JPH08259644A - Active energy ray-curable resin composition - Google Patents

Abstract

PURPOSE: To obtain an active energy ray-curable resin composition useful for coating film excellent in contamination resistance, scratch resistance, flexibility, etc., comprising a specific urethane acrylate component, ethylenic unsaturated monomer component and photopolymerization initiator. CONSTITUTION: This composition comprises (A) a urethane acrylate component prepared by reaction between (i) a bisphenol-type polyol of formula I (R1 O and R2 O are each a 2-4C alkylene oxide; R3 and R4 are each H or methyl; (n) and (m) are each integer and (n+m)=1-20), (ii) a polyisocyanate and (iii) a hydroxyl-contg. acrylate, (B) an ethylenic unsaturated monomer component [pref. an acrylic monomer of formula II (R1 is H or methyl; R2 is a 2-4C alkylene; R3 is phenyl or an alkyl; (n) is an integer of 1-10), and (C) a photopolymerizatlon initiator, and pref. furthermore, (D) a phosphorus compound. It is preferable that the weight ratio A/B be (90:10) to (30:70).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable resin composition which is cured by irradiation with active energy rays such as ultraviolet rays, and more specifically, it has excellent stain resistance, scratch resistance, flexibility and adhesion. The present invention relates to a urethane acrylate-based active energy ray-curable resin composition having excellent coating film performance.

[0002]

2. Description of the Related Art In recent years, active energy ray-curable coating materials which are cured by irradiation with active energy rays such as ultraviolet rays have been widely used in place of organic solvent-based coating materials due to environmental pollution and energy saving. This is because it contains a resin and a monomer that can be cured by irradiation with active energy rays such as ultraviolet rays, and the monomer also serves as a solvent, so that there is an advantage that the solvent does not volatilize during coating film formation. As the active energy ray-curable resin, oligomers such as polyester acrylate, urethane acrylate, and epoxy acrylate having an acrylic double bond at the molecular end, styrene-based, and acrylic-based monomers are used.

Among these, urethane acrylic (urethane acrylate) resins have a good balance of physical properties, and coating compositions using the resins include coatings for decorative boards, varnishes for paper, paints for woodworking, hard coats, adhesives, Widely used in applications such as resist materials. In such coating agent applications, performances such as stain resistance, scratch resistance (scratch resistance), flexibility (elongation), and adhesion of the formed coating film are required, and these required performances are required. Various examinations have been made to satisfy them. For example, a method of using an alkylene oxide-modified (meth) acrylate of benzyl alcohol as a reactive diluent for the purpose of improving stain resistance, surface hardness, fast curing property, solvent resistance, etc. (JP-A-6-329738). Or flexibility,
A method of blending an organically modified polysiloxane having a dimethylsiloxane structural unit for the purpose of improving stain resistance, scratch resistance (scratch resistance), etc. (JP-A-2-189)
No. 323), a method using a polycarbonate diol (Japanese Patent Application Laid-Open No. 5-70534) for the purpose of improving curability, scratch resistance, stain resistance, flexibility (flexibility), weather resistance and the like. There is.

[0004]

However, the technique disclosed in Japanese Patent Laid-Open No. 6-329738 aims at rapid curing property, and although the surface hardness is taken into consideration, there is a drawback that it is inferior in flexibility. In addition, Japanese Patent Laid-Open No. 2-18
Even in the technology disclosed in Japanese Patent No. 9323, there is still room for improvement in flexibility and adhesion to an object to be coated.
There is still room for improvement in the adhesiveness to the object to be coated with the technology disclosed in Japanese Patent Laid-Open No. 70534 as well, and in stain resistance, scratch resistance (scratch resistance), flexibility (elongation), and adhesion. The actual situation is that an active energy ray-curable resin composition of urethane acrylic resin that forms an excellent coating film is desired.

[0005]

The inventors of the present invention have conducted extensive studies in view of the above circumstances, and as a result, have found that bisphenol type polyol (A1), polyisocyanate (A2) and hydroxyl group-containing acrylate represented by the following chemical formula 1. (A3)
A urethane acrylic resin composition comprising a urethane acrylate component (A), an ethylenically unsaturated monomer component (B) and a photopolymerization initiator obtained by reacting the above is useful as an active energy ray-curable resin composition, The inventors have found that a coating film having excellent stain resistance, scratch resistance (scratch resistance), flexibility (elongation), and adhesion is formed, and completed the present invention.

Embedded image (However, R ₁ O and R ₂ O are alkylene oxides having 2 to 4 carbon atoms, R ₃ and R ₄ are hydrogen or a methyl group, and n and m are integers and represent n + m = 1 to 20, respectively.)

Urethane acrylate component (A) of the present invention
Is obtained by reacting a bisphenol type polyol (A1) represented by the following chemical formula 1, a polyisocyanate (A2) and a hydroxyl group-containing acrylate (A3).

Embedded image (However, R ₁ O and R ₂ O are alkylene oxides having 2 to 4 carbon atoms, R ₃ and R ₄ are hydrogen or methyl groups, and n and m are integers and represent n + m = 1 to 20, respectively.) Bisphenol type polyol (A1) is not particularly limited as long as it is represented by the above Chemical formula 1, but n + m is 2 to 14 and R
Alkylene oxides represented by ₁ O and R ₂ O are ethylene oxide or propylene oxide (especially R
₁ and R ₂ are the same) are preferably used.

The polyisocyanate (A2) may be aromatic, aliphatic, cycloaliphatic, or alicyclic polyisocyanate or a mixture thereof, and among them, tolylene diisocyanate (TDI) and diphenylmethane diisocyanate. (MDI), hydrogenated diphenylmethane diisocyanate (H-MDI), polyphenylmethane polyisocyanate (crude MDI), modified diphenylmethane diisocyanate (modified MDI), hydrogenated xylylene diisocyanate (H-XDI), xylylene diisocyanate (XDI) ), Hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), or other aromatic polyisocyanates or trimer compounds of these polyisocyanates,
Aliphatic polyisocyanates such as isiphorone diisocyanate (IPDI) and reaction products of these polyisocyanates and polyols are preferably used. Further, as the hydroxyl group-containing acrylate (A3), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2
-Hydroxypropyl methacrylate, 2-hydroxyethyl acryloyl phosphate, 4-butylhydroxy acrylate, caprolactone-modified 2-hydroxyethyl acrylate and the like can be mentioned, and among them, 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate are preferably used.

Urethane acrylate component (A) of the present invention
The method for producing is not particularly limited as long as it is a method of reacting (A1) to (A3), and a known method can be adopted.
For example, a method in which (A1) to (A3) are mixed together and reacted, or after (A1) and (A2) are reacted to form a urethane isocyanate intermediate containing one or more isocyanate groups per molecule, A method of reacting the intermediate with (A3), a method of reacting (A2) with (A3) to form a urethane acrylate intermediate containing one or more isocyanate groups per molecule, and then the intermediate with (A1) And the like.

Further, in producing the urethane acrylate component (A) of the present invention, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, other than the above-mentioned (A1) as a polyol component, Dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, polycaprolactone, tri Methylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol,
Polyhydric alcohols such as sorbitol, mannitol, glycerin and polyglycerin, and reaction products of these polyhydric alcohols with polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid and isophthalic acid. It is also very useful to use a polyester polyol, a caprolactone-modified polyol, a polyolefin-based polyol, a polybutadiene-based polyol, and the like, which are different from each other, in order to further improve the stain resistance.

The ethylenically unsaturated monomer component (B) of the present invention is not particularly limited as long as it is a monomer having an ethylenically unsaturated bond, and includes methyl (meth) acrylate, ethyl (meth) acrylate and propyl (meth). Acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate,
Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl ( (Meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate,
Carbitol acrylate, benzyl acrylate, allyl acrylate, phenoxyethyl acrylate, styrene, vinyltoluene, chlorostyrene, α-methylstyrene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, acryloxyethyl phosphate, 2-
Vinyl pyridine, 2-ethylhexyl acrylate, 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, ethyl carbitol acrylate, polypropylene glycol diacrylate, polyethylene glycol (# 200, # 400, # 60
0) diacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 1,6-hexanediol diacrylate,
Examples thereof include trimethylolpropane triacrylate and EO (ethylene oxide) -modified trimethylolpropane triacrylate, and among them, an alkylene oxide-modified acrylic monomer represented by the following chemical formula 2 is preferable, and n is 4 to 6 and R is R. ethylene or propylene _two carbon atoms 2 or 4 is preferably used.

[0011]

Embedded image (However, R ₁ is hydrogen or a methyl group, and R ₂ has ₂ to 4 carbon atoms.
Alkylene group, R ₃ is a phenyl group or an alkyl group, n
Each represent an integer of 1 to 10) In the present invention, it is of course possible to use the compound represented by the above Chemical formula 2 in combination with the above-mentioned other compound having an ethylenically unsaturated bond, if necessary. is there.

In the present invention, in addition to the above (A) and (B), it is necessary to use a photopolymerization initiator, and as the photopolymerization initiator, cobalt octenoate, cobalt naphthenate, manganese octenoate is used. , Manganese naphthenate, methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, t-butyl perbenzoate, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-. Butyl ether, benzoin phenyl ether, anthraquinone, naphthoquinone, hivaloin ethyl ether, benzyl ketal,
1,1-dichloroacetophenone, pt-butyldichloroacetophenone, 2-chlorothioxanthone, 2,
2-diethoxyacetophenone, Michler's ketone,
2,2-dichloro-4-phenoxyacetophenone,
2,2-dimethoxy-2-phenylacetophenone, benzophenone, 2-methylthioxanthone, phenylglyoxylate, α-hydroxyisobutylphenone,
Dibenzosparone, benzophenone amines (N-methyldiethanolamine, triethylamine, etc.), benzyl diphenyl disulfide, tetramethyl thiuram monosulfide, azobisisobutyronitrile, dibenzyl, diacetyl, acetophenone, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one methylbenzoyl formate and the like can be mentioned.

In the present invention, by using the above-mentioned components (A) and (B) and the photopolymerization initiator, it is of course possible to obtain the effects of the present invention, but the resin composition of the present invention is used. It is also very important to further blend a phosphorus compound (C) for the purpose of improving the adhesiveness with a vinyl chloride resin when used for coating. The phosphorus compound (C) is preferably a radical-polymerizable vinyl monomer containing phosphorus (ethylenically unsaturated monomer), specifically, EO (ethylene oxide) -modified phosphoric acid triacrylate, EO (ethylene oxide). ) Modified phosphoric acid methacrylate, EO (ethylene oxide) modified phosphoric acid dimethacrylate, ethylene oxide / caprolactone modified phosphoric acid dimethacrylate, and the like are mentioned, and E containing phosphorus as shown in the following chemical formula 3
O (ethylene oxide) modified dimethacrylate and ethylene oxide / caprolactone modified phosphoric acid dimethacrylate can be preferably used.

Embedded image

In the present invention, the compounding amount of the above-mentioned (A) to (C) is not particularly limited, but in the compounding ratio of (A) and (B), the compounding weight ratio of (A) / (B) is 90 /. 10-30
/ 70 is preferable, and more preferably 80/2
When the compounding weight ratio of (A) exceeds 0 to 40/60, the scratch resistance decreases, and conversely, when the compounding weight ratio of (B) exceeds the above compounding weight ratio, stain resistance decreases. It tends to be unfavorable. Further, the compounding amount of the phosphorus compound (C) in the total amount of (A) to (C) is preferably 2% by weight or less, and the effect of the present invention can be obtained even if (C) is added in an amount of more than 2% by weight. It's still useless.

In the present invention, an organic solvent or the like can be added as necessary for adjusting the viscosity. Examples of the organic solvent include acetone, methyl ethyl ketone, a ketone solvent such as cyclohexanone, methyl acetate, and the like. Ester solvents such as ethyl acetate, butyl acetate, ethyl lactate, methoxyethyl acetate, ether solvents such as diethyl ether, ethylene glycol dimethyl ether, dioxane, etc.
Aromatic solvents such as toluene and xylene, aliphatic solvents such as pentane and hexane, methylene chloride, chlorobenzene,
Examples thereof include halogen-based solvents such as chloroform, alcohol-based solvents such as isopropyl alcohol and butanol.

When used as a paint, a pigment, a filler, a leveling agent, a thermoplastic resin or the like is often added as an additive. Examples of the pigment include titanium white, cyanine blue, cream yellow, watching red, red iron oxide, carbon black and aniline black. Examples of the thermoplastic resin include cellulose acetate butyrate, nitrocellulose, vinyl chloride resin, vinyl acetate resin, acrylic resin and copolymers thereof, butylated melamine, butylated urea and the like. It is also possible to use it together with a wax type unsaturated polyester resin or the like. Examples of other additives include phosphoric acid, tartaric acid, phosphorous acid, fats and oils, silicone oil, surfactants and the like.

As a method for forming a coating film from the resin composition of the present invention, the coating film applied to the object to be coated is irradiated with active energy rays to be cured. As the energy rays, far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, X
In addition to electromagnetic waves such as rays and γ rays, electron rays, proton rays, neutron rays and the like can be used. However, coating film formation (curing)
The curing method by ultraviolet irradiation is advantageous in terms of speed, availability of the radiation irradiation device, price, and the like. The ultraviolet rays referred to in the present invention mainly include light in the wavelength range of 150 to 450 nm, and irradiation is performed using a chemical lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp or the like. Also,
As a coating method, a known method such as a curtain coater, a roll coater, a flow rotor, a spray or a dipping can be adopted. The thickness of the coating film cannot be generally determined depending on the object to be coated and the application, but is usually 5 to 20.
It can be suitably selected from the range of 0 μm.

Further, as the object to be coated, vinyl chloride resin,
It can be widely used from plastics such as polyethylene terephthalate (PET), polymethacrylate, polycarbonate, nylon (polyamide) to wood, metal plate, paper, concrete, among others, vinyl chloride resin, polyethylene terephthalate (PET) ,
In plastics such as polycarbonate and nylon, stain resistance, scratch resistance, which are the features of the present invention,
Flexibility, adhesion, etc. can be fully exhibited. The above-mentioned plastics coated with the resin composition of the present invention, wood, paper, metal plates, etc. are various building materials, furniture,
It is useful for printing paper, can products, household appliances, etc.

[0019]

[Operation] In the present invention, since a specific urethane acrylate component is used, the formed coating film is
It has excellent stain resistance, scratch resistance, flexibility, and adhesion.

[0020]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, “%” and “part” mean weight basis unless otherwise specified. Example 1 As a bisphenol type polyol (A1), "BPX-3
3 "(manufactured by Asahi Denka Co., Ltd., n = m = 3 propylene oxide-modified bisphenol A type diol) 1 mol, 2 mol of isophorone diisocyanate (IPDI) as polyisocyanate (A2), 2-hydroxyethyl acrylate (A3) After batch charging 2 mol into the toluene solvent,
As a catalyst, di-n-butyltin dilaurate (A1) ~ (A
Add 0.01 parts to 100 parts total of 3),
The reaction was carried out at 0 ° C for 10 hours to obtain a urethane acrylate component (A). Next, 75 parts of the obtained urethane acrylate component (A) was added to the ethylenically unsaturated monomer component (B).
As “AMP-60G” (manufactured by Shin-Nakamura Chemical Co., Ltd., n =
6 phenoxy polyethylene glycol acrylate)
25 parts, and 4 parts of "I-184" (1-hydroxycyclohexyl phenyl ketone manufactured by Ciba-Geigy) as a photopolymerization initiator were blended to obtain a resin composition of the present invention.

The resulting resin composition was examined for stain resistance, scratch resistance, flexibility (elongation) and adhesion according to the following procedures. (Stain resistance) White measuring paper with resin composition (manufactured by Taiyu Equipment Co., Ltd.)
5m / m after coating with 100μ applicator on top
A coating film was formed by passing under a mercury lamp of 80 W / cm at a line speed of in. Then, shoe paint is applied to the surface of the coating film in a circle with a diameter of 20 mm and a thickness of 2 mm and left for 24 hours, and then wiped with a cloth impregnated with methanol, and then with a cloth impregnated with petroleum. Finally, the shoe ink was wiped off with a waste cloth impregnated with benzine, and the application mark was measured with a Macbeth reflection densitometer, and the difference from the measured value of the coating surface on which the shoe ink was not applied was obtained.

(Scratch resistance) After coating the resin composition on a glass plate with a 100 μ applicator, 5 m / m
A coating film was formed by passing under a mercury lamp of 80 W / cm four times at a line speed of in. Then, the surface of the coating film was scratched with a nail and examined for the presence or absence of a nail mark generated on the surface.
The evaluation criteria are as follows. ○ --- No nail marks are observed. △ --- When you look closely, it is slight, but traces are observed. × −−− Clearly noticeable nail marks.

(Flexibility (elongation)) 5 m / m after coating the resin composition on a glass plate with a 100 μ applicator
After passing under a mercury lamp of 80 W / cm four times at a line speed of in to form a coating film, the coating film was stripped from the glass plate into strips (10 mm x 150 mm),
Autograph at ℃ and 65% RH (tensile speed 10mm / m
In), elongation at break (%) was measured. (Adhesiveness) After coating the resin composition on a vinyl chloride plate with a bar coater (# 20), a coating film was formed by passing it under a mercury lamp of 80 W / cm four times at a line speed of 5 m / min. After that, make 100 squares / cm ² squares on the coating film according to the JIS K 5400 cross-cut test at room temperature, apply cellophane tape from the top and roll it sufficiently, then peel off the cellophane tape at a stretch and peel it off with a vinyl chloride board. The number of squares remaining on the top was measured.

Examples 2 to 7 and Comparative Examples 1 to 3 Resin compositions were prepared in the same manner as in Example 1 according to the compounding compositions of (A) to (C) shown in Tables 1 and 2, and were prepared in the same manner as in Example 1. The stain resistance, scratch resistance, flexibility (elongation) and adhesion were examined. Table 3 shows the evaluation results of Examples and Comparative Examples.

[0025]

[Table 1] Blend composition of urethane acrylate component (A) Component ( A1) Component (A2) Component (A3) Component type Blending amount (mol) Type Blending amount (mol) Type Blending amount (mol) Example 1 BPX-33 1 IPDI 2 2HEA 2 〃 2 BPX-33 1 IPDI 3 2HEA 4 〃 3 BPE-100 1 TDI 5 2HEA 5 〃 4 BPE-100 1 TDI 7 2HPA 9 〃 5 BPX-55 2 H-MDI 11 2HPA 15 〃 6 BPX 55 4 H-MDI 19 2HEA 24 〃 7 BPX-55 1 XDI 11 2HEA 15 Comparative Example 1 T-650 1 IPDI 2 2HEA 2 〃 2 P-1000 1 IPDI 2 2HEA 2 〃 3 F7-68 1 IPDI 2 2HEA 2 Note ) In Examples 3 to 5, 1 mol of propylene oxide-modified polyol of glycerin (manufactured by Asahi Denka Co., Ltd., trade name: G-700) was used in combination as a polyol component. In Example 6, 2 mol of polyester triol (manufactured by Asahi Denka Co., Ltd., trade name: YT-650) was further used as a polyol component. In Example 7, a propylene oxide-modified polyol of glycerin (Asahi Denka Co., Ltd.) was used as a polyol component.
Made, product name: G-700) 1 mol and polytetramethylene diol (made by DuPont, product name: T-650) 1 mol together. The abbreviations are as follows.

BPX-33; manufactured by Asahi Denka Co., Ltd., trade name:
BPX-33, propylene oxide-modified bisphenol A-type diol with n = m = 3 BPE-100; Asahi Denka Co., Ltd., trade name: BPE-1
00, n = m = 3, propylene oxide-modified bisphenol A type diol BPX-55; Asahi Denka Co., Ltd., trade name: BPX-5
5, propylene oxide-modified bisphenol A-type polyol with n = m = 5 T-650; manufactured by DuPont Co., Ltd., trade name: T-65
0, polytetramethylene diol P-1000; Asahi Denka Co., Ltd., trade name: P-100
0, polypropylene glycol F7-68 having a molecular weight of 1000; manufactured by Asahi Denka Co., Ltd., trade name: F7-68, polyester diol IPDI; isophorone diisocyanate TDI; tolylene diisocyanate H-MDI; hydrogenated diphenylmethane diisocyanate XDI; xylylene di Isocyanate 2HEA; 2-hydroxyethyl acrylate 2HPA; 2-hydroxypropyl acrylate

[0027]

[Table 2] Component (A) Component (B) Component (C) Component Blending amount Types Blending amount Type Blending amount Example 1 75 AMP-60G 25 --- 〃 2 65 AMP-60G 35 PM-21 11〃 375 M -102 25 --- 〃 4 75 DPM-A 24 PM-21 1〃 5 75 ME-3 24 PM-21 1〃 6 75 M-120 24 PM -21 1〃 7 75 AMP-60G 24 PM-21 Comparison Example 1 75 AMP-60G 25 --- 〃 2 75 AMP-60G 25 --- 〃 3 75 AMP-60G 25 ---

Note) The abbreviations are as follows. AMP-60G; Shin-Nakamura Chemical Co., Ltd., trade name: AMP
-60G, n = 6 phenoxy polyethylene glycol acrylate M-102; manufactured by Toagosei Co., Ltd., trade name: M-102,
N = 4 phenoxy polyethylene glycol acrylate DPM-A; manufactured by Kyoeisha Chemical Co., Ltd., trade name: DPM-
A, methoxytripropylene glycol acrylate ME-3; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: PE-3,
Methoxytriethylene glycol acrylate M-120; manufactured by Toagosei Co., Ltd., trade name: M-120,
2-Ethylhexyl carbitol acrylate PM-2; manufactured by Nippon Kayaku Co., Ltd., trade name: Kayamer PM-
2. Phosphorus-containing ethylene oxide-modified dimethacrylate represented by the above chemical formula 3

[0029]

[Table 3] Stain resistance Scratch resistance Flexibility (elongation) Adhesion Example 1 0.01 ○ 60% 96/100 〃 2 0.01 ○ 54% 95/100 〃 3 0.03 ○ 50% 92 / 100 〃 4 0.01 ○ 55% 96/100 〃 5 0.02 ○ 65% 99/100 〃 6 0.02 ○ 65% 98/100 〃 7 0.03 ○ 63% 96/100 Comparative Example 10 .28 △ 55% 92/100 〃 2 0.15 △ 50% 90/100 〃 3 0.18 × 65% 94/100 Note) Adhesion is (the number of coating squares remaining on the vinyl chloride plate) / ( Represents the total number of squares.

[0030]

In the present invention, since the specific urethane acrylate component is used, the formed coating film is excellent in stain resistance, scratch resistance, flexibility and adhesion.

Claims (5)

[Claims] 1. A urethane acrylate component (A) obtained by reacting a bisphenol type polyol (A1) represented by the following chemical formula 1, a polyisocyanate (A2) and a hydroxyl group-containing acrylate (A3), and an ethylenically unsaturated monomer component. An active energy ray-curable resin composition comprising (B) and a photopolymerization initiator. Embedded image (However, R ₁ O and R ₂ O are alkylene oxides having 2 to 4 carbon atoms, R ₃ and R ₄ are hydrogen or a methyl group, and n and m are integers and represent n + m = 1 to 20, respectively.) 2. The active energy ray-curable resin composition according to claim 1, wherein the ethylenically unsaturated monomer component (B) is an acrylic monomer represented by the following chemical formula 2. Embedded image (However, R ₁ is hydrogen or a methyl group, and R ₂ has ₂ to 4 carbon atoms.
Alkylene group, R ₃ is a phenyl group or an alkyl group, n
Each represents an integer of 1 to 10) 3. A blending weight ratio (A) of the urethane acrylate component (A) and the ethylenically unsaturated monomer component (B).
/ (B) is 90/10 to 30/70, The active energy ray-curable resin composition according to claim 1 or 2, wherein 4. The active energy ray-curable resin composition according to claim 1, further comprising a phosphorus compound (C). 5. The active energy ray-curable resin composition according to claim 4, wherein the compounding amount of the phosphorus compound (C) in the total amount of (A) to (C) is 2% by weight or less. .