JP2003012966A - Photocurable antifogging agent composition and production method for antifog coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a one-component antifogging agent composition which, when cured by the irradiation with low-energy light, gives a cured film excellent in the retention of antifog properties. SOLUTION: This antifogging agent composition is prepared by compounding (a) 100 pts.wt. acrylic monomer having an amide bond (e.g. acrylamide or N- methylacrylamide) with (b) 10-100 pts.wt. urethane polymer having an average mol.wt. of 2,000-20,000, (c) 5-400 pts.wt. polyalkylene glycol acrylate, (d) 10-200 pts.wt. alkyl polyol polyacrylate, and (e) a photocatalyst in an amount of 0.1-10 wt.% of the sum of ingredients (a) to (d) (solid basis).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable antifogging agent composition and a method for producing an antifogging coated article. The present invention relates to an antifogging agent composition for forming a coating film excellent in antifogging property, and a method for producing an antifogging coated article, which comprises applying the antifogging agent composition to obtain a coated article.

[0002]

2. Description of the Related Art Plastics and inorganic glasses conventionally used as transparent materials have the drawback that when the surface temperature is below the dew point, the surface becomes cloudy and the transparency is impaired. Various proposals have hitherto been made as an anti-fogging method for preventing such fogging.

For example, a method for forming a water-absorbing film by copolymerizing a hydrophilic acrylate monomer having an alcoholic hydroxyl group with a specific polyfunctional monomer or by crosslinking a water-soluble polymer such as polyvinyl alcohol. It has been known. Further, a method of kneading a surfactant into a resin constituting a molded article, or a method of applying a composition containing a surfactant to the surface of a substrate is known.

[0004]

However, in the method for forming a water-absorbing film, the water-absorbing property of the film is controlled by the degree of cross-linking. Was difficult to satisfy. In addition, the methods (1) and (2) have a problem that the surfactant flows out due to water and the antifogging property is significantly reduced.

Further, with respect to the antifogging of a lamp such as a headlight mounted on a vehicle such as an automobile, even if the lamp is used in a high temperature environment, that is, at a temperature of 60 to 140 ° C. It is required that the appearance, coating film strength and adhesiveness of the constituent lenses such as plastics be maintained for a long period of time.

As a method for solving these problems, for example, Japanese Patent Laid-Open No. 8-27290 discloses a UV-curable antifogging agent composition in which a hydrophobic compound is used as a primer and a hydrophilic monomer is formed as a top coat. A method of manufacturing an article is disclosed.

However, this method has a problem in practical workability. In other words, a heat-curable primer is used, and not only heating at 120 ° C for about 2 hours is required for curing, but also it is inferior in workability because it is a two-component type, and at the time of curing, a very large energy (UV Irradiation amount 2000mJ / cm
² ) needed.

Further, Japanese Patent Application Laid-Open No. 6-32997 discloses an ultraviolet-curable antifogging composition obtained by block-copolymerizing a hydrophilic monomer and a hydrophobic monomer. However, this composition had the drawback of low moisture resistance and poor anti-fog properties.

Further, in Japanese Patent Laid-Open No. 6-107967, N-
A method for producing a heat-curable antifog composition by block- or graft-copolymerizing methylol acrylamide or the like is disclosed. However, this anti-fogging agent composition has a problem that it requires 80 ° C. × 60 minutes or 120 ° C. × 30 minutes for curing, resulting in poor workability.

The present invention has been made in order to solve these problems, and is an antifogging agent composition having a one-component, cured film formed by low energy light irradiation and having excellent antifogging durability, And it aims at providing the manufacturing method of an anti-fogging coated article.

[0011]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have obtained the following findings. That is, when a polyoxyethylene-based compound is used as the antifogging component, it is easily oxidized to deteriorate the antifogging property over time, and when a polyfunctional acrylate is used, the antifogging coating film It was found that since the cross-linking reaction progressed and the cross-linking density increased with time, the permeation of water into the coating film decreased compared to the initial stage, and as a result, the antifogging property decreased with time.

As an antifogging component, an acrylamide-based monomer that is not easily deteriorated by oxidation is used, and a gin property (toughness) for preventing an excessive increase in crosslinking density due to the progress of crosslinking reaction over time. It has been found that by blending a urethane resin as an imparting component and using polyethylene glycol acrylate as a cross-linking component (hardness improving component), the above-mentioned deterioration of the antifogging property is significantly improved. Further, they have found that by adding an alkyl diol diacrylate, it is possible to secure anti-fogging property while maintaining the film hardness, and in particular, the adhesion to polycarbonate, and have completed the present invention.

The antifogging agent composition of the present invention comprises, as described in claim 1, (a) an acrylic monomer having an amide bond represented by the general formula 2, and (b) an average molecular weight of 2,000. ~ 2
It is characterized in that it contains 0,000 urethane polymer, (c) polyalkylene glycol acrylate, (d) alkyl polyol polyacrylate and (e) photocuring catalyst.

[Chemical 2] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a dimethylaminopropyl group, R ³ is a hydrogen atom, and a carbon number 1 ~ 4 represents a linear or branched alkyl group or a dimethylaminopropyl group.)

In the antifog composition of the present invention, as described in claim 2, the component (b) is added to 100 parts by weight of the amide bond-containing acrylic monomer of the component (a). 10 to 100 parts by weight of a urethane polymer, 5 to 400 parts by weight of a polyalkylene glycol acrylate as a component (c), and 10 to 200 parts by weight of an alkyl polyol polyacrylate as a component (d) are blended, respectively, and (e)
The photocuring catalyst is contained in a proportion of 0.1 to 10 parts by weight based on 100 parts by weight (solid content) of the components (a), (b), (c) and (d). It is desirable to be characterized. Further, as described in claim 3, a polyurethane acrylate having an average molecular weight of 2,000 to 10,000 can be used as the component (b).

Further, as described in claim 4, a surfactant can be further contained. The content of the surfactant is 0.1 to 20 with respect to the total 100 parts by weight (solid content) of the components (a), (b), (c) and (d). It is desirable to use parts by weight. Furthermore, as described in claim 5, a polyether-modified silicone oil can be used as a surfactant.

The method for producing an antifogging coated article according to the present invention, as set forth in claim 6, is any one of claims 1 to 5.
The step of applying the photocurable antifogging agent composition according to the item 1 to a substrate, and irradiating the applied antifogging agent composition with light to form an antifogging coating film on the surface of the substrate. And a step of performing. Then, in the method for producing an antifogging coated article of the present invention, as described in claim 7, in the light irradiation step, the output is 80 to 160 W / cm, the illuminance is 10 to 150 mW / cm ² , and the integrated light amount is 50 to 200 m.
It is desirable to irradiate with ultraviolet rays under the condition of J / cm ² .

The present invention will be described in more detail below.

Examples of the N-substituted or unsubstituted (meth) acrylamide compound represented by the above general formula (1) of the component (a) used in the present invention include (meth) acrylamide and N-methyl (meth). Acrylamide, N, N'-
Dimethyl (meth) acrylamide, N-ethyl (meth)
Acrylamide, N, N'-diethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N
-Isopropyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, diacetone (meth) acrylamide, N- (meth) acryloylpiperidine, N- (meth) acryloylmorpholine and the like can be mentioned. Any of these monomers can be obtained as a commercial product, but it is also possible to use those synthesized according to a known method.

The urethane polymer as the component (b) is not particularly limited in kind as long as it is a urethane polymer having an average molecular weight (number average molecular weight) of 2,000 to 20,000, but polyurethane (meth) acrylate is particularly preferably used. desirable. Polyurethane (meth) acrylate having an average molecular weight of 2,000 to 10,000 is suitable.

This polyurethane (meth) acrylate can be obtained by subjecting a polyisocyanate having two or more isocyanate groups in the molecule to a urethanization reaction with a compound having a (meth) acrylate group and a hydroxyl group in the molecule. . At this time, various polyol components may be used together.

As the polyisocyanate having two or more isocyanate groups in the molecule, o-tolylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,
4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4 '
-Aromatic isocyanates such as diisocyanate and naphthalene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornylene diisocyanate, lysine diisocyanate and other aliphatic or alicyclic isocyanates Kind of things can be mentioned.

Further, one or more burettes or isocyanurates of these isocyanate monomers,
Adducts obtained by urethanization reaction of an isocyanate compound with various polyols can also be used as the polyisocyanate raw material.

Examples of the polyalkylene glycol acrylate of the component (c) used in the present invention include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di ( A monomer having two (meth) acryloyl groups such as ethylene oxide or propylene oxide adduct di (meth) acrylate such as (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate; Trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Examples thereof include monomers having three (meth) acryloyl groups obtained by adding ethylene oxide or propylene oxide to glycerin tri (meth) acrylate and the like. Among these, in terms of anti-fog durability,
The use of polyethylene glycol diacrylate is preferred.

Examples of the (d) component alkyl polyol polyacrylate used in the present invention include ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate and 1,3-butanediol di (meth). ) Acrylate, neopentyl glycol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1, Monomers having two (meth) acryloyl groups such as 10-decanediol di (meth) acrylate, dibromoneopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, and dimethyloltricyclodecane di (meth) acrylate. ; Trimethylolup Lopantri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Monomers having three (meth) acryloyl groups such as glycerin tri (meth) acrylate; tetramethylolmethane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta Examples thereof include diacrylates and polyfunctional acrylates obtained by reacting an alkyl diol with acrylic acid, such as monomers having four or more (meth) acryloyl groups such as (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Of these, the alkyl diol diacrylate compound is preferably used in consideration of the durability of the antifogging property.

The photocuring catalyst as the component (e) may be any one of the above (a) to (a) when exposed to actinic rays such as ultraviolet rays and visible rays.
The type is not particularly limited as long as it has a property of polymerizing the (meth) acrylate compound of the component (d).

As the photocuring catalyst which is activated by ultraviolet rays,
For example, sulfides such as sodium methyl dithiocarbamate sulfide, tetramethyl thiuram monosulfide, diphenyl monosulfide, dibenzothiazoyl monosulfide and disulfide; thioxanthone derivatives such as thioxanthone, ethylthioxanthone, 2-chlorothioxanthone, diethylthioxanthone and diisopropylthioxanthone. Diazo compounds such as hydrazone, azoisobutyronitrile, benzenediazonium; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, dimethylaminobenzophenone, Michler's ketone, benzyl anthraquinone,
Aromatic carbonyl compounds such as t-butylanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, 2-chloroanthraquinone, benzyldimethylketal, and methylphenylglyoxylate; 1-hydroxycyclohexylphenyl ketone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2,2-diethoxyacetophenone, 2,2-dimethoxyacetophenone, etc. Acetophenone derivative of: 4
-Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate,
Dialkylaminobenzoic acid esters such as isopropyl 4-diethylaminobenzoate; peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide; 9-phenylacridine, 9-p. Acridine derivatives such as -methoxyphenylacridine, 9-acetylaminoacridine and benzacridine; 9,10-dimethylbenzphenazine, 9-methylbenzphenazine,
Phenazine derivatives such as 10-methoxybenzphenazine; quinoxaline derivatives such as 4,4 ', 4 "-trimethoxy-2,3-diphenylquinoxaline; 2,4,5
-Triphenylimidazoyl dimer; halogenated ketones; acylated phosphorus compounds such as acylphosphine oxide and acylphosphonate.

Examples of the photocuring catalyst which is activated by visible light include 2-nitrofluorene, 2,4,6-tris (trichloromethyl) -1,3,5-triazine,
Examples include 3,3′-carbonylbiscoumarin and thiomichler ketone.

If the blending amount of the photocuring catalyst in the antifogging agent composition increases, problems such as yellowing of the cured coating or brittleness of the cured coating occur, and if less, curing is insufficient. , A total of 1 of the components (a) to (d)
It is desirable to set 0.1 to 10 parts by weight with respect to 00 parts by weight (solid content).

In the antifogging composition of the present invention, it is desirable to further add a surfactant in order to improve the leveling property and the like. As the surfactant, one or more known nonionic surfactants, anionic surfactants, cationic surfactants and zwitterionic surfactants can be used.

Examples of the nonionic surfactant include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether and polyoxyethylene oleyl ether, polyoxyethylene octylphenol, polyoxyethylene nonylphenol and the like. Polyoxyethylene alkylaryl ethers, polyoxyethylene acyl esters such as polyoxyethylene glycol monostearate, polypropylene glycol ethylene oxide adducts, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate Oxyethylene sorbitan fatty acid esters, alkyl phosphates, polyoxyethylene alkyl ether Phosphoric acid esters such as esters, sugar esters, cellulose ethers, and polyethers (poly oxyethylene) modified silicone oils, etc. are used.

Examples of the anionic surfactant include fatty acid salts such as sodium oleate and potassium oleate, higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzenesulfonate and sodium alkylnaphthalenesulfonate. Alkylbenzene sulfonates and alkylnaphthalene sulfonates, naphthalene sulfonic acid formalin condensates, dialkyl sulfosuccinates, etc.
Dialkyl phosphate salt, polyoxyethylene sulfate salt such as sodium polyoxyethylene alkylphenyl ether sulfate, and the like are used.

Examples of the cationic surfactant include amine salts such as ethanolamines, laurylamine acetate, triethanolamine monoformate, stearamidoethyldiethylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and diamine. Quaternary ammonium salts such as lauryldimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride and stearyldimethylbenzylammonium chloride are used.

Examples of the zwitterionic surfactant include fatty acid type amphoteric surfactants such as dimethylalkyllaurylbetaine and dimethylalkylstearylbetaine, sulfonic acid type amphoteric surfactants such as dimethylalkylsulfobetaine, and alkylglycine. used.

From the viewpoint of the durability of the effect, it is preferable to use a nonionic surfactant, and in particular, the use of a polyether-modified silicone oil is preferable from the viewpoint of the durability of the antifogging property and the prevention of the appearance change of the coating film. Are suitable.

The mixing ratio of these surfactants is preferably 0.1 to 20 parts by weight in terms of solid content based on 100 parts by weight of the components (a) to (d) described above, and more preferably, It is preferably 0.1 to 10 parts by weight. When the content of the surfactant is less than 0.1 part by weight, long-term antifogging property cannot be obtained, and when it exceeds 20 parts by weight, the water resistance and strength of the coating film are lowered, which is not preferable.

As a method of mixing the surfactant, a composition comprising the components (a), (b), (c) and (d) is mixed with water or an organic solvent or a mixed solvent of water and an organic solvent. It is possible to employ a method in which a surfactant is added to the solution after being dissolved and dispersed in the solution. Further, a surfactant may be added together with the components (a) to (d).

As the solvent used at this time, alcohol solvents such as water, methanol, ethanol, n-propanol, isopropanol, n-butanol and diacetone alcohol, methyl cellosolve, ethyl cellosolve,
Butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, and other alcohol ether solvents, methyl ethyl ketone, methyl isobutyl ketone, and other ketone solvents, methyl acetate, ethyl acetate, butyl acetate, and other ester solvents, benzene, toluene, xylene And the like, and amide solvents such as formamide and dimethylformamide. Among these, alcohol-based solvents, alcohol ether-based solvents and mixed solvents thereof are particularly suitable.

In the photocurable antifogging composition of the present invention, various additives such as an ultraviolet absorber, a curing catalyst and an antioxidant can be blended if necessary.

Examples of the UV absorber include commercially available benzotriazole UV absorbers, benzophenone UV absorbers, benzoate UV absorbers, triazine UV absorbers and hindered amine UV absorbers. Further, as the photopolymerization accelerator, N-methyldiethanolamine, 4,4-dimethylaminobenzophenone,
Examples thereof include 2,4-diethylthioxanthone such as 4-dimethylaminoisobenzoate and 4-dimethylaminoethylbenzoate.

Each of these additives can be added in a proportion of 0.1 to 50 parts by weight with respect to 100 parts by weight of the photocurable antifogging agent composition of the present invention.

Next, a method for producing an antifogging coated article by performing antifogging processing using the photocurable antifogging composition of the present invention will be described. That is, in the method for producing an antifogging coated article of the present invention, the antifogging agent composition is applied to a substrate by a known means, and then an actinic ray such as ultraviolet rays is irradiated to cure the coating film.

Examples of the base material include plastics such as acrylic resin and polycarbonate or molded articles of a predetermined shape (for example, plate shape or lens shape) made of inorganic glass. Particularly in the anti-fogging process for vehicle lighting, after applying the anti-fog composition to the inner surface of a plastic lens such as polycarbonate or polymethylmethacrylate by ordinary coating means, the composition is cured by irradiation with ultraviolet rays. Form a film.

A high-pressure mercury lamp can be used as the ultraviolet irradiation means. The irradiation conditions are, for example, output 80 to 16
0W / cm, illuminance 100-150mW / cm ² (wavelength 350nm), integrated light intensity 50
~ 200mJ / cm ² (wavelength 350nm) is desirable.

The above-mentioned base material may be subjected to a pretreatment for the purpose of further improving the adhesiveness. Examples of the pretreatment include corona discharge treatment, glow discharge treatment, treatment with ionizing active rays such as ultraviolet rays, electron beams, and radiation; surface roughening treatment; chemical treatment; primer treatment.

The coating environment is not particularly limited. That is,
When the conventional antifogging coating agent is applied in an environment in which the relative humidity exceeds 60% (RH), the coating film may be whitened after curing and the appearance may be deteriorated. It is not necessary to control the humidity during coating for objects.

As a coating means, a roll coating method, a spray coating method, a dipping method, a brush coating method, a spin coating method, a flow coating method and the like, which are usual means for coating a coating material, can be applied.

The antifogging agent composition of the present invention does not require a primer and can be composed of a single solution, and at the same time, can be irradiated with low energy light to form a cured film having a high antifogging property. In addition, since urethane acrylate is contained and the coating film has toughness and does not easily shrink, the added components are less likely to come off, and as a result, the antifogging property is improved. Further, since the coating film does not shrink over time due to post-curing and the antifogging property is not deteriorated, the antifogging durability is excellent under high temperature environment and humidity condition, and the antifogging property is not deteriorated. Further, a film having excellent antifogging property while maintaining hardness, and particularly excellent adhesion to polycarbonate can be obtained.

A vehicle lamp incorporating a plastic lens, which is an article having antifogging properties imparted by the antifogging agent composition of the present invention, is of course not only the appearance and adhesion of the coating film in an actual use environment. Therefore, the antifogging property and the coating film strength can be maintained for an extremely long period of time.

[0049]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below with reference to examples, but the present invention is not limited thereto. It should be noted that the display of the number of parts indicates parts by weight.

Example 1 First, an antifogging composition (coating solution) was prepared as follows. That is, 6.0 parts of acrylamide,
3.3 parts of methanol, UF8001 (trade name of urethane acrylate manufactured by Kyoeisha Chemical Co., Ltd.) 7.3 parts, light acrylate 9EG-A (trade name of polyethylene glycol diacrylate manufactured by Kyoeisha Chemical Co., Ltd.) 19.0 parts, KS-HDDA (Nippon Kayaku
Trade name of hexanediol diacrylate manufactured by Co., Ltd.) 15
Part, 3.0 parts of Irgacure 907 (trade name of Ciba Specialty Chemicals Co., Ltd.) which is a photopolymerization catalyst, and 1.7 parts of TSF4440 (trade name of GE Toshiba Silicones Co., Ltd.) which is a polyether-modified silicone oil are mixed to obtain a uniform mixture. After making a solution, propylene glycol monomethyl ether
It was diluted to 0% to obtain a coating solution.

Then, the obtained coating solution was coated on a polycarbonate plate by flow coating under the conditions of 25 ° C. and relative humidity of 50%, and output was 160 W with a high pressure mercury lamp (manufactured by USHIO Electric Co., Ltd.) and illuminance. The coating film was cured by irradiating with ultraviolet light under the conditions of 100 mW / cm ² (350 nm), integrated light amount of 150 mJ / cm ² , and irradiation distance of 95 mm. Thus, an antifogging agent-coated article was obtained. In addition, the integrated light amount of ultraviolet rays is UV-1 manufactured by Oak Manufacturing Co., Ltd.
It was measured by 0.

Example 2 An antifogging composition (coating solution) was prepared in the same manner as in Example 1. Next, apply this coating solution to the coating environment at 25 ° C. × 7.
0% RH In the same manner as in Example 1 except that the above was applied, the coating was applied onto a polycarbonate plate and irradiated with ultraviolet rays to cure the coating film. Thus, an antifogging agent-coated article was obtained.

Example 3 An antifogging composition (coating solution) was prepared in the same manner as in Example 1. Next, this coating solution was coated on a polycarbonate plate in the same manner as in Example 1 except that the coating method was spray coating, and the coating film was cured by irradiating ultraviolet rays to obtain an antifogging agent-coated article.

Example 4 An antifogging composition (coating solution) was prepared as follows. That is, 6.0 parts of acrylamide, 3.3 parts of methanol, UX4101 (trade name of urethane acrylate manufactured by Nippon Kayaku Co., Ltd.), 7.3 parts, light acrylate 9EG-A1
9.0 parts, KS-HDDA 15 parts, photopolymerization catalyst Irgacure 907 3.0 parts and polyether modified silicone oil TSF4440 1.7 parts were mixed to form a uniform solution, which was then mixed with propylene glycol monomethyl ether. It was diluted to 50% to obtain a coating solution.

Next, the obtained coating solution was coated on a polycarbonate plate by flow coating under the conditions of 25 ° C. and 50% relative humidity, and the output was 160 W and the illuminance was measured by a high pressure mercury lamp (USHIO Electric Co., Ltd.). The coating film was cured by irradiating with ultraviolet light under the conditions of 100 mW / cm ² (350 nm), integrated light amount of 150 mJ / cm ² , and irradiation distance of 95 mm. Thus, an antifogging agent-coated article was obtained.

Example 5 An antifogging composition (coating solution) was prepared in the same manner as in Example 4. Next, apply this coating solution to the coating environment at 25 ° C. × 7.
0% RH In the same manner as in Example 4 except that the above was applied, the coating was applied onto a polycarbonate plate and irradiated with ultraviolet rays to cure the coating film. Thus, an antifogging agent-coated article was obtained.

Example 6 An antifogging composition (coating solution) was prepared in the same manner as in Example 4. Then, this coating solution was coated on a polycarbonate plate and irradiated with ultraviolet rays to cure the coating film in the same manner as in Example 4 except that the coating method was spray coating, to obtain an antifogging agent-coated article.

Example 7 The curing conditions of the coating film by ultraviolet irradiation were: output 80 W, illuminance 50 m
An antifogging agent-coated article was produced in the same manner as in Example 1 except that W / cm ² (350 nm), the cumulative light amount was 75 mJ / cm ² , and the irradiation distance was 95 mm.

Example 8 The curing conditions of the coating film by ultraviolet irradiation were: output 80 W, illuminance 50 m
An antifogging agent-coated article was produced in the same manner as in Example 2 except that W / cm ² (350 nm), the cumulative light amount was 75 mJ / cm ² , and the irradiation distance was 95 mm.

Example 9 The curing conditions of the coating film by ultraviolet irradiation were: output 80 W, illuminance 50 m
An antifogging agent-coated article was produced in the same manner as in Example 3 except that W / cm ² (350 nm), cumulative light amount 75 mJ / cm ² , and irradiation distance 95 mm were used.

Example 10 Curing conditions of a coating film by ultraviolet irradiation were set as follows: output 80 W, illuminance 50 m
An antifogging agent-coated article was produced in the same manner as in Example 4 except that W / cm ² (350 nm), the cumulative light amount was 75 mJ / cm ² , and the irradiation distance was 95 mm.

Example 11 The curing conditions of the coating film by ultraviolet irradiation were: output 80 W, illuminance 50 m
An antifogging agent-coated article was produced in the same manner as in Example 5 except that W / cm ² (350 nm), the cumulative light amount was 75 mJ / cm ² , and the irradiation distance was 95 mm.

Example 12 The curing conditions of the coating film by ultraviolet irradiation were: output 80 W, illuminance 50 m
An antifogging agent-coated article was produced in the same manner as in Example 6 except that W / cm ² (350 nm), cumulative light amount 75 mJ / cm ² , and irradiation distance 95 mm were used.

Comparative Examples 1 to 3 and 7 to 9 Antifogging was performed in the same manner as in Examples 1 to 3 and 7 to 9 except that light acrylate 9EG-A which was polyethylene glycol diacrylate was not added. An agent coated article was produced.

Comparative Examples 4 to 6 and 10 to 12 Antifogging agent-coated articles were prepared in the same manner as in Examples 4 to 6 and Examples 10 to 12 except that UX-4101 which was a urethane acrylate was not added. Manufactured. It should be noted that Comparative Examples 1 and 1 and Comparative Examples 2 and 2, ..., Comparative Examples 12 and 12 correspond to Examples having the same numbers.

(1) Then, the physical properties of the antifogging coatings of the antifogging agent-coated articles produced in Examples 1 to 12 and Comparative Examples 1 to 12 were evaluated by the following methods.

(1) Appearance before curing During curing when the coating liquid is applied in each environment (10
Min) to examine the change in appearance. The colorless and transparent ones are indicated by ◯, and the white turbid ones are indicated by x.

(2) Curability Immediately after curing by irradiation with ultraviolet rays, the state of the coating film when touching the coating film was examined. ○: tack-free one: ○, scratched one: △, sticky one: x Expressed as

(3) Adhesion A cross-cut cellophane adhesive tape peeling test was carried out in accordance with JIS D0202. That is, make 100 crosscuts on the surface of the coating film with a cutter knife to reach the base material, attach cellophane adhesive tape (manufactured by Nichiban Co., Ltd.), peel it in the direction perpendicular to the adhesive surface, and leave it without peeling. The number of cross cuts was measured. Remaining number 100/100 is a, 80 to 99/100 is b, less than 80/100
Each piece is represented by c.

(4) Coating strength The appearance change of the coating left in each environment was visually evaluated. And, those with no change in appearance were marked with ◯, and those with a change in appearance were marked with x.

(5) Breath test The coating film left under each environment was placed in a thermostatic chamber at 25 ° C.
The coating film was blown and the state of haze was visually evaluated. The case where the coating film does not fog at all is indicated by ⊚, the case where the water droplets spread instantaneously is indicated by ∘, the case where some fog is seen is indicated by △, and the case where the entire surface is fogged is indicated by ×.

(6) 40 ° C. steam test The coating film placed in a thermostatic chamber at 25 ° C. was exposed to warm steam at 40 ° C. for 5 minutes, and the time until clouding started was measured. Then, ⊚ indicates that it does not fog at all, ∘ indicates that the water droplets spread instantly, Δ indicates that the water drops are slightly clouded, and x indicates that the entire surface is cloudy.

(7) Coating strength (coating hardness) A pencil scratching test according to JIS K5400 was carried out,
The hardness of the scratched pencil was entered.

The environmental conditions (A) to (E) of the test pieces used in each of the above tests are as shown below. (A) Physical properties of coating film immediately after curing by UV irradiation in the initial environment (B) Physical properties of coating film after standing at 80 ° C for 100 hours when the heat-resistant substrate is polycarbonate (C) Relative humidity-resistant coating film at 50 ° C Physical properties of coating film after being left for 100 hours in an environment of 98% humidity (D) Thermal cycle resistance coating film is kept at 90% relative humidity for 2 hours at 80 ° C., then -40
The condition of leaving each for 2 hours at ℃ is 1 cycle,
Physical properties of coating film after 20 cycles (E) Condensation test In an environment with relative humidity of 90% at 38 ° C, 5 ° C while tapping the antifogging surface of the coating film from the opposite side to 5 ° C
Physical properties of coating film after exposure for minutes

The evaluation results are shown in Tables 1 and 2.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

EFFECT OF THE INVENTION According to the antifogging agent composition of the present invention, a cured coating having a high antifogging property can be formed by irradiation with light having a low energy, and a primer is not required, so that the composition of one liquid is used. Since it is possible, it has high productivity. Further, since the cured coating is tough and does not easily shrink, the added components are less likely to come off, and the anti-fogging sustainability is excellent. Furthermore, the antifogging property is secured while the hardness is maintained, and a film having excellent adhesion to polycarbonate is obtained.

A vehicle lamp incorporating a plastic lens, which is an article having antifogging properties imparted by the antifogging agent composition of the present invention, has not only the appearance and adhesion of a coating film in an actual use environment. , The antifogging property and the coating film strength are maintained for a very long time.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09D 183/04 C09D 183/04 F term (reference) 4J027 AC03 AC06 AG01 AG23 AG24 AJ01 BA14 BA20 BA21 BA25 BA26 BA27 CA10 CA31 CB10 CC04 CC05 CD08 4J038 DG002 DL032 FA091 FA151 FA161 FA281 JA25 JA32 JA62 JA66 JA70 JA73 JB01 JB06 JB08 JB13 JB16 JB28 JB32 JB33 JB36 JC08 JC09 JC14 JC20 JC20 NA07 PA07 NA17 NA11 NA17 NA17 NA02 NA04 NA17 NA11 NA02

Claims (7)

[Claims] 1. An (a) acrylic monomer having an amide bond represented by the general formula 1, and (b) an average molecular weight of 2,000.
A photocurable antifogging composition comprising: ~ 20,000 urethane polymer, (c) polyalkylene glycol acrylate, (d) alkylpolyol polyacrylate and (e) photocuring catalyst. [Chemical 1] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a dimethylaminopropyl group, R ³ is a hydrogen atom, and a carbon number 1 ~ 4 represents a linear or branched alkyl group or a dimethylaminopropyl group.) 2. 100 parts by weight of the amide bond-containing acrylic monomer as the component (a), 10 to 100 parts by weight of the urethane polymer as the component (b), and polyethylene glycol acrylate as the component (c). 5 to 400 parts by weight,
Component (d), an alkyl diol diacrylate 10-2
100 parts by weight (solid content) of (e) the photocuring catalyst, and 100 parts by weight (solid content) of the components (a), (b), (c) and (d).
The photocurable antifog composition according to claim 1, wherein the photocurable antifog composition is contained in a proportion of 0.1 to 10 parts by weight. 3. The component (b) has an average molecular weight of 2,000.
The photo-curable antifogging agent composition according to claim 1 or 2, wherein the composition is a polyurethane acrylate of about 10,000. 4. A surfactant is further contained, and the content of this surfactant is 100 parts by weight in total of the above components (a), (b), (c) and (d) ( The photocurable antifogging agent composition according to any one of claims 1 to 3, wherein the amount is 0.1 to 20 parts by weight based on the solid content). 5. The photocurable antifogging composition according to claim 4, wherein the surfactant is a polyether-modified silicone oil. 6. A step of applying the photocurable antifogging composition according to any one of claims 1 to 5 to a base material, and irradiating the applied antifogging composition with light. And a step of forming an antifogging coating film on the surface of the substrate, the method for producing an antifogging coated article. 7. In the light irradiation step, an output of 80 to 160 W / cm,
7. The method for producing an antifogging coated article according to claim 6, which comprises irradiating with ultraviolet light under the conditions of an illuminance of 10 to 150 mW / cm ² and an integrated light quantity of 50 to 200 mJ / cm ² .