased in order to improve the adhesion or the abrasion resistance, there is a problem that cracking easily occurs during curing, and the manufacturer is eager to improve.

In the improvement of the adhesion, Patent Document 1 proposes a method of blending various polymers having good adhesion into a coating material or a hard coating material, but the scratch resistance is not sufficient. Further, in Patent Documents 2 and 3, the cured film is applied to the surface of the substrate, and an inorganic hard layer is provided thereon, but sufficient adhesion is not obtained.

Patent Literatures 4 and 5 disclose a resin laminate comprising a coating layer and a substrate, wherein the coating layer has a film in which a polymer nanoparticle having an ultraviolet absorbing ability is highly dispersed in a siloxane matrix (Si-O skeleton). Internal structure. The resin laminate has excellent abrasion resistance and initial adhesion between the substrate and the coating layer. However, when the resin laminate is used for a member such as a window with a wiper, which is accompanied by severe friction, it is resistant to abrasion. There is still room for improvement in terms of sex and wear resistance. Moreover, there is still room for improvement in terms of durability (boil resistance).

Patent Document 1: Japanese Patent Laid-Open No. Hei 11-43646

Patent Document 2: Japanese Patent Laid-Open Publication No. SHO 58-29835

Patent Document 3: Japanese Patent Laid-Open No. 64-4343

Patent Document 4: WO 2006/022347 pamphlet

Patent Document 5: WO 2007/099784 brochure

The present invention has been made in view of the above circumstances, and an object thereof is to provide a coating liquid which forms a cured film which is excellent for a substrate, an inorganic hard material layer, a transparent conductive film, and a photocatalyst layer even without using a primer. Adhesive property, and excellent properties such as abrasion resistance, scratch resistance, flex resistance, weather resistance (UV absorbing ability), durability (boil resistance), and hardening of the coating liquid A cured film having the above characteristics and a resin laminate having the cured film on a substrate; and a method for producing the cured film and the resin laminate.

The present inventors conducted an intensive study on the formation of a coating liquid for forming a cured film having the above characteristics, and as a result, obtained the following knowledge.

The present inventors have found that a hydrolyzed condensate comprising a decane compound having an alkoxy group, an organic polymer fine particle containing a copolymer containing a monomer unit having an ultraviolet absorbing group, a colloidal cerium oxide, a hardening catalyst, and The coating liquid of the dispersion medium is heated and hardened to obtain a cured film having desired characteristics, and the cured film is formed on the substrate or the layers of the inorganic hard layer, the transparent conductive film, and the photocatalyst layer and the substrate. In order to obtain the desired resin laminate.

The present invention has been completed based on the above knowledge findings.

That is, the present invention provides a coating liquid, a cured film, a resin laminate, and a method for producing the cured film and the resin laminate.

[1] A coating liquid comprising the following components (A) to (E):

(A) a hydrolysis-condensation product of alkane-containing decane compound of the following (A-1) to (A-5) components,

(A-1) a tetraalkoxydecane compound,

(A-2) an organoalkoxydecane compound containing no amine group, epoxy group or isocyanate group,

(A-3) a decane compound having an amine group and an alkoxy group,

(A-4) a decane compound having an epoxy group and an alkoxy group,

(A-5) a blocked isocyanatodecane compound having an alkoxy group;

(B) an organic polymer microparticle containing a copolymer comprising a monomer unit having an ultraviolet absorbing group;

(C) colloidal cerium oxide;

(D) hardening catalyst;

(E) Dispersing medium.

[2] The coating liquid according to [1], which further comprises (F) cerium oxide treated by decane compound, and (G) dispersion stabilizer.

[3] The coating liquid according to [1] or [2], wherein the component (A-1) is a tetraalkoxydecane compound represented by the following formula (1):

Si(OR ¹ ) ₄ ......(1)

[wherein, R ¹ represents an alkyl group having a carbon number of 1 to 4 or an alkyl group having an ether bond; and a plurality of R ^{1 's} may be the same or different).

[4] The coating liquid according to [1] or [2], wherein the component (A-2) is an organoalkoxydecane having no amine group, epoxy group or isocyanate group represented by the following formula (2) Compound:

R ² _a Si(OR ³ ) _4-a ......(2)

Wherein R ² represents an alkyl group or a fluoroalkyl group having a carbon number of 1 to 10; a vinyl group; a phenyl group; or an alkyl group having a carbon number of 1 to 3 substituted with a methacryloxy group, and R ³ represents An alkyl group having 1 to 4 carbon atoms or an alkyl group having an ether bond, a represents 1 or 2; when R ² is plural, plural R ^{2 's} may be the same or different, and a plurality of OR ³ may be the same Can be different].

[5] The coating liquid according to [1] or [2], wherein the component (A-3) is a decane compound having an amine group and an alkoxy group represented by the following formula (3):

R ⁴ _b Si(OR ⁵ ) _4-b ......(3)

Wherein R ⁴ represents an alkyl group having a carbon number of 1 to 4; a vinyl group; a phenyl group; or an alkyl group selected from a methacryloxy group, an amine group (-NH ₂ group), an aminoalkyl group [-( CH ₂ ) _x -NH ₂ group (wherein x is an integer of 1 to 3)], and one or more groups of an alkylamino group [-NHR group (wherein R is an alkyl group having 1 to 3 carbon atoms)] The substituted carbon number is 1 to 3 alkyl groups, and at least one of R ⁴ represents an alkyl group having 1 to 3 carbon atoms substituted by an amine group or an aminoalkyl group or an alkylamine group. R ⁵ represents an alkyl group having a carbon number of 1 to 4, and b represents 1 or 2; when R ⁴ is plural, a plurality of R ⁴ may be the same or different, and a 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 decane compound having an epoxy group and an alkoxy group represented by the following formula (4):

R ⁶ _c Si(OR ⁷ ) _4-c ......(4)

Wherein R ⁶ represents an alkyl group having a carbon number of 1 to 4; a vinyl group; a phenyl group; or is selected from a methacryloxy group, a glycidoxy group, a 3,4-epoxycyclohexyl group. The carbon number substituted by one or more kinds of groups is 1 to 3 alkyl groups, and at least one of R ⁶ represents a carbon number of 1 to 3 substituted by a glycidoxy group or a 3,4-epoxycyclohexyl group. The alkyl group; R ⁷ represents an alkyl group having a carbon number of 1 to 4, and c represents 1 or 2; when R ⁶ is plural, a plurality of R ⁶ may be the same or different, and a plurality of OR ⁷ may be the same. Can be different].

[7] The coating liquid according to [1] or [2], wherein the component (A-5) is a blocked isocyanatodecane compound having an alkoxy group represented by the following formula (5):

R ⁸ _d Si(OR ⁹ ) _4-d ......(5)

Wherein R ⁸ represents an alkyl group having a carbon number of 1 to 4; a vinyl group; a phenyl group; or a carbon number substituted with one or more groups selected from the group consisting of a methacryloxy group and a blocked isocyanate group; It is an alkyl group of 1 to 3, and at least one of R ⁸ represents an alkyl group having 1 to 3 carbon atoms which is substituted with a blocked isocyanate group; R ⁹ represents an alkyl group having 1 to 4 carbon atoms, and d represents 1 Or 2; when R ⁸ is a plurality of cases, the plurality of R ⁸ may be the same or different, and the plurality of OR ⁹ may be the same or different].

[8] The coating liquid according to any one of [1] to [7], which is a hydrolyzed condensate to (A-1) component, (A-2) component, and (A-4) component ( B) The component (A-5) is added to the reaction product obtained by contacting the component (E) and reacted, and then the component (A-3) is further added and reacted.

[9] The coating liquid according to any one of [1] to [7], which is characterized by comprising (A-1) component, (A-2) component, (A-4) component and ( After the component (A-5) is added to the reaction product obtained by heating the mixture of the components B to (E) and reacted, the component (A-3) is further added and reacted.

[10] A cured film obtained by curing the coating liquid according to any one of the above [1] to [9].

[11] A resin laminate comprising: a substrate; and a cured film of [10] directly formed on the substrate.

[12] A resin laminate comprising: a substrate; a cured film of [10] formed on the substrate; and an inorganic layer formed on the cured film.

[13] A resin laminate comprising: a substrate; a cured film of [10] formed on the substrate; and a transparent conductive film formed on the cured film.

[14] A resin laminate comprising: a substrate, a cured film of [10] formed on the substrate, 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], wherein the substrate has irregularities.

[19] The resin laminate of any one of [11], [12], [17], [18], wherein the substrate has an elliptical cylindrical shape.

[20] The resin laminate according to any one of [11], [12], [17], wherein the substrate is cylindrical.

[21] The resin laminate according to any one of [11], wherein the surface of the substrate on which the cured film is not formed has a resin layer.

[22] The resin laminate according to any one of [11], [12], [14], wherein the thickness of the cured film is 0.5 to 6 μm.

[23] The resin laminate according to any one of [11], [12], wherein the substrate is a polyester resin, a polycarbonate resin or a polyolefin resin.

[24] A method for producing a cured film, comprising the step of heating and hardening the coating liquid according to any one of the above [1] to [9].

[25] A method for producing a resin layered body, comprising the steps of: applying a coating liquid according to any one of [1] to [9] to a substrate, and drying the coating liquid; The step of thermoforming the base material, and the step of curing the coating liquid to form a coating layer.

[26] The method for producing a resin laminate according to [25], further comprising the step of providing a resin layer on a surface of the resin laminate obtained by curing the coating liquid without a coating layer.

[27] A method of producing a resin laminate, comprising the step of forming a cured film obtained by curing the coating liquid according to any one of [1] to [9] above, and hardening the hardening film. A step of forming a transparent conductive film on the film.

[28] A method for producing a resin laminate, comprising the step of forming a cured film obtained by curing the coating liquid according to any one of the above [1] to [9] on a substrate, and the hardening The step of forming a photocatalyst layer on the film.

According to the present invention, it is possible to provide a coating liquid which forms a cured film which has good adhesion to a substrate or an inorganic hard material layer, a transparent conductive film and a photocatalyst layer, and which is excellent even without using a primer. Characteristics such as abrasion resistance, scratch resistance, flex resistance, weather resistance (UV absorption capacity), and durability (boiling resistance).

Moreover, according to the present invention, it is possible to provide a cured film having the above characteristics obtained by curing the coating liquid, and having a substrate or a layer between the inorganic hard material layer, the transparent conductive film, and the photocatalyst layer and the substrate. A resin laminate of the cured film, and a method for producing the cured film and the resin laminate.

First, the coating liquid of the present invention will be described.

[coating liquid]

The coating liquid of the present invention is characterized by comprising the following components (A) to (E).

((A) component)

The coating liquid of the present invention contains a hydrolysis-condensation product of five compounds of the following (A-1) to (A-5) as a hydrolysis-condensation product of the alkoxy group-containing decane compound of the component (A). The hydrolysis condensate may be a hydrolysis condensate of a single compound in (A-1) to (A-5), or may be a hydrolysis containing a mixture of any two or more of (A-1) to (A-5). Condensate.

In the present invention, the alkane compound having an alkoxy group means an alkoxydecane compound and/or a partial condensate thereof; and a partial condensate of an alkoxydecane compound means a part of an alkoxydecane compound. A polyalkoxydecane compound or a polyorganooxyoxydecane compound obtained by forming a siloxane chain (Si-O bond) in a molecule.

In addition, the hydrolysis-condensation product of the alkane compound having an alkoxy group means a state in which the alkoxy group-containing decane compound before the hydrolysis condensation is contained in addition to the hydrolysis-condensation product containing the alkoxy group-containing decane compound.

<(A-1) compound>

The compound (A-1) is a tetraalkoxydecane compound. Further, a partial condensate (polyalkoxydecane compound) bonded by a siloxane chain (Si-O bond) may also be used. These compounds may be used alone or in combination of two or more.

The tetraalkoxydecane compound and a partial condensate thereof can be represented by the following formula (1), and a compound represented by the following formula (6) is particularly preferable as the compound (A-1).

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; and a plurality of R ^{1 's} may be the same or different).

[Chemical 1]

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

In the above formulae (1) and (6), examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and various butyl groups; Examples of the OR ^{1 in} which R ¹ is an alkyl group having an ether bond and having 1 to 4 carbon atoms include, for example, 2-methoxyethoxy group, 3-methoxypropoxy group and the like.

The tetraalkoxydecane compound of the compound (A-1) may, for example, be tetramethoxynonane, tetraethoxydecane, tetra-n-propoxydecane, tetraisopropoxydecane or tetra-n-butoxydecane. , tetraisobutoxy decane, and the like.

Further, examples of the polyalkoxydecane compound include "M Silicate 51", "Silicate 40", and "Silicate 45" manufactured by Tama Chemical Industry Co., Ltd.; "Methyl citrate 51" manufactured by Colcoat Co., Ltd. "Methyl citrate 53A", "Ethyl citrate 40", "Ethyl citrate 48" and the like.

<(A-2) compound>

The compound (A-2) is an organoalkoxydecane compound containing no amine group, epoxy group or isocyanate group. Further, a partial condensate thereof can also be used. These compounds may be used alone or in combination of two or more.

The compound (A-2), the organoalkoxydecane compound and a partial condensate thereof are preferably a bifunctional alkoxydecane or a trifunctional alkoxydecane, and can be represented, for example, by the following formula (2), and is particularly suitable. It is a compound represented by the following general formula (7).

R ² _a Si(OR ³ ) _4-a ......(2)

Wherein R ² is an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group; a vinyl group; a phenyl group; or an alkyl group having 1 to 3 carbon atoms substituted by a methacryloxy group, and R ³ is carbon a number of 1 to 4 alkyl groups or an alkyl group having an ether bond, a is 1 or 2; when R ² is plural, plural R ^{2 's} may be the same or different, and a plurality of OR ³ may be the same or different ].

[Chemical 2]

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

In the above formulae (2) and (7), the alkyl group having 1 to 10 carbon atoms may be any of a linear chain and a branched chain, and examples thereof include methyl group, ethyl group, and n-propyl group. The group, the isopropyl group, the various butyl groups, various hexyl groups, various octyl groups, and various fluorenyl groups; and examples of the fluoroalkyl group include a trifluoroethyl group and a trifluoropropyl group. Further, examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a 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 above formula (1).

In the organoalkoxydecane compound represented by the formula (2), examples of the trifunctional alkoxydecane include methyltrimethoxydecane, methyltriethoxydecane, and methyltripropoxyl. Decane, methyl tributoxydecane, methyl-tris(2-methoxyethoxy)decane, ethyltrimethoxydecane, ethyltriethoxydecane, ethyltripropoxydecane, B Tris-butoxy decane, ethyl-tris(2-methoxyethoxy)decane, hexyltrimethoxydecane, hexyltriethoxydecane, hexyltripropoxydecane, hexyltributyloxydecane, Fluorine-based trimethoxy decane, decyl triethoxy decane, decyl tripropoxy decane, decyl tributoxy decane, fluorine having a fluorine atom introduced into a substituent, such as trifluoropropyltrimethoxy decane Alkyl (trialkoxy)decane, phenyltrimethoxydecane, phenyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, γ-methylpropenyloxypropyl Trimethoxy decane and the like. Further, examples thereof include methyldimethoxy(ethoxy)decane having two alkoxy groups, ethyldiethoxy(methoxy)decane, and the like.

Examples of the bifunctional alkoxydecane include dimethyldimethoxydecane, dimethyldiethoxydecane, bis(2-methoxyethoxy)dimethylnonane, and diethyldiethylamine. Oxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, and the like.

Specific examples of the polyorgano alkoxydecane compound include "MTMS-A" manufactured by Tama Chemical Industry Co., Ltd.; "SS-101" manufactured by Colcoat Co., Ltd.; Toray-Dow Corning "AZ-6101", "SR2402", "AY42-163" manufactured by the company.

<(A-3) compound>

The compound (A-3) is a decane compound having an amine group and an alkoxy group, and is an alkoxydecane compound containing no epoxy group or isocyanate group. Further, a partial condensate (polyorgano alkoxydecane compound containing an amine group) may also be used. These compounds may be used alone or in combination of two or more.

The organoalkoxydecane compound containing an amine group and a partial condensate thereof as the compound (A-3) can be represented, for example, by the following formula (3).

R ⁴ _b Si(OR ⁵ ) _4-b ......(3)

Wherein R ⁴ is an alkyl group having 1 to 4 carbon atoms; a vinyl group; a phenyl group; or an alkyl group selected from a methacryloxy group, an amine group (-NH ₂ group), an amino group [-(CH) ₂ ) an _x- NH ₂ group (wherein x is an integer of 1 to 3)]), and an alkylamino group [-NHR group (wherein R is an alkyl group having 1 to 3 carbon atoms) Substituting an alkyl group having 1 to 3 carbon atoms; at least one of R ⁴ is an alkyl group having 1 to 3 carbon atoms substituted by an amine group or an aminoalkyl group or an alkylamine group R ⁵ is an alkyl group having 1 to 4 carbon atoms, and b is 1 or 2; when R ⁴ is plural, plural R ^{4 's} may be the same or different, and a plurality of OR ⁵ may be the same or different.

In the above formula (3), an alkyl group having 1 to 3 carbon atoms and an alkyl group having 1 to 4 carbon atoms are as described in the above formula (1) or (2).

Specific examples of the organoalkoxydecane compound containing an amine group represented by the formula (3) include N-(2-aminoethyl)-3-aminopropylmethyldimethoxy group. Decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldiethoxydecane, N -(2-Aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-methylamine Propyltrimethoxydecane, N-methylaminopropyltriethoxydecane, and the like.

In addition, examples of the polyorgano alkoxydecane compound containing an amine group include "KBP-90" manufactured by Shin-Etsu Silicones Co., Ltd., and the like.

<(A-4) compound>

The compound (A-4) is a decane compound having an epoxy group and an alkoxy group, and is an alkoxydecane compound containing no amine group or isocyanate group. Further, a partial condensate (polyoxyalkoxydecane compound containing an epoxy group) may also be used. These compounds may be used alone or in combination of two or more.

As the compound (A-4), an epoxy group-containing organoalkoxydecane compound and a partial condensate thereof. For example, it can be 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 an alkyl group selected from the group consisting of a methacryloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group. One or more substituents are substituted with an alkyl group having 1 to 3 carbon atoms; at least one of R ⁶ is substituted by a glycidoxy group or a 3,4-epoxycyclohexyl group having a carbon number of 1 to 3 Alkyl; R ⁷ is an alkyl group having 1 to 4 carbon atoms, and c is 1 or 2; when R ⁶ is plural, a plurality of R ⁶ may be the same or different, and a plurality of OR ⁷ may be the same or different. ].

The alkyl group having 1 to 3 carbon atoms and the alkyl group having 1 to 4 carbon atoms in the above formula (4) is as described in the above formula (1) or (2).

Specific examples of the epoxy group-containing organoalkoxydecane compound represented by the formula (4) include 3-glycidoxypropylmethyldimethoxydecane and 3-epoxypropyl. Oxypropylmethyldiethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4-epoxy Ethylcyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, and the like.

<(A-5) compound>

The compound (A-5) is a blocked isocyanatodecane compound having an alkoxy group (generally, also referred to as a blocked isocyanate decane compound), and contains a blocked isocyanate group but does not contain Amino and epoxy alkoxydecane compounds. Further, a partial condensate (polyorgano alkoxy decane compound containing a blocked isocyanate group) may also be used. These compounds may be used alone or in combination of two or more.

Further, the term "blocked isocyanatodecane compound" means that the isocyanate group is protected from blocking by a blocking agent such as hydrazine, and is further blocked by heating to cause isocyanate. A base activated (regenerated) isocyanatodecane compound (generally, also known as an isocyanate decane compound).

The organoalkoxydecane compound containing a blocked isocyanate group and a partial condensate thereof as the compound (A-5) can be represented, for example, by the following 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 a carbon number substituted with one or more groups selected from the group consisting of a methacryloxy group and a blocked isocyanate group; The alkyl group of 1 to 3, at least one of R ⁸ is an alkyl group having 1 to 3 carbon atoms substituted by a blocked isocyanate group; R ⁹ is an alkyl group having 1 to 4 carbon atoms, and d is 1 or 2; When R ⁸ is a plurality of cases, the plurality of R ⁸ may be the same or different, and the plurality of OR ⁹ may be the same or different].

In the above formula (5), an alkyl group having 1 to 3 carbon atoms and an alkyl group having 1 to 4 carbon atoms are as described in the above formula (1) or (2).

Specific examples of the organoalkoxydecane compound having a blocked isocyanate group represented by the above formula (5) include 3-isocyanatopropyltrimethoxydecane and 3-isocyanato group. Propyltriethoxydecane, 3-isocyanatopropylmethyldimethoxydecane, 3-isocyanatopropylmethyldiethoxydecane, 3-isocyanatopropylethyl The isocyanate group in the compound such as diethoxydecane is protected by a blocking agent. Among these, as a preferable compound, 3-blocked isocyanatopropyl triethoxy decane is mentioned.

As the terminal blocking agent for the isocyanate group, an anthracene compound such as acetone oxime, 2-butanone oxime, cyclohexanone oxime or methyl isobutyl ketone oxime; an indoleamine such as ε-caprolactam; Alkylphenols such as phenol (cresol, nonylphenol, etc.); dialkylphenols such as 3,5-xylenol and di-tert-butylphenol; trialkylphenols such as trimethylphenol; Malonic acid diester such as diethyl diacetate; active methylene compound such as acetamidine acetone, ethyl acetate such as ethyl acetate; methanol such as methanol, ethanol or n-butanol; a hydroxyl group-containing ether such as a fiber or a butyl cellosolve; a hydroxyl group-containing ester such as ethyl lactate or amyl lactate; a mercaptan such as butyl mercaptan or hexyl mercaptan; acetanilide, acrylamide, and dimerization. Hydrazines such as decylamine; imidazoles such as imidazole and 2-ethylimidazole; pyrazoles such as 3,5-dimethylpyrazole; triazoles such as 1,2,4-triazole; Amines such as amines and phthalimides. Further, 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 contains organic polymer fine particles (hereinafter sometimes referred to as polymer ultraviolet absorbing resin fine particles) as the component (B), and the organic polymer fine particles contain a copolymer containing a monomer unit having an ultraviolet absorbing group.

The polymer ultraviolet ray absorbing resin fine particles are, for example, a skeleton having a function of exhibiting an ultraviolet absorbing agent in a side chain (benzophenone-based, benzotriazole-based, or tertiary) Acrylic monomer (hereinafter referred to as ultraviolet absorbing acrylic monomer) and other ethylenically unsaturated compounds (acrylic acid, methacrylic acid and derivatives thereof, styrene, vinyl acetate, etc.) Aggregated. The conventional ultraviolet absorber is generally a low molecular weight of 200 to 700. In contrast, the weight average molecular weight of the polymer ultraviolet absorbing resin particles is usually more than 10,000. The polymer ultraviolet ray absorbing resin particles are improved in compatibility with plastics, heat resistance, and the like, and the disadvantages of the low molecular weight ultraviolet ray absorbent which have existed from the prior art are improved, and the weather resistance can be imparted for a long period of time.

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

[Chemical 3]

[wherein, X represents a hydrogen atom or a chlorine atom, R ¹⁰ represents a hydrogen atom, a methyl group, or a tertiary alkyl group having a carbon number of 4 to 8, and R ¹¹ represents a linear or branched carbon number of 2~ 10 is an alkyl group, R ¹² represents a hydrogen atom or a methyl group, and p represents 0 or 1].

[Chemical 4]

Wherein R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents a substituted or unsubstituted linear or branched alkyl group having 2 to 10 carbon atoms, and R ¹⁵ represents a hydrogen atom or a hydroxyl group. R ¹⁶ represents a hydrogen atom, a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms.

Specific examples of the benzotriazole-based compound represented by the above formula (8) include, for example, 2-(2'-hydroxy-5'-(meth)acryloxyphenyl)-2H- Benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-(meth)acryloxymethylphenyl)-2H-benzotriazole, 2-[2' -hydroxy-5'-(2-(methyl)acryloxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tert-butyl-5'- (2-(Methyl)acryloxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2-[2'-hydroxy-3'-methyl-5'-(8-( Methyl)propenyloxyoctyl)phenyl]-2H-benzotriazole or the like.

Specific examples of the benzophenone-based compound represented by the above formula (9) include, for example, 2-hydroxy-4-(2-(methyl)propenyloxyethoxy)benzophenone. , 2-hydroxy-4-(4-(methyl)propenyloxybutoxy)benzophenone, 2,2'-dihydroxy-4-(2-(methyl)acryloxyethoxy ethoxylate Benzophenone, 2,4-dihydroxy-4'-(2-(methyl)propenyloxyethoxy)benzophenone, 2,2',4-trihydroxy-4'- (2-(Methyl)acryloxyethoxyethoxy)benzophenone, 2-hydroxy-4-(3-(methyl)propenyloxy-2-hydroxypropoxy)benzophenone, 2-hydroxy-4-(3-(methyl)propenyloxy-1-hydroxypropoxy)benzophenone or the like.

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 usually in terms of the ultraviolet absorbing ability, other physical properties, and economy of the cured film. 5~70% by mass, preferably about 10~60% by mass.

In the coating liquid of the present invention, the polymer ultraviolet absorbing resin fine particles used as the component (B) are averaged from the viewpoints of manufacturability, dispersibility in a coating liquid, coating properties of a coating liquid, and transparency of a cured film. The particle diameter is preferably in the range of 1 to 200 nm, more preferably in the range of 1 to 100 nm. Further, the average particle diameter of the polymer ultraviolet absorbing resin 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; as the dispersion medium, for example, water, methanol, ethanol, propanol, 1-methyl is preferably exemplified. a lower alcohol such as oxy-2-propanol; a cellosolve such as a 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. Further preferably, the dispersion medium is water. When the dispersion medium is water, it can be used in the hydrolysis and condensation reaction of a decane compound which is necessary for forming a matrix having Si-O bonds derived from the above (A) component, and is therefore preferable.

The method for producing the polymer ultraviolet absorbing resin fine particles used as the component (B) is not particularly limited, and a conventionally known method such as an emulsion polymerization method or a fine suspension polymerization method can be employed.

The emulsion polymerization method is a method of using a emulsifier comprising an aqueous dispersion medium, an anionic or nonionic surfactant, and a water-soluble polymerization initiator to form a UV-absorbing acrylic monomer as a monomer, and The mixture of the monomer-copolymerized ethylenically unsaturated monomers is emulsified into fine droplets, and polymerization is carried out in the surfactant microcap layer containing the above monomer mixture to obtain a dispersion of the polymer ultraviolet absorbing resin fine particles.

On the other hand, the fine suspension polymerization method is as follows: First, the above monomer mixture, an oil-soluble polymerization initiator, an emulsifier, and other additives as needed are added to an aqueous medium and premixed, and then homogenized by a homogenizer. The treatment is carried out to adjust the particle size of the oil droplets. Then, the homogenized solution is sent to a polymerization vessel to carry out a polymerization reaction, thereby obtaining a dispersion of the polymer ultraviolet absorbing resin fine particles.

The polymerization temperature in any of the above methods is about 30 to 80 °C.

Examples of the water-soluble polymerization initiator used for the emulsion polymerization include water-soluble peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide; and such initiators or cumene hydroperoxide. a hydroperoxide such as a third butyl hydroperoxide; a redox initiator combined with a reducing agent such as acidic sodium sulfite, ammonium sulfite or ascorbic acid; 2,2'-azobis(2-methylpropane)水溶性) a water-soluble azo compound such as a dihydrochloride salt.

On the other hand, examples of the oil-soluble polymerization initiator used for the fine suspension polymerization include diacyl peroxides, ketone peroxides, and peroxyesters. Oil-soluble organic peroxides such as peroxydicarbonate; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) Such as azo compounds and the like.

Specific examples of the polymer ultraviolet absorbing resin fine particles which can be used as the component (B) include a coating polymer ultraviolet absorbers ULS-700, ULS-1770, and ULS-383MA manufactured by One Society of Oils and Fats Co., Ltd. , ULS-1383MA, ULS-383MG, ULS-385MG, ULS-1383MG, ULS-1385MG, ULS-635MH, etc.; UV-absorbing resin coatings NCI-905-20EM and NCI-905 manufactured by Nikko Chemical Research Institute Co., Ltd. -20EMA (polymer ultraviolet absorber formed by copolymer of styrene monomer and benzotriazole monomer).

In the present invention, the polymer ultraviolet absorbing resin fine particles may be used singly or in combination of two or more kinds as the component (B).

((C) component)

The coating liquid of the present invention contains colloidal cerium oxide as the component (C).

The so-called colloidal cerium oxide used in the present invention also refers to colloidal cerium oxide or colloidal ceric acid. In water, it refers to a colloidal suspension of cerium oxide having a Si-OH group on the surface by hydration, and is formed by adding hydrochloric acid to an aqueous solution of sodium citrate. Recently, a new preparation method has been developed, which is dispersed in a non-aqueous solution, and a fine powder produced by a vapor phase method, and has a particle diameter of from several nm to several μm. The average particle diameter is preferably from about 1 to 200 nm. The composition of the particles is indefinite, and there is also a formation of a siloxane coupling (-Si-O-, -Si-O-Si-) and a high molecular weight. The surface of the particles is porous and generally negatively charged in water. Further, the above average particle diameter can be measured by a laser diffraction scattering method.

As a commercial item, the "Ultra High Purity Colloidal Antimony Oxide" Quartron PL series (product name: PL-1, PL-3, PL-7) manufactured by Fuso Chemical Industry Co., Ltd.; "Purified organosol", manufactured by Nissan Chemical Industries Co., Ltd. "colloidal cerium oxide (product name: Snowtex 20, Snowtex 30, Snowtex 40, Snowtex O, Snowtex O-40, Snowtex C, Snowtex N, Snowtex S, Snowtex 20L, Snowtex OL, etc.) and "organic cerium oxide sol (product name: methanol cerium oxide 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, PAM-ST Wait)".

In the present invention, the colloidal ceria may be used singly or in combination of two or more kinds as the component (C).

((D) component)

The coating liquid of the present invention contains a curing catalyst as the component (D).

The catalyst for hydrolyzing and condensing (curing) the decane compound (A-1) to (A-5) in the component (A), for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or sub Mineral acids such as nitric acid, perchloric acid, aminosulfonic acid; formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, citric acid, tartaric acid, succinic acid, maleic acid, glutamic acid, lactic acid, p-toluene Organic acids such as acids.

Further, examples thereof include lithium hydroxide, sodium hydroxide, potassium hydroxide, n-hexylamine, dimethylamine, tributylamine, diazabicycloundecene, ethanolamine, dimethylaniline formate, and benzoic acid. Tetraethylammonium salt, sodium acetate, potassium acetate, sodium propionate, sodium glutamate, potassium propionate, sodium formate, potassium formate, benzamidine trimethylammonium acetate, tetramethylammonium acetate, tin octylate, etc. Organometallic salts; tetraisopropyl titanate, tetrabutyl titanate, triisobutoxyaluminum, aluminum triisopropoxide, aluminum acetoacetate, Lewis acid such as SnCl ₄ , TiCl ₄ , ZnCl _{4 ,} and the like.

Among these hardening catalysts, even if the amount of the components (B) and (C) is increased, the dispersion can be increased, and the transparency of the obtained film can be improved. Therefore, an organic acid can be preferably used. In particular, an organic carboxylic acid can be used, of which acetic acid can be preferably used.

In the present invention, as the component (D), the curing catalyst may be used singly 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 in which the above-mentioned respective component particles are dispersed in a dispersion medium. The dispersion medium to be used in the present invention is not particularly limited as long as it can uniformly disperse and disperse the above-mentioned respective component particles. Examples of the water removal include alcohols, aromatic hydrocarbons, and ethers. An organic dispersion medium such as a ketone or an ester. In the organic dispersion medium, specific examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, n-hexanol, and n-octanol. , 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 glycol monomethyl ether acetate, diacetone alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, and the like.

Specific examples of the other dispersion medium include cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, and 1,4-diene. Alkane, 1,2-dimethoxyethane, xylene, dichloroethane, toluene, methyl acetate, ethyl acetate, ethoxyethyl acetate, and the like.

Among these dispersion media, water and alcohols are preferred from the viewpoint of the performance of the dispersion medium.

In the present invention, the dispersion medium may be used singly or in combination of two or more kinds as the component (E).

((F) component)

The coating liquid of the present invention is preferably a cerium oxide containing a decane compound treated (pretreated) as the component (F).

The term "pretreatment" as used herein refers to changing the surface state of cerium oxide by reacting an OH group of cerium oxide with a sterol group of a decane compound to form a covalent bond. The decane-treated cerium oxide does not generate agglomerates or precipitates even when mixed with a sol (for example, colloidal cerium oxide or the like) in which anionic particles are dispersed, and the decane-treated cerium oxide can be dispersed in both water and alcohol. in.

The cerium oxide to be used is not particularly limited, but is preferably in the form of particles and has an average particle diameter of from 1 to 200 nm. From the viewpoint of transparency, the average particle diameter is preferably from 1 to 100 nm. In addition, when the component (F) is added to the coating liquid of the present invention from the viewpoint of improving the dispersibility, it is preferably added after being dispersed in a dispersion medium such as water or alcohol.

The "dispersion" of the component (F) means a state in which the dispersed phase (solid) is suspended and suspended in a dispersion medium (liquid). Further, the term "sol" refers to a colloid in which a liquid is a dispersion medium and a solid is a dispersed particle, and is sometimes referred to as a colloidal solution. Further, the average particle diameter of the above cerium oxide microparticles can be measured by a laser diffraction scattering method.

The dispersion medium is based on the above component (E), and is preferably water or an alcohol. In particular, the alcohol is an alcohol produced from the decane compound described in the components (A-1) to (A-5) in the component (A), and the alcohol described in the component (E), and particularly preferably It is dispersed in a lower alcohol such as methanol, ethanol, n-propanol, isopropanol or 1-methoxy-2-propanol. Further, the water or the alcohol as the dispersion medium may be used singly or in combination of two or more.

The component (F) is a dispersion obtained by reacting a surface-charged cerium oxide sol with a decane compound to modify the surface thereof, and is preferably added to the coating of the present invention without causing aggregation, precipitation, or gelation. In the liquid. The decane compound also completely contains an alkoxydecane or a hydrolysis condensate thereof. Therefore, since the correct solid concentration in the dispersion state cannot be obtained, the total amount of the amount of the cerium oxide which is the raw material and the amount of the complete condensate of the alkoxysilane is divided by the total amount of the input amount. The percentage expressed as a percentage of the solid matter concentration.

<Method for producing (F) component>

The method for producing the cerium oxide fine particles of the raw material to be used is not particularly limited. However, since it is difficult to react with the decane compound in the powder state, it is suitably used as a dispersion liquid. The acid-stabilized cationic cerium oxide sol using an acidic dispersion stabilizer can be suitably used from the viewpoint of promoting the hydrolysis reaction of the decane compound, and it is preferable that the average particle diameter is 1 to 200 nm. From the viewpoint of imparting transparency, the average particle diameter is preferably from 1 to 100 nm. 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 can be used alone or in combination. Among them, the organic carboxylic acid has a coordination effect with respect to a metal, and therefore, from the viewpoint of further reacting cerium oxide with a decane compound, the dispersion stabilizer is preferably a cerium oxide sol which is a mineral acid, more preferably hydrochloric acid.

As a commercial item, "Needral H-15" by Domus Chemical Co., Ltd., etc. are mentioned.

The decane compound of the raw material to be used can be defined in the same manner as the above-mentioned component (A), and it is preferred to form a decyl alcohol bond with a sterol group of the component (A) and the component (C) when the cured film is produced. It is the above compound (A-1). These may be used alone or in combination.

Further, as the decane compound in the component (F), in addition to the above tetraalkoxy decane and its hydrolysis condensate or polyalkoxydecane, an organic alkoxysilane or a hydrolysis condensate thereof or a polyorganoalkane may be used in combination. Oxydecane is used. Specific examples of the organoalkoxydecane include those having one or more organic substituents in the component (A), and more preferably (A-2) to (A-5).

The surface treatment structure may be a completely two-layer structure, or may be a structure in which a respective alkoxydecane or a hydrolysis condensate thereof or a polyalkoxydecane is mixed.

Since the OH group of the surface layer of the cerium oxide particles has high reactivity, when only the organoalkoxysilane is used as it is in the surface treatment, aggregation and gelation of only cerium oxide are promoted due to the difference in the reaction rate. Therefore, as the surface treatment of cerium oxide in the component (F), it is preferred that, first, the cerium oxide surface layer is treated with a highly reactive tetraalkoxy decane or a hydrolysis condensate thereof, and secondly, organic The alkoxydecane or its hydrolysis condensate is reacted and treated.

Thus, a structure having a part of the organic substituent is formed in the decane-treated layer of the component (F), whereby the sterol group of the component (A) and the component (C) can be suitably formed into a decane when the cured film is produced. The key can further improve the softness of the cured film.

When the surface of the cationic cerium oxide sol is not subjected to surface treatment with a decane compound, aggregation with a component having an anionic property in the coating liquid of the present invention causes aggregation and gelation, which makes it difficult to add. Therefore, in order to stably disperse it in the coating liquid of the present invention, it is necessary to react the OH group of the surface layer portion of the cerium oxide microparticles of the cationic cerium oxide sol with the sterol group of the decane compound and perform surface treatment as described above.

In the component (F), the amount of the decane compound used for the surface treatment is considered in consideration of the mass of the metal oxide as the decane compound. The metal oxide of the decane compound is, for example, defined by the following formula.

R ¹ _m R ² _n SiO _((4-mn)/2)

(wherein R ¹ and R ² are each independently an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group; a vinyl group; a phenyl group; or an alkyl group selected from a methacryloxy group, an amine group, an amino group, or an alkyl group; The alkyl group having 1 to 3 carbon atoms substituted by one or more of the alkylamino group, the glycidoxy group, the 3,4-epoxycyclohexyl group and the blocked isocyanate group, and m and n are each independently Is 0, 1, or 2, and m+n is 0, 1, or 2).

The mass of the total mass of the metal oxide in the sol (the total amount of CeO ₂ and R ¹ _m R ² _n SiO _((4-mn)/2)) (R ¹ _m R ² _n SiO _((4- The ratio of _mn)/2) ) is preferably 50% by mass or less, more preferably 2% to 40% by mass. If it is less than this, cerium oxide itself may be aggregated or gelled, and if it is more than this, the decane compound itself may react and aggregate and gel.

The specific method for producing the component (F) can be carried out by the following method.

A first liquid mixture comprising a cationic cerium oxide sol and the above component (E) is prepared, followed by mixing one or more decane compound (A) components, thereby preparing a second liquid. After aging at room temperature, the mixture is further stirred at room temperature or under heating to prepare a component (F). The component (E) may be further added after the preparation of the component (F) for dilution, or may be added to another dispersion medium for displacement of the dispersion medium.

Further, in the case of using an alkoxysilane in combination, it is more preferable to employ the following method.

A first liquid mixture comprising a cationic cerium oxide sol and the following component (E) is prepared, followed by mixing with a tetraalkoxy decane (component (A)), whereby a second liquid is prepared. After aging at room temperature, the organoalkoxydecane (component (A)) was mixed to prepare a third mixed liquid. Further, the component (F) is prepared by stirring at room temperature or by heating. The component (E) may be further added after the preparation of the component (F) for dilution, or may be added to another dispersion medium for displacement of the dispersion medium.

The decane-treated cerium oxide sol added to the coating liquid of the present invention was visually confirmed to be agglomerated at the bottom of the container even after being left at room temperature for one week after the production. The sol standing time until the addition to the coating liquid of the present invention is not particularly limited.

In the present invention, the cerium oxide sol may be used singly or in combination of two or more kinds as the component (F).

((G) component)

The coating liquid of the present invention preferably contains a dispersion stabilizer as the component (G).

The dispersion stabilizer is used for stably dispersing the reactants of the decane compounds (A-1) to (A-5) and the components (B), (C) and (F) in the coating liquid to suppress aggregation and sedimentation. Gelling additive. In the coating liquid of the present invention, the fine particles of the components (B), (C) and (F) are preferably in a state of being dispersed without causing aggregation, sedimentation and gelation, and for example, a colloid which is stably suspended and suspended is preferably used. status.

In order to utilize the condensation reaction upon thermal hardening, it is preferred that the coating liquid of the present invention terminates the metal alkoxide to an OH body before coating. Therefore, it is desirable to maintain an acidic condition which promotes the hydrolysis reaction and suppresses the condensation reaction. Further, the carboxylic acid itself not only has an effect as an acid, but also has a coordination effect on the metal, and thus becomes an effective additive for stabilizing the alkoxide, so that an organic acid can be utilized, in which the organic carboxy can be better utilized. The acid is used as the component (G). 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. Further, since the coating liquid of the present invention forms a cured film by thermal curing, it is preferred to have a boiling point which does not remain in the cured film during thermal curing, and it is more preferable to use acetic acid.

In the present invention, the dispersion stabilizer may be used singly or in combination of two or more kinds as the component (G).

(optional addition)

In the coating liquid of the present invention, in addition to the above components (A) [(A-1) to (A-5)] to (E), various known additives to be used in the previous coating liquid may be appropriately contained as needed.

Examples of the additive component to be contained as necessary include a leveling agent and a flexibility imparting agent, and examples thereof include a lubricity imparting agent, an antioxidant, a blueing agent, an antistatic agent, and an antifoaming agent. (foaming inhibitor), light stabilizer, weather resistance imparting agent, coloring agent, fine particle dispersing agent (precipitation preventing agent), and particulate surface active modifier.

<leveling agent>

In the coating liquid of the present invention, a leveling agent may be added in order to improve the smoothness of the obtained cured film and the fluidity at the time of coating, and examples of the additives include a polyfluorene-based leveling agent and a fluorine-based leveling agent. An acrylic leveling agent, an ethylene leveling agent, and a leveling agent which combines a fluorine type and an acrylic type. All of the above leveling agents can act on the surface of the coating film to lower the surface tension. The above leveling agents have various characteristics and can be used as intended. When the surface tension is lowered, the polyfluorene-based leveling agent and the fluorine-based leveling agent are strong, and when the acrylic-based leveling agent and the vinyl-based leveling agent are recoated, it is less likely to cause poor wetting. advantageous.

As a specific example of the polyoxymethylene-based leveling agent, a copolymer of a polyalkylene oxide and a polydimethylsiloxane can be used. As a commercial product of a polyoxane-based leveling agent, FZ-2118, FZ-77, FZ-2161, etc. manufactured by Toray Dow Corning Co., Ltd.; KP321, KP323, KP324 manufactured by Shin-Etsu Chemical Co., Ltd. , KP326, KP340, KP341, etc.; TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452 ^, TSF4453, TSF4460, etc. manufactured by Momentive Performance Materials Japan Co., Ltd.; BYK-300, BYK-302, BYK manufactured by BYK Chemie Japan Co., Ltd. -306, BYK-307, BYK-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, BYK-3570 and other polyether modified eucalyptus oil (polyalkylene oxide modified eucalyptus oil).

Further, in the case where it is necessary to have heat resistance of 150 ° C or more, it is preferred to modify the polyester or the aralkyl modified sulfonate having a benzene ring. As a commercial item of the polyester modified eucalyptus oil, BYK-310, BYK-315, BYK-370, etc., manufactured by BYK Chemie Japan Co., Ltd.; and a commercial product of an aralkyl modified oyster oil having a benzene ring; For example, BYK-322, BYK-323, etc. manufactured by BYK Chemie Japan Co., Ltd. may be mentioned.

As the fluorine-based leveling agent, a copolymer of a polyalkylene oxide and a fluorocarbon compound or the like can be used.

As a commercial item of a fluorine-based leveling agent, the MEGAFAC series manufactured by DIC Corporation, and the FC series manufactured by Sumitomo 3M Co., Ltd., etc. are mentioned.

As a commercial item of the acrylic leveling agent, BYK-350, BYK-352, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380N, which are manufactured by BYK Chemie Japan Co., Ltd., BYK-381, BYK-392, etc., introduced with fluorine BYK-340.

By blending such a leveling agent, the appearance of the cured film can be improved, and even if it is formed into a film, it can be uniformly coated. The amount of the leveling agent used is preferably from 0.01 to 10% by mass, more preferably from 0.02 to 5% by mass, based on the total amount of the coating liquid.

The method of blending the leveling agent may be formulated in the preparation of the coating liquid, or may be formulated into the coating liquid immediately before the formation of the cured film, or may be formulated in two stages before the preparation of the coating liquid and the formation of the cured film.

<Flexibility imparting agent>

In order to increase the softness of the obtained cured film, the coating liquid of the present invention may contain a flexibility imparting agent as a stress relieving agent.

As the flexibility imparting agent, for example, a polyfluorene resin or the like can be used.

As a commercial product of a polyoxyxene resin, a Resin MK series manufactured by Wacker Co., Ltd., for example, Belsil PMS MK (a polymer comprising a repeating unit (unit T) of CH ₃ SiO _3/2 , and is also included to 1% by mass of (CH ₃ ) ₂ SiO _2/2 unit (unit D); and KR-242A manufactured by Shin-Etsu Chemical Co., Ltd. (containing 98% by mass of unit T and 2% by mass of dimethyl group) Unit D and containing Si-OH terminal group), KR-251 (containing 88% by mass of unit T and 12% by mass of dimethyl unit D and containing Si-OH terminal group), KR-220L (including formula CH) ₃ unit Y of SiO _3/2 and containing Si-OH (sterol) terminal group) and the like.

(Preparation of coating liquid containing (A) to (E) components) <Content of each component>

The content of each component in the coating liquid of the present invention can be appropriately selected, and the content of each component is preferably selected in the range shown below.

In addition to the dispersion medium of the component (E), the content of each component relative to the total amount of the components (A) [(A-1) to (A-5)] to (D) is expressed by mass%. Further, the components (B) and (C) which are preferably used in a dispersed state are calculated only by the respective solid materials, and those contained in the dispersion medium (E) component contained in each component are included.

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 from about 0.1 to 40% by mass, preferably from 1 to 30% by mass. The content of the component (A-3) is usually from about 0.1 to 30% by mass, preferably from 0.3 to 20% by mass. The content of the component (A-4) is usually from about 0.1 to 30% by mass, preferably from 0.3 to 20% by mass. The content of the component (A-5) is usually from about 0.1 to 50% by mass, preferably from 1 to 40% by mass.

The content of the component (B) is usually from about 0.1 to 50% by mass, preferably from 1 to 40% by mass. The content of the component (C) is usually from about 0.1 to 70% by mass, preferably from 1 to 50% by mass. The content of the component (D) is usually from 0.001 to 30% by mass, preferably from 0.001 to 20% by mass. The content of the (E) component is usually about 5 to 1000 parts by mass, preferably 20 to 800, based on the total mass parts of the components (A)[(A-1) to (A-5)] to (D). Parts by mass.

Further, there is no particular limitation on the molar ratio of the (A-3) component to the (A-5) component, and it is preferably 1:1 to 1:5, more preferably 1:2 to 1:4. . When the blending molar ratio of the component (A-3) to the component (A-5) is within the above range, the durability of the obtained cured film is further improved.

<Preparation method of coating liquid containing (A) to (E) components>

The coating liquid of the present invention is preferably a reaction product obtained by bringing a hydrolysis condensate of the component (A-1), the component (A-2) and the component (A-4) into contact with the components (B) to (E). After the component (A-5) is added and reacted, the component (A-3) is further added and reacted. Further, it is further preferred to use a reaction product obtained by heating a mixture comprising the components (A-1), (A-2), (A-4) and (B) to (E). After the component (A-5) is added and reacted, the component (A-3) is further added and reacted.

Specifically, it is preferred to carry out the following operations to prepare a coating liquid.

Preferably, first, a first mixed liquid containing at least (A-1), (A-2), (A-4), (B), (D), and (E) components is prepared, followed by mixing (C) The second mixed liquid was prepared as a component, and the component (A-5) was further mixed to prepare a third mixed liquid. Finally, the component (A-3) was mixed to prepare a coating liquid.

When the components are separated and prepared as described above, the solution stability of the solution (there is no gelation or the like) is improved, which is preferable.

In particular, when the amount of water in the solution is increased by the addition amount of the components (B) and (C), the effect is further exerted. For example, after mixing the components (A-1), (A-2), (A-4), (B), (D), and (E), the component (C) is added. Then, the component (A-5) is mixed, and finally, the component (A-3) is mixed. Further, after the coating liquid is prepared, the component (E) is further added, whereby the coating liquid can be diluted.

It is known that the solution storage stability of the mixed material of the coating liquid of the present invention easily affects the pH value of the solution (for example, "Application of the Sol-Gel Method in Nanotechnology/Editor: As a Flower" CMC publication). In the preparation of the coating liquid of the present invention, the acidic component is mixed as the component (D), and the alkaline component is mixed as the component (A-3) and the component (D). Therefore, the pH of the solution changes depending on the mixing order.

As the pH value of the solution, for example, the pH of the solution to be evaluated by a portable pH meter (manufactured by Hanna Co., Ltd., trade name: Checker-1) corrected by the pH standard solution is preferably the first mixed liquid and the first The second mixture was pH ≦6, so that the third mixture and the final mixture were pH ≦7. In particular, if the pH of the solution exceeds 8 when the third liquid mixture is mixed with the component (A-3), there is a possibility that the stability of the solution is lowered. It is preferred that the solution remains in an acidic state from the start of preparation of the coating liquid until the completion of the preparation. That is, it is preferred to prepare a coating liquid in the order in which such conditions are maintained.

Further, it is preferred that the first mixed liquid, the second mixed liquid, and the third mixed liquid are subjected to heat treatment after mixing the respective components. The temperature is preferably from 30 ° C to 130 ° C, more preferably from 50 ° C to 90 ° C, and the heat treatment time is preferably from 30 minutes to 24 hours, more preferably from 1 hour to 8 hours. The mixing and heating method is not particularly limited as long as it can be uniformly mixed and heated. By heating in this manner, the condensation reaction of the components (A-1), (A-2), (A-3), (A-4) and (A-5) in the solution proceeds, and the boiling resistance is promoted. Sex and other durability improvements. The reactions of the components (A-1), (A-2), (A-3), (A-4) and (A-5) can be analyzed by solution Si-NMR (nuclear magnetic resonance). This can be designed into a suitable structure. If it is less than 30 ° C or less than 30 minutes, the reaction is extremely slow, and when it exceeds 130 ° C or exceeds 24 hours, (A-1), (A-2), (A-3) The reaction of the components (A-4) and (A-5) is excessively carried out, and the solution is gelated or highly viscous, so that there is a possibility that the coating cannot be applied.

It is also preferred to carry out heat treatment of the final liquid (coating liquid) after mixing the component (A-3). When it is mixed at room temperature, it is easily affected by the stirring efficiency, and when the dispersion degree of the component (A-3) is low, the transparency of the cured film (the total light transmittance is lowered, the mist is lowered). Degree rises). The temperature is preferably from 30 ° C to 130 ° C, more preferably from 50 ° C to 90 ° C, and the time is preferably from 5 minutes to 10 hours, more preferably from 15 minutes to 6 hours. The mixing and heating method is not particularly limited as long as it can be uniformly mixed and heated. If it is less than 30 ° C or less than 5 minutes, the effect of heat treatment is insufficient, and if it exceeds 130 ° C or exceeds 10 hours, the solution gelatinizes or becomes highly viscous, so that it cannot be coated. Hey.

In the examples described later, the evaluation results of the cured film produced by using the coating liquid obtained after standing for one week are described, and the solution standing time until the production of the cured film is not particularly limited.

(Preparation of coating liquid containing (A) to (G) components) <Content of each component>

The content of each component in the coating liquid containing the components (A) to (G) of the present invention can be appropriately selected, and the content of each of the components (A) to (E) is in addition to the dispersion medium of the component (E). % indicates the content of each component relative to the total amount of (A) [(A-1) to (A-5)] to (G) components, and may contain (A) to (E) components. The same applies to the coating liquid.

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

<Preparation method of coating liquid containing (A) to (G) components>

The coating liquid is preferably obtained by bringing a hydrolysis condensate of the components (A-1), (A-2), (A-4) and (A-5) into contact with the components (B) to (G). The component (A-3) is added to the reaction product and reacted. Specifically, it is preferred to prepare a coating liquid by the following operation.

Preferably, first, a first mixed liquid containing at least (A-1), (A-2), (A-4), (B), and (D), (E), (G) components is prepared. Then, the components (C) and (F) were mixed to prepare a second mixed liquid, and the components (A-5) were further mixed to prepare a third mixed liquid. Finally, the component (A-3) was mixed to prepare a coating liquid.

When the components are separated and prepared as described above, the solution stability of the solution (there is no gelation or the like) is improved, which is preferable. This effect is further exerted especially when the amount of water in the solution is increased due to an increase in the amount of the components (B), (C) and (F).

For example, after mixing the components (A-1), (A-2), (A-4), (B), and (D), (E), and (G), add (C) and (F). ingredient. Then, the component (A-5) is mixed, and finally, the component (A-3) is mixed.

Further, the component (E) can be diluted by further adding a coating liquid after the preparation of the coating liquid.

Further, as a further preferred method for preparing a coating liquid, the hydrolysis condensate of the components (A-1), (A-2), and (A-4) and (B), (C), (D), and (E) can be used. (F) and (A-5) are added to the reaction product obtained by contacting the component (G), and reacted, and (A-3) component is added to the obtained reaction product, and reacted to prepare a reaction product. Coating solution.

Specifically, the mixture comprising the components (A-1), (A-2), (A-4), (B), (C), (D), (E), and (G) is heated. The component (F) and (A-5) are added to the obtained reaction product and heated, and then the component (A-3) is added to the obtained reaction product and heated to obtain a coating liquid. By adopting 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 hydrolysis condensate of the components (A-1), (A-2), (A-4) and (A-5) and (B), (C), (D), (E) and The component (F) is added to the reaction product obtained by contacting the components with G), and the component (A-3) is added to the obtained reaction product to carry out a reaction, whereby a coating liquid can also be prepared.

Specifically, for example, (A-1), (A-2), (A-4), (A-5), (B), (C), (D), (E), and (G) are included. The component (F) is added to the reaction product obtained by heating the mixture of the components and heated, and then the component (A-3) is added to the obtained reaction product and heated, whereby a coating liquid is obtained. By adopting 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, it is also possible to add (A- to the reaction product obtained by bringing the hydrolysis condensate of the components (A-1), (A-2) and (A-4) into contact with the components (B) to (G). 5) The component is reacted, and the component (A-3) is added to the obtained reaction product and reacted to prepare a coating liquid.

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 (A-5). The component is heated and then the component (A-3) is added to the obtained reaction product and heated to obtain a coating liquid. By adopting 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 solution storage stability of the mixed material of the coating liquid of the present invention easily affects the pH value of the solution (for example, "Application of the Sol-Gel Method in Nanotechnology/Editor: As a Flower" CMC publication). In the preparation of the coating liquid of the present invention, since the acidic component is mixed as the components (D) and (G), and the alkaline component is mixed as the components (A-3) and (D), the pH of the solution varies depending on the mixing order. Variety.

As the pH value of the solution, for example, the pH of the solution to be evaluated by a portable pH meter (manufactured by Hanna Co., Ltd., trade name: Checker-1) corrected by the pH standard solution is preferably the first mixed liquid and the first The second mixture was pH ≦6, so that the third mixture and the final mixture were pH ≦7. In particular, if the pH of the solution exceeds 8 when the third liquid mixture is mixed with the component (A-3), there is a possibility that the stability of the solution is lowered. It is preferred that the solution remains in an acidic state from the start of preparation of the coating liquid until the completion of the preparation. That is, it is preferred to prepare a coating liquid in the order of maintaining the above conditions.

Further, it is preferred that the first mixed liquid, the second mixed liquid, and the third mixed liquid are subjected to heat treatment after mixing the respective components. The temperature is preferably from 30 ° C to 130 ° C, more preferably from 50 ° C to 90 ° C, and the heat treatment time is preferably from 30 minutes to 24 hours, more preferably from 1 hour to 8 hours. The mixing and heating method is not particularly limited as long as it can be uniformly mixed and heated. By heating in this manner, the condensation reaction of the components (A-1), (A-2), (A-3), (A-4), and (A-5) in the solution proceeds, and is durable. Sex (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, whereby a suitable structure can be designed. . If it is less than 30 ° C or less than 30 minutes, the reaction is extremely slow, and when it exceeds 130 ° C or exceeds 24 hours, (A-1), (A-2), (A-3) The reaction of the components (A-4) and (A-5) is excessively carried out, and the solution is gelated or highly viscous, so that the coating cannot be applied.

Further, it is also preferred that the final liquid (coating liquid) after mixing the component (A-3) is subjected to heat treatment. When it is mixed at room temperature, it is easily affected by the stirring efficiency, and when the degree of dispersion of the component (A-3) is low, the transparency of the cured film is lowered (the total light transmittance is lowered, After the haze rises). The temperature is preferably from 30 ° C to 130 ° C, more preferably from 50 ° C to 90 ° C, and the time is preferably from 5 minutes to 10 hours, more preferably from 15 minutes to 6 hours. The mixing and heating method is not particularly limited as long as it can be uniformly mixed and heated. If it is less than 30 ° C or less than 5 minutes, the effect of heat treatment is insufficient, and if it exceeds 130 ° C or exceeds 10 hours, the solution gelatinizes or becomes highly viscous, so that it cannot be coated. Hey.

In the following examples, the evaluation results of the cured film produced by using the coating liquid obtained after standing for one week are described, and the solution standing time until the production of the cured film is not particularly limited.

Further, since the component (F) used in the present invention is acid-stable, when it is mixed with another dispersion, in order to prevent aggregation, precipitation, and gelation during mixing, it is more preferable to be in the same acidic sol. Mix. For example, when the sol of the alkali-stable anionic fine particles is directly mixed with the component (F), the pH range in which the dispersion can be stably dispersed is removed, and there is a possibility that the dispersion cannot be maintained.

(Use of coating liquid)

The coating liquid of the present invention is excellent in transparency, resin adhesion, weather resistance, abrasion resistance, and scratch resistance, and can be used as a coating material for various transparent organic members. Specifically, it can be used as a resin window, a resin window such as a building, a large-area transparent member such as a road soundproof wall or an arcade, a measuring instrument such as an instrument panel, a resin window of a building, a transparent plastic part, a spectacle lens, A face coating material or a primer material for transparent organic members such as goggles, transfer film, and plastic greenhouse.

Further, since the transparency is very high, coloring is also easy, and compatibility with various coloring pigments is excellent. Therefore, it can be used as a raw material for various coating materials or as a primer material before coating. For example, it can be applied to interior and exterior decoration of automobiles, industrial machinery, steel furniture, interior and exterior decoration of buildings, home appliances, plastic products, and the like. Further, since the coating liquid of the present invention is sufficiently adhered to the metal and has high acid resistance, it is also resistant to acid rain which has recently been regarded as a problem. Therefore, it is particularly suitable for a member for outdoor use such as a vehicle body or an aluminum wheel. As a very similar application to paints, it can be used in various inks because of its high colorability and compatibility with pigments.

Moreover, the coating liquid of the present invention can be applied to precision members used in the field of electrical and electronic, optical, and the like by utilizing high transparency, high adhesion, excellent abrasion resistance, and scratch resistance. For example, in various displays such as a plasma display, a liquid crystal display, and an organic EL (electroluminescence) display, various anti-reflection films, polarizing films, gas barrier films, retardation films, conductive films, and the like must be used. A film which is one of its functions can also be used as a member of these. In addition, hard coating materials for optical disk substrates, coating materials for optical fibers, touch panels, and coating materials for solar cell panels are also listed as applications utilizing high transparency, high adhesion, excellent abrasion resistance, and scratch resistance. . Various protective films are used for color filters, hologram elements, CCD (charge coupled device) cameras, etc., and such protective films are required not only to have transparency, abrasion resistance, scratch resistance, and adhesion. Moreover, consideration of manufacturing issues also requires a certain degree of low viscosity. The coating liquid of the present invention can be controlled to a desired viscosity by composition adjustment, and thus can also be used as the above protective film. Further, the coating liquid of the present invention is a material which not only has a hard coating property but also can be bent and deformed, and can also be used for a flexible display which has recently been studied.

Further, the coating liquid of the present invention can also transmit electromagnetic waves in the near-infrared region well. Therefore, it can also be applied to a radio wave transmitting and receiving antenna, an RFID (Radio Frequency Identification) data carrier, a coating material such as a vehicle radar device, and the like.

Examples of other uses include coating agents for various transparent decorations, various skin materials (car seats, interior doors for automobiles, sofas, furniture, etc.), sliding parts (brake pads, etc.), and bundles of fibers. Agent, gas barrier coating agent, and the like.

Hereinafter, the cured film of the present invention will be described.

[hardened 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 usual method.

Specifically, a known method such as spraying, dipping, shower coating, bar coating, or roll coating is used for the substrate of the resin molded article (the injection molded article, the film, or the sheet) which is a target of the cured film. The coating liquid is applied to form a coating film.

The thickness of the coating film depends on the form in which the formed cured film is finally used.

In the first aspect, as the thickness of the coating film, the thickness of the cured film is preferably 0.5 to 6 μm, more preferably 0.5 to 3 μm. Thereafter, it is heated and hardened under appropriate curing conditions, usually at room temperature to 190 ° C, preferably 80 to 140 ° C for 10 minutes to 24 hours, preferably 30 minutes to 3 hours, thereby obtaining the desired Hardened film.

In the second aspect, as the thickness of the coating film, the thickness of the cured film is preferably from 1 to 50 μm, more preferably from 2 to 20 μm. Thereafter, the hardening is carried out under suitable curing conditions, usually at 80 to 190 ° C, preferably at 100 to 140 ° C for 10 minutes to 24 hours, preferably 30 minutes to 3 hours, thereby obtaining the desired hardening. membrane.

The cured film obtained from the coating liquid containing the components (A) to (E) of the present invention has organic polymer fine particles (component (B)) and colloidal cerium oxide (component (C)) dispersed in the film.

The dispersed state is preferably an island structure of an inorganic organic mixture. The particle size of the organic polymer fine particles and the colloidal ceria which are equivalent to the island structure island is preferably 200 nm or less, more preferably 100 nm or less, and is uniformly dispersed without being aggregated.

The total light transmittance of the cured film of the present invention is preferably 80% or more, more preferably 85% or more, and the haze value is preferably 10% or less, more preferably 5% or less. Such a cured film has high transparency.

Further, the matrix having Si-O bonds dispersed by the organic polymer fine particles (component (B)) and the colloidal cerium oxide (component (C)) are derived from (A-1), (A-2), (A- 3), (A-4) and (A-5) components.

Further, the present invention provides a method for producing a cured film, which comprises the step of heating and hardening the above-described coating liquid of the present invention.

Further, the cured film obtained by the coating liquid containing the components (A) to (G) of the present invention has organic polymer fine particles (component (B)), colloidal cerium oxide (component (C)), and oxide dispersed in the film.铈 particles ((F) component).

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 is excellent in ultraviolet resistance and has high transparency.

Further, a matrix having Si-O bonds dispersed by organic polymer fine particles (component (B)), colloidal cerium oxide (component (C)), and cerium oxide particles (component (F)) is derived from each component (A). .

Further, the present invention provides a method for producing a cured film, which comprises the step of heating and hardening the above-described coating liquid of the present invention.

Hereinafter, the resin laminate of the present invention will be described.

[resin laminate]

The resin laminate includes a substrate and a resin layer formed on the substrate.

The resin layer formed on the substrate may be one layer or two or more layers.

Hereinafter, the resin laminate of the present invention will be described in detail.

The first resin laminate system of the present invention has the laminate of the above-described cured film of the present invention on a substrate or between an inorganic layer (inorganic hard layer) and a substrate. Moreover, the second resin layered system of the present invention has a substrate, a cured film of the present invention formed on the substrate, and a laminate of a transparent conductive film formed on the cured film. Further, the third resin layered system of the present invention has a substrate, a cured film of the present invention formed on the substrate, and a laminate of photocatalyst layers formed on the cured film. Hereinafter, the first to third resin laminates are collectively referred to as the resin laminate of the present invention.

The method of forming the above-mentioned cured film by using the coating liquid of the present invention is as shown in the above description of the cured film of the present invention. The resin laminate of the present invention has excellent abrasion resistance, scratch resistance, flex resistance and boiling resistance, and its use is as shown in the application description of the coating liquid of the present invention described above.

The resin laminate of the present invention is not particularly limited as long as it has the above configuration. For example, it can be used for: windshields for two-wheeled vehicles, tricycles, windows for automobiles, rail vehicles, construction machinery vehicles, roofs for construction machinery vehicles, components for interior decoration of automobiles, components for exterior decoration of automobiles, components for motorcycles, trucks The outer cover of the cargo box, the internal and external decorative components of various vehicles such as electric cars, airplanes, ships, etc.; household appliances such as audiovisual equipment, washing machines, rice cookers, electric cookers, IH (Induction Heating) cooking stoves, Components such as furniture, mobile phones, notebook computers, remote control devices, etc.; exterior materials for furniture, building materials, window shades for windows, buildings, etc., interiors for walls, ceilings, floors, etc. Decorative exteriors, siding and other exterior walls, fences, roofs, door leaves, gables and other decorative exteriors, window frames, door leaves, handrails, sills, sills and other furniture decorative materials, downlights, street lights, etc. Lighting parts, plasma, liquid crystal, organic EL, etc., solar cells, anti-reflection film; optical lens, optical disk, mirror Glasses for correcting glasses, sunglasses, sports goggles, safety glasses, etc., optical components such as window glass; containers for bottles, cosmetic containers, lotions, bath soaps, hand soaps, confections, snacks, beverages, etc. Containers, small boxes, and other packaging containers and packaging materials; in addition, they can be used for: Japanese-style pinballs and other components, suitcases, etc., toilet seats, table mats, clocks, whiteboards, protective shields, and miscellaneous goods.

Examples of the automotive interior decorative member include an instrument panel, a console box, a meter cover, an instrument panel, an indicator panel, a door trim, a door lock ring, a steering wheel, a window lift switch seat, a center instrument cluster, and a control panel. , shift lever sleeves, switches, ashtrays, etc.

Examples of the automobile exterior decorative member include a weatherproof lining, a bumper, a bumper guard, a side fender, a body panel, a door, a spoiler, a hood, a body guard, and a trunk lid. , front grille, support base, wheel cover, center pillar, rear view mirror, center decoration, side trim strips, door trim strips, window trim strips, etc., windows, headlights, taillights, lamp mirrors, door visors, Windshield parts, etc.

Moreover, examples of the member for the motorcycle include a casing, a fender, a fuel tank cap, a tank lid, and the like.

Examples of the household appliances, furniture, and the like such as the above-described audio-visual equipment, washing machine, rice cooker, electric cooker, and IH cooking oven include a front panel, a control panel, a touch panel, a membrane switch panel, a button, a logo, a surface decorative material, and the like. .

Examples of the above-mentioned building materials include a road-transparent sound-absorbing panel, a soundproof panel around a railway and a factory, an arcade, a windproof panel, a snow shelter, a carport, a bicycle parking lot, a bus stop, a sunroom, a veranda, and the like. Lighting materials such as entrances or hemispherical roofs, windows for buildings, plastic greenhouses, etc.

Examples of the components of the mobile phone, the notebook computer, and the remote control device include a casing, a display window, a keypad, a button, and the like.

(substrate)

As the substrate, at least one of resin, metal, wood, rubber, concrete, stone, ceramic, leather, paper, cloth, and fiber may be used, but a resin substrate (resin substrate) is preferably used. .

Examples of the substrate include a resin, a film, a sheet, and the like. The film or sheet is produced by a known molding method such as an extrusion molding method, an aeration method, or a solution casting method, and the like may be extended in a uniaxial and/or biaxial direction as needed. The type of the resin in the substrate is not particularly limited, and can be appropriately selected from various resins depending on the use of the obtained resin laminate.

Further, the substrate of the present invention may have irregularities and may be cylindrical, elliptical cylindrical, prismatic or the like regardless of the shape of the substrate.

Further, the resin laminate of the present invention may have a space inside it, and when it has an internal space, another resin layer may be laminated on the inner wall portion.

Therefore, the shape of the substrate of the present invention is not particularly limited, and the resin laminate of the present invention comprises a resin laminate obtained by insert molding or insert molding as described below.

In the present invention, examples of the resin that can be used for the substrate include polyethylene, polypropylene, and a cycloolefin resin (for example, "Arton" manufactured by JSR Co., Ltd., and "Zeonor" manufactured by Zeon Co., Ltd., Japan. , "Zeonex"), polyolefin resin such as polymethylpentene; polyester resin such as polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate; a cellulose resin such as cellulose acetate, cellulose triacetate or cellulose acetate butyrate; a styrene resin such as polystyrene, aligned polystyrene or acrylonitrile-butadiene-styrene resin (ABS resin); a quinone imine resin such as polyimine, polyether sulfimine or polyamidoximine; a melamine resin such as nylon; a ketone resin such as polyether ketone or polyether ether ketone; polyfluorene or polyether Anthraquinone resin; vinyl chloride resin such as polyvinyl chloride or polyvinylidene chloride; acrylic resin such as polymethyl methacrylate; polycarbonate resin, polyphenylene sulfide, polyacetal, modified polyphenylene Ether, polyvinyl alcohol, epoxy resin, fluororesin, etc.; Bonding together a plurality of kinds of polymer alloys polymer blends. Further, it may be a laminated structure in which a plurality of layers of the above resin are laminated. Among the above resins, preferred are polyester resins, polyolefin resins, and polycarbonate resins.

The base material which uses these resins as a raw material may be either transparent or translucent, and may be a coloring or an uncolored one, and may be appropriately selected according to the use. When it is used for optical use, it is preferred that it is excellent in transparency and is not colored. Among the above resins, polycarbonates excellent in transparency, mechanical properties, heat resistance and the like are particularly preferable.

The thickness of the substrate is not particularly limited and may be appropriately selected depending on the case, 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 to a substrate, and in order to further improve the adhesion, it is necessary to form at least a side of the substrate with a cured film by an oxidation method, a roughening method, or the like. The surface is surface treated. Examples of the oxidation method include a plasma treatment such as a corona discharge treatment, a low pressure plasma method, or an atmospheric piezoelectric slurry method, a chromic acid treatment (wet type), a flame treatment, a hot air treatment, an ozone ‧ an ultraviolet irradiation treatment, and the like. The electron beam treatment, the ITRO treatment, and the like, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatment methods can be appropriately selected depending on the kind of the substrate, and in general, in terms of hardening and workability, a corona discharge treatment method is preferably used. Further, the surface treatment or the undercoat layer may be provided by using a decane coupling agent.

(inorganic hard layer)

The inorganic hard material layer in the first resin laminate may be selected depending on the function to be imparted, and is not particularly limited. For example, when it is desired to impart abrasion resistance to the inorganic hard layer, the inorganic hard layer is preferably a SiO _x (1.8≦x≦2) film, a SiN _y (1.2≦y≦4/3) film or Amorphous carbon film.

The above SiO _x (1.8≦x≦2) film and SiN _y (1.2≦y≦4/3) film are formed by film formation by, for example, the following chemical vapor deposition method or physical vapor deposition method. In terms of metrology, the response was not completed. Therefore, a defect portion in which an oxygen atom or a nitrogen atom is not introduced can be formed in the inorganic hard material layer, and x and y have a range in the SiO _x and SiN _y films.

Further, a composite in which cerium oxide and cerium nitride which are prepared by simultaneously introducing oxygen and nitrogen are also suitable.

Further, the hardness of the inorganic hard layer may be such that the increase in haze is less than 10% in the evaluation using the TABER abrasion tester as shown in the examples. Alternatively, it may be about 500 HV or more in terms of micro Vickers hardness.

The thickness of the inorganic hard layer is, for example, preferably 1 μm or more, more preferably 1 to 8 μm. Further, in the method for producing an inorganic hard material layer described below, it is preferred that the inorganic hard material layer is directly laminated on the cured film.

The inorganic hard 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 vapor deposition method, and a sputtering method.

The inorganic hard material layer formed by the thin film formation technique carried out under vacuum as described above usually has a property of being in close contact with the inorganic component but not adhering to the organic component. In the case of the resin laminate of the present invention, since the cured film has an inorganic ‧ organic mixed structure in which the organic fine particles are encapsulated in the Si—O matrix, the adhesion between the inorganic hard layer and the cured film is good.

As a specific example of laminating an inorganic hard material layer by a CVD method, a case where SiO _x (1.8 ≦ x ≦ 2) is formed on a cured film by a plasma CVD method will be described.

The plasma CVD method refers to a method in which a raw material gas is introduced into a plasma state having a high energy density to be decomposed, and a target material is coated on a substrate by a chemical reaction. In the present invention, a laminate including a substrate and a cured film is placed in a plasma CVD apparatus, and after the inside of the apparatus is vacuumed, SiO _x (1.8 ≦ x ≦ 2) is introduced while adding argon gas to the plasma CVD apparatus. When the gas flow rate of each of the membranes becomes stable, electric power is applied to generate plasma, and a SiO _x (1.8 ≦ x ≦ 2) film is formed on the cured film.

An inorganic layer is hard when SiO _x (1.8 ≦ x ≦ 2) the case of film, forming _{SiO x (1.8 ≦ x ≦ 2} ) of the film material, for example silicon raw material gas and oxygen gas.

The ruthenium material gas which forms the SiO _x (1.8 ≦ x ≦ 2) film is preferably a decane gas or an organic ruthenium compound gas.

Examples of the decane gas to be suitably used include SiH ₄ gas, Si ₂ H ₆ gas, and Si ₃ H ₈ gas.

The organic ruthenium compound is preferably selected from those having a carbon-containing group bonded to the ruthenium. Specific examples of the organic ruthenium compound which is suitably used include tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, ethyl trimethoxy decane, tetramethyl dioxane, and dimethyl. Oxy dimethyl decane, diethoxy dimethyl decane, methyl triethoxy decane, octamethylcyclotetraoxane, and the like.

These organic hydrazine compounds may be used alone or in combination of two or more.

In the case where the raw material gas of the SiO _x (1.8 ≦ x ≦ 2) film is decane gas, N ₂ O gas is exemplified as the oxygen source gas which is suitably used.

Further, in the case where the raw material gas of the SiO _x (1.8 ≦ x ≦ 2) film is an organic ruthenium compound gas, examples of the oxygen source gas which is suitably used include N ₂ O gas, O ₂ gas, and O ₃ gas.

The flow rate of the above-mentioned ruthenium raw material gas and oxygen raw material gas is, for example, 1 to 500 cm ³ /min, preferably 1 to 300 cm ³ /min. Further, the flow rate of argon gas, for example, 20 ~ 400cm ³ / min, preferably 100 ~ 300cm ³ / min.

The plasma CVD apparatus to be used is not particularly limited as long as it is generally used, and for example, a parallel plate electrode type, a capacitive coupling type, an inductive coupling type or the like can be used. The pressure in the plasma CVD apparatus is, for example, preferably about 1.33 to 133 Pa, and particularly preferably about 2.7 Pa.

The frequency of the power source used in power application can be widely used in the range of sound waves to microwaves.

When the SiO _x (1.8≦x≦2) film is formed on the cured film by the above plasma CVD method, an organic germanium compound is used as the germanium source gas and the organic germanium compound is liquid or solid at normal temperature, and organic is added. The container of the hydrazine compound is heated as a whole and used for gasification.

In the above case, the flow rate of organic silicon compound gas and a material gas of oxygen, for example, controlled to 1 ~ 10cm ³ / min, and the argon flow is controlled, for example, 20 ~ 400cm ³ / minute introduced with the plasma CVD apparatus (direct Gasification introduction method).

Further, in addition to the above-described direct gasification introduction method, when the organic ruthenium compound is a liquid, argon gas may be used as a carrier gas, for example, argon gas may be introduced into the organic ruthenium compound at a flow rate of 20 to 400 cm ³ /min. In the temperature-controlled container, the organic ruthenium compound is bubbled, and the organic ruthenium compound vapor is introduced into the plasma CVD apparatus together with argon gas (foaming introduction method using a carrier gas).

In the method for producing an inorganic hard material layer, when the inorganic hard material layer is a SiN _y (1.2 ≦ y ≦ 4/3) film, a material gas of a SiN _y (1.2 ≦ y ≦ 4/3) film is formed, for example. It is a raw material gas and a nitrogen raw material gas.

Examples of the raw material gas which is suitably used include a decane gas such as SiH ₄ gas, Si ₂ H ₆ gas, or Si ₃ H ₈ gas.

Further, examples of the nitrogen source gas which is suitably used include N ₂ gas and NH ₃ gas.

In the method of producing the inorganic hard material layer, when the inorganic hard material layer is an amorphous carbon film, a hydrocarbon gas is preferably used as a material gas for forming the amorphous carbon film.

Further, when the concentration of the hydrocarbon gas is high, H ₂ gas may be simultaneously introduced for dilution.

In the above-described method for producing an inorganic hard material layer by the CVD method, a material gas is used as a raw material of the inorganic hard material layer, but the invention is not limited thereto. For example, the vapor deposition material of the inorganic hard material layer described below may be vaporized and used.

As a specific example of laminating an inorganic hard material layer by the PVD method, a case where an inorganic hard material layer is laminated by ion plating will be described.

The ion plating method refers to introducing a reactive gas or the like into a vacuum vapor deposition device, and generating a gas plasma in the device by various methods to ionize and accelerate one of the generated vapor deposition particles (atoms and molecules). A method in which a substrate placed in a vacuum is irradiated with vapor-deposited particles and ions thereof to form a thin film of a vapor deposition material on a substrate. That is, the so-called ion plating method refers to a composite technology of vacuum evaporation technology and plasma technology.

The above ion plating method is disclosed, for example, in Japanese Laid-Open Patent Publication No. SHO 58-29835.

In the present invention, the laminate of the substrate and the cured film and the vapor deposition material of the inorganic hard layer are disposed at predetermined positions in the vacuum vapor deposition apparatus, and an inert gas such as argon gas or helium gas is generated to generate plasma. And a reactive gas introduction device such as O ₂ , N ₂ , acetylene or air, if necessary, applies a high-frequency voltage in the vicinity of the vapor deposition material to plasma the vapor deposition material, thereby laminating the inorganic hard material on the cured film. on.

As a vapor deposition material of the inorganic hard material layer, when the inorganic hard material layer is a SiO _x (1.8 ≦ x ≦ 2) film, cerium oxide or the like is exemplified, and in the inorganic hard material layer, SiN _y (1.2 ≦ y ≦ 4 / 3) In the case of a film, a tantalum nitride or the like may be mentioned, and in the case where the inorganic hard material layer is an amorphous carbon film, DLC (diamond-like carbon) or the like may be mentioned.

The material for vapor deposition of the inorganic hard material layer may be a material which is to be formed into an inorganic hard material layer.

Further, the vapor deposition material of the inorganic hard material layer in the ion plating method is not limited to a solid. For example, in the case of a raw material which is difficult to evaporate the vapor deposition material, the raw material gas (the raw material gas and the oxygen source gas) of the inorganic hard material layer may be introduced into a vacuum vapor deposition apparatus to carry out reactive vapor deposition to laminate an inorganic hard material. Layer of matter.

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 a high-frequency voltage is not particularly limited as long as it can perform high-frequency discharge. The high frequency voltage is, for example, about 0.5 kV to 8.0 kV.

In the above ion plating method, in order to carry out vapor deposition on the surface layer of the cured film in high-frequency discharge, heating methods such as resistance heating, electron beam heating, high-frequency induction heating, and laser beam heating may be employed, and evaporation may be performed as needed. The raw material evaporates.

The method of laminating the inorganic hard layer using the PVD method is not limited to the ion plating method. As described above, the inorganic hard material layer can be laminated by a vacuum deposition method, a sputtering method, or the like.

The vacuum vapor deposition method refers to a method in which a raw material is heated and evaporated in a vacuum to transport the evaporated particles to the surface of the substrate, and the evaporated particles are rearranged on the surface of the substrate to form a thin film. In the vacuum evaporation method, the degree of vacuum is usually 1.3 × 10 ^-2 Pa or less.

The sputtering method refers to forming an inert gas into a plasma, and then causing the obtained positive ions to strike the raw material to knock out elemental atoms on the surface of the raw material, attaching and/or depositing on the substrate located in the vicinity thereof to form a thin film. The method.

(transparent conductive film)

The transparent conductive film in the second resin laminate of the present invention can be selected depending on the function to be imparted, and is not particularly limited. For example, in the case where an electrical property of a low electrical resistance is to be imparted to the transparent conductive film, the transparent conductive film is preferably zinc oxide, AZO (aluminum-doped zinc oxide) or GZO (gallium-doped zinc oxide) or the like. Main component material, or ITO (tin-doped indium oxide), SnO ₂ (tin oxide), IZO (zinc-doped indium oxide), ICO (indium-doped indium oxide), ATO (antimony-doped tin oxide), FTO (fluorine-doped A material that is transparent and electrically conductive, such as tin oxide, is not mainly composed of zinc oxide.

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

When the transparent conductive film is made into an amorphous film, the coverage ratio is good, so that the film thickness can be further reduced, which is preferable. Examples of the amorphous transparent conductive film material include IZO (zinc-doped indium oxide), ZTO (zinc oxide-tin oxide)-based film, IZTO (indium oxide-zinc oxide-tin oxide)-based, tin oxide-based film, and the like. Further, a system in which an oxide having electrical characteristics, optical characteristics, and mechanical properties is imparted to the film is added.

When the surface resistance value is set to a high resistance value, it can be adjusted by selecting a material or by using a film thickness or a film formation condition. For example, when the surface resistance value is lowered, a crystalline material having a good (low) electrical resistivity such as ITO can be used for the transparent conductive film. Moreover, the surface resistance value can be lowered by increasing the film thickness. However, when the film thickness of the transparent conductive film is made small, the transmittance can be expected to be improved.

In addition, the surface resistance value may be appropriately determined depending on the purpose of use, and if it is used for a photovoltaic element, a photoelectric conversion element, a liquid crystal, a touch panel or the like, the surface resistance value is preferably 10 Ω/□ or more and 5000 Ω/ □ Below, it is better to be 100 Ω/□ or more and 2000 Ω/□ or less. Further, the thickness of the transparent conductive film is, for example, preferably 5 nm or more, more preferably 10 to 300 nm. Further, in the method of forming a transparent conductive film described below, it is preferred that the transparent conductive film is directly laminated on the cured film.

Further, the optimum film thickness of each layer can be determined, for example, by the following method.

First, the film thickness of the transparent conductive film in which the necessary surface resistance value can be obtained is determined according to the use. Next, the refractive index of the material used in the cured film is set to a fixed value, and the film thickness of the cured film is changed by an optimization algorithm to determine the film thickness of the cured film which can obtain the highest transmittance or the lowest reflectance. .

Further, the transparent conductive film provided on the cured film may be a single layer or a multilayer film of two or more layers. For example, a transparent conductive film of two or more layers may be provided in consideration of transmittance (reflectance) of a substrate having a conductive multilayer film, and an antireflection film having a high refractive index may be further provided. Further, even in the case where the antireflection film is formed, it is not limited to one layer, and a multilayer structure (for example, two to six layers) which can obtain a desired transmittance (reflectance) can be formed.

(Method of Manufacturing Resin Laminate)

Hereinafter, a method of producing the second resin laminate of the present invention will be described.

The method for producing a resin laminate according to the present invention includes the step (a) of forming a cured film obtained by curing the coating liquid containing the components (A) to (E) on a substrate, and the cured film. Step (b) of forming a transparent conductive film thereon.

Further, the above step (a) is as shown in the description of the above coating liquid and cured film.

(Formation of transparent conductive film)

In the second resin laminate system of the present invention, a cured film is formed between the transparent conductive film and the substrate, and the transparent conductive film is preferably a chemical vapor deposition method (CVD method) or a physical vapor deposition method (PVD method). Or a coating method is formed on the cured film. Specific examples of the CVD method include a plasma CVD method, a photo CVD method, and a mist method. Specific examples of the PVD method include an ion plating method, a vacuum vapor deposition method, and a sputtering method. Specific examples of the coating method include a spray method, a spin coating method, a bar coating method, a knife coating method, and an inkjet method.

The transparent conductive film formed by the thin film formation technique performed under vacuum generally has a property of being in close contact with an inorganic component but not adhering to an organic component. In the case of the resin laminate of the present invention, since the cured film has an inorganic ‧ organic mixed structure in which the organic fine particles are encapsulated 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 by a sputtering method will be described.

The sputtering method refers to the process of causing an inert gas to be a plasma, and causing the obtained positive ions to strike the raw material to knock out elemental atoms on the surface of the raw material, causing them to adhere and/or accumulate in the vicinity thereof. A method of forming a film on a substrate.

In this case, the target system uses an ITO sintered body. A laminate including a substrate and a cured film is placed in a sputtering apparatus, and a vacuum of 10 ^-5 Pa or less is usually applied to the apparatus, and argon gas is introduced thereto, and 0.1 to 10 kW/cm ² is applied under a vacuum of about 0.1 to 10 Pa. The left and right DC power is generated to generate plasma to form an ITO film on the cured film.

In the case where the transparent conductive film is an ITO film, the raw material for forming the ITO film is, for example, an indium oxide sintered body target to which 10% by mass of SnO ₂ is added. In order to control conductivity and optical characteristics, there is also a case where oxygen is mixed into argon gas.

The method of laminating the transparent conductive film by the PVD method is not limited to the above-described sputtering method, and the transparent conductive film can be laminated by a vacuum deposition method, an ion plating method, or the like.

The vacuum vapor deposition method refers to a method in which a raw material is evaporated by heat in a vacuum, and the evaporated particles are transported to the surface of the substrate to re-arrange the evaporated particles on the surface of the substrate 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 refers to introducing a reactive gas or the like into a vacuum vapor deposition device, and generating a gas plasma in the device by various methods to ionize and accelerate one of the generated vapor deposition particles (atoms and molecules). A method in which a substrate placed in a vacuum is irradiated with vapor-deposited particles and ions thereof to form a thin film of a vapor deposition material on a substrate. That is, the so-called ion plating method refers to a composite technology of vacuum evaporation technology and plasma technology.

A specific example of laminating a transparent conductive film by a CVD method will be described for a case where a ZnO film is formed on a cured film by a plasma CVD method.

The plasma CVD method refers to a method in which a raw material gas is introduced into a plasma state having a high energy density to be decomposed, and a target material is coated on a substrate by a chemical reaction.

In the second resin laminate of the present invention, a laminate including a substrate and a cured film is placed in a plasma CVD apparatus, and after the inside of the apparatus is vacuumed, ZnO film is introduced into the plasma CVD apparatus while introducing argon gas. When the flow rate of each gas becomes stable, electric power is applied to generate a plasma, thereby forming a ZnO film on the cured film.

(photocatalyst layer)

The photocatalyst material used in the photocatalyst layer of the third resin laminate of the present invention is not particularly limited, and conventionally known ones such as titanium dioxide, barium titanate, barium titanate, sodium titanate, zirconium dioxide, and α can be used. -Fe ₂ O ₃ , tungsten oxide, cadmium sulfide, zinc sulfide, and the like. These may be used alone or in combination of plural kinds. Among these, titanium dioxide, especially anatase type titanium dioxide, can be used as a practical photocatalyst. Further, in order to promote the activity of the photocatalyst, a conventionally known photocatalyst promoter may be added. The photocatalyst promoter may, for example, be preferably a platinum group metal such as platinum, palladium, rhodium or iridium, and these may be used singly or in combination of plural kinds. From the viewpoint of photocatalytic activity, the amount of the photocatalyst promoter to be added is usually selected in the range of 1 to 20% by mass based on the photocatalyst.

The formation method of the photocatalyst layer is as follows, and in the case of the wet method, a polyfluorene-based compound is usually used in the matrix of the photocatalyst layer. For example, an alkoxydecane such as polyorganosiloxane or tetraethoxysilane is hydrolyzed and then condensed to form a matrix.

(Method of Manufacturing Resin Laminate)

Hereinafter, a method of producing the third resin laminate of the present invention will be described.

The method for producing a resin laminate of the present invention comprises the step (a) of forming the above-mentioned cured film of the present invention on a substrate, and the step (b) of forming a photocatalyst layer on the cured film. Further, the above step (a) is as shown in the description of the above cured film.

The method of forming the photocatalyst layer on the cured film is not particularly limited, and various methods can be used. For example, a PVD method such as a vacuum deposition method or a sputtering method; a dry method such as a metal spray method, a wet method using a coating liquid, or the like can be given. As the coating liquid used in the wet method, it is preferred to use a component other than the photocatalyst particles dispersed in a suitable inorganic binder (for example, a polyoxo compound).

The coating liquid can be applied by a known method such as a dip coating method, a spin coating method, a spray coating method, a bar coating method, a blade coating method, a roll coating method, a knife coating method, a die coating method, a gravure coating method, or the like. It dries or hardens to form a photocatalyst 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 is not fully utilized. If it exceeds 2 μm, the photocatalytic function is not significantly improved even if the thickness is larger than this.

The resin laminate of the present invention may be a molded body (a molded body of a resin laminate). The molded body of the resin laminate can be produced by thermoforming. Examples of the hot forming include vacuum forming, vacuum forming, pressure forming, plug assist molding, and press molding.

(substrate for thermoforming)

Hereinafter, a substrate for thermoforming (hereinafter simply referred to as "substrate") will be described.

In order to perform heat forming, a sheet or film mainly composed of a thermoplastic resin having a softening point of the substrate of from about 50 to 300 ° C is preferably used, and examples thereof include polycarbonate, polypropylene, and polyethylene. Polystyrene, acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-styrene resin (AS resin), methyl methacrylate-styrene resin (MS resin), polyester resin, acrylic acid A resin, a vinyl chloride resin, a fluorine resin, or the like may be used, and a polymer alloy ‧ polymer blend obtained by mixing the above polymers may be used. Further, it may be a laminated structure in which a plurality of layers of the above resin are laminated.

A decorative layer may also be provided on the surface of the substrate on which the cured film is not formed. Examples of the decorative layer include an ink layer, a high-brightness ink layer, and a metal deposition layer. Further, the decorative layer may be a single layer or a laminated layer combined with each other.

Next, the thickness of the substrate will be described.

The thickness of the substrate sheet or film for insert molding is preferably from 5 μm to 0.7 mm. When it is less than 5 μm, there is a problem that the film strength is low and the film is broken at the time of molding. Moreover, when it exceeds 0.7 mm, it is difficult to produce the insert molding sheet in a wound state, and it is inferior in productivity.

Hereinafter, an example of the thermoforming method will be described, but the present invention is not limited to the following description.

A substrate sheet which is not thermoformed is placed in the injection molding mold so that the surface on the side of the cured film faces the movable mold, and vacuum forming is performed by vacuum suction holes of the movable mold to perform preliminary molding. Then, the injection resin is filled in the in-mold surface on the side where the cured film is not formed, and the injection resin is integrated with the base material sheet.

In addition, after the base material sheet which has been subjected to hot forming is provided in the injection molding die, the injection resin is molded on the surface of the surface on which the cured film is not formed, and the injection resin is integrated with the base material sheet.

Thermoforming is carried out in order to form the base material sheet for forming into irregularities or cylindrical or elliptical cylinders. Examples of the thermoforming method include vacuum forming (including plug assist molding, etc.), vacuum pressure forming, pressure forming, press molding, and extrusion molding.

In order to mount the substrate sheet which has been thermoformed in the injection molding die, trimming is performed so that the unnecessary portion is cut to conform to the shape of the injection molding die.

The method of dressing is not particularly limited, and examples thereof include a die cutting method, a laser cutting method, a water spray method, a cutter pressing method, and a Thomson pressing method. Furthermore, it is also possible to perform trimming simultaneously during hot forming.

A substrate which is not thermoformed is placed in the injection molding die so that the surface on the side of the cured film faces the movable mold, and vacuum forming is performed by vacuum suction holes of the movable mold to perform preliminary molding. Then, the injection resin was filled on the side of the surface where the cured film was not formed. The conditions for the in-mold injection molding are not particularly limited, and can be adjusted within the range of the usual injection molding conditions. Further, the injection molding machine can use either a vertical injection molding machine or a horizontal injection molding machine.

After the base material sheet which has been subjected to thermoforming is placed in the injection molding die, the injection resin is filled on the surface side where the cured film is not formed.

The conditions for the injection molding of the insert mold are not particularly limited, and can be adjusted within the range of the usual injection molding conditions. Further, the injection molding machine can use either a vertical injection molding machine or a horizontal injection molding machine.

The injection molding die has a mechanism for filling the injection resin on the surface side of the substrate sheet which is not thermoformed, on which the cured film is not formed.

In the case of a vertical injection molding machine, it is fixed by gravity if it is placed in the lower mold of the mold. In the case where it is necessary to be placed in the mold above the mold, there are a method of fixing the substrate sheet which has been thermoformed by vacuum suction from the mold, a method of covering with the convex portion of the mold, and utilizing The method of fixing the pin, etc. In the case of the horizontal injection molding machine, there is a method of vacuum suction and fixing on either the fixed side or the movable side, and a method of covering with a convex portion of the mold, and utilizing The method of fixing the pin, etc.

Furthermore, the present invention also provides a method for producing a cured film, comprising the steps of: heating and hardening the coating liquid of the present invention; and a method for producing a resin laminate, characterized by comprising coating the above-described present invention The step of applying a liquid to the substrate, the step of drying the coating liquid, the step of thermoforming the substrate, and the step of curing the coating liquid to form a coating layer.

Furthermore, in the method for producing a resin laminated body, the resin layered body obtained by curing the coating liquid is further provided with a resin layer provided on a surface of the resin laminate which does not have a coating layer.

Example

The invention is illustrated in more detail by way of examples, but the invention is not limited by the examples.

Further, as long as it is not specifically mentioned, the characteristics in each example are obtained in accordance with the following methods.

(1) Oxidized content (% by mass) derived from inorganic components in the cured film

The sample obtained by thermally hardening the coating liquid was subjected to thermogravimetric measurement on a Teflon (registered trademark) petri dish (temperature at 20 ° C / min under nitrogen, room temperature to 800 ° C), according to which it was at 800 ° C. The residue is obtained.

(2) Content of organic polymer particles in the cured film (% by mass)

Calculated by calculation. Specifically, the hydrolysis of the components (A-1) to (A-5) and the completion of the condensation reaction ((A) component), organic polymer microparticles (component (B)), and colloidal ceria (C) The mass % of the organic polymer microparticles in the total mass of the component).

(3) Solution stability of the coating solution

The film was sealed and stored at room temperature for 14 days, and the presence or absence of gelation was judged by visual observation. For those who are not gelled, the viscosity is measured by the tuning fork vibrating viscometer SV-10 of A & D Co., Ltd., and the rate of change from the initial period of 3 times is marked as "○", which will exceed 3 The double is marked as "X".

(4) Film appearance

The appearance of the cured film was visually observed, and the foreign matter, the speckle pattern, and the white turbidity were confirmed, and those which did not confirm the above were described as "good".

(5) Total light transmittance and haze

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

(6) Wear resistance

Using a wear wheel CS-10F and a TABER abrasion tester (rotary wear tester) (manufactured by Toyo Seiki Co., Ltd., model: TS), a 500 rpm TABER abrasion test was carried out at a load of 4.9 N, and the haze before the TABER abrasion test was performed. The difference (f) between the haze after the TABER abrasion test was less than 15 and was marked as "○", and the difference in haze was 15 or more 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 reciprocating 50 times at 2000 mm/sec, the damage of the surface was visually evaluated. Those who are completely undamaged are marked as "1", those who are slightly damaged are marked as "2", and those who have suffered damage to more than half of the parts that are rubbed are marked as "3".

In Examples 12 to 16 and Comparative Examples 7 to 11, steel wool #0000 (load 9.8 N) was used, and after reciprocating 50 times at 2000 mm/sec, the damage of the surface was visually evaluated. Those who are completely undamaged are marked as "1", those who are slightly damaged are marked as "2", and those who have suffered damage to more than half of the parts that are rubbed are marked as "3".

(8) Adhesion

According to JIS K 5400, a sample (hardened film) was cut into the slits of 11 vertical and horizontal sides at intervals of 2 mm using a razor blade to form 100 meshes, and a commercially available cellophane tape was used with a finger pad ("CT-24 (width) 24mm)", manufactured by Nichiban Co., Ltd.), after being sufficiently adhered to the sample, it is quickly peeled off at an angle of 90° in the immediate direction, and the number of meshes (X) in which the cured film is not peeled off and expressed is represented by X/100. The adhesion of the cured film was evaluated.

(9) Boiling resistance (adhesion after boiling for 5 hours)

The 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 the adhesion was carried out in the same manner as in the above (8).

(10) Weather resistance

The xenon arc lamp weathering test was carried out for 1000 hours (Atlas Ci65, output power was 6.5 kW, black panel temperature was 63 ° C, relative humidity was 50%). The weather resistance was evaluated by the change in the adhesion of the cured film before and after the test.

(11) Flexibility

A test for producing a resin laminate in the same manner as in each example except that a polycarbonate standard plate (trade name: ECK100) manufactured by Sumitomo Bakelite Co., Ltd., 100 mm × width 50 mm × thickness 1 mm was used as the substrate. kind.

The both ends of the sample were held by fingers, and forced bending was performed 10 times on a curve having a radius of 50 mm, and those having no crack on the layer were marked as "○", and those having cracks were marked as "×".

(12) Heat resistance

The heat resistance test (manufactured by TABAI, PS-222) was carried out 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 particle dispersion structure

Using a TEM (transmission electron microscope) to observe the cross-section of the cured film, 10 organic particles present in the region of 1 μm square were selected, and Freesoft: NIH Image manufactured by National Institute of Health, USA was used. 1.63 to obtain the average particle size. When the average particle diameter of the organic fine particles is 200 nm or less, "○" is used, and when the average particle diameter is larger than 200 nm, the particle diameter is 200 nm or less. The case of an amoeba having a particle diameter of 200 nm or more is referred to as "Δ".

(14) Inorganic particle dispersion structure

The average particle diameter of each of the colloidal cerium oxide microparticles in the cured film was determined in the same manner as in the above (13). The average particle diameter of 200 nm or less is referred to as "○", and the average particle diameter of more than 200 nm is referred to as "x".

Moreover, in the examples and comparative examples, the details of the raw materials described by the trade names are as follows.

(A-1) Component: M Silicate 51 "Polyalkyloxydecane as a partial condensate of tetramethoxydecane (average three to pentamer)" manufactured by Tama Chemical Industry Co., Ltd.

(A-2) Component: MTMS-A "Polyorganoalkoxydecane as a partial condensate of methyltrimethoxydecane" manufactured by Tama Chemical Industry Co., Ltd.

(A-2) Component: SR2402 "Polyorganoalkoxydecane as a partial condensate of methyltrimethoxydecane" manufactured by Toray Dow Corning Co., Ltd.

(B) component: ULS-1385MG (ultraviolet absorption skeleton: benzotriazole) manufactured by Yoshisei Oil & Fats Co., Ltd. (water dispersion/solid content concentration: 30% by mass)

(B) component: ULS-385MG (ultraviolet absorption skeleton: benzophenone) manufactured by Yoshisei Oil & Fats Co., Ltd. (water dispersion/solid content concentration: 30% by mass)

(C) Component: IPA-ST-L (colloidal cerium oxide)

Nissan Chemical Industry Co., Ltd. (isopropyl alcohol dispersion, colloidal cerium oxide concentration of 30% by mass, average particle size of 40~50nm (manufacturer published value))

[Examples 1 to 11 and Comparative Examples 1 to 6] Example 1 (1) Manufacturing of coating liquid

The preparation was carried out in accordance with the ingredients and the amounts shown in Table 1.

Into a sample tube having a volume of 50 ml, 0.80 g of organic polymer microparticles: ULS-1385MG (component (B) and (E)) was added, and while stirring at 500 rpm, 1-methoxyl was sequentially added dropwise over 1 minute. Base-2-propanol ((E) component) 4.25 g, water ((E) component) 0.50 g, acetic acid ((D) component) 0.50 g, M Silicate 51 ((A-1) component 0.40 g, MTMS- A ((A-2) component) 1.10 g, dimethoxy-3-glycidoxypropylmethyl decane (component (A-4)) 0.55 g, 20% by mass of p-toluenesulfonic acid methanol solution ( (D) Component + (E) Component) 0.05 g. Then, the mixture was stirred at 500 rpm for 60 minutes at room temperature, and then allowed to stand for one day, and this was used as the solution A.

To a sample tube having a volume of 20 ml, 0.31 g of 3-isocyanatopropyltriethoxydecane and 0.35 g of 2-butanone oxime (blocking agent for isocyanate group) were placed, and stirred at 500 rpm at room temperature. After a minute, let stand for one day and use it as liquid C. The blocking of the isocyanate group was confirmed by the disappearance of the signal of the isocyanate group in the ¹³ C-NMR. The total amount of 3-isocyanatepropyltriethoxydecane and 2-butanone oxime is defined as the amount of the blocked isocyanatodecane compound: (A-5).

Into a 200 ml three-necked flask equipped with a cooling tube, a solution A and a stir bar were added, and while stirring at 500 rpm, IPA-ST-L (component (+) (E) component) was added dropwise as a liquid B for 5 minutes. Stir at room temperature for 60 minutes. Then, it was heated under a nitrogen stream at 600 rpm and 80 ° C for 3 hours. Then, the solution C was added, and the mixture was stirred at 80 ° C for 4 hours under the same conditions, and then allowed to stand at room temperature overnight.

Further, 0.40 g of 3-aminopropyltrimethoxydecane (component (A-3)) as a D solution was added dropwise thereto over 2 minutes. After stirring at room temperature for 10 minutes, it was further heated under a nitrogen stream at 700 rpm and 80 ° C for 3 hours.

Then, it was allowed to stand for 1 week to obtain a coating liquid.

(2) Production of laminated body

As a polycarbonate substrate [manufactured by Idemitsu Kosan Co., Ltd., trade name: Tarflon, product number: IV2200R (weathering grade), thickness: 3 mm (total light transmittance: 90%, haze value: 0.5%)] was used. Substrate.

The coating liquid obtained in the above (1) was applied to the surface of a polycarbonate molded body having a thickness of 3 mm by a stick coater at a thickness of 3 μm, and was thermally hardened at 130 ° C for 2 hours. Thereby, a laminate including a substrate and a cured film is produced.

The obtained coating liquid and laminated body were evaluated. The evaluation results are shown in Table 2.

Example 2~11

The coating liquid was produced in the same manner as in Example 1 in accordance with the components and the amounts shown in Table 1, and a laminate was produced. The evaluation results of the obtained coating liquid and laminated body are shown in Table 2.

Comparative example 1

The preparation was carried out in accordance with the ingredients and the amounts shown in Table 3.

Into a sample tube having a volume of 50 ml, 0.90 g of ULS-1385MG (component (B) and (E)) was added, and while stirring at 500 rpm, 1-methoxy-2-prop was sequentially added dropwise over 1 minute. Alcohol ((E) component) 2.00 g, water ((E) component) 0.09 g, acetic acid ((D) component) 3.20 g, methyltrimethoxydecane ((A-2) component) 2.00 g, dimethoxy Base-3-glycidoxypropylmethyldecane (component (A-4)): 0.96 g, 5% by mass of a methanol solution of p-toluenesulfonic acid (component (D) + (E)) 0.20 g. Then, after stirring at 500 rpm for 60 minutes at room temperature, it was left to stand for one day, and it was made into the A liquid.

0.16 g of 3-isocyanatopropyltriethoxydecane and 0.36 g of 2-butanone oxime (blocking agent for isocyanate group) were placed in a sample tube having a volume of 20 ml, and stirred at 500 rpm at room temperature. After a minute, let stand for one day and use it as liquid C. The blocking of the isocyanate group was confirmed by the disappearance of the signal of the isocyanate group in the ¹³ C-NMR. The total amount of 3-isocyanatepropyltriethoxydecane and 2-butanone oxime is defined as the amount of the blocked isocyanatodecane compound: (A-5).

A liquid and a stirrer were placed in a 200 ml three-necked flask equipped with a cooling tube, and while stirring at 500 rpm, IPA-ST-L (component (+) (E) component) of 7.00 g was added dropwise over 5 minutes. Stir at room temperature for 10 minutes. Then, it was heated under a nitrogen stream at 600 rpm and 80 ° C for 3 hours. Then, the solution C was added, and the mixture was stirred at 80 ° C for 4 hours under the same conditions, and then allowed to stand at room temperature overnight.

Further, 0.40 g of 3-aminopropyltrimethoxydecane (component (A-3)) as a D solution was added dropwise thereto over 2 minutes. After stirring at room temperature for 10 minutes, it was further heated under a nitrogen stream at 700 rpm and 80 ° C for 3 hours.

Then, it was allowed to stand for 1 week to obtain a coating liquid. (Comparative Example 1 is a coating liquid produced by using the component (A-1) in the coating liquid of Example 1, and the content of the organic polymer fine particles in the cured film is the same as in Example 1. By). Then, using the coating liquid, a laminate including a substrate and a cured film was produced in the same manner as in Example 1 (2).

The obtained coating liquid and laminated body were evaluated. The evaluation results are shown in Table 4.

Comparative example 2~6

The coating liquid was produced in the same manner as in Comparative Example 1 in accordance with the components and the amounts shown in Table 3, and a layered product was produced. (Comparative Examples 2 and 3 show the coating liquid produced by using the component (A-1) in the coating liquids of Examples 2 and 3, and the content of the organic polymer fine particles in the cured film and the examples. 2 and 3 are the same amount. Further, Comparative Example 4 is a coating liquid produced by using the component (A-5) in the coating liquid of Example 3, and is an organic polymer content in the cured film. The same amount as in Example 3. The comparative example 5 is a coating liquid produced by using the component (A-5) and the component (C) in the coating liquid of Example 3, and is used in the cured film. The content of the organic polymer was the same as that of Example 3. The comparative example 6 shows the coating liquid produced by using the component (A-1) and the component (C) in the coating liquid of Example 3, and The content of the organic polymer in the cured film was the same as in Example 3.

The obtained coating liquid and laminated body were evaluated. The evaluation results are shown in Table 4.

[Table 1]

[Table 2]

[table 3]

[Table 4]

As is clear from Tables 1 to 4, the coating liquid of the present invention, the cured film obtained therefrom and the laminates (Examples 1 to 11) were all acceptable in substantially all evaluation items.

The solution stability, film appearance, transparency, adhesion, and boiling resistance of Comparative Examples 1 to 3 and Comparative Example 6 containing no component (A-1) were good, but the scratch resistance was inferior to those of Examples 1 to 11. Relatively poor. Further, in Comparative Examples 4 and 5 containing no component (A-5), the film appearance, transparency, and adhesion were good, but solution stability and boiling resistance were inferior to those of Examples 1 to 11.

Examples 12 to 16

The coating liquid of Example 1 was applied to the surface of a polycarbonate (PC) formed body having a thickness of 3 mm or a corona-treated polypropylene sheet by a bar coater at a thickness of 3 μm [Idemitsu Unitech Co., Ltd. Made by the company, the product name: Superpurelay, product number: SG-140TC, thickness 300μm (total light transmittance 94%, haze value 2.3%)], it is thermally hardened at 130 ° C for 2 hours. Thereby, a laminate including a substrate and a cured film was produced. Further, a layered body was obtained by forming a film of an inorganic hard substance layer on the layered body produced above by the following method.

The obtained laminate including the substrate, the cured film, and the inorganic hard layer was evaluated. The evaluation results are shown in Table 5.

Film formation of inorganic hard layer (1) SiO _x

The produced laminate including the substrate and the cured film is placed in a plasma CVD apparatus, and evacuated until the degree of vacuum in the apparatus reaches 2.7×10 ⁻³ Pa, and the temperature of the substrate is raised to 100° C., and 5 is maintained. In minutes, the substrate was degassed. Thereafter, after returning to room temperature, the gas was evacuated until the degree of vacuum in the apparatus reached 2.7 × 10 ^-4 Pa.

After the degree of vacuum was 2.7 × 10 ^-4 Pa, SiH ₄ gas, N ₂ O gas and Ar gas were introduced into the apparatus, and the gas flow rate was: SiH ₄ gas flow rate was 1 cm ³ /min, and N ₂ O gas flow rate was 200 cm ³ /min, Ar gas flow rate is 300 cm ³ /min, and when the vacuum degree is stabilized at about 2.7 Pa, electric power is applied to generate plasma, thereby forming a SiO _x (1.8 ≦ x ≦ 2) film having a film thickness of 5 μm on the cured film. (Inorganic hard layer).

(2) Amorphous carbon film

The produced laminate including the substrate and the cured film is placed in a plasma CVD apparatus, and evacuated until the degree of vacuum in the apparatus reaches 2.7×10 ⁻³ Pa, and the temperature of the substrate is raised to 100° C., and 5 is maintained. In minutes, the substrate was degassed. Thereafter, after returning to room temperature, the gas was evacuated until the degree of vacuum in the apparatus reached 2.7 × 10 ^-4 Pa.

To a plasma CVD apparatus having a vacuum of 2.7 × 10 ^-4 Pa, a gas flow rate of CH ₄ gas flow rate of 1 cm ³ /min, H ₂ gas flow rate of 150 cm ³ /min, and Ar gas flow rate of 300 cm ³ /min CH ₄ gas, H ₂ gas, and Ar gas were introduced, and when the degree of vacuum was stabilized at about 2.7 Pa, electric power was applied to generate plasma, and an amorphous carbon film (inorganic hard material layer) having a film thickness of 7 μm was formed.

(3) SiN _y

The produced laminate including the substrate and the cured film is placed in a plasma CVD apparatus, and evacuated until the degree of vacuum in the apparatus reaches 2.7×10 ⁻³ Pa, and the temperature of the substrate is raised to 100° C., and 5 is maintained. In minutes, the substrate was degassed. Thereafter, after returning to room temperature, the gas was evacuated until the degree of vacuum in the apparatus reached 2.7 × 10 ^-4 Pa.

Into the plasma CVD apparatus to SiH ₄ gas flow rate of 1cm ³ / min, NH ₃ gas flow rate of 200cm ³ / min, Ar gas flow rate gas flow 400cm ³ / min of introducing SiH ₄ gas, NH ₃ gas and an Ar gas When the degree of vacuum was stabilized at about 2.7 Pa, electric power was applied to generate plasma, and a SiN _y (1.2 ≦ y ≦ 4/3) film (inorganic hard layer) having a film thickness of 7 μm was formed.

(4) SiO ₂

The produced laminate including the substrate and the cured film was placed in an ion plating apparatus, and the evaporation source was SiO ₂ crystal grains. The exhaust 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 the introduction of the gas was stopped, 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 film was cooled for 20 minutes while maintaining the vacuum in the apparatus to form a SiO ₂ (1.8 ≦ x ≦ 2) film (inorganic hard layer) having a film thickness of 1.5 μm on the cured film.

Comparative Example 7~11

Using the coating liquid of Comparative Example 1, a laminate was obtained in the same manner as in Examples 12 to 16.

The obtained laminate including the substrate, the cured film, and the inorganic hard layer was evaluated. The evaluation results are shown in Table 5.

[table 5]

As is clear from Table 5, the laminates (Examples 12 to 16) using the coating liquid of Example 1 were all qualified in almost all evaluation items.

In Comparative Examples 7 to 11, the laminate of the coating liquid of Comparative Example 1 was used, and the film appearance, transparency, abrasion resistance, and scratch resistance were good, but the adhesion and boiling resistance were compared with those of Examples 12 to 16. difference.

[Examples 17 to 20 and Comparative Examples 12 to 14]

The characteristics of the above examples are obtained in accordance with the following methods.

(1) Oxidized content (% by mass) derived from inorganic components in the cured film

The sample obtained by thermally hardening the coating liquid was subjected to thermogravimetric measurement on a Teflon (registered trademark) petri dish (temperature at 20 ° C / min under nitrogen, room temperature to 800 ° C), according to which it was at 800 ° C. The residue is obtained.

(2) Content of organic polymer particles in the cured film (% by mass)

Calculated by calculation. Specifically, the hydrolysis of the components (A-1) to (A-5) and the completion of the condensation reaction ((A) component), organic polymer microparticles (component (B)), and colloidal ceria (C) ) The mass % of the organic polymer fine particles in the total mass of the cerium oxide (component (F)).

(3) Cerium oxide content in the cured film (% by mass)

Calculated by calculation.

(4) Solution stability of the coating solution

The film was sealed and stored at room temperature for 14 days, and the presence or absence of gelation was judged by visual observation. For those who are not gelled, the viscosity is measured by the tuning fork vibrating viscometer SV-10 of A & D Co., Ltd., and the rate of change compared with the initial period is 3 times or less, which is more than 3 The double is recorded as "X".

(5) Film appearance

The appearance of the cured film was visually observed, and the foreign matter, the speckle pattern, and the white turbidity were confirmed, and those which did not confirm the above were described as "good".

(6) Total light transmittance and haze

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

(7) Abrasion resistance and scratch resistance

For the evaluation of wear resistance, a 500 rpm TABER abrasion test was carried out under a load of 4.9 N using a wear wheel CS-10F and a TABER abrasion tester (rotary wear tester) (manufactured by Toyo Seiki Co., Ltd., model: TS). The difference between the haze before the TABER abrasion test and the haze after the TABER abrasion test (ΔH) is less than 15 and is indicated as "○", and the difference in haze is 15 or more is indicated as "x".

The evaluation of the scratch resistance was carried out by visually evaluating the surface by using steel wool #0000 (load 4.9 N) and reciprocating 50 times at 2000 mm/sec in Examples 17 to 20 and Comparative Examples 12 to 14. Damaged situation. Those who are completely undamaged are marked as "1", those who are slightly damaged are marked as "2", and those who have suffered damage to more than half of the parts that are rubbed are marked as "3".

(8) Adhesion

According to JIS K 5400, a sample (hardened film) was cut into the slits of 11 vertical and horizontal sides at intervals of 2 mm using a razor blade to form 100 meshes, and a commercially available cellophane tape was used with a finger pad ("CT-24 (width) 24mm)", manufactured by Nichiban Co., Ltd.), after being sufficiently adhered to the sample, it is quickly peeled off at an angle of 90° in the immediate direction, and the number of meshes (X) in which the cured film is not peeled off and expressed is represented by X/100. The adhesion of the cured film was evaluated.

(9) Boiling resistance

The 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 the adhesion was carried out in the same manner as in the above (8).

(10) Weather resistance

The xenon arc lamp weathering test was carried out for 2,400 hours (Ci65 from Atlas, the output power was 6.5 kW, the black panel temperature was 63 ° C, and the relative humidity was 50%). The weather resistance was evaluated by the change in the adhesion of the cured film before and after the test.

(11) Flexibility

A resin laminate was produced in the same manner as in each example except that a polycarbonate standard plate (trade name: Polyca-Ace, product number: ECK100) manufactured by Sumitomo Bakelite Co., Ltd. of 100 mm × width 50 mm × thickness 1 mm was used as the substrate. Sample of the body.

The both ends of the sample were held by fingers, and forced bending was performed 10 times on a curve having a radius of 50 mm, and those having no crack on the layer were marked as "○", and those having cracks were marked as "×".

(12) Heat resistance

The heat resistance test (manufactured by TABAI, PS-222) was carried out 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 particle dispersion structure

The cross-section of the cured film was observed by TEM (transmission electron microscope), and 10 organic fine particles present in the region of 1 μm square were selected, and averaged using Freesoft: NIH Image 1.63 manufactured by National Institute of Health, USA. Particle size. When the average particle diameter of the organic fine particles is 200 nm or less, "○" is used, and when the average particle diameter is larger than 200 nm, the particle diameter is 200 nm or less. The case of an amoeba having a particle diameter of 200 nm or more is referred to as "Δ".

(14) Inorganic particle dispersion structure

The average particle diameter of each of the cerium oxide fine particles and the colloidal cerium oxide fine particles in the cured film was determined in the same manner as in the above (13). Those having an average particle diameter of 200 nm or less are referred to as "○", and those having an average particle diameter of more than 200 nm are referred to as "x".

Moreover, in the examples and comparative examples, the details of the raw materials described in the trade names are as follows.

(A) component: M Silicate 51 "Poly alkoxy decane which is a partial condensate of tetramethoxy decane (average three to pentamer)" manufactured by Tama Chemical Industry Co., Ltd. (B) Ingredients: ULS-1385MG (UV absorption skeleton: benzotriazole)

Manufactured by Yosuke Oil & Fat Industry Co., Ltd. (water dispersion/solids concentration is 30% by mass)

(B) Ingredients: ULS-385MG (UV absorption skeleton: benzophenone)

Manufactured by Yosuke Oil & Fat Industry Co., Ltd. (water dispersion/solids concentration is 30% by mass)

(C) Component: IPA-ST-L (colloidal cerium oxide)

Nissan Chemical Industry Co., Ltd. (isopropyl alcohol dispersion, colloidal cerium oxide concentration of 30% by mass, average particle size of 40~50nm (manufacturer published value))

(F') component: Needral U-15 (cationic cerium oxide aqueous dispersion)

Manufactured by Doki Chemical Co., Ltd. (water dispersion, cerium oxide concentration of 15% by mass, average particle size of 8 nm or less, pH of 3.5 (manufacturer catalogue value))

(Further, using a Zetasizer Nano series Nano-ZS manufactured by Malvern, the zeta potential was measured on Needral U-15 at 20 ° C, the dispersion medium was water, and the cumulative number of times was 50 times, and the result was +28.8 mV, confirming cerium oxide. The particles are cationic).

(F') Ingredients: Needral H-15 (acid-stable cerium oxide aqueous dispersion)

Made by Dumu Chemical Co., Ltd. (water dispersion, cerium oxide concentration is 15~16% by mass, stabilizer: hydrochloric acid is less than 1.0% by mass, pH is 1-3 (manufacturer's published value))

(Further, using a Zetasizer Nano series Nano-ZS manufactured by Malvern, the zeta potential was measured on Needral H-15 at 20 ° C, the dispersion medium was water, and the cumulative number of times was 50 times, and the result was +53.7 mV, confirming cerium oxide. The particles are cationic).

(1) Preparation of component (F) (dispersion F1)

Manufactured according to the composition and input amount of Table 6.

Into a sample tube having a volume of 50 ml, 10.0 g of Needral H-15 ((F') component) was placed, and while stirring at 500 rpm, 1-methoxy-2-propanol was sequentially added dropwise over 1 minute (( E) component: 7.0 g, tetraethoxy decane (component (A)) 2.23 g. Then, after stirring at room temperature for 90 minutes, it was allowed to stand at room temperature for 90 minutes. This was placed in a 100 ml three-necked flask equipped with a cooling tube, and stirred at 500 rpm while stirring at 500 rpm for 4 hours under a nitrogen stream. Then, it was allowed to stand at room temperature for one week to prepare a dispersion F1 (component (F)) containing a reaction product of a decane compound and cerium oxide.

(2) Dispersibility test of (F) component with anionic microparticle sol

Into a sample tube having a volume of 10 ml, 1.0 g of IPA-ST-L ((C) component, IPA dispersion sol in which an anionic colloidal cerium oxide was dispersed) and a stir bar were placed, and the mixture was stirred at 400 rpm while being dropped for 1 minute. 1.0 g of a dispersion F1 (component (F)) containing a reaction product of a decane compound and cerium oxide was added, followed by stirring at room temperature for 1 hour. It was visually confirmed that the dispersion state after the completion of the stirring was such that aggregation did not occur due to aggregation, precipitation, or gelation.

(3) Preparation of component (F) (dispersion F2)

Manufactured according to the composition and input amount of Table 6.

10.0 g of Needral H-15 ((F') component) was placed in a sample tube having a volume of 50 ml, and 1-methoxy-2-propanol ((E) was added dropwise thereto for 1 minute while stirring at 500 rpm. Component) 7.0 g, tetraethoxy decane (component (A)) 1.49 g. Then, after stirring at room temperature for 90 minutes, it was allowed to stand at room temperature for 90 minutes. This and the stirrer were placed in a 100 ml three-necked flask equipped with a cooling tube, and while stirring at 500 rpm, 0.30 g of 3-glycidoxypropyltrimethoxydecane (component (A)) was added dropwise over 1 minute. Stir at room temperature for 120 minutes. One side was heated at 500 rpm and heated at 80 ° C for 9 hours under a nitrogen stream. Then, it was allowed to stand at room temperature for one week to prepare a dispersion F2 (component (F)) containing a reaction product of a decane compound and cerium oxide.

In the same manner as in the dispersibility test of the above (2), it was confirmed that the dispersion liquid F2 was not aggregated, precipitated, or gelated and dispersed.

[Table 6]

Examples 17~18 (4) Manufacturing of coating liquid

Prepared according to the ingredients and input amounts of Table 7.

The organic polymer microparticles: ULS-1385MG (Example 17) or ULS-385MG (Example 18) ((B) component + (E) component) 0.85 g were placed in a sample tube having a volume of 50 ml, and stirred at 500 rpm. On the other hand, 1-methoxy-2-propanol ((E) component) 4.25 g, water ((E) component) 0.50 g, acetic acid ((G) component) 2.80 g, M Silicate 51 were added dropwise over 1 minute. ((A-1) component) 0.40 g, methyltrimethoxydecane (component (A-2)) 1.51 g, dimethoxy-3-glycidoxypropylmethyldecane ((A-4) ) Component) 0.55 g, 20% by mass of a p-toluenesulfonic acid methanol solution ((D) component + (E) component) 0.05 g. Then, after stirring at 500 rpm for 60 minutes at room temperature, it was left to stand for one day, and it was made into the A liquid.

Into a 200 ml three-necked flask equipped with a cooling tube, a solution A and a stir bar were added, and while stirring at 500 rpm, IPA-ST-L (component (+) (E) component) was added dropwise as a liquid B for 5 minutes. Stir at room temperature for 20 minutes. Then, the mixture was heated and stirred under a nitrogen stream at 500 rpm and 80 ° C for 7 hours, and then allowed to stand overnight at a temperature to obtain an A' solution.

To a sample tube having a volume of 20 ml, 0.31 g of 3-isocyanatopropyltriethoxydecane and 0.35 g of 2-butanone oxime (blocking agent for isocyanate group) were placed, and stirred at 500 rpm at room temperature. After a minute, let stand for one day and use it as liquid C. The blocking of the isocyanate group was confirmed by the disappearance of the signal of the isocyanate group in the ¹³ C-NMR. The total amount of 3-isocyanatepropyltriethoxydecane and 2-butanone oxime is defined as the amount of the blocked isocyanatodecane compound: (A-5).

While stirring the A' liquid at 650 rpm, 3.26 g of a dispersion F1 ((F) component + (E) component) containing a reaction product of a decane compound and cerium oxide was added dropwise over 5 minutes, and the mixture was stirred at room temperature for 20 minutes. Then, the solution C was added over 5 minutes, and stirred at room temperature for 10 minutes. Then, the mixture was heated and stirred under a nitrogen stream at 650 rpm and 80 ° C for 4 hours, and then allowed to stand at room temperature overnight.

Further, 0.40 g of 3-aminopropyltrimethoxydecane (component (A-3)) as a D solution was added dropwise thereto over 2 minutes. After stirring at room temperature for 10 minutes, it was heated under a nitrogen stream at 450 rpm and 80 ° C for 3 hours.

Then, it was allowed to stand for 1 week to obtain a coating liquid.

(5) Production of laminated body

As a polycarbonate substrate [manufactured by Idemitsu Kosan Co., Ltd., trade name: Tarflon, product number: IV2200R (weathering grade), thickness: 3 mm (total light transmittance: 90%, haze value: 0.5%)] was used. Resin substrate.

The coating liquid obtained above was applied to the surface of a polycarbonate molded body having a thickness of 3 mm by a bar coater so as to have a cured film of 7 μm, and was thermally cured at 130 ° C for 2 hours. Laminated body.

The obtained coating liquid and laminated body were evaluated. The evaluation results are shown in Table 8.

Example 19~20

In the above "(4) Production of Coating Liquid", the dispersion liquid F2 was used instead of the dispersion liquid F1, and the coating liquid of the example was prepared in accordance with the components and the amounts of the amounts shown in Table 7, and a laminate was produced. The evaluation results of the obtained coating liquid and laminated body are shown in Table 8.

Comparative example 12~14

In the above "(4) Production of coating liquid", Needral U-15 or Needral H-15 shown in Table 7 was used instead of the dispersion liquid F1, and the coating liquid of the comparative example was prepared in accordance with the components and the input amount of Table 7. And make a layered body. The evaluation results of the obtained coating liquid and laminated body are shown in Table 8.

[Table 7]

[Table 8]

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

[Examples 21 to 32, Comparative Examples 15 to 26] Example 21~32 [Production of Resin Laminate]

The coating liquids 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, as shown in the following <Thermal curing conditions of the substrate and the cured film> The laminate comprising the substrate and the cured film is formed by thermosetting at a temperature and for a time suitable for the substrate to be used.

Next, a transparent conductive film was formed on the produced laminate including the substrate and the cured film by the following method to obtain a resin laminate.

The results of evaluation of the obtained resin laminate including the substrate, the cured film, and the transparent conductive film are shown in Table 9.

<Thermal hardening conditions of the substrate and the 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 Co., Ltd., trade name: Emblt, grade: S, thickness 25 μm (total light transmittance 89%, haze value 2.5%)], 100 ° C ,2 hours

(3) Polypropylene [manufactured by Idemitsu Unitech Co., Ltd., trade name: Purethermo, thickness 250 μm (total light transmittance 94%, haze value 8.5%)], 100 ° C, 2 hours

<Method of Forming Transparent Conductive Film> (1) IZO film

The produced laminate including the substrate and the cured film was placed in a sputtering apparatus (Shimadzu HSM-552), and evacuated until the degree of vacuum in the apparatus reached 1.0 × 10 ^-4 Pa. Thereafter, argon gas was introduced into the apparatus, and the pressure inside the apparatus was adjusted to 0.2 Pa. The target system was sintered with a target of IZO (In ₂ O ₃ : ZnO = 90: 10% by mass). A transparent conductive film having a film thickness of 20 nm or a film thickness of 120 nm was formed by sputtering a DC (direct current) output power of 100 W. The substrate temperature is room temperature.

(2) IZTO film

The target system was formed in the same manner as in the above (1) using an IZTO target (In ₂ O ₃ :ZnO:SnO ₂ =20:40:40% by mass).

(3) ZTO film

The target system was formed in the same manner as in the above (1) using a ZTO target (ZnO: SnO ₂ = 10: 90% by mass).

(4) SnO ₂ film

The SnO ₂ sintered body target was used for the target system, and a SnO ₂ film was formed in the same order as in the above (1).

(5) ITO film

The target system was formed in the same manner as in the above (1) using an ITO target (In ₂ O ₃ :SnO ₂ = 90: 10% by mass). After the formation, heat treatment was performed in an atmosphere at 120 ° C for 1 hour in an atmosphere.

Comparative example 15~26

A transparent conductive film was directly formed on the substrate used in Example 21 without forming a cured film, and a resin laminate was obtained.

The results of evaluation of the obtained laminate including the substrate and the transparent conductive film are shown in Table 10.

The characteristics of each of Examples 21 to 32 and Comparative Examples 15 to 26 were obtained in accordance with the following procedures.

(1) Film appearance

The appearance of the resin laminate was visually observed, and the presence or absence of the foreign matter, the speckle pattern, and the crack was confirmed. The case where the above was not confirmed was indicated as "○", and the case where the above was confirmed was referred to as "x".

(2) Total light transmittance and haze

The total light transmittance and haze of the resin laminate were measured using a direct reading haze meter (manufactured by Suga Test Machine Co., Ltd., HGM-2DP).

(3) Surface hardness

According to JIS K5600-5-4, the surface of the transparent conductive film of the resin laminated body was evaluated using a pencil scratch hardness tester (manual type) (manufactured by Imoto Seisakusho Co., Ltd.).

(4) Scratch resistance

Using steel wool #0000, after reciprocating 10 times on the surface of the transparent conductive film of the resin laminate with a load of 4.9 N and 2000 mm/sec, the damaged state of the surface of the transparent conductive film was evaluated by visual observation in three steps. Those who are completely undamaged are marked as "1", those who are slightly damaged are marked as "2", and those who have suffered damage to more than half of the parts that are rubbed are marked as "3".

(5) Adhesion

According to JIS K 5400, the surface of the transparent conductive film of the resin laminated body was cut into the slits of 11 vertical and horizontal lines at intervals of 2 mm by a blade of a razor to form 100 meshes, and a commercially available cellophane tape was used with a finger pad ("CT-24" (width: 24 mm), manufactured by Nichiban Co., Ltd.), after sufficiently adhering to the surface of the transparent conductive film, the film was quickly peeled off at an angle of 90 ° C in the near direction, and the number of meshes (X) in which the transparent conductive film was not peeled off and remained X/100 indicates that the adhesion to the transparent conductive film was evaluated.

(6) Moisture resistance

In the moisture resistance test (small environment tester, manufactured by Espec Co., Ltd., SH-221), the adhesion was evaluated after standing at 100 ° C and 95 RH% for 100 hours. The adhesion was evaluated in the same manner as in the above (5).

(7) Flexibility

The both ends of the resin laminate sample were held by a finger, and forced bending was performed on a curve having a radius of 50 mm for 10 times. The presence or absence of cracks or peeling was confirmed on the laminate layer, and those not confirmed were marked as "○", and it was confirmed. These are recorded as "X".

(8) specific resistance

The specific resistance of the surface of the transparent conductive film of the resin laminate was measured by a four-probe method using a low resistivity meter Loresta-EP (manufactured by Mitsubishi Chemical Corporation).

(9) Carrier concentration

The carrier concentration was determined by the van der Pole method. The Hall measuring apparatus and its measurement conditions are as follows.

‧ Hall measuring device

Made by Dongyang Technology Co., Ltd.: Resi Test8310

‧Measurement conditions

Measuring temperature: room temperature (25 ° C)

Measuring magnetic field: 0.5T

Measuring current: 10 ^-12 ~ 10 ^-4 A

Measurement mode: AC (alternating current)

(10) Crystallinity of transparent conductive film

The determination of crystallinity was carried out by X-ray diffraction measurement. The measurement conditions of X-ray diffraction (XRD, X-ray diffraction) are as follows. Those who have no clear crystallographic peaks are regarded as amorphous.

‧X-ray diffraction measuring device

Manufactured by Rigaku Co., Ltd.: Ultima-III

‧Measurement conditions

X-ray: Cu-Kα ray (wavelength not 1.5406 , using a graphite monochromator for monochromization)

Output power: 50kV-120mA

2θ-θ reflection method, continuous scanning (1.0°/min)

2θ measurement angle: 5~80°

Sampling interval: 0.02°

Slit DS, SS: 2/3°, RS: 0.6 mm

[Table 9]

[Table 10]

As is clear from Tables 9 and 10, the resin laminates including the base material, the cured film, and the transparent conductive film (Examples 21 to 32) were all qualified in almost all evaluation items.

In Comparative Examples 15 to 26 in which the cured film was not sandwiched, Comparative Examples 15 to 18 and 23 to 26 in which polycarbonate was used as the substrate exhibited good film appearance, adhesion, and flex resistance, but transparency and surface. The hardness, scratch resistance, and electrical conductivity were inferior to those of Examples 21 to 24 and 29 to 32. Further, in Examples 19 and 20 in which polypropylene was used as the substrate, the film appearance, surface hardness, scratch resistance, adhesion, and flex resistance were inferior to those of Examples 25 and 26. In Comparative Examples 21 and 22 in which polyethylene terephthalate was used as the substrate, the film appearance, optical properties, adhesion, and flex resistance were good, but surface hardness, scratch resistance, and electrical conductivity were the same as in Example 27. 28 is relatively poor.

[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 by a bar coater at a temperature of 2 to 5 μm, and was heated at 130 ° C for 2 hours. After hardening, a laminate including a substrate and a cured film is produced.

Then, after applying the photocatalytic top coating agent "ST-K211" manufactured by Ishihara Sangyo Co., Ltd. on the cured film of the laminated body including the substrate and the cured film, the thickness after the heat treatment is about 0.5 μm. The photocatalyst layer was formed by heat treatment at 100 ° C for 30 minutes.

The results of evaluation of the obtained resin laminate including the substrate, the cured film, and the photocatalyst layer are shown in Table 11.

Example 34

A resin laminate including 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. The results of the evaluation thereof are shown in Table 11.

Example 35

A resin laminate including 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. The results of the evaluation thereof are shown in Table 11.

Comparative Example 27

A resin laminate including 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. The results of the evaluation thereof are shown in Table 11.

Comparative Example 28

The coating liquid obtained in Example 1 was replaced with the primer "ST-K300" manufactured by Ishihara Sangyo Co., Ltd., and coated to have a thickness of about 0.3 μm after drying, in the same manner as in the examples. In the same manner, a resin laminate including a substrate, a cured film, and a photocatalyst layer was produced in the same manner. The results of the evaluation thereof are shown in Table 11.

Comparative Example 29

In the same manner as in the primer of Comparative Example 28, the same amount of the primers "ST-K102a" and "ST-K102b" manufactured by Ishihara Satoshi Co., Ltd. was applied in such a manner that the thickness after drying and heating reached about 3 μm. (ST-K102), after drying at room temperature for 5 minutes, and heating at 100 ° C for 30 minutes, a resin laminate including a substrate, a cured film, and a photocatalyst layer was produced in the same manner as in Example 33. The results of the evaluation thereof are shown in Table 11.

The characteristics of each of Examples 33 to 35 and Comparative Examples 27 to 29 were determined in accordance with the following procedures.

1. Evaluation of resin laminates (1) Photocatalyst function

As an indicator of whether or not the photocatalytic function is expressed, the degree of hydrophilicity (generally, if it has hydrophilicity with a contact angle with water of 40 or less, it is said to have antifouling property). As a measure of the extent to which the photocatalyst function is exhibited, the contact angle is measured by the following method.

Ultraviolet rays of 1 mW/cm ^{2 were} irradiated to the side of the photocatalyst layer with a black light blue lamp, and the change with time of the contact angle was measured. At the contact angle, 20 ml of ion-exchanged water was dropped onto the photocatalyst layer by means of a micro-syringe, and water droplets were measured using an image processing contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., CA-A).

(2) Total light transmittance and haze

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

(3) Yellowness (YI)

It was measured in accordance with JIS K7105 using SZ-optical SENSOR (manufactured by Nippon Denshoku Industries Co., Ltd.).

(4) Wear resistance

Using a wear wheel CS-10F and a TABER abrasion tester (rotary wear tester) (manufactured by Toyo Seiki Co., Ltd., model: TS), a 500 rpm TABER abrasion test was carried out at a load of 4.9 N, and the haze before the TABER abrasion test was performed. The difference (f) between the haze after the TABER abrasion test is less than 15 and is indicated as "○", and the difference in haze is 15 or more as "x".

(5) scratch resistance

Using steel wool #0000 (load 4.9 N), the surface of the photocatalyst layer of the resin laminate was reciprocated 50 times at 2000 mm/sec, and the surface of the photocatalyst layer was visually evaluated for damage. Those who are completely undamaged are marked as "1", those who are slightly damaged are marked as "2", and those who have suffered damage to more than half of the parts that are rubbed are marked as "3".

(6) Adhesion

According to JIS K 5400, the surface of the photocatalyst layer of the resin laminated body was cut into the slits of 11 vertical and horizontal directions at intervals of 2 mm by a blade of a razor to form 100 meshes, and a commercially available cellophane tape was used with a finger pad ("CT-24 ( The width is 24 mm), and the surface of the photocatalyst is sufficiently adhered to the surface of the photocatalyst, and the photocatalyst layer is not peeled off and the number of grids remaining (X) is represented by X/100. To evaluate the adhesion of the photocatalyst layer.

(7) Weather resistance

The Xenon arc lamp weathering test (Ci65 from Atlas, output power is 6.5kw, black panel temperature is 63°C, humidity is 50%), and the weather resistance is evaluated by the degree of change of parameters such as haze, yellowness and adhesion. Sex.

[Table 11]

The evaluation of any of Examples 33 to 35 was excellent in abrasion resistance, scratch resistance, and weather resistance as compared with Comparative Examples 27 to 29.

Examples 36 to 43 and Comparative Examples 30 to 33 (formed 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 (manufactured by Mitsubishi Gas Co., Ltd., trade name: Iupilon Sheet) at a film thickness of 2 to 3 μm at 20 ° C. This was dried for 240 minutes as a pre-hardening, and a polycarbonate sheet for molding was produced. The formed sheet for forming was vacuum-formed, and then placed in an injection molding die, and the injection molding resin containing polycarbonate was prepared under the conditions of a resin temperature of 270 ° C and a resin pressure of 50 MPa. The product manufactured by the company, trade name: Tarflon, is injected onto the surface on which the pre-cured film is not formed, thereby producing a molded body of the resin laminate. Further, the molded body was cured at 120 ° C for 1 minute. The evaluation results of the following items (1) to (3) are shown in Table 12 for the molded body of the resin laminate.

(1) Film appearance

The appearance of the cured film surface of the molded body was visually observed, and the foreign matter, the speckle pattern, and the crack were confirmed, and those who did not confirm the number were marked as "○", and those who confirmed it were referred to as "x".

(2) scratch resistance

After reciprocating 10 times using steel wool #0000 (load 4.9 N), the damage of the surface was evaluated by visual observation. Those who are completely undamaged are marked as "1", those who are slightly damaged are marked as "2", and those who have suffered damage to more than half of the parts that are rubbed are marked as "3".

(3) Adhesion

According to JIS K 5400, the cured film surface of the molded body was cut into the slits of 11 vertical and horizontal directions at intervals of 2 mm by a razor blade to form 100 meshes, and a commercially available cellophane tape was used with a finger pad ("CT-24 (width) 24mm)", manufactured by Nichiban Co., Ltd.), after being sufficiently adhered to the cured film surface of the molded body, it is quickly peeled off at an angle of 90° in the immediate direction, and the cured film is not peeled off from the substrate and the number of meshes remaining (X ) is expressed by X/100, and the adhesion of the cured film is evaluated.

Examples 37~39

A molded body was produced in the same manner as in Example 36. The polycarbonate sheet for molding was produced in accordance with the pre-hardening temperature, the pre-hardening time, the post-hardening temperature, and the post-hardening 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 (manufactured by Japan Polypropylene Co., Ltd., trade name: Wintec) having a thickness of 0.3 mm so as to have a film thickness of 2 to 3 μm. The film was dried by pre-curing at 20 ° C for 240 minutes to prepare a polypropylene sheet for molding. The formed sheet for forming was vacuum-molded, and then placed in an injection molding die, and an injection molding resin containing polypropylene was produced under the conditions of a resin temperature of 270 ° C and a resin pressure of 40 MPa. [Products manufactured by Prime Polymer Co., Ltd. Name: Prime Polypro] is injected onto the surface on which the pre-hardened film is not formed, thereby producing a molded body of a resin laminate. Further, the molded body was cured at 120 ° C for 30 seconds. The evaluation results are shown in Table 12.

Examples 41 to 43

A molded body was produced in the same manner as in Example 40. The polypropylene sheet for molding was produced in accordance with the pre-hardening temperature, the pre-hardening time, the post-hardening temperature, and the post-hardening time shown in Table 12. The evaluation results are shown in Table 12.

Comparative example 30~33

A molded body was produced in the same manner as in Example 36, Example 39, Example 40, and Example 43 using the coating liquid of Comparative Example 1. The evaluation results are shown in Table 12.

[Table 12]

As is clear from Table 12, Examples 36 to 43 are molded bodies of the resin laminate using the coating liquid of Example 1, and were all qualified in almost all evaluation items.

In Comparative Examples 30 to 33, the molded article of the resin laminate of the coating liquid of Comparative Example 1 was used, and the film appearance and adhesion were good, but the scratch resistance was inferior to those of Examples 36 to 43.

Industrial availability

By using the coating liquid of the present invention, in addition to automobile interior parts such as instrument covers, windshields for two-wheeled vehicles and tricycles, resin-made windows (various windows), resin building materials windows, roofs for construction equipment, and road light-transmissive panels (Music panel), for correction, can be deployed to eyeglass lenses such as sunglasses, sports glasses, safety glasses, monitors such as plasma, liquid crystal, and organic EL, and electronic devices such as optical discs, mobile phone parts, touch panels, and solar cells. Various parts of resin materials such as equipment parts, lighting parts such as street lamps, windshields and protective shields, especially polycarbonate materials; can be suitably used as glass substitute members.

Claims (29)

A coating liquid comprising the following components (A) to (E), and by hydrolyzing a condensate of (A-1), (A-2) and (A-4) with (B)~( E) (A-5) is added to the reaction product obtained by the contact and reacted, and then (A-3) is added and reacted: (A) The following (A-1) to (A-5) a hydrolysis condensate of a decyl compound having an alkoxy group: (A-1) a tetraalkoxy decane compound, (A-2) an organoalkoxy decane compound containing no amine group, epoxy group or isocyanate group (A-3) a decane compound having an amine group and an alkoxy group, (A-4) a decane compound having an epoxy group and an alkoxy group, and (A-5) a blocked isocyanic acid having an alkoxy group a decane compound; (B) an organic polymer microparticle comprising a copolymer comprising a monomer unit having an ultraviolet absorbing group; (C) a colloidal cerium oxide; (D) a hardening catalyst; and (E) a dispersion medium. The coating liquid of claim 1, which further comprises (F) a cerium oxide-treated cerium oxide, and (G) a dispersion stabilizer. The coating liquid of claim 1 which is prepared by using the above (A) to (E) as raw materials. The coating liquid of claim 3, which further comprises (F) a cerium oxide-treated cerium oxide, and (G) a dispersion stabilizer as a raw material. The coating liquid according to any one of claims 1 to 4, wherein the component (A-1) or (A-1) is a tetraalkoxy decane compound represented by the following 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; and a plurality of R ^{1 's} may be the same or different). The coating liquid according to any one of claims 1 to 4, wherein the component (A-2) or (A-2) is an amine group, an epoxy group, and an isocyanate group represented by the following formula (2). Organic alkoxydecane compound: R ² _a Si(OR ³ ) _4-a (2) wherein R ² represents an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group or a vinyl group. a phenyl group or an alkyl group having 1 to 3 carbon atoms substituted by a methacryloxy group; R ³ represents an alkyl group having 1 to 4 carbon atoms or an alkyl group having an ether bond; a represents 1 or 2; In the case where R ² is plural, a plurality of R ^{2 's} may be the same or different, and a plurality of OR ^{3 's} may be the same or different]. The coating liquid according to any one of claims 1 to 4, wherein the component (A-3) or (A-3) is a decane compound having an amine group and an alkoxy group represented by the following formula (3): R ⁴ _b Si(OR ⁵ ) _4-b (3) [wherein R ⁴ represents an alkyl group having a carbon number of 1 to 4, a vinyl group, a phenyl group, or a fluorene selected from methyl methacrylate. An oxy group, an amine group (-NH ₂ group), an aminoalkyl group [-(CH ₂ ) _x -NH ₂ group (wherein x is an integer of 1 to 3)], an alkylamino group [-NHR group (wherein , R is an alkyl group having 1 to 3 carbon atoms substituted by one or more groups of the alkyl group having 1 to 3 carbon atoms; and at least one of R ⁴ represents an amino group or an aminoalkyl group or Any one of the alkylamino groups substituted with an alkyl group having 1 to 3 carbon atoms; R ⁵ represents an alkyl group having 1 to 4 carbon atoms; b represents 1 or 2; and when R ⁴ is plural The plurality of R ⁴ may be the same or different, and the plurality of OR ⁵ may be the same or different]. The coating liquid according to any one of claims 1 to 4, wherein the component (A-4) or (A-4) is a decane compound having an epoxy group and an alkoxy group represented by the following formula (4): R ⁶ _c Si(OR ⁷ ) _4-c (4) wherein R ⁶ represents an alkyl group having a carbon number of 1 to 4, a vinyl group, a phenyl group, or a selected from methyl propylene The alkyl group having 1 or more carbon atoms substituted by one or more groups of a nonyloxy group, a glycidoxy group, and a 3,4-epoxycyclohexyl group; at least one of R ⁶ represents a propylene oxide group An alkyl group having 1 to 3 carbon atoms substituted by an oxy group or a 3,4-epoxycyclohexyl group; R ⁷ represents an alkyl group having 1 to 4 carbon atoms; c represents 1 or 2; and R ⁶ is plural In the case of the case, the plurality of R ⁶ may be the same or different, and the plurality of OR ⁷ may be the same or different]. The coating liquid according to any one of claims 1 to 4, wherein the component (A-5) or (A-5) is an blocked isocyanato group having an alkoxy group represented by the following formula (5). a decane compound: R ⁸ _d Si(OR ⁹ ) _4-d (5) wherein R ⁸ represents an alkyl group having a carbon number of 1 to 4, a vinyl group, a phenyl group, or a selected from The alkyl group having 1 to 3 carbon atoms substituted by one or more groups of the methacryloxy group and the blocked isocyanate group; at least one of R ⁸ represents the number of carbons substituted by the blocked isocyanate group Is an alkyl group of 1 to 3; R ⁹ represents an alkyl group having a carbon number of 1 to 4; d represents 1 or 2; and when R ⁸ is plural, a plurality of R ⁸ may be the same or different, and a plurality of OR ⁹ Can be the same or different]. A cured film obtained by hardening a coating liquid according to any one of claims 1 to 9. A resin laminate comprising: a substrate; and a cured film as claimed in claim 10 directly formed on the substrate. A resin laminate comprising a substrate, a cured film of claim 10 formed on the substrate, and an inorganic layer formed on the cured film. A resin laminate comprising a substrate, a cured film of claim 10 formed on the substrate, and a transparent conductive film formed on the cured film. A resin laminate comprising a substrate, a cured film of claim 10 formed on the substrate, and a photocatalyst layer formed on the cured film. The resin laminate according to any one of claims 11 to 14, wherein the cured film has a thickness of 0.1 to 50 μm. The resin laminate according to claim 13, wherein the transparent conductive film has a carrier concentration of 1 × 10 ¹⁸ /cm ³ or more. The resin laminate according to any one of claims 11 to 14, wherein the substrate is a resin substrate. The resin laminate according to claim 11 or 12, wherein the substrate has irregularities. The resin laminate according to claim 17, wherein the substrate has irregularities. The resin laminate according to claim 11 or 12, wherein the substrate is an elliptical cylinder shape. The resin laminate according to claim 11 or 12, wherein the substrate is cylindrical. The resin laminate according to claim 11 or 12, wherein a resin layer is provided on a surface of the substrate on which the cured film is not formed. The resin laminate according to any one of claims 11, 12 and 14, wherein the cured film has a thickness of 0.5 to 6 μm. The resin laminate according to any one of claims 11, 12 and 14, wherein the substrate is a polyester resin, a polycarbonate resin or a polyolefin resin. A method of producing a cured film, comprising the step of heating and hardening a coating liquid according to any one of claims 1 to 9. A method for producing a resin laminate, comprising the steps of: applying a coating liquid according to any one of claims 1 to 9 to a substrate, drying the coating liquid, and thermoforming the substrate The step of curing the coating liquid to form a coating layer. The method for producing a resin laminate according to claim 26, further comprising the step of providing a resin layer on a surface of the resin laminate obtained by curing the coating liquid without a coating layer. A method for producing a resin laminated body, comprising the steps of: forming a cured film obtained by hardening a coating liquid according to any one of claims 1 to 9 on a substrate, and forming a transparent conductive film on the cured film The steps. A method for producing a resin laminate, comprising: forming a coating on a substrate to harden a coating liquid according to any one of claims 1 to 9. A step of forming a cured film, and a step of forming a photocatalyst layer on the cured film.