JP2002302522A - Photocurable resin composition and coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide, using inexpensive materials, a photocurable resin composition prevented from warpages that may occur on photocuring the photocurable resin, and also excellent in folding processability and the like through making the cured coating film therefrom flexible. SOLUTION: This photocurable resin composition comprising (I) an acrylic resin which is obtained by reacting (meth) acrylic acid with (d) a copolymer produced by copolymerization between (a) compound having in one molecule one glycidyl group and one polymerizable unsaturated bond, (d) a hydroxy group-containing (meth) acrylic ester or an unsaturated compound having in one molecule one hydroxy group and one polymerizable unsaturated bond and (c) another unsaturated compound having in one molecule one polymerizable unsaturated bond, (II) a photopolymerizable monomer having in one molecule one or two or more photopolymerizable unsaturated bond (s) and (III) a photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photo-resin composition and a coating which can be cured by irradiation with ultraviolet rays or electron beams or by heating. In particular, curlability and bending workability can be improved by compounding a hydroxyl group-containing (meth) acrylate or an unsaturated compound (b) having one hydroxyl group and one polymerizable unsaturated bond in one molecule. It became.

[0002]

2. Description of the Related Art A photocurable resin composition having a glass transition temperature of 20 ° C. or higher has a high cohesive force at the time of photocuring. .
A hydroxyl group-containing (meth) acrylic acid ester, or 1
Compound (a) which does not contain an unsaturated compound (b) having one hydroxyl group and one polymerizable unsaturated bond in the molecule, but has one glycidyl group and one polymerizable unsaturated bond in the molecule (a) And an acrylic resin (I) obtained by reacting (meth) acrylic acid with a copolymer (d) obtained by copolymerizing an unsaturated compound (c) having one polymerizable unsaturated bond in one molecule. ) Is a tough cured film by light curing, which breaks when folded, making bending difficult.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to prevent warpage that occurs when a photocurable resin is photocured. Further, it is an object of the present invention to provide a photocurable resin composition which is made of a cured coating film which is flexible and which is excellent in bending workability, using an inexpensive material.

[0004]

The present invention relates to the following. (1) Compound (a) having one glycidyl group and one polymerizable unsaturated bond in the molecule, (meth) acrylate ester containing hydroxyl group, or one hydroxyl group and the polymerizable unsaturated bond in one molecule (B) and one polymerizable unsaturated bond in one molecule other than (a) and (b).
Resin (I) obtained by reacting (meth) acrylic acid with copolymer (d) obtained by copolymerizing unsaturated compound (c) having one polymerizable compound, and a photopolymerizable unsaturated bond in one molecule Having one or two or more photopolymerizable monomers (I
A photocurable resin composition comprising I) and a photopolymerization initiator (III). (2) Compounds (a) wherein the co-union (d) has one glycidyl group and one polymerizable unsaturated bond in the molecule
45% by weight, a hydroxyl group-containing (meth) acrylate,
Or 10 to 45% by weight of an unsaturated compound (b) having one hydroxyl group and one polymerizable unsaturated bond in one molecule and polymerizable unsaturated bond in one molecule other than (a) and (b). 1
Is obtained by copolymerizing 20 to 60% by weight of an unsaturated compound (c) having two or more unsaturated compounds (c), and the weight ratio (I) / (II) of the acrylic resin (I) and the photopolymerizable monomer (II) Is 95
/ 5 to 70/30, the amount of the photopolymerization initiator (III) is 0.1 to 10% by weight based on the total of (I) and (II), and the organic solvent (IV) is ), (II)
(1) The photocurable resin composition according to (1), which contains 30 to 80% by weight based on the total of (III). (3) The weight average molecular weight of the copolymer (d) is 7,000
The photocurable resin composition according to (1) or (2) above. (4) The glass transition temperature of the copolymer (d) is -40 to 2
The photocurable resin composition according to claim 1, wherein the temperature is 0 ° C. (5) A paint containing the photocurable resin composition according to any one of (1) to (4).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The compound (a) having one glycidyl group and one polymerizable unsaturated bond in the molecule used in the present invention is represented by the following general formula (I).

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A hydroxyl group-containing (meth) acrylate or an unsaturated compound (b) having one hydroxyl group and one polymerizable unsaturated bond in one molecule is represented by the following general formula (II): Is done.

[0007]

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Further, (a) and (b) used in the present invention
As the unsaturated compound (c) having one polymerizable unsaturated bond in one molecule other than the above, various esters of aromatic and acrylic acid or methacrylic acid having an unsaturated group are preferable. Examples of aromatics containing an unsaturated group include styrene. Further, as examples of various esters of acrylic acid or methacrylic acid, methyl (meth) acrylate ((meth) acrylate indicates acrylate and methacrylate; the same applies hereinafter), ethyl (meth) acrylate, n
-Propyl (meth) acrylate, n-butyl (meth)
Acrylate, isobutyl (meth) acrylate, t-
Butyl (meth) acrylate, ethylhexyl (meth)
Alkyl (meth) acrylates such as acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, and tridecyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth)
Alkoxyalkyl (meth) acrylates such as acrylates, alkoxyalkoxyalkyl (meth) acrylates such as 2-methoxyethoxyethyl (meth) acrylate, 2-ethoxyethoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) A) acrylate, methoxytriethylene glycol (meth) acrylate, butoxytriethylene glycol (meth) acrylate, alkoxy (poly) alkylene glycol (meth) acrylate such as methoxydipropylene glycol (meth) acrylate, pyrenoxide adduct (meth) acrylate, Dia such as N, N dimethylaminoethyl (meth) acrylate, N, N diethylaminoethyl (meth) acrylate One or a mixture of two or more kinds of such Kill aminoalkyl (meth) acrylate.

The components (a), (b) and (c) are copolymerized by a known method such as solution polymerization in the presence of a radical polymerization initiator to obtain a copolymer (d). You. Here, as the compounding ratio, the component (a) is preferably 25 to 45% by weight, more preferably 30 to 40% by weight, and the component (b) is preferably 10 to 45% by weight, more preferably 20 to 45% by weight. 40% by weight and 20 to 60% by weight, more preferably 40 to 50% by weight, of the component (c) (all based on the total amount of the components (a), (b) and (c)). When the component (a) is less than 25% by weight, the curability and the performance of the cured film obtained when a photocurable resin is used as a coating material tend to be generally deteriorated, and 45% by weight. If it exceeds, the crosslink density increases, so that the cohesive force increases and the film tends to be warped, and the flexibility tends to be poor and the bending workability tends to be poor. If the component (b) is less than 10% by weight, the coating film tends to be tough and crack when bent. If the content is more than 45% by weight, the compatibility with the solvent deteriorates,
Synthesis tends to be difficult.

The weight average molecular weight (gel permeation chromatography, standard polystyrene equivalent) of the copolymer (d) thus obtained is preferably at least 7,000, more preferably at least 10,000. 7,0
If it is less than 00, the curability and the performance of the cured coating film obtained when a photocurable resin is used as a coating material tend to be generally reduced.

The copolymer (d) preferably has a glass transition temperature of -40 to 20 ° C, more preferably -30.
-10 ° C. If the temperature is lower than −40 ° C., the curability and the performance of the cured film obtained when a photocurable resin is used as a coating material tend to decrease generally. The cohesive force of the resin increases and the resin tends to be warped.

Next, the copolymer (d) is reacted with (meth) acrylic acid by an addition reaction of an epoxy group and a carboxyl group to obtain an acrylic resin (I). Is equivalent to 1 / 0.8 of the epoxy group of the copolymer (d) / (meth) acrylic acid.
It is preferable to mix them so as to be １ ／ 1/1. 1/0.
If it is less than 8, the curability and coating film performance of the obtained resin composition tend to decrease overall. Further, in the case of 1/1 or more, the (meth) acrylic acid remains unreacted in the resin composition obtained, and skin irritation increases and workability decreases. The reaction can be performed by a known method in the presence of a basic catalyst, a phosphorus-based catalyst, and the like.

Further, the resin composition of the present invention contains, as the component (II), a photopolymerizable monomer having one or more polymerizable unsaturated bonds in one molecule. Examples of the photopolymerizable monomer (II) include trihydroxyethyl isocyanuric acid tri (meth) acrylate. These components (II) may be used alone or as a mixture of two or more.

The compounding ratio of the components (I) and (II) is preferably (I) / (II), preferably 95/5 to 50/50.
(Weight ratio, solid content conversion), more preferably 80 /
20 to 70/30. If the component (II) is less than 20% by weight, the coating properties and workability of the obtained resin composition tend to decrease. If it is 30% by weight or more, the cured coating film tends to be warped, and the curability of the coating film tends to be further reduced.

Further, the resin composition of the present invention comprises (II)
As the component I), for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetone, p
-Dimethylaminoacetophenone, p-dimethylaminopropiophenone, pp'-bisdiethylaminobenzophenone, Michler's ketone, benzoin methyl ether, benzyl dimethyl ketal, benzoin isopropyl ether, benzophenone, methyl benzoyl formate, 4-NN'- Dimethylacetophenones, 2-
Methyl- {4- (methylthio) phenyl} -2-morpholino-1-propanone, 2--4-dimethylthioxanthone, oligo {2-hydroxy-2-methyl-1-} 4
-(1-methylvinyl) phenyl} propanone and the like. These photopolymerization initiators can be used alone or in combination of two or more.

The photopolymerization initiator (III) is preferably used in an amount of 0.1 to 10% by weight, based on the total solid content of the acrylic resin (I) and the photopolymerizable monomer (II). It is more preferably used in an amount of 1 to 10% by weight, even more preferably 3 to 5% by weight. This amount is 0.1% by weight
When the amount is less than the above, photocuring tends to be insufficiently hardened, and when the amount exceeds 10% by weight, the physical properties of the obtained coating film tend to be generally deteriorated.

The curable resin composition of the present invention may further contain (i) a hydrocarbon-based organic solvent such as toluene or xylene, an ester-based organic solvent such as ethyl acetate or butyl acetate, or a ketone-based solvent such as methyl ethyl ketone. Organic solvents (IV) such as organic solvents, (ii) unsaturated triester resins, vinyl ester resins, vinyl urethane resins, vinyl ester urethane resins, solid phenol resins, polyisocyanates, polyepoxides, epoxy-terminated polyoxazolidones, acrylic resins, Natural and synthetic high molecular substances such as alkyd resins, urea resins, melamine resins, polydiene elastomers, saturated polyesters, saturated polyethers, tung oil, soybean oil, castor oil, epoxidized oil and other fats and oils, iii) calcium carbonate, talc, mica, clay, silica powder , Colloidal silica, barium sulfate, aluminum hydroxide, zinc stearate, zinc oxide,
Various fillers and pigments such as red iron and azo pigments, (iv)
Hydroquinone, hydroquinone monomethyl ether,
A coating material can be obtained by adding a polymerization inhibitor such as benzoquinone, pt-butylcatechol, and 2,6-di-t-butyl-4-methylphenol.

The preferred amount of each component added is (i) 30 to 80% by weight, more preferably 5 to 80% by weight of organic solvent (IV) based on the sum of (I), (II) and (III).
0 to 70% by weight. If the amount of the organic solvent (IV) is less than 30% by weight, the viscosity tends to be high and coating suitability tends to be poor. If it exceeds 80% by weight, the viscosity tends to be low and coating suitability tends to be low.

(Ii) represents (I), (II) and (II)
It is preferably at most 30% by weight based on the total of I). If it exceeds 30% by weight, the curability tends to decrease.

(Iii) represents (I), (II) and (II)
It is preferably at most 20% by weight based on the total of I). If it exceeds 20% by weight, coating suitability and curability tend to decrease.

(Iv) represents (I), (II) and (II)
It is preferably 0.5% by weight or less based on the total of I). 0.
If it exceeds 5% by weight, the curing time tends to be long, the workability tends to decrease, and the properties of the cured coating film also tend to be poor.

Further, the photocurable resin composition of the present invention may be made of a metal material such as iron or aluminum, an inorganic building material such as a calcium silicate plate, a valve cement plate, a lightweight concrete plate, a lightweight cellular concrete plate, an asbestos cement plate, a mortar, or the like. It can be used as a photo-curable paint for wood, paper, plastic substrates and the like. Also, a leveling agent and other modifiers can be added.

The photocurable resin composition of the present invention is suitable as a coating material, and a coating film excellent in curability, hardness, stain resistance, solvent resistance and bending workability can be obtained at low cost.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on embodiments. The molecular weight of the present invention was measured as follows.

[Method for measuring molecular weight] Equipment used: Hitachi L6000 type high performance liquid chromatography Column: Gelpack R400, R450 and R400M
(Trade name of Hitachi Chemical Co., Ltd.) Eluent: Tetrahydrofuran Column temperature: 25 ° C. Liquid volume: 1.6 ml / min Detector: Hitachi L3350 type differential refractometer

[Glass transition temperature] The Tg of the acrylic resin (d) was calculated according to the following equation.

[0027]

(Equation 1)

Here, wi is the weight% of the monomers (a), (b) and (c) each having an unsaturated bond, and Tgi is the monomer (a), ( b) and (c)
Is the Tg (unit: absolute temperature) of the homopolymer.

Example 1 (Polymerizable monomer component composition) 300 parts by weight of glycidyl methacrylate 200 parts by weight of 2-hydroxyethyl methacrylate 200 parts by weight of butyl methacrylate 300 parts by weight of 2-ethylhexyl acrylate Reaction solution 1,000 parts by weight of toluene were charged therein and heated to 135 ° C. while stirring under nitrogen gas pressurization (+1.5 kgf / cm ² atmosphere. At 135 ° C., 1,000 parts by weight of the polymerizable monomer component, t 30 parts by weight of -butylperoxy-2-ethylhexanoate were added dropwise over 2 hours, and after completion of the addition, the reaction was continued at 135 ° C. for 4 hours to synthesize a copolymer (d). d) has a weight average molecular weight of 10,000 and a glass transition temperature of -13.
° C. Next, to 1000 parts by weight of the copolymer (d), 73 parts of acrylic acid, 4.5 parts by weight of triphenylphosphine (manufactured by Hokuko Chemical Industry Co., Ltd .: TPP) and 0.8 parts by weight of hydroquinone monomethyl ether were added, followed by adding 105 parts. The mixture was stirred while heating at about 12 hours to obtain Compound (I) having an acid value of 3 and a solid content of 50% by weight. Next, 140 parts by weight of the compound (I) and polyethylene glycol 300 diacrylate (New Frontier PE300 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
30 parts by weight and 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) were stirred to form a uniform solution to obtain a photocurable resin composition.

Example 2 (Polymerizable monomer component composition) Glycidyl methacrylate 300 parts by weight Acrylic acid 2-hydroxyethyl ester 200 parts by weight Acrylic acid ethyl ester 200 parts by weight Acrylic acid 2-ethylhexyl ester 300 parts by weight Reaction solution 1,000 parts by weight of toluene were charged therein and heated to 135 ° C. while stirring under nitrogen gas pressurization (+1.5 kgf / cm ² atmosphere. At 135 ° C., 1,000 parts by weight of the polymerizable monomer component, t 30 parts by weight of -butylperoxy-2-ethylhexanoate were added dropwise over 2 hours, and after completion of the addition, the reaction was continued at 135 ° C. for 4 hours to synthesize a copolymer (d). d) has a weight average molecular weight of 10,000 and a glass transition temperature of -30.
° C. Next, to 1000 parts by weight of the copolymer (d), 73 parts of acrylic acid, 4.5 parts by weight of triphenylphosphine (manufactured by Hokuko Chemical Industry Co., Ltd .: TPP) and 0.8 parts by weight of hydroquinone monomethyl ether were added, followed by adding 105 parts. The mixture was stirred while heating at about 12 hours to obtain Compound (I) having an acid value of 3 and a solid content of 50% by weight. Next, 140 parts by weight of the compound (I) and polyethylene glycol 300 diacrylate (New Frontier PE300 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
30 parts by weight and 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) were stirred to form a uniform solution to obtain a photocurable resin composition.

Example 3 (Polymerizable monomer component composition) 300 parts by weight of glycidyl methacrylate 400 parts by weight of 2-hydroxyethyl methacrylate 200 parts by weight of 2-ethylhexyl methacrylate 100 parts by weight of ethyl acrylate Reaction solution 1,000 parts of butyl acetate was charged therein, and heated to 135 ° C. while stirring under a nitrogen gas pressurized atmosphere (+1.5 kgf / cm ² atmosphere). 30 parts by weight of t-butylperoxy-2-ethylhexanoate was added dropwise over 2 hours, and after completion of the addition, the reaction was continued at 135 ° C. for 4 hours to synthesize a copolymer (d). (D) has a weight average molecular weight of 23,000 and a glass transition temperature of -2.
1 ° C. Next, to 1000 parts by weight of the copolymer (d), 73 parts of acrylic acid, 4.5 parts by weight of triphenylphosphine (manufactured by Hokuko Chemical Industry Co., Ltd .: TPP) and 0.8 parts by weight of hydroquinone monomethyl ether were added, followed by adding 105 parts. The mixture was stirred while heating at about 12 hours to obtain Compound (I) having an acid value of 3 and a solid content of 50% by weight. Next, 200 parts by weight of the compound (I) and 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) were stirred to make a uniform solution, and a photocurable resin composition was obtained. Was.

Comparative Example 1 (Polymerizable monomer component composition) 370 parts by weight of glycidyl methacrylate 200 parts by weight of methyl methacrylate 100 parts by weight of butyl methacrylate 330 parts by weight of styrene 1,000 parts by weight of toluene in the reaction solution The mixture was heated to 135 ° C. while stirring under an atmosphere of nitrogen gas pressurization (+1.5 kgf / cm ^{2. At} 135 ° C., 1,000 parts by weight of the polymerizable monomer component, t-butylperoxy-2-ethyl Hexanoate (30 parts by weight) was added dropwise over 2 hours, and after completion of the addition, the reaction was continued at 135 ° C. for 4 hours to synthesize a copolymer (d) having a weight average molecular weight of 10. 2,000 and glass transition temperature 68 ° C
Met. Next, to 1000 parts by weight of the copolymer (d), 90 parts of acrylic acid, 4.5 parts by weight of triphenylphosphine (manufactured by Hokuko Chemical Co., Ltd .: TPP) and 0.8 parts by weight of hydroquinone monomethyl ether were added, followed by adding 105 parts. About 1 at ℃
The mixture was stirred with heating for 2 hours to obtain a compound (I) having an acid value of 3 and a solid content of 50% by weight. Next, 140 parts by weight of the compound (I) and polyethylene glycol 300 diacrylate (New Frontier PE300 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
30 parts by weight and 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) were stirred to form a uniform solution to obtain a photocurable resin composition.

Comparative Example 2 (Polymerizable monomer component composition) Glycidyl methacrylate 370 parts by weight Cyclohexyl methacrylate 200 parts by weight 2-Ethylhexyl acrylate 300 parts by weight Styrene 130 parts by weight Toluene 1,000 in the reaction solution And heated to 135 ° C. with stirring under an atmosphere of nitrogen gas (+1.5 kgf / cm ² ). At 135 ° C., 1,000 parts by weight of the polymerizable monomer component, t-butyl peroxy-2 -Ethyl hexanoate (30 parts by weight) was added dropwise over 2 hours, and after completion of the addition, the reaction was continued at 135 ° C. for 4 hours to synthesize a copolymer (d), and the obtained copolymer (d) had a weight average molecular weight. Is 10,000 and the glass transition temperature is -5 ° C
Met. Next, to 1000 parts by weight of the copolymer (d), 90 parts of acrylic acid, 4.5 parts by weight of triphenylphosphine (manufactured by Hokuko Chemical Co., Ltd .: TPP) and 0.8 parts by weight of hydroquinone monomethyl ether were added, followed by adding 105 parts. About 1 at ℃
The mixture was stirred with heating for 2 hours to obtain a compound (I) having an acid value of 3 and a solid content of 50% by weight. Next, 140 parts by weight of the compound (I) and polyethylene glycol 300 diacrylate (New Frontier PE300 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
30 parts by weight and 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) were stirred to form a uniform solution to obtain a photocurable resin composition.

Comparative Example 3 (Polymerizable monomer component composition) 300 parts by weight of glycidyl methacrylate 200 parts by weight of acrylic acid 2-hydroxyethyl ester 300 parts by weight of butyl methacrylate 200 parts by weight of methacrylic acid methyl ester Toluene (1,000 parts) was charged and heated to 135 ° C. while stirring under nitrogen gas pressure (+1.5 kgf / cm ² atmosphere. At 135 ° C., 1,000 parts by weight of the polymerizable monomer component, t-butyl) 30 parts by weight of peroxy-2-ethylhexanoate was added dropwise over 2 hours, and after completion of the addition, the reaction was continued at 135 ° C. for 4 hours to synthesize a copolymer (d). Has a weight average molecular weight of 10,000 and a glass transition temperature of 32 ° C.
Met. Next, to 1000 parts by weight of the copolymer (d), 71 parts of acrylic acid, 4.5 parts by weight of triphenylphosphine (manufactured by Hokko Chemical Industry Co., Ltd .: TPP) and 0.8 parts by weight of hydroquinone monomethyl ether were added, followed by adding 105 parts. About 1 at ℃
The mixture was stirred with heating for 2 hours to obtain a compound (I) having an acid value of 3 and a solid content of 50% by weight. Next, 200 parts by weight of the compound (I) and 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) were stirred to make a uniform solution, and a photocurable resin composition was obtained. Was.

Comparative Example 4 (polymerizable monomer component composition) 300 parts by weight of glycidyl methacrylate 300 parts by weight of 2-hydroxyethyl methacrylate 200 parts by weight of butyl methacrylate 200 parts by weight of methyl methacrylate 1,000 parts of butyl acetate was charged, and heated to 135 ° C. while stirring under nitrogen gas pressure (+1.5 kgf / cm ² atmosphere. At 135 ° C., 1,000 parts by weight of the polymerizable monomer component, t- 30 parts by weight of butyl peroxy-2-ethylhexanoate were added dropwise over 2 hours, and after completion of the addition, the reaction was continued at 135 ° C. for 4 hours to synthesize a copolymer (d). ) Has a weight average molecular weight of 17,000 and a glass transition temperature of 51.
° C. Next, to 1000 parts by weight of the copolymer (d), 71 parts of acrylic acid, 4.5 parts by weight of triphenylphosphine (manufactured by Hokko Chemical Industry Co., Ltd .: TPP) and 0.8 parts by weight of hydroquinone monomethyl ether were added, followed by adding 105 parts. The mixture was stirred while heating at about 12 hours to obtain Compound (I) having an acid value of 3 and a solid content of 50% by weight. Next, 200 parts by weight of the compound (I) and 3 parts by weight of 1-hydroxycyclohexylphenyl ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals) are stirred to form a uniform solution, and a photocurable resin composition is obtained. Was.

Application Example and Evaluation of Cured Coating Properties 1 The photocurable resin compositions obtained from the above Examples and Comparative Examples were coated on pulp paper 15 cm long and 10 cm wide by a bar coater so that the thickness of the cured film was 20 μm. After applying with 6
The solvent was volatilized by being left in a hot air dryer at 0 ° C. for 5 minutes. It was placed on a conveyor moving at a speed of 5 m / min equipped with one 80 w / cm high-pressure mercury lamp and cured by irradiation. The resulting cured coating film was evaluated for curl and bending workability. (1) Curling property The sheet was placed on a conveyer equipped with one 80 w / cm high-pressure mercury lamp and moving at a speed of 5 m / min, cured by irradiation, and then the paper coated with the coating film was visually checked for warpage. The evaluation criteria are shown below. Float warp within 1 cm at both ends: ◎ Float warp within 3 cm at both ends: ○ Curl of pulp paper less than 1 rotation: △ Curl of pulp paper more than 1 rotation: × (2) Bending processability The pulp paper thus folded was actually folded, and the number of times until the coating film was cracked was evaluated.

Application Example and Evaluation of Cured Film Properties 2 The photocurable resin compositions obtained from the above Examples and Comparative Examples were applied on pulp paper of 15 cm in length and 10 cm in width so that the thickness of the cured film was 100 μm. Then, the solvent was volatilized by being left in a hot air dryer at 60 ° C. for 5 minutes. 5m / equipped with one 80 w / cm high pressure mercury lamp
It was placed on a conveyor moving at a speed of 10 minutes and irradiated and cured twice. The properties of the obtained cured coating film were evaluated. (1) Curability Number of irradiations until complete curing (2) Pencil hardness Evaluation was performed based on JIS K5400 pencil scratch test. (3) Magic Stain Resistance The paint film was stained using red and black oily magic and allowed to stand at room temperature for 6 hours, then wiped with n-butanol, and the degree and condition of the stain of the paint film were comprehensively observed. (4) Thinner resistance The surface of the coating film is made 50% using absorbent cotton impregnated with xylene.
After repeated rubbing, the state of the coating film surface was observed.

The results of evaluation of curl properties and bending workability are shown in the table.

[0039]

[Table 1]

[0040]

Industrial Applicability The curable resin composition of the present invention is suitable as a coating material and can provide a coating film which is excellent in curability, hardness, stain resistance, solvent resistance, curling properties and bending workability at a low cost.

Continued on the front page F term (reference) 4J027 AA01 AA02 BA29 CB10 CC04 CD08 4J038 CG001 CG002 CG141 CG142 FA111 FA112 FA231 FA232 GA01 GA03 GA07 KA03 MA13 MA14 PA17 4J100 AL03R AL09Q AL10P CA05 JA01

Claims (5)

[Claims] 1. A compound (a) having one glycidyl group and one polymerizable unsaturated bond in the molecule, a hydroxyl group-containing (meth) acrylate, or one compound having one hydroxyl group in the molecule.
Compound (b) having one and one polymerizable unsaturated bond and (c) an unsaturated compound having one polymerizable unsaturated bond in one molecule other than (a) and (b) Resin (I) obtained by reacting (meth) acrylic acid with the copolymer (d) obtained by the above method, a photopolymerizable monomer having one or two or more photopolymerizable unsaturated bonds in one molecule. A photocurable resin composition comprising a monomer (II) and a photopolymerization initiator (III). 2. A compound (a) in which the co-union (d) has one glycidyl group and one polymerizable unsaturated bond in the molecule.
25 to 45% by weight, hydroxyl group-containing (meth) acrylic acid ester, or 10 to 45% by weight of an unsaturated compound (b) having one hydroxyl group and one polymerizable unsaturated bond in one molecule
And an acrylic resin (I) obtained by copolymerizing 20 to 60% by weight of an unsaturated compound (c) having one polymerizable unsaturated bond in one molecule other than (a) and (b). )
And the weight ratio (I) / (II) of the photopolymerizable monomer (II) is 95/5 to 70/30, and the photopolymerization initiator (III)
Is 0.1 to 10 with respect to the sum of (I) and (II).
% Of the organic solvent (IV) and (I), (I)
The photocurable resin composition according to claim 1, which is contained in an amount of 30 to 80% by weight based on the total of I) and (III). 3. The copolymer (d) having a weight average molecular weight of 7,
The photocurable resin composition according to claim 1, which has a molecular weight of 000 or more. 4. The glass transition temperature of the copolymer (d) is -4.
The photocurable resin composition according to claim 1, wherein the temperature is 0 to 20 ° C. 5. 5. A coating comprising the photocurable resin composition according to claim 1.