JPH07224118A - Curable composition and method for curing the same - Google Patents

Abstract

PURPOSE:To provide the subject composition comprising a specific (meth) acrylamide, a hydrolyzable silane compound, and a polymerization initiator, excellent in transparency, weather resistance, surface hardness, marring resistance, abrasion resistance and clouding resistance, and useful for window glass, spectacle lenses, etc. CONSTITUTION:This composition comprises (A) a compound of formula I (R1 is H, CH3; R2 is R1, ethyl; R3 is R2, propyl) or a compound of formula II [A is a group of formula:-(CH2)n-(n is 4-6), a group of formula: -(CH2)2O-], e.g. N-methylacrylamide or N-methacryloyl pyrrolidine, (B) a silane compound having a hydrolyzable group bound to a silicon atom, such as tetramethoxysilane or dimethyldimethoxysilane or its hydrolyzate, and (C) a polymerization initiator such as benzoylperoxide, potassium persulfate (and sodium sulfite) or benzophenone.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition having excellent scratch resistance, weather resistance, surface hardness, processability, transparency and antifogging property, and a method for curing the same. More specifically, one or more monomers of a specific (meth) acrylamide derivative containing (meth) acrylamide, a silane compound having a hydrolyzable group at a silicon atom, or a hydrolyzate thereof and a polymerization initiator are used. And a curable composition obtained by adding a compound having surface activity to the curable composition, and a method for curing them.

[0002]

2. Description of the Related Art Plastic materials are used for various purposes by taking advantage of their excellent workability such as light weight and impact resistance. However, their hardness is insufficient and the surface is apt to be scratched, so that they are vulnerable to organic solvents. It has a drawback that it is easily treated and its heat resistance is insufficient. In order to solve these points, organic hard coat agents such as melamine, urethane, acrylic,
Furthermore, silicone-based hard coating agents having improved scratch resistance and weather resistance, and inorganic-based hard coating agents for coating metal oxides by vapor deposition or sputtering have been developed. Also, articles such as inorganic glass, transparent ceramics, plastic materials, etc. that utilize transparency for windows of houses and passenger cars, mirror surfaces, spectacle lenses, goggles, visors, etc. have high temperature and humidity, or have a large temperature or humidity difference. When used on a boundary surface, etc., when the temperature drops below the dew point, moisture condenses on the surface and dew adheres. As a result, small droplets of condensed water often scatter light, resulting in loss of transparency and clouding, which is generally known. In order to solve the above problems, there have been developed products in which the surface wettability is improved by coating a substance having a hydrophilic group, coating a surfactant or kneading into a hydrophilic substance. Furthermore, an antifogging coating composed of fine particle silica and an organic material having improved hardness has been developed.

[0003]

Various methods as described above have been developed as a method for improving the surface hardness of a plastic substrate. However, scratch resistance and weather resistance are insufficient with organic hard coat agents. Therefore, the inorganic hard coating agent has a problem in productivity. Further, although the silicone hard coat agent has improved weather resistance and the like, it has drawbacks such as adhesion, durability and productivity. For example, in order to impart scratch resistance to a plastic substrate, a method of coating an organopolysiloxane resin on the plastic surface has been proposed, but white turbidity occurs after long-term immersion in water, resulting in poor adhesion to the substrate. It was Further, in the method of coating a composition containing a silane coupling agent and colloidal silica, there was a phenomenon that hardness was lowered by immersion in hot water. The method of coating a composition composed of a silyl group-containing vinyl resin and an acrylic resin also has a drawback that spot-like turbidity occurs due to long-term immersion in water.

As a method of imparting antifogging property to a transparent substrate,
For example, JP-A-55-69678 proposes an antifogging agent comprising a photocurable ethylenically unsaturated compound having a hydrophilic group and a photocurable ethylenically unsaturated compound having no hydrophilic group. There is. However, with this antifogging agent, the wettability of the surface by the hydrophilic group is low and the antifogging property is low. Further, Japanese Patent Application Laid-Open No. 53-39347 proposes a method for forming an antifogging film mainly containing a composition consisting of polyvinyl alcohol and silica. The antifogging film obtained by this method has low hardness. , Especially when absorbing water, it is not practical because it is easily scratched by nails. US Patent 3479
No. 308 proposes a method of improving the wettability of the surface of an article by applying various surfactants or kneading into a hydrophilic substance. However, these methods only temporarily impart antifogging property to the article and cannot expect a continuous antifogging effect. Further, JP-A-58-32664 proposes an antifogging film comprising polyvinyl alcohol, fine particle silica, an organic silicon compound and a hydrolyzate thereof with improved durability. This technology is an antifogging coating that has greatly improved the drawbacks of the prior art, but it has a much higher hardness for window glass, automobile glass, etc., where the surface hardness is not sufficient and is required. Is required.

As described above, a plastic material having sufficient scratch resistance, surface hardness and durability while maintaining transparency, or a transparent material having excellent antifogging performance, durability and surface hardness are still being developed. Absent. Therefore, the object of the present invention is to provide a curable composition for forming a novel cured product having sufficient surface hardness, scratch resistance, and durability while maintaining transparency, and further excellent antifogging performance and surface hardness. A curable composition for forming a novel cured product having Yet another object of the present invention is to provide a method for curing such novel curable compositions.

[0006]

As a result of extensive studies in view of the above points, the present invention has revealed that one or more monomers of a specific (meth) acrylamide derivative containing (meth) acrylamide and a silicon atom. After polymerizing a monomer of a curable composition containing a silane compound having a hydrolyzable group or its hydrolyzate and a polymerization initiator, the silane compound is hydrolyzed and cured to improve transparency. It has been found that a material having excellent scratch resistance, weather resistance, surface hardness and workability can be obtained without damage. Furthermore, after polymerizing a monomer of the curable composition in which a surfactant is added to the curable composition, the silane compound is hydrolyzed and cured to prevent the fog and the antifogging property without impairing the transparency. The inventors have found that a material having excellent durability, weather resistance and surface hardness can be obtained, and have reached the present invention.

That is, the present invention provides a (meth) acrylamide represented by the general formula (I) (Chemical Formula 3) or (II) (Chemical Formula 4).

[0008]

[Chemical 3] (In the above formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, a methyl group or an ethyl group, and R ₃ represents a hydrogen atom, a methyl group, an ethyl group or a propyl group.)

[0009]

[Chemical 4] [In the above formula, R ₁ is a hydrogen atom or a methyl group, and A is (C
H ₂ ) _n (where n is 4 to 6) or (CH ₂ ) ₂ O
Represents (CH ₂ ) ₂ . ] N-alkyl or N-
One or two of alkylene-substituted (meth) acrylamides
The present invention relates to a curable composition comprising a silane compound having at least one kind of a monomer and a hydrolyzable group on a silicon atom or a hydrolyzate thereof and a polymerization initiator, and further adding a compound having surface activity. And a method for curing a curable composition, characterized in that after curing a monomer of the curable composition, the silane compound is hydrolyzed and cured. The present invention also relates to a curing method characterized by using the curable composition as a coating film.

The monomer used in the present invention is an N-alkyl or N-alkylene substituted (meth) containing a (meth) acrylamide represented by the general formula (I) or (II).
Although it is acrylamide, an N-substituted (meth) acrylamide derivative is more preferable in terms of affinity with a silane compound. The N-substituted (meth) acrylamide derivative is N
-Alkyl or N-alkylene substituted (meth) acrylamides, specifically, for example, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide,
N, N-diethyl acrylamide, N-ethyl methacrylamide, N-methyl-N-ethyl acrylamide, N
-Isopropylacrylamide, N-n-propylacrylamide, N-isopropylmethacrylamide, N-
n-Propylmethacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-
Acryloylhexahydroazepine, N-acryloylmorpholine and the like can be mentioned.

It is essential that the monomer constituting the composition of the present invention contains at least (meth) acrylamide or at least one of the above monomers. The monomer may be used in combination with at least one monomer selected from the following hydrophilic monomer, ionic monomer and lipophilic monomer.

Specific examples of the hydrophilic monomer include diacetone acrylamide, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, various methoxypolyethylene glycol (meth) acrylates, and N-vinyl-2. -Pyrrolidone and the like can be used, or vinyl acetate, glycidyl methacrylate and the like can be introduced by copolymerization and hydrolyzed to impart hydrophilicity.

Examples of the ionic monomer include acrylic acid, methacrylic acid, vinyl sulfonic acid, allyl sulfonic acid, methacryl sulfonic acid, styrene sulfonic acid and 2-
Acrylamido-2-phenylpropanesulfonic acid, 2
-Acrylamide-2-methylpropanesulfonic acid, acids such as (meth) acrylate of ethylenoxide-modified phosphoric acid and salts thereof, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylamino Ethyl acrylate,
N, N-dimethylaminopropylmethacrylamide, N,
Mention may be made of amines such as N-dimethylaminopropylmaryamide and salts thereof. It is also possible to introduce various acrylates, methacrylates, acrylamides, methacrylamides, acrylonitriles and the like by copolymerization and hydrolyze them to impart ionicity.

Examples of the lipophilic monomer include N, N-di-n-propylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, Nn-hexylacrylamide and Nn-hexylmethacryl. N-alkyl (meth) acrylamide derivatives such as amide, N-n-octyl acrylamide, N-n-octyl methacrylamide, N-tert-octyl acrylamide, N-dodecyl acrylamide, N-dodecyl methacrylamide, N, N-di Glycidyl acrylamide,
N, N-diglycidylmethacrylamide, N- (4-glycidoxybutyl) acrylamide, N- (4-glycidoxybutyl) methacrylamide, N- (5-glycidoxypentyl) acrylamide, N- (6 -N- (ω-glycidoxyalkyl) (meth) acrylamide derivatives such as -glycidoxyhexyl) acrylamide, ethyl acrylate, methyl methacrylate, butyl methacrylate, butyl acrylate, lauryl acrylate, 2
-(Meth) acrylate derivatives such as ethylhexyl methacrylate, glycidyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride,
Examples thereof include olefins such as vinylidene chloride, ethylene, propylene and butene, styrene, divinylbenzene, α-methylstyrene, butadiene and isoprene.

The quantitative ratio between the (meth) acrylamide derivative and the above-mentioned monomer varies depending on the combination of those monomers, and cannot be generally stated. However, generally, the hydrophilic or ionic monomer accounts for 80% by weight or 4% of the total amount of the monomers, respectively.
It is 0% by weight or less, preferably 60% by weight or 30% by weight, and more preferably 40% by weight or 20% by weight or less, respectively. On the other hand, the lipophilic monomer content is 80% by weight or less, preferably 60% by weight or less, and more preferably 40% by weight or less in the total amount of the monomers.

Next, in order to further improve scratch resistance and surface hardness, it is desirable to use a crosslinkable monomer in combination. The crosslinkable monomer is a monomer having two or more polymerizable groups in the molecule, that is, an unsaturated bond, and when the crosslinkable monomer is contained as a constituent component, the crosslinkable monomer has 3 Dimensionally cross-linked structure is formed and mechanical strength is improved, and when applied to a substrate etc., adhesion to the substrate is also improved,
It may have a form in which an inorganic component having excellent durability is dispersed.

Specific examples of the crosslinkable monomer include alkylenebisacrylamide such as methylenebisacrylamide and ethylenebisacrylamide, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth). ) Alkylene glycol di (meth) such as acrylate
Polyalkylene glycol di (meth) acrylates such as acrylates, polyethylene glycol di (meth) acrylates, polypropylene glycol di (meth) acrylates, glycerin, its condensates, polyhydric alcohols such as trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Di-, tri-, tetra-, penta- or hexa- (meth) acrylic acid ester, di- or tri- (meth) acrylate of ethylenoxide modified phosphoric acid, bisphenol A di (meth) acrylate, various modified bisphenol A di (meth) acrylate, various modified bisphenol Di (meth) acrylate of various bisphenol derivatives such as S di (meth) acrylate, polyester (meth) acrylate, urethane acrylate, epoxy acrylate, and isocyanate Isocyanurate or di or tri (meth) acrylate various modified isocyanurate, N, N
-Diallyl acrylamide, triacrylic formal,
Examples thereof include N, N-di (meth) acryloylimide, divinylbenzene and diallyl phthalate.

Further, a monomer having a functional group which induces crosslinking may be copolymerized by post-treatment such as heating after polymerization. Examples of such post-crosslinkable monomers include N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, Nn-propoxymethylacrylamide, Nn-butoxymethylacrylamide. ,
Examples thereof include N-alkoxymethyl (meth) acrylamide derivatives such as N-n-butoxymethylmethacrylamide, N-isobutoxymethylacrylamide and Nt-octoxymethylacrylamide.

As the polymerization initiator for polymerizing the monomer of the present invention, a general polymerization initiator can be used, and a thermal decomposition type polymerization initiator which decomposes by heat or the like to start polymerization, radicals by a redox reaction There are redox-based polymerization initiators that are generated, photopolymerization initiators that start polymerization by irradiation with ultraviolet rays, and the like. Examples of the thermal decomposition type polymerization initiator include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide,
1,1,3,3-tetramethylbutyl peroxide,
Organic peroxides such as 2,5-dimethylhexane-2,5-dihydroperoxide and cumene hydroperoxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl perphenyl acetate, t-butyl peroxide Organic peresters such as oxylaurate, cumyl perbivalate, azo compounds such as azobisisobutyronitrile, dimethylazoisobutyronitrile, inorganic peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide, etc. can give.

Examples of the redox type polymerization initiator include the above-mentioned peroxides such as potassium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide, sodium bisulfite, triethanolamine and sulfuric acid An example of the polymerization initiator is a system in combination with a reducing agent such as ammonium ferrous iron.

The photopolymerization initiator can be classified into two types: an intramolecular bond cleavage type in which the photopolymerization initiator itself is cleaved and an intermolecular hydrogen abstraction type in which the photopolymerization initiator abstracts hydrogen from the hydrogen donor. Examples of the intramolecular bond cleavage type photoinitiator include 4-t-butyltrichloroacetophenone, 4-phenoxydichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, and 2-hydroxy. -2-methyl-1-
Phenyl (4-dodecyl) propan-1-one, 4-
(2-Hydroxyethoxyphenyl) -2-hydroxy-2-methylpropan-1-one, acetophenone such as 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, Examples thereof include benzoin compounds such as benzyl dimethyl ketal.

As the intermolecular hydrogen abstraction type photopolymerization initiator, benzophenone, methyl o-benzoylbenzoate,
4-phenylbenzophenone, chlorobenzophenone,
Hydroxybenzophenone, 3.3'-dimethyl-4-
Benzophenone series such as methoxybenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-
Examples thereof include thioxanthone compounds such as isopropylthioxanthone, 2.4-dimethylthioxanthone and 2.4-diethylthioxanthone. Further, specific photoinitiators include methylphenylglyoxy ester, benzyl, camphorquinone, dibenzosuberone, 2-ethylanthraquinone and the like. The above-mentioned polymerization initiators may be used alone or in combination of two or more, or may be used in combination with the sensitizer shown below.

As the sensitizer, triethanolamine, methyldiethanolamine, triisopropanolamine, 4.4'-diethylaminophenone, ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate which act as hydrogen donors are used. , 2-dimethylaminobenzoic acid and the like.

Examples of the silane compound having a hydrolyzable group in the silicon atom of the present invention include tetramethoxysilane,
Tetraalkoxysilanes such as tetraethoxysilane, tetrabutoxysilane, trimethoxyneopentoxysilane, dimethoxydineopentoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltritriethoxysilane, phenyltrimethoxy. Alkyltrialkoxysilanes such as silane, methacryloxypropyltrimethoxysilane,
Dialkyldialkoxysilanes such as dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, aminomethyltriethoxysilane, N
-Β-aminoethylaminomethyltrimethoxysilane,
N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N- (trimethoxysilylpropyl) -ethylenediamine, N-
(Dimethoxymethylsilylpropyl) -ethylenediamine and other aminoalkylalkoxysilanes, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β-
Epoxyalkylalkoxysilanes such as (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane,

Mercaptoalkylalkoxysilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane, and halogenated alkylalkoxys such as γ-chloropropyltrimethoxysilane and 3,3,3-trichloropropyltrimethoxysilane. Hydrosilane compounds such as silane, alkyltriacyloxysilane, alkenyltrialkoxysilane, alkenyltriacyloxysilane, aryltrialkoxysilane, trimethoxysilane and triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyl Trimethoxyethoxysilane, allyltriethoxysilane, vinyltris- (β-methoxyethoxy) silane, vinyltrichlorosilane, Le vinyl dichlorosilane, .gamma.
(Meth) acryloxypropyltrimethoxysilane, γ
Examples include monomers and polymers of unsaturated bond-containing silane compounds such as-(meth) acryloxypropylmethyldimethoxysilane. These silane compounds may be used alone or in combination of two or more. The silane compound having a hydrolyzable group on the silicon atom may be in the state as it is, or may be in the state of being hydrolyzed or in the state of being partially condensed.

The composition ratios of the above-mentioned components constituting the curable composition of the present invention vary depending on the properties of the components used and cannot be unconditionally defined, but in general, the above general formulas (I) and (I
2 to 98% by weight of a specific N-substituted (meth) acrylamide represented by I), a silane compound having a hydrolyzable group at a silicon atom or 2 to 98% by weight of a hydrolyzate thereof, and a polymerization initiator 0.1 to 10 When the cross-linking monomer is contained, the content of the cross-linking monomer is 75% by weight or less, preferably 5 to 90% by weight of the specific N-substituted (meth) acrylamide, and a hydrolyzable group on the silicon atom. Of the silane compound or its hydrolyzate of 5 to 90% by weight and a polymerization initiator of 0.2 to 6% by weight. When the crosslinking monomer is contained, the crosslinking monomer is 70% by weight or less. is there. When the content of the silane compound having a hydrolyzable group on the silicon atom or its hydrolyzate is too small, the hardness of the cured product when cured cannot have a sufficient hardness. When cured, phase separation occurs and the transparency is impaired, and the cured product becomes extremely brittle.

In order to adjust the viscosity of the above-mentioned curable composition, it may be diluted with the following solvent depending on the application such as coating film formation. The solvent to be diluted is water, alcohol such as methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, ketone such as cyclohexanone, halogenated hydrocarbon such as chloroform, benzene, aromatic hydrocarbon such as toluene, ethylene glycol monomethyl ether, Examples include various cellosolves such as ethyl ether and butyl ether, various esters such as ethyl acetate and ethyl chloroacetate, and cyclic ethers such as dimethylformamide and tetrahydrofuran. Among the above, polar organic solvents are preferable, and they may be used alone or in combination of two or more kinds. At that time, the concentration of the composition is approximately 5% by weight or more.

Next, in the case of imparting antifogging performance, a compound having a surface active ability may be added when the above-mentioned curable composition is cured. The following surfactants can be used as the compound having surface activity. Any of anionic, nonionic, cationic and amphoteric surfactants can be used. In addition, the above have a molecular weight of 200 to 100 depending on their molecular weight.
0 low molecular weight system, 1000-10,000 medium molecular weight system, 10
It is classified into more than 000 polymer systems. In addition, 2 in the molecule
Also included are reactive surfactants having a heavy bond and capable of polymerization.

For example, as the anionic surfactant,
Roquinic acid soap which is fatty acid soap, sodium oleate, sodium stearate, sodium palmitate, or potassium salt thereof, ethanolamine salt,
Cyclohexylamine salt, N-acyl amino acid and salts thereof include lauroyl sarcosine, pamitoyl sarcosine, oleyl sarcosine, lauroyl methylalanine, N-acyl-N-methylglycine, N-acyl-N.
-Methyl-β-alanine, N-acyl glutamic acid and their sodium salts, potassium salts, organic salts, sodium polyoxyethyl lauryl ether carboxylic acid as alkyl ether carboxylic acid salts, and their potassium salts, organic salts, acylated peptides As coconut oil fatty acid collagen peptide sodium and their potassium salts, organic salts, as alkylbenzene sulfonic acid salts dodecylbenzene sulfonic acid sodium salt and these potassium salts, organic salts, as alkylnaphthalene sulfonic acid salts dodecyl naphthalene sulfonic acid sodium salt And their potassium salts, organic salts, dialkylsulfosuccinic acid ester salts such as sodium dioctylsulfosuccinate, sodium dihexylsulfosuccinate and potassium thereof , Organic salts,

As α-olefin sulfonate, α-
Sodium olefin sulfonate and potassium salts thereof, organic salts, N-acylmethyl taurine is N-
Sodium lauroyl methyl taurine, sodium N-stearoyl methyl taurine and their potassium salts, organic salts, as a sulfated oil, funnel oil, sulfated castor oil, and higher alcohol sulfate ester salts, sodium lauryl sulfate, sodium myristyl sulfate, cetyl sulfate. Sodium, sodium stearyl sulphate, hydrogenated coconut oil fatty acid sodium glyceryl sulphate and their potassium salts, organic salts, sodium lauryl ether sulphate as alkyl ether sulphate, sodium polyoxyethylene lauryl ether sulphate and their potassium salts, organic salts, poly Examples of the oxyethylenalkyl phenyl ether sulfate include sodium polyoxyethylene nonylphenyl ether sulfate and potassium salts thereof, organic salts, and phosphoric acid ester salts. Is sodium lauryl phosphate, sodium oleyl phosphate sodium polyoxyethylenoyl ether phosphate, sodium dipolyoxyethylenoylyl phosphate, sodium tripolyoxyethylenoylyl phosphate, sodium diphenyl ether phosphate and their potassium salts, organic salts As perfluoroalkylcarboxylic acid salt, sodium perfluorolauryl acid and potassium salt thereof, organic salt, as perfluoroalkyl phosphoric acid ester salt, sodium perfluorolauryl phosphate and potassium salt thereof, organic salt,
Further, anionic carboxyl-modified silicone oil and the like can be mentioned.

Further, as a reactive anionic surfactant having a double bond in the molecule, styrene having skeleton as a skeleton is substituted with an ionic group on an aromatic ring, and a hydrocarbon group is substituted at an unsaturated bond portion. Agent, a (meth) acrylic acid ester as a skeleton and an anionic group introduced at its ester site, a (meth) acrylic acid ester-based surfactant, and itaconic acid as a skeleton having an anionic group as at least one of the carboxylic acid sites. Introduced itaconic acid-based surfactant, maleic acid-based surfactant with similar structure, fumaric acid-based surfactant, allylic interface in which a polymerizable allyl group is introduced into ester moiety of sulfosuccinic acid substituted with sulfonic acid group Examples thereof include an activator and an anionic surfactant having two or more of these unsaturated bonds.

Among the nonionic surfactants, the alkyl and alkylallyl polyoxyethylene ethers include polyoxyethylene lauryl ether, polyoxyethylenoleyl ether and octaethylene glycol mono-.
n-dodecyl ether, polyoxyethylene nonylphenyl ether, alkylallyl formaldehyde condensed polyoxyethylene ether as polyoxyethylene nonylphenyl formaldehyde condensate, polyoxyethylene polyoxypropylene block polymer as polyoxyethylene polyoxypropylene cetyl ether poly Oxyethylene polyoxypropylene decyl tetraether, polyoxyethylene glycerol monooleate as polyoxyethylene ether of glycerin ester, polyoxyethylene glyceryl monostearate, polyoxyethylene sorbitan monolaurate as polyoxyethylene ether of sorbitan ester, Polyoxyethylene sorbitan tristearate,
Polyoxyethylene sorbitan monoisostearate,
Polyoxyethylene castor oil and hydrogenated castor oil are polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, and polyoxyethylene sorbitol fatty acid ester are polyoxyethylene sorbitol tetreolate, polyoxyethylene sorbitol hexastearate, polyoxyethylene. Sorbitol monolaurate, polyethylene glycol fatty acid ester as ethylene glycol monostearate, polyoxyethylene monostearate, polyethylene glycol distearate, polyethylene glycol diisostearate, stearic acid monoglyceride, stearic acid diglyceride as glycerin ester,

Sorbitan monolaurate, sorbitan monostearate, sorbitan tristearate, propylene glycol monostearate as a propylene glycol ester, sugar monostearate as a sucrose ester, and stearyl monoethanolamide and stearyl as a fatty acid alkanolamide. Diethanol amide, polyoxyethylene stearic acid amide as polyoxyethylene fatty acid amide, polycoythylenolenoic acid amide, polyoxyethylene stearyl amine, polyoxyethylene oleylamine as polyoxyethylene alkylamine, lauryl dimethyl as alkylaminoxide Aminoside and perfluoroalkyl ethylenoxide side products include polyoxyfluoroethylene Fluoro lauryl ether, perfluoroalkyl perfluoro lauryl dimethylamine oxide as amino, dimethylsulfoxide, styrene or olefin-modified silicone oil as a silicone, polyether-modified silicone oil, alcohol-modified silicone oil, fluorine-modified silicone oil and the like. In addition, as a reactive nonionic surfactant having an unsaturated bond, a polyoxyethylenealkylbenzenesulfonyloxy group was introduced into the ester site of the ester site via hydroxypropane or a polyoxyethylenealkylbenzenesuccinyl group was introduced via hydroxypropane ( (Meth) acrylic acid-based surfactants, itaconic acid-based surfactants in which itaconic acid has a carboxylic acid moiety substituted with a polyoxyethylenalkyl group, maleic acid-based surfactants of the same structure, and these molecules 2 unsaturated bonds in
Three or more nonionic surfactants Allyl surfactants in which an aliphatic quaternary ammonium is introduced into allyl groups directly or through hydroxypropane, and cationic surfactants having two or more unsaturated bonds in their molecules Agents and the like.

Among the amphoteric surfactants, carboxybetaine includes lauryldimethylaminoacetic acid betaine, lauryldihydroxyethylbetaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, and aminocarboxylic acid salts include sodium laurylaminopropylate and potassium salts thereof. , Organic salts, 2-lauryl-N-carboxymethyl-N-as imidazolinium betaine
Examples of hydroxyethyl imidazolinium betaine, lecithin include egg yolk lecithin, soybean lecithin, and perfluoroalkyl betaine include perfluorolauryl betaine. Further, as a high molecular weight high molecular weight surfactant, carboxymethyl cellulose, livinyl alcohol, polyacrylamide derivative, poly long chain alkyl methacrylate, poly-4-vinyl pyridine type polysoap, polyoctylstyrene-co-styrene sulfonic acid type polysoap, Examples thereof include polyoxyethylene polyoxypropylene polyoxyethylene, formalin condensate of naphthalene sulfonic acid, and octadecene / maleic anhydride copolymer.

The compounds having the above-mentioned surface activity may be added alone or in combination of two or more kinds.
If the addition amount of the compound having surface activity is too small, sufficient antifogging performance cannot be imparted, and conversely, if it is too large, the hardness of the cured product cannot be improved. About 0.1 to 30% by weight based on the curable composition
And preferably 0.5 to 20% by weight.

In the curable composition of the present invention, various curing accelerators can be used in combination for the purpose of promoting curing. As the curing accelerator, a curing accelerator that accelerates hydrolysis of a silane compound having a hydrolyzable group on a silicon atom is used.
Examples of these curing accelerators include various organic acids and their acid anhydrides, amines, amino acids, metal acetylacetonates, organometallic salts, Lewis acids, organic carboxylates of alkali metals, carbonates and the like. . It is also possible to use two or more of these curing accelerators in combination.

Next, a method for curing the curable composition of the present invention will be described based on an example of forming a coating film.
The curable composition may be put into a mold or the like as a molding base material and cured according to the present invention to be molded into an arbitrary shape. Alternatively, the curable composition may be applied to the mold and cured according to the present invention to mold. After forming the coating film on the mold, it is also possible to put the molding base material in the mold and mold it.

A typical curing method is to form the curable composition in the form of a film on a substrate, and then donate heat of an amount of energy required to polymerize the monomer or irradiate it with an ultraviolet ray to form an organic substance. After curing the monomer to form a film, the silane compound having a hydrolyzable group on the silicon atom, which is an inorganic substance, is hydrolyzed and condensed by hydrolysis without phase separation to form a coating film. Let them do it. In this way, after the monomer which is an organic substance is first polymerized, the silane compound which is an inorganic substance is hydrolyzed and condensed to be cured.

The formation of such a coating film is carried out by applying it to a substrate. Generally, the substrate used is polyester, polystyrene, polymethyl methacrylate, polycarbonate, nylon, polyurethane, polyethylene terephthalate, phenol aldehyde, urea formaldehyde. And the like, inorganic materials such as glass, silicon, silicon oxide, and ceramics, and fine paper, art paper, paper such as release paper, and wood-based materials. It is also possible to use a material obtained by laminating two or more of these materials or forming a thin film of another material on the surface of a certain material by a method such as vapor deposition. Furthermore, the surface of the above-mentioned substrate has a grainy surface,
It can also be used after being subjected to treatments such as electrolytic etching, chemical etching, electrolytic oxidation and corona discharge. There are various shapes of the above-mentioned substrate depending on its application.
Examples thereof include those processed into various shapes such as a film shape, a flat plate shape, a curved surface shape, a corrugated plate shape, and a pipe shape. Further, the surface thereof may be a smooth one such as glass to a porous one such as a foamed sheet.

The coating method is not particularly limited and various methods can be adopted. Specifically, for example, air doctor coater, blade coater, rod coater, knife coater, squeeze coater, impregnation coater, reverse roll coater, transfer roll coater, gravure roll coater, kiss roll coater, cast coater, spray coater, curtain coater, calendar coater. Various coating methods such as an extraction coater, a flow coating method, a brush coating method, a dipping method, and a spray method can be used. The coating method may be appropriately selected in consideration of the shape and material of the substrate. The thickness of the coating film is about 1
Depending on the viscosity of the coating liquid and the selection of the coating method at about 500μ,
The thickness can be set arbitrarily.

The coated substrate may be heated or irradiated with ultraviolet rays as it is, or may be heated or irradiated with ultraviolet rays after being preheated and dried by irradiation with hot air or infrared / far infrared rays. When the above substrate is eroded, it is preferable to immediately heat or irradiate with ultraviolet rays after coating.

Even when the coating film is formed on the substrate in advance, if the coating film formed on the substrate is not swollen or attacked by the curable composition of the present invention, The curable composition of the present invention can be applied thereon. Even if a previously formed coating film is corroded, it is possible to irradiate ultraviolet rays immediately after coating.

Next, the monomer which is an organic substance is polymerized and cured by heating or irradiation of ultraviolet rays. The heating conditions may be those which carry out general thermal polymerization. Since it varies depending on the amount of the polymerization initiator used, the substrate used, etc., the heating temperature is generally 30 ° C to 180 ° C, preferably 40 ° C to 170 ° C.
The heating time is 10 minutes to 24 hours, preferably 30 minutes to 2
It's 0 hours. As a heating method, a known method such as a method using a heater or a high frequency, or a method using irradiation with light such as infrared rays can be used. When the substrate is attacked, it is preferable to heat at a relatively low temperature for a long time to polymerize.

The ultraviolet irradiation conditions are as follows:
Varies depending on the amount of photopolymerization initiator added and coating thickness
Therefore, it can not be said unequivocally, but the general ultraviolet rays are shown below.
UV intensity, time, and UV
The amount of linear energy may be used. That is, 50 mW / cm
²~ 1500mW / cm²Preferably 100 mW / cm ²
~ 1200mW / cm²UV irradiation intensity of 0.01 seconds
-90 seconds, preferably 0.1 second to 60 seconds. UV rays
Irradiation energy amount is 5 mJ / cm²~ 3000m
J / cm²Preferably 10 mJ / cm²~ 2500 mJ /
cm²Is.

If there is a possibility that the substrate will be deformed by the irradiation of ultraviolet rays, it may be cured by repeatedly irradiating it with ultraviolet irradiation energy that does not deform the substrate. There is no particular limitation on the lamp that emits ultraviolet rays that can be applied in the present invention, as long as it is a source of ultraviolet rays. Conventionally used lamps such as a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp, and an ultraviolet fluorescent lamp can be used. The output of the lamp is 0.1 to 500 W / cm. The irradiation of ultraviolet rays may be carried out with the object to be irradiated fixed or moved by a belt conveyor method.

The curing method by ultraviolet irradiation is an effective method in vacuum and in an inert gas atmosphere, but it can also be performed in air or the like in which oxygen is present.
As described above, the monomer that is an organic substance is polymerized and cured by heating or UV irradiation, and then it is hydrolyzed and cured by hydrolyzing and condensing a silane compound having a hydrolyzable group on the silicon atom that is an inorganic substance. Let them do it. The method of curing an inorganic substance by hydrolysis is generally performed by subjecting a cured product obtained by polymerizing and curing an organic substance to heat treatment or heat treatment in a steam atmosphere.

As a heating method, a known method such as a method using a heater or a high frequency or a method using light irradiation such as infrared rays can be used. The heat treatment temperature varies depending on the heat resistance of the substrate, the coating film composition, the film thickness, etc.
C. to 250.degree. C., preferably 40.degree. C. to 200.degree. If the heat treatment temperature is too high, the coating film will turn yellow and the transparency will be impaired. In the heat treatment in the steam atmosphere, the hydrolysis treatment can be performed more efficiently than the simple heat treatment. The larger the amount of water vapor is, the higher the hydrolysis efficiency is, and the supersaturated state may be obtained.

The treatment time varies depending on the coating composition, treatment method, treatment temperature, etc., but it is 1 second to 180 seconds, preferably 60 seconds to 120 seconds in the case of heat treatment by high frequency, and in the case of heat treatment by other methods. 20 to 3000 minutes,
Preferably, the silane compound, which is an inorganic substance, can be cured by heat treatment for 30 minutes to 2400 minutes.

There is no limitation on the pressure during the hydrolysis treatment, and it is possible to treat at any pressure, and by increasing the pressure, it is possible to treat in a relatively short time. Furthermore, the most efficient hydrolysis treatment can be achieved by high-frequency heating under saturated steam and the hydrolysis treatment. As described above, the silane compound, which is an inorganic substance, is hydrolyzed and hydrolyzed and condensed to be cured, and then dried by air drying or heating to produce a coating film.

In the production of a coating film of the curable composition of the present invention, it is possible to preliminarily cure the coating composition according to the above-mentioned method and then to superimpose it thereon to produce a coating film according to the above-mentioned method. A layered coating film can be formed. The curable composition of the present invention is applied to the surface of a substrate, and the coating film cured according to the method described above has flexibility without impairing transparency, and excellent scratch resistance and weather resistance that cannot be achieved with an organic material. And a surface hardness, and a coating film produced by the method described above by further adding a compound having surface activity to the curable composition has excellent antifogging performance without impairing transparency. It has durability, surface hardness, and weather resistance.

Further, in addition to the above-mentioned coating film shape, it is possible to cure it in a plate shape, a bar shape, or other complicated shapes. In each molding step, after the monomer is polymerized by heating, etc., it is heated. A cured product having an arbitrary shape can be obtained by hydrolyzing and condensing the silane compound by a hydrolysis treatment such as. In the production of a cured product having the above-mentioned shape,
In order to cure the entire cured product, it is necessary to make the curing conditions more severe than in the case of producing a coating film. For example, the polymerization time of the monomer and the hydrolysis treatment time of the silane compound may be generally lengthened in proportion to the thickness of the cured product to perform the curing, and the curing conditions include not only the curing treatment time but also the composition of the cured composition. In consideration of this, the curing temperature and the like may be appropriately changed. In particular, the addition of a curing accelerator that accelerates the hydrolysis treatment after polymerizing the monomer is very effective for curing the entire cured product.
The cured product obtained by the above method is cured not only on the surface but also in the entire interior of the cured product in a state in which organic and inorganic compounds are uniformly mixed, and the cured product is preferably cured up to a thickness of 50 mm for practical use. It is possible. However, if it takes longer time, it can be applied to a thickness exceeding it.

The cured product of any shape thus obtained has flexibility without impairing transparency, and has excellent scratch resistance, weather resistance, and surface hardness which could not be achieved with organic materials. ing. Further, the curable composition of the present invention can be mixed with various fillers, pigments and the like. filler,
Various pigments such as calcium carbonate, magnesium carbonate, titanium oxide, iron oxide, various silicas, and glass fibers can be used. It can be used in applications where transparency is not required, such as paints, coating materials for various substances,
It is also effective as a surface treatment agent.

[0053]

EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1 6.00 g of γ-glycidoxypropyltrimethoxysilane was dissolved in a mixed solvent of 47.52 g of ethanol, 5.94 g of toluene and 5.94 g of butyl cellosolve, and N-acryloylpyrrolidine (hereinafter After uniformly dissolving 10.5 g of N-APR) and 3.5 g of urethane acrylate (Aronix M-1100: manufactured by Toagosei Kagaku Co., Ltd.), 2-hydroxy-2-methyl-1-phenylpropane-1. -On 0.
6 g was added as a photopolymerization initiator to prepare a mixed solvent 74.2.
5% by weight, γ-glycidoxypropyltrimethoxysilane 7.50% by weight, N-APR 13.125% by weight, urethane acrylate 4.375% by weight, 2-hydroxy-2-methyl-1-phenylpropane-1- On 0.7
A curable composition consisting of 5% by weight was prepared.

5 g of the curable composition was dropped on one side of a 10 cm square polycarbonate plate and uniformly coated by a flow coating method. After air-drying, short-time irradiation was repeated with three 100 W / cm UV lamps in a nitrogen atmosphere (oxygen concentration of 2% or less), and the total UV irradiation energy amount was 1500 mJ.
It was irradiated so as to have a density of / cm ² to polymerize an organic monomer. Next, hydrolysis treatment was performed at a relative humidity of 95% and a heating temperature of 85 ° C. for 5 hours to hydrolyze and condense the silane compound, which is an inorganic substance, to cure the coating, thereby obtaining a coating film. The coating film was transparent and glossy, and the film thickness was 20 μm. The characteristics of the coating film thus obtained were evaluated as shown below. (A) Adhesiveness: 1 mm wide cross cut 1 on the cured coating film
Cell 00 was formed and a cellophane adhesive tape was attached to the cross-cut surface, which was strongly pulled in the direction perpendicular to the coating film, and the peeled state of the coating film was observed. The observation result represents the total number of crosscuts in the denominator, and the numerator represents the number of crosscuts that did not exfoliate. (B) Surface hardness: Carried out according to JIS K-5400 and expressed in pencil hardness. (C) Scratch resistance: The surface of the test piece was rubbed with # 0000 steel wool several times by hand to observe the degree of scratching of the coating film, and the scratch resistance was judged according to the following criteria. ◯: No scratch even if rubbed strongly Δ: Some scratches when rubbed strongly ×: Scratch easily (d) Water resistance test: 1 in a constant temperature water bath at 25 ° C
After immersion for 70 hours, the presence or absence of abnormalities such as transparency, peeling state and breakage of the coating film was observed. (E) Weather resistance test: temperature 63 ± 3 ° C., rainfall 18 minutes / 1
A test with a sunshine weather meter was carried out under the test condition of operating for 20 minutes. The change in appearance was observed after the accelerated exposure test for 500 hours. The results are shown in Table 1.

Example 2 After the procedure of Example 1 was repeated except that 14.0 g of N-APR was used and no urethane acrylate was added in the preparation of the curable composition of Example 1, A coating film was produced in the same manner as in Example 1. The thickness of the obtained coating film was 23 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 In the preparation of the curable composition of Example 1, the same procedure as in Example 1 was carried out except that N-APR was changed to acrylamide. A coating film was manufactured. The thickness of the obtained coating film was 22 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 After the same procedure as in Example 1 except that N, A-dimethylacrylamide was used instead of N-APR in the preparation of the curable composition of Example 1,
A coating film was produced in the same manner as in Example 1. The thickness of the obtained coating film was 20 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 5 The procedure of Example 1 was repeated, except that N-APR was changed to N-isopropylacrylamide in the preparation of the curable composition of Example 1,
A coating film was produced in the same manner as in Example 1. The thickness of the obtained coating film was 19 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 6 In the preparation of the curable composition of Example 1, urethane acrylate (Aronix M-1
100: Toa Gosei Kagaku Co., Ltd.) was prepared in the same manner as in Example 1 except that dipentaerythritol hexaacrylate was used, and then a coating film was produced in exactly the same manner as in Example 1. The thickness of the obtained coating film was 20 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 7 In the preparation of the curable composition of Example 1, 13.125% by weight of N-APR was added as N-.
After preparing in the same manner as in Example 1 except that the amount of APR was changed to 7.875% by weight and the amount of 2-hydroxyethyl acrylate was changed to 5.25% by weight, a coating film was produced by the same method as in Example 1. The thickness of the obtained coating film was 22 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[Example 8] In the preparation of the curable composition of Example 1, 13.125% by weight of N-APR was added as N.
-APR was prepared in the same manner as in Example 1 except that the amount of APR was changed to 10.50% by weight and the amount of acrylic acid was changed to 2.625% by weight, and then a coating film was produced by the same method as in Example 1. The thickness of the obtained coating film was 24 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 9 In the preparation of the curable composition of Example 7, 2-hydroxyethyl acrylate was added to n-
After preparing in the same manner as in Example 1 except that butyl acrylate was used, a coating film was produced in exactly the same manner as in Example 1. The thickness of the obtained coating film was 18 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 10 In the preparation of the curable composition of Example 1, 7.50% by weight of γ-glycidoxypropyltrimethoxysilane was added to 5.70% by weight of γ-glycidoxypropyltrimethoxysilane. , N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane 1.
After preparing in the same manner as in Example 1 except that the content was changed to 80% by weight, a coating film was produced by the same method as in Example 1. The thickness of the obtained coating film was 21 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[Example 11] 47.52 g of ethanol,
3.05 g of γ-glycidoxypropyltrimethoxysilane, 0.96 g of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, and an ethoxy group were added to a mixed solvent consisting of 5.94 g of toluene and 5.94 g of butyl cellosolve. Having polysiloxane (weight average molecular weight 10,70
0) Dissolve 5.67 g of 35 wt% ethanol solution,
Further, N-APR 10.5 g, urethane acrylate (Aronix M-1100: manufactured by Toagosei Kagaku Co., Ltd.) 3.
After uniformly dissolving 5 g, 0.6 g of 2-hydroxy-2-methyl-1-phenylpropan-1-one was added as a photopolymerization initiator to obtain a mixed solvent of 74.25% by weight and γ-
Glycidoxypropyltrimethoxysilane 3.81% by weight, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane 1.20% by weight, polysiloxane 2.
48% by weight, N-APR 13.125% by weight, urethane acrylate 4.375% by weight, 2-hydroxy-2-
A curable composition consisting of 0.75% by weight of methyl-1-phenylpropan-1-one was prepared. A coating film was produced using the curable composition in the same manner as in Example 1. The thickness of the coating film was 23 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 12 21.00 g of ethanol was placed in a 4-neck 100 ml flask equipped with a stirrer, a reflux condenser and a thermometer, and 48.52 g of tetraethoxysilane was dissolved with stirring, and then water 10. A solution prepared by dissolving 1.20 g of hydrochloric acid in 08 g was gradually added dropwise to this ethanol solution of tetraethoxysilane, and the reaction temperature was kept constant at 80 ° C. for 5 hours with stirring to carry out hydrolysis reaction of tetraethoxysilane. A decomposed silane compound was obtained. At this time, the SiO ₂ concentration was 17.5% by weight and the viscosity was 41.3 poise. The hydrolyzed silane compound (22.86 g) and γ-glycidoxypropyltrimethoxysilane (2.00 g) were dissolved in a mixed solvent of ethanol (22.86 g), toluene (5.94 g) and butyl cellosolve (5.94 g), and N-APR10. After uniformly dissolving 5 g and 3.5 g of urethane acrylate (Aronix M-1100: manufactured by Toagosei Kagaku Co., Ltd.), 0.6 g of 2-hydroxy-2-methyl-1-phenylpropan-1-one was photopolymerized. Add as an initiator, mixed solvent 7
4.25 wt%, hydrolyzed silane compound 5.00 wt%, γ-glycidoxypropyltrimethoxysilane 2.50 wt%, N-APR 13.125 wt%, urethane acrylate 4.375 wt%, 2- Hydroxy-
2-Methyl-1-phenylpropan-1-one 0.75
A curable composition consisting of wt% was prepared. A coating film was produced from the curable composition in the same manner as in Example 1.
The thickness of the coating film was 22 μm, and a transparent and glossy coating film was obtained. The coating film test piece was evaluated in the same manner as in Example 1,
The results are shown in Table 1.

[Example 13] A curable composition was prepared in exactly the same manner as in Example 1, except that the polycarbonate plate was changed to a polymethyl methacrylate plate in the production of the coating film of Example 1. A coating film was produced by the same method as in 1. The thickness of the obtained coating film was 20 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Example 14 In the preparation of the curable composition of Example 1, ethanol 47.52g, toluene 5.9
A curable composition was obtained in the same manner as in Example 1 except that 59.4 g of ethanol was used instead of the mixed solvent consisting of 4 g and 5.94 g of butyl cellosolve. 5 g of the curable composition
Was dropped on one side of a 10 cm square glass plate and uniformly applied by a flow coating method. After air-drying, in a nitrogen atmosphere (oxygen concentration of 2% or less), three 100 W / cm UV lamps were irradiated to irradiate the UV energy to 1500 mJ / cm ² to polymerize the organic monomer. It was Then, a hydrolysis treatment was carried out at a relative humidity of 95% and a heating temperature of 85 ° C. for 5 hours to hydrolyze and condense the silane compound which was an inorganic substance to further cure the film to obtain a coating film. The obtained coating film was transparent and glossy, and the film thickness was 22 μm. The characteristics of the coating film test piece were evaluated in the same manner as in Example 1, and the results are shown in Table 1.
It was shown to.

[Examples 15 to 16] A curable composition was prepared in exactly the same manner as in Example 1, and then 5 g of the curable composition was prepared.
Was dropped on one side of a 10 cm square polycarbonate plate and uniformly applied by a flow coating method. After air-drying, irradiation with three 100 W / cm UV lamps was repeated for a short time in a nitrogen atmosphere (oxygen concentration of 2% or less), and the total amount of UV irradiation energy was irradiated to 1500 mJ / cm ² , which was a single organic substance. Polymerization of the polymer was carried out. Then, in the case of Example 15, heat treatment was performed at a heating temperature of 120 ° C. for 2 hours, and Example 16
In the case of, the relative humidity is 95% and the output power is 500W.
After a minute treatment, the silane compound, which is an inorganic substance, was hydrolyzed and condensed to obtain a coating film. The thickness of the obtained coating film was 19 μm in Example 15 and 20 μm in Example 16, and a transparent and glossy coating film was obtained in both Examples 15 and 16. The coating film test piece was evaluated in the same manner as in Example 1,
The results are shown in Table 1.

Example 17 A curable composition was prepared in exactly the same manner as in Example 1, and 5 g of the curable composition was added to 10 parts.
It was dripped onto one side of a glass plate of cm square, and applied uniformly by a flow coating method. After air drying, in a nitrogen atmosphere (oxygen concentration 2%
The following) was irradiated with three 100 W / cm UV lamps so that the amount of UV irradiation energy would be 1500 mJ / cm ² to polymerize the monomer which is an organic substance. Then, a heat treatment was performed at a heating temperature of 300 ° C. for 2 hours to hydrolyze and condense the silane compound, which is an inorganic substance, to cure the silane compound, thereby obtaining a coating film. The thickness of the obtained coating film was 20 μm and the coating film turned yellow. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1. Thus, when the heat treatment temperature is high, the coating film turns yellow and the transparency is impaired, but the scratch resistance, water resistance and the like are not deteriorated, so that it can be used depending on the purpose.

[Example 18] In the preparation of the curable composition of Example 1, only 1.4 g of ethanol was used as a mixed solvent,
2-hydroxy-2-methyl-1-phenylpropane-
It was prepared in the same manner as in Example 1 except that 1-one was changed to azobisisobutyronitrile. The curable composition was prepared by using a polymethylmethacrylate plate having a plate thickness of 2 mm and a width of 100 × 100 mm and a spacer made of silicon rubber with a distance of 2 m.
It was injected into a cell assembled to have a size of m and heated at 60 ° C. for 6 hours to polymerize a monomer which is an organic substance. Next, this polymer was taken out and hydrolyzed at a relative humidity of 95% and a heating temperature of 85 ° C. for 5 hours to hydrolyze and condense the silane compound which is an inorganic substance to be cured to obtain a plate-shaped cured product. The cured product is hard, transparent and glossy, and the plate thickness is 18 mm.
Met. The properties of the cured product thus obtained were evaluated in the same manner as in Example 1 except that the adhesiveness evaluation in Example 1 was omitted, and the results are shown in Table 1.

[Comparative Example 1] N-APR (15.0 g) and urethane acrylate (Aronix M-1100: Toagosei Kagaku Co., Ltd.) were added to a mixed solvent consisting of 47.52 g of ethanol, 5.94 g of toluene and 5.94 g of butyl cellosolve.
(Manufactured by Mitsui Chemicals Co., Ltd.), 5.0 g of which were uniformly dissolved,
-Methyl-1-phenylpropan-1-one (0.6 g) was added as a photopolymerization initiator to prepare a mixed solvent of 74.25% by weight, N-APR of 18.75% by weight, urethane acrylate of 6.25% by weight, 2- Hydroxy-2-methyl-1-
A curable composition consisting of 0.75% by weight of phenylpropan-1-one was prepared. A coating film was produced from the curable composition in the same manner as in Example 1. The thickness of the coating film is 19
A transparent coating having a thickness of μm was obtained. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 18.54 g of γ-glycidoxypropyltrimethoxysilane was dissolved in a mixed solvent of 47.52 g of ethanol, 5.94 g of toluene and 5.94 g of butyl cellosolve, and N-APR of 1.095 was added.
g, urethane acrylate (Aronix M-110
0: Toagosei Kagaku Co., Ltd.) (0.365 g) was uniformly dissolved, and then 2-hydroxy-2-methyl-1-phenylpropan-1-one (0.6 g) was added as a photopolymerization initiator and mixed. Solvent 74.25% by weight, γ-glycidoxypropyltrimethoxysilane 23.175% by weight, N-AP
R1.369% by weight, urethane acrylate 0.456
A curable composition consisting of 0.75% by weight of 2-hydroxy-2-methyl-1-phenylpropan-1-one was prepared. A coating film was produced from the curable composition in the same manner as in Example 1. The coating film was cracked in the process of hydrolysis, resulting in a very brittle and cloudy coating film. The coating film test pieces were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

[0074]

[Table 1] [Example 19] A curable composition was prepared in exactly the same manner as in Example 1, and then 6.4 g of polyoxyethylene lauryl ether was added and uniformly mixed to obtain a curable composition having antifogging performance. Prepared. A coating film was produced from the curable composition in the same manner as in Example 1. The thickness of the coating film was 21 μm. The characteristics of the coating film thus obtained were evaluated as shown below. (A) Adhesiveness: 1 mm wide cross cut 1 on the cured coating film
Cell 00 was formed and a cellophane adhesive tape was attached to the cross-cut surface, which was strongly pulled in the direction perpendicular to the coating film, and the peeled state of the coating film was observed. The observation result represents the total number of crosscuts in the denominator, and the numerator represents the number of crosscuts that did not exfoliate. (B) Surface hardness: Carried out according to JIS K-5400 and expressed in pencil hardness. (C) Scratch resistance: The surface of the test piece was rubbed with # 0000 steel wool several times by hand to observe the degree of scratching of the coating film, and the scratch resistance was judged according to the following criteria. ◯: No scratch even if strongly rubbed Δ: Slightly scratched if strongly rubbed ×: Scratch easily (d) Anti-fog property: Set a test piece at the saturated steam outlet of 40 ° C. based on JIS S4030 Then, the state of water condensation on the surface of the test piece was observed. The state was evaluated by the following symbols. ◯: It was not clouded at all, and water condensed in the form of a water film. State 8
I kept it for more than an hour. B: No clouding occurred, but water condensed into large drops.

X: It was cloudy and could not be seen through. After the above test, the test piece was left overnight and dried, and then the same test was repeated again to repeat the antifogging durability test. (E) Water resistance test: The test piece was placed in a constant temperature water bath at 25 ° C. for 1
After immersion for 70 hours, the presence or absence of abnormalities such as transparency, peeling state and breakage of the coating film was observed. (F) Weather resistance test: temperature 63 ± 3 ° C., rainfall 18 minutes / 1
A test with a sunshine weather meter was carried out under the test condition of operating for 20 minutes. The change in appearance was observed after the accelerated exposure test for 500 hours. The results are shown in Table 2.

Example 20 A curable composition was prepared in exactly the same manner as in Example 1, and then 6.4 g of methacryloxyethyl phosphate was added and uniformly mixed to give a curability imparting antifogging performance. A composition was prepared. The production of a coating film of the curable composition was carried out by the same method as in Example 19. The thickness of the coating film was 22 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated for characteristics in the same manner as in Example 19, and the results are shown in Table 2.

[Example 21] A curable composition was prepared in exactly the same manner as in Example 1, and then 6.4 g of distearyltrimethylammonium chloride was added and uniformly mixed to give an antifogging property. A composition was prepared. The production of a coating film of the curable composition was carried out by the same method as in Example 19. The thickness of the coating film was 20 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated for characteristics in the same manner as in Example 19, and the results are shown in Table 2.

[Example 22] A curable composition was prepared in exactly the same manner as in Example 10, and then 6.4 g of polyoxyethylene lauryl ether was added and uniformly mixed to give an anti-fogging property. A composition was prepared. The production of a coating film of the curable composition was carried out by the same method as in Example 19.
The thickness of the coating film was 21 μm, and a transparent and glossy coating film was obtained. The coating film test pieces were evaluated for characteristics in the same manner as in Example 19, and the results are shown in Table 2.

Comparative Example 3 A curable composition was prepared in exactly the same manner as in Comparative Example 1, and then 6.4 g of polyoxyethylene lauryl ether was added and uniformly mixed to give a curability imparting antifogging performance. A composition was prepared. The production of a coating film of the curable composition was carried out by the same method as in Example 19. The thickness of the coating film was 20 μm, and a transparent coating film was obtained. The coating film test pieces were evaluated for characteristics in the same manner as in Example 19, and the results are shown in Table 2.

[0080]

[Table 2]

[0081]

【The invention's effect】

(1) The cured product obtained by curing the curable composition of the present invention maintains transparency and has weather resistance that has not been conventionally obtained with an organic material, and has a high surface hardness. And has excellent wear resistance. Because of these excellent properties, it is preferably applied to hard coats such as plastic substrates, and the life and aesthetics of these substrates can be improved. (2) A cured product obtained by adding a compound having surface activity to the cured composition of the present invention and maintaining the transparency allows water to be condensed into a film on the surface for a long period of time without lowering the surface hardness. Therefore, it has excellent surface hardness, weather resistance, and durable anti-fogging performance. From this,
It is suitable for imparting antifogging properties to glass substrates as well as transparent plastic substrates. (3) Since the cured product produced by the present invention is a composite of an organic substance and an inorganic substance while maintaining transparency, it can exhibit gloss, smoothness and durability that cannot be exhibited by the organic substance. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C09D 133/26 PFW

Claims (4)

[Claims] 1. A (meth) acrylamide represented by the general formula (I) (formula 1) or (II) (formula 2): (In the above formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a hydrogen atom, a methyl group or an ethyl group, and R ₃ represents a hydrogen atom, a methyl group, an ethyl group or a propyl group.) [In the above formula, R ₁ is a hydrogen atom or a methyl group, and A is (C
H ₂₎ n (where, n is 4-6) or (CH _{2) 2} O
Represents (CH ₂ ) ₂ . ] -Containing N-alkyl or N-
One or two of alkylene-substituted (meth) acrylamides
A curable composition comprising one or more kinds of monomers, a silane compound having a hydrolyzable group on a silicon atom or a hydrolyzate thereof, and a polymerization initiator. 2. A curable composition obtained by further adding a compound having surface activity to the curable composition according to claim 1. 3. A method for curing a curable composition, which comprises polymerizing the monomer of the curable composition according to claim 1 or 2 and then hydrolyzing and curing the silane compound. 4. The curing method according to claim 3, wherein the curable composition is used as a coating film.