WO2013157624A1 - Active energy ray-curing type coating agent composition - Google Patents

Abstract

[Problem] To provide an active energy ray-curing type coating agent composition capable of providing a cured coating film that has excellent adhesion properties to a substrate, in particular a metal substrate, said adhesive properties having followability when bending the substrate, and is highly resistant to solvents. [Solution] An energy active ray-curing type coating agent composition that comprises, as curing components, the following components (A) to (C) at the ratios specified below: (A) 10-92 wt%, relative to the sum of the curing components, of a (meth)acrylate oligomer carrying two or more (meth)acryloyl groups and having a diene skeleton or a hydrogenated diene skeleton; (B) 8-90 wt%, relative to the sum of the curing components, of a (meth)acrylate carrying a C_4-20 alkyl, alkenyl, cycloalkyl or cycloalkenyl group in the ester moiety and having a (meth)acryloyl group; and (C) 0-50 wt%, relative to the sum of the curing components, of a compound having an ethylenically unsaturated bond, said compound being different from the aforesaid components (A) and (B).

Description

Active energy ray-curable coating agent composition

The present invention forms a coating layer of a cured film on the surface of a substrate by irradiation with an active energy ray such as an electron beam or ultraviolet ray, and provides good adhesion without causing swelling or peeling even when the coating layer is immersed in an organic solvent. The present invention relates to an active energy ray-curable coating agent composition capable of exhibiting properties.
The composition of the present invention is suitably used as a coating agent for a metal substrate, and is suitably used for producing an electrode protective material for a lithium ion battery that requires not only adhesion to metal but also solvent resistance. And can be used in these technical fields.
In the present specification, acrylate and / or methacrylate is represented by (meth) acrylate, acryloyl group and / or methacryloyl group is represented by (meth) acryloyl group, and acrylic acid and / or methacrylic acid is represented by (meth) acrylic acid. .

Conventionally, as a coating agent excellent in solvent resistance, a trifunctional or more polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups, a bifunctional bridge ring having 2 (meth) acryloyl groups Photocurable composition comprising (meth) acrylate having structure, photopolymerization initiator (Patent Document 1), polyisobutylene having (meth) acryloyl group and hydrolyzable group in molecule, photoinitiator and moisture curing catalyst Thermosetting composition comprising a light and moisture curable composition (Patent Document 2), an epoxy resin, rubber-like polymer fine particles, an inorganic filler, a heat-latent epoxy curing agent, and high softening point polymer fine particles (Patent Document 3) ), A cationically polymerizable compound containing an epoxy compound having a specific chemical structure, a radically polymerizable compound, a photocationic polymerization initiator, and a photoradical polymerization Photocurable composition comprising an initiator (Patent Document 4), film and sheet comprising polyolefin and polyvinyl alcohol, compatibilizer, plasticizer, processing aid, and antioxidant (Patent Document 5) ) Etc. are disclosed.

On the other hand, there are reports on techniques for dispersing elastomers in reactive resins and techniques for introducing elastomer components into reactive resin skeletons. 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 Special Table 2002-537408 Publication Japanese Patent Publication No. 61-48544 JP-A-2-208314 Japanese Patent Laid-Open No. 6-16773 JP-A-3-278333

Generally, in order to improve 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 problem, 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. It is to provide an active energy ray-curable coating agent composition having a followability to the above and excellent in solvent resistance.

As a result of various studies to solve the above problems, the present inventors have two or more (meth) acryloyl groups and have a diene skeleton or a hydrogenated diene skeleton. A composition containing a (meth) acrylate oligomer, a (meth) acrylate having a hydrocarbon having 4 to 20 carbon atoms in an ester site, and, if necessary, a compound having an ethylenically unsaturated group other than these (meth) acrylates The present invention has been completed by finding that it has excellent adhesion, excellent followability to bending of the substrate, and excellent solvent resistance. The present invention will be described in detail below.

According to the composition of the present invention, the obtained coating cured film (hereinafter, also simply referred to as “cured film”) is excellent in adhesion to a substrate, particularly adhesion to a metal substrate, and the adhesion is It has the ability to follow the bending of the substrate and has excellent solvent resistance.

The present invention relates to an active energy ray-curable coating agent composition containing the following components (A) to (C) in the following proportions as curable components.
(A) a (meth) acrylate oligomer having two or more (meth) acryloyl groups and having a diene skeleton or a hydrogenated diene skeleton [hereinafter referred to as “component (A)”]: curing 10 to 92% by weight in the total amount of sex ingredients
(B) a (meth) acrylate having an alkyl group having 4 to 20 carbon atoms, an alkenyl group, a cyclic alkyl group or a cyclic alkenyl group at the ester site and having one (meth) acryloyl group [hereinafter referred to as “(B) Component "): 8 to 90% by weight in the total amount of the curable component
(C) a compound having an ethylenically unsaturated group, which is a compound other than components (A) and (B) [hereinafter referred to as “component (C)”]: 0 to 50% by weight in the total amount of curable components
In the present invention, the curable component means the components (A) to (C), and is a compound having an ethylenically unsaturated group and a component that is cured by irradiation with active energy rays.

As the component (A), polybutadiene, polyisoprene and / or a (meth) acrylate oligomer having a skeleton obtained by hydrogenation thereof is preferable, and a compound having a number average molecular weight of 500 to 50,000 is preferable.

The component (B) includes an alkyl (meth) acrylate having an alkyl group having 4 to 20 carbon atoms, a (meth) acrylate having a cyclic alkyl group having 6 to 20 carbon atoms, and an alkyl group having 4 to 20 carbon atoms. A (meth) acrylate having a (poly) alkylene oxide group and / or a (meth) acrylate of an alkylphenol alkylene oxide adduct having an alkyl group having 4 to 20 carbon atoms is preferred.

The component (C) preferably includes (c1) 3 to 50% by weight of a compound having two or more ethylenically unsaturated groups in the molecule in the total amount of the curable component.
The component (C) includes (c2) a compound having a hydrophilic group and one ethylenically unsaturated group in the molecule in an amount of 0.0001 to 30% by weight in the total amount of the curable component. preferable.

Furthermore, a composition containing (D) a radical photopolymerization initiator in an amount of 0.1 to 20% by weight based on the total amount of curable components is preferred. Moreover, the composition containing a fluorescent agent, a pigment | dye or / and a pigment, and the composition containing an antistatic agent are also preferable.
The components (A) to (C) and other components will be described below.
The specific compounds mentioned in the description of the following components (A) to (C) may be used alone or in combination of two or more.

1． Component (A) The component (A) is a (meth) acrylate oligomer having two or more (meth) acryloyl groups and having a diene skeleton or a hydrogenated diene skeleton.
The (meth) acryloyl group in the component (A) may have a side chain or a terminal, preferably a compound having a (meth) acryloyl group at the terminal, particularly preferably a (meth) acryloyl at both terminals. A compound having a group.

The number average molecular weight (hereinafter referred to as “Mn”) of the component (A) is preferably a compound of 500 to 100,000, more preferably 1000 to 50,000.
By using a compound having Mn of 500 or more, peeling between the cured film and the substrate can be prevented, and by using a compound having 100,000 or less, the components (B) and (C) can be prevented. Compatibility becomes good and it can mix uniformly in a composition.
In the present invention, Mn (number average molecular weight) is a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter referred to as “GPC”) into polystyrene.

As the component (A), an oligomer in which a polydiene or hydrogenated polydiene skeleton and two or more (meth) acryloyl groups are bonded by a urethane bond (hereinafter referred to as “(A1)”), a polydiene or a hydrogenated polydiene skeleton and two Oligomer (hereinafter referred to as “(A2)”) in which the (meth) acryloyl group is bonded by an ester bond, a reaction product of an isoprene polymer, an acid anhydride adduct, and a hydroxyl group-containing (meth) acrylate [hereinafter referred to as “(A3 ) "]] And the like.

As the component (A), (A1) and (A2) are preferable, and (A1) is preferable in terms of excellent mechanical properties of the cured product, and a urethane (meth) acrylate oligomer having two (meth) acryloyl groups is more preferable. preferable.
Further, the urethane (meth) acrylate oligomer having two (meth) acryloyl groups in (A1) includes polydiene diol or hydrogenated polydiene diol (a) [hereinafter referred to as “compound (a)”], diisocyanate. A (meth) acryloyl group obtained by reacting a compound (b) [hereinafter referred to as “compound (b)”] and a hydroxyl group-containing (meth) acrylate (c)) (hereinafter referred to as “compound (c)”) 2 One urethane (meth) acrylate oligomer is preferred.

Examples of the compound (a) include polybutadiene diol, polyisoprene diol, and polyethylene propylene diol as polydiene diol. Examples of the hydrogenated polydiene diol include hydrogenated polybutadiene diol, hydrogenated polyisoprene diol, and hydrogenated polyethylene propylene diol. Among these compounds, polybutadiene diol, polyisoprene diol, hydrogenated polybutadiene diol, and hydrogenated polyisoprene diol are preferable.
The Mn of the compound (a) is preferably 500 to 10,000, more preferably 1,000 to 10,000.

In the present invention, in addition to the compound (a), other polyols other than the compound (a) may be used in combination as necessary.
For example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, 1,4-butanediol, polybutylene glycol, 1,6-hexanediol, neo Pentyl glycol, cyclohexanedimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin, polyglycerin Polyhydric alcohols such as polytetramethylene glycol;
A polyether polyol having at least one structure of polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide block or random copolymerization;
A polyester polyol which is a condensate of the polyhydric alcohol or polyether polyol and a polybasic acid such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid;
Examples include caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol, and polyolefin-based polyols.

As the compound (b), various compounds can be used as long as they are compounds having two isocyanate groups in one molecule.
Specific examples include tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and the like. it can.

As the compound (c), various compounds can be used as long as they are (meth) acrylates having a hydroxyl group.
Specific examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate caprolactone modified product, and glycidol di (meth) acrylate. Etc.
Among these, hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and butanediol mono (meth) acrylate are preferable.

Specific examples of (A2) include an esterification reaction product of two or more hydroxyl-containing polydienes or hydrogenated polydienes and (meth) acrylic acid or (meth) acrylic acid halides, two or more hydroxyl-containing polydienes or hydrogen And a transesterification product of a modified polydiene and (meth) acrylate.
Examples of esterification reaction products include esterification reaction products of polybutadiene diol and (meth) acrylic acid, esterification reaction products of polyisoprene diol and (meth) acrylic acid, and esters of hydrogenated polybutadiene diol and (meth) acrylic acid. Reaction product, esterification reaction product of hydrogenated polyisoprenediol and (meth) acrylic acid, esterification reaction product of polybutadienediol and (meth) acrylic acid chloride, esterification reaction of polyisoprenediol and (meth) acrylic acid chloride And an esterification reaction product of hydrogenated polybutadiene diol and (meth) acrylic acid chloride, and an esterification reaction product of hydrogenated polyisoprenediol and (meth) acrylic acid chloride.
Examples of transesterification products include transesterification products of polybutadiene diol and alkyl (meth) acrylate, transesterification products of polyisoprediol and alkyl (meth) acrylate, and hydrogenated polybutadiene diol and alkyl (meth) acrylate. Examples include transesterification products and transesterification products of hydrogenated polyisoprediol and alkyl (meth) acrylate.

Specific examples of (A3) include a reaction product of an isoprene polymer, a maleic anhydride adduct, and hydroxyethyl (meth) acrylate.

Component (A) is commercially available. Specific examples of (A1) include “TEA-1000” (polybutadiene urethane acrylate oligomer, Mn: about 3,000) manufactured by Nippon Soda Co., Ltd., Nippon Soda Co., Ltd. "TEAI-1000" (hydrogenated polybutadiene-based urethane acrylate oligomer), Nippon Soda Co., Ltd. "TE-2000" (polybutadiene-based urethane methacrylate oligomer), Sartomer "CN9014" (polybutadiene-based urethane acrylate), Sartomer “CN301” (polybutadiene dimethacrylate) manufactured by Sartomer, “CN303” (polybutadiene dimethacrylate) manufactured by Sartomer, “CN307” (polybutadiene diacrylate) manufactured by Sartomer, and the like.
Specific examples of (A2) include “BAC-45” (polybutadiene diacrylate, Mn: 5,000) manufactured by Osaka Organic Chemical Industry Co., Ltd.
Specific examples of (A3) include “UC-203” manufactured by Kuraray Co., Ltd. (an esterified oligomer of maleic anhydride adduct of isoprene polymer and 2-hydroxyethyl methacrylate, Mn: about 30,000). Can be mentioned.
Among these compounds, “TEAI-1000”, “TEA-1000”, “CN9014”, “CN307”, and “BAC-45” having an acryloyl group are preferable from the viewpoint of good photocurability.

As the component (A), polybutadiene, polyisoprene and / or a (meth) acrylate oligomer having a skeleton in which these are hydrogenated are preferable.
A more preferable example of the (meth) acrylate oligomer having a polybutadiene skeleton is a compound in which (meth) acryloyl groups are bonded to both ends of polybutadiene.
The compound is commercially available. Examples of the compound having an acryloyl group bonded to both ends of polybutadiene include BAC-45 (Mn: 5,000) manufactured by Osaka Organic Chemical Industry Co., Ltd. ) Examples of the compound having an acryloyl group bonded thereto include TEA-1000 (Mn: about 3,000) and TE-2000 (Mn: about 3,000) manufactured by Nippon Soda Co., Ltd.

As a preferable compound of the (meth) acrylate oligomer having a polyisoprene skeleton, the above-described (A3) can be mentioned.
As described above, the compound is commercially available, and examples thereof include Kuraray Co., Ltd. UC-203 (Mn about 30,000), which is an esterified product of polyisoprene maleic anhydride adduct and 2-hydroxyethyl methacrylate. be able to.

Preferable compounds of the (meth) acrylate oligomer having a hydrogenated skeleton of polybutadiene or polyisoprene include compounds in which a urethane (meth) acryloyl group is bonded to both ends of the hydrogenated polybutadiene skeleton.
Such compounds are commercially available, and examples thereof include TEAI-1000 (Mn: about 3,000 to 9,000) manufactured by Nippon Soda Co., Ltd.

The proportion of the component (A) needs to be 10 to 92% by weight, preferably 15 to 85% by weight, based on the total amount of the curable component.
If the proportion of the component (A) is less than 10% by weight, there is a possibility that sufficient adhesion to the substrate cannot be obtained after the cured film is immersed in an organic solvent, while if it exceeds 92% by weight, At the time of curing by irradiation with active energy rays, stress concentrates between the substrate interface and the cured film, and the adhesion may be reduced.

2. Component (B) Component (B) has an alkyl group having 4 to 20 carbon atoms, an alkenyl group, a cyclic alkyl group or a cyclic alkenyl group (hereinafter, these groups are collectively referred to as “alkyl group etc.”) at the ester site. And (meth) acrylate having one (meth) acryloyl group.
Examples of the ester moiety having an alkyl group having 4 to 20 carbon atoms in the component (B) include
Examples thereof include alkyl groups, alkenyl groups, cyclic alkyl groups and cyclic alkenyl groups, and (poly) alkylene oxide groups having an alkyl group, alkenyl group, cyclic alkyl group, cyclic alkenyl group or alkyl group-containing aromatic group.
The “(poly) alkylene oxide group” means a group having one or more alkylene oxide units.
The cyclic alkyl group and the cyclic alkenyl group may be a functional group further having an alkyl group in a part of the cyclic skeleton.
In the component (B), a compound having 3 or less carbon atoms, such as an alkyl group, may be difficult to handle due to strong volatility and odor, or insufficient compatibility with the component (A). On the other hand, a compound having 21 or more carbon atoms such as an alkyl group may have extremely poor compatibility with other components. As the alkyl group or the like of the component (B), a compound having 6 to 18 carbon atoms is preferable, and a compound having 8 to 12 carbon atoms is more preferable from the viewpoint of handling the composition.

Examples of the compound having an alkyl group include n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl ( 4 to 4 carbon atoms such as (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, n-stearyl (meth) acrylate and isostearyl (meth) acrylate Examples include alkyl (meth) acrylates having 20 alkyl groups.
Examples of the compound having an alkenyl group include pentenyl (meth) acrylate, hexyl (meth) acrylate, butenyl (meth) acrylate and hexenyl (meth) acrylate.
Examples of compounds having a cyclic alkyl group include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and t-butylcyclohexyl (meth) acrylate. Examples thereof include (meth) acrylate having a cyclic alkyl group having 6 to 20 carbon atoms.
Examples of the compound having a cyclic alkenyl group include cyclohexenyl (meth) acrylate and dicyclopentenyl (meth) acrylate.

Examples of the (poly) alkylene oxide group having an alkyl group or the like include an alkyl group-containing (poly) alkylene oxide group, a cyclic alkyl group-containing (poly) alkylene oxide group and an alkyl group-containing aromatic group (poly) alkylene oxide Groups and the like.
Examples of the compound having an alkyl group-containing (poly) alkylene oxide group include alkyl carbitol (meth) acrylates such as butyl carbitol (meth) acrylate and 2-ethylhexyl carbitol (meth) acrylate.
Examples of the compound having a cyclic alkyl group-containing (poly) alkylene oxide group include dicyclopentenyloxyethyl (meth) acrylate.
Examples of the compound having a (poly) alkylene oxide group having an alkyl group-containing aromatic group include 4 to 20 carbon atoms such as (meth) acrylate of nonylphenol ethylene oxide adduct and (meth) acrylate of nonylphenol propylene oxide adduct. (Meth) acrylates of alkylphenol alkylene oxide adducts having an alkyl group of
In this case, the number of repeating alkylene oxide units is preferably 1 to 8.

Among these compounds, the component (B) is an alkyl (meth) acrylate having an alkyl group having 4 to 20 carbon atoms, a (meth) acrylate having a cyclic alkyl group having 6 to 20 carbon atoms, or 4 to 20 carbon atoms. (Meth) acrylate having an alkyl group-containing (poly) alkylene oxide group and / or (meth) acrylate of an alkylphenol alkylene oxide adduct having an alkyl group having 4 to 20 carbon atoms is preferred.

The proportion of the component (B) needs to be 8 to 90% by weight, preferably 10 to 75% by weight, based on the total amount of the curable component.
If the ratio of component (B) is less than 8% by weight, due to the influence of component (A), stress is concentrated between the substrate interface and the cured film at the time of curing by irradiation with active energy rays, resulting in decreased adhesion. The effect of component (B) can no longer be seen. On the other hand, when the proportion of the component (B) exceeds 90% by weight, the active energy curability of the composition is lowered, a large amount of energy is required to obtain a cured film, productivity is lowered, and solvent resistance is obtained. May become insufficient.

3. Component (C) The component (C) is a compound having an ethylenically unsaturated group, and is a compound other than the components (A) and (B).
The proportion of the component (C) needs to be 0 to 50% by weight, preferably 10 to 30% by weight in the total amount of the curable component. When the proportion of the component (C) exceeds 50% by weight, when the component (C) is a compound having one ethylenically unsaturated group, the resulting cured film easily swells and peels off with respect to the organic solvent. If the component (C) is a compound having two or more ethylenically unsaturated groups, the stress at the interface between the cured film and the substrate may increase and peeling may occur easily.

Examples of the ethylenically unsaturated group in component (C) include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group, an allyl group and the like, and among these, the copolymerization with other components is excellent ( A (meth) acryloyl group is preferred.

As the component (C), various compounds can be used as long as they have an ethylenically unsaturated group. Examples of preferred compounds include compounds having two or more ethylenically unsaturated groups in the molecule [ Hereinafter referred to as “component (c1)”, and compounds having a hydrophilic group and an ethylenically unsaturated group in the molecule [hereinafter referred to as “component (c2)”].
Hereinafter, the components (c1) and (c2) will be described.

1) Component (c1) The component (c1) is a compound having two or more ethylenically unsaturated groups in the molecule.
By including (c1) component, the solvent resistance of the cured film (coating layer) obtained can be improved significantly.

Examples of the ethylenically unsaturated group in the component (c1) include (meth) acryloyl group, vinyl group, allyl group and the like as described above, and among these, it is excellent in copolymerizability with other components (meth). An acryloyl group is preferred.

As the component (c1), a compound having two (meth) acryloyl groups [hereinafter referred to as “bifunctional (meth) acrylate”] and a compound having three or more (meth) acryloyl groups [hereinafter referred to as “trifunctional” The above (meth) acrylate ”is preferred.

Specific examples of the bifunctional (meth) acrylate include 1,6-hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and polypropylene. Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, neopentyl glycol di ( And di (meth) acrylates of alkylene oxide adducts of meth) acrylate and bisphenol A.

Specific examples of tri- or higher functional (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Examples include pentaerythritol hexa (meth) acrylate and tris (2- (meth) acryloyloxyethyl) isocyanurate.

Among these compounds, 1,6-hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are more preferable.

Component (c1) is commercially available. Specifically, Aronix M-305 (a mixture of pentaerythritol tri and tetraacrylate), M-309 (trimethylolpropane triacrylate), M-310 (manufactured by Toagosei Co., Ltd.) Trimethylolpropane propylene oxide modified (3 mole) triacrylate), M-315 (isocyanuric acid ethylene oxide modified tritriacrylate), M-320 (trimethylolpropane propylene oxide modified (6 mole) triacrylate), M-350 (tri Methylolpropane ethylene oxide modified triacrylate), M-360 (trimethylolpropane ethylene oxide modified (6 mol) triacrylate), M-402 (dipentaerythritol pentaacrylate and hexaacrylate) Compounds), M-404 (dipentaerythritol pentaacrylate and hexaacrylate mixture), M-408 (ditrimethylolpropane tetraacrylate), M-450 (pentaerythritol and tetraacrylate mixture), and the like.

The proportion of the component (c1) is preferably 3 to 50% by weight, more preferably 5 to 30% by weight in the total amount of the curable component.
By setting the proportion of the component (c1) to 3% by weight or more, the cured film can have excellent solvent resistance, while by setting it to 50% by weight or less, the adhesion to the substrate is excellent. It is possible to prevent the cured product from becoming too hard to follow the deformation of the substrate such as bending.

2) Component (c2) The component (c2) is a compound having a hydrophilic group and one ethylenically unsaturated group in the molecule.
By including (c2) component, the adhesiveness to the base material of the cured film (coating layer) obtained can be improved significantly.
Examples of the ethylenically unsaturated group in component (c2) include (meth) acryloyl group, (meth) acrylamide group, vinyl group, allyl group, etc., as described above. Since it is excellent, (meth) acryloyl group and (meth) acrylamide group are preferable.
Examples of the hydrophilic group include a hydroxyl group and an acidic group, and examples of the acidic group further include a carboxyl group, a phosphoric acid group, and a sulfone group.

When the component (c2) is a compound having a hydroxyl group as a hydrophilic group, a hydroxyl group-containing (meth) acrylate and a hydroxyl group-containing (meth) acrylamide are preferable.
Specific examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, and hydroxyhexyl (meth) acrylate. And hydroxyalkyl (meth) acrylates such as hydroxyoctyl (meth) acrylate; and pentaerythritol mono (meth) acrylate and trimethylolpropane include mono (meth) acrylates of polyols such as mono (meth) acrylate. Specific examples of the hydroxyl group-containing (meth) acrylamide include N-hydroxyethyl (meth) acrylamide.

When the component (c2) is a compound having a carboxyl group as a hydrophilic group, a carboxyl group-containing (meth) acrylate is preferable.
Specific examples of the carboxyl group-containing (meth) acrylate include (meth) acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, and monohydroxyethyl (meth) acrylate phthalate.
When the component (c2) is a compound having a phosphate group as a hydrophilic group, a phosphate group-containing (meth) acrylate is preferable.
Specific examples of the phosphoric acid group-containing (meth) acrylate include esterified products of phosphoric acid and (meth) acrylic acid.

When the component (c2) is a compound having a hydroxyl group as a hydrophilic group, it is preferably 3 to 30% by weight, more preferably 5 to 20% by weight, based on the total amount of the curable component.
By setting the proportion of the component (c2) to 3% by weight or more, the adhesion can be improved, and by setting it to 30% by weight or less, it is possible to prevent a decrease in solvent resistance.
The ratio when the component (c2) is a compound having an acidic group as a hydrophilic group is preferably 0.0001 to 20% by weight, more preferably 0.001 to 5% by weight in the total amount of the curable component. It is.
By setting the proportion of the component (c2) to 0.0001% by weight or more, it is possible to further improve the adhesion to the metal. On the other hand, by setting it to 20% by weight or less, corrosion of the metal substrate that is weak against acid is prevented. Can be prevented.

3) Other compounds (C) having an ethylenically unsaturated group include compounds having an ethylenically unsaturated group other than the above (c1) and (c2) [hereinafter referred to as “component (c3)”]. It can be used for the purpose of adjusting secondary performance such as glass transition temperature, water permeability and water absorption depending on the purpose and application.

As the component (c3), various compounds can be used as long as they contain an ethylenically unsaturated group, and examples thereof include vinyl compounds and (meth) acrylates, with (meth) acrylates being preferred.

Specific examples of (meth) acrylate include (meth) acrylate having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”) and one (meth) acryloyl group (meth) ) Acrylamide compounds (hereinafter referred to as monofunctional (meth) acrylamide compounds).

As monofunctional (meth) acrylate,
Monofunctional (meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate;
Epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate;
Aromatic monofunctional (meth) acrylates such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, o-phenylphenoxy (meth) acrylate and p-cumylphenolethylene (meth) acrylate;
Monofunctional (meth) acrylates having maleimide groups such as (meth) acryloyloxyethyl hexahydrophthalimide; and 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane and 3 Examples include alkoxyl group-containing monofunctional (meth) acrylates such as-(meth) acryloxypropylmethyldiethoxysilane and 3- (meth) acryloxypropyltriethoxysilane.

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, etc. 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 vinyl compound include N-vinylcaprolactam and N-vinylpyrrolidone.

The content ratio of the component (c3) is preferably 0 to 30% by weight, more preferably 25% by weight or less in the total amount of the curable component.

4). Other Components The composition of the present invention comprises the above components (A) to (C) as essential components, but various components that are usually used as coating agents are blended depending on the purpose and application. Can do.
Preferred components include photo radical polymerization initiators (hereinafter referred to as “component (D)”). Besides these, photo acid generators, silane coupling agents, antioxidants, ultraviolet absorbers, light stability Agents, tackifiers, thiol compounds, plasticizers, fillers, fluorescent agents, dyes, pigments, dispersants and / or antistatic agents.

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 an absorber or / and a light stabilizer. For the purpose of improving the interfacial bond strength between the cured film and the substrate, it is preferable to use a photoacid generator and / or a silane coupling agent. 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 that facilitates the detection of the location of defective 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, it is preferable to use a fluorescent agent or a dye.
Hereinafter, these components will be specifically described.
In addition, the specific compound mentioned by description of the other component may use the said compound independently, and may be used in combination of 2 or more types.

1) Component (D) The component (D) is a radical photopolymerization initiator.
Component (D) is a compound that generates radicals by irradiation with active energy rays and initiates polymerization of a compound having an ethylenically unsaturated group. When an electron beam is used as the active energy ray, it is not always necessary to add the component (D).

Specific examples of the component (D) 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-morpholinopropan-1-one 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl- Aromatic ketone compounds such as phenyl) 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-Benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis Benzophenone compounds such as (diethylamino) benzophenone and 4-methoxy-4'-dimethylaminobenzophenone;
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6- Acylphosphine oxide compounds such as dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl-oxy]- And thioxanthone compounds such as 2-hydroxypropyl-N, N, N-trimethylammonium chloride and 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-phenyl-propan-1-one is more preferred.
Also, 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)-is used for the purpose of improving the curability inside the cured film. Phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6-dimethoxybenzoyl) -2,4,4- Acylphosphine oxide compounds such as trimethylpentylphosphine 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-methyl) Benzyl) -1- (4-morpholin-4-yl-phenyl) - - is preferably used in combination with butan-1-one and the like.

The content ratio of the component (D) is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the total curable components. (D) By making the ratio of a component 0.1 weight part or more, it can make the photocurability of a composition favorable and can make it excellent in adhesiveness, and a cured film can be 20 weight part or less. The internal curability can be improved, and the adhesion to the substrate can be improved.

2) Photoacid generator The photoacid generator is a compound that generates an acid by irradiating a composition containing this component with active energy rays. By using this component, the adhesion of the resulting cured film to the substrate is improved. 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 sulfonium salts, iodonium salts, diazonium salts, selenium salts, pyridinium salts, ferrocenium salts, phosphonium salts, onium salts such as thiopyrinium salts, and more preferably aromatic sulfonium salts and aromatics. Group iodonium salt. Examples of the anion component include BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , and B (C ₆ F ₅ ) ₄ ⁻ , with PF ₆ ⁻ and B (C being particularly preferable. ₆ F _{5) 4} ^- it is.

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

The blending ratio of the photoacid generator may be appropriately set depending on the purpose, and is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the curable components. 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.

3) Silane coupling agent A silane coupling agent 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.

Specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3 -Aminopropyltrimethoxysilane, 3-mercaptopropylmethyl Silane, 3-mercaptopropyl trimethoxy silane and the like.

The blending ratio of the silane coupling agent may be appropriately set according to the purpose, and 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 curable components.
When the blending ratio is 0.1 parts by weight or more, the adhesive strength of the composition can be improved. On the other hand, when the blending ratio is 10 parts by weight or less, it is possible to prevent the adhesive force from changing over time.

4) Antioxidant Antioxidant is mix | blended in order to improve durability, such as the heat resistance of a cured film, and a weather resistance.
Examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
Examples of phenolic antioxidants include hindered phenols such as di-t-butylhydroxytoluene. Examples of commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by Adeka Corporation.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphites and triaryl phosphites. Commercially available products of these derivatives include, for example, manufactured by Adeka Co., Ltd., Adeka Stab PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010 Etc.
Examples of the sulfur-based antioxidant include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include the combined use of phenolic antioxidants and phosphorus antioxidants, and the combined use of phenolic antioxidants and sulfurous antioxidants.
The blending ratio of the antioxidant may be appropriately set according to the purpose, and 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 curable component. .
When the blending ratio is 0.1 parts by weight or more, the durability of the composition can be improved. On the other hand, when it is 5 parts by weight or less, curability and adhesion can be improved.

5) 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 blending ratio of the light stabilizer may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight based on 100 parts by weight of the curable components. . 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.

6) Ultraviolet absorber An ultraviolet absorber is mix | blended in order to improve the light resistance of a cured film.
Examples of the UV absorber include triazine UV absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole UV absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
The blending ratio of the ultraviolet absorber may be appropriately set according to the purpose, and is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight based on 100 parts by weight of the curable components. is there. When the blending ratio is 0.01% by weight or more, the light resistance of the cured film can be improved, and when it is 5% by weight or less, the curability of the composition is excellent. be able to.

7) Tackifier The tackifier (tackifier) can 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 such as 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.

The blending ratio of the tackifier may be appropriately set depending on the purpose, and is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the curable components. 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.

8) Thiol compound The composition of the present invention has a cured film having excellent adhesion to a substrate, but a thiol compound may be added as necessary according to the purpose of further adhesion improvement and the type of substrate. it can. 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 Sri tall tetrakis thiopropionate, pentaerythritol tetrakis (3-mercapto butyrate), trimethylolpropane tris (3-mercapto butyrate) and trimethylolethane tris (3-mercapto butyrate), and the like.
Among these, when the storage stability of the composition is required, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate) and trimethylolethane tris (3-mercaptobutyrate) are used. It is preferable to use secondary thiols such as (rate).
The blending ratio of the thiol compound is preferably 0.1 to 30 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the total curable components. 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.

9) Plasticizer A plasticizer may be added to the composition of the present invention for the purpose of further improving the adhesion to the substrate.
As the plasticizer, those compatible with the essential components in the composition of the present invention are preferable, and examples thereof include polymers, oligomers, phthalates, and castor oils.
Examples of the oligomer or polymer include polyisoprene-based, polybutadiene-based, and xylene-based oligomers or polymers. These oligomers or polymers are commercially available, and examples thereof include Kuraray LIR series, Degussa polyoil series, and the like.
The blending ratio of the plasticizer may be appropriately set according to the purpose, and is preferably 300 parts by weight or less, more preferably 200 parts by weight or less, with respect to 100 parts by weight of the total curable components.

10) Filler The composition of this invention can use the filler normally used with a coating agent.
In addition, when the obtained cured film requires insulation, carbon black such as acetylene black, carbon nanotubes, etc. are added as fillers for the purpose of partially reducing the resistance value for the purpose of detecting defective parts. May be.
What is necessary is just to set the mixture ratio of a filler suitably according to the objective, and 50 weight part or less is preferable with respect to 100 weight part of curable components total, More preferably, it is 20 weight part or less.

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 Black k 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, Printr 3 ES rintex 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 manufactured by KH Chemicals, SWENT CG100, SG65, SG76, and CG200 manufactured by Sigma-Aldrich.
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.

In addition, when 1 part by weight or more of carbon black or carbon nanotube is used, it is preferable that the composition is hardened by irradiating it with an electron beam because it is difficult for ultraviolet rays and visible light to pass through the composition.

11) Fluorescent agent / dye / pigment The composition of the present invention can be used as a so-called clear coat agent in which the cured film is transparent, but on the substrate, the composition is coated on the substrate. For the purpose of confirming the presence or absence or visually confirming the presence or absence of a cured film after irradiation with active energy rays, a fluorescent agent, a dye or / and 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 oil-soluble tar dyes, carotene dyes and annatto dyes.

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 lithol red, helio bordeaux, pigment scarlet and permanent red 2B; alizarin, indanthrone 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. 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 surface of a substrate having a coating film or 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 is more preferable because it can be determined with a high sensitivity even with a very small number of added parts such as 0.0001 parts by weight and has little influence on the curing rate and internal curability of the composition.

As the blending ratio of the fluorescent agent, the dye and the pigment becomes too large, the curability of the composition may be deteriorated when ultraviolet rays or visible rays are used as active energy rays. Is preferred.
In any case, the blending 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 with respect to 100 parts by weight of the curable components.

12) Dispersant When a filler such as carbon black, a pigment, or the like is blended in the composition of the present invention, a dispersant may be added to prevent the sedimentation or aggregation of these.
The amount of the dispersant used is preferably 0.001 to 10 parts by weight, 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, DISPERBYK-by Big Chemie Japan Co., Ltd. , DISPERBYK-2009, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, BYK-P104 / P104-P104B , BYK- 077, BYK-220S, ANTI-TERRA-U / U100, ANTI-TERRA-204 / 205, DISPERBYK-204 / 205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBY 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, DISP RBYK-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. Floren 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, AF-1005, NAF-250 and the like can be mentioned, but are 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.

13. Antistatic Agent The composition of the present invention has excellent 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 Elique LS-30, Elique PS-909 and Elique SEI-52 manufactured by Yoshimura Oil Chemical Co., Ltd .;
Lion Akzo Co., Ltd.'s ARCARD C-50, ARCARD T-50, Daiichi Kogyo Seiyaku Co., Ltd., Kachiogen L, Colcoat Co., Ltd. Colcoat NR-121X, Colcoat NR-121X-9, Colcoat NR- Quaternary ammonium salt type antistatic agents such as 121X-9IPA and Nopcostat 092 manufactured by San Nopco Co., Ltd .;
An imidazoline type antistatic agent such as Nopcostat SN A-2 manufactured by San Nopco, Inc .; 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.

The content ratio of the antistatic agent is preferably 0.5 to 15 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 antistatic agent can also improve visibility by further combining a pigment.
Examples of the dye used in combination with the antistatic agent include the same compounds as described above.
The combined proportion of the antistatic agent and the dye is preferably 0.0005 to 2 parts by weight.

5). As a method for producing the active energy ray-curable coating composition, the components (A) to (C) may be produced by further stirring and mixing other components as required according to a conventional method. it can.
In this case, heating can be performed as necessary. The heating temperature may be appropriately set according to the components used, the substrate, the purpose, etc., but is preferably 30 to 80 ° C.

The composition of the present invention is such that a cured film coated and cured on a 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. 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, with respect to the dialkyl carbonate content weight: cyclic carbonate content weight.

6). Method of Use The composition of the present invention can be used in various applications as a coating agent. In particular, the composition of the present invention can be used for applications that require followability to substrate deformation and solvent resistance.

As a method of using the composition of the present invention, a conventional method may be used. The step of applying the composition of the present invention to a part or all of the substrate, and the active energy applied to the coated composition. The method of including the process of irradiating and hardening a line | wire is illustrated.

Examples of the substrate include metals and plastic films.
The composition of the present invention can be preferably used as a coating agent for a base metal substrate.
As the metal, a conductive metal is preferable, and aluminum, copper, and the like are more preferable. The substrate shape is preferably a film shape or a foil. Aluminum foil (also referred to as film-like aluminum stretched like 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 resin, polyvinylidene chloride, cellulosic resin, polyethylene, polypropylene, polystyrene, ABS resin, polyamide, polyester, polycarbonate, polyurethane, polyvinyl alcohol, triacetyl cellulose, cycloolefin polymer, Examples include polymethyl methacrylate, acrylic / styrene resin, ethylene-vinyl acetate copolymer, and chlorinated polypropylene.
The 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.

Coating to the substrate may be performed by a conventionally known method, natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, air blade , Curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater and curtain coater.

The coating thickness of the composition of the present invention to 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 40 μm. It is.

Also, before applying to the base material, the surface of the base material can be activated in order to increase the interlayer adhesion. Examples of the surface activation treatment include plasma treatment, corona discharge treatment, chemical treatment, surface roughening treatment and etching treatment, and flame treatment, and 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, and examples thereof include 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.
In the case of curing with an electron beam, various devices can be used as the EB irradiation device that can be used, and examples thereof include a Cockloft-Waltsin type, a bandegraph type, and a resonance transformer type device.

7). As described above, the composition of the present invention can be preferably used as a coating agent for a metal substrate, and the coating agent for a film-like metal substrate. More preferably.
The method for producing a metal substrate having a cured film using the composition of the present invention (hereinafter also referred to as a film-coated metal substrate production method) is applied to a part or all of the metal substrate on the composition of the present invention. And a step of irradiating the applied composition with an active energy ray and curing it.

The cured film obtained by the composition of the present invention and the method for producing a metal substrate with a film has excellent followability to deformation of a metal substrate, particularly a film-like metal substrate, and solvent resistance. It can be suitably used for electrode protective coating agents used for materials, board circuit protection materials for electric bicycles, lithium ion batteries and the like.
Hereinafter, the metal substrate manufacturing method will be described.

1) Metal substrate 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, an electrode protective material for PDP, a substrate circuit protective material for an electric bicycle, 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 layer 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, but also as an insulating coating agent. Has excellent performance.

2) Coating process The method for producing a metal substrate with a film of the present invention includes a process (coating process) of applying the 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 this case 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 to 40 μm.
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.

3) Curing Step The method for producing a metal substrate with a film of the present invention preferably includes a step (curing step) of irradiating the coated composition with an active energy ray to cure.
As the active energy rays used in this case, 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 formed by the method for producing a metal substrate with a film of the present invention has excellent performance of not peeling from the metal substrate after being immersed in a dialkyl carbonate and cyclic carbonate mixed organic solvent at 25 ° C. for 24 hours. .

The insulating coating layer cured on a desired film-like metal substrate can be produced by the method for producing a metal substrate with a film of the present invention using the composition of the present 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. In the following examples, “parts” means parts by weight.

1. Examples 1 to 25, Comparative Examples 1 to 4 (Production of active energy ray-curable coating agent composition)
The components shown in Tables 1 to 4 below were dissolved by heating and stirring at 60 ° C. for 1 hour in the ratios shown in Tables 1 to 4 to produce active energy ray-curable coating agent compositions.

The numbers in Tables 1 to 4 mean the number of copies. Abbreviations in Tables 1 to 4 are as follows.
1) Component (A) TEAI1000: Oligomer having urethane acryloyl groups at both ends of the hydrogenated polybutadiene skeleton [TEAI-1000 manufactured by Nippon Soda Co., Ltd.]
BAC45: an oligomer having an acryloyl group at both ends of the polybutadiene skeleton (BAC-45, manufactured by Osaka Organic Chemical Industry Co., Ltd.)
TE2000: an oligomer having urethane methacryloyl groups at both ends of the polybutadiene skeleton (TE-2000 manufactured by Nippon Soda Co., Ltd.)
UC203: an oligomer having a methacryloyl group which is an esterified product of polyisoprene maleic anhydride adduct and 2-hydroxyethyl methacrylate (UC-203 manufactured by Kuraray Co., Ltd.)

2) Component (B) LA: Lauryl acrylate [Kyoeisha Chemical Co., Ltd. Light Acrylate LA]
SA: Stearyl acrylate [Kyoeisha Chemical Co., Ltd. Light acrylate SA]
・ IBXA: Isobornyl acrylate [Kyoeisha Chemical Co., Ltd. light acrylate IB-XA]
FA-512: dicyclopentenyloxyethyl acrylate [manufactured by Hitachi Chemical Co., Ltd., FA-512AS]
M-120: 2-ethylhexyl carbitol acrylate [Aronix M-120 manufactured by Toagosei Co., Ltd.]
IBX: Isobornyl methacrylate [Kyoeisha Chemical Co., Ltd. light ester IB-X]
M-111: Nonylphenol ethylene oxide modified (average number of added moles≈1) acrylate [Aronix M-111 manufactured by Toagosei Co., Ltd.]
M-113: Nonylphenyl (polyethyleneoxy) acrylate (average number of moles of ethylene oxide added = 4 moles) [Aronix M-113 manufactured by Toagosei Co., Ltd.]

3) Component (C)
(1) Component (c1) NP-A: Neopentyl glycol diacrylate [Kyoeisha Chemical Co., Ltd. Light acrylate NP-A]
・ HX-A: 1,6-hexanediol diacrylate [Kyoeisha Chemical Co., Ltd. Light acrylate 1,6HX-A]
M-309: trimethylolpropane triacrylate [Aronix M-309 manufactured by Toagosei Co., Ltd.]
UA-306H: polyfunctional urethane acrylate obtained from a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate [Urethane acrylate UA-306H manufactured by Kyoeisha Chemical Co., Ltd.]
M-313: Mixture product of isocyanuric acid ethylene oxide-modified tritriacrylate and isocyanuric acid ethylene oxide-modified tritriacrylate [Aronix M-313, manufactured by Toagosei Co., Ltd.]
M-245: Bisphenol F ethylene oxide 4 molar modified diacrylate [Aronix M-245 manufactured by Toagosei Co., Ltd.]
DCPA: tricyclodecane dimethylol diacrylate [Kyoeisha Chemical Co., Ltd. light acrylate DCP-A]

(2) Component (c2) HBA: 4-hydroxybutyl acrylate [Osaka Organic Chemical Industry Co., Ltd. 4-HBA]
HPA: 2-hydroxypropyl acrylate [Kyoeisha Chemical Co., Ltd. light ester HOP-A]
HEAA: N-hydroxyethyl acrylamide [HEAA manufactured by Kojin Co., Ltd.]
P-2M: 2-methacryloyloxyethyl acid phosphate [Light Ester P-2M manufactured by Kyoeisha Chemical Co., Ltd.]
MAA: methacrylic acid [GE-110 manufactured by Mitsubishi Gas Chemical Co., Ltd.]
-HOP: 2-hydroxypropyl methacrylate [Kyoeisha Chemical Co., Ltd. light ester HOP]

(3) (c3) component BzMA: benzyl methacrylate [Kyoeisha Chemical Co., Ltd. light ester BZ]
THFMA: Tetrahydrofurfuryl methacrylate [Kyoeisha Chemical Co., Ltd. light ester THF]
DMAA: N, N-dimethylacrylamide [manufactured by Kojin DMAA]
ACMO: acryloyl morpholine [ACMO manufactured by Kojin Co., Ltd.]
M-106: o-phenylphenoxyethyl acrylate [Aronix M-106 manufactured by Toagosei Co., Ltd.]

4) Component (D) Irg184: 1-hydroxycyclohexyl phenyl ketone (IRGACURE184 manufactured by BASF)
Dar 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (DAROCUR 1173 manufactured by BASF)
Irg651: 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE651 manufactured by BASF)
IRG379: 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one [IRGACURE379EG manufactured by BASF Corporation]
TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (DAROCUR TPO manufactured by BASF)

5) Other components : KE-311: Rosin ester (KE-311 manufactured by Arakawa Chemical Industries, Inc., tackifier)
KBM503: 3-methacryloxypropyltriethoxysilane (KBM-503, silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.)
OB: 2,5-thiophenezyl bis (5-tert-butyl-1,3-benzoxazole [UVITEX OB manufactured by BASF Corp.]
TMTP: trimethylolpropane tristhiopropionate [manufactured by Sakai Chemical Co., Ltd. trimethylolpropane tristhiopropionate (TMTP)]
CPI: propylene carbonate solution of p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate [CPI-100P manufactured by San Apro Co., Ltd.]

2. Production of Metal Substrate Having Cured Film The following tests were conducted using aluminum foil [manufactured by Nippon Foil Co., Ltd., trade name: Nippaku foil (thickness: 12 μm)] as a film-like metal substrate.
The composition obtained above was applied to the aluminum 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 (manufactured by Eye Graphics Co., Ltd.) was used. It was cured at a conveyor speed of 10 m / min to produce a metal substrate having a cured film as a test specimen.
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).
Although coating / active energy ray irradiation was performed at 25 ° C., the composition containing stearyl acrylate as component (B) was crystallized at room temperature, so the coating / active energy ray was applied at 60 ° C. Irradiation was performed.
The obtained specimen 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 4.

1) Evaluation method
(1) A mark X was cut with a cutter on the surface of the cured film of the initial adhesion test specimen, a mending tape manufactured by Sumitomo 3M Co., Ltd. was affixed thereon and peeled off by hand for evaluation. The adhesion was evaluated according to the following three levels.
A: The cured film was not peeled off from the aluminum foil surface, and further, the cured film was not peeled off from the cut portion.
○: Although the cut portion was slightly cut, the cured film almost remained on the aluminum foil.
X: The cured film adhered to the tape side.

(2) The deformation resistance adhesion test specimen 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.
○: 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.

(3) Solvent resistance: The appearance test specimen was 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 blown with an air gun to surface The solvent was volatilized, the appearance of the cured film was visually evaluated, and the following three levels were evaluated.
○: 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 coating film was peeled off by wind pressure.

(4) Solvent resistance: insulation The tester was applied to the surface of the cured film of the test body that was evaluated for its appearance and the non-coated portion of the aluminum foil, the conductivity was examined, and the following two levels were evaluated.
◯: There was no conduction and good insulation was maintained.
X: Conductivity was recognized.

2) Evaluation results The compositions of Examples 1 to 25, which are the compositions of the present invention, have a cured film with excellent adhesion to the substrate and followability to deformation, adhesion to the substrate after immersion in an organic solvent, It was also excellent in insulation.
Furthermore, the substrate with a cured film formed using the composition of Example 21 containing a fluorescent brightener was irradiated with a flashlight NS365HBS (manufactured by Nitride Semiconductor Co., Ltd.) equipped with a 365-nm UV-LED. When it did, although the cured film part emitted light, the base-material part without a cured film did not light-emit, and the presence or absence of the cured film was able to be discriminate | determined easily.
On the other hand, the compositions of Comparative Examples 1 and 4 that do not contain the component (B) and the compositions of Comparative Examples 2 and 3 that do not contain the component (A) have a cured film that adheres to adhesion and deformation. Property, and substrate adhesion after immersion in an organic solvent and insulation cannot be satisfied.

3. Examples 26 to 27 (active energy ray-curable coating agent composition containing carbon black)
The components shown in Table 6 below were dissolved by heating and stirring at 60 ° C. for 1 hour to produce an active energy ray-curable coating agent composition. Carbon black # 3050B (particle size: 50 nm * arithmetic average diameter obtained by observing carbon black particles with an electron microscope. Specific surface area: 50 m ² / g * from nitrogen adsorption amount S The specific surface area (JISK6217) determined by the BET formula (hereinafter referred to as “# 3050”) was used.
In Example 27, DISPERBYK-2001 (manufactured by Big Chemie 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 7.
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.

4). Examples 28 to 29 (active energy ray-curable coating composition containing a conductive antistatic agent)
The components shown in Table 8 below were dissolved by heating and stirring at 60 ° C. for 1 hour to produce an active energy ray-curable coating agent composition. Note that Sanconol A600-50R (imidolithium conductive antistatic agent, imide lithium content 50%, referred to as “A600”) manufactured by Sanko Chemical Industry Co., Ltd. was used as the conductive antistatic agent.
In Example 29, the following dyes were further used as the dyes.
・ Kaya-B: Blue pigment (Kayaset Blue A-2R 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.
Further, in these examples, R8340 was used to measure the (insulation) resistance value of the cured film.
The results are shown in Table 9.
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 composition of the present invention is suitable as a coating agent for various substrate surfaces, particularly as a coating agent for metal substrates, as an electrode protective material for PDP, a substrate circuit protective material for electric bicycles, and a positive electrode protective material for lithium ion batteries. Can be used.

Claims (21)

1. An active energy ray-curable coating composition comprising the following components (A) to (C) in the following proportions as curable components:
   (A) (Meth) acrylate oligomer having two or more (meth) acryloyl groups and having a diene skeleton or a hydrogenated diene skeleton: 10 to 92% by weight in the total amount of the curable component
   (B) (meth) acrylate having an alkyl group having 4 to 20 carbon atoms, an alkenyl group, a cyclic alkyl group or a cyclic alkenyl group at the ester site and having one (meth) acryloyl group: in the total amount of the curable component 8 to 90% by weight
   (C) a compound having an ethylenically unsaturated group, which is a compound other than the components (A) and (B): 0 to 50% by weight in the total amount of the curable component
2. 2. The active energy ray-curable coating composition according to claim 1, wherein the component (A) is polybutadiene, polyisoprene and / or an oligomer having a skeleton obtained by hydrogenation thereof.
3. The active energy ray-curable coating composition according to claim 1 or 2, wherein the component (A) is a compound having a number average molecular weight of 500 to 50,000.
4. The component (B) is
   An alkyl (meth) acrylate having an alkyl group having 4 to 20 carbon atoms,
   (Meth) acrylate having a cyclic alkyl group having 6 to 20 carbon atoms,
   2. A (meth) acrylate having an alkyl group-containing (poly) alkylene oxide group having 4 to 20 carbon atoms and / or a (meth) acrylate of an alkylphenol alkylene oxide adduct having an alkyl group having 4 to 20 carbon atoms. The active energy ray-curable coating agent composition according to any one of claims 3 to 4.
5. The component (C) according to any one of claims 1 to 4, wherein (c1) a compound having two or more ethylenically unsaturated groups in the molecule is contained in an amount of 3 to 50% by weight in the total amount of the curable component. 2. The active energy ray-curable coating agent composition according to item 1.
6. The component (C) comprises (c2) 0.0001 to 30% by weight of a compound having a hydrophilic group and one ethylenically unsaturated group in the molecule in the total amount of the curable component. Item 6. The active energy ray-curable coating agent composition according to any one of Items 5.
7. The active energy ray according to any one of claims 1 to 6, further comprising (D) 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. A curable coating agent composition.
8. The active energy ray-curable coating composition according to any one of claims 1 to 7, further comprising a fluorescent agent, a dye or / and a pigment.
9. The active energy ray-curable coating agent composition according to any one of claims 1 to 8, further comprising an antistatic agent.
10. A cured film coated and cured on a metal substrate 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 substrate. The active energy ray-curable coating composition according to any one of claims 1 to 9.
11. The active energy ray-curable coating agent composition according to claim 10, which is a metal base coating agent.
12. The active energy ray-curable coating agent composition according to claim 11, wherein the substrate is a film-like metal substrate.
13. The active energy ray-curable coating agent composition according to claim 11 or 12, wherein the metal substrate is aluminum.
14. A metal substrate having a cured film in which a cured film of the active energy ray-curable coating agent composition according to any one of claims 11 to 13 is formed on a surface of the metal substrate.
15. A step of applying the active energy ray-curable coating composition according to any one of claims 1 to 13 to a part or all of the metal substrate; and
    The manufacturing method of the metal base material which has a process which irradiates an active energy ray to the coated composition, and makes it harden | cure.
16. The method for producing a metal substrate having a cured film according to claim 15, wherein the metal substrate is a film-like metal substrate.
17. The method for producing a metal substrate having a cured film according to claim 15 or 16, wherein the metal substrate is aluminum.
18. The method for producing a metal substrate having a cured film according to claim 17 or 18, wherein the metal substrate is a film-like metal substrate and a positive electrode metal of a lithium ion battery.
19. 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. A method for producing a metal substrate having the cured film according to item 1.
20. The active energy ray-curable coating agent 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 coating agent composition on the substrate using fluorescence,
    A method for producing a metal substrate having the cured film according to any one of claims 15 to 19.
21. The active energy ray-curable coating agent composition contains an antistatic agent,
    A step of detecting a defective portion of the cured film by lowering the resistance value of the cured film after curing by the active energy ray,
    A method for producing a metal substrate having the cured film according to any one of claims 15 to 19.