JPWO2013151001A1 - Active energy ray-curable composition, metal substrate having cured film, and method for producing the same - Google Patents

Abstract

An object of the present invention is to provide an active energy ray-curable composition capable of obtaining a cured coating film excellent in adhesion to a substrate and solvent resistance, a metal substrate having a cured film obtained by curing the composition, and It is to provide a manufacturing method. The active energy ray-curable composition of the present invention comprises (Component A) 10 to 70% by weight of epoxy (meth) acrylate, (Component B) having two or more ethylenically unsaturated groups, and other than Component A 3 to 40% by weight of the compound, (Component C) 27 to 75% by weight of the compound having an aromatic group and one ethylenically unsaturated group, and (Component D) an ethylenically unsaturated group other than the components A to C. It contains 0 to 30% by weight of a saturated compound. However, said content rate is based on the case where the total amount of component AD which is a sclerosing | hardenable component is 100 weight%.

Description

  The present invention relates to an active energy ray-curable composition, a metal substrate having a cured film, and a method for producing the same.

The present invention forms a coating layer cured / crosslinked by irradiation of active energy rays such as electron beams or ultraviolet rays on the surface of a metal substrate, and causes swelling or peeling even when the resulting coating layer is immersed in an organic solvent. Active energy ray-curable composition (hereinafter also referred to as composition) capable of exhibiting good adhesion to a metal substrate without failure, and a metal substrate having a cured film and a method for producing the same It is.
The composition of the present invention is suitably used as a coating agent for metal substrates, and is suitable for the production of electrode protection materials such as lithium ion batteries that require not only adhesion to metals but also solvent resistance. It is used and can be used in these technical fields.

Conventionally, as a coating agent excellent in solvent resistance, it has a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups and a bifunctional bridged ring structure having 2 (meth) acryloyl groups ( A photocurable composition comprising a (meth) acrylate, a photopolymerization initiator (Patent Document 1), a polyisobutylene having a (meth) acryloyl group and a hydrolyzable group in the molecule, a light comprising a photoinitiator and a moisture curing catalyst, and Moisture curable composition (Patent Document 2), epoxy resin, rubber-like polymer fine particles, inorganic filler, heat latent epoxy hardener and thermosetting composition comprising high softening point polymer fine particles (Patent Document 3), specific Consists of a cationically polymerizable compound containing an epoxy compound having a chemical structure, a radically polymerizable compound, a photocationic polymerization initiator, and a photoradical polymerization initiator. Disclosed is a curable composition (Patent Document 4), a film and sheet comprising a polyolefin and polyvinyl alcohol, a compatibilizer, a plasticizer, a processing aid, and an antioxidant (Patent Document 5). ing.
On the other hand, there are reports on a technique for dispersing an elastomer in a reactive resin and a technique for introducing an elastomer component into a reactive resin skeleton. A copolymer having a chemical structure derived from an epoxy resin and a polysiloxane structure and having an epoxy group as a functional group (Patent Document 6, Patent Document 7, Patent Document 8), and a (meth) acrylate having a polybutadiene skeleton in the molecule A low-moisture permeability hot-melt adhesive (Patent Document 9) or the like using a resin is disclosed.

Japanese Patent No. 2953598 JP 2000-178535 A JP 2000-347203 A JP 2002-256062 A Japanese translation of PCT publication No. 2002-537408 Japanese Examined Patent Publication No. 61-48544 JP-A-2-208314 JP-A-6-16773 JP-A-3-278333

In general, in order to increase the solvent resistance of a cured film such as a coating agent cured by active energy rays, it is necessary to increase the crosslink density of the cured film, and thus the cured film tends to be hard. When such a cured film forming material (active energy ray curable composition) is used as a coating agent, the cured film formed on the substrate cannot follow the deformation of the substrate due to heat cycle, and the coating layer cannot be formed. Often cracked or peeled off. Further, in applications where the base material is bent and deformed, for example, an electrode material for a lithium ion battery, the coating layer may be peeled off when the base material is bent.
On the other hand, when the coating agent has a low crosslinking density and is flexible, for example, in the electrode material of a lithium ion battery, there is a problem that it is dissolved by an organic solvent used as an electrolytic solution or peeled off from a substrate due to swelling. there were.
The object of the present invention is to solve the above-mentioned problems, that is, the obtained coating cured film is excellent in adhesion to a substrate, particularly adhesion to a metal substrate, and the adhesion is further improved by bending the substrate. The active energy ray hardening-type composition which has followability | trackability and excellent in solvent resistance, and the metal base material which has the cured film which hardened | cured the said composition, and its manufacturing method are provided.

  The above object has been achieved by the means described in <1>, <15> and <16> below. It is shown below with <2>-<14> and <17>-<21> which are preferable embodiments.

<1> (Component A) 10 to 70% by weight of epoxy (meth) acrylate, (Component B) having 2 or more ethylenically unsaturated groups and 3 to 40% by weight of compounds other than Component A (Component C) 27 to 75% by weight of a compound having an aromatic group and one ethylenically unsaturated group, and (Component D) 0 to 30% by weight of an ethylenically unsaturated compound other than components A to C An active energy ray-curable composition comprising: However, said content rate is based on the case where the total amount of component AD which is a sclerosing | hardenable component is 100 weight%.
<2> The active energy ray-curable composition according to <1>, containing 0.001 to 30% by weight of component D,
<3> (Component E) The active energy according to <1> or <2> above, further containing 0.1 to 20 parts by weight of a radical photopolymerization initiator with respect to 100 parts by weight of the total amount of the curable component. Wire curable composition,
<4> The active energy ray-curable composition according to any one of the above <1> to <3>, wherein Component A is an epoxy (meth) acrylate having an aromatic group,
<5> The active energy ray-curable composition according to any one of the above <1> to <4>, wherein component A is a bisphenol-type epoxy (meth) acrylate,
<6> The active energy ray-curable composition according to any one of the above <1> to <5>, wherein Component B is a compound having two or more (meth) acryloyl groups,
<7> The active energy ray-curable composition according to any one of the above <1> to <6>, wherein Component C is a compound having two or more aromatic rings,
<8> The active energy ray-curable composition according to any one of the above <1> to <7>, further containing a fluorescent agent, a dye or / and a pigment,
<9> The active energy ray-curable composition according to any one of <1> to <8>, further containing an antistatic agent,
<10> After the cured film obtained by applying and curing the composition on a metal substrate is immersed in a mixed organic solvent of dialkyl carbonate and cyclic carbonate at 25 ° C. for 24 hours, the cured film is removed from the metal substrate. The active energy ray-curable composition according to any one of the above <1> to <9>, which does not peel off,
<11> The active energy ray-curable composition according to any one of the above <1> to <10>, which is a coating agent for a substrate,
<12> The active energy ray-curable composition according to <11>, wherein the substrate is a metal substrate,
<13> The active energy ray-curable composition according to <12>, wherein the base material is a film-like metal base material.
<14> The active energy ray-curable composition according to <13>, wherein the metal substrate is aluminum,
<15> A metal substrate having a cured film in which a cured film of the active energy ray-curable composition according to any one of <12> to <14> is formed on the surface of the metal substrate,
<16> The step of applying the active energy ray-curable composition according to any one of the above <12> to <14> to a part or all of the metal substrate, and the applied composition A method for producing a metal substrate having a cured film, comprising a step of irradiating an object with active energy rays and curing the product,
<17> The method for producing a metal substrate having the cured film according to <16>, wherein the metal substrate is a film-like metal substrate,
<18> The method for producing a metal substrate having a cured film according to <16> or <17>, wherein the metal substrate is aluminum,
<19> The method for producing a metal substrate having a cured film according to <17> or <18>, wherein the metal substrate is a film-like metal substrate and is a positive electrode metal of a lithium ion battery,
<20> The above <16> to <<, wherein the cured film cured by irradiation with active energy rays does not peel off from the metal substrate after being immersed in a dialkyl carbonate and cyclic carbonate mixed organic solvent at 25 ° C. for 24 hours. 19>, a method for producing a metal substrate having a cured film according to any one of
<21> The step of confirming the presence or absence of a coating film or a cured film of the composition on a substrate using fluorescence before or after curing with an active energy ray, wherein the active energy ray-curable composition contains a fluorescent agent. Furthermore, the manufacturing method of the metal base material which has a cured film as described in any one of said <16>-<20>.

  According to the active energy ray-curable composition of the present invention, the resulting coating cured film (hereinafter also simply referred to as “cured film”) has excellent adhesion to a substrate, particularly adhesion to a metal substrate. In addition, the adhesion has followability to bending of the substrate and is excellent in solvent resistance. Moreover, according to the manufacturing method of the metal base material which has the cured film which hardened | cured the said composition, the cured film which show | plays the same effect is obtained.

Hereinafter, the present invention will be described in detail.
In the present specification, acrylate and / or methacrylate are represented as (meth) acrylate, acryloyl group and / or methacryloyl group as (meth) acryloyl group, and acrylic acid and / or methacrylic acid as (meth) acrylic acid. .

(Active energy ray-curable composition)
Hereinafter, the active energy ray-curable composition of the present invention (hereinafter also simply referred to as a composition) will be described in detail.
The active energy ray-curable composition of the present invention comprises (Component A) epoxy (meth) acrylate (hereinafter also referred to as Component A) at 10 to 70% by weight,
(Component B) having 2 or more ethylenically unsaturated groups and 3 to 40% by weight of a compound other than Component A (hereinafter also referred to as Component B);
(Component C) 27 to 75% by weight of a compound having an aromatic group and one ethylenically unsaturated group (hereinafter also referred to as Component C),
(Component D) An ethylenically unsaturated compound other than components A to C (hereinafter also referred to as component D) is contained in an amount of 0 to 30% by weight.
However, said content rate is based on the case where the total amount of component AD which is a sclerosing | hardenable component is 100 weight%. Component D is an optional component.
In the present invention, the “curable component” means the components A to D, is a compound having an ethylenically unsaturated group, and means a component that is cured by irradiation with active energy rays. In the present invention, the “curable component” means components A to C in the case of a composition containing components A to C, and further components A to D in the case of a composition containing component D described later. Means.

  Hereinafter, components A to C as essential components and components D to F as optional components contained in the composition of the present invention will be described in order.

(Component A) Epoxy (meth) acrylate Component A in the present invention is epoxy (meth) acrylate.
Epoxy (meth) acrylate is a compound obtained by adding (meth) acrylic acid to an epoxy resin. That is, it is a compound having a (meth) acryloyl group and an epoxy resin skeleton obtained by an addition reaction between a terminal epoxy group of an epoxy resin and (meth) acrylic acid.

Examples of the epoxy resin include aromatic epoxy resins and aliphatic epoxy resins.
Here, the epoxy resin means a compound having an average of two or more epoxy groups in the molecule and cured by reaction. In accordance with common practice in this field, in this specification, a compound having two or more curable epoxy groups in a molecule is referred to as an epoxy resin regardless of the molecular weight of the compound.
That is, the epoxy equivalent of the epoxy resin is preferably 87 to 1,000 g / eq, more preferably 125 to 600 g / eq.

  Specific examples of the aromatic epoxy resin include resorcinol diglycidyl ether; di- or polyglycidyl ether of bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene and its alkylene oxide adducts; phenol novolac type epoxy resin and cresol novolac type Novolak type epoxy resins such as epoxy resins; glycidyl phthalimide; o-phthalic acid diglycidyl ester and the like.

  Specific examples of the aliphatic epoxy resin include diglycidyl ethers of alkylene glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol; diglycidyl ethers of polyethylene glycol and polypropylene glycol, etc. Diglycidyl ethers of polyalkylene glycols; diglycidyl ethers of neopentyl glycol, dibromoneopentyl glycol and alkylene oxide adducts thereof; di- or triglycidyl ethers of trimethylolethane, trimethylolpropane, glycerin and alkylene oxide adducts thereof; Of polyhydric alcohols such as di-, tri- or tetraglycidyl ethers of pentaerythritol and its alkylene oxide adducts Ether; hydrogenated bisphenol A and di- or polyglycidyl ethers of alkylene oxide adducts; tetrahydrophthalic acid diglycidyl ether; hydroquinone diglycidyl ether, and the like.

In addition to these aromatic epoxy resins and aliphatic epoxy resins, epoxy compounds having a triazine nucleus as a skeleton, such as TEPIC (manufactured by Nissan Chemical Industries, Ltd.), Denacol EX-310 (manufactured by Nagase Chemical Industries, Ltd.), etc. And compounds described in pages 289 to 296 of the document “Polymer Processing”, separate volume epoxy resin (separate volume, Vol. 22, Volume 22 Epoxy resin (Polymer Publishing Society, published in 1973)) Etc.
In the above, the alkylene oxide of the alkylene oxide adduct is preferably ethylene oxide or propylene oxide.

  Component A is not particularly limited, and a compound obtained by a known synthesis method can be used. Specifically, (meth) acrylic acid is preferably reacted at a ratio of 0.7 to 1.5 equivalents, more preferably 0.9 to 1.1 equivalents per 1 equivalent of epoxy group of the epoxy resin. The resulting compound is preferred.

The epoxy resin is not limited to these, and epoxy resins having various structures and epoxy resins having various epoxy equivalents can be used.
In the present invention, as the component A, among the above-described compounds, an epoxy resin compound such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenol type epoxy resin, or a novolac type epoxy resin, (meth) acrylic acid and Compounds obtained by reaction are preferred.
As the bisphenol A type epoxy resin, jER-827 (epoxy equivalent: 180 to 190 g / eq), jER-828 (epoxy equivalent: 184-194 g / eq), jER-834 (epoxy equivalent: 230) manufactured by Mitsubishi Chemical Corporation. ˜270 g / eq) and the like can be mentioned as preferred examples.
Moreover, as a bisphenol F type epoxy resin, Mitsubishi Chemical Corporation jER-806 (epoxy equivalent: 160-170 g / eq), jER-807 (epoxy equivalent: 160-175 g / eq) etc. are mentioned as a preferable example. Can do.
Furthermore, as component A, bisphenol A type epoxy (meth) acrylate is more preferable because it has high curability and improves the heat resistance of the resulting cured product.

  Since component A uses an epoxy compound as a raw material, the raw material often contains chlorine. When there is much chlorine content, there exists a possibility of bringing about corrosion to a metal base material, and it is preferable that there is little chlorine content. However, most of the chlorine contained is chemically stable bound chlorine, and since the proportion of chlorine compounds that dissociate and cause corrosion in normal operating environments is very small, a certain amount of chlorine is acceptable. Often. The amount of chlorine contained in Component A is preferably 8% by weight or less in Component A, and more preferably 1% by weight or less.

Component A may be used alone or in combination of two or more.
The content ratio of component A needs to be 10 to 70% by weight, preferably 15 to 40% by weight, when the total amount of the curable components is 100% by weight. When the proportion of component A exceeds 70% by weight, the viscosity of the composition becomes too high to obtain a cured film having a uniform film thickness. On the other hand, if it is less than 10% by weight, the adhesion to the substrate is lowered.

(Component B) a compound other than Component A having two or more ethylenically unsaturated groups Component B in the present invention is a compound other than Component A having two or more ethylenically unsaturated groups. is there. By containing component B, the solvent resistance of the cured film is improved.
Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a styryl group, a (meth) acryl group, a (meth) acryloxy group, and a (meth) acrylamide group. Component B is preferably a (meth) acrylate compound.
Although the number of ethylenically unsaturated groups should just be 2 or more in 1 molecule, 2-6 are preferable and 3-6 are more preferable.
Component B is preferably an unsaturated carboxylic acid ester obtained by reacting an unsaturated carboxylic acid and a polyhydric alcohol, or an unsaturated carboxylic acid amide obtained by reacting an unsaturated carboxylic acid and a polyvalent amine.

As a preferable specific example of Component B, as (meth) acrylate having two (meth) acryloyl groups, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and nonanediol di ( Di (meth) acrylates of aliphatic diols such as (meth) acrylate, neopentyl glycol di (meth) acrylate;
Di (meth) acrylates of alicyclic diols such as tricyclodecane dimethylol di (meth) acrylate;
Di (meth) acrylate of an isocyanuric acid alkylene oxide adduct;
Examples include di (meth) acrylates of alkylene oxide adducts of bisphenol compounds such as di (meth) acrylates of alkylene oxide adducts of bisphenol A and di (meth) acrylates of alkylene oxide adducts of bisphenol F.
In addition, as an example of the alkylene oxide adduct in the above, an ethylene oxide adduct, a propylene oxide adduct, ethylene oxide, a propylene oxide adduct, etc. are mentioned.

Preferred examples of (meth) acrylate having 3 or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Examples include penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tri (meth) acrylate of isocyanuric acid ethylene oxide adduct.
Moreover, polyfunctional urethane (meth) acrylate which is a reaction product of a hydroxyl group-containing poly (meth) acrylate such as pentaerythritol tri (meth) acrylate and polyisocyanate can also be used.

  Among these compounds, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, di (meth) acrylate of isocyanuric acid ethylene oxide adduct, isocyanuric acid ethylene oxide More preferred are adduct tri (meth) acrylate and bisphenol A ethylene oxide adduct di (meth) acrylate.

  Commercial products of Component B include Aronix M-211B (diacrylate of bisphenol A ethylene oxide adduct), M-305 (a mixture of pentaerythritol tri and tetraacrylate), M-309 (trimethylolpropane) manufactured by Toagosei Co., Ltd. Triacrylate), M-310 (trimethylolpropane propylene oxide (3 mol) adduct triacrylate), M-313 (mixture of triacrylate of isocyanuric acid ethylene oxide adduct and diacrylate of isocyanuric acid ethylene oxide adduct) , M-315 (triacrylate of ethylene oxide isocyanurate adduct), M-320 (triacrylate of trimethylolpropane propylene oxide (6 mol) adduct), M-350 (trimethylol) Lopanethylene oxide adduct triacrylate), M-360 (trimethylolpropane ethylene oxide adduct (6 mol) triacrylate), M-402 (dipentaerythritol penta and hexaacrylate mixture), M-404 (dipenta Preferable examples include erythritol penta and hexaacrylate mixture), M-408 (ditrimethylolpropane tetraacrylate), M-450 (pentaerythritol tri and tetraacrylate mixture) and the like.

In addition to the above, an oligomer can also be used as Component B, and urethane (meth) acrylate, polyester (meth) acrylate and polyether (meth) acrylate are preferably mentioned.
The weight average molecular weight of the oligomer is preferably 1,000 to 40,000, and more preferably 1,000 to 15,000.
In the present invention, the weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography into polystyrene.

  As the urethane (meth) acrylate oligomer, various compounds can be used, such as a compound obtained by reacting a polyol having a polyether skeleton, a polyester skeleton or a polycarbonate skeleton with an organic polyisocyanate reaction product and a hydroxy group-containing (meth) acrylate. Preferably mentioned. More preferable urethane (meth) acrylate is bifunctional urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with a reaction product of a diol having a polyether skeleton, a polyester skeleton or a polycarbonate skeleton and an organic diisocyanate. Can be mentioned.

Here, examples of the polyol having a polyether skeleton include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Examples of the polyol having a polyester skeleton include an esterification reaction product of a diol such as a low molecular weight diol or polycaprolactone diol and an acid component such as a dibasic acid or an anhydride thereof.
Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol.
Examples of the dibasic acid or an anhydride thereof include adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid, and anhydrides thereof.
Examples of the polycarbonate polyol include a reaction product of the low molecular weight diol or / and bisphenol such as bisphenol A and a carbonic acid dialkyl ester such as ethylene carbonate and carbonic acid dibutyl ester.

  Organic polyisocyanates include tolylene diisocyanate, 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, 1,6-hexane diisocyanate trimer, hydrogenated tolylene diisocyanate, hydrogenated 4 , 4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, paraphenylene diisocyanate, tolylene diisocyanate dimer, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate interadduct, 4,4'-dicyclohexylmethane diisocyanate , Trimethylolpropane tris (tolylene diisocyanate) adduct, isophorone diisocyanate and the like are preferable.The organic polyisocyanate is preferably an organic diisocyanate.

  As hydroxy group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxy Preferred examples include hydroxyalkyl (meth) acrylates such as octyl (meth) acrylate, pentaerythritol tri, di or mono (meth) acrylate, and trimethylolpropane di or mono (meth) acrylate.

  The method for synthesizing the urethane (meth) acrylate oligomer is not particularly limited, and a known synthesis method can be used. In the presence of an addition catalyst such as dibutyltin dilaurate, the organic isocyanate to be used and the polyol component are heated and stirred to carry out the addition reaction. Furthermore, it can be obtained by adding hydroxyalkyl (meth) acrylate, stirring and heating to cause addition reaction.

Examples of the polyester (meth) acrylate oligomer include a dehydration condensate of polyester polyol and (meth) acrylic acid.
Here, examples of the polyester polyol include a reaction product of a carboxylic acid with a polyol or an anhydride thereof.
Polyols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, tetramethylene glycol, hexamethylene glycol, neo Low molecular weight polyols such as pentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol and dipentaerythritol, and their alkylene oxide adducts Etc.
As the carboxylic acid or anhydride thereof, dibasic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid, fumaric acid, maleic acid, hexahydrophthalic acid, tetrahydrophthalic acid and trimellitic acid, or anhydrides thereof Thing etc. are mentioned.

  Examples of the polyether (meth) acrylate oligomer include polyalkylene glycol (meth) diacrylate, and examples thereof include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polytetramethylene glycol di (meth) acrylate. .

Component B may be used alone or in combination of two or more.
The content ratio of Component B needs to be 3 to 40% by weight, preferably 5 to 20% by weight, when the total amount of the curable components is 100% by weight. When the proportion of component B exceeds 40% by weight, the adhesion to the substrate is deteriorated, and the cured film of the composition of the present invention becomes too hard, so that it cannot follow the deformation of the substrate such as bending. On the other hand, if it is less than 3% by weight, the solvent resistance is lowered.

(Component C) Compound having an aromatic group and one ethylenically unsaturated group Component C in the present invention is a compound having an aromatic group and one ethylenically unsaturated group. Component C is blended for the purpose of imparting good flexibility to the cured film.
Component C is not particularly limited as long as it is a compound having one ethylenically unsaturated group and at least one aromatic group in one molecule.
Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a styryl group, a (meth) acryl group, a (meth) acryloxy group, and a (meth) acrylamide group. Component C is preferably a (meth) acrylate compound.
Aromatic groups include monocyclic aromatic hydrocarbon groups such as phenyl, tolyl, xylyl, cumenyl, and cumyl groups, condensed polycyclic aromatic hydrocarbon groups such as naphthyl, anthryl, and phenanthryl. Preferred examples thereof include a biphenyl group (phenylphenyl group), a p-cumylphenyl group, and a terphenyl group of an aromatic hydrocarbon group composed of a plurality of aromatic rings.
Component C is more preferably a compound having two or more aromatic rings in one molecule, and more preferably a compound having a phenylphenyl group and a p-cumylphenyl group.

Preferred specific examples of component C include phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxy (polyalkyleneoxy) (meth) acrylate, phenyl (meth) acrylate, which contains a phenyl group as an aromatic group. Benzyl (meth) acrylate and adducts of phenylglycidyl ether and (meth) acrylic acid, monohydroxyethyl phthalate (meth) acrylate, etc .; o-phenylphenoxyethyl containing a phenylphenyl group (biphenyl group) as an aromatic group (Meth) acrylate, m-phenylphenoxyethyl (meth) acrylate, p-phenylphenoxyethyl (meth) acrylate, o-phenylphenoxypropyl (meth) acrylate, m-phenylphenoxypropyl ( ) Acrylate, p-phenylphenoxypropyl (meth) acrylate, o-phenylphenoxy (polyalkyleneoxy) (meth) acrylate, m-phenylphenoxy (polyalkyleneoxy) (meth) acrylate, p-phenylphenoxy (polyalkyleneoxy) ) (Meth) acrylate, o-phenylphenyl (meth) acrylate, m-phenylphenyl (meth) acrylate and p-phenylphenyl (meth) acrylate, adduct of o-phenylphenylglycidyl ether and (meth) acrylic acid, etc .; And p-cumylphenoxyethyl (meth) acrylate, p-cumylphenoxypropyl (meth) acrylate, p-cumylphenoxy (polyalkyleneoxy) containing p-cumylphenyl group as an aromatic group (Meth) acrylate and p- cumylphenyl (meth) acrylate.
Examples of (meth) acrylamide include N-aromatic group-containing alkyl (meth) acrylamides such as N-benzyl (meth) acrylamide; N, N-diaromatic group-containing alkyls such as N, N-dibenzyl (meth) acrylamide ( And (meth) acrylamide.
In the above compound, “polyalkyleneoxy” means a compound having 2 to 10 repeating alkylene oxide units such as ethylene oxide and propylene oxide.
Among these compounds, phenoxyethyl acrylate, p-cumylphenol ethylene oxide adduct acrylate, and o-phenylphenoxyethyl acrylate are more preferable.
Examples of the component C other than (meth) acrylate include styrene, N-vinyl carbazole, vinyl naphthalene, vinyl phenyl ether, and allyl phenyl ether as vinyl compounds.

Component C can be used alone or in combination of two or more.
In component C, in order to improve solvent resistance, it is particularly preferable that the aromatic group contains a phenylphenyl group or a p-cumylphenyl group.
The content ratio of Component C needs to be 27 to 75% by weight, preferably 40 to 72% by weight when the total amount of the curable components is 100% by weight. When the content ratio of Component C exceeds 75% by weight, the solvent resistance is deteriorated, and the cured film is peeled off by dissolution or swelling with an organic solvent. On the other hand, if it is less than 27% by weight, sufficient flexibility cannot be obtained, and the cured film is peeled off due to deformation of the substrate such as bending.

(Component D) An ethylenically unsaturated compound other than components A to C Component D in the present invention is an ethylenically unsaturated compound other than components A to C. Component D adjusts secondary performance such as glass transition temperature, water permeability, and water absorption rate of the cured film depending on the application, and is not necessarily an essential component in the present invention.
Component D is an ethylenically unsaturated group-containing compound other than essential components A to C, and is an optional component, and any component can be used.
As component D, various compounds containing an ethylenically unsaturated group can be used as long as they are other than components A to C. N-vinyl compounds other than components A to C, (meth) acrylate compounds and / or (meta ) Acrylamide compounds are preferred, and (meth) acrylate compounds having one (meth) acryloyl group in one molecule (hereinafter referred to as monofunctional (meth) acrylate compounds) and / or (meth) acrylamide compounds ( Hereinafter, a monofunctional (meth) acrylamide compound) is more preferable.

  The monofunctional (meth) acrylate compound as component D is not particularly limited as long as it is other than components A to C, and includes an unsaturated ester of (meth) acrylic acid and an aliphatic alcohol compound. The (meth) acrylate compound which has one (meth) acryloyl group can be mentioned preferably. Examples of the aliphatic group in the aliphatic alcohol compound include a linear, branched, or alicyclic hydrocarbon group having 1 to 30 carbon atoms, and may be a group having a heterocycle containing a hetero atom.

Preferable specific examples of the monofunctional (meth) acrylate compound include alkyl (meta) such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate and lauryl acrylate. ) Acrylate;
Monofunctional (meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate;
Monofunctional (meth) acrylates having an alicyclic group such as isobornyl (meth) acrylate and dicyclopentadienyl (meth) acrylate;
Monofunctional (meth) acrylates having an alkoxyalkyl group such as alkyl carbitol (meth) acrylate such as ethyl carbitol (meth) acrylate and 2-ethylhexyl carbitol (meth) acrylate; glycidyl (meth) acrylate;
Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate;
(Meth) acrylate having a maleimide group such as (meth) acryloyloxyethyl hexahydrophthalimide;
Acidic monomers such as (meth) acrylic acid, esterified product of phosphoric acid and (meth) acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate;
Such as 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylmethyldiethoxysilane and 3- (meth) acryloxypropyltriethoxysilane An alkoxyl group containing (meth) acrylate etc. can be mentioned.

Specific examples of monofunctional (meth) acrylamide compounds include N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl (meth) acrylamide. N-alkyl (meth) acrylamides such as N-sec-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide; N-hydroxyethyl (meth) acrylamide and the like N-hydroxyalkyl (meth) acrylamide;
N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di- n-propyl (meth) acrylamide,
N, N-diisopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide and N, N-dihexyl (meth) acrylamide N, N-dialkyl (meth) acrylamide; and (meth) acryloyl morphol Phosphorus etc. are mentioned.

  Examples of the N-vinyl compound include N-vinylcaprolactam and N-vinylpyrrolidone.

Component D is blended for the purpose of adjusting various physical properties of the cured film obtained from the composition of the present invention, and the above-described compounds may be used depending on the purpose.
When it is desired to improve the surface hardness of the cured film obtained by the composition of the present invention, it is preferable to use a component D having a homopolymer glass transition temperature higher than room temperature. Examples of the component D include isobornyl (meth) acrylate, acryloylmorpholine, N, N-dimethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide and the like.
On the other hand, regardless of the same type, when laminating a plurality of substrate films, if you want to adhere through the cured film obtained from the composition of the present invention, it is preferable to reduce the surface hardness of the cured film, In this case, as the component D, a homopolymer having a glass transition temperature lower than room temperature is preferable. Examples of the component D include ethyl carbitol acrylate, butyl carbitol acrylate, and 2-ethylhexyl carbitol acrylate.
In addition, the composition obtained by the present invention has sufficient adhesion to the substrate by itself, but if it is desired to further improve the adhesion to the substrate as necessary, the component D is polar. (Meth) acrylate having a high value can be preferably used.
Examples of such component D include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; (meth) acrylic (Meth) acrylates having maleimide groups such as Lolyloxyethylhexahydrophthalimide; Acids such as (meth) acrylic acid, esterified products of phosphoric acid and (meth) acrylic acid, and ω-carboxypolycaprolactone mono (meth) acrylate A monomer etc. can be mentioned.

Component D may be used individually by 1 type, or may be used in combination of 2 or more type.
The content of component D is preferably 0.001 to 30% by weight, more preferably 0.005 to 28% by weight, and more preferably 5 to 25% by weight when the total amount of components A to D is 100% by weight. It is particularly preferred that

(Component E) Photoradical polymerization initiator The composition of the present invention preferably contains (Component E) a photoradical polymerization initiator.
Component E is preferably a photoradical polymerization initiator that generates radicals upon irradiation with active energy rays and initiates polymerization of a compound having an ethylenically unsaturated group. As the active energy rays, ultraviolet rays, visible rays, infrared rays, electron beams and the like are used. However, when an electron beam is used as the active energy rays, it is not always necessary to add the component E.

  Preferred examples of component E include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1 -One, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4-1 (Methylvinyl) phenyl] propanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1 -[4- (Methylthio)] phenyl] -2-morpholinopropane-1 ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholine-4- Aromatic ketone compounds such as ylphenyl) butan-1-one, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-octylcarbazole, methyl phenylglyoxylate, ethyl anthraquinone and phenanthrenequinone; benzophenone 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2-benzophenone, 1- [ 4- (4-Benzoylphenylsulfani) ) Phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and 4-methoxy Benzophenone compounds such as -4'-dimethylaminobenzophenone; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl (2,4,6- Acylphosphine oxide compounds such as trimethylbenzoyl) phenyl phosphinate and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; thioxanthone, 2-chlorothioxanthone, 2,4- Diethylthioki Sandone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride And thioxanthone compounds such as fluorothioxanthone.

Among these compounds, α-hydroxyphenyl ketones are preferable because they have good surface curability even in the case of thin film coating in the atmosphere. Specifically, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2 -Methyl-1-phenylpropan-1-one is more preferred.
Further, when it is necessary to increase the thickness of the cured film, for example, when it is necessary to make it 50 μm or more, bis (2,4,6-trimethylbenzoyl) phenyl is used for the purpose of improving the curability inside the cured film. Phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Acylphosphine oxide compounds such as phosphine oxide, 2-methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzene) It is preferable to use a Jill) -1- (4-morpholin-4-yl-phenyl) butan-1-one and the like.

0.1-20 weight part is preferable with respect to 100 weight part of total amounts of a sclerosing | hardenable component, and, as for the content rate of the component E in the composition of this invention, it is more preferable that it is 1-10 weight part. By making the content ratio of component E 0.1 parts by weight or more, the photocurability of the composition can be made good, and by making it 20 parts by weight or less, the adhesion to the substrate is made good. be able to.
Component E may be used alone or in combination of two or more.

(Component F) Other components The composition of the present invention contains component A to component C as essential components and component D and component E as optional components, but various components may be further blended depending on the purpose. it can.
Specifically, photoacid generator, antioxidant, ultraviolet absorber, light stabilizer, silane coupling agent, tackifier, thiol compound, plasticizer, filler, fluorescent agent, dye, pigment, dispersant or / And antistatic agent etc. [hereinafter referred to as (component F) other components, also simply referred to as component F. ] Can be blended.

For example, for the purpose of maintaining sufficient durability against outdoor heat and light for a long period of time, such as solar cell applications, in order to increase the durability of the cured film, such as heat resistance and weather resistance, antioxidants, ultraviolet rays It is preferred to use absorbers and light stabilizers. For the purpose of improving the interfacial adhesive strength between the cured film and the substrate, it is preferable to use a photoacid generator or / and a silane coupling agent as Component F. For the purpose of improving adhesion, it is preferable to use a thiol compound that is effective by reducing the stress with the substrate interface. It is preferable to use a filler such as a conductive material or an antistatic agent that facilitates the detection of the location of poor insulation. For the purpose of facilitating process management in which a coating film of the composition or a cured film after irradiation with active energy rays can be easily confirmed, a fluorescent agent or a dye can be preferably used.
Hereinafter, the component F is demonstrated concretely.

<Photo acid generator>
The photoacid generator is a compound that generates an acid by irradiating a composition containing this component with active energy rays. By using a photo-acid generator, the adhesiveness with respect to the base material of the cured film obtained improves. Since the main reaction of the composition of the present invention is a radical reaction, it is unclear what kind of participation this component is involved in, but it has some modification effect on the surface of the metal substrate. Presumed to be.

As the photoacid generator, a compound known as a photocationic polymerization initiator can be used. Specific examples include onium salts such as sulfonium salts, iodonium salts, diazonium salts, selenium salts, pyridinium salts, ferrocenium salts, phosphonium salts, and thiopyrinium salts. Of these, aromatic sulfonium salts and aromatic iodonium salts are preferred. Examples of the anion component include BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , and B (C ₆ F ₅ ) ₄ ⁻ . Of these, PF ₆ ^- and B (C ₆ F ₅ ) ₄ ^- are particularly preferred.

The photo acid generator is commercially available, and examples thereof include the following compounds.
As aromatic sulfonium salts, Dow Chemical's Syracure UVI-6922 and UVI-6974, Adeka Optomer SP-150, SP-152, SP-170, and SP-172 manufactured by Adeka Corporation, Examples thereof include CPI-100P and CPI-101A manufactured by San Apro Co., Ltd.
Examples of aromatic iodonium salts include GE Toshiba Silicone Corporation UV-9380C, Rhodia PHOTOINITITOR 2074, Wako Pure Chemical Industries, Ltd. WPI-116 and WPI-113, Nippon Soda Co., Ltd. CI-5102, and the like. Can be mentioned.

  What is necessary is just to set suitably as a compounding ratio of a photo-acid generator according to the objective, 0.1-20 weight part is preferable with respect to 100 weight part of curable components total, More preferably, 0.5-10 weight part Particularly preferred is 1 to 5 parts by weight. By setting the blending ratio of the photoacid generator to 0.1 to 20 parts by weight, the adhesion can be improved while preventing the corrosion of the base material.

<Antioxidant>
Examples of the antioxidant used in the present invention include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
As a phenolic antioxidant, hindered phenols, such as di-t-butylhydroxytoluene, can be mentioned preferably, for example. As what is marketed, Ade-20 Co., Ltd. AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. are mentioned.
Preferable examples of the phosphorus antioxidant include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphite, triaryl phosphite, and the like. Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. Etc.
Examples of sulfur-based antioxidants include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
These antioxidants may be used alone or in combination of two or more. Preferred combinations of these antioxidants include the combined use of a phenolic antioxidant and a phosphorus antioxidant, and the combined use of a phenolic antioxidant and a sulfurous antioxidant.
The content ratio when using the antioxidant is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the total amount of the curable component. When the content ratio is 0.1 parts by weight or more, the durability of the composition can be improved. On the other hand, when the content ratio is 5 parts by weight or less, curability and adhesive strength can be improved.

<Light stabilizer>
Examples of the light stabilizer used in the present invention include hindered amine light stabilizers. Examples of commercially available products include BASF Corporation TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100. These antioxidants may be used alone or in combination of two or more.
The content ratio of the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the total amount of the curable component. By setting it as 0.01 weight part or more, durability of the coating film obtained from a composition can be improved, and favorable sclerosis | hardenability is acquired by setting it as 5 weight part or less.

<Ultraviolet absorber>
Examples of the ultraviolet absorber used in the present invention include triazine ultraviolet absorbers such as TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 479 manufactured by BASF, and benzotriazole ultraviolet absorbers such as TINUVIN 900, TINUVIN 928, and TINUVIN 1130. Can be preferably mentioned.
These ultraviolet absorbers may be used alone or in combination of two or more.
As for the content rate when using a ultraviolet absorber, 0.01-5 weight part is preferable with respect to 100 weight part of total amounts of a sclerosing | hardenable component, More preferably, it is 0.1-1 weight part.
By making the content ratio of the ultraviolet absorber 0.01 parts by weight or more, the light resistance of the cured film can be improved, while by making it 5 parts by weight or less, the curability of the composition is improved. It can be excellent.

<Silane coupling agent>
The silane coupling agent used for this invention is mix | blended in order to improve the interface adhesive strength of a cured film and a base material.
The silane coupling agent is not particularly limited as long as it can contribute to improvement in adhesion to the substrate.
Preferable specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycol. Sidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3- Aminopropyltrimethoxysilane, 3-mercaptopropyl Chill dimethoxysilane, 3-mercaptopropyl trimethoxy silane and the like.

The content ratio when using the silane coupling agent is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the curable component.
By setting the content ratio of the silane coupling agent to 0.1 parts by weight or more, the adhesive strength of the composition can be improved. On the other hand, by setting the content to 10 parts by weight or less, changes in the adhesive strength with time are prevented. be able to.
A silane coupling agent may use the above-mentioned compound individually by 1 type, or may use 2 or more types.

<Tackifier>
A tackifier (tackifier) may be added to the composition of the present invention for the purpose of further improving the adhesion to the substrate.
These types are not particularly limited, and examples thereof include rosin resins, rosin phenol resins, terpene resins, petroleum resins, phenol resins, ketone resins, amide resins, and epoxy resins. Specifically, examples of the rosin-based resin include raw material rosins such as gum rosin, wood rosin, tall oil rosin, and rosin derivatives corresponding thereto. As the rosin phenolic resin, for example, rosin phenolic resin obtained by copolymerizing rosin and phenol such as gum rosin, wood rosin, tall oil, etc., and corresponding rosin phenolic resin are esterified, hydrogenated, disproportionated, Examples include dimerized rosin phenol resin. Examples of the terpene resin include terpene resins obtained by polymerizing terpenes such as α-pinene and β-pinene. Examples of the petroleum resin include aliphatic hydrocarbon petroleum resins, such as aromatic hydrocarbon petroleum resins, and alicyclic hydrocarbon petroleum resins such as norbornene resin. Examples of phenolic resins include phenol resins obtained by polycondensation of phenols such as phenol and cresol and aldehydes. Examples of the ketone resins include ketone resins obtained by polycondensation of ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, and methylcyclohexanone with formaldehyde. Examples of amide resins include hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine, 1,3- or 1,4-bis (amino A diamine such as methyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine, and a dicarboxylic acid such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid. Polycondensed polyamides, for example, polyamides polycondensed with aminocarboxylic acids such as ε-aminocaproic acid and 11-aminoundecanecarboxylic acid, such as polyamides polycondensed with lactams such as ε-caprolactam and ω-laurolactam, etc. It is done. Examples of the epoxy resin include sorbitol polyglycidyl ether, polyglycol polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and the like.

  What is necessary is just to set suitably as a usage-amount of a tackifier, according to the objective, and 5-100 weight part is preferable with respect to 100 weight part of total amounts of a sclerosing | hardenable component. The tackifier may be present uniformly in the composition or may be unevenly distributed. Further, the haze of the composition is not particularly limited as long as it does not hinder active energy ray curing.

<Thiol compound>
Although the composition of this invention is excellent in the adhesiveness with respect to the base material of a cured film, according to the objective of the further adhesive improvement, or the kind of base material, a thiol compound can be added as needed. In the curing process, the thiol compound can relieve stress between the cured film and the substrate interface and further improve the adhesion.

As the thiol compound, both a monofunctional thiol compound having one thiol group in the molecule and a polyfunctional thiol compound having a plurality of thiol groups in the molecule can be used. Specific examples include thioglycolic acid, monoethanolamine thioglycolate, methyl thioglycolate, octyl thioglycolate, methoxybutyl thioglycolate, ethylene glycol bisthioglycolate, butanediol bisthioglycolate, hexanediol Bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, 3-mercaptopropionic acid, methyl mercaptopropionate, methoxybutyl mercaptopropionate, octyl mercaptopropionate, tridecyl mercaptopropionate, ethylene glycol bis Thiopropionate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, pentae Mention may be made of Sri toll tetrakis thio propionate.
The mixing ratio of the thiol compound is preferably 0.1 to 30 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the curable component. The adhesiveness with respect to a base material can be improved by making the number of added parts 0.1 parts by weight or more, and good solvent resistance can be obtained by making the added parts 30 parts by weight or less.

<Plasticizer>
A plasticizer can also be added to the composition of the present invention for the purpose of further improving the adhesion to the substrate.
As a plasticizer, what is compatible with the essential component in the composition of this invention is preferable, and a polymer, an oligomer, phthalates, castor oil, etc. can be mentioned.
Examples of the oligomer or polymer include polyisoprene-based, polybutadiene-based, and xylene-based oligomers or polymers.
These oligomers or polymers are commercially available. Examples of the polyisoprene polymer include LIR series manufactured by Kuraray Co., Ltd., and examples of the polybutadiene polymer include polyoil series manufactured by Degussa. Examples of the xylene-based oligomer include Nikanol series (Nikanol Y-50, L, H, and G) manufactured by Fudou Co., Ltd.
What is necessary is just to set suitably the content rate of a plasticizer according to the objective, 300 weight part or less is preferable with respect to 100 weight part of total amounts of a sclerosing | hardenable component, More preferably, it is 200 weight part or less.

<Filler>
In the composition of the present invention, a filler usually used in a coating agent can be used.
Furthermore, when insulation of the obtained cured film is required, carbon black such as acetylene black, carbon nanotubes, or the like may be added as a filler for the purpose of lowering the resistance value for the purpose of detecting a defective part. .
What is necessary is just to set suitably the content rate of a filler according to the objective, 50 weight part or less is preferable with respect to 100 weight part of total amounts of a sclerosing | hardenable component, More preferably, an effect is acquired by addition of 20 weight part or less. Many.

Various compounds can be used as carbon black. Specifically, Mitsubishi Chemical Corporation # 2650, # 2600, # 2350, # 2300, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, MA600, # 750B , # 650B, # 52, # 47, # 45, # 45L, # 44, # 40, # 33, # 32, # 30, # 25, # 20, # 10, # 5, # 95, # 85, # 260, MA77, MA7, MA8, MA11, MA100, MA100R, MA100S, MA230, MA220, MA14, # 4000B, # 3030B, # 3050B, # 3250B, # 3230B, # 3400B, Color Black manufactured by Orion Engineered Carbons FW200, Color Black FW2, Color Black FW2V, Color Bl ack FW1, Color Black FW18, Special Black 6, Color Black S170, Color Black S160, Special Black5, Special Black4, Special Black4A, Printex 150T, Printex U, Printex V, Printex 140U, Printex 140V, Printex 95, Printex 90, Printex 85, Printex 80, Printex 75, Printex 55, Printex 45, Printex 40, Printex P, Printex 60, Printex L6, Printex L, Printex 300, Printex 30, Printex 3 ES, 23 Printex 35, Printex 25, Printex 200, Printex A, Printex G, can be exemplified Printex XE2 like.
The blending ratio when using carbon black is preferably 5 parts by weight or less, and more preferably 2 parts by weight or less, based on 100 parts by weight of the total curable components.

Various compounds can be used as the carbon nanotube, and both single-walled carbon nanotubes and multi-walled carbon nanotubes can be used.
Specific examples of multi-walled carbon nanotubes include Baytubes C70P and C150P manufactured by Bayer MaterialScience, CNTM5 and CNTM15, CNTM30, CNTM40, and CNTM60 manufactured by NANOCS, and VGCF-H manufactured by Showa Denko K.K. it can.
Examples of the single-walled carbon nanotube include KH SWCNT HP, Sigma-Aldrich SWENT CG100, SG65, SG76, and CG200, which are carbon nanotubes manufactured by KH Chemicals.
As a preferable blending ratio when using carbon nanotubes, 5 parts by weight or less, more preferably 0.01 parts by weight or less is preferable with respect to 100 parts by weight of the total curable components. By setting it as the said mixture ratio, it can prevent that a carbon nanotube aggregates and becomes a lump and the handling property of a coating agent composition is impaired.

  Moreover, when using 1 weight part or more of carbon black or a carbon nanotube, since it becomes difficult to transmit an ultraviolet-ray or visible light to a composition, it is preferable to irradiate and harden an electron beam.

<Fluorescent agent, dye, pigment>
The composition of the present invention can be used as a so-called clear coat agent in which a cured film is transparent. On the base material, after coating the composition on the base material, the presence or absence of a coating film can be confirmed, or the active energy can be determined. For the purpose of visually confirming the presence or absence of a cured film after irradiation with a beam, a fluorescent agent, a dye and / or a pigment may be added.

Specific examples of the fluorescent agent include benzoxazolylthiophene derivatives and distyryl / biphenyl derivatives.
Fluorescent agents are commercially available, and examples thereof include BASF Corporation UVITEX OB, UVITEX NFW Liquid, and the like.

  Specific examples of the dye include an oil-soluble tar dye, a carotene dye, and an anato dye.

Examples of the pigment include organic pigments and inorganic pigments.
Specific examples of organic pigments include insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, benzidine yellow and pyrazolone red; soluble azo pigments such as Ritol Red, Helio Bordeaux, Pigment Scarlet and Permanent Red 2B; Alizarin, Indantron And derivatives from vat dyes such as thioindigo maroon; phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green; quinacridone organic pigments such as quinacridone red and quinacridone magenta; perylene organic pigments such as perylene red and perylene scarlet; Isoindolinone organic pigments such as indolinone yellow and isoindolinone orange; pyranthrone organic pigments such as pyranthrone red and pyranthrone orange Thioindigo organic pigments; condensed azo organic pigments; benzimidazolone organic pigments; quinophthalone organic pigments such as quinophthalone yellow; isoindoline organic pigments such as isoindoline yellow; and other pigments such as flavanthrone yellow and acylamide Examples include yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, and dioxazine violet.
Specific examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine blue, bitumen, and oxidation. Examples include chrome green, cobalt green, amber, titanium black, and synthetic iron black. Note that the carbon black exemplified as the filler can also be used as an inorganic pigment.

When a fluorescent agent is used, the presence or absence of a cured film can be easily determined by irradiating the substrate surface having a coating film or a cured film of the composition with black light or UV-LED. The presence or absence of a cured film can be easily determined visually.
Which of the fluorescent agent and the dye is used may be appropriately set according to the purpose. From the viewpoint of ease of determination, a dye is preferable, but the curing rate and internal curability of the composition may be lowered. On the other hand, the fluorescent agent can be determined with high sensitivity even with a very small number of added parts such as 0.0001 parts by weight with respect to 100 parts by weight of the total amount of the curable components, and further to the curing speed and internal curability of the composition. Since there is almost no influence, it is more preferable.

The content ratio of the fluorescent agent and the dye is preferably as small as possible from the viewpoint of curability of the composition when ultraviolet rays or visible rays are used as active energy rays.
In any case, the content ratio of the fluorescent agent and the dye is preferably 1 part by weight or less, more preferably 0.1 part by weight or less, based on 100 parts by weight of the total amount of the curable component.

<Dispersant>
When a filler such as carbon black, a pigment, or the like is blended with the composition of the present invention, a dispersant may be added to prevent the sedimentation and aggregation.
The amount of the dispersant used is preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the total amount of filler and pigment.
Examples of the dispersant include a low molecular weight copolymer. Those having carboxylic acid in the molecule, those having amine or ammonium salt, or those having both, polyether, phosphoric acid ester of polyether polymer, modified polyester, fatty acid derivative, modified soybean lecithin, etc. These can be used and may contain a silicone-based additive.

  Specific examples include DISPERBYK-170 / 171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183 / 185, DISPERBYK-184, DISPERBYK-2000, DISPERBYK-2001, DISPERB manufactured by Big Chemie Japan Co., Ltd. 2008, DISPERBYK-2009, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, BYP-104P 9076, BYK-9 77, BYK-220S, ANTI-TERRA-U / U100, ANTI-TERRA-204 / 205, DISPERBYK-204 / 205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBYK 109, DISPERBYK-110 / 111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162 / 163, DISPERBYK-164, 163 DISPERBYK-167, DISPE BYK-168, etc., manufactured by Evonik Degussa, TEGO Dispers 610, TEGO Dispers 610S, TEGO Dispers 630, TEGO Dispers 650, TEGO Dispers 655, TEGO Dispers 655, TEGO Dispers 655, TEGO Dispers 655, TEGO Dispers 655, TEGO Dispers 655, TEGO Dispers 655 TEGO Dispers 710 etc., Kyoeisha Chemical Co., Ltd. florene DOPA-15B, DOPA-15BHFS, DOPA-17HF, DOPA-22, DOPA-33, G-600, G-700, G-820, G-900, NC- 500, KDG-2400, AF-205, AF-405, AF-505, AF-1000, It can be mentioned F-1005, NAF-250, etc., but not limited thereto.

  When using fillers, pigments, etc., when these dispersants are not used, a uniform composition can be obtained by stirring before coating. The stirring method is not particularly limited, and any method can be used. Examples thereof include a disper, a planetary stirring and defoaming device, and an ultrasonic stirring device.

<Antistatic agent>
The composition of the present invention is excellent in insulating properties, but the resistance value can be further reduced by adding an antistatic agent as necessary. Moreover, a defective part can be detected by reducing the resistance value of a cured film by mix | blending an antistatic agent.
As the antistatic agent, a conductive antistatic agent is preferable. Examples of the conductive antistatic agent include cationic compounds such as alkali metal salts, quaternary ammonium salts, imidazolium salts and pyridinium salts, organic boron complexes, and ionic liquids. These antistatic agents are also preferable in that they dissolve in the composition and do not settle.

As the conductive antistatic agent, a cationic compound is preferable, and an alkali metal salt is preferable. As the alkali metal salt, a lithium metal salt is more preferable.
Specific examples of the lithium metal salt include imidolithium, lithium triflate such as lithium tris (trifluoromethanesulfonyl) methane, and lithium trifluoromethanesulfonate.

As the cationic compound, various commercially available products can be used.
Specific examples thereof include, for example, alkylamine quaternary ammonium salt type antistatic agents such as Elix LS-30, Elix PS-909 and Elix SEI-52 manufactured by Yoshimura Oil Chemical Co., Ltd .;
Lion Akzo Co., Ltd. Arcade C-50, Arcade T-50, Daiichi Kogyo Seiyaku Co., Ltd. Kachiogen L, Colcoat Co., Ltd. Colcoat NR-121X, Colcoat NR-121X-9, Colcoat NR A quaternary ammonium salt type antistatic agent such as -121X-9IPA and Nopcostat 092 manufactured by San Nopco;
An imidazoline type antistatic agent such as Nopcostat SN A-2 manufactured by San Nopco Co., Ltd .; and Sanconol MEK-50R (chemical name: lithium bis (trifluoromethanesulfonyl) imide) manufactured by Sanko Chemical Co., Ltd., Sanconol PETA-20R And alkali metal salt type antistatic agents such as Sanconol A600-30R, Sanconol PEO-20R, Sanconol A600-50R and Sanconol A400-50R.

  As a content rate of an antistatic agent, 0.5-15 weight part is preferable with respect to 100 weight part of total amounts of a sclerosing | hardenable component, More preferably, it is 1-10 weight part.

The antistatic agent can also improve visibility by further combining a dye.
Examples of the dye used in combination with the antistatic agent include the same compounds as described above.
When the antistatic agent and the dye are used in combination, the content ratio of the dye is preferably 0.0005 to 2 parts by weight with respect to 100 parts by weight of the total amount of the curable component.

(Method for producing active energy ray-curable composition)
The composition of the present invention can be produced by stirring and mixing components D to F, which are other optional components, as necessary, in addition to components A to C which are essential components. .
In this case, heating can be performed as necessary. What is necessary is just to set suitably as a heating temperature according to the component which the composition to be used contains, the base material which coats a composition, the intended purpose, etc., but 30-80 degreeC is preferable.

In the active energy ray-curable composition of the present invention, the cured film coated and cured on the metal substrate does not peel from the metal substrate after being immersed in a dialkyl carbonate and cyclic carbonate mixed organic solvent at 25 ° C. for 24 hours. It is preferable.
The mixing ratio of the dialkyl carbonate and the cyclic carbonate is preferably 95: 5 to 55:45, more preferably 80:20 to 60:40, in terms of dialkyl carbonate content: cyclic carbonate content.

(Method of using active energy ray-curable composition)
As a use of the composition of this invention, it can be used for various uses, and can be preferably used especially as a coating agent.

  As a method of using the composition of the present invention, a conventional method may be followed, and a step of coating the active energy ray-curable composition of the present invention on a part or all of the substrate, and coating The method of irradiating an active energy ray to a composition and making it harden | cure is illustrated.

In the present invention, examples of the substrate include metals and plastics.
As the metal, a conductive metal is preferable, and aluminum, copper, and the like are more preferable. The substrate shape is preferably a film or foil. Aluminum foil (also referred to as film-like aluminum stretched like a thin paper obtained by rolling aluminum, aluminum foil), copper foil, and the like are more preferable, and aluminum foil is particularly preferable.
Examples of the material in the plastic film include polyvinyl chloride, polyvinylidene chloride, cellulose resin, polyethylene, polypropylene, polystyrene, ABS resin, polyamide, polyester, polycarbonate, polyurethane, polyvinyl alcohol, triacetyl cellulose, cycloolefin polymer, poly Examples include methyl methacrylate, acrylic / styrene resin, ethylene-vinyl acetate copolymer, and chlorinated polypropylene.
The active energy ray-curable composition of the present invention can be preferably used as a coating agent for a film-like substrate.
Furthermore, it can be preferably used as a coating agent in which the film-like substrate is a metal substrate, and can also be preferably used as a coating agent in which the metal substrate is aluminum.

  As a coating method for the base material, a conventionally known method may be followed. Natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, Examples include air blades, curtain flow coaters, comma coaters, gravure coaters, micro gravure coaters, die coaters, and curtain coaters.

  The coating thickness of the composition of the present invention on the substrate may be selected according to the use of the substrate to be used and the coated material, but is preferably 1 to 100 μm, more preferably 5 to 5 μm. 40 μm.

  In addition, before applying to the substrate, an activation treatment can be performed on the surface of the substrate in order to increase the interlayer adhesion. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, roughening treatment and etching treatment, or flame treatment, and a plurality of these may be used in combination.

The composition after coating is irradiated with active energy rays to form a cured film, that is, a coating layer.
Examples of the active energy rays include visible light, ultraviolet rays, X-rays, and electron beams, but ultraviolet rays are preferable because inexpensive devices can be used.
Various light sources can be used as the light source when cured by ultraviolet rays, such as a pressurized or high pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, a carbon arc lamp, and an LED (light emitting diode). It is done.
In the case of curing with an electron beam, various devices can be used as an electron beam irradiation device that can be used, and examples thereof include a Cockloft-Waltsin type, a bandegraph type, and a resonant transformer type device.

(Metal substrate coating agent, metal substrate having a cured film and method for producing the same)
As described above, the composition of the present invention can be preferably used as a coating agent for metal substrates.
The metal substrate having the cured film of the present invention is a metal substrate in which the cured film of the active energy ray-curable composition of the present invention is formed on the surface of the metal substrate.
A method for producing a metal substrate having a cured film using the composition of the present invention (hereinafter also referred to as a method for producing a metal substrate with a film) includes a part or all of the active energy of the present invention on the metal substrate. It includes a step of applying a wire curable composition, and a step of irradiating the applied composition with an active energy ray to cure.

The cured film obtained by the composition of the present invention and the method for producing a metal substrate with a film is excellent in followability and solvent resistance to deformation of a metal substrate, particularly a film-like metal substrate. Panel) electrode protective material, electric bicycle substrate circuit protective material, and an electrode protective coating agent used for lithium ion batteries and the like.
Hereinafter, a method for producing a metal substrate with a film will be described.

<Metal base material>
The metal substrate used in the method for producing a metal substrate with a film of the present invention is preferably aluminum, copper or the like. The substrate shape is preferably a film shape or a foil shape. Aluminum foil, copper foil and the like are more preferable, and aluminum foil is particularly preferable.
As the film-like metal substrate used, a PDP electrode protective material, an electric bicycle substrate circuit protective material, and a positive electrode metal of a lithium ion battery are preferable. In particular, in a lithium ion battery application, an aluminum foil is suitably used as a metal substrate. It is done.
The cured film on the metal substrate formed by the method for producing a metal substrate with a film of the present invention is not only excellent in followability and solvent resistance to the deformation of the metal substrate described above, but also as an insulating coating agent. Has excellent performance.

<Coating process>
The film-coated metal substrate production method of the present invention includes a step (coating step) of applying the active energy ray-curable composition of the present invention to a part or all of the metal substrate.
As a coating method for the metal substrate, a conventionally known method may be used, and the same method as described above may be mentioned.
The coating thickness of the composition of the present invention on the substrate in the coating step may be selected according to the substrate to be used and the application of the coated coating agent, but is preferably 1 to 100 μm. More preferably, it is 5-40 micrometers.
The coating of the composition of the present invention on the substrate is preferably performed on a part or all of the film-like metal substrate as necessary.

<Curing process>
The method for producing a metal substrate with a film of the present invention preferably includes a step (curing step) of irradiating the applied composition with an active energy ray and curing it.
As the active energy ray in the curing step, the same active energy rays as described above can be used.

The cured film formed by the composition of the present invention and the method for producing a metal substrate with a film has good resistance to an organic solvent. The cured film formed by the composition of the present invention and the method for producing a metal substrate with a film has good resistance to various organic solvents, and particularly used as an electrolyte in an electrode material of a lithium ion battery. Good resistance to organic solvents. For example, it has good resistance to organic solvents such as dialkyl carbonates such as diethyl carbonate, cyclic carbonates such as ethylene carbonate, and mixed organic solvents thereof.
The cured film cured by irradiating the active energy ray formed by the method for producing a metal substrate with a film of the present invention is immersed in a dialkyl carbonate and cyclic carbonate mixed organic solvent at 25 ° C. for 24 hours. Excellent performance without peeling.

  The insulation coating layer hardened | cured on the desired film-form metal base material can be manufactured with the metal base material manufacturing method with a film | membrane of this invention using the composition of this invention. The insulating coating layer produced using the present invention has excellent substrate adhesion, solvent resistance, and insulation.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited thereto.
In the following examples, “parts” means parts by weight, and “%” means% by weight.

(Examples 1 to 24 and Comparative Examples 1 to 4)
<Preparation of active energy ray-curable composition>
Components A to F shown in Tables 1 to 5 below were dissolved by heating and stirring at 60 ° C. for 1 hour to produce active energy ray-curable compositions.

  The numbers in parentheses in Tables 1 to 5 mean the number of “parts”. “-” Means not contained. The abbreviations in each table are as follows.

<Component A>
OT-2501: Bisphenol A type epoxy acrylate (Aronix OT-2501 manufactured by Toagosei Co., Ltd.)
400EA: Polyethylene glycol (average number of repetitions = 9) diglycidyl ether epoxy acrylate (Kyoeisha Chemical Co., Ltd. epoxy ester 400EA)
80 MFA: epoxy acrylate of glycerin diglycidyl ether (epoxy ester 80 MFA manufactured by Kyoeisha Chemical Co., Ltd.)

<Component B>
M-305: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Aronix M-305, manufactured by Toagosei Co., Ltd.)
M-309: trimethylolpropane triacrylate (Aronix M-309 manufactured by Toagosei Co., Ltd.)
M-402: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Aronix M-402, manufactured by Toagosei Co., Ltd.)
OT-1501: polyether urethane acrylate (Aronix OT-1501 manufactured by Toagosei Co., Ltd.)
M-313: Mixture of triacrylate of isocyanuric acid ethylene oxide adduct and diacrylate of isocyanuric acid ethylene oxide adduct (Aronix M-313, manufactured by Toagosei Co., Ltd.)
M-211B: Diacrylate of bisphenol A ethylene oxide adduct (ethylene oxide average addition mole number = 4) (Aronix M-211B, manufactured by Toagosei Co., Ltd.)

<Component C>
M-106: o-phenylphenoxyethyl acrylate (Aronix M-106 manufactured by Toagosei Co., Ltd.)
M-110: acrylate of p-cumylphenol ethylene oxide adduct (Aronix M-110 manufactured by Toagosei Co., Ltd.)
POA: phenoxyethyl acrylate (Aronix M-100 manufactured by Toagosei Co., Ltd.)
M-5700: 2-hydroxy-3-phenoxypropyl acrylate (Aronix M-5700 manufactured by Toagosei Co., Ltd.)
BzMA: benzyl methacrylate (Kyoeisha Chemical Co., Ltd. light ester BZ)
TO-1317: adduct of o-phenylphenylglycidyl ether and acrylic acid (Aronix TO-1317, manufactured by Toagosei Co., Ltd.)
M-5400: monohydroxyethyl acrylate phthalate (Aronix M-5400 manufactured by Toagosei Co., Ltd.)

<Component D>
IBXA: Isobornyl acrylate (Kyoeisha Chemical Co., Ltd. light acrylate IB-XA)
・ ACMO: Acryloyl morpholine (ACMO manufactured by Kojin Co., Ltd.)
DMAA: N, N-dimethylacrylamide (DMAA manufactured by Kojin Co., Ltd.)
・ HEAA: N-hydroxyethylacrylamide (HEAA manufactured by Kojin Co., Ltd.)
P-2M: 2-methacryloyloxyethyl acid phosphate (Kyoeisha Chemical Co., Ltd. light ester P-2M)
MAA: methacrylic acid (GE-110 manufactured by Mitsubishi Gas Chemical Company, Inc.)
M-5300: ω-carboxy-polycaprolactone monoacrylate (average number of moles of caprolactone added: about 2) (Aronix M-5300 manufactured by Toagosei Co., Ltd.)

<Component E>
・ Irg184: 1-hydroxycyclohexyl phenyl ketone (IRGACURE184 manufactured by BASF Japan Ltd.)
Dar 1173: 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 1173 manufactured by BASF Japan Ltd.)
IRG379: 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one (IRGACURE379EG manufactured by BASF)
Irg819: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE819 manufactured by BASF)

<Component F>
OB: 2,5-thiophenezyl bis (5-tert-butyl-1,3-benzoxazole (UVITEX OB manufactured by BASF)
TMTP: trimethylolpropane tristhiopropionate (manufactured by Sakai Chemical Co., Ltd., trimethylolpropane tristhiopropionate (TMTP))
KBM-503: 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Production of cured coating film>
The following experiment was conducted using an aluminum foil nipper foil (thickness: 12 μm) manufactured by Nippon Foil Co., Ltd. as a film-like metal substrate.
The active energy ray-curable composition obtained above was applied to the aluminum foil nipper foil film to a thickness of 25 μm by a bar coater (# 16-18), and a 120 W / cm condensing type high-pressure mercury lamp (eye The cured film as a test specimen was formed by curing at a conveyor speed of 10 m / min.
The ultraviolet intensity was 1,250 mW / cm ² and the integrated light amount was 1,800 mJ / cm ² (both values at a light source wavelength of 365 nm).
The obtained test body was cut into a length of 15 cm and a width of 25 mm, and the following evaluation was performed. The results are shown in Table 6.

(Initial adhesion)
Using a cutter, 100 mm of 2 mm square grids are prepared on the cured film surface of the specimen, and Nichiban Co., Ltd. cello tape (registered trademark) is pasted on it and peeled off by hand. The number of remaining films was counted and evaluated. The adhesion was evaluated according to the following three levels. The results are shown in Table 6.
A: The number of remaining films was 80 mm or more.
○: The number of remaining films was 60 to 80%.
X: The number of remaining films was 59 mm or less.

(Deformation resistant adhesion)
The test body was wound around a metal rod having a diameter of 10 mm, and the followability of the cured film when the aluminum foil was deformed was evaluated according to the following two levels. The results are shown in Table 6.
○: Following the deformation of the base material, it did not peel off.
X: It peeled without being able to follow a deformation | transformation of a base material.

(Solvent resistance: cured film appearance)
The test specimen is immersed in a mixed solution of diethyl carbonate / ethylene carbonate = 70/30 (weight ratio) overnight (at 25 ° C. for 24 hours), taken out, and then air is blown off with an air gun to volatilize the solvent on the surface. The appearance was evaluated visually, and the following three levels were evaluated. The results are shown in Table 6.
○: The appearance of the cured film was unchanged from that before immersion.
Δ: The surface of the cured film was wavy due to wind pressure.
X: The cured film was peeled off or the cured film was peeled off by wind pressure.

(Solvent resistance: insulation)
A tester was applied to the cured film surface of the test specimen after the appearance was evaluated and the non-coated portion of the aluminum foil, the electrical conductivity was examined, and the following two levels were evaluated. The results are shown in Table 6.
◯: There was no conduction and good insulation was maintained.
X: Conductivity was recognized.

<Evaluation results>
The active energy ray-curable compositions of the present invention (Examples 1 to 24) are excellent in adhesion to a substrate and followability to deformation, and excellent in adhesion to a substrate and insulation after immersion in an organic solvent. there were. Furthermore, when the base material with a cured film formed using the composition of Example 16 containing a fluorescent agent is irradiated with a flashlight NS365HBS (manufactured by Nitride Semiconductor Co., Ltd.) equipped with a 365-nm UV-LED. The cured film portion emitted light, but the substrate portion without the cured film did not emit light, and the presence or absence of the cured film could be easily determined.
The compositions of Comparative Examples 1 to 4 did not satisfy the adhesion, the followability to deformation, the substrate adhesion after immersion in an organic solvent, and the insulating properties.

(Examples 25 to 28 (production of active energy ray-curable coating composition containing carbon black))
The components shown in Table 7 below were dissolved by heating and stirring at 60 ° C. for 1 hour to produce an active energy ray-curable coating agent composition. As carbon black, # 3050B (particle size: 50 nm, specific surface area: 50 m ² / g, hereinafter referred to as “# 3050”) manufactured by Mitsubishi Chemical Corporation was used.
The particle size of the carbon black is an arithmetic average diameter obtained by observing the carbon black particles with an electron microscope, and the specific surface area is a specific surface area (based on JISK6217) obtained from the nitrogen adsorption amount by the S-BET formula. .
In Example 28, DISPERBYK-2001 (manufactured by Big Chemie Japan Co., Ltd., hereinafter referred to as “DISP”) was further used as a dispersant.
Using the obtained composition, 2. A metal substrate having a cured film was produced in the same manner as described above.
The obtained test body was cut into a length of 15 cm and a width of 25 mm, and the initial adhesion, deformation resistance, and solvent resistance (appearance) were evaluated.
Furthermore, in these examples, the (insulation) resistance value of the cured film was measured using ULTRA HIGH RESISTANCE METER R8340 (hereinafter referred to as “R8340”) manufactured by Advantest Corporation.
The results are shown in Table 8.
The composition of the present invention is excellent in insulation, but by adding carbon black as necessary, the resistance value can be reduced and the visibility in the coating process can be improved.

  The numbers in parentheses in Table 7 mean the “number of copies”.

(Examples 29 to 33 (production of an active energy ray-curable coating agent composition containing a conductive antistatic agent))
The components shown in Table 9 below were dissolved by heating and stirring at 60 ° C. for 1 hour to produce an active energy ray-curable coating agent composition. In addition, as a conductive antistatic agent, Sanko Chemical A600-50R (imidolithium conductive antistatic agent, imide lithium content 50%, “A600”) manufactured by Sanko Chemical Industry Co., Ltd. was used.
In Examples 32 and 33, the following two dyes were further used as the dye.
・ Kaya-B: Blue dye (Kayaset Blue A-2R manufactured by Nippon Kayaku Co., Ltd.)
・ Kaya-R: Red pigment (Kayaset Red B manufactured by Nippon Kayaku Co., Ltd.)
Using the obtained composition, 2. A metal substrate having a cured film was produced in the same manner as described above.
The obtained test body was cut into a length of 15 cm and a width of 25 mm, and the initial adhesion, deformation resistance, and solvent resistance (appearance) were evaluated.
Furthermore, in these examples, R8340 was used to measure the (insulation) resistance value of the cured film.
The results are shown in Table 10.
Although the composition of the present invention is excellent in insulation, it is possible to reduce the resistance value and improve the visibility in the coating process by adding a conductive antistatic agent as necessary.

  The numbers in parentheses in Table 9 mean the “number of copies”.

  The active energy ray-curable composition of the present invention is used as a coating agent for various substrate surfaces, particularly as a coating agent for metal substrates, as a PDP electrode protective material, an electric bicycle substrate circuit protective material, and a lithium ion battery positive electrode protection. It can be suitably used for materials and the like.

Claims (21)

(Component A) 10 to 70% by weight of epoxy (meth) acrylate,
(Component B) 3 to 40% by weight of a compound having two or more ethylenically unsaturated groups and other than Component A;
(Component C) 27 to 75% by weight of a compound having an aromatic group and one ethylenically unsaturated group;
(Component D) 0 to 30% by weight of an ethylenically unsaturated compound other than components A to C,
Active energy ray-curable composition.
However, said content rate is based on the case where the total amount of component AD which is a sclerosing | hardenable component is 100 weight%.   The active energy ray hardening-type composition of Claim 1 which contains the component D 0.001-30 weight%.   The active energy ray-curable composition according to claim 1 or 2, further comprising (Component E) 0.1 to 20 parts by weight of a radical photopolymerization initiator with respect to 100 parts by weight of the total amount of the curable component.   The active energy ray hardening-type composition of any one of Claims 1-3 whose component A is the epoxy (meth) acrylate which has an aromatic group.   The active energy ray hardening-type composition of any one of Claims 1-4 whose component A is a bisphenol-type epoxy (meth) acrylate.   The active energy ray-curable composition according to any one of claims 1 to 5, wherein Component B is a compound having two or more (meth) acryloyl groups.   The active energy ray-curable composition according to any one of claims 1 to 6, wherein Component C is a compound having two or more aromatic rings.   The active energy ray-curable composition according to any one of claims 1 to 7, further comprising a fluorescent agent, a dye or / and a pigment.   The active energy ray-curable composition according to any one of claims 1 to 8, further comprising an antistatic agent.   A cured film obtained by coating and curing the composition on a metal base material is immersed in a dialkyl carbonate and cyclic carbonate mixed organic solvent at 25 ° C. for 24 hours, and then the cured film does not peel from the metal base material. The active energy ray-curable composition according to any one of claims 1 to 9, wherein   The active energy ray hardening-type composition of any one of Claims 1-10 which is a coating agent of a base material.   The active energy ray hardening-type composition of Claim 11 whose said base material is a metal base material.   The active energy ray hardening-type composition of Claim 12 whose said base material is a film-form metal base material.   The active energy ray-curable composition according to claim 12 or 13, wherein the metal substrate is aluminum.   The metal base material which has a cured film in which the cured film of the active energy ray hardening-type composition of any one of Claims 12-14 was formed in the metal base material surface. A step of applying the active energy ray-curable composition according to any one of claims 12 to 14 to a part or all of the metal substrate, and
And a step of irradiating the applied composition with an active energy ray to cure the composition.   The manufacturing method of the metal base material which has a cured film of Claim 16 whose said metal base material is a film-form metal base material.   The manufacturing method of the metal base material which has a cured film of Claim 16 or 17 whose said metal base material is aluminum.   The manufacturing method of the metal base material which has a cured film of Claim 17 or 18 whose said metal base material is a film-form metal base material and is a positive electrode metal of a lithium ion battery.   The cured film cured by irradiating with active energy rays does not peel from the metal substrate after being immersed in a dialkyl carbonate and cyclic carbonate mixed organic solvent at 25 ° C. for 24 hours. The manufacturing method of the metal base material which has a cured film as described in a term. The active energy ray-curable composition contains a fluorescent agent,
Before or after curing with an active energy ray, further comprising the step of confirming the presence or absence of a coating film or a cured film of the active energy ray curable composition on the substrate using fluorescence.
The manufacturing method of the metal base material which has a cured film of any one of Claims 16-20.