JPH10204327A - Active energy ray-curable resin composition, and method for forming film therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a cured film excellent in film properties by the exposure to an active energy ray. SOLUTION: 100 pts.wt. compsn. comprising 10-50wt.% N-methylol(meth) acrylamide and/or N-alkoxymethyl(meth)acrylamide, 5-60wt.% carbonylated unsatd. monomer, and 5-60wt.% unsatd. resin having on average about at least one polymerizable double bond per molecule and a wt. average mol.wt. of 500-20,000 is compounded with 0.1-10 pts.wt. active-energy-ray polymn. initiator and 0.1-20 pts.wt. polyhydrazide compd. to give an active-energy-ray-curable resin compsn., which is applied to the surface of a substrate in a cured thickness of 1-50μm and cured by the exposure to an active energy ray.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel active energy ray-curable resin composition and a method for forming a film using the same.

[0002]

2. Description of the Related Art Conventionally, active energy ray-curable resin compositions which are cured by active energy rays such as ultraviolet rays and electron beams have been widely used for applications such as paints, inks and adhesives. In general, paints such as thermosetting paints and lacquers do not have sufficient coating hardness immediately after finishing, and after a certain period of time (cooling, drying, etc.), winding, stacking, and transport of products are performed. Therefore, there is a disadvantage that productivity is poor. In contrast, active energy ray-curable resin compositions can be cured in seconds and do not require heating, thus enabling high-speed curing and drying that could not be achieved with thermosetting paints and lacquer types. Widely used for suitable applications.

[0003] The active energy ray-curable resin composition has the above-mentioned advantages, but when irradiated with active energy rays in the presence of air, the surface of the coating film (portion in contact with air). However, a major problem remains that the hardness of the coating surface is not sufficient because the curing of the film causes curing inhibition by oxygen. In particular, compositions such as paints and inks are
When a coating thickness of less than μm is cured in air, poor curing is noticeable.

[0004] In the active energy ray-curable resin composition, in order to improve the above-mentioned drawback of poor curing, the active energy ray is usually irradiated in an atmosphere of an inert gas such as nitrogen gas or air. There is known a method of irradiating an active energy ray on a coating surface on which a transparent film for blocking is stuck or curing the coating surface (Japanese Patent Application Laid-Open No. 8-60026).

[0005] However, the former method has a drawback that the equipment cost for providing the inert gas and the trouble of handling it are required, and the latter method is difficult when the film is attached and bubbles or the like are involved. However, there are drawbacks such as poor curing, and difficulty in sticking on articles having complicated shapes (three-dimensional).

[0006]

SUMMARY OF THE INVENTION The present invention relates to a method for improving the curability of the coating surface, which is a drawback of the conventional active energy ray-curable resin composition, by curing the active energy ray in the presence of air. The purpose of the present invention is to provide a possible resin composition.

[0007]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, in particular,
-A resin composition obtained by combining a specific amount of methylol (meth) acrylamide and / or N-alkoxymethyl (meth) acrylamide, a carbonyl group-containing unsaturated monomer and a polyhydrazide compound solves all conventional problems. The inventors have found that the present invention has been completed.

That is, the present invention provides: (A) N-methylol (meth) acrylamide and / or N-alkoxymethyl (meth) acrylamide 1
0 to 50% by weight, (B) 5 to 60% by weight of a carbonyl group-containing unsaturated monomer, and (C) a weight average molecular weight of 500 to 20 having an average of at least one polymerizable double bond in one molecule.
(D) 0.1 to 10 parts by weight of an active energy ray polymerization initiator, and (E) a polyhydrazide compound 0 based on 100 parts by weight of a resin composition containing 5 to 60% by weight of an unsaturated resin. 1. An active energy ray-curable resin composition characterized by comprising 1 to 20 parts by weight. (B) The active energy ray-curable resin composition described above, wherein the carbonyl group-containing unsaturated monomer is diacetone (meth) acrylamide, and A method for forming a coating film, comprising applying the active energy ray-curable resin composition to a substrate surface so that the applied amount is 1 to 50 μm in cured film thickness, and then irradiating with an active energy ray to cure the composition. About.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS When a conventional active energy ray-curable resin composition is irradiated with an active energy ray in the presence of air, the curing of the coating surface is inhibited by oxygen. On the other hand, since the resin composition of the present invention particularly contains a carbonyl group-containing unsaturated monomer and a polyhydrazide compound, the active energy ray is obtained by the reaction between the carbonyl group of the monomer and the hydrazide group of the polyhydrazide compound. Curing of the coating surface, which was insufficient with curing, can be performed.

In the N-alkoxymethyl (meth) acrylamide (A) used in the resin composition of the present invention, the alkoxyl group includes, for example, OCH3, OC2H5,
(CH2) 2CH3, OCH (CH3) 2, O (CH
2) 3CH3, OCH2CH (CH3) 2, O (CH
2) Linear and branched C1-8 alkoxyl groups such as 4CH3 and O (CH2) 5CH3 are included.

Examples of N-alkoxymethyl (acryl) amide include N-methoxymethylacrylamide, N-methoxyethylacrylamide, N-methoxypropylacrylamide, N-methoxybutylacrylamide,
-Butoxymethylacrylamide is mentioned as a representative unsaturated monomer.

The carbonyl group-containing unsaturated monomer (B) used in the resin composition of the present invention has at least one unsaturated monomer per molecule.
Monomers having one keto group or aldehyde group and one radically polymerizable double bond, ie, polymerizable monoolefinically unsaturated aldehyde compounds and keto compounds. Representative specific examples include, for example, diacetone (meth) acrylamide, acrolein, formylstyrene, (meth) acrylamide pivalinaldehyde, diacetone (meth) acrylate, acetonyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate acetyl Acetate, vinyl alkyl ketone and the like can be mentioned. Of these, diacetone (meth) acrylamide is preferred.

The unsaturated resin (C) used in the resin composition of the present invention has an average of about 1 or more, preferably 1 to 3 per molecule.
The weight average molecular weight having four polymerizable double bond groups is 5
It is from 00 to 20,000, preferably from 600 to 5,000. If the number of polymerizable double bonds is less than about 1 on average, the performance of the cured film, such as hardness, solvent resistance, and weather resistance, deteriorates. On the other hand, when the weight average molecular weight is less than 500, the performance of the cured film such as hardness, workability, and water resistance deteriorates.
If it exceeds 00, workability such as printing and painting deteriorates, which is not preferable.

As the unsaturated resin (C), conventionally known resins used in active energy ray-curable resin compositions can be appropriately selected and used. As the unsaturated resin (C), for example, a polymerizable double bond is introduced into a resin such as a urethane resin, an acrylic resin, an alkyd resin, a polyester resin, a silicone resin, a fluororesin, a spirane resin, a polyether resin, and an epoxy resin. Resin. Examples of the polymerizable double bond group include a vinyl group, a (meth) acryloyl group, a styryl group, and a group derived from maleic acid.

Representative examples of the unsaturated resin (C) include, for example, urethane resin acrylate, acrylic resin acrylate, acrylic resin malate, alkyd resin acrylate, polyester resin acrylate, polyester resin malate, silicone resin acrylate, fluororesin acrylate, and spirane resin. Acrylates, polyether resin acrylates, epoxy resin acrylates and the like can be mentioned.

The unsaturated resin (C) includes, for example, urethane resin, acrylic resin, alkyd resin, polyester resin,
Hydroxyl-containing resins such as silicone resin, fluororesin and polyether resin, and carboxyl-containing unsaturated compounds such as (meth) acrylic acid and (maleic anhydride) or isocyanate groups such as inisocyanatoethyl (meth) acrylate Reactant with unsaturated compound; Reactant of isocyanate group-containing resin such as urethane resin and acrylic resin with hydroxyl group-containing unsaturated monomer such as hydroxyethyl (meth) acrylate; acrylic resin (radical of glycidyl (meth) acrylate) A) a polymer) and an epoxy resin (such as a bisphenol / epichlorohydrin type) and a carboxyl group-containing unsaturated compound such as (meth) acrylic acid and maleic acid. These reactions can be performed by a conventionally known method.

The trade name of the unsaturated resin (C) is, for example, NK Ester A-BPE-4 (Shin Nakamura Chemical Co., Ltd.)
Product name, epoxy acrylate, weight average molecular weight of about 512, degree of unsaturation “number of polymerizable unsaturated bonding groups per 1000 molecular weight, having the same meaning” about 2), Actilane 210TP30 (manufactured by Nippon Siebel Hegner) , Trade name, urethane acrylate, weight average molecular weight about 190
0, degree of unsaturation of about 1), Viscote well 700 (trade name, polyether acrylate, weight average molecular weight of about 510, degree of unsaturation of about 4; manufactured by Osaka Organic Chemical Industry Co., Ltd.), Shikko U
V7550B (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
Urethane acrylate, weight average molecular weight about 2400, degree of unsaturation about 1.2), epoxy acrylate EB3201
(Daicel UCB, trade name, epoxy acrylate, weight average molecular weight about 604, degree of unsaturation about 3.1)
And the like.

The unsaturated resin (C) may contain a hydroxyl group. The hydroxyl group has a three-dimensional network structure by a condensation reaction with a functional group of the N-methylol (meth) acrylamide and / or N-alkoxymethyl (meth) acrylamide of the component (A) with a methylol group or an N-alkoxyl group. Can form a coating film excellent in various performances. The content of the hydroxyl group is preferably about 1 or more, more preferably about 1 to 20 on average in one molecule.

The unsaturated resin (C) may be liquid or solid at normal temperature. In the case of a solid, it is preferable to use it after diluting it with the reactive diluent (F) described below.

The mixing ratio of the above components (A) to (C) is in the following range by total measurement of the three components.

Component (A): 10 to 50% by weight, preferably 20 to 40% by weight. If the amount is less than 10% by weight, the surface curability of the coating film deteriorates, while if it exceeds 50% by weight, the viscosity of the composition decreases, and the coating workability, printing workability, water resistance of the coating film and the like deteriorate.

Component (B): 5 to 60% by weight, preferably 10 to 50% by weight. If the amount is less than 5% by weight, the curability of the coating surface deteriorates, while if it exceeds 60% by weight, the viscosity of the composition decreases, and the coating workability, printing workability, coating film performance and the like deteriorate.

Component (C): 5 to 60% by weight, preferably 10 to 50% by weight. When the amount is less than 5% by weight, coating workability and printing workability deteriorate, while when the amount is more than 60% by weight, film surface hardening property deteriorates.

In addition to the components (A) to (C) described above, a reactive diluent (F) can be added as required. As the reactive diluent (F), the above-mentioned (A) to (A)
Other than the component (C), conventionally known liquids having a weight average molecular weight of less than 500 and liquid at room temperature can be used.

As the reactive diluent (F), for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
tertbutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl Alkyl or cycloalkyl ester monomers of (meth) acrylic acid such as carbitol (meth) acrylate, isobornyl (meth) acrylate; methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxybutyl (meth) (Meth) acrylic acid alkoxyalkyl ester monomers such as acrylate and trimethylolpropane tripropoxy (meth) acrylate; aromatic vinyls such as styrene, α-methylstyrene and vinyltoluene Α, β-ethylenically unsaturated carboxylic acid monomers such as (meth) acrylic acid and maleic acid; acrylic phosphate ester monomers such as dimethyl phosphate ethyl acrylate and diethyl phosphate ethyl acrylate; glycidyl (meth) acrylate; Epoxy group-containing unsaturated monomers such as epoxycyclohexylmethyl (meth) acrylate and glycidyl ether; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate (meta) A) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate,
Hydroxyl group-containing unsaturated monomers such as (poly) alkylene glycol monoacrylates and adducts of these monomers with lactones (eg, ε-caprolactone); aromatic alcohols such as benzyl (meth) acrylate; ) Ester with acrylic acid; glycidyl (meth)
Acrylate or (meth) acrylic acid hydroxyalkyl ester and capric acid, lauric acid, linoleic acid,
Adducts with monocarboxylic acid compounds such as oleic acid, and adducts of (meth) acrylic acid with monoepoxy compounds such as "Cadura E10" (manufactured by Shell Chemical); ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether And alkyl chain ethers such as octyl vinyl ether; cyclopentyl vinyl ether, cyclohexyl vinyl ether, 1,4
Cycloalkyl vinyl ethers such as cyclohexane dimethanol divinyl ether; allyl ethers such as allyl glycidyl ether and allyl ethyl ether; perfluorobutylethyl (meth) acrylate, perfluoroisononylethyl (meth) acrylate, perfluorooctylethyl ( Fluorine-containing unsaturated monomers such as (meth) acrylate; (meth) acryloylmorpholine, 2-
Vinylpyridine, 1-vinyl-2-pyrrolidone, vinylcaprolactam, dimethyl (meth) acrylamide,
Nitrogen-containing unsaturated monomers such as N, N-dimethylethyl (meth) acrylate and diacetone acrylamide; (poly) ethylene glycol, (poly) propylene glycol
In a molecule obtained by subjecting a polyhydric alcohol compound such as toluene, hexanediol, neopentyl glycol, trimethylolpropane, glycerin and a carboxyl group-containing monomer such as (meth) acrylic acid to an esterification reaction. And a monomer having two or more polymerizable double bonds.

The trade name of the reactive diluent (D) is, for example, Aronix M-110 (manufactured by Toagosei Co., Ltd.)
Trade name, weight average molecular weight 310), Aronix M-3
05 (Toagosei Co., Ltd., trade name, weight average molecular weight 2)
98), Aronix M-101 (manufactured by Toagosei Co., Ltd., trade name, weight average molecular weight 236), Viscote well 2
15 (manufactured by Osaka Organic Synthetic Chemical Industry Co., Ltd., trade name, weight average molecular weight 212, neopentyl glycol diacrylate), Kayamer PM2 (manufactured by Nippon Kayaku Co., Ltd., trade name, acrylic phosphate monomer), etc. No.

The amount of the reactive diluent (F) is usually about 0 to 60% by weight, preferably about 5 to 50% by weight, based on the total weight of the components (A) to (C) and (F). % By weight.

As the active energy ray polymerization initiator (D) used in the resin composition of the present invention, a conventionally known one can be used. Specifically, for example, 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine,
2,4-trichloromethyl- (4'-methoxynaphthyl) -6-triazine, 2,4-trichloromethyl-
(Piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine,
2- [2- (5-methylfuran-2-yl) ethenyl]-
4,6-bis (trichloromethyl) -S-triazine,
2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2-
(4-dimethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2-dimethylaminoethyl) amino] -4,
6-bis (trichloromethyl) -S-triazine, 2-
[2- (3,4-dimethoxyphenyl) ethenyl] -4,
6-bis (trichloromethyl) -S-triazine, 2-
(4-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -S-triazine, 2,4,6-
Triazine compounds such as tris (trichloromethyl) -S-triazine and tris (chloromethyl) triazine, 4-phenoxydichloroacetophenone, 4-te
r-butyl-dichloroacetophenone, 4-ter-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl)
-2-hydroxy-2-methylpropan-1-one, 1
-(4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyphenoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone,
2-methyl-1- [4- (methylthio) phenyl] -2
Acetophenone compounds such as morpholinopropane-1, thioxanthone, 2-chlorothioxanthone,
Thioxanthone compounds such as methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone and 2,4-dichlorothioxanthone; benzoin compounds such as benzoin and benzoin methyl ether; dimethylbenzylketal and acylophosphine oxide. Can be As the trade name, for example, Irgacure 651 (manufactured by Ciba-Geigy, trade name, acetophenone-based photopolymerization initiator), Irgacure 184 (manufactured by Ciba-Geigy, trade name, acetophenone-based photopolymerization initiator), Irgacure 1850 (manufactured by Ciba-Geigy) , Trade name, acetophenone-based photopolymerization initiator), Irgacure 9
07 (manufactured by Ciba-Geigy, trade name, aminoalkylphenone-based photopolymerization initiator), Irgacure 369 (manufactured by Ciba-Geigy, tradename, aminoalkylphenone-based photopolymerization initiator), 2,4,6-trimethylbenzoyldiphenylphosphine Oyside etc.). These can be used alone or in combination of two or more.

Among these, a triazine compound having a halogen atom is preferred. The compound emits a halogen atom when irradiated with an active energy ray and serves as a radical generator. As the triazine-based compound, a triazine derivative in which a hydrogen atom portion of a hydrocarbon bond constituting triazine is substituted with CCl 3 is preferable.

The mixing ratio of the component (D) is as follows:
The amount is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the components (C) and (D) as required. If the amount is less than 0.1 part by weight, the curability of the coating film is deteriorated, whereas if it exceeds 10 parts by weight, the effect on the curability is not significant.

The polyhydrazide compound (E) used in the resin composition of the present invention has a hydrazide group (—CO—
As long as it contains two or more NH-NH2), a conventionally known one can be used without particular limitation. Representative specific examples, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, eicoic acid diacid dihydrazide and the like C2-40 aliphatic carboxylic acid dihydrazide, Aromatic polyhydrazides such as phthalic dihydrazide, terephthalic dihydrazide, isophthalic dihydrazide, pyromellitic dihydrazide, pyromellitic trihydrazide, and pyromellitic tetrahydrazide; and monoolefins such as maleic dihydrazide, fumaric dihydrazide, itaconic dihydrazide. Unsaturated dihydrazide, bissemicarbazide, polyacrylic acid polyhydrazide, 1,
Other polyhydrazides such as 3-bis (hydrazi / carboethyl) -5-isopropylhydantoin and the like can be mentioned.

The mixing ratio of the component (E) is (A)
The amount is 0.1 to 20 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the components (C) and (D) if necessary. When the amount is less than 0.1 part by weight, the curability of the film is deteriorated.

In the resin composition of the present invention, if necessary, a photopolymerization accelerator, a thermosetting accelerator, a filler, a coloring agent, a pigment, a fluidity regulator, a repelling inhibitor and the like can be blended.

The resin composition of the present invention can be used for paints, inks, adhesives and the like.

[0035] The resin composition of the present invention comprises paper, plastic,
The present invention can be applied to substrates such as metals and combinations thereof.

In the film forming method of the present invention, the active energy ray-curable resin composition is applied to the substrate (including printing).
After that, a film can be formed by irradiating with active energy rays.

The coating can be performed by a conventionally known method, for example, a spray, roll coater, gravure coater, screen, or the like. The thickness of the coating is preferably in the range of about 1 to 50 microns, preferably about 3 to 20 microns in terms of cured film thickness.

The active energy rays include, for example, ultraviolet rays, β rays, and electron rays from a mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide, a gallium lamp, and the like. Although the irradiation amount of the ultraviolet ray is not particularly limited, it is usually 1
It is preferably in the range of 0 to 2000 mj / cm2. In the case of an electron beam, it is preferable to irradiate an electron beam of 50 to 300 Kev usually for 1 to 20 Mrad.

[0039]

The present invention will be described in more detail with reference to examples.

Example 1 N-methoxymethylacrylamide (20 parts by weight), diacetone acrylamide (10 parts by weight), and polyester acrylate (isophthalic acid / terephthalic acid / neopentyl glycol / ethylene glycol / diethylene glycol in a mixture of about 1 mol each at 240 ° C.) To obtain a hydroxyl group-containing polyester having a hydroxyl value of 60 mg KOH / g, and then reacting it with acrylic acid.The resin has a weight average molecular weight of about 180.
0, the number of polymerizable unsaturated bonding groups per 1,000 molecular weight "unsaturation degree" is about 1.0. 30 parts by weight, Aronix M-110 (manufactured by Toagosei Co., Ltd., trade name, weight average molecular weight 310, reactive diluent) 30 parts by weight, tripropylene glycol diacrylate (reactive diluent) 10 parts by weight, 1 part by weight of 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, lucilin TPO (B
ASF Company, trade name, acylphosphine oxide) 1
Parts by weight, 2 parts by weight of Irgacure 907 (manufactured by Ciba Geigy, trade name, aminoalkylphenone-based photopolymerization initiator), and 1.0 part by weight of 1,3-bis (hydradi / carboethyl) -5-isopropylhydantoin are mixed. Thus, the composition of Example 1 was obtained.

The composition of Example 1 was applied to a polyethylene terephthalate film (film thickness: 100 μm) with a bar coater so as to have a thickness of 10 μm, and irradiated with a metal halide lamp at 200 mj / cm 2.

The obtained coating film has good drying properties (Note 1, the same applies hereinafter) without any coating abnormality, good adhesion (Note 2, hereinafter the same) without peeling, and pencil hardness (Note 3, the same applies hereinafter). Hereinafter the same)
Was good in H. Water resistance (Note 3) was good.

Example 2 30 parts by weight of N-isobutoxymethylacrylamide, 15 parts by weight of diacetone acrylamide, UV 755
0B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name, urethane acrylate, weight average molecular weight: about 2,400, glass transition temperature: 103 ° C., degree of unsaturation: about 1.2), 20 parts by weight, 2-hydroxy-3-phenoxypropyl acrylate ( 10 parts by weight of a reactive diluent), 10 parts by weight of Aronix M110 (similar to the above), 10 parts by weight of tripropylene glycol diacrylate (reactive diluent), viscote well 215 (Osaka Organic Synthetic Chemical Industry Co., Ltd.) Made, product name,
Weight average molecular weight 212, reactive diluent, neopentyl glycol diacrylate) 5 parts by weight, 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine 1 part by weight, lucirin TPO (same as above) 3) and 5 parts by weight of phthalic dihydrazide were mixed to obtain a composition of Example 2.

The composition of Example 2 was applied to a polybutylene terephthalate film (film thickness: 100 μm) with a bar coater so that the film thickness became 5 μm, and 25 μm was applied by a high pressure mercury lamp.
Irradiation was performed at 0 mj / cm2.

The obtained coating film had good drying properties without any coating abnormality, good adhesion without peeling, and good water resistance.

Example 3 30 parts by weight of N-butoxymethylacrylamide, 20 parts by weight of diacetone acrylamide, epoxy acrylate EB3201 (trade name, manufactured by Daicel U.S.C.
Epoxy acrylate, weight average molecular weight about 604, degree of unsaturation about 3.1) 30 parts by weight, Aronix M-110
(Same as above) 10 parts by weight, hydroxybutyl acrylate (reactive diluent) 10 parts by weight, Biscoat V
Well 215D (same as above) 20 parts by weight, 1,4-
10 parts by weight of cyclohexanedimethanol divinyl ether (reactive diluent) and 50 parts by weight of titanium dioxide were mixed and dispersed to produce a white enamel. Next, 5 parts by weight of Irgacure 1850 (manufactured by Ciba-Geigy, trade name, acylphosphine oxide-based photopolymerization initiator) and 150 parts by weight of Irgacure 369 (trade name, aminoalkylphenone-based photopolymerization initiator, manufactured by Ciba-Geigy) 2 Parts by weight, 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, and 7 parts by weight of 1,3-bis (hydradi / carboethyl) -5-isopropylhydantoin were mixed, and the composition of Example 3 was mixed. I got

The composition of Example 3 was applied to a corona-treated polyethylene terephthalate film (film thickness 100 μm) with a bar coater so as to have a thickness of 6 μm, and irradiated with a metal halide lamp at 300 mj / cm 2.

The resulting coating film had good drying properties without any coating abnormality, good adhesion without peeling, and good water resistance.

Example 4 30 parts by weight of N-methoxymethyl acrylamide, 5 parts by weight of diacetone acrylamide, acryl acrylate (methyl methacrylate / n-butyl acrylate /
65. Ethyl acrylate / glycidyl acrylate.
A product obtained by reacting acrylic acid with a radical copolymer of 0 g / 4.4 g / 5.0 g / 25.6 g. Weight average molecular weight about 10,000, glass transition temperature 50 ° C., degree of unsaturation about 2) 25 parts by weight, hexanediol diacrylate (reactive diluent) 20 parts by weight, tripropylene glycol diacrylate (reactive diluent) 20 parts by weight Then, 0.5 part by weight of eicoic diacid dihydrazide and 4 parts by weight of Irgacure 907 (same as above) were mixed to obtain a composition of Example 4.

The composition of Example 4 was coated on coated paper to a thickness of 8 μm.
m was applied with a roll coater and irradiated with a metal halide lamp at 150 mj / cm 2.

The obtained coating film had good drying properties without any coating abnormality, good adhesion without peeling, and good water resistance.

Example 5 N-methoxymethylacrylamide (20 parts by weight), diacetone acrylamide (20 parts by weight), Viscoat well 700
(Osaka Organic Chemical Industry Co., Ltd., trade name, polyester acrylate, weight average molecular weight about 510, degree of unsaturation about 4) 30 parts by weight, Aronix M-110 (same as above) 15 parts by weight, hexanediol 15 parts by weight of diacrylate (reactive diluent), 1,3-bis (hydradi / carboethyl) -5-isopropylhydantoin 5
Parts by weight, 1 part by weight of phthalocyanine blue pigment, 2,4-
Trichloromethyl- (4'-methoxyphenyl) -6
The composition of Example 5 was obtained by mixing and dispersing 1.5 parts by weight of triazine.

The composition of Example 5 was applied to a corona-treated polypropylene film (thickness: 100 μm) with a bar coater so as to have a thickness of 5 μm, and 8 Mrad with an electron beam.
After the irradiation, heating was performed at 60 ° C. for 30 seconds.

The obtained coating film had good drying properties without any coating abnormality, good adhesion without peeling, and good water resistance.

Comparative Example 1 A composition of Comparative Example 1 was obtained in the same manner as in Example 1, except that 20 parts by weight of N-methoxymethylacrylamide was completely replaced with tripropylene glycol diacrylate. Then, a test was performed in the same manner as in Example 1. As a result, the dryness of the coating film was markedly poor with fingerprints, the adhesion was extremely poor, and the hardness of the coated film was poor at 3B. Water resistance was poor due to blistering and whitening.

Comparative Example 2 A composition of Comparative Example 2 was obtained in the same manner as in Example 1, except that 10 parts by weight of diacetone acrylamide was replaced by the entire amount of tripropylene glycol diacrylate. Then, a test was performed in the same manner as in Example 1. As a result, the dryness of the coating film was markedly poor with fingerprints, the adhesion was extremely poor, and the hardness of the coated film was poor at 3B. Water resistance was poor due to blistering and whitening.

Comparative Example 3 A composition of Comparative Example 3 was obtained in the same manner as in Example 1, except that 30 parts by weight of the polyester acrylate was replaced by the entire amount of tripropylene glycol diacrylate. Then, a test was performed in the same manner as in Example 1. As a result, the dryness of the coating film was markedly poor with fingerprints, the adhesion was extremely poor, and the hardness of the coated film was poor at 3B. Water resistance was poor due to blistering and whitening.

Comparative Example 4 A composition of Comparative Example 4 was obtained in the same manner as in Example 2, except that 15 parts by weight of diacetone acrylamide was replaced by the entire amount of tripropylene glycol diacrylate. Then, a test was performed in the same manner as in Example 2. As a result, the dryness of the coating film was markedly poor with fingerprints, the adhesion was extremely poor, and the water resistance was poor due to blistering and whitening.

Comparative Example 5 A composition of Comparative Example 5 was obtained in the same manner as in Example 3, except that 20 parts by weight of diacetone acrylamide was replaced by the entire amount of tripropylene glycol diacrylate. Then, a test was performed in the same manner as in Example 3. As a result, the dryness of the coating film was markedly poor with fingerprints, the adhesion was extremely poor, and the hardness of the coated film was poor at 3B. Water resistance was poor due to blistering and whitening.

Comparative Example 6 A composition of Comparative Example 6 was obtained in the same manner as in Example 1, except that 5 parts by weight of diacetone acrylamide was replaced by the entire amount of tripropylene glycol diacrylate. Then, a test was performed in the same manner as in Example 4. As a result, the dryness of the coating film was markedly poor with fingerprints, the adhesion was extremely poor, and the hardness of the coated film was poor at 3B. Water resistance was poor due to blistering and whitening.

Comparative Example 7 A composition of Comparative Example 7 was obtained in the same manner as in Example 5, except that 20 parts by weight of diacetone acrylamide was replaced by the entire amount of tripropylene glycol diacrylate. Then, a test was performed in the same manner as in Example 5. As a result, the dryness of the coating film was markedly poor with fingerprints, the adhesion was extremely poor, and the hardness of the coated film was poor at 3B. Water resistance was poor due to blistering and whitening.

Test method and evaluation method of coating film performance Drying of coating film: After pressing strongly with the thumb from the surface of the coating film for about 5 seconds, the degree of abnormality of the coating film such as a fingerprint mark on the coating film surface was observed. Performed at 20 ° C.

Adhesion: A 1 mm wide cut is made on the coating with a sharp blade so as to reach the material from the coating, and an adhesive cellophane tape is adhered to the coating. Evaluation was based on criteria. Good: Each cut was thin and smooth on both sides, with no peeling at the intersection of the cut and the square at a glance. Inferior: There was slight peeling at the intersection of the cut, and at the intersection of the cut and the glance at the square There was no peeling at a glance, and the area of the defect was 5 times the area of the entire square.
%, Inferior or at the intersection of cuts,
The area of the defective part is 5 to 15% of the area of the entire square. The area of the defective part is extremely poor, and the width of the peeling due to the cut is large, and the area of the defective part exceeds 15% of the area of the entire square.

Coating film hardness: Performed according to JIS K-5400. The evaluation was performed by the breaking method.

Water resistance: The coating film after immersion in tap water at 30 ° C. for 2 days was observed, and the presence or absence of abnormalities such as a decrease in gloss, blistering, whitening and the like were evaluated by comparing with those before the test.

[0066]

Since the composition of the present invention has the above-mentioned constitution, it exerts a remarkable effect of forming a cured film having excellent film properties by irradiation with active energy rays in the presence of air. Things.

Claims (3)

[Claims] (A) 10 to 50% by weight of N-methylol (meth) acrylamide and / or N-alkoxymethyl (meth) acrylamide, (B) 5 to 60% by weight of carbonyl group-containing unsaturated monomer, (C) On average about 1 in one molecule
Having a weight average molecular weight of 50 or more having two or more polymerizable double bonds.
(D) 0.1 to 10 parts by weight of an active energy ray polymerization initiator and (E) polyhydrazide with respect to 100 parts by weight of a resin composition containing 5 to 60% by weight of an unsaturated resin of 0 to 20,000. An active energy ray-curable resin composition comprising 0.1 to 20 parts by weight of a compound. 2. The active energy ray-curable resin composition according to claim 1, wherein the carbonyl group-containing unsaturated monomer (B) is diacetone (meth) acrylamide. 3. The method according to claim 1, wherein the active energy ray-curable resin composition is applied to the surface of a base material so that the applied amount is 1 to 50 μm in cured film thickness, and then the composition is cured by irradiation with active energy rays. A method for forming a film.