JPH0810695A - Manufacture of antifogging coated product - Google Patents

Abstract

PURPOSE:To provide a method for manufacturing an antifogging coated product with antifogging and waterproofing properties. CONSTITUTION:A composition A consisting of a polymer with a repeating structural unit expressed by the formula -(CH2-CR1R2-) (in the formula, R1 is hydrogen atom or methyl group; R2 is a side chain with an epoxy group), a hydrophobic monomer having at least, two (meth)acryloyl group in one molecule and a photopolymerization initiator, is applied as an undercoat, on the surface of a base, and is optically cured. Next, a solution B of a hydrophilic polymer with a repeating structural unit expressed by the formula -(CH2-CR3R4-) (in the formula, R3 is hydrogen or methyl; R4 is a side chain with a carboxyl group), is applied to the cured coat, and then is thermally set.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an antifogging article, and more particularly to lenses for eyeglasses and cameras having antifogging performance, window glasses, windshields of automobiles, shields for helmets, underwater eyeglasses. The present invention relates to a method for producing an optical article such as the above, or an antifogging article used for a mirror or the like used in a bathroom or a washroom.

[0002]

2. Description of the Related Art Ordinary plastics, inorganic glass, and the like used as transparent materials have a drawback in that when the surface temperature falls below the dew point, the surface becomes cloudy and the transparency is impaired.

As a conventional method for preventing the cloudiness of the surface, for example, a hydrophilic acrylate monomer having an alcoholic hydroxyl group is copolymerized with a specific polyfunctional monomer, or a water-soluble polyvinyl alcohol or the like is used. A method of forming a water-absorbing film by crosslinking a polymer, a method of kneading a surfactant in the resin of a molded article,
A method of applying a composition containing a surfactant to the surface of a substrate is known.

[0004]

However, according to the above method, since the water absorption of the film is controlled by the degree of cross-linking, it is difficult to achieve both the antifogging property and the water resistance due to the water absorption of the film. is there. Further, the methods (1) and (2) also have a problem that the antifogging property is significantly lowered when the surfactant flows out by water.

As a method of solving these problems, for example, in Japanese Patent Publication No. 61-40695, after a hydrophobic monomer mixture having two or more unsaturated groups is prepolymerized and gelled, A method in which a hydrophilic monomer having a hydrophilic group such as a carboxylic acid group, a sulfonic acid group, a sulfuric acid group, a phosphoric acid group, an amino group, and a hydroxyl group and a polymerizable unsaturated group is brought into contact with the surface to copolymerize on the surface. Is proposed. However, it is difficult to control the degree of prepolymerization by this method.

The present invention has been made for the purpose of solving the above-mentioned conventional problems and providing a method for producing an antifogging coated article having both antifogging property and water resistance.

[0007]

[Means for Solving the Problems] First, claim 1 of the present application
The above-mentioned invention (hereinafter referred to as the first invention) will be described.
The present invention 1 is a plastic molded body substrate or an inorganic glass substrate.
On the surface of the material, ─ [CH₂--CR₁R₂─] (where R₁Represents a hydrogen atom or a methyl group, R ₂ Represents a side chain having an epoxy group) ... A polymer having a repeating structural unit represented by the general formula (1) and one molecule
Having at least two (meth) acryloyl groups in
Composition A consisting of a hydrophobic monomer and a photopolymerization initiator
It has a first step of applying as a coating layer and photo-curing.

In the first step of the first aspect of the present invention, a plastic plate-shaped molded product such as acrylic resin or polycarbonate, an inorganic glass plate or the like is used as the substrate. These substrates may be subjected to a pretreatment, if necessary, for the purpose of further improving the adhesion. Particularly when the substrate is an inorganic glass plate, pretreatment with a silane coupling agent is effective.

As a method of providing an undercoat layer on a substrate,
A conventionally known method can be applied, for example, spray coating,
Various methods such as bar coating, dipping, roll coating and spin coating are used.

As the polymer having the repeating structural unit represented by the above general formula (1), a polymerizable monomer having an epoxy group may be polymerized alone or in combination of two or more kinds, or
Alternatively, it can be obtained by copolymerization of a polymerizable monomer having an epoxy group and a polymerizable monomer having no epoxy group.

Examples of the polymerizable monomer having an epoxy group include glycidyl (meth) acrylate, β-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate and 4,5-epoxypentyl ( (Meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, allyl glycidyl ether and the like are used.

As the polymerizable monomer having no epoxy group, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p
-Ethylstyrene, 2,4-dimethylstyrene, pn
-Hexyl styrene, pn-octyl styrene, p-
Styrenes such as methoxystyrene and p-phenylstyrene, vinyl acetates such as vinyl acetate, vinyl propionate and vinyl butyrate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
N-butyl (meth) acrylate, isobutyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, -2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate , (Meta)
Benzyl acrylate, isobornyl (meth) acrylate, dicyclopentanyl methacrylate, (meth) acrylic acid ester such as 2-hydroxyethyl (meth) acrylate, vinyl methyl ether, vinyl toluene ether, vinyl ethyl ether, etc. Vinyl ethers, vinyl methyl ketone, vinyl ethyl ketone, and other vinyl ketones are used.

These may be used alone or in combination of two or more. Further, in order to prevent gelation due to crosslinking during polymerization, it is necessary to use a polymerizable monomer having no epoxy group that does not react with the epoxy group under the conditions of polymerization.

When the amount of the repeating structural unit having an epoxy group in the polymer containing the repeating structural unit represented by the above general formula (1) is small, the hydrophilic polymer is not fixed in the second step. Since it is not sufficiently performed, it is preferably contained in an amount of 20 mol% or more.

As the hydrophobic monomer having at least two (meth) acryloyl groups in one molecule, for example, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, bisphenol A di (Meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, dicyclope Tani diacrylate, neopentyl glycol di (meth) acrylate, tris (acryloyloxyethyl) isocyanurate, tris and (methacryloxyethyl) isocyanurate, difunctional or more urethane acrylates or polyester acrylates are used.

These may be used alone or in combination of two or more. If the amount of the hydrophobic monomer is too large, the amount of the epoxy group-containing polymer becomes relatively small, and the hydrophilic polymer is not sufficiently fixed in the second step. If it is too small, the hardness is insufficient. Therefore, 10 to 500 parts by weight is preferable with respect to 100 parts by weight of the polymer having the repeating structural unit represented by the general formula (1).

Any photopolymerization initiator may be used as long as it has a property of polymerizing the hydrophobic monomer by actinic rays such as ultraviolet rays and visible rays. As such a photopolymerization initiator, those described in detail in "UV Curing System" (written by Kiyomi Kato) published by Sogo Gijutsu Center Co., Ltd. are specifically used. The following are examples of those activated by.

(1) Sulfides such as sodium methyldithiocarbamate sulfide, tetramethylthiuram monosulfide, diphenylmonosulfide, diphenylmonosulfide, dibenzothiazoyl monosulfide and disulfide.

(2) Thioxanthone derivatives such as thioxanthone, ethylthioxanthone, 2-chlorothioxanthone, diethylthioxanthone and diisopropylthioxanthone. (3) Diazo compounds such as hydrazone, azoisobutyronitrile and benzenediazonium.

(4) Benzoin, benzoylmethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, dimethylaminobenzophenone, Michler's ketone, benzylanthraquinone,
Aromatic carbonyl compounds such as t-butylanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, 2-chloroanthraquinone, benzylmethylketal and methylphenylglyoxylate.

(5) 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, Acetophenone derivatives such as 2,2-diethoxyacetophenone and 2,2-diethoxyacetophenone.

(6) Dialkylaminobenzoic acid esters such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylbenzoate, butyl 4-dimethylaminobenzoate, isopropyl 4-diethylaminobenzoate and the like.

(7) Benzoyl peroxide, di-t
--Peroxides such as butyl peroxide, dicumyl peroxide, cumene hydroperoxide, etc. (8) Acridine derivatives such as 9-phenylacridine, 9-p-methoxyphenylacridine, 9-acetylaminoacridine and benzacridine. (9) Phenazine derivatives such as 9,10-dimethylbenzphenazine, 9-methylbenzphenazine and 10-methoxybenzphenazine.

(10) Quinoxaline derivatives such as 4,4 ', 4 "-trimethoxy-2,3-diphenylquinoxaline. (11) 2,4,5-triphenylimidazoyl dimer. (12) Halogenated ketone. (13) An acylated phosphorus compound such as acylphosphine oxide or acylphosphonate.

As those which are activated by visible light, for example, 2-nitrofluorene, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 3,3'-
Carbonyl biscoumarin, thiomichler ketone, etc. are mentioned.

If the amount of the photopolymerization initiator is too large, problems such as yellowing and brittleness of the film will occur, and if it is too small, curing will be insufficient. Therefore, 100 parts by weight of the hydrophobic monomer is used. 0.1 to 10 parts by weight is preferable.

In the composition A, a curing agent for epoxy resin or a curing catalyst is added if necessary. These are described in "High Functionality of Epoxy Resin and Development of Applications" (written by Eiichita) published by CMC.

The curing agent for epoxy resin is, for example,
Carboxylic anhydrides such as succinic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and mellitic anhydride, and diethylenetriamine, triethylenetetramine, tetraethylenepentamine, morpholine, pyrrolidine, cyclohexylamine, pentaethylenehexamine. And other polyfunctional amine compounds.

As the curing catalyst for epoxy resin, a compound having a tertiary amine group is preferably used, and examples thereof include diethylaminomethylphenol (DMP-10), tridimethylaminomethylphenol (DMP-30) and triethanolamine. , Low molecular compounds such as benzylmethylamine, hexamethylenetetramine, N, N'-dimethylpiperazine, triethylenediamine, quinoline, N-methylmorpholine, dimethylaniline, dimethylcyclohexylamine, and N, N-dimethylaminoethyl (meth) Tertiary amino group-containing polymerizable monomers such as acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropylacrylamide,
Alternatively, a homopolymer or a copolymer thereof may be used. The amount of the epoxy resin curing agent or curing catalyst added is appropriately determined depending on the type.

A monomer having a carboxyl group is added to the composition A, if necessary. Examples of the monomer having a carboxyl group include (meth) acrylic acid and 2-
(Meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth)
Acryloyloxyethyl hexahydrophthalic acid, ω-
Carboxy-polycaprolactone monoacrylate,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, glycerol (meth) acrylate, epichlorohydrin-modified ethylene glycol di (meth) acrylate, triglycerol A hydroxyl group-containing (meth) acrylate such as di (meth) acrylate, epichlorohydrin-modified trimethylolpropane triacrylate, epichlorohydrin-modified glycerol triacrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol pentaacrylate,
Examples thereof include partial ester reaction products with carboxylic acid anhydrides such as succinic anhydride, phthalic anhydride, pyromellitic anhydride, and mellitic anhydride. These may be used alone or in combination of two or more.

Other compounds containing an epoxy group are added to the composition A, if necessary. Examples of such a compound include bisphenol A or its ethylene oxide-modified derivative, bisphenol F or its ethylene oxide-modified derivative, polyphenol such as novolac resin, ethylene glycol, propylene glycol, glycerin, neopentyl glycol. , Polymethyl alcohol such as trimethylolpropane and pentaerythritol, and polyglycidyl ether which is a reaction product of epichlorohydrin, alicyclic epoxy resin, glycidyl (meth) acrylate, β-glycidoxyethyl (meth) acrylate, 3,4-Epoxybutyl (meth) acrylate, 4,5-Epoxypentyl (meth)
Examples thereof include monomers such as acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.

Composition A is optionally diluted with a solvent. As such a solvent, a general organic solvent can be used, and specifically, methanol, ethanol, n
-Propanol, isopropanol, n-butanol,
Examples thereof include alcohols such as benzyl alcohol, ketones such as acetone, methyl ethyl ketone and cyclohexane, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, ethyl acetate, tetrahydrofuran, toluene and the like. These solvents may be used alone or in combination of two or more.

Further, the present invention 1 is formed by the first step.
On the cured coating,₂--CR₃R_Four─] (where R₃Represents a hydrogen atom or a methyl group, R _Four Represents a side chain having a carboxyl group) ... Dissolution of a hydrophilic polymer having a repeating structural unit represented by the general formula (2)
It has the 2nd process of apply | coating the liquid B and heat-hardening it.

Various methods such as dipping, spin coating and spray coating can be applied as the method of applying the solution B on the cured coating.

The hydrophilic polymer having the repeating structural unit represented by the above general formula (2) is prepared by polymerizing a polymerizable monomer having a carboxyl group, alone or in combination of two or more kinds, or a carboxyl group. It can be obtained by the copolymerization of the polymerizable monomer having ## STR4 ## with another polymerizable monomer having a hydrophilic group.

Examples of the polymerizable monomer having such a carboxyl group include (meth) acrylic acid and 2
(Meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth)
Acryloyloxyethyl hexahydrophthalic acid, ω-
Carboxy-polycaprolactone monoacrylate or the like is used.

Other copolymerizable hydrophilic monomers include:
As the hydrophilic group, hydroxyl group, sulfonic acid or sulfonate group, primary, secondary and tertiary amino group or amide group, quaternary ammonium group, carboxylate group, phosphoric acid or phosphate group, polyethylene glycols, morpholine group,
Those having one or more sulfate groups and the like are preferably used, and specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-acrylamide-2- Methyl propane sulfonic acid, sodium sulfonate ethoxy (meth) acrylate, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N-isopropylacrylamide, N, N-dimethylaminopropylacrylamide, 2-methacryloxyethyltrimethylammonium chloride, sodium (meth) acrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, polyethylene glycol (meth) acrylate, mol Reno acrylate, p- styrenesulfonic acid, such as sodium p- styrenesulfonic acid. These may be used alone or in combination of two or more.

When the amount of the carboxy group in the hydrophilic polymer is too small, the addition reaction with the epoxy group does not sufficiently occur,
Since the amount of the hydrophilic polymer immobilized on the surface becomes small, it is preferable that the content of the repeating structural unit is 10 mol% or more.

As a solvent for dissolving the hydrophilic polymer,
Water or a mixed system of water and an organic solvent is preferably used, but an organic solvent alone can be used as long as it has high polarity. As the organic solvent that can be used at this time, for example,
Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and benzyl alcohol, ketones such as acetone, methyl ethyl ketone and cyclohexane, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, ethyl acetate, tetrahydrofuran, dimethylformamide. , Dimethyl sulfoxide, water and the like. These may be used alone or in combination of two or more.

Further, the cured film obtained in the second step of the present invention 1 may be subjected to alkali treatment, if necessary. In particular, it is effective when the hydrophilic polymer has an acid group such as a carboxylic acid group, a sulfonic acid group and a phosphoric acid group, and it is preferable to make a salt of an alkali metal or the like by this treatment.
Specifically, an aqueous solution of sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or the like, an alcohol solution or the like can be used. In this case, the concentration of the alkaline solution is preferably 0.1 to 5% by weight so as not to damage the coating.

The invention according to claim 2 of the present application (hereinafter,
The present invention 2) will be described. First, the present invention 2
Is a polymer having a repeating structural unit represented by the general formula (1) similar to that of the present invention 1 on the surface of a plastic molded body substrate or an inorganic glass substrate, and at least one polymer in one molecule. A composition C comprising a compound having a (meth) acryloyl group and at least one carboxyl group and a photopolymerization initiator is applied as an undercoat layer and heat-cured.
It has a process of.

The compound having at least one (meth) acryloyl group and at least one carboxyl group in one molecule used in the first step of the present invention 2 includes (meth) acrylic acid and 2- (meth) acrylic acid. ) Acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, ω-carboxy-polycaprolactone monoacrylate and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, glycerol di (meth) acrylate, epichlorohydrin-modified ethylene glycol di (meth) acrylate, triglycerol di (Meth) acrylate, epichlorohydrin trimethylolpropane triacrylate, epichlorohydrin-modified glycerol triacrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol pentaacrylate, and other hydroxyl group-containing (meth) acrylates, and phthalic anhydride, succinic anhydride, trianhydride. Mellitic acid, pyromellitic dianhydride,
Examples thereof include partial ester reaction products with carboxylic acid anhydrides such as mellitic anhydride. These may be used alone or in combination of two or more.

If the addition amount of the compound having at least one (meth) acryloyl group and at least one carboxyl group in one molecule is too large, the number of carboxyl groups that do not participate in the thermosetting reaction will increase, so that the final amount will be increased. The coating film has poor water resistance, and if it is too small, thermosetting does not proceed sufficiently, so 0.5 to 5 equivalents relative to the epoxy group in the polymer having the repeating structural unit represented by the general formula (1). Is preferred.

In the composition C, if necessary, the same curing agent or curing catalyst for epoxy resin as that added to the composition A of the present invention 1 is added.

In the composition C, in order to improve the crosslink density of the final coating, a hydrophobic bifunctional or higher functional (meth) acrylate monomer having no carboxyl group is added if necessary.

Examples of such (meth) acrylate monomers include pentaerythritol tri (meth) acrylate.
Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane triacrylate, propylene oxide Modified trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, bisphenol A di (meth)
Acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, dicyclopentanyl diacrylate, neopentyl glycol di (meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, and bifunctional The above urethane acrylate and polyester acrylate are used. These may be used alone or in combination of two or more.

When the amount of such a bifunctional or higher functional (meth) acrylate monomer having no carboxyl group is too large, the coating film is likely to be corroded. Therefore, it is preferably 30% by weight or less in the composition C.

In the composition C, if necessary, another compound having an epoxy group similar to that added to the composition A of the present invention 1 is added. Further, the composition C is diluted with the same solvent as the composition A of the present invention 1 if necessary.

As the photopolymerization initiator, the same one as in the present invention 1 is used, but if the addition amount is too large, problems such as yellowing or brittleness of the film occur, and it is too small. And curing will be insufficient, so 100 parts by weight of a compound having at least one (meth) acryloyl group and at least one carboxyl group in one molecule,
0.1 to 10 parts by weight is preferable.

In addition, the present invention 2 provides the cured film formed in the first step with at least one (meta) in one molecule.
The method has a second step of irradiating with actinic rays and photocuring the composition D comprising a hydrophilic monomer having an acryloyl group and a photopolymerization initiator in contact with each other.

The hydrophilic monomer having at least one (meth) acryloyl group in one molecule includes a hydroxyl group, a sulfonate group, a primary, secondary and tertiary amino group or an amide group as a hydrophilic group, Those having one or more primary ammonium base, carboxylate group, phosphoric acid or phosphate group, polyethylene glycol chain, morpholino group, sulfate group and the like are preferable.

Examples of such hydrophilic monomers include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, sodium sulfonate ethoxy (meth) acrylate, (meth) acrylamide,
N, N-dimethylaminoethyl (meth) acrylate,
N, N-diethylaminoethyl (meth) acrylate,
N-isopropylacrylamide, N, N-dimethylaminopropylacrylamide, 2-methacryloxyethyltrimethylammonium chloride, sodium (meth) acrylate, ω-carboxy-polycaprolactone monoacrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, polyethylene Examples thereof include glycol (meth) acrylate and acryloylmorpholine.
These may be used alone or in combination of two or more.

As the photopolymerization initiator, the one used in the first step is used, and the addition amount thereof is 0.1 to 10 parts by weight with respect to 100 parts by weight of the hydrophilic monomer. Is preferred.

The composition D is diluted with the same solvent as the composition A of the present invention 1, if necessary. Especially when the hydrophilic monomer is solid, a solvent is required. Further, the cured film obtained in the second step of the present invention 2 may be subjected to alkali treatment, if necessary, in the same manner as the cured film obtained in the first step of the present invention 1.

[0055]

In the method for producing an antifogging coated article of the present invention 1, first, a heavy-weight resin having a repeating structural unit represented by the above general formula (1) is formed on the surface of a plastic molded body substrate or an inorganic glass substrate. Coalesce and at least 2 (meta) in one molecule
In the first step of applying a composition A consisting of a hydrophobic monomer having an acryloyl group and a polymerization initiator as an undercoat layer and photocuring the composition, at least two (meth) acryloyl groups are contained in one molecule. A cured film having a high hardness can be formed from a mixture of an acrylic polymer having a crosslinked structure obtained by polymerizing a hydrophobic monomer and a polymer having an epoxy group, and then formed by the first step. In the second step of applying the solution B of the hydrophilic polymer having the repeating structural unit represented by the above general formula (2) to the cured coating and heating and curing the same, the epoxy group on the surface of the cured coating and hydrophilic Since the hydrophilic polymer having a hydrophilic group can be fixed on the cured film by reacting with the carboxyl group of the water-soluble polymer, an anti-fog coated article having excellent anti-fog property and water resistance can be produced. It can be.

The method for producing an antifogging coated article of the present invention 2 is as follows:
First, a polymer having a repeating structural unit represented by the above general formula (1) and at least one (meth) acryloyl group in one molecule are formed on the surface of a plastic molded body substrate or an inorganic glass substrate. In the first step of applying a composition C comprising a compound having at least one carboxyl group and a photopolymerization initiator as an undercoating layer and heating and curing the composition C, a repeating structural unit represented by the general formula (1) is included. By reacting the epoxy group of the polymer with the carboxyl group of the compound having at least one (meth) acryloyl group and at least one carboxyl group in one molecule, the photopolymerization initiator is dispersed to form the (meth) acrylate group. It is possible to form a cured coating composed of the polymer having, and then, in the cured coating formed by the first step, at least one (meth) in one molecule. In the second step of irradiating with actinic rays and photocuring the composition D comprising the hydrophilic monomer having acryloyl group and the photopolymerization initiator, the (meth) The acryloyl group and the (meth) acryloyl group of the hydrophilic monomer can be reacted to form a hydrophilic group, and the photopolymerization initiator dispersed in the cured coating can be formed inside the cured coating. Since it is possible to cause a cross-linking reaction between the (meth) acryloyl groups that remain after being decomposed to form a cured film having excellent hardness, an anti-fog coated article having excellent anti-fog properties and water resistance is produced. can do.

[0057]

[First step]

(1) Synthesis of epoxy group-containing polymer In a dark container, in a brown container, 30 g of ethyl acetate, 10 g of glycidyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name "Light Ester G"), and 50 m of azobisisobutyronitrile
g, and after bubbling nitrogen gas for 10 minutes,
It was placed in a hot water bath at 60 ° C. and reacted for 7 hours. Then, the solution was poured into petroleum ether to precipitate and collect the polymer.

(2) Preparation of Composition A 2 g of the polymer obtained by the operation of (1) was dissolved in 20 g of methyl ethyl ketone, and dipentaerythritol hexaacrylate (trade name "Kayarad D" manufactured by Nippon Kayaku Co., Ltd.) was added thereto.
PHA ") 2 g, 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba-Geigy, trade name" Irgacure 184 ") 100 mg, and ethyl 4-dimethylaminobenzoate (manufactured by Nippon Kayaku, trade name" Kayacure EP "
A ") 50 mg was added to form a uniform solution.

(3) Coating / Curing The composition A obtained in (2) was coated on a glass plate by dip coating, and photocured by a conveyor type exposure machine at a belt speed of 2.0 m / min.

[Second Step] (4) Thermosetting A solution B obtained by mixing 5 g of a 25% aqueous solution of polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 20 g of ethanol on the cured film obtained in (3). Is applied by dip coating and 150 ℃
It was heat-cured for 30 minutes. After that, the excess adhered portion was removed by washing with water.

(5) Alkali treatment The glass plate obtained in (4) was immersed in a 3% NaCO ₃ aqueous solution at 30 ° C. for 1 minute and then washed with water to obtain a coated article.
The obtained coated article was evaluated for antifogging property and water resistance. The results are shown in Table 1.

Regarding the evaluation of anti-fogging property, JIS S
Apply cooling water to one side of the glass along 4030 2
While keeping the temperature at 5 ° C., the anti-fog property when 42 ° C. water vapor was applied to the other surface of the glass plate for 3 minutes was evaluated in 4 grades of 1 to 4 grades. ○, 3rd grade △, 4
The grade was set to x. As for the evaluation of water resistance, after being immersed in water at 25 ° C. for 24 hours, the anti-fog property was evaluated in the same four grades as above.

Example 2 As solution B, 2 g of acrylic acid, 6 g of 2-acrylamido-2-methylpropanesulfonic acid, 40 mg of azobisisobutyronitrile and 30 parts of dimethylformamide.
A coated article was obtained in the same manner as in Example 1 except that a mixture with mg was reacted at 60 ° C. for 6 hours under a nitrogen gas atmosphere, and 2 g of the solution after the reaction was diluted with 8 g of ethanol. Then, the same evaluation as in Example 1 was performed. The results are also shown in Table 1.

Example 3 As a solution B, 2 g of acrylic acid, 4 g of N, N-dimethyl acrylamido acid, and azobisisobutyronitrile 6
A mixture of 0 mg, 12 g of water, and 12 g of ethanol was reacted under a nitrogen gas atmosphere at 60 ° C. for 6 hours, and 2 g of the solution after the reaction was diluted with 8 g of ethanol. Similarly, to obtain a coated article,
The same evaluation as in Example 1 was performed. The results are also shown in Table 1.

Example 4 In a dark place, 30 g of ethyl acetate, 10 g of 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Chemical Industries, Ltd., trade name "M-100"), and 50 mg of azoisobutyronitrile were placed in a dark container in the dark. Was charged, nitrogen gas was bubbled for 10 minutes, and then the mixture was allowed to react in a hot water bath at 60 ° C. for 7 hours. Then, the solution was poured into petroleum ether to precipitate and collect the polymer, and an epoxy group-containing polymer was obtained.

1.5 g of this polymer was dissolved in 4 g of methyl ethyl ketone, and pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “Kayarad PET-
30 "), 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Geigy, brand name" Irgacure EPA ") 100 mg, and ethyl 4-dimethylaminobenzoate (manufactured by Nippon Kayaku, brand name" Kayacure EP ").
A ”) was added in the same manner as in Example 2, except that
The coated article was obtained and evaluated in the same manner as in Example 1. The results are also shown in Table 1.

Example 5 A coated article was obtained in the same manner as in Example 4 except that an acrylic plate was used as the substrate and the thermosetting conditions were 70 ° C. and 5 hours, and the same evaluation as in Example 1 was performed. It was The results are also shown in Table 1.

Example 6 A polycarbonate plate was used as the substrate and the thermosetting condition was set to 70.
A coated article was obtained in the same manner as in Example 4 except that the temperature was 5 hours, and the same evaluation as in Example 1 was performed. The results are also shown in Table 1.

Comparative Example 1 A coated article was obtained in the same manner as in Example 1 except that the second step was not performed, and the same evaluation as in Example 1 was performed. The results are also shown in Table 1.

Comparative Example 2 A coated article was obtained in the same manner as in Example 1 except that the first step was not performed, and the same evaluation as in Example 1 was performed. The results are also shown in Table 1.

Comparative Example 3 5 g of polyacrylic acid (manufactured by Wako Pure Chemical Industries, 25% aqueous solution)
And 15 g of sodium dodecylbenzene sulfonate,
After applying a mixture consisting of 80 g of water to a glass plate, 8
The coated article was obtained by drying at 0 ° C. for 1 hour, and the same evaluation as in Example 1 was performed. The results are also shown in Table 1.

[0072]

[Table 1]

As is clear from Table 1, in each of the examples of the present invention, the antifogging property and the water resistance are excellent, whereas in the case of Comparative Example 1, the antifogging property and the water resistance are excellent. The water resistance is poor, and in Comparative Examples 2 and 3, the water resistance is poor.

Example 7 [First Step] (1) Synthesis of Epoxy Group-Containing Polymer In a dark container, 30 g of ethyl acetate and glycidyl methacrylate (Kyoeisha Chemical Co., Ltd., trade name “Light Ester G”) were placed in a brown container. 10 g and azobisisobutyronitrile 50 m
g, and after bubbling nitrogen gas for 10 minutes,
It was placed in a hot water bath at 60 ° C. and reacted for 7 hours. Then, the solution was poured into petroleum ether to precipitate and collect the polymer.

(2) Preparation of Composition C 2 g of the polymer obtained by the operation of (1) was dissolved in 20 g of methyl ethyl ketone, and 2-acryloyloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd., trade name "HOA-MS"). ))
1.8 g and 1-hydroxycyclohexyl phenyl ketone (trade name "Irgacure 18" manufactured by Ciba Geigy)
4 ") 100 mg and ethyl 4-dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd., trade name" Kayacure EPA ") 5
0 mg was added to make a uniform solution.

(3) Application / Curing The composition A obtained in (2) was applied to a glass plate by dip coating and cured at 120 ° C. for 30 minutes.

[Second Step] (4) Photocuring A glass plate provided with the cured coating obtained in (3) was treated with 50 g of dimethylformamide and 2-acrylamido-2.
-Methyl propane sulfonic acid (Nitto Chemical Co., Ltd., trade name "TBES-Q") 5 g, 1-hydrocyclohexyl phenyl ketone (Ciba Geigy Co., trade name "Irgacure 184") 200 mg, and 4-dimethylaminobenzoic acid It was irradiated with ultraviolet rays for 1 minute while being immersed in a solution D consisting of a mixture with 100 mg of ethyl acidate (manufactured by Nippon Kayaku Co., Ltd., trade name "Kayacure EPA"). After that, the excess adhered portion was removed by washing with water.

(5) Alkali treatment The glass plate obtained in (4) was immersed in a 3% NaCO ₃ aqueous solution at 30 ° C. for 1 minute and then washed with water to obtain a coated article.
The obtained coated article was evaluated for antifogging property and water resistance in the same manner as in Example 1. The results are shown in Table 2.

Example 8 As a solution D, 50 g of ethanol, 5 g of 2-methacryloxyethyltrimethylammonium chloride (manufactured by Kyoeisha Chemical Co., Ltd., trade name "DQ-100") and 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Geigy Co.,
Product name "Irgacure 184") 200 mg and 4-
A coated article was obtained in the same manner as in Example 7, except that a mixture with 100 mg of ethyl dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd., trade name "Kayacure EPA") was used and no alkali treatment was performed. The same evaluation as in Example 1 was performed. The results are also shown in Table 2.

Example 9 As solution D, 50 g of ethanol and 5 g of acrylic acid
And 1-hydroxycyclohexyl phenyl ketone (trade name "Irgacure 184" manufactured by Ciba Geigy) 2
00 mg and ethyl 4-dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd., trade name "Kayacure EPA") 100 mg
In the same manner as in Example 7 except that a mixture of
The coated article was obtained and evaluated in the same manner as in Example 1. The results are also shown in Table 2.

Example 10 As solution D, 50 g of ethanol, 5 g of ethylene oxide-modified phosphoric acid acrylate, 200 mg of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba-Geigy, trade name “Irgacure 184”), and 4-dimethylaminobenzoic acid A coated article was obtained in the same manner as in Example 7 except that a mixture with 100 mg of ethyl (Nippon Kayaku Co., Ltd., trade name “Kayakyu EPA”) was used, and the same evaluation as in Example 1 was performed. The results are also shown in Table 2.

Example 11 [First Step] (1) Synthesis of Epoxy Group-Containing Polymer In a dark brown container, 30 g of ethyl acetate and 3,4-epoxycyclohexylmethyl methacrylate (commercially available from Daicel Chemical Industries, Ltd., product) 10 g of "M-100") and 50 mg of azobisisobutyronitrile were added, and after bubbling nitrogen gas for 10 minutes, the mixture was placed in a water bath at 60 ° C and reacted for 7 hours. Then, the polymer was recovered by throwing the solution into petroleum ether to precipitate the polymer.

(2) Preparation of composition C 2 g of the obtained polymer was dissolved in 20 g of methyl ethyl ketone, and 1.8 g of 2-acryloyloxyphthalic acid (Kyoeisha, trade name "HOA-MPL") and 1 -Hydroxycyclohexyl phenyl ketone (Ciba Geigy, trade name "Irgacure 184") 100 mg, 4
— Ethyl dimethylaminobenzoate (manufactured by Nippon Reagent Co., trade name "Kayacure EPA") 50 mg was added to obtain a uniform solution.

(3) Coating / Heat Curing The composition C obtained in (2) was applied to an acrylic plate by dip coating and cured at 70 ° C. for 5 hours.

[Second Step] (4) Photocuring Water 20 g, ethanol 20 g, and 2-acrylamido-2-methylpropanesulfonic acid (manufactured by Nitto Kagaku Co., Ltd., trade name “TBAS-Q”) 5 g were uniformly mixed. N solution
a ₂ CO ₃ is neutralized, and further, 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Geigy, trade name “Irgacure 184”) 200 mg and 4-dimethylaminobenzoate ethyl (manufactured by Nippon Kayaku Co., Ltd.) , And the product name "Kayakyu EPA") was added to prepare a solution D.

The solution D was irradiated with ultraviolet rays for 1 minute while the acrylic plate provided with the cured coating obtained in (3) was dipped. Then, the excess adhered portion was removed by washing with water to obtain a coated article. The obtained coated article was evaluated for antifogging property and water resistance in the same manner as in Example 1. The results are shown in Table 2.

Example 12 A coated article was obtained in the same manner as in Example 11 except that a polycarbonate plate was used as the base material. The obtained coated article was evaluated for antifogging property and water resistance in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 4 A coated article was obtained in the same manner as in Example 7 except that the second step was not performed. The obtained coated article was evaluated for antifogging property and water resistance in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 5 A coated article was obtained in the same manner as in Example 7, except that the first step was not performed. The obtained coated article was evaluated for antifogging property and water resistance in the same manner as in Example 1. The results are shown in Table 2.

[0090]

[Table 2]

As is clear from Table 2, in the case of the examples of the present invention, the antifogging property and the water resistance are excellent, while in the case of Comparative example 4, the antifogging property and the water resistance are excellent. Is bad,
In the case of Comparative Example 5, the water resistance is poor.

[0092]

EFFECTS OF THE INVENTION Since the method for producing an antifogging coated article according to the present invention 1 and 2 has the above-mentioned constitution, the antifogging coated article excellent in antifogging property and water resistance is also provided. Can be manufactured.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B05D 7/24 R 7415-4F 302 P 7415-4F U 7415-4F C08J 7/04 S C09D 133 / 06 PFZ

Claims (2)

[Claims] 1. A plastic molded body substrate or inorganic glass
On the surface of the substrate, the general formula- [CH₂--CR₁R₂─] (expression
Medium, R₁Represents a hydrogen atom or a methyl group, R ₂Epoki
A repeating structural unit represented by
And a polymer having at least two (
A) Hydrophobic monomer having an acryloyl group and photopolymerization
Photocuring by applying Composition A consisting of the initiator as an undercoat layer
The first step to cure and the curing formed by the first step
General formula- [CH₂--CR ₃R_Four─] (where R
₃Represents a hydrogen atom or a methyl group, R_FourIs carboxyl
Represents a side chain having a group)
The solution B of the hydrophilic polymer having
Producing an anti-fog coated article characterized by comprising two steps
Build method. 2. A plastic molded body substrate or inorganic glass
On the surface of the substrate, the general formula- [CH₂--CR₁R₂─] (expression
Medium, R₁Represents a hydrogen atom or a methyl group, R ₂Epoki
A repeating structural unit represented by
With a polymer having at least one (meth)
A) acryloyl group and at least one carboxyl group
A composition C comprising a compound having
A first step of applying as an undercoat layer and curing by heating,
The cured film formed by the step 1 has a small amount in one molecule.
Hydrophilic monomer having at least one (meth) acryloyl group
A composition D composed of a monomer and a photopolymerization initiator was brought into contact with each other.
From the second step of irradiating with actinic rays and photo-curing
A method for producing an antifogging coated article, comprising: