JPH11140109A - Visible light or actinic radiation curable, non-fogging composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which is made into a cured film having an excellent hardness and excellent long-lasting surface non-fogging properties by employing a (meth)acrylate containing a plurality of OH and (meth)acryloyl groups and a reactive surfactant. SOLUTION: A (meth)acrylate having two or more of OH groups and two or more of (meth)acryloyl groups obtained by reacting preferably n-valent polycarboxylic acid ((n) is 2-10), 0.6n-3.0n mol, relative to 1 mole of the polycarboxylic acid, of an epoxy compound having two epoxy groups and 0.2n-5.0n mol of a (meth)acrylic acid are reacted such that the number of carboxylic groups is 1.6-2.4 times the number of mole of the epoxy compound, and a reactive surfactant preferably having a propenyl or a (meth)allyl group [for example, a compound represented by the formula (wherein, A<3> is an ethylene group; (c) is 5; and X<2> is H)] are empolyed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a visible light or active energy ray for forming a cured coating film having excellent surface hardness, antifogging property and sustainability on a substrate such as plastic, glass and metal. The composition of the present invention relates to a reflector such as a bathroom mirror and a cosmetic mirror, sunglasses, eyeglass lenses, a cover glass for watches, ski goggles, underwater glasses and a meter. It can be used for a transparent body or the like such as a cover, and can be awarded in the technical field where these are used. In this specification, an acryloyl group or a methacryloyl group is a (meth) acryloyl group, an acrylate or a methacrylate is a (meth) acrylate, an acrylic acid or a methacrylic acid is a (meth) acrylic acid, an allyl group or a methallyl group. (Meth) allyl group.

[0002]

2. Description of the Related Art Reflectors such as mirrors and metals, plastic plates such as acrylic plates and polycarbonates, and transparent bodies such as glass are not suitable for use in places with high temperatures and high humidity or places with large differences in temperature and humidity. The surface may be clouded due to dew condensation and lose transparency.
In order to solve these problems, conventionally, a method of applying an antifogging composition comprising a non-reactive surfactant to a substrate surface has been performed. In the early stage, although the anti-fogging effect was exhibited, once the treated surface was wiped, the anti-fogging property was reduced, that is, the anti-fogging durability was lacking. There is also a method of applying an antifogging composition comprising a hydrophilic polymer diluted with an organic solvent to the surface of a substrate, but the coating film hardness is insufficient and the solvent resistance is insufficient. In addition, the antifogging property was not satisfactory. Further, since the antifogging composition contains an organic solvent, there are also problems in working environment such as danger such as ignition and fire and odor.

[0003]

In order to solve the above-mentioned problems, an essentially solvent-free antifogging composition which is cured by active energy rays such as ultraviolet rays and electron beams has recently been proposed. Specifically, an antifogging composition comprising a UV-curable resin containing a hydrophilic group and a UV-curable resin containing no hydrophilic group (JP-A-55-69678), a hydrophilic polymer and various hydrophilic compounds An antifogging composition comprising (meth) acrylate has been proposed (JP-A-3-31369).
However, these compositions have a problem that antifogging property is not exhibited in an environment under high humidity. Further, an antifogging composition comprising a hydrophilic monomer and a non-reactive surfactant has also been proposed (Japanese Patent Application Laid-Open No. 3-2).
No. 15589), when the cured coating film surface was wiped, the anti-fogging property was reduced, and the composition lacked anti-fogging durability (repeated anti-fogging property). The present inventors have conducted intensive studies in order to find an antifogging composition capable of forming a cured coating film having excellent surface hardness and excellent antifogging properties and its durability.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a specific (meth) acrylate and a surfactant having a reactivity with the (meth) acrylate are combined. It has been found that the resulting composition forms a cured coating film having excellent surface hardness, excellent antifogging property and its durability, and has completed the present invention. Hereinafter, the present invention will be described in detail.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION [A] Component The component [A] of the present invention may be any of various (meth) acrylates having at least two hydroxyl groups and at least two (meth) acryloyl groups in the molecule. Compounds can be used. [A]
Examples of the component include a reaction product of an epoxy compound having two or more epoxy groups and (meth) acrylic acid [hereinafter referred to as (meth) acrylate (i)]. Here, examples of the epoxy compound having two or more epoxy groups include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, pentanediol diglycidyl ether, hexanediol diglycidyl ether, and neopentyl glycol. Diglycidyl ether of alkanediol such as diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether And polypropylene glycol diglycidyl ether Diglycidyl ether of bisphenol such as diglycidyl ether of alkylene glycol, diglycidyl ether of bisphenol A and diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol such as diglycidyl ether of hydrogenated bisphenol A and diglycidyl ether of hydrogenated bisphenol F Ethers and polyglycidyls of polyols such as di- or triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, polyglycidyl ether of pentaerythritol, polyglycidyl ether of sorbitol and polyglycidyl ether of sorbitan and polyglycidyl ether of polyglycerol Ether and the like.

As the (meth) acrylate (i), those obtained by reacting an epoxy compound with (meth) acrylic acid according to a conventional method can be used. For example, without solvent or in an organic solvent,
A method in which an epoxy compound and (meth) acrylic acid are added, and the mixture is heated and stirred at 60 to 140 ° C. in the presence of a catalyst may be used. When an organic solvent is used, the solvent is preferably removed by distillation under reduced pressure. Here, examples of the organic solvent include benzene, toluene, xylene, cyclohexane, butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. As a catalyst, tertiary amines such as N, N-dimethylbenzylamine, triethylamine and N, N-dimethylaniline, quaternary ammonium salts such as tetradiethylammonium chloride, tetrabutylammonium bromide and benzyltrimethylammonium chloride, and dimethylamine hydrochloride And secondary amine hydrochlorides such as diethylamine hydrochloride, and phosphorus compounds such as triphenylphosphine.
In the reaction, a polymerization inhibitor may be added as necessary. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, catechol, phenothiazine, and N-nitrosophenylhydroxylamine aluminum salt.

The component (A) is preferably a reaction product of an epoxy compound, a polycarboxylic acid and (meth) acrylic acid (referred to as (meth) acrylate (ii)). Here, examples of the epoxy compound include the same compounds as described above, and examples of the polyvalent carboxylic acid include succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, itaconic acid,
Examples include phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, citric acid, malic acid, and butanetetracarboxylic acid. Preferred examples of the (meth) acrylate (ii) include an epoxy compound having two epoxy groups, a divalent carboxylic acid, and a reaction product of (meth) acrylic acid, which are represented by the following formula (1). And the like.

[0008]

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In the formula (1), R 'is a hydrogen atom or a methyl group, R is a residue obtained by removing a carboxyl group from a polycarboxylic acid, and R ¹ is a residue obtained by removing a glycidyl group from an epoxy compound. .

An epoxy compound having two epoxy groups, a reactant of trivalent carboxylic acid and (meth) acrylic acid, for example, include a compound represented by the following formula (2).

[0011]

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In the present invention, the (meth) acrylate (ii) is an n-valent polycarboxylic acid (n = 2 to 10).
And 0.6 n to 3.0 nmol of an epoxy compound having two epoxy groups, and 0.2 n to 5.0 n
The (meth) acrylate obtained by reacting the (meth) acrylic acid with a mole of carboxyl group within the range of 1.6 to 2.4 times the number of moles of the epoxy compound is a curable composition. It is more preferable because the cured coating film has excellent adhesion to the substrate.

In the case where the epoxy compound is reacted at a ratio of less than 0.6 nmol with respect to 1 mol of the n-valent polyvalent carboxylic acid, the viscosity of the obtained product is increased. Depending on the case, gelling may occur, while those reacted at more than 3.0 nmol may have a higher content of di (meth) acrylate in which only (meth) acrylic acid is added to the epoxy compound, and thus may be cured. The film may become brittle, or the adhesion of the cured coating film to the substrate may decrease. The total number of carboxyl groups can be calculated by the sum of the value obtained by multiplying the number of moles of n-valent polycarboxylic acid by n and the number of moles of (meth) acrylic acid, which is 1.6 to 2 times the number of moles of the epoxy compound. It is preferably in the range of 4 times. When the total number of carboxyl groups is less than 1.6 times the number of moles of the epoxy compound, the viscosity of the product becomes high, and the product may be gelled in some cases. Since unreacted (meth) acrylic acid remains in the product, odor and skin irritation may become a problem, or the adhesion to the substrate may decrease.

The n-valent polycarboxylic acid has a valence of 2
To 10 are preferred. In the case where n is 1, the cured coating film of (meth) acrylate (ii) does not have a three-dimensional structure, so that the cured coating film may have insufficient water resistance, solvent resistance and scratch resistance. On the other hand, when n exceeds 10, there are cases where it is difficult to handle due to high viscosity. As the polyvalent carboxylic acid, an aliphatic or aromatic carboxylic acid having 4 to 20 carbon atoms is preferably used. Specific examples of the polyvalent carboxylic acid include the same compounds as those described above.

The epoxy compound having two epoxy groups is preferably an epoxy compound having an oxyalkylene group, and more preferably an epoxy compound having 1 to 10 oxyalkylene groups. Specifically, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and other oxyalkylene groups such as oxypropylene And an oxybutylene group, an oxyhexylene group, etc., and may have two or more oxyalkylene groups in one molecule.

As the (meth) acrylate (ii), those obtained by reacting a polyvalent carboxylic acid, an epoxy compound and (meth) acrylic acid by an ordinary method can be used. Specifically, the (meth) acrylate (ii) It may be obtained by the same method as described in i). Preferably, it is obtained by first reacting a polyvalent carboxylic acid and an epoxy compound, and then reacting the reaction product with (meth) acrylic acid.

[Component (B)] As the reactive surfactant of the component (B) in the present invention, various reactive surfactants can be used as long as they have an unsaturated group. Preferred examples of the unsaturated group include a propenyl group and a (meth) allyl group. Two or more reactive surfactants can be used in combination.

Reactive surfactant having a propenyl group Examples of the reactive surfactant having a propenyl group include the following compounds.

[0019]

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However, in the formula (3), R ² , R ³ , R
⁴ , a, A ¹ and X ¹ are as shown below. · R ^2: having 6 to 30 carbon atoms, an alkyl group, an alkenyl group, an alkylaryl group and aralkyl aryl group · R ^3: a hydrogen atom, having 6 to 30 carbon atoms, an alkyl group, an alkenyl group, an alkylaryl group and Aralkylaryl group ・ R ⁴ : hydrogen atom or propenyl group ・ a: an integer of 0 to 100 ・ A ¹ : alkylene group having 2 to 4 carbon atoms ・ X ¹ : hydrogen atom or sulfate [—SO ₃ L and L , Alkali metal, NH ₄ and alkanolamine residues, etc.)

In R ² , examples of the alkyl group include a hexyl group, a heptyl group, an octyl group, a nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Examples include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an eicosyl group. Examples of the alkenyl group include a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group,
Decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group and the like. Examples of the alkylaryl group include a monobutylphenyl group, a dibutylphenyl group, a sec-butylphenyl group, a disec-butylphenyl group, a tert-butylphenyl group, an octylphenyl group, a nonylphenyl group, a dinonylphenyl group, and a dodecylphenyl group. And a didecylphenyl group. Examples of the aralkylaryl group include a styrenated phenyl group, a benzylphenyl group, and a cumylphenyl group. The aralkylaryl group may be a di- or tri-form of the aralkyl group, or may be a group obtained by substituting these with an alkyl group.

R ³ has 6 to 30 carbon atoms;
Specific examples of the alkyl group, alkenyl group, alkylaryl group and aralkylaryl group include the same groups as those described for R ² .

The preferred range of a is 1 to 50, more preferably 1 to 20.

The alkylene group having 2 to 4 carbon atoms of A ¹ is, for example, an ethylene group, a propylene group, a butylene group or an isobutylene group. They may be combined. A ¹ is preferably an ethylene group.

X ¹ is preferably a hydrogen atom because the cured coating film of the resulting composition has excellent antifogging durability.

In the formula (3), the propenyl group includes trans and cis stereoisomers, and in the present invention, either isomer or a mixture of the isomers can be used.

Preferred examples of the compound represented by the formula (3) include a compound represented by the following formula (4).

[0028]

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The compound represented by the formula (4) is a compound represented by the formula (3), wherein R ² is a nonylphenyl group, and R ³ and R ⁴ are hydrogen atoms.

○ Reactive surfactant having (meth) allyl group As the reactive surfactant having (meth) allyl group,
For example, a compound represented by the following formula (5) can be mentioned.

[0031]

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However, in the formula (5), R ⁵ , R ⁶ ,
b, c, A ² , A ³ and X ² have the following meanings. · R ^5: having 6 to 30 carbon atoms, an alkyl group, an alkenyl group, an alkylaryl group and aralkyl aryl group · R ^6: a hydrogen atom or a methyl group · b: 0 to 100 integer · c: 0 to 100 integer A ² : alkylene group having 2 to 4 carbon atoms A ³ : alkylene group having 2 to 4 carbon atoms X ² : hydrogen atom or sulfate [—SO ₃ L, L is an alkali metal, NH ₄ and alkanol Amine residues, etc.)

In R ⁵ , having 6 to 30 carbon atoms;
Specific examples of the alkyl group, alkenyl group, alkylaryl group, and aralkylphenyl group include the same as those described for R ² in the formula (3).

The preferred ranges of b and c are respectively 1 to
50, more preferably 1 to 20, respectively.

Specific examples of A ² and A ³ are the same as those described for A ¹ in the above formula (3). As A ² and A ³ , an ethylene group is preferable.

It is preferable that X ² is a hydrogen atom because the cured coating film of the obtained composition has excellent antifogging durability.

Preferred examples of the compound represented by the formula (5) include a compound represented by the following formula (6).

[0038]

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The compound represented by the formula (6) is a compound represented by the formula (5), wherein R ⁵ is a nonylphenyl group, R ⁶ is a hydrogen atom and b is 0.

The other reactive surfactant having a (meth) allyl group includes a compound represented by the following formula (7).

[0041]

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However, in the formula (7), R ⁷ , R ⁸ ,
d, e, A ⁴ , A ⁵ and X ³ have the following meanings. · R ^7: having 6 to 30 carbon atoms, an alkyl group, an alkenyl group, an alkylaryl group and aralkyl aryl group · R ^8: a hydrogen atom or a methyl group · d: 0 to 100 integer · e: 0 to 100 integer · a ⁴ represents an alkylene group · a ⁵ C2-4: alkylene group · X ³ C2-4: hydrogen atoms or sulfate [-SO ₃ L, as the L, alkali metal, NH ₄ and alkanol Amine residues, etc.)

R ⁷ has 6 to 30 carbon atoms,
Specific examples of the alkyl group, alkenyl group, alkylaryl group, and aralkylphenyl group include the same as those described for R ² in the formula (3).

The preferred ranges of d and e are respectively 1 to
50, more preferably 1 to 20, respectively.

Specific examples of A ⁴ and A ⁵ are the same as those described for A ¹ in the above formula (3). As A ⁴ and A ⁵ , an ethylene group is preferable.

X ³ is preferably a hydrogen atom because the cured film of the composition obtained has excellent antifogging durability.

The other reactive surfactant having a (meth) allyl group includes a compound represented by the following formula (8).

[0048]

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However, in the formula (8), R ⁹ , R ¹⁰ ,
Y, A ⁶ , f, g and h have the following meanings. R ⁹ : alkyl group, alkenyl group, alkylaryl group, aralkylaryl group having 1 to 36 carbon atoms R ¹⁰ : hydrogen atom or methyl group Y: halogen, OH, NO ₃ .A ⁶ : carbon number 2 An alkylene group of 4 to 4; f: an integer of 1 to 100; g: 1 or 2; h: 1 or 2;

In R ⁹ , the alkyl group having 1 to 36 carbon atoms includes methyl, ethyl, butyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and the like. Group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, 2-ethylhexyl group, 2-dodecylhexadecyl group, 2-octyldodecyl group and isostearyl group. Carbon number 1
Examples of the alkenyl group having 36 include hexenyl, pentenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl and octadecenyl.
Specific examples of the alkylaryl group and the aralkylphenyl group include the same as those described for R ² in the formula (3).

The preferred range of f is 1 to 50, more preferably 1 to 20.

Specific examples of A ⁶ include the same as those described for A ¹ in the formula (3). A ⁶
Is preferably an ethylene group.

The other reactive surfactant having a (meth) allyl group includes a compound represented by the following formula (9).

[0054]

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However, in the formula (9), R ¹¹ , R ¹² , R
¹³ , i, A ⁷ and X ⁴ have the following meanings. · R ^11: having 6 to 30 carbon atoms, an alkyl group, an alkenyl group, an alkylaryl group and aralkyl aryl group · R ^12: a hydrogen atom, or having 6 to 30 carbon atoms, an alkyl group, an alkenyl group, and alkylaryl group , An aralkylaryl group · R ¹³ : hydrogen atom or methyl group · i: an integer of 0 to 100 · A ⁷ : alkylene group having 2 to 4 carbon atoms · X ⁴ : hydrogen atom or sulfate [-SO ₃ L, as L Include alkali metal, NH ₄ and alkanolamine residues, etc.)

R ¹¹ has 6 to 30 carbon atoms;
Specific examples of the alkyl group, alkenyl group, alkylaryl group, and aralkylphenyl group include the same as those described for R ² in the formula (3).

R ¹² has 6 to 30 carbon atoms;
Specific examples of the alkyl group, alkenyl group, alkylaryl group, and aralkylphenyl group include the same as those described for R ² in the formula (3).

The preferred range of i is 1 to 50, more preferably 1 to 20.

[0059] Specific examples of A ⁷ include the same ones as mentioned in A ¹ in the formula (3). A ⁷
Is preferably an ethylene group.

X ⁴ is preferably a hydrogen atom because the cured film of the composition obtained has excellent antifogging durability.

The compounding ratio of the component (B) is such that the component (A) or the component (A) is further mixed with a mono or polyalkylene glycol di (meth) acrylate or /
And when the following other (meth) acrylates are blended, the total amount thereof (hereinafter, these are referred to as curable components) 10
1 to 40 parts by weight per 0 parts by weight is preferred. When the proportion is less than 1 part by weight, the anti-fogging property of the obtained cured coating film becomes insufficient. On the other hand, when it exceeds 40 parts by weight, the curability of the composition is reduced or the water resistance of the obtained cured coating film is reduced. And the cured coating film may crack or crack. A more preferable mixing ratio of the reactive surfactant is 3 to 30 parts by weight.

Component [C] In the present invention, a mono- or polyalkylene glycol di (meth) acrylate of component [C] can be blended in addition to the above-mentioned essential components [A] and [B].
Thereby, the hardness of the obtained cured coating film becomes excellent. In the mono or polyalkylene glycol di (meth) acrylate, examples of the raw material alkylene glycol include ethylene glycol, propylene glycol, and butylene glycol. The number of repeating alkylene oxide units is preferably from 1 to 50, and more preferably from 3 to 25. If the number of repetitions exceeds 50, the resulting cured coating film may have too high a hydrophilicity, and may have poor water resistance. In addition, the di (meta)
Two or more acrylates can be used in combination. Specific examples of the di (meth) acrylate include alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and butylene glycol di (meth) acrylate, and diethylene glycol di (meth) acrylate. Acrylates, dialkylene glycol di (meth) acrylates such as dipropylene glycol di (meth) acrylate and dibutylene glycol di (meth) acrylate, di (meth) acrylate of triethylene glycol, tripropylene glycol di (meth) acrylate and triacrylate Trialkylene glycol di (meth) acrylates such as butylene glycol di (meth) acrylate,
Tetraalkylene glycol di (meth) acrylates such as tetraethylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate and tetrabutylene glycol di (meth) acrylate;
And polyalkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and polybutylene glycol di (meth) acrylate.

In the composition of the present invention, it is more preferable to use ethylene glycol di (meth) acrylate as the component [C], since the resulting cured coating film is excellent in antifogging property and its durability. The di (meth) acrylate is represented by the following formula (10).

[0064]

CH ₂ = C (R ¹⁴ ) COO (CH ₂ CH ₂ O) _n OC (R ¹⁴ ) = CH ₂ (10)

[However, in the formula (10), R ¹⁴ is a hydrogen atom or a methyl group, and n is an integer of 1 to 50. In the formula (1), when n exceeds 50, the resulting cured coating film may have too strong hydrophilicity and may have poor water resistance. A preferred range for n is 3-25.

The preferred ratio of the components (A) and (C) is
Based on the total amount of the components [A] and [C], the component [A] is 10 to 90% by weight and the component [C] is 90 to 10% by weight.
And more preferably 30 to 70% by weight of the component (A).
And component (C) is 70 to 30% by weight.

Other components Various components can be added to the visible light or active energy ray-curable antifogging composition of the present invention, if necessary. For example, organic solvents, water or reactive diluents can be included to reduce the viscosity of the composition.

Examples of the organic solvent include ketones such as methyl ethyl ketone and methyl isobutyl ketone; acetates such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol and isopropyl alcohol; Cellosolves such as methyl cellosolve and ethyl cellosolve, and cellosolve acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and the like can be used, and two or more of these can be used in combination.

As the reactive diluent, a compound having a (meth) acryloyl group in a low-viscosity molecule is preferable. Specifically, tetrahydrofurfuryl (meth) acrylate, acryloyl morpholine [as a commercial product,
There is ACMO manufactured by Kojin Co., Ltd.
Examples include isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate, and hexanediol di (meth) acrylate. In addition to these, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate, polyethylene glycol monohydroxy mono (meth) acrylate and polypropylene glycol monohydroxy mono Polyalkylene glycol monohydroxy mono (meth) acrylate such as (meth) acrylate, polypropylene glycol di (meth) acrylate, hydroxyethyl (meth)
Examples include succinic acid adduct of acrylate, succinic acid adduct of hydroxypropyl (meth) acrylate, and phenylglycidyl ether adduct of (meth) acrylic acid. These may be used in combination of two or more.

When water is added, the component (A), or the components (A) and (C), are dissolved in water or exist in water in the form of an emulsion.

When an organic solvent or water is blended, the blending ratio is preferably 100 parts by weight or less based on 10 parts by weight of the curable component. When the reactive diluent is blended, the blending ratio is preferably 100 parts by weight or less based on 10 parts by weight of the component [A] or the components [A] and [C].

In order to improve the hardness, flexibility and the like of the obtained cured coating film, a di- or poly (meth) acrylate other than the above-mentioned (meth) acrylate may be blended. Specifically, di (meth) acrylate of an ethylene oxide or propylene oxide adduct of bisphenol F, di (meth) acrylate of an ethylene oxide or propylene oxide adduct of bisphenol A,
Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane ethylene oxide or propylene oxide adduct tri (meth) acrylate, pentaerythritol ethylene oxide or propylene Oxide adduct tri (meth) acrylate, dipentaerythritol penta or hexa (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate. As the polyester acrylate, for example, Aronix M-610 manufactured by Toagosei Co., Ltd.
0, M-6200, M-6250, M-710
0, M-8030, M-8060, M-810
0, M-8530, M-8560 and M-905
0 and the like. Examples of the urethane acrylate include Aronix M-1100 and TOM Gosei Co., Ltd.
-1200, M-1210, M-1310 and M
-1600 and Nippon Gohsei Chemical Co., Ltd.
V7000B, UV2000B and UV1700B
And the like. Epoxy acrylates include, for example, Lipoxy SP-1509 and SP
-4010 and SP-6006.

The composition of the present invention may contain a stabilizer in order to prevent gelation during storage and maintain storage stability. Suitable stabilizers include, for example, phenols such as hydroquinone, hydroquinone monomethyl ether, t-butylhydroquinone and catechol, quinones such as benzoquinone, naphthoquinone and diphenylbenzoquinone, phenothiazine and copper salts. The use ratio of these stabilizers is preferably 0.0001 to 0.1 part by weight based on 100 parts by weight of the curable component.

The visible light or active energy ray-curable antifogging composition of the present invention can be easily cured by active energy rays such as visible light, ultraviolet rays and electron beams. When curing with visible light or ultraviolet light, a commonly used photopolymerization initiator or photosensitizer is blended. Specific examples of the photopolymerization initiator include the following compounds. As an acetophenone-based photopolymerization initiator,
2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone [Irgacure-907 from Ciba Geigy], benzyl dimethyl ketal [Irgacure 651 from Ciba Geigy], 1-hydroxycyclohexyl phenyl ketone [Irgacure from Ciba Geigy] 184], diethoxyacetophenone [First Cure DEAP manufactured by Fast Chemical], 2-hydroxy-2-methyl-1-phenylpropan-1-one [Darocur 1173 manufactured by Ciba Geigy], 4- (2-hydroxyethoxy) phenyl (2- (Hydroxy-2-propyl) ketone [Irgacure 2959, manufactured by Ciba-Geigy]
And 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone [Irgacure 369 manufactured by Ciba Geigy]. Examples of the benzoin ether-based photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Benzophenone-based photopolymerization initiators include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzoyl-
4'-methyl-diphenyl sulfide and 2,4,6
-Trimethylbenzophenone and the like. Examples of the thioxanthone-based photopolymerization initiator include 2-isopropylthioxanthone, 2,4-diethylthioxanthone,
4-dichlorothioxanthone and 1-chloro-4-propoxythioxanthone. Examples of the phosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.
Other examples include camphorquinone. Specific examples of the photosensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine,
Methyl dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4-dimethylaminobenzophenone and 4,4
-Diethylaminobenzophenone and the like.

The mixing ratio of the photopolymerization initiator and the photosensitizer may be in accordance with a conventional method. 0.01
If the amount is less than 10 parts by weight, polymerization cannot be sufficiently performed, and
If the amount exceeds the weight part, the amount of the curable component is relatively reduced, so that the properties of the cured coating film may be deteriorated. A particularly preferred amount of the initiator to be used is 0.1 to 10 parts by weight. When the composition is cured by irradiation with an electron beam or radiation, a photopolymerization initiator may not be blended.

In addition to the above, general-purpose fillers, polymers and the like can be added to the composition of the present invention, if necessary.

Method of Use The composition of the present invention may be used in accordance with a conventional method. For example, the composition is applied to a substrate such as plastics such as polycarbonate and polyacrylate, glass and metal, and then applied with visible light or active light. A method of curing by irradiating an energy ray may be used. As a method of applying the composition of the present invention to a substrate, spray coating, flow coating, roll coating, bar coating and dip coating,
Any of the usual coating methods can be employed. or,
Irradiation conditions of visible light or active energy rays may be in accordance with a conventional method.

[0078]

The reason why the composition of the present invention can form a cured coating film having excellent surface hardness, anti-fogging property and excellent durability on a substrate is unknown, but the composition of the present invention is unknown. Even after wiping the cured coating surface after coating, the surfactant is not removed, so that the antifogging durability is excellent.

[0079]

The present invention will be described more specifically below with reference to examples and comparative examples. In addition, the part or% in each example is
Unless otherwise specified, it is based on weight.

Synthesis Example 1 207.6 Epolite 200E (diglycidyl ether of tetraethylene glycol) manufactured by Kyoeisha Chemical Co., Ltd. was added as an epoxy compound to a reactor equipped with a stirrer and a thermometer.
g (0.67 mol), 96.5 g (1.34) of acrylic acid
Mol), 3.0 g of dimethylamine hydrochloride as a reaction catalyst
And 0.3 g of hydroquinone as a polymerization inhibitor were charged and reacted at 100 ° C. for 9 hours with stirring to obtain a component [A].

Synthesis Example 2 In a reactor equipped with a stirrer and a thermometer, 34.6 g (0.18 mol) of citric acid (anhydrous) was used as a polycarboxylic acid, and Epolite 100 manufactured by Kyoeisha Chemical Co., Ltd. was used as an epoxy compound.
207.6 g (0.67 mol) of E (diglycidyl ether of diethylene glycol) and 3.0 g of dimethylamine hydrochloride as a reaction catalyst were charged, and stirred at 90 ° C. for 2 hours.
Allowed to react for hours. 57.9 g of acrylic acid was added to the reaction mixture.
(0.8 mol) and 0.3 g of hydroquinone as a polymerization inhibitor, and the mixture was further reacted at 100 ° C. for 9 hours with stirring to obtain a component [A].

Examples 1 to 8 and Comparative Examples 1 and 2 The components shown in Table 1 were mixed according to a conventional method to prepare an antifogging composition. The following evaluation was performed about the obtained composition. The results in Examples and Comparative Examples are shown in Tables 2 and 3, respectively.

[0083]

[Table 1]

In Table 1, abbreviations have the following meanings. -M-240: tetraethylene glycol diacrylate, Aronix M-240 manufactured by Toagosei Co., Ltd.-M-220: tripropylene glycol diacrylate, Aronix M-220 manufactured by Toagosei Co., Ltd.-NE-5: The above formula ( In the compound represented by 6),
A compound wherein A ³ is an ethylene group, c is 5 and X ² is a hydrogen atom, Adecaria Soap NE-5 manufactured by Asahi Denka Kogyo KK
(Reactive surfactant)-NE-10: a compound represented by the formula (6), wherein A ³ is an ethylene group, c is 10, and X ² is a hydrogen atom, Asahi Denka Kogyo Co., Ltd. Adekaria Soap NE
-10 (reactive surfactant) NE-40P: a compound represented by the formula (6), wherein A ³ is an ethylene group, c is 40, and X ² is a hydrogen atom. Adecaria Soap NE
-40P (reactive surfactant) • SE-10N: In the compound represented by the formula (6), A ³ is an ethylene group, c is 10, and X ² is SO ₃ NH.
_4, compound, manufactured by Asahi Denka Co., Ltd. ADEKAREASOAP SE-10 N (reactive surfactant) · RN-10: In the compound represented by the formula (4), A ¹ is an ethylene radical, a is 10, a compound in which X ¹ is a hydrogen atom, Aqualon RN-1 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
0 (reactive surfactant) HS-5: In the compound represented by the formula (4),
A compound wherein A ¹ is an ethylene group, a is 5 and X ¹ is SO ₃ NH ₄ , Aqualon HS-5 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
(Reactive surfactant)-T-82: polyoxyethylene sorbitan oleyl ester, Adeka Estol T-82 manufactured by Asahi Denka Kogyo KK
(Non-reactive surfactant) ・ IGC-184: Irgacure 184 (photopolymerization initiator) manufactured by Ciba-Geigy Corporation

Evaluation method-A curable polycarbonate plate was coated with the composition obtained by using a bar coater # 10, and a 80 W / cm high-pressure mercury lamp was applied thereto.
Ultraviolet rays were irradiated under the conditions of a lamp height of 10 cm and a conveyor speed of 10 m / min, and the number of irradiations until the cured coating film was touched with a finger and tack was eliminated was evaluated.

Repeated anti-fogging property The cured coating film was exposed to steam at 80 ° C. for 1 minute to evaluate whether or not the cured coating film became cloudy. Also, after repeated evaluation, after wiping off moisture on the cured coating film surface with paper after the evaluation,
The operation of exposing the cured coating film to steam at 80 ° C. for 1 minute was repeated 5 times in total, and evaluated. In Table 2, ○, Δ, and × represent the following meanings. ○ It does not fog. △ Somewhat cloudy. × Cloudy.

Pencil Hardness The cured coating film was measured for pencil hardness according to JIS 5400.

[0088]

[Table 2]

[0089]

[Table 3]

[0090]

According to the composition of the present invention, a cured coating film having excellent surface hardness, excellent antifogging property and excellent durability can be formed on a base material. It can be applied to various required substrates and applications.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09K 3/18 C09K 3/18 // C08G 59/17 C08G 59/17

Claims (4)

[Claims] 1. Visible light or activity comprising [A] a (meth) acrylate having two or more hydroxyl groups and two or more (meth) acryloyl groups in a molecule and [B] a reactive surfactant. Energy ray-curable antifogging composition. 2. The composition according to claim 1, further comprising [C] a mono- or polyalkylene glycol di (meth) acrylate.
The visible light or active energy ray-curable antifogging composition as described in the above. 3. The visible light or active energy ray-curable antifogging composition according to claim 1, wherein the component (A) is a (meth) acrylate shown below. ○ 0.6n to 1 mol of n-valent polycarboxylic acid (n = 2 to 10)
3.0 nmol of the epoxy compound having two epoxy groups and 0.2 nm to 5.0 nmol of (meth) acrylic acid are combined with 1.6 to 2.4 times the number of carboxyl groups of the epoxy compound by mole. (Meth) acrylate obtained by reacting within the following range. 4. The composition according to claim 1, wherein the component (B) is a propenyl group or (meth)
The visible light or active energy ray-curable antifogging composition according to any one of claims 1 to 3, which is a reactive surfactant having an allyl group.