JPH0533252B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a laminate with excellent embossing properties. More specifically, the present invention 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 made by blending pigments, fillers, etc. with unsaturated polyester resins, and have been used for embossing of flexible substrates such as plastic films. It is used as a composition for However, this composition causes cracking of the coating film and poor adhesion during embossing, and does not have sufficient performance as an embossing composition. In addition, a typical thermosetting coating resin composition is a solvent-based coating resin composition using epoxy resin, but although it has excellent adhesion, it also lacks sufficient embossability. The major drawbacks include a poor working environment, a short pot life, and a tendency for plate jams to occur during screen printing. 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> A flexible substrate made of a synthetic resin film is coated with the following curable coating resin composition, and then the curable coating resin composition is screened onto a flexible substrate for embossing. The object of the present invention is to provide a laminate which is printed and cured and has excellent embossing properties, and also has excellent easy-to-print properties and adhesion properties. <Structure of the Invention> As a result of extensive research in order to solve the defects of the conventional curable coating resin compositions described above, the present inventors have found that polyalkylene glycol or polyhydric alcohol is added to a part of the photopolymerizable compound. The present inventors have discovered that the deficiencies of conventional curable coating resin compositions can be solved by incorporating acrylate and/or methacrylate, which are alkylene oxide adducts. That is, the present invention is 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 A curable resin composition containing methacrylate (D) and other photopolymerizable compounds in the following proportions. (A)/[(B)+(C)+(D)]=10/90~90/10 (weight ratio) (B)/[(B)+(C)+(D)]=10/100 ~80/100( 〃
) (C)/[(C)+(D)]=10/90 to 90/10(〃) The epoxy compound (A) having two or more epoxy groups in the molecule used in the present invention is 1 It is an epoxy compound having two or more epoxy groups in the molecule, and its epoxy equivalent is 100 to 4000, preferably
It is 100-1000. Representative compounds include bisphenol A,
Bisphenol F, halogenated bisphenol A
Representative examples include bisphenol type epoxy resins which are diglycidyl ethers such as 2 and novolac type epoxy resins which are polyglycidyl ethers such as phenol novolak and cresol novolak.
Polyglycidyl ethers of polyhydric phenols with a valence of more than 2, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and other polyhydric alcohols with a valence of 2 or more. Bonded to the nitrogen atom of polyglycidyl ethers of phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, polyglycidyl esters of divalent or higher polyvalent carboxylic acids such as adipic acid, aniline, isocyanuric acid, etc. polyglycidyl ethers in which active hydrogen is substituted with a glycidyl group, vinylcyclohexene diepoxide obtained by epoxidizing the olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-
3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-
Alicyclic polyepoxy compounds such as 5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, N,N,N',N'-tetraglycidylmethaxylene diamine, N,N,N', Examples include aminopolyepoxy compounds such as N'-tetraglycidyl-1,3-bis(aminomethyl)cyclohexane. These epoxy compounds can be used alone or in combination of two or more. In addition, one epoxy group is added in the molecule of allyl glycidyl ether, phenyl glycidyl ether, etc.
It can also be used in combination with its own epoxy compounds. Among these epoxy compounds having at least two epoxy groups in the molecule, preferred epoxy compounds include diglycidyl ether of bisphenol A, phenol novolak type polyepoxy compounds, and cresol novolak type polyepoxy compounds. can give. The photopolymerizable compound (B) having a carboxyl group in the molecule used in the present invention is a compound represented by the following general formula (). (In the formula, R ₁ represents hydrogen or a methyl group, R ₂ and R ₃ each represent an aliphatic, aromatic, or alicyclic residue, A represents an ester bond, and m and n each represent 1 to 1. Indicates a positive integer of 3.) In the general formula (), R ₂ has 2 to 2 carbon atoms.
10 or a hydroxyl group-containing hydrocarbon group, R ₃
is a di- to tetravalent aliphatic polybasic acid residue having 2 to 10 carbon atoms, a di- to tetravalent aromatic polybasic acid residue having 6 to 15 carbon atoms, or a residue having 6 to 10 carbon atoms. Preferably, it is a certain di- to tetravalent alicyclic polybasic acid residue. Examples of the compound represented by the general formula () 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, hexahydrophthalic acid mono(meth)acryloyloxyethyl ester, endo-bicyclo(2.2.1)-5-heptene-2,3-dicarboxylic acid mono(meth) ) Acryloyloxyethyl ester, mono-2-(meth)acryloyloxy-tetrahydrophthalate
1-(phenoxymethyl)ethyl ester, phthalic acid mono-2-hydroxy-3-(meth)acryloyloxypropyl ester, succinic acid mono-
Examples include 2-hydroxy-3-(meth)acryloyloxypropyl ester. Examples of the compound where m=1 and n=2 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 the compound where m=2 and n=1 include phthalic acid mono-[2,3-bis(meth)acryloyloxyisopropyl] ester, methyltetrahydrophthalic acid mono-[2,3-bis(meth)
Examples include acryloyloxyisopropyl] ester, tetrahydrophthalic acid mono-[2,3-bis(meth)acryloyloxyisopropyl] ester, and succinic acid mono-[2,3-bis(meth)acryloyloxyisopropyl] ester. Examples of the compound where m=2 and n=2 include trimellitic acid mono-[4,5-bis(meth)acryloyloxyneopentyl] ester, trimellitic acid mono-[3,4-bis(meth)acryloyloxyisobutyl] ] Esters, etc. Examples of compounds where m=3 and n=2 include trimellitic acid mono-[3,4,5-tris(meth)
Examples include acryloyloxyneopentyl ester. Examples of compounds where m=3 and n=3 include pyromellitic acid mono-[3,4,5-tris(meth)
Examples include acryloyloxyneopentyl ester. These photopolymerizable compounds (B) having a carboxyl group in the molecule may be used alone or in combination of two or more. Photopolymerizable compound used in the present invention (B+C+
The amount of the photopolymerizable compound (B) containing a carboxyl group in the molecule in D) is 10 to 80% by weight. If the amount is less than 10% by weight, the curability of the resulting resin composition will be significantly poor. In the present invention, acrylate and/or methacrylate (C), which is an alkylene oxide adduct of polyalkylene glycol or polyhydric alcohol, is essential. Among these acrylates and/or methacrylates (C), compounds having one photopolymerizable double bond in the molecule include, for example, ()
Polyoxyalkylene glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, or substituted alkyl mono(meth)acrylates such as alkoxypolyoxyalkylene glycol mono(meth)acrylate, ( ) Mono(meth)acrylates of alkylene oxide adducts of bisphenol A, such as ethylene oxide and propylene oxide adducts of bisphenol A; hydrogenated bisphenol A, such as ethylene oxide and propylene oxide adducts of hydrogenated bisphenol A; These include mono(meth)acrylates of alkylene oxide adducts. Examples of compounds having two photopolymerizable double bonds in the molecule include () diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate. Polyoxyalkylene glycol di(meth)acrylates such as meth)acrylate and polypropylene glycol di(meth)acrylate; di()alkylene oxide adducts of bisphenol A such as ethylene oxide and propylene oxide adducts of bisphenol A; Examples include meth)acrylates, 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 compounds having three or more photopolymerizable double bonds in the molecule include poly(), which is an alkylene oxide adduct of three or more aliphatic polyhydric alcohols such as ()glycerin, pentaerythritol, arabitol, and sorbitol; Examples include meth)acrylates and poly(meth)acrylates which are alkylene oxide adducts of trivalent or higher halogen-substituted aliphatic polyhydric alcohols. The number of moles of alkylene oxide added to the acrylate or/and methacrylate (C) of the alkylene oxide adduct of polyhydric alcohol used in the present invention is from 1 to 18, preferably from 3 to 14. and methacrylates. Other photopolymerizable compounds (D) 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 styrene compounds such as ()styrene, α-methylstyrene, and chlorostyrene, ()methyl (meth)acrylate, Ethyl (meth)acrylate, n- and i-propyl (meth)acrylate, n-,
sec- and t-butyl (meth)acrylate,
2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)
Alkyl (meth)acrylates such as acrylate, alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, allyloxyalkyl such as phenoxyethyl (meth)acrylate (meth)acrylates, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, halogen-substituted alkyl (meth)acrylates, and heterocycle-containing (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate. , () One in the molecule obtained by reacting a terminal isocyanate group-containing compound obtained by reacting a diisocyanate compound and one or more alcoholic hydroxyl group-containing compounds in advance with an alcoholic hydroxyl group-containing (meth)acrylate. urethane-modified mono(meth)acrylates having a (meth)acryloyloxy group,
() Epoxy mono(meth)acrylates obtained by reacting acrylic acid or methacrylic acid with a compound having one or more epoxy groups in the molecule, and () Acrylic acid or methacrylic acid and polycarboxylic acid as the carboxylic acid component. Examples include oligoester mono(meth)acrylates obtained by reacting an acid with a dihydric or higher polyhydric alcohol as an alcohol component. Examples of photopolymerizable compounds having two photopolymerizable double bonds in the molecule include alkylene glycol di(meth)acrylates such as ()ethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate. ,()
Bisphenol A such as bis(acryloxyethoxy)bisphenol A, bis(acryloxyethoxy)tetrabromobisphenol A, bis(acryloxypolyethoxy)bisphenol A
The terminal isocyanate group-containing compound obtained by reacting the di(meth)acrylates, ()diisocyanate compound and two or more alcoholic hydroxyl group-containing compounds in advance is further reacted with the alcoholic hydroxyl group-containing (meth)acrylates. Acrylic acid or/and methacrylic acid is reacted with the resulting urethane-modified di(meth)acrylates having two (meth)acryloyloxy groups in the molecule, and a compound having two or more epoxy groups in the molecule. Epoxy di(meth)acrylates obtained by () oligoester di(meth) obtained by reacting acrylic acid or methacrylic acid and polycarboxylic acid as the carboxylic acid component with a polyhydric alcohol of dihydric or higher valence as the alcohol component There are acrylates, etc. Examples of photopolymerizable compounds having three or more photopolymerizable double bonds in the molecule include ()trimethylolpropane tri(meth)acrylate;
Poly(meth)acrylates of trivalent or higher aliphatic polyhydric alcohols such as trimethylolethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, poly(meth)acrylates of trivalent or higher halogen-substituted aliphatic polyhydric alcohols ) acrylates, () diisocyanate compounds and 3
3 or more (meth)acryloyloxy groups in the molecule obtained by further reacting a terminal isocyanate group-containing compound obtained by reacting 3 or more alcoholic hydroxyl group-containing compounds with a (meth)acrylate containing an alcoholic hydroxyl group. and epoxy poly(meth)acrylates obtained by reacting a compound having three or more epoxy groups in the molecule with acrylic acid or/and methacrylic acid. Epoxy compound (A) used in the present invention and the above photopolymerizable compound having a carboxyl group in the molecule
The blending ratio of the mixture of (B), acrylate or/and methacrylate (C), which is an alkylene oxide adduct of polyalkylene glycol or polyhydric alcohol, and other photopolymerizable compounds (D) is epoxy compound (A): photopolymerizable sexual compound [(B)+(C)+(D)]=10:90
~90:10 (weight ratio), preferably
The range is 20:80 to 80:20 (weight ratio). The mixing ratio of the other photopolymerizable compound (D) and the acrylate or/and methacrylate (C) of the alkylene oxide adduct of polyalkylene glycol or polyhydric alcohol is (C):(D)=10:90-90. :10 (weight ratio)
It is preferably in the range of 20:80 to 80:20. If the amount of the epoxy compound (A) is less than 10% by weight, the reaction with the photopolymerizable compound (B) having a carboxyl group in the molecule is substantially too small, making it difficult to obtain a cured product with excellent adhesion. Takumata, epoxy compound
If the amount of (A) exceeds 90% by weight, the viscosity of the curable resin composition becomes high, making it difficult to handle, and the advantage of the curing reaction with actinic rays, i.e., rapid curing, cannot be utilized. . The blending 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 10% by weight.
If it is less than 100%, cracks in the coating film may occur during embossing, and the photopolymerizable compound (D) and the acrylate or/and alkylene oxide adduct of polyalkylene glycol or polyhydric alcohol may be damaged.
If the blending amount of (C) in the total of (C) and methacrylate (C) exceeds 90% by weight, the curability will be poor and at the same time 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, and includes, for example, ketals such as benzyl dimethyl ketal, benzoin methyl ether, benzoin ethyl ether, benzoin-i-propyl ether, benzoin,
Benzoins such as α-methylbenzoin, 9,
Anthraquinones such as 10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, and 2-ethylanthraquinone; benzophenones such as benzophenone, p-chlorobenzophenone, and p-dimethylaminobenzophenone;
2-hydroxy-2-methylpropiophenone,
Propiophenones such as 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropiophenone, suberones such as dibenzosuberone, diphenyl disulfide, tetramethylthiuram disulfide, Examples include sulfur-containing compounds such as 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 amount of this photoinitiator is preferably 0.05 to 20% by weight based on the total amount of the epoxy compound (A) and the photopolymerizable compound [(B) + (C) + (D)]. is 0.5-10% by weight. 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. As a reaction accelerator,
For example, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2
-Ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 1-vinyl-2-methylimidazole, 1-
Benzyl-2-methylimidazole, 2-phenylimidazole, 1-vinyl-2-ethylimidazole, imidazole, 2-phenyl-4-methylimidazole, 1-vinyl-2,4-dimethylimidazole, 1-vinyl-2- Imidazoles such as ethyl-4-methylimidazole, benzyldimethylamine, 2,4,6-tridimethylaminophenol, triethanolamine, triethylamine, N,N'-dimethylpiperidine, α
-Methylbenzyldimethylamine, N-methylmorpholine, N,N-dimethylaminoethanol,
These include tertiary amines such as N,N-diethylaminoethanol, N,N-dipropylaminoethanol, and dimethylaminomethylphenol, and tertiary amine salts such as triacetate and tribenzoate of tridimethylaminomethylphenol. or in combination of two or more. In the present invention, the amount of these reaction accelerators added is the same as that of the epoxy compound (A) and the photopolymerizable compound [(B)+(C)+
(D)] is 0.05 to 5% by weight, preferably 0.1 to 3.5% by weight. In addition to the above-mentioned additives, the curable coating resin composition of the present invention may contain various additives and compounding agents such as known fillers, colorants, surface smoothing agents, antifoaming agents, etc., as necessary. I can do it. The flexible substrate used in the present invention is a synthetic resin film such as polyethylene terephthalate, polyimide, polyamide, or a copolymer thereof, or epoxy resin, and its thickness is approximately 10 mm.
~200μ. The laminate for embossing of the present invention is obtained by coating a flexible substrate made of a synthetic resin film with a curable coating resin composition and curing it. The method for curing the curable coating resin composition used in 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. is polymerized to form a carboxyl group-containing polymer, and then heated to form an epoxy compound.
It consists of two steps: (A) and the carboxyl group contained in the above polymer are reacted and completely cured. Photopolymerization reaction conditions include light intensity of 20 mw/cm ² ~
The time is preferably 0.1 seconds to 15 minutes at 200 mw/cm ² .
The thermosetting reaction conditions include a temperature of 40°C to 250°C.
The time is preferably 10 seconds to 120 minutes. As active light, ultraviolet rays, electron beams, etc. are used. Light sources used for ultraviolet irradiation include sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps,
Use a metahalide lamp, xenon lamp, etc. 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 flexible substrate is coated with a curable resin composition containing pigments such as color ink, and after curing, a conductive paste is further applied and embossing is performed to obtain a membrane switch. I can do it. (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, simply parts and %
"" indicates parts by weight and % by weight, respectively. Performance measurements in Examples and Comparative Examples were conducted in accordance with the following method. <Adhesion> Cured film cross-cut cellophane tape peel test (JIS D0202) was followed. <Embossability> The cured film was heated to 120°C and embossed by dropping it from a distance of 25cm under a load of 300g using a "DuPont impact tester", and cracks in the film were checked visually and using a universal projector. The presence or absence of occurrence was measured. <Package-hiding property> The pay-hiding property of the cured film was visually determined. Example 1 50 parts of Epicote 1001 (manufactured by Yuka Ciel Epoxy Co., Ltd.), a bisphenol A type epoxy compound, 24 parts of succinic acid monoacryloyloxyethyl ester
A resin composition (α) consisting of 26 parts of tetrahydrofurfuryl acrylate and 20 parts of polyethylene glycol #600 diacrylate were placed in a container and mixed and stirred at room temperature to obtain a transparent resin composition (1). To 90 parts of the obtained resin composition (1), 5 parts of benzyl dimethyl ketal and 2 parts of N,N-diethylaminoethanol were added.
1 part, 3 parts of a surface smoothing agent, and 10 parts of a toning pigment were mixed, stirred, and then uniformly kneaded with a three-roll mill to obtain a curable coating resin composition (A) used in 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 then printed under a 5.6 KW water-cooled high-pressure mercury lamp.
Curing was performed at a distance of 15 cm with an integrated light intensity of 770 mJ/cm ² . The performance was then measured after heating at 120°C for 30 minutes. Adhesion: 100/100 Embossability: No cracking Hiding performance: 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 and stirred at room temperature. A transparent resin composition (2) was obtained. 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 were added to 90 parts of the obtained resin composition (2), and after mixing and stirring, the mixture was mixed with three rolls. Knead evenly,
A curable coating resin composition (B) used in 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 Hiding performance: Good Example 3 The resin composition (α) of Example 1 and 20 parts of polyethylene glycol #200 diacrylate were placed in a container, and mixed and stirred at room temperature. A transparent resin composition (3) was obtained. 5 parts of benzyl dimethyl ketal, 2 parts of N,N-diethylaminoethanol, 3 parts of a surface smoothing agent, and 10 parts of toning pigment were added to 90 parts of the obtained resin composition (3), and after mixing and stirring, the mixture was mixed with three rolls. The mixture was uniformly kneaded to obtain a curable coating resin composition (C) used in the present invention. Next, it was printed and cured in exactly the same manner as in Example 1,
Its performance was measured. Adhesion: 100/100 Embossability: No cracking Hiding performance: Good example 4 Di(meth)acrylate 20 of the resin composition (α) of Example 1 and the adduct of 2 moles of propylene oxide of bisphenol A A portion of the mixture was 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), 5 parts of benzyl dimethyl ketal,
Blend 2 parts of N,N-diethylaminoethanol, 3 parts of surface smoothing agent, and 10 parts of toning pigment, and after mixing and stirring,
The mixture was uniformly kneaded using three rolls to obtain a curable coating resin composition (D) used in the present invention. 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 Hiding performance: Good Comparative Example 1 The resin composition (α) of Example 1 was mixed with 5 parts of benzyl dimethyl ketal, 2 parts of N,N-diethylaminoethanol, and a smooth surface. 3 parts of the agent and 10 parts of the toning pigment were blended and mixed to obtain a resin composition (1'). Then, it was printed, cured, and its performance was measured. Adhesion: 100/100 Embossability: Cracking Occurrence Hiddenness: Good Comparative Example 2 20 parts of bis(acryloxyethoxy)bisphenol A was blended and mixed with the resin composition (α) of Example 1 to form a resin composition. (2′) was obtained. 90 parts of the obtained resin composition (2'), 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 were mixed, printed, and cured to measure its performance. Adhesion: 70/100 Embossability: Cracking Occurrence Hiding performance: Poor Comparative Example 3 20 parts of trimethylolpropane triacrylate was added to the resin composition (α) of Example 1 and mixed to form a resin composition (3′). I got it. Obtained resin composition (3′)
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 were mixed, printed, and cured to measure its performance. Adhesion: 50/100 Embossability: Frequent cracking Hiddenness: The results of Defective Examples 1 to 4 and Comparative Examples 1 to 3 are summarized in Table 1. 【table】

Claims (1)

[Scope of Claims] 1. A laminate for embossing, which is obtained by coating and curing the following curable coating resin composition on a flexible substrate made of a synthetic resin film. (A) Epoxy compound having two or more epoxy groups in the molecule (B) Photopolymerizable compound having carboxyl group in the molecule and represented by the following general formula () (In the formula, R ₁ represents hydrogen or a methyl group, R ₂ and R ₃ each represent an aliphatic, aromatic, or alicyclic residue, A represents an ester bond, and m and n each represent 1 to 1. (Indicates a positive integer of 3.) (C) Acrylate and/or methacrylate of polyalkylene glycol or alkylene oxide adduct of polyhydric alcohol (D) Curing made by blending other photopolymerizable compounds in the following proportions. mold resin composition. (A)/[(B)+(C)+(D)]=10/90~90/10 (weight ratio) (B)/[(B)+(C)+(D)]=10/100 ~80/100( 〃
) (C)/[(C)+(D)]=10/90~90/10( 〃 )