JP2002003575A - Uv curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new UV curable resin composition having good curing ability, cohesiveness and low odor of the coating. SOLUTION: This UV curable resin composition comprises a compound having one or more epoxy groups(s) in a molecule, an initiator of photo-cationic polymerization and a compound having one or more maleimide group(s) in a molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel ultraviolet ray-curable resin composition having good curability and adhesion, and having a low film odor.

[0002]

2. Description of the Related Art UV-curable compositions are used in various fields because they cure and crosslink in a short time by irradiation with ultraviolet rays. UV-curable compositions are broadly divided into photo-cationic polymerization systems and photo-radical polymerization systems, and UV-curable compositions utilizing photo-cationic polymerization using epoxy groups are not affected by oxygen during curing. Due to its advantages, it has begun to be studied in various fields as a composition for inks and coatings.
However, the photosensitivity tends to be inferior to that of active energy ray-curable radical polymerization utilizing unsaturated double bonds.
Further, the photo-cationic polymerization type is better with respect to the initial adhesion, but tends to deteriorate with time. In order to take advantage of these photocationic polymerization systems and improve the disadvantages, a cation-radical hybrid curing type using a compound having an epoxy group, an acrylate ester and a photoinitiator has been proposed. However, since at least two kinds of cation initiators and radical initiators are required, the cost becomes higher and the odor of the formed coating film becomes a problem, so that it is not sufficient.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an ultraviolet-curable resin composition having good curability, good adhesion to various substrates such as plastic films and metal plates, and little odor of the coating film formed after irradiation with ultraviolet light. To provide articles and coatings.

[0004]

Means for Solving the Problems As described above, it is difficult to improve the curability and adhesion and reduce the odor of the coating film by using an ultraviolet curing system as long as the conventional technology is followed. Based on the properties, as a result of intensive research to solve the conventional disadvantages of the photocationic curing system, an ultraviolet curing type that solves the problem by using a compound having a specific maleimide group together with the photocationic polymerizable material A composition was found and led to the present invention.

That is, the constitution of the present invention is characterized by containing a compound having one or more epoxy groups in a molecule, a cationic photopolymerization initiator and a compound having one or more maleimide groups in a molecule. It is a UV-curable resin composition.

Further, according to the constitution of the present invention, a compound having one or more maleimide groups in a molecule is composed of a carboxylic acid having a maleimide group represented by the following general formula (1) and one or more maleimide groups in one molecule. An ultraviolet curable resin composition which is an ester compound obtained by reacting an alcohol having an alcoholic hydroxyl group or an epoxy resin having one or more epoxy groups.

[0007]

Embedded image (Where R is a linear alkylene group having 1 to 18 carbon atoms, a branched alkylene group having 2 to 24 carbon atoms,
An alkylene group having 2 to 24 carbon atoms having a hydroxyl group,
It represents at least one organic group selected from the group consisting of a cycloalkylene group, an aryl group and an arylalkylene group. )

More preferably, the content of the compound having one or more epoxy groups in the molecule is 30 to 90% by weight, the content of the cationic photopolymerization initiator is 1 to 10% by weight, An ultraviolet curable resin composition having a content of a compound having at least one maleimide group in an amount of 5 to 50% by weight.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention is characterized by containing a compound having one or more epoxy groups in a molecule, a cationic photopolymerization initiator and a compound having one or more maleimide groups in a molecule. It is an ultraviolet curable resin composition to be described below.

First, the compound having one or more epoxy groups in the molecule used in the present invention includes an alicyclic epoxy compound, an oxetane compound, a glycidyl ether compound and the like, and an alicyclic epoxy compound is exemplified. if,
Including 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate,
"Siracure UVR-6110 or UVR-61
05 ”(product of Union Carbide, USA),“ C
Y-179 "(product of Ciba Geigy, Switzerland) or" Celoxide 2021 or -2021P "(product of Daicel Chemical Industries, Ltd.), for example, Cyracure UVR-6128 (product of Union Carbide, USA), Daicel Chemical Industries Company, Celoxide 208
0,2081,2083,3000,2000, Eporide GT-301,302,401,403, CYCLOMER
M100, M101, A200 and the like.

As oxetane compounds, 2-hydroxymethyl-2-methyloxetane, 2-hydroxymethyl-2-ethyloxetane, 2-hydroxymethyl-2-
Propyl oxetane, 2-hydroxymethyl-2-butyl oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene and the like. For example, OXT-212,221, (Toa Gosei Chemical) (stock)
Products).

Further, as a glycidyl ether compound,
Bisphenol A diglycidyl ether and the like can be used,
For example, EPCLON-840, 850, 860, 105
0, 2055, 3050, 4050, 7050, 83
0,835,520,152,153, N-665, N-6
Compounds such as 73, N-680, N-695 (product of Dainippon Ink and Chemicals, Inc.) and epoxidized soybean oil.

As the cationic photopolymerization initiator, only typical representative ones are exemplified. Triphenylsulfonium hexafluorophosphonate salt, triphenylsulfonium hexafluoroantimonate salt, diphenyliodohexafluorophosphonate salt are exemplified. In addition to phonate salts, etc., furthermore, Cyracure UVI6990 (a product of Union Carbide, USA), Irgacure 26
1 (product of Ciba Geigy, Switzerland), RH-2074
(Rhone Poulins, France), Optmer SP
Compounds that generate a cationic species by active energy rays, particularly ultraviolet rays, such as 150 and SP-151 (product of Asahi Denka Kogyo KK).

As the compound having one or more maleimide groups in the molecule, various carboxylic acids having a maleimide group (maleimide carboxylic acid) represented by the general formula (1):
An ester compound obtained by reacting an alcohol having one or more alcoholic hydroxyl groups or an epoxy resin having one or more epoxy groups in one molecule is exemplified. That is, a maleimide carboxylic acid group-containing ester compound or an epoxy ester compound can be used.

[0015]

Embedded image (Where R is a linear alkylene group having 1 to 18 carbon atoms, a branched alkylene group having 2 to 24 carbon atoms,
An alkylene group having 2 to 24 carbon atoms having a hydroxyl group,
It represents at least one organic group selected from the group consisting of a cycloalkylene group, an aryl group and an arylalkylene group. )

The maleimide carboxylic acid can be prepared from maleic anhydride and various primary aminocarboxylic acids by a known technique [for example, D, H, Rich et al.
"Journal of Medical Chemistry (J.Me
d.Chem) ", Volume 18, pages 1004 to 1010 (197
5)).

The above-mentioned primary aminocarboxylic acid includes
For example, asparagine, alanine, β-alanine, arginine, isoleucine, glycine, glutamine, tryptophan, threonine, valine, phenylalanine, homophenylalanine, α-methyl-phenylalanine,
Lysine, leucine, cycloleucine, 3-aminopropionic acid, α-aminobutyric acid, 4-aminobutyric acid, aminovaleric acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 2
-Aminocaprylic acid, 3-aminocaprylic acid, 6-aminocaprylic acid, 8-aminocaprylic acid, 2-aminononanoic acid, 4-aminononanoic acid, 9-aminononanoic acid, 2-
Aminocapric acid, 9-aminocapric acid, 10-aminocapric acid, 2-aminoundecanoic acid, 10-aminoundecanoic acid, 11-aminoundecanoic acid, 2-aminolauric acid, 11-aminolauric acid, 12-aminolauric acid, 2-aminotridecanoic acid, 13-aminotridecanoic acid, 2-aminomistinic acid, 14-aminomistinic acid, 2-aminopentadecanoic acid, 15-aminopentadecanoic acid, 2-aminopalmitic acid, 16-aminopalmitic acid, 2- Aminoheptadecanoic acid, 17-aminoheptadecanoic acid, 2-aminostearic acid, 18-aminostearic acid, 2-aminoeicosanonic acid, aminocyclohexanecarboxylic acid, aminomethylcyclohexanecarboxylic acid, 2-amino-3-propion Acid, 3-amino-3-phenylp While such acid may be mentioned, but not limited thereto, as long as the primary amino acid, either can be used. In addition, lactams such as pyrrolidone, δ-valerolactam and ε-caprolactam can also be used.

Examples of the alcohol having one or more alcoholic hydroxyl groups include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol, ethylene glycol, propanediol, propylene glycol, and tetraethylene glycol. Modified ethylene oxide, propylene oxide, butylene oxide of alkylene glycols such as methylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, etc. Modified products, tetrahydrofuran modified products, etc., among which, among these, alkylene glycols Various modified are preferred. Furthermore,
A copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran,
A copolymer of ethylene glycol and tetrahydrofuran,
Hydrocarbon polyols such as polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, and hydrogenated polybutadiene glycol; polyalkylene glycols such as polytetramethylene hexaglyceryl ether (a modified product of hexaglycerin in tetrahydrofuran) and polytetramethylene glycol , Ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol,
Hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol,
Diglycerol, ditrimethylolpropane, ε-caprolactone-modified, γ-butyrolactone-modified, δ-valerolactone-modified, methyl valerolactone-modified alkylene glycols such as dipentaerythritol, and aliphatics such as adipic acid and dimer acid Aliphatic polyester polyols which are reactants of dicarboxylic acids and polyols such as neopentyl glycol and methylpentanediol, aromatic polyester polyols which are reactants of aromatic dicarboxylic acids such as terephthalic acid and polyols such as neopentyl glycol Fumaric acid and phthalic acid of polyhydric hydroxyl group compounds such as polyester polyols, polycarbonate polyols, acrylic polyols, and polytetramethylene hexaglyceryl ether (tetrahydrofuran-modified hexaglycerin) Transesterification of polyhydric hydroxyl group-containing compounds obtained by esterification with dicarboxylic acids such as isophthalic acid, itaconic acid, adipic acid, sebacic acid, and maleic acid, and polyhydric hydroxyl group-containing compounds such as glycerin, and fatty acid esters of animals and plants. Examples thereof include compounds containing a polyvalent hydroxyl group such as monoglyceride obtained by the reaction, but are not limited thereto.

Examples of the epoxy resin (polyepoxide) having one or more epoxy groups that can be used as a compound that reacts with maleimide carboxylic acid include (methyl) epichlorohydrin, bisphenol A and bisphenol F, ethylene oxide and propylene oxide thereof. Epibis epoxy resin, epoxy novolak resin, phenol, biphenol, etc. and reaction product of (methyl) epichlorohydrin synthesized from modified products,
Aromatic epoxy resins such as glycidyl esters of terephthalic acid, isophthalic acid and pyromellitic acid, and (poly)
Ethylene glycol, (poly) propylene glycol,
Glycols such as (poly) butylene glycol, (poly) tetramethylene glycol and neopentyl glycol, and polyglycidyl ethers of alkylene oxide modified products thereof, trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol, pentaerythritol, Aliphatic polyhydric alcohols such as sorbitol, 1,4-butanediol and 1,6-hexanediol, and glycidyl ethers of alkylene oxide-modified glycidyl ethers and glycidyls of carboxylic acids such as adipic acid, sebacic acid, maleic acid and itaconic acid Esters, glycidyl ethers of polyester polyols of polyhydric alcohols and polycarboxylic acids, copolymers of glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate, and higher fatty acids Glycidyl esters, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, aliphatic epoxy resins such as epoxidized polybutadiene, and the like.

According to the production method described above, the compound having one or more maleimide groups in the molecule used in the present invention,
That is, a maleimide carboxylic acid group-containing ester compound and an epoxy ester compound (maleimide derivative) can be obtained, but the production method of the compound used in the present invention is not limited to these.

When the amount of the maleimide compound is less than 5% by weight, a large amount of a cationic photopolymerization initiator is required to maintain curability, the odor generated by UV irradiation becomes a problem, and the amount exceeds 50% by weight. Then, curing becomes slow due to a decrease in the amount of the cationic photocurable component.

The maleimide derivative of the present invention has a content of 200 to 4
It has a specific spectral sensitivity at 00 nm, and can be polymerized by irradiating ultraviolet light or visible light having a wavelength of 180 to 500 nm in the absence of a photo-radical polymerization initiator, especially at wavelengths of 254 nm, 313 nm, and 365 nm. Is effective for curing the maleimide derivative of the present invention. Further, the maleimide derivative of the present invention can be cured by irradiation with energy rays other than ultraviolet rays or by heat. Further, the maleimide derivative of the present invention can be cured either in the air or in an inert gas.

Examples of such a light source of ultraviolet or visible light having a wavelength of 180 to 500 nm include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, chemical lamps, black light lamps, and mercury-xenon. Lamps, short arc lamps, helium cadmium lasers, argon lasers, sunlight.

The maleimide derivative of the present invention is cured by irradiation with ultraviolet light or visible light, but a known and commonly used photoradical polymerization initiator may be further added in order to carry out the curing reaction more efficiently. As the photoradical polymerization initiator, diethoxyacetophenone, 2-hydroxy-
2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- ( 2-
Acetophenones such as hydroxy-2-propyl) ketone and 1-hydroxycyclohexyl-phenylketone;
Benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; acylphosphine oxides such as acylphosphine oxides such as 2,4,6-trimethylbenzoindiphenylphosphine oxide; benzyl, methylphenylglyoxyester, benzophenone and o-benzoyl Methyl-4-phenylbenzophenone benzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t
-Butylperoxycarbonyl) benzophenone, 3,
Benzophenones such as 3'-dimethyl-4-methoxybenzophenone;2-isopropylthioxanthone;
Thioxanthones such as 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 10-butyl-2-chloroacridone, 2-
Ethyl anthraquinone, 9,10-phenanthrene quinone, camphor quinone and the like.

Further, the active energy ray-curable resin obtained in the present invention can be cured by irradiation with ultraviolet rays only by adding the above-mentioned photo-radical polymerization initiator. A sensitizer can be used in combination.

The ultraviolet-curable resin composition containing the maleimide carboxylic acid group-containing ester compound and the epoxy ester compound (maleimide derivative) according to the present invention is prepared by adding a curable compound other than the maleimide derivative to the curable compound. They can be used together as long as they are not damaged.

Examples of the curable compound that can be used in combination with the maleimide derivative include, for example, a maleimide derivative other than the above-mentioned maleimide derivative, a (meth) acryloyl derivative,
(Meth) acrylamide derivatives, vinyl ether derivatives, vinyl carboxylate derivatives, styrene derivatives, unsaturated polyesters, and the like.

Examples of such maleimide derivatives include monofunctional maleimides such as N-butylmaleimide and N-phenylmaleimide, and polyfunctional maleimides such as N, N'-phenylenebismaleimide. Examples of the (meth) acryloyl derivative include, for example, monofunctional (meth) acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, isobornyl acrylate, and acrylic acid Monofunctional (meth) acrylates such as -2-methoxyethyl, 3-methoxybutyl acrylate, and phenoxyethyl acrylate; trimethylolpropane tri (meth) acrylate dipentaerythritol hexa (meth) acrylate; VISCOAT # 2311HP, VISCOAT # 220, VISCOAT DMA, VISCOAT # 335
HP, Biscoat # 310, Biscoat # 312, Biscoat # 295, Biscoat # 300, Biscoat # 3
60 (manufactured by Osaka Organic Chemicals), Aronix M-101,
Aronix M-110, Aronix M-208, Aronix M-215, Aronix M-305, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-350, Aronix M-360, Aronix M-400, Aronix M-408, Aronix M-450, Aronix M-9050 Aronix M-5700, (manufactured by Toa Gosei Chemical Industry) and the like can also be used. Examples of the vinyl ether derivative include, for example, hydroxybutyl vinyl ether,
Monofunctional vinyl ethers such as triethylene glycol methyl vinyl ether, and polyfunctional vinyl ethers such as triethylene glycol divinyl ether and 1,4-cyclohexanemethanol divinyl ether are exemplified. As the vinyl carboxylate derivative, for example, vinyl acetate,
And vinyl cinnamate. Examples of the styrene derivative include styrene, divinylstyrene, and the like. As unsaturated polyesters, for example, maleic esters such as dimethyl malate and diethyl malate;
Fumaric acid esters such as dimethyl fumarate and diethyl fumarate; and esters of polyunsaturated carboxylic acids such as maleic acid and fumaric acid with polyhydric alcohols.
The curable compound that can be used in combination with the maleimide derivative is not limited to these.

Inorganic pigments and organic pigments can be used as colorants, waxes can be used as lubricants, quinone derivatives such as methoquinone, and aluminum salts of N-nitrosophenylhydroxylamine can be used as storage stabilizers. Further, various hard resins such as acrylic resin, unsaturated polyester resin, saturated polyester resin, xylene resin, petroleum resin and the like can be used as the extender.

The ultraviolet-curable composition of the present invention treats plastic films such as polyethylene terephthalate film, nylon film, polypropylene film, and vinyl chloride film, and the surfaces of steel sheets, aluminum, plated steel sheets, tin-free steel, etc. laminated with them. It can be used for metal plate substrates etc.

The active energy ray-curable composition of the present invention thus obtained may contain a wax, a silicone resin, an alcohol compound, a vinyl ether compound, various solvents, and the like, if necessary.

The addition of a petroleum resin, a xylene resin, a rosin-modified phenol resin, or the like also has the effect of lowering the surface tension and is effective. It is also effective to add an acrylic resin, a polyester resin, a polydiallyl phthalate resin or the like to impart various physical properties.

In the active energy ray-curable composition of the present invention, the pigment system is also excellent in curability, and as the pigment, an inorganic pigment such as titanium oxide, an organic pigment such as phthalocyanine blue, an extender pigment, and a rust preventive pigment can be used. .

The active energy ray-curable composition of the present invention obtained as described above is applied or printed on a substrate,
It can be cured by irradiation with active energy rays, particularly ultraviolet rays.

Examples of the coating or printing method include ordinary coating or printing methods such as spray coating, roller coating, nachoral coater coating, reverse coater coating, coater coating for 2P cans, gravure printing, lithographic printing, surface printing, and screen printing. Can be used.

The active energy ray-curable composition of the present invention has excellent curability and can be used, for example, in paints such as gloss varnishes and base coats, inks, printing materials, and surface treatment agents.

[0037]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the scope of these Examples.

(Synthesis Example 1) 65.5 g of 6-aminocaproic acid and 400 ml of acetic acid were charged into a 1-L three-necked flask equipped with a dropping funnel, a condenser and a stirrer, and stirred at room temperature with maleic anhydride. A solution consisting of 49.0 g and 300 ml of acetic acid was dropped from the dropping funnel over 2 hours. After completion of the dropwise addition, stirring was further continued for 1 hour, and then the reaction was terminated. The resulting precipitate was collected by filtration and recrystallized from methanol to obtain 111 g of maleamic acid N-caproate.

Next, 45.8 g of maleamic acid N-caproate and 40.4 g of triethylamine were placed in a 1 L three-necked flask equipped with a Dean-Stark type fractionator and a stirrer.
g and 500 ml of toluene, and the reaction was continued at reflux temperature for 1 hour while removing generated water. The residue obtained by distilling off toluene from the reaction mixture was adjusted to pH 2 with 0.1N hydrochloric acid, and then adjusted to pH 2 with 100 ml of ethyl acetate.
Extracted times. The organic phase was separated, dried by adding magnesium sulfate, and then ethyl acetate was distilled off under reduced pressure. The obtained crude product was recrystallized from water to obtain 19 g of pale yellow crystals of maleimidocaproic acid.

Synthesis Example 2 In Synthesis Example 1, 38.3 aminoacetic acid was used instead of 65.5 g of 6-aminocaproic acid.
Synthesis was carried out in the same manner as in Reference Example 1 except that g was used. The obtained crude product was recrystallized from methanol and purified to obtain 13 g of maleimide acetic acid.

(Synthesis Example 3) Polytetramethylene glycol having a number average molecular weight of 1,000 (“PTGL1000” manufactured by Hodogaya Chemical Co., Ltd., gel, etc.) was placed in a 200 ml eggplant-shaped flask equipped with a Dean-Stark type fractionator. Polystyrene equivalent value by permeation chromatography (hereinafter abbreviated as GPC): number average molecular weight 2,
100, weight average molecular weight 5,000) 20 g, Synthesis Example 1
Was charged with 9.8 g of maleimidocaproic acid obtained in the above, 1.2 g of p-toluenesulfonic acid, 0.06 g of 2,6-tert-butyl-p-cresol and 15 ml of toluene, and 240
The reaction was continued while stirring for 4 hours while removing water generated under the conditions of torr and 80 ° C. The reaction mixture was dissolved in 200 ml of toluene, and saturated sodium bicarbonate 10
The mixture was washed three times with 0 ml and once with 100 ml of saturated saline to obtain 18 g of a pale yellow liquid of the maleimide derivative A.

(Synthesis Example 4) In Synthesis Example 3, 20 g of polytetramethylene glycol having a number average molecular weight of 1,000 was used.
In place of polytetramethylene glycol having a number average molecular weight of 250 (“PTGL25 manufactured by Hodogaya Chemical Co., Ltd.”
0 ") In the same manner as in Synthesis Example 3 except that 5 g was used, 4 g of a pale yellow liquid of a maleimide derivative B was obtained.

(Synthesis Example 5) The pale yellow color of the maleimide derivative C was obtained in the same manner as in Synthesis Example 3 except that 7.2 g of maleimide acetic acid synthesized in Synthesis Example 2 was used in place of 9.8 g of maleimide caproic acid. 13 g of liquid were obtained.

(Blending of paints of Examples 1 to 5 and Comparative Examples 1 to 3) The samples prepared in the above synthesis examples were blended with the paints shown in Table 1 below. In addition, UVR-6105 in the table
Is an alicyclic epoxy compound manufactured by Union Carbide, and includes 3,4-epoxycyclohexylmethyl-3,
4-epoxycyclohexylcarboxylate.
S-3000 is limonene dioxide (Celloxide 3000) manufactured by Daicel Chemical Industries, Ltd., UVI-
6990 is a triphenylsulfonium hexafluorophosphonate salt manufactured by Union Carbide;
r-184 is 1-hydroxycyclohexyl-phenylketone, an acetophenone-based photoradical polymerization initiator manufactured by Ciba Specialty Chemicals. Comparative Examples 1 and 2
Is the composition of the cationic photopolymerization system currently used.
In Comparative Example 3, a paint using trimethylolpropane triacrylate (TMPTA), which is generally used as a monomer, was blended as a hybrid curing type in which a photocationic polymerization material and a photoradical polymerization material were combined.

[0045]

[Table 1]

The paint thus prepared was applied to a bar coater # 4.
Corona discharge treated PET film (30μm), 2P
It was applied to an aluminum plate for cans. The film was passed under one 160 W / cm high pressure mercury lamp at a speed of 40 m / min to cure the coating film. Thereafter, the adhesiveness, pencil hardness, curability, and coating film odor were evaluated. Table 2 shows the results. In addition, evaluation was performed as follows.

Initial Adhesion A cross mark was put on the coating film with a cutter, and a cellotape (registered trademark) was used.
Perform a peel test to test whether the coating film is in close contact with the substrate. The evaluation is ○ unless peeled off. If peeled off, it will be x.

Adhesion over time After irradiation of the coating film with ultraviolet rays, the adhesion after one day is evaluated. The evaluation criteria are the same as those for the initial adhesion evaluation.

Pencil hardness (PH) Measured according to JIS K-5400-6-14.

Solvent Resistance Solvent resistance was evaluated by rubbing the coated film with methyl ethyl ketone impregnated gauze and indicating the number of reciprocations until the coated film was dissolved and peeled off, and used as an index of curability.

Odor The odor of the film immediately after UV irradiation was evaluated by the following sensory evaluation by a plurality of persons. (Evaluation criteria) 5: No odor at all. 4: There is a slight odor, but it disappears after a while. 3: There is an odor, but it will be considerably reduced after a while. 2: There is a worrisome odor. 1: Odor.

[0052]

[Table 2]

[0053]

According to the present invention, there is provided an ultraviolet-curable resin composition and coating having good curability, good adhesion to various substrates such as plastic films and metal plates, and little odor of a coating film formed after irradiation with ultraviolet light. Agent can be obtained.

Claims (3)

[Claims] 1. An ultraviolet-curable resin composition comprising a compound having one or more epoxy groups in a molecule, a cationic photopolymerization initiator, and a compound having one or more maleimide groups in a molecule. . 2. The compound having one or more maleimide groups in a molecule has a maleimide group-containing carboxylic acid represented by the following general formula (1) and one or more alcoholic hydroxyl groups in one molecule: The ultraviolet-curable resin composition according to claim 1, which is an ester compound obtained by reacting an alcohol or an epoxy resin having one or more epoxy groups. Embedded image (Where R is a linear alkylene group having 1 to 18 carbon atoms, a branched alkylene group having 2 to 24 carbon atoms,
An alkylene group having 2 to 24 carbon atoms having a hydroxyl group,
It represents at least one organic group selected from the group consisting of a cycloalkylene group, an aryl group and an arylalkylene group. ) 3. The content of the compound having one or more epoxy groups in the molecule is 30 to 90% by weight, the content of the photocationic polymerization initiator is 1 to 10% by weight, and the content of the compound is 1 or more in the molecule. 3. The ultraviolet-curable resin composition according to claim 1, wherein the content of the compound having a maleimide group is 5 to 50% by weight. 4.