JPS61171721A - Laminate - Google Patents

Abstract

PURPOSE:To obtain a laminate with good embossing processability, by curing following coating, on a flexible base, a composition comprising epoxy compound, carboxyl group-contg. photopolymerizable compound, specific (meth)acrylate and a second photopolymerizable compound in specific proportion. CONSTITUTION:The objective laminate can be obtained by curing following coating, on a flexible base such as plastic film, a curing-type resin composition prepared by blending (A) an epoxy compound having in one molecule at least two epoxy groups (perf. bisphenol A diglycidyl ether), (B) a photopolymerizable compound having in one molecule COOH [e.g., (meth)acrylic acid], (C) a (meth) acrylate from alkylene oxide adduct of either polyalkylene glycol or polyhydric alcohol, and (D) a second photopolymerizable compound in such weight ratios as to be 10/90-90/10, 10/100-80/100 and 10/90-90/10 for A/(B+C+D), B/(B+C+D) and C/(C+D), respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a laminate with excellent embossing properties. More specifically, it relates to a laminate using a curable coating resin composition that is cured by actinic light such as ultraviolet rays and then completely cured by heating, and which is used for emblems, switches, etc. .

<Relationship with prior art> Conventionally, UV-curable resin compositions for coating have generally been compositions containing unsaturated polyester resins, pigments, fillers, etc. It is used as a processing composition. but,
This composition causes cracking and poor adhesion of one coat during embossing, and does not have sufficient performance as an embossing composition.

In addition, typical thermosetting coating resin compositions include solvent-based coating resin compositions using epoxy resins, but although they have excellent adhesion, they also lack sufficient embossability. The major disadvantages of this method include a poor working environment, a short pot life, and a high tendency for screen printing to jam.

Further, these coating resin compositions are required to have sufficient adhesion to the conductive paste on which a conductive paste is printed in some cases. However, conventional compositions do not have sufficient adhesion.

<Object of the Invention> The main object of the present invention is to provide a curable coating resin composition useful as a coating resin composition for embossing.

A further object of the present invention is to screen print a curable coating resin composition onto a flexible substrate and cure it to provide a laminate that has excellent embossing properties, easy payability, and adhesion. be.

<Structure of the Invention> The present inventors have solved the defects of the conventional curable coating resin compositions by blending acrylate and/or methacrylate, which is an alkylene oxide adduct of the conventional curable coating resin. We have found that this can be solved and have arrived at the present invention.

That is, the present invention is a laminate obtained by coating a flexible substrate with the coating resin composition described below and curing it.

(4) Epoxy compound having two or more epoxy groups in the molecule (B) Photopolymerizable compound having carboxyl group in the molecule (C) Acrylate and/or alkylene oxide adduct of polyalkylene glycol or polyhydric alcohol methacrylate CD) A curable resin composition containing other photopolymerizable compounds in the following proportions.

GA) / C(Bj+(c)+(D)) = 10
/90~90/10 (coulometric ratio) A (B) /
((B) + (Cri + (DJ) = 10/100~8
0/100 (u)(c)/((c) + (D)
] = 10/90 to 90/10 (n) Epoxy compound having two or more epoxy groups in the molecule used in the present invention) is an epoxy compound having two or more epoxy groups in one molecule. , its epoxy equivalent is 10
0 to 4,000, preferably 100 to 1,000.

Typical fishing force compounds include bisphenol type epoxy resins, which are diglycidyl ethers such as bisphenol A, bisphenol F, and halogenated bisphenol A, and novolac epoxy resins, which are diglycidyl ethers such as phenol novolak and cresol novolac2. Polyglycidyl ethers of polyhydric phenols with a valence of 2 or more, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, etc. Polyglycidyl ethers, phthalic acid, isophthalic acid, tetrahydro-7
Polyglycidyl esters of divalent or higher polyhydric carboxylic acids such as talic acid, hexahydrophthalic acid, and adipic acid;
Polyglycidyl ethers such as aniline and incyanuric acid in which the active hydrogen bonded to the nitrogen atom is replaced with a glycidyl group, vinylcyclohexene dieboxide obtained by epoxidizing the olefin bond in the molecule, 3.4-epoxycyclohexylmethyl-3 , 4-Ephoxycyclohexanecarboxylate, alicyclic polyepoxy compounds such as 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, N,N , N'.

N'-tetraglycidyl metaxylene diamine, N.

N,N',N'-tetraglycidyl-1,3-bis(
Examples include aminopolyepoxy compounds such as aminomethyl) cyclohexane. These epoxy compounds can be used alone or in combination of two or more.

Further, epoxy compounds having one epoxy group in the molecule such as allyl glycidyl ether and phenyl glycidyl ether can also be used in combination.

Among these epoxy compounds having at least two epoxy groups in the molecule, preferred epoxy compounds include:
Examples include diglycidyl ether of bisphenol A, phenol novolak type polyepoxy compounds, and cresol novolak type polyepoxy compounds.

Examples of the photopolymerizable compound (B) having a carboxyl group in the molecule used in the present invention include (1) unsaturated carboxylic acid compounds such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, and fumaric acid; (11) There are compounds represented by the following general formula (I).

(OH2: O-coo square + R2 → A(-R, ++ coo
H)n...(I) (wherein, R1 represents hydrogen or a methyl group, R2 and R5 each represent an aliphatic, aromatic, or alicyclic residue, and A represents an ester bond. In the general formula (I), R2 is a divalent to tetravalent hydrocarbon group having 2 to 10 carbon atoms or a hydroxyl group-containing hydrocarbon group. It is preferable that R3 has 2 to 1 carbon atoms.
0 divalent to 4 aliphatic polysalt lfi, a residue, 2 to 4 valent aromatic polybasic acid residue having 6 to 15 carbon atoms, or 2 to 4 having 6 to 10 carbon atoms It is preferable that it is a valent alicyclic polybasic acid residue.

Examples of the compound represented by the general formula (I) include the following compounds.

Examples of the compound where m=1 and n=1 include succinic acid mono(meth)acryloyloxyethyl ester (acryloyloxyethyl ester and methacryloyloxyethyl ester).

The rest will be abbreviated in the same way. ), phthalic acid mono(meth)acryloyloxyethyl ester, maleic acid mono(meth)
Acryloyloxyethyl ester, tetrahydrophthalic acid mono(meth)acryloyloxyethyl ester, hexahydroheptalic acid mono(meth)acryloyloxyethyl ester, poly/dobicyclo(2.2.1)
-5-hebutene-2,3-dicarboxylic acid mono(meth)acryloyloxyethyl ester, tetrahydrophthalic acid mono-2-(meth)acryloyloxy-1-(phenoxymethyl)ethyl ester, 7-talic acid mono-2 −
Examples include hydroxy 7-3-(meth)acryloyloxypropyl ester and succinic acid mono-2-hydroxy-3-(meth)acryloyloxypropyl ester.

Examples of the compound where m=l and m=z include trimellitic acid mono-2-(meth)acryloyloxyethyl ester.

Examples of the compound where m=1 and n:3 include pyromellitic acid mono-2-(meth)acryloyloxyethyl ester.

Examples of compounds where m=2 and n=1 include heptalic acid mono-[2,3-bis(meth)acryloyloxyisoglobil] ester, methyltetrahydrophthalic acid mono-[2,3-bis( meth)acryloyloxyisoglobil] ester, tetrahydrophthalic acid heptano(2,
Examples thereof include 3-bis(meth)acryloyloxyisopropyl] ester and succinic acid mono-[2,3-bis(meth)acryloyloxyisopropyl]ester.

Examples of compounds where m=2 and n=2 include trimellitic acid mono-[4,5-bis(meth)acryloyloxyneopentyl] ester, trimellitic acid mono-[3,
Examples include 4-bis(methaneacryloyloxyisobutyl) ester.

Examples of the compound where m=3 and n=2 include trimellitic acid mono-[: 3,4.5-tris(meth)acryloyloxyneopentyl] ester.

An example of the compound where m=3 and n=3 is pyromellitic acid mono-(3+4,5 tris(meth)acryloyloxyneopentyl) ester.

Among the above-mentioned compounds, as the photopolymerizable compound (B),
Particularly preferred is (11). These photopolymerizable compounds (B) having a carboxyl group in the molecule may be used alone or in combination of two or more.

The photopolymerizable compound (Bl) containing a carboxyl group in the molecule in the photopolymerizable compound (B+C!+D) used in the present invention is 10 to 80% by weight. When the amount is less than 1, the curability of the resin composition obtained is significantly inferior.

In the present invention, polyalkylene glycol or poly(C)
Examples of compounds having one photopolymerizable double bond in the molecule include (1) polyoxyalkylene glycol mono(meth)acrylate such as polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate; Acyl mono(meth)acrylates, mono(meth)acrylates of alkylene oxide adducts of bisphenol A such as (I) ethylene oxide and propylene oxide adducts of bisphenol A, ethylene oxide and propylene oxide adducts of hydrogenated bisphenol A, etc. mono(meth) alkylene oxide adduct of hydrogenated bisphenol A
There are acrylates, etc.

Examples of compounds having two photopolymerizable double bonds in the molecule include (1) diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, diglobylene glycol di(meth)acrylate, and polyalcohol di(meth)acrylate. Ren glycol di(meth)acrylate,
Polyoxyalkylene glycol di(meth)acrylates such as polyalkylene glycol di(meth)acrylate, di(meth)acrylates of alkylene oxide adducts of bisphenol A such as ethylene oxide and propylene oxide adducts of (II> bisphenol A) , di(meth)acrylates of alkylene oxide adducts of hydrogenated bisphenol A, such as ethylene oxide and propylene oxide adducts of hydrogenated bisphenol A, and the like.

Examples of the 11 compounds having three or more photopolymerizable double bonds in the molecule include (1) alkylene oxide addition of three or more aliphatic polyhydric alcohols such as glycerin, pentaerythritol, arabitol, and tol; These include poly(meth)acrylates, which are poly(meth)acrylates, and poly(meth)acrylates, which are alkylene oxide adducts of trivalent or higher halogen-substituted aliphatic polyhydric alcohols.

Acrylate (addition model of C-alkylene oxide).

Other photopolymerizable compounds Φ) used in the present invention are photopolymerizable compounds having one or more photopolymerizable double bonds in the molecule, and include the following compounds.

Examples of photopolymerizable compounds having one photopolymerizable double bond in the molecule include (1) styrene compounds such as styrene, α-methylstyrene, and chlorostyrene; (I) methyl (meth) ) Acrylate, ethyl (meth)
Acrylate, n- and 1-propyl (meth)acrylate, n-,880- and t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
Alkyl (meth)acrylates such as lauryl (meth)acrylate and stearyl (meth)acrylate, methoxyether (meth)acrylate, and ethoxyether (
Alkoxyalkyl (meth)acrylates such as meth)acrylate, butoxyethyl (meth)acrylate, hydroxyalkyl(meth)acrylate such as allyloxyalkyl(meth)acrylate-ILz-hydroxyethyl(meth)acrylate, etc. ) acrylates, halogen-substituted alkyl (meth)acrylates, heterocycle-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate,
(I) A terminal inocyanate group-containing compound obtained by reacting a diisocyanate compound and one or more alcoholic hydroxyl group-containing compounds in advance is further reacted with an alcoholic hydroxyl group-containing (meth)acrylate; urethane-modified mono(meth)acrylates having one or more (meth)acryloyloxy groups, V) Epoxy mono(meth)acrylates obtained by reacting a compound having one or more epoxy groups in the molecule with acrylic acid or methacrylic acid. ) acrylates, and (7) oligoester mono(meth)acrylates obtained by reacting acrylic acid or methacrylic acid and polycarboxylic acids as carboxylic acid components with polyhydric alcohols of dihydrity or more as alcohol components, etc. be.

Examples of photopolymerizable compounds having two photopolymerizable double bonds in the molecule include (1) ethylene glycol di(
meth)acrylate, propylene glycol di(meth)
Alkylene glycol di(meth)acrylates such as acrylate, di(meth)acrylates of bisphenol A such as (phantom bis(acryloxyethoxy)bisphenol A1 bisnol A1 bis(acryloxypoly+toxy)bisphenol A, I) A terminal inocyanate group-containing compound obtained by reacting a diisocyanate compound and two or more alcoholic hydroxyl group-containing compounds in advance, and further reacting an alcoholic hydroxyl group-containing (meth)acrylate, resulting in two groups in the molecule. Urethane-modified di(meth)acrylates having a (meth)acryloyloxy group, Ov) Evoxy di(meth) obtained by reacting a compound having two or more epoxy groups in the molecule with acrylic acid or/and methacrylic acid. (7) Oligoester di(meth)acrylates obtained by reacting acrylic acid or methacrylic acid as a carboxylic acid component and a polyhydric carboxylic acid with a polyhydric alcohol having a valence of 2 or more as an alcohol component.

Examples of photopolymerizable compounds having three or more photopolymerizable double bonds in the molecule include (1) trimesololethane tri(meth)acrylate, trimesololethane tri(meth)acrylate, p-meth Erythritol tetra(meth)acrylate'"50'□Mu"077 group poly17'"-"17) M! J i.

(meth)acrylates, poly(meth)acrylates of trivalent or higher halogen-substituted aliphatic polyhydric alcohols, (I
) A terminal isocyanate group-containing compound obtained by reacting a diisocyanate compound and a compound containing three or more alcoholic hydroxyl groups in advance, is further reacted with an alcoholic hydroxyl group-containing (meth)acrylate.
Urethane-modified poly(meth)acrylates having 3 or more (meth)acryloyloxy groups, (1) 3 or more in the molecule
Examples include epoxy poly(meth)acrylates obtained by reacting a compound having 1 or more epoxy groups with acrylic acid and/or methacrylic acid.

Epoxy compound (4) used in the present invention, photopolymerizable compound (B) having a carboxyl group in the molecule, and acrylate or/and methacrylate (C) of alkylene oxide adduct of polyalkylene glycol or polyhydric alcohol. and other photopolymerizable compounds (D)
The blending ratio of the mixture is: epoxy compound (A); photopolymerizable metal ((B) + (C) + (D)) = lO:
It is in the range of 90 to 9o:1o (weight ratio), preferably in the range of 20:80 to 80:20 (weight ratio).Also, other photopolymerizable compound (D) and polyalkylene glycol or polyhydric The mixing ratio of acrylate or/and methacrylate (C) of alkylene oxide adduct of alcohol is (c):(D)=1010 to 90:10
(weight ratio: 7), preferably 20:80 to 8
The range is 0:20.

If the amount of the epoxy compound (4) is less than 10% by weight,
Photopolymerizable compound (B) having a carboxyl group in the molecule
The reaction with the epoxy compound (4) is substantially too small, making it difficult to obtain a cured product with excellent adhesion.
If it exceeds 0% by weight, the viscosity of the curable resin composition becomes high, making it difficult to handle and failing to take advantage of the advantage of curing reaction with one actinic ray, that is, rapid curing.

If the amount of (C) in the total of other photopolymerizable compounds (D) and acrylate or/and methacrylate (C) of alkylene oxide adducts of polyalkylene glycol or polyhydric alcohol is less than 10% by weight, embossing is difficult. In this case, cracking of the coating film occurs, and the acrylate of the photopolymerizable compound (D) and the fullylene oxide adduct of polyalkylene glycol or polyhydric alcohol is ( If the amount of C) exceeds 90% by weight, the curability will be poor and the durability will not be sufficient.

In the present invention, a photoinitiator is generally used in combination. The photoinitiator is a compound that promotes the photopolymerization reaction of a photopolymerizable compound, such as ketals such as benzyl dimethyl ketal, benzoin methyl ether, benzoin ethyl ether, pentuin-1-propyl ether,
Benzoins such as benzoin and α-methylbenzoin, anthraquinones such as 9.10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, and 2-ethelanthraquinone, benzophenone, p-chlorobenzophenone, p-dimethylaminobenzophenone, etc. Benzophenones, propiophenones such as 2-hydroxy-2-methylpropiophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropiophenone, suberones such as cypenzosuberone, diphenyl disulfide, tetra Examples include sulfur-containing compounds such as methylthiuram disulfide and thioxanthone, and pigments such as methylene blue, eosin, and fluorescein, which may be used alone or in combination of two or more.

In the present invention, the blending amount of this photoinitiator is the epoxy compound (4) and the photopolymerizable compound C (B) + (Cri +
The amount is from 0.05 to 201 parts, preferably from 0.5 to 10 parts by weight, based on the total amount of the rice cakes (CD) and (CD).

In the present invention, when it is necessary to promote the reaction between an epoxy group and a carboxyl group, it is effective to add a reaction promoter. Examples of the reaction accelerator include 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-lanticylimidazole, 2-heptadecylimidazole, 1-vinyl- 2-methylimidazole, l-
Benzyl-2-methylimidazole, 2-phenyl
Hayashimitasole, 1-vinyl-2-ethylimidazole, imidazole, 2-phenyl-4-methylimidazole, 1-vinyl-2,4-dimethylimidazole, 1
-Imidazoles such as vinyl-2-ethyl-4-methylimidazole, benzyldimethylamine, 2,4.6
-) Lydimethylaminephenol, triethanolamine, triethylamine, N,N'-dimethylpiperidine, a-methylbenzyldimethylamine, N-methylmorpholine, N,N-dimethylaminoethanol, N
, N-diethylaminoethanol, N,N-dipropylaminoethanol, tertiary amines such as dimethylaminomethylphenol, tertiary amine salts such as triacetate and tribenzoate of tridimethylaminomethylphenol, etc., alone. or in combination of two or more.

In the present invention, the amount of these reaction accelerators added is 0.05 to 5% by weight based on the total amount of the epoxy compound (Al and photopolymerizable compound [(g)) + (C + φ)].
Preferably it is 0.1 to 3.5% by weight.

The curable coating resin composition of the present invention contains, in addition to the above-mentioned additives, 1
Various additives and compounding agents such as known fillers, colorants, surface smoothing agents, and antifoaming agents can be added as necessary.

Flexible substrates used in the present invention include polyethylene terephthalate, polyimide, polyamide, or copolymers thereof, synthetic resin films such as epoxy resin, and fiber-reinforced resin boards such as glass fiber-reinforced epoxy resin boards. The thickness is approximately lO-200μ.

The laminate of the present invention is obtained by coating a curable coating resin composition on a flexible substrate and curing it.

The method for curing the curable coating resin composition of the present invention is to first prepare a mixture of a photopolymerizable compound (B) having a carboxyl group and another photopolymerizable compound ((C) + (D)) by irradiation with actinic rays. Polymerize to form a carboxyl group-containing polymer, and then heat to react the jepoxy compound object) with the carboxyl group contained in the polymer to completely cure it.
Consists of stages. The photopolymerization reaction conditions include a light amount of 20 f
Time 0.1 at W/cIN~200 rW/crA
Preferably, the time is from seconds to 15 minutes. The thermosetting reaction conditions are as follows:
The time is preferably 10 seconds to 120 minutes at a temperature of 40°C to 250°C.

As active light, ultraviolet rays, electron beams, etc. are used. As a light source used for ultraviolet irradiation, sunlight, a chemical lamp, a low pressure mercury lamp, a pressure mercury lamp, a metahalide lamp, a xenon lamp, etc. are used.

As the heat source used for heating, for example, known heating methods such as an infrared heater, hot air heating, and high frequency heating plate are used.

The curing reaction of the curable coating resin composition used in the present invention is essentially different from that of conventional ultraviolet curable coating resin compositions or thermosetting coating resin compositions. A coating film with excellent embossing properties and good payability can be obtained.

Therefore, the laminate of the present invention can be used as a membrane switch. That is, a membrane switch can be obtained by coating a flexible substrate with a curable resin composition containing pigments such as coloring ink and curing it, then applying a conductive paste and performing embossing. can.

Taking advantage of these advantages, the curable coating resin composition of the present invention with excellent embossing properties can be used in fields such as sealing, paint, ink, and adhesive applications in addition to embossing. It is.

(Examples) Hereinafter, examples will be given to specifically explain the present invention, but the present invention is not limited to these examples at all. In the examples, parts and parts by weight indicate parts by weight, respectively.

Performance measurements in Examples and Comparative Examples were performed according to the following method.

<Adhesion> Cured film cross-cut cellophane tape peel test (J Engineering S DO202) K was followed.

<Embossability> The cured film was heated to 120℃ using a "Devon impact tester"
During use, the coating was embossed by being dropped from a distance of 25 clI under a load of 300 liters, and the presence or absence of cracks in the coating film was measured by visual inspection and using a universal projector. ! 1° Penetration hiding property> The hiding property of the cured film was visually judged.

Example 1 Epicote 1, a bisphenol A type epoxy compound
A resin composition (α) consisting of 50 parts of 001 (manufactured by Yuka Shell Epoxy Co., Ltd.), 24 parts of succinic acid monoacryloyloxyethyl ester, and 26 parts of tetrahydrofurfuryl acrylate, and 20 parts of polyethylene glycol #600 diacrylate were placed in a container. The mixture was mixed and stirred at room temperature to obtain a transparent resin composition (1).

90 parts of the resulting resin composition (1) were blended with 5 parts of benzyl dimethyl ketal, 2 parts of N,N-diethylamine ethanol, 3 parts of a surface smoothing agent, and 10 parts of a toning pigment, and after mixing and stirring, the mixture was uniformly mixed with three rolls. and kneaded to obtain a curable coating resin composition <Al of the present invention.

The obtained curable resin composition (A) was printed on a corona-treated 125 μm thick polyethylene terephthalate film using a 300 mesh polyester screen plate, and heated under a 5.6Ql water-cooled high-pressure mercury lamp under a 15C1l+
It was cured at a distance of 770 mJ/cd with an integrated light intensity of 770 mJ/cd.

The performance was then measured after heating at 120° C. for 30 minutes.

Adhesion: 100/100 Embossability: No cracking Concealability: Good Example 2 The resin composition (α) of Example 1 and 20 parts of polypropylene glycol #400 diacrylate were placed in a container and mixed at room temperature. The mixture was stirred to obtain transparent resin composition eyelids (2). 90 parts of the resulting resin composition (2) were blended with 5 parts of benzyl dimethyl ketal, 2 parts of N,N-diethylaminoethanol, 3 parts of a surface smoothing agent, and 10 parts of a toning pigment, and after mixing and stirring, the mixture was mixed with three rolls. The mixture was uniformly kneaded to obtain a curable coating resin composition (Bl) of the present invention.

Next, it was printed and cured in exactly the same manner as in Example 1, and its performance was measured.

Closeness: 100/Zo.

Embossability: No cracking Concealability: Good Example 3 The resin composition (α) of Example 1 and 20 parts of polyethylene glycol #+200 diacrylate were placed in a container, mixed and stirred at room temperature, and then made transparent. A resin composition (3) was obtained. The obtained resin composition (3190 parts) was blended with 5 parts of benzyl dimethyl ketal, 2 parts of N,N-diethylaminoethanol, 3 parts of a surface smoothing agent, and 10 parts of a toning pigment. After mixing and stirring, the mixture was uniformly mixed with a three-roll roll. The mixture was kneaded to obtain a curable coating resin composition (C) of the present invention.

Next, it was printed and cured in exactly the same manner as in Example 1, and its performance was measured.

Adhesion: Zoo/100 Embossability: No cracking Concealability: Good Example 4 Di(meth)acrylate of the resin composition (α) of Example 1 and the adduct of 2 moles of propylene oxide of bisphenol A −
) were placed in a container and mixed and stirred at room temperature to obtain a resin composition (4). 90 parts of the obtained resin composition (4) were mixed with 5 parts of benzyl dimethyl ketal, 2 parts of N,N-diethylaminoethanol, 3 parts of a surface smoothing agent, and 10 parts of a toning pigment, and after mixing and stirring, the mixture was mixed with three rolls. The wires were mixed uniformly, and a curable coating resin composition of the present invention was obtained.

Next, it was printed and cured in exactly the same manner as in Example 1, and its performance was measured.

Adhesion: 100/100 Embossability: No cracking Concealability: Good Comparative Example 1 The resin composition (α) of Example 1 contains benzyl dimethyl ketal 11, 2 parts NlN-diethylaminoethanol, and a surface smoothing agent. 3 parts and 10 parts of toning pigment were blended and mixed to obtain a resin composition (Gin).Then, it was printed, cured, and its performance was measured.

Adhesion: 100/100 Embossability: Cracks concealment: Good Comparative Example 21 20 parts of bis(acryloxyethoxy)bisphenol A was added to the resin composition (α) of Example 1, mixed, and the resin composition was prepared. A powder was obtained. 9 parts of the resulting resin composition ((a) were mixed with 5 parts of benzyl dimethyl ketal, 2 parts of 12.N-diethylamine ethanol, 3 parts of a surface smoothing agent, and 10 parts of a toning pigment. Then, it was printed, cured, and its performance was measured.

Density: 70/Zo.

Embossability: Crack occurrence Hiddenness: Defective Comparative Example 3 20 parts of trimethylolpropane triacrylate was added to the resin composition (α) of Example 1, and the resin composition (3'
) was obtained. The obtained resin composition (3') 5 parts of K-benzyl dimethyl ketal, 2 parts of N,N-diethylaminoethanol, 3 parts of a surface smoothing agent, and 10 parts of a toning pigment were mixed, printed, and cured to test its performance. It was measured.

Adhesion: 50/100 Embossability: Frequent cracking Concealability: Defective Examples 1 to 4 and Comparative Examples 1 to 3 are summarized in Table 1 K.

Claims (1)

[Scope of Claims] A laminate obtained by coating a flexible substrate with the following curable coating resin composition and curing it. (A) Epoxy compound having two or more epoxy groups in the molecule (B) Photopolymerizable compound having carboxyl group in the molecule (C) Acrylate and/or alkylene oxide adduct of polyalkylene glycol or polyhydric alcohol
Alternatively, a curable resin composition containing methacrylate (D) and other photopolymerizable compounds in the following proportions. (A)/[(B)+(C)+(D)]=10/90~9
0/10 (weight ratio) (B)/[(B)+(C)+(D)]=10/100~
80/100(〃) (C)/[(C)+(D)]=10/90~90/10
(〃)