JP2001131445A - Coating film resin composition and resin molded article with coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an excellent anti-fogging coating film which has excellent anti-fogging performance and good adhesion between the coating film and a molded article and does not cause reduction in hardness of the coating film upon absorbing water. SOLUTION: A coating film resin composition comprises 100 pts.wt. polymerizable monomer mixture composed of 10-80 wt.% polyethylene glycol di(meth)acrylate, 0.1-20 wt.% di(meth)acrylate, 0.1-40 wt.% hydrophilic monomer, and 0.1-50 wt.% colloidal silica whose surface has been modified with a hydrolyzate of a (meth)acrylic functional silane compound and a hydrolyzate of a hydrophilic non-(meth)acrylic functional silane compound, 0.1-10 pts.wt. nonionic surface active agent having an HLB of 6-11, 0.1-5 pts.wt. anionic surface active agent, and 0.01-10 pts.wt. polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a coating film and a resin molded product coated with a coating film comprising a cured product thereof.

[0002]

2. Description of the Related Art Polycarbonate resins and acrylic resins are used in many fields such as goggles, shields and spectacle lenses as substitutes for glass because of their excellent transparency, low cost and light weight, and easy molding. However, since molded products made of these resins are hydrophobic, if there is a sudden change in temperature and humidity, or if they are placed on interfaces with different temperatures and humidity, condensed water will form fine particles on the surface of the molded product. Water droplets are formed and light is scattered, resulting in clouding of the molded article. For this reason, when used in applications in which transparency is important, such as goggles and shields, fogging of the molded article due to the condensation is a serious problem.

[0003] In order to solve such a problem, studies have been made to absorb or diffuse water condensed by surface treatment of a molded article to prevent fogging due to condensation.

[0004]

Problems to be Solved by the Invention Japanese Patent Laid-Open No. 50-2965
No. 6, JP-A-50-71770, JP-A-57
Japanese Patent Application Laid-Open No. 69043/1990 and Japanese Patent Application Laid-Open No. 216185/1990 disclose that a hydrophilic polymer, a surfactant or a solution containing them is applied to the surface of a molded article and dried to form a coating film. A technique for imparting anti-fogging properties by absorbing or diffusing water that has been made hydrophilic and condensed has been disclosed. However, although these techniques can provide anti-fogging properties, they have the drawback that the coating film softens when water is absorbed and is easily damaged, and the anti-fogging effect is easily lost by wiping the molded product surface.

[0005] On the other hand, JP-A-54-78782, JP-A-56-8258, JP-A-57-72856, JP-A-59-217783, and the like use a heat-curable coating agent. A technique for forming a hydrophilic crosslinked coating film on the surface of a molded article is disclosed. However, even with these techniques, the antifogging property, the coating strength, and the adhesion between the coating and the molded product could not be improved in a well-balanced manner. In addition, the formation of a crosslinked coating film requires a heat treatment at a high temperature for a long period of time, which is problematic in terms of productivity and energy cost.

[0006] Japanese Patent Application Laid-Open No. 6-136165 discloses a technique for forming an antifogging coating film by photo-curing. However, the antifogging property, the coating strength, and the adhesion between the coating film and the substrate are all considered. No good has been obtained.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, a specific resin composition for a coating film is applied to a resin molded product and cured to obtain an anti-fog. Excellent performance, thermoformability, coating film adhesion and scratch resistance,
A resin molded article coated with an excellent coating film having no reduction in anti-fog performance due to thermoforming or a decrease in hardness upon water absorption was found.

[0008] That is, the gist of the present invention is the following component (a):
(B) 100 parts by weight of a polymerizable monomer mixture containing the following amounts of (c) and (d), 0.1 to 10 parts by weight of a nonionic surfactant having an HLB of 6 to 11, and an anionic surfactant The resin composition for a coating film comprises 0.1 to 5 parts by weight and 0.01 to 10 parts by weight of a polymerization initiator.

Polyethylene glycol di (meth) acrylate (a) 10 to 80% by weight Di (meth) acrylate (b) represented by the following general formula (1) 0.1 to 20% by weight

Embedded image (R ¹ represents CH ₃ or H, and i represents an integer of 2 to 10.) 0.1 to 40% by weight of a hydrophilic monomer (c) copolymerizable with the components (a) and (b) (meta Colloidal silica (d) having a surface modified with a hydrolyzate of an acrylic-functional silane compound and a hydrolyzate of a hydrophilic non-functional silane compound 0.1 to 60% by weight In the above-mentioned resin composition for a coating film, Preferably, the (meth) acryl-functional silane compound comprises a Michael addition product of a mercapto group-containing silane or amino group-containing silane and polyethylene glycol di (meth) acrylate.

[0010] In the above-mentioned resin composition for a coating film, the hydrophilic non-functional silane compound may be formed by a Michael addition reaction between a mercapto group-containing silane or an amino group-containing silane and a hydrophilic monofunctional (meth) acrylic monomer. It is preferably made of a material.

Further, in the above-mentioned resin composition for a coating film, the nonionic surfactant is preferably a compound represented by the following general formula (2).

Embedded image (R ² is an alkyl group or an alkylphenyl group, j is 1
Represents an integer of from 30 to 30. Furthermore, in the resin composition for a coating film described above, the anionic surfactant is preferably a compound represented by the following general formula (3).

Embedded image (R ³ is an alkyl group or an alkylphenyl group, R ⁴ is-
It represents an OZ or _{-O- (CH 2 CH 2 O)} k -R 3. Z represents an alkali metal or ammonium salt, and k represents an integer of 1 to 30. The gist of the present invention resides in a resin molded article coated with a coating film composed of a cured product of the above-described resin composition for a coating film.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The average molecular weight of polyethylene glycol di (meth) acrylate (a), which is a component of a polymerizable monomer mixture constituting the resin composition for a coating film of the present invention, is 2
00 to 2000, preferably 200 to 100.
More preferably, it is 0. (Meth) acrylate is methacrylate or acrylate.
When the average molecular weight is too low, a coating film (hereinafter, appropriately referred to as a “coating film”) formed of a cured product of the resin composition for a coating film is insufficient in hydrophilicity, and good anti-fog performance cannot be obtained. If it is too high, the hardness of the coating film will be insufficient. Adhesion between the coating film and the resin molded product (hereinafter referred to as "adhesion of the coating film as appropriate") is good, and in order to obtain a coating film having high antifogging performance and hardness, an average molecular weight of less than 200 to 400 is required. And an average molecular weight of 400 to 20
Preference is given to the combination with the one of 00. Average molecular weight 200-3
A combination of 50 and an average molecular weight of 400 to 1000 is more preferred. The content of the polyethylene glycol di (meth) acrylate (a) in the polymerizable monomer mixture is 10 to 80% by weight, and preferably 20 to 60% by weight.

The general formula (1) which is a component of the polymerizable monomer mixture
As the di (meth) acrylate (b) represented by
1,4-butanediol di (meth) acrylate, 1,
5-pentanediol di (meth) acrylate, 1,6
-Hexanediol di (meth) acrylate, 1,9-
Nonanediol di (meth) acrylate is exemplified. The content of these di (meth) acrylates (b) in the polymerizable monomer mixture is from 0.1 to 20% by weight,
Preferably it is 2 to 15% by weight. Content is 0.1
When the amount is lower than the weight%, when the coating film is placed under high temperature and high humidity, the hardness of the coating film is reduced and the adhesion of the coating film is easily reduced. On the other hand, if it is higher than 20% by weight, the water absorption of the coating film is reduced, and good antifogging performance cannot be obtained.

The hydrophilic monomer (c) which is a component of the polymerizable monomer mixture is a hydrophilic monomer copolymerizable with the above-mentioned polyethylene glycol di (meth) acrylate (a) and di (meth) acrylate (b). It is a functional monomer. Specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, (meth) acryloylmorpholine, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth)
Acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-vinylpyrrolidone, polyethylene glycol (meth) acrylate, alkylphenoxypolyethylene glycol (meth) acrylate, and the like are included. (Meth) acryloyl is methacryloyl or acryloyl. (Meth) acrylamide is methacrylamide or acrylamide. Among them, (meth) acrylamide-based monomers are particularly preferable because they can improve the adhesion and hydrophilicity of the coating film and can enhance the ability to hold a surfactant in the coating film. Hydrophilic monomer (c) in polymerizable monomer mixture
Is 0.1 to 40% by weight, preferably 1 to 20% by weight. When the content is less than 0.1% by weight, the hydrophilicity of the coating film is deteriorated. If it is higher than 40% by weight, the strength of the coating film, particularly the strength of the coating film upon absorbing water, is reduced.

The surface of the colloidal silica (d), which is a component of the polymerizable monomer mixture, has been modified with a hydrolyzate of a (meth) acryl-functional silane compound and a hydrolyzate of a hydrophilic non-functional silane compound. Colloidal silica. The content of the surface-modified colloidal silica (d) in the polymerizable monomer mixture is 0.1 to 60% by weight, and 20 to 6% by weight.
It is preferably 0% by weight. Here, "the surface is modified with the hydrolyzate" means that the hydrolyzate of the silane compound is retained on a part or all of the surface of the colloidal silica by a condensation reaction, and the surface characteristics of the colloidal silica are improved. It means being quality. In addition, colloidal silica that has undergone a condensation reaction of the hydrolyzate and is retained at the same time is also included in the “hydrolyzate-modified surface” colloidal silica (d).

The surface modification in the present invention can be easily performed, for example, by adding a silane compound to a colloidal silica sol and causing hydrolysis or a hydrolysis and condensation reaction. As a catalyst for performing the hydrolysis reaction of the silane compound, an inorganic acid or an organic acid can be used. Examples of the inorganic acid include hydrohalic acids such as hydrochloric acid, hydrofluoric acid, and hydrobromic acid, sulfuric acid, nitric acid, and phosphoric acid. Organic acids include formic acid, acetic acid, oxalic acid,
Examples include acrylic acid and methacrylic acid. Examples of the dispersion medium of the colloidal silica sol include water; alcohols such as methanol, ethanol, and isopropyl alcohol; ketones such as acetone and methyl isobutyl ketone; and ethers such as tetrahydrofuran and dioxane.

The hydrolysis and condensation reaction of the silane compound is carried out at room temperature to
It is preferable to carry out the reaction at a temperature of about 120 ° C. for about 30 minutes to 24 hours. More preferably, the reaction is carried out at a temperature from room temperature to about the boiling point of the solvent for about 1 to 10 hours. When the surface modification of colloidal silica is carried out with a hydrolyzate of a (meth) acryl-functional silane compound and a hydrolyzate of a hydrophilic non-functional silane compound,
After the surface modification with the hydrolyzate of the acrylic functional silane compound, it is preferable to perform the surface modification with the hydrolyzate of the hydrophilic non-functional silane compound. If surface modification is first performed with a hydrolyzate of a hydrophilic non-functional silane compound, colloidal silica may aggregate, making it difficult to obtain a good coating resin composition.

The hydrolyzate of a (meth) acryl-functional silane compound that modifies the surface of colloidal silica is a hydrolysis of a Michael addition reaction product of a silane containing a mercapto group or a silane containing an amino group with polyethylene glycol di (meth) acrylate. It is preferably made of a material.

The mercapto group-containing silane as a raw material of the (meth) acryl-functional silane compound is preferably represented by the following general formula (4).

Embedded image (R ⁵ is a monovalent hydrocarbon group or a fluorinated alkyl group,
R ⁶ represents a divalent substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms. X represents a hydrolyzable group such as an alkoxy group, an amino group, or an isopropenoxy group, and a represents an integer of 1 to 3. ) Examples of R ⁵ include methyl, ethyl, propyl, butyl, phenyl, octadecyl, 2-phenylethyl, vinyl, 3,3,3-trifluoropropyl, 2- (perfluoroethyl) ethyl, and 2- (perfluoro Butyl) ethyl and the like.

Examples of R ⁶ include groups such as methylene, ethylene, butylene, hexylene, propylene, and decylene; unsubstituted divalent hydrocarbon groups represented by the following general formula (5);
And a divalent hydrocarbon group having a substituent such as -hydroxypropyl.

Embedded image Examples of these mercapto group-containing silanes include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane Silane, γ-mercaptopropylethyldiethoxysilane, γ-mercaptopropylbutyldimethoxysilane, δ-mercaptobutyltrimethoxysilane, δ
-Mercaptopropyltriethoxysilane, δ-mercaptobutylmethyldimethoxysilane, δ-mercaptobutylethyldimethoxysilane, δ-mercaptobutylmethyldiethoxysilane, δ-mercaptobutylethyldiethoxysilane, γ-mercaptoisobutyltrimethoxysilane, γ -Mercaptoisobutylmethyldimethoxysilane, γ-mercaptobutyltrimethoxysilane, γ
-Mercaptobutylmethyltrimethoxysilane, γ-mercapto-2-hydroxypropyltrimethoxysilane, γ-mercapto-2-hydroxypropyltriethoxysilane, γ-mercapto-2-hydroxypropylmethyldimethoxysilane, γ-mercapto-2- Examples include hydroxypropylethyldiethoxysilane, γ-mercaptopropyldimethylmethoxysilane, γ-mercaptopropyldiethylethoxysilane, β-mercaptoethyltrimethoxysilane, β-mercaptoethyltriethoxysilane, γ-mercaptopropyltriaminosilane, and the like.

The polyethylene glycol di (meth) acrylate as a raw material of the (meth) acryl-functional silane compound preferably has an average molecular weight of 400 or less. If the average molecular weight is too high, agglomeration occurs when mixed with colloidal silica, and a good coating resin composition cannot be obtained.

As a Michael addition reaction product of a mercapto group-containing silane and polyethylene glycol di (meth) acrylate, those represented by the general formula (6) are preferable.

Embedded image (R ⁷ is a monovalent hydrocarbon group or a fluorinated alkyl group,
R ⁸ represents a divalent substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, and R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a methyl group. X represents a hydrolyzable group, a represents an integer of 1 to 3, and m represents an integer of 1 to 9. On the other hand, the amino group-containing silane as a raw material of the (meth) acryl-functional silane compound is N- (2-aminoethyl-silane).
(3-Aminopropyl) trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like are preferable.

As the Michael addition reaction product of the amino group-containing silane and polyethylene glycol di (meth) acrylate, those represented by the general formula (7) are preferable.

Embedded image (R ¹¹ is a monovalent hydrocarbon group or a fluorinated alkyl group,
R ¹² is a divalent substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, R ¹³ and R ¹⁴ are each independently a hydrogen atom or a methyl group, and R ¹⁵ is a hydrogen atom or 1 to 10 carbon atoms.
Represents a monovalent hydrocarbon group. X is a hydrolyzable group, a is 1
An integer of 1 to 3, and n represents an integer of 1 to 9. Although these Michael addition reactions proceed at room temperature without a catalyst, the catalyst can increase the reaction rate. As the catalyst, metal alkoxide, piperidine, 4
Quaternary ammonium salts, tertiary phosphines and the like. Among them, tertiary phosphine is preferred from the viewpoint of high catalytic activity and easy handling, and triphenylphosphine is more preferred. Further, by performing the reaction in a solvent, the reaction rate can be further increased. As the solvent, a highly polar solvent such as alcohol is preferable. When the solvent is removed after the completion of the reaction, a low-boiling alcohol such as ethanol or isopropanol is more preferable.

A comparison between the (meth) acryl-functional silane compounds represented by the general formulas (6) and (7) shows that the dispersion stability of the surface-modified colloidal silica and the anti-fog performance of the obtained coating film are compared. The one represented by the general formula (6) is more preferable in terms of balance between the coating film hardness and the film adhesion.

In general, when a resin composition for a coating film containing a polyfunctional (meth) acrylate monomer as a main component is applied to a resin molded product and then cured to form a coating film, a resin molded product by a so-called anchor effect is used. In order to obtain adhesion to the resin, a method of applying the resin composition for a coating film, allowing the resin composition to penetrate into a resin molded product for a certain period of time, and curing the resin composition is often used.

At this time, in the resin composition for a coating film containing a polyfunctional (meth) acrylate monomer as a main component and colloidal silica dispersed therein, the resin composition for a coating film penetrates into a resin molded product. Therefore, in the cured coating film, colloidal silica may take a form concentrated on the coating film surface. In that case, when the surface modification of the colloidal silica is performed only with the (meth) acryl-functional silane compound, the crosslink density of the coating film surface at the time of curing becomes extremely high, and the antifogging performance may be reduced.

Therefore, in the present invention, a hydrolyzate of a (meth) acryl-functional silane compound and a hydrolyzate of a hydrophilic non-functional silane compound are used in combination as components for modifying the surface of colloidal silica. Thereby, even when the colloidal silica (d) is concentrated on the surface of the coating film, the crosslink density of the coating film does not increase excessively, and the antifogging performance can be maintained.

The hydrolyzate of the hydrophilic non-functional silane compound is obtained from the hydrolyzate of a Michael addition reaction product of a mercapto group-containing silane or an amino group-containing silane and a hydrophilic monofunctional (meth) acrylic monomer. Preferably,

The mercapto group-containing silane and amino group-containing silane as raw materials for the hydrophilic non-functional silane compound include those described above.

The hydrophilic monofunctional (meth) acrylic monomer as a raw material of the hydrophilic non-functional silane compound includes N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, (Meth) acrylamide-based monomers such as N, N-dimethylaminopropyl (meth) acrylamide and N-isopropyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate,
Examples include 2-hydroxybutyl acrylate, (meth) acryloyl morpholine, polyethylene glycol (meth) acrylate, and alkylphenoxy polyethylene glycol (meth) acrylate.

As the hydrophilic nonfunctional silane compound, a compound represented by the general formula (8), which is a Michael addition reaction product of a (meth) acrylamide-based monomer and a mercapto group-containing silane, is obtained as a coating film. This is particularly preferred because it can increase the adhesion and anti-fog performance of the polymer and the holding power of the added surfactant in the coating film.

Embedded image (R ¹⁶ is a monovalent hydrocarbon group or a fluorinated alkyl group, R ¹⁷ is a divalent substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, and R ¹⁸ is an alkyl group having 1 to 5 carbon atoms. X represents a hydrolyzable group, and a represents an integer of 1 to 3.) The nonionic surfactant constituting the resin composition for a coating film of the present invention has an HLB of 6 to 11. Here, the HLB is a hydrophilic-lipophilic balance, and is represented by the following general formula (9), where the molecular weight of the hydrophilic group is Mw and the molecular weight of the lipophilic group is Mo.

Embedded image When the HLB is lower than 6, the antifogging performance of the coating film is reduced. When the HLB is higher than 11, the adhesion of the coating film deteriorates. The content of the nonionic surfactant is 0.1 to 10 parts by weight, more preferably 1 to 7 parts by weight, based on 100 parts by weight of the polymerizable monomer mixture. When the content of the nonionic surfactant is lower than 0.1 part by weight, it is difficult to balance the antifogging performance with the coating film hardness. When the amount is higher than 10 parts by weight, the adhesion of the coating film is reduced, and when the molded article coated with the coating film is left, a large amount of bleeding of the nonionic surfactant is observed from the coating film surface. Occurs. The nonionic surfactant is preferably represented by the general formula (2).

Examples of the surfactant represented by the general formula (2) include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octyl phenyl ether. And polyoxyethylene nonyl phenyl ether.

The anionic surfactant constituting the resin composition for a coating film of the present invention is preferably one represented by the general formula (3). This can be obtained by completely or partially neutralizing the phosphoric acid residue of the polyoxyethylene alkyl ether phosphoric diester alone or a mixture of the phosphoric monoester and the phosphoric diester. Further, it can be obtained by completely or partially neutralizing a phosphoric acid residue of a phosphoric acid diester alone or a mixture of a phosphoric acid monoester and a phosphoric acid diester of polyoxyethylene alkylphenyl ether. Specific examples of the polyoxyethylene alkyl ether include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like. Specific examples of polyoxyethylene alkyl phenyl ether include polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether and the like. The content of the anionic surfactant is 100 parts of the polymerizable monomer mixture.
It is 0.1 to 5 parts by weight with respect to parts by weight. Content is 0.
If the amount is less than 1 part by weight, the antifogging performance after the heat history deteriorates. When the amount is higher than 5 parts by weight, undissolved matter of the anionic surfactant is precipitated in the resin composition for coating film or foaming property is increased, and a large amount of foam is generated at the time of stirring and dissolving, thereby deteriorating the appearance of the coating film. .

[0034] As the polymerization initiator constituting the resin composition for a coating film, any one can be used. As the polymerization initiator, benzophenone, Michler's ketone, benzoin, benzoin ethyl ether, benzoin isopropyl ether,
Benzoin isobutyl ether, methylbenzoyl formate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl)
-2-idoxy-2-methylpropan-1-one, benzyldimethylketal, benzyldiethylketal,
Diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, isopropylthioxanthone, 2,4-diethyl Photoinitiators such as thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile,
Thermal polymerization initiators such as benzoyl peroxide and di-tert-butyl peroxide are included. These polymerization initiators may be used alone or in combination of two or more.

[0035] The content of the polymerization initiator is determined based on the polymerizable monomer mixture 1
It is 0.01 to 10 parts by weight with respect to 00 parts by weight. When the content of the polymerization initiator is lower than 0.01 part by weight, the hardness of the obtained coating film decreases. If the amount is higher than 10 parts by weight, coloring of the coating film and deterioration of antifogging performance occur.

The method of applying the resin composition for a coating film of the present invention to the surface of a resin molded product includes a roll coater method, a knife coater method, a dip coat method, a spray coat method and the like. In order to obtain a resin molded product coated with a coating film having good antifogging performance, the thickness of the polymerized and cured coating film is preferably 5 to 100 μm. Therefore, it is preferable to select a coating method that can obtain a desired film thickness according to the viscosity of the resin composition for a coating film. While producing the resin plate, the resin composition for a coating film is applied to the resin plate and polymerized and cured to obtain a resin plate coated with the coating film continuously.

As a method of polymerizing and curing the resin composition for a coating film, a thermal polymerization method, a photopolymerization method, or the like can be used, but a photopolymerization method is preferably used in terms of energy cost and the like. Also, during polymerization, to avoid polymerization inhibition by oxygen,
It is preferable to polymerize and cure under an atmosphere of an inert gas such as nitrogen. It is also preferable to polymerize and cure under an atmosphere in which the resin composition for a coating film is covered with a resin film or a mold and the air is shut off.

[0038] If necessary, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a solvent, a thickener, an inorganic filler and the like can be added to the resin composition for a coating film.

[0039] Examples of the resin molded article to be coated with the coating film made of the cured product of the resin composition for a coating film of the present invention include molded articles of acrylic resin, polycarbonate resin, polystyrene resin, polyester resin and the like. A molded article of an acrylic resin or a polycarbonate resin is preferable in terms of the transparency of the resin and the adhesion of the coating film. A resin molded article coated with a coating film composed of a cured product of the coating resin composition of the present invention has excellent scratch resistance, durability and anti-fog properties, ski goggles, a helmet shield, a meter cover, an eyeglass lens, Suitable for nameplates and the like.

[0040]

The present invention will be described below with reference to examples. still,
The present invention is not limited to the following examples. In each of the examples, unreacted components such as polyethylene glycol di (meth) acrylate and hydrophilic monomer added in excess when modifying the surface of the colloidal silica are the polymerizable monomer mixture. Are listed in Table 1 as components constituting In addition, each physical property of the resin molded article coated with the coating film (hereinafter, appropriately referred to as “sample”) was evaluated under the following conditions.

(1) Anti-fogging property (1-1) Evaluation by exhalation The sample was conditioned at 23 ° C. in a 50 RH% environment for 24 hours, and then from the distance of 20 to 30 mm to the coating surface in the same environment. Exhaled air was blown to observe and evaluate the state of cloudiness. ：: There is no clouding or deterioration of transparency even when breath is blown 10 times for 2 seconds. Δ: There is no clouding even when breath is blown for 2 seconds.
Blowing occurs by blowing breath for 2 seconds. (1-2) Durability evaluation Environment of 60 RH% at 23 ° C and 95 RH% at 40 ° C. The sample was placed on the boundary with the environment such that the coating film had an environment side of 95 RH% at 40 ° C., and the change in transparency was visually observed for 1 hour and evaluated. ：: No fogging occurred, the entire surface of the coating film was uniformly wetted, and the state of good transparency continued for 1 hour. ×: Transparency decreased due to generation of fogging or uneven wetting of the coating film. Adhesion of film A 100 mm grid of 1 mm x 1 mm was made on the sample coating film with a cutter, and an adhesive tape (Nichiban Co., Ltd.)
The adhesive tape was rapidly peeled off three times, and the number of grids not peeled was counted to evaluate the adhesion.

(3) Scratch resistance (Δ haze) 25.4 mm in diameter with # 000 steel wool
Was placed on the coating side of the sample, and the sample was reciprocated 100 times at a distance of 20 mm while applying a load of 1000 g, and the difference between the haze value before and after the abrasion was determined by the following formula as Δhaze. ΔHaze (%) = Haze value after abrasion (%) − Haze value before abrasion (%) (4) Moisture resistance After leaving the sample in an environment of 60 ° C. and 95 RH% for 5 days, the coating film was nailed. The scratch resistance of the coating film upon rubbing was evaluated. ○: No damage at all △: Scratched ×: Coating falls off when rubbed (5) Thermoformability After heating the sample for 10 minutes in a hot air drying oven at 165 ° C., apply it using a wooden mold with a curvature radius of 40 mm. Single curved surface bending was performed so that the film surface was on the concave side, and the occurrence of cracks was observed.

Example 1 A flask A was charged with 156 parts by weight of isopropanol and dimethylacrylamide (hereinafter referred to as “DMA”).
A), 100 parts by weight of γ-mercaptopropyltrimethoxysilane KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.), and 45 parts by weight of a 3% by weight solution of triphenylphosphine in isopropanol. In addition, the solution was reacted at room temperature for 3 days to synthesize a hydrophilic non-functional silane compound.

Then, 71 ml of isopropanol was added to flask B.
70 parts by weight of NK ester A-200 (manufactured by Shin-Nakamura Chemical Co., Ltd .; hereinafter, referred to as “A-200”) which is polyethylene glycol diacrylate having a molecular weight of 200,
14 parts by weight of KBM-803 and 9.1 parts by weight of a 3% by weight solution of triphenylphosphine in isopropanol were sequentially added, and the solution was heated to 60 ° C. and reacted for 3 hours to synthesize an acrylic-functional silane compound.

[0045] IPA which is a colloidal silica having a solid content of 30% by weight using isopropanol as a dispersion medium is added to the obtained reaction solution.
234 parts by weight of -ST (manufactured by Nissan Chemical Industries, Ltd.)
Next, 6 parts by weight of a 0.01 N hydrochloric acid aqueous solution was added, and
The mixture was stirred at a temperature of 1 hour for 1 hour to modify the surface of the colloidal silica with a hydrolyzate of an acrylic functional silane compound.

To flask B, 56 parts by weight of the mixture containing the hydrophilic non-functional silane compound in flask A and 6 parts by weight of a 0.01 N hydrochloric acid aqueous solution were added, and the mixture was further reacted at 60 ° C. for 1 hour to form colloidal silica. The surface was modified.

Next, NK ester A-4 which is polyethylene glycol diacrylate having a molecular weight of 400 was added to the reaction solution.
00 (manufactured by Shin-Nakamura Chemical Co., Ltd .; hereinafter, referred to as “A-400”) is 53 parts by weight, and Emulgen 905 (manufactured by Kao Corporation), which is a nonionic surfactant having an HLB of 9.2, is 7 parts by weight. 4.2 parts by weight of LO-529 (manufactured by Toho Chemical Industry Co., Ltd.), which is a phosphanol anionic surfactant of the formula (3), is added, and the mixture is distilled under reduced pressure using a rotary evaporator. I left.

To 100 parts by weight of this reaction solution, 5 parts by weight of 1,6 hexanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., hereinafter referred to as “C6DA”) and 2,4,6-trimethyl as a polymerization initiator 1.5 parts by weight of Lucirin TPO (manufactured by BASF, hereinafter referred to as “TPO”) which is diphenylphosphine oxide was added and dissolved to produce a resin composition for a coating film.

[0049] The resin composition for coating film was applied on a 2 mm-thick polycarbonate plate (dialite manufactured by Mitsubishi Rayon Co., Ltd .; hereinafter, referred to as "PC plate") preheated in a hot air drying oven at 60 ° C. . Furthermore, a biaxially stretched film made of polyethylene terephthalate having a thickness of 50 μm (Teijin Corporation)
(Hereinafter referred to as “PET film”) and ironed with a rubber roll having a JIS hardness of 40 ° to make the thickness of the resin composition for coating film 12 μm. After leaving for 50 seconds, output 1
A 210 mm distance from a 20 w / cm ozone-less type metal halide lamp was passed through a PC plate at a speed of 1.6 m / min with the PET film surface facing the lamp side, and polymerized and cured. Thereafter, the PET film was peeled off, and a PC board was passed at a speed of 1.6 m / min with the coating surface facing the lamp side at a distance of 210 mm from a high pressure mercury lamp of an ozone-less type having an output of 120 w / cm to carry out polymerization curing. It was completed to obtain a PC board coated with a coating film. In addition, the temperature on the surface of the PET film was 40 to 43 ° C. from the time when the thickness of the resin composition for coating film was set to 12 μm until the irradiation with the metal halide lamp.

Table 1 shows the evaluation results of the PC boards coated with the obtained coating films.

Example 2 A resin composition for a coating film was produced in the same manner as in Example 1 except that the amount of C6DA was changed to 10 parts by weight, and a PC plate was coated with the coating film. Table 1 shows the evaluation results.

Example 3 A resin composition for a coating film was produced in the same manner as in Example 1, except that 100 parts by weight of acryloylmorpholine (hereinafter referred to as “ACMO”) was used instead of 100 parts by weight of DMAA. Then, the coating film was coated on a PC plate. Table 1 shows the evaluation results.

Comparative Example 1 A resin composition for a coating film was produced in the same manner as in Example 1 except that C6DA was not added.
The coating was applied to a PC board. Table 1 shows the evaluation results.

Comparative Example 2 A resin composition for a coating film was produced in the same manner as in Example 1, except that the amount of C6DA was changed to 25 parts by weight, and a PC plate was coated with the coating film. Table 1 shows the evaluation results.

Comparative Example 3 In the same manner as in Example 1, the surface of colloidal silica was modified with a hydrolyzate of an acrylic functional silane compound.

Next, 12 parts by weight of A-200 was added to the reaction solution.
A mixture of 68 parts by weight of A-400, 7 parts by weight of Emulgen 905 and 4.2 parts by weight of Phosphanol LO-529 was added, and volatile components were distilled off under reduced pressure using a rotary evaporator.

To 100 parts by weight of this reaction solution, 5 parts by weight of C6DA and 1.5 parts by weight of TPO were added and dissolved to prepare a resin composition for coating, and the polycarbonate plate was coated with the coating. Table 1 shows the evaluation results.

Comparative Example 4 200 parts by weight of IPA-ST were added to a flask, and then 12 parts by weight of KBM-103 (manufactured by Shin-Etsu Chemical Co., Ltd.), a phenyltrimethoxysilane, and 0.01 N hydrochloric acid aqueous solution 4 .5 parts by weight, 6
After stirring at 0 ° C. for 1 hour, the surface of the colloidal silica was modified with a hydrolyzate of a non-hydrophilic non-functional silane compound.

Next, 46.8 parts by weight of A-200, 31.2 parts by weight of A-400 and Emulgen 905 were added to the reaction mixture.
4.5 parts by weight and Phosphanol LO-529 in 2.
Volatile components were distilled off under reduced pressure from the mixture added by 7 parts by weight using a rotary evaporator.

[0060] To 104.8 parts by weight of the reaction solution, 1 TPO was added.
5 parts by weight were added and dissolved to produce a resin composition for a coating film, and the polycarbonate plate was coated with the coating film. Table 1 shows the evaluation results.

[Comparative Example 5] KBM which is γ-methacryloxypropyltrimethoxysilane instead of KBM-103
-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used to produce a resin composition for a coating film in the same manner as in Comparative Example 4 except that the surface of colloidal silica was modified with a hydrolyzate of an acrylic functional silane compound. Then, the coating film was coated on the polycarbonate plate. Table 1 shows the evaluation results.

Comparative Example 6 A hydrophilic non-functional silane compound was synthesized in the same manner as in Example 1.

Next, 234 parts by weight of IPA-ST, 56 parts by weight of a mixture containing a hydrophilic non-functional silane compound and 0.1 part by weight of IPA-ST were added.
6 parts by weight of a 01N aqueous hydrochloric acid solution was added. Colloidal silica aggregated into a gel by the addition of the hydrophilic non-functional silane compound, and a resin composition for a coating film could not be produced.

[0064]

[Table 1]

[0065]

According to the present invention, antifogging performance, thermoformability,
A resin molded article coated with an excellent coating film having excellent adhesion and abrasion resistance of the coating film, and having no reduction in antifogging performance due to thermoforming or a decrease in hardness upon water absorption can be obtained. The cured product of the resin composition for a coating film of the present invention is suitable for the above-mentioned coating film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08J 7/04 CFD C08J 7/04 CFDA C09D 5/02 C09D 5/02 // C08L 101: 00 C08L 101: 00

Claims (6)

[Claims] 1. Nonionic surfactant having a HLB of 6 to 11 and a polymerizable monomer mixture containing the following components (a), (b), (c) and (d) in the following amounts: .1 to
A resin composition for coating films comprising 10 parts by weight, 0.1 to 5 parts by weight of an anionic surfactant and 0.01 to 10 parts by weight of a polymerization initiator. Polyethylene glycol di (meth) acrylate (a)
10 to 80% by weight Di (meth) acrylate (b) represented by the following general formula (1) 0.1 to 20% by weight (R ¹ represents CH ₃ or H, and i represents an integer of 2 to 10.) 0.1 to 40% by weight of a hydrophilic monomer (c) copolymerizable with the components (a) and (b) (meta ) 0.1-60% by weight of colloidal silica (d) whose surface is modified with a hydrolyzate of an acrylic functional silane compound and a hydrolyzate of a hydrophilic non-functional silane compound 2. The method according to claim 1, wherein the (meth) acryl-functional silane compound comprises a Michael addition reaction product of a silane containing a mercapto group or a silane containing an amino group and polyethylene glycol di (meth) acrylate. A resin composition for coating films. 3. A hydrophilic non-functional silane compound comprising a Michael addition reaction product of a mercapto group-containing silane or amino group-containing silane and a hydrophilic monofunctional (meth) acrylic monomer. Item 3. The resin composition for a coating film according to Item 1 or 2. 4. The resin composition for a coating film according to claim 1, wherein the nonionic surfactant is a compound represented by the following general formula (2). Embedded image (R ² is an alkyl group or an alkylphenyl group, j is 1
Represents an integer of from 30 to 30. ) 5. The resin composition for a coating according to claim 1, wherein the anionic surfactant is a compound represented by the following general formula (3). Embedded image (R ³ is an alkyl group or an alkylphenyl group, R ⁴ is-
It represents an OZ or _{-O- (CH 2 CH 2 O)} k -R 3. Z represents an alkali metal or ammonium salt, and k represents an integer of 1 to 30. ) 6. A resin molded article coated with a coating film comprising a cured product of the resin composition for a coating film according to any one of claims 1 to 5.