JP5935668B2 - Active energy ray-curable coating agent composition - Google Patents

Description

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 this specification, acrylate and / or methacrylate is (meth) acrylate, acryloyl group and / or methacryloyl group is (meth) acryloyl group, acrylamide and / or methacrylamide is (meth) acrylamide, and acrylic acid. And / or methacrylic acid is represented as (meth) acrylic acid.

  Conventionally, as a coating agent having excellent solvent resistance, a trifunctional or higher polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups, and 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 radical photopolymerization initiator. Film, sheet and molding processing composition (Patent Document 5) comprising a photocurable composition comprising an agent (Patent Document 4), a polyolefin and polyvinyl alcohol, a compatibilizer, a plasticizer, a processing aid, and an antioxidant. Etc. are disclosed.

  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

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 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. It is to provide an active energy ray-curable coating agent composition having followability with respect to water and excellent in solvent resistance.

As a result of various studies to solve the above-mentioned problems, the present inventors have found urethane (meth) acrylate, a compound having a hydrophilic group and one ethylenically unsaturated group, a cyclic hydrocarbon group and one. The composition containing an ethylenically unsaturated group and a composition containing another ethylenically unsaturated compound as required, the resulting cured product is excellent in adhesion, and further excellent in followability to bending of the substrate, And it discovered that it was excellent also in solvent resistance, and completed this invention.
Hereinafter, the present invention will be described in detail.

  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, as the curable component, relates to the following (A) ~ (D) component of the active energy ray-curable metal substrate coating composition comprising in the following proportions.
(A) Urethane (meth) acrylate having a weight average molecular weight of 1,000 to 60,000 (hereinafter referred to as “component (A)”): 5 to 50% by weight in the total amount of the curable component
(B) Compound having hydrophilic group and one ethylenically unsaturated group [hereinafter referred to as “component (B)”]: 5 to 45% by weight in the total amount of the curable component
(C) have a cyclic hydrocarbon group and one ethylenically unsaturated group, a compound having no hydrophilic group, (B) other than the component compounds: 5 to 65 in the curable composition the total amount weight%,
(D) A compound having an ethylenically unsaturated group, which is a compound other than the components (A) to (C) and includes a compound having two or more (meth) acryloyl groups as an essential component : Curability 0.5 to 40% by weight in the total amount of ingredients
In addition, in this invention, a sclerosing | hardenable component means the said (A)-(E) component, is a compound which has an ethylenically unsaturated group, and means the component hardened | cured by irradiation of an active energy ray.

  As the component (A), a reaction product of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth) acrylate is preferable.

As the component (B), one or more selected from the group consisting of a compound having a hydroxyl group and a (meth) acryloyl group, a compound having a carboxyl group and a (meth) acryloyl group, and a compound having an amide group and a (meth) acryloyl group Is preferred.
As the compound having a hydroxyl group and a (meth) acryloyl group, a compound containing hydroxyalkyl (meth) acrylate is preferable.
As the compound having a carboxyl group and a (meth) acryloyl group, those containing (meth) acrylic acid are preferable.
Examples of the compound having an amide group and a (meth) acryloyl group include (meth) acryloylmorpholine, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and / or N-hydroxyethyl (meth) acrylamide. The thing containing is preferable.

The component (C) preferably includes a compound having an aromatic group and a (meth) acryloyl group or / and a compound having an alicyclic group and a (meth) acryloyl group.
As the compound having an aromatic group and a (meth) acryloyl group, those containing phenylphenyl group-containing (meth) acrylate, cumyl group-containing (meth) acrylate or / and phenyl group-containing (meth) acrylate are preferable.
Examples of the compound having an alicyclic group and a (meth) acryloyl group include a cyclohexyl group-containing (meth) acrylate, an isobornyl group-containing (meth) acrylate, a tricyclodecane group-containing (meth) acrylate and / or a dicyclopentenyl group ( Those containing (meth) acrylate are preferred.

(D) Ingredient are those comprising a compound having two or more (meth) acryloyl group as an essential component.

The composition of the present invention preferably further comprises (E) a radical photopolymerization initiator (hereinafter referred to as “component (E)”) in an amount of 0.1 to 20% by weight based on the total amount of the curable components.
Furthermore, the thing containing a fluorescent agent, a pigment | dye or / and a pigment is preferable.

  In the composition of the present invention, after the cured film coated and cured on the 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. Although it does not peel, it is preferable.

The composition of the present invention is a coating agent for a metal substrate, and the metal substrate is preferably a film substrate, and aluminum is preferable as the metal substrate.

The present invention also relates to a metal substrate having a cured film in which the cured film of the coating composition for active energy ray-curable metal substrate is formed on the surface of the metal substrate.

The present invention also includes a step of coating the active energy ray-curable metal substrate coating composition on a part or all of the metal substrate , and
The present invention also relates to a method for producing a metal substrate having a cured film, which includes a step of irradiating the applied composition with an active energy ray to cure.
As the metal substrate, a film-like metal substrate is preferable, and as the metal substrate, aluminum is preferable. Further, the metal substrate is a film-like metal substrate, and the metal substrate is a positive electrode metal of a lithium ion battery. A production method is preferred.
In this case, it is preferable that the cured film cured by irradiating active energy rays is not peeled off from the metal substrate after being immersed in a dialkyl carbonate and cyclic carbonate mixed organic solvent at 25 ° C. for 24 hours.
The active energy ray-curable coating agent composition contains a fluorescent agent,
Before or after curing with an active energy ray, having a cured film further comprising a step of confirming the presence or absence of a coating film or a cured film of the coating composition for the active energy ray-curable metal substrate on the substrate using fluorescence. It also relates to a method for producing a metal substrate.

Hereinafter, the essential components (A) to (D) will be described.
In addition, the specific compound quoted by description of the following (A)-(D) component may use the said compound independently, and may be used in combination of 2 or more types.

1. Component (A) Component (A) is a urethane (meth) acrylate having a weight average molecular weight of 1,000 to 60,000.
As the component (A), various urethane (meth) acrylates can be used, and specific examples include urethane (meth) acrylates having a polyester skeleton, a polyether skeleton, or a polycarbonate skeleton.

As the component (A), both oligomers and polymers can be used, and those having a weight average molecular weight (hereinafter referred to as “Mw”) of 1,000 to 60,000 are used, and 1,000 to 55,000. Is preferable, more preferably 1,000 to 50,000, and particularly preferably 1,500 to 40,000.
In the case of urethane (meth) acrylate having an Mw of less than 1,000, the resulting cured film has a large stress with the base material interface, resulting in low adhesion to the base material, In the case of urethane (meth) acrylate having an Mw exceeding 60,000, the cured film obtained tends to swell with respect to the organic solvent, so that sufficient solvent resistance cannot be obtained.
In the present invention, Mw is a value obtained by converting a molecular weight measured by gel permeation chromatography into polystyrene.

More specifically, examples of the component (A) include a reaction product of a polyol, an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate, and the polyol and the organic polyisocyanate reaction product include a hydroxyl group-containing (meth) acrylate. A compound obtained by reacting is preferred.
The component (A) is a urethane (meth) acrylate having two (meth) acryloyl groups [hereinafter also referred to as bifunctional urethane (meth) acrylate. It is preferably a bifunctional urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with a reaction product of a diol having a polyester, polyether or polycarbonate skeleton and an organic diisocyanate. .

As the polyol, a diol having a polyester skeleton, a diol having a polyether skeleton, and a diol having a polycarbonate skeleton are preferable.
Examples of the polyol having a polyester skeleton include an esterification reaction product of a diol component 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, tetramethylene 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 polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
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.
The organic polyisocyanate is preferably an organic diisocyanate.

Examples of hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and hydroxy Hydroxyalkyl (meth) acrylates such as octyl (meth) acrylate; polyol-containing polyol poly (meth) acrylates such as pentaerythritol tri, di or mono (meth) acrylate, and trimethylolpropane di or mono (meth) acrylate Can be mentioned.
As the hydroxyl group-containing (meth) acrylate, hydroxyalkyl (meth) acrylate is preferable.

(A) As a manufacturing method of a component, what is necessary is just to follow a conventional method,
1) In the presence of a urethanization catalyst, a polyol and an organic polyisocyanate are heated and stirred to carry out an addition reaction to produce a prepolymer having an isocyanate, and then a hydroxyalkyl (meth) acrylate is added thereto, followed by heating and stirring to cause an addition reaction. Examples thereof include a production method and 2) a production method in which a polyol, an organic polyisocyanate, and a hydroxyalkyl (meth) acrylate are heated and stirred in the presence of a urethanization catalyst.
(A) As a component, what was obtained by the manufacturing method of said 1) is preferable.
Examples of the urethanization catalyst include tin-based catalysts such as dibutyltin dilaurate, iron-based catalysts such as tris (acetylacetonato) iron, and zinc-based catalysts such as bis (acetylacetonato) zinc.

(A) The ratio of a component needs to be 5 to 50 weight% in the total amount of a sclerosing | hardenable component, Preferably it is 10 to 45 weight%.
When the proportion of the component (A) is less than 5% by weight, the solvent resistance of the cured film becomes insufficient, and the cured film is easily peeled off by solvent immersion. The density becomes too high, and the initial adhesion to the substrate becomes insufficient.

2. Component (B) The component (B) is a compound having a hydrophilic group and one ethylenically unsaturated group.
In this invention, the adhesiveness to a base material can be improved by containing (B) component. In addition, since the glass transition point of the cured composition film can be increased, the tack of the cured film surface can be reduced. Thereby, when the member with a cured film obtained is piled up, it can also prevent that members will fuse | melt. In addition, since the inhibition of curing under an air atmosphere can be suppressed, a composition having good curability can be obtained.

Examples of the hydrophilic group include a hydroxyl group, an acidic group, and an amide group. Examples of the acidic group further include a carboxyl group, a phosphoric acid group, and a sulfone group.
Examples of the ethylenically unsaturated group include vinyl bonds such as vinyl groups, allyl groups, and styryl groups, and (meth) acryloyl groups. As the ethylenically unsaturated group, a (meth) acryloyl group is preferable because of excellent copolymerizability with other components.
Hereinafter, a compound having a hydroxyl group, a compound having an acidic group, and a compound having an amide group will be described in accordance with the type of the hydrophilic group.

2-1. When the compound (B) component having a hydroxyl group is a compound having a hydroxyl group as a hydrophilic group, examples thereof include a hydroxyl group-containing (meth) acrylate and a hydroxyl group-containing vinyl ether.
Specific examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and hydroxypentyl. And hydroxyalkyl (meth) acrylates such as (meth) acrylate, hydroxyhexyl (meth) acrylate and hydroxyoctyl (meth) acrylate; and 2-hydroxy-3-phenoxypropyl (meth) acrylate.

  Specific examples of the hydroxyl group-containing vinyl ether include 4-hydroxybutyl vinyl ether, 4-hydroxycyclohexyl vinyl ether and the like. Examples of the hydroxyl group-containing allyl ether include 1,1,1-trimethylolpropane monoallyl ether, 1,1,1-trimethylolpropane diallyl ether, ethylene glycol monoallyl ether, 3-allyloxy-1,2-propanediol, and the like. Can be mentioned.

As the hydroxyl group-containing (meth) acrylate, hydroxyalkyl (meth) acrylate is preferable.
Among these, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are preferable because of excellent adhesion to the substrate.

2-2. When the compound (B) component having an acidic group is a compound having an acidic group as a hydrophilic group, examples thereof include a compound having a carboxyl group and a compound having a phosphoric acid group.

When the component (B) is a compound having a carboxyl group as a hydrophilic group, a compound having a carboxyl group and a (meth) acryloyl group is preferred.
Specific examples of the compound having a carboxyl group and a (meth) acryloyl group include acidic groups such as (meth) acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, and monohydroxyethyl (meth) acrylate phthalate. (Meth) acrylate is mentioned.

When the component (B) is a compound having a phosphate group as a hydrophilic group, a phosphate group-containing (meth) acrylate is preferable.
Specific examples of the acid group-containing (meth) acrylate include esterified products of phosphoric acid and (meth) acrylic acid, 2- (meth) acryloyloxyethyl acid phosphate, and the like.

2-3. When the compound (B) component having an amide group is a compound having an amide group as a hydrophilic group, a (meth) acrylamide compound having at least one substituent on the nitrogen atom is exemplified.

  Examples of the substituent include an alkyl group, a hydroxyalkyl group, an aryl group, and an alkylaminoalkyl group. In the case of an alkyl group, a ring structure including a nitrogen atom may be formed.

  As the component (B), a compound represented by the following general formula (1) is preferable.

[However, in the general formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ² and R ³ in one molecule may be the same group or different groups. R ² and R ³ may be bonded as a cyclic hydrocarbon. ]

The hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group, which may be linear or branched. The alkyl group may be an alkyl group further having a hydroxyl group, an aromatic group, and a diaminoalkyl group.
Specific examples of the alkyl group include a methyl group, a propyl group, a butyl group, a butyl group, and a hexyl group.
Examples of the alkyl group having a hydroxyl group include a hydroxymethyl group and a hydroxyethyl group.
Examples of the alkyl group having an aromatic group include a benzyl group.
Examples of the alkyl group having a hydroxyl group include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.
Examples of the dialkylaminoalkyl group include N, N-dimethylaminoethyl group and N, N-dimethylaminopropyl group. In addition, examples in which R ² and R ³ are cyclic hydrocarbons include aminocyclohexyl groups and morpholino groups.
Among these, an alkyl group having 1 to 3 carbon atoms and a morpholino group are preferable because they can be easily obtained and the glass transition point of the homopolymer is high. Further, those having an N-hydroxyalkyl group are preferable because they have higher initial adhesion.

Specific examples of the compound include N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-sec-butyl ( N-alkyl (meth) acrylamides such as (meth) acrylamide, Nt-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide;
N-aromatic group-containing alkyl (meth) acrylamides such as N-benzyl (meth) acrylamide;
N-hydroxyalkyl (meth) acrylamides such as N-hydroxyethyl (meth) acrylamide;
N, N-dialkylaminodialkyl (meth) acrylamides such as N, N-dimethylaminoethyl (meth) acrylamide and 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, N-dialkyl (meth) acrylamides of n-butyl (meth) acrylamide and N, N-dihexyl (meth) acrylamide;
And N, N-diaromatic group-containing alkyl (meth) acrylamides such as N, N-dibenzyl (meth) acrylamide; and (meth) acryloylmorpholine.

  Among these compounds, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acryloylmorpholine and N-hydroxyethylacrylamide are preferable because of excellent adhesion to the substrate. Further, (meth) acryloylmorpholine is particularly excellent in the initial adhesiveness of the obtained cured film since the solvent resistance of the obtained cured film is particularly excellent, and N-hydroxyethylacrylamide is more preferable.

2-4. Preferred compounds (B) include, among the compounds described above, compounds having a hydroxyl group and a (meth) acryloyl group, compounds having a carboxyl group and a (meth) acryloyl group, and compounds having an amide group and a (meth) acryloyl group. One or more selected from the group consisting of
As the compound having a hydroxyl group and a (meth) acryloyl group, hydroxyalkyl (meth) acrylate is preferable.
As the compound having a carboxyl group and a (meth) acryloyl group, (meth) acrylic acid is preferable.
Examples of the compound having an amide group and a (meth) acryloyl group include (meth) acryloylmorpholine N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide and / or N-hydroxyethyl (meth) acrylamide. preferable.

The ratio of (B) component needs to be 5-45 weight% in the total amount of a sclerosing | hardenable component, Preferably it is 10-40 weight%.
If the proportion of the component (B) is less than 5% by weight, the adhesion to the substrate becomes insufficient. On the other hand, if it exceeds 45% by weight, the solvent resistance of the cured film is lowered, There is a risk of peeling.

3. Component (C) Component (C), have a cyclic hydrocarbon and one ethylenically unsaturated group, a compound having no hydrophilic group is a compound other than component (B).
By including (C) component, the softness | flexibility of the cured film obtained can be improved.
Component (C), have a cyclic hydrocarbon and one ethylenically unsaturated group in the molecule is not particularly limited as long as it is a compound having no hydrophilic group.

  The cyclic hydrocarbon includes heterocycles such as alicyclic groups, aromatic groups, and cyclic ethers. These rings may have a substituent such as an alkyl group, an alkoxyl group, or a halogen.

The alicyclic group includes a monocyclic alicyclic group such as a cyclohexyl group, a polycyclic alicyclic group such as an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, a tricyclodecanenyl group, and an adamantyl group. Etc.
As the alicyclic group in the component (C), a cyclohexyl group, an isobornyl group, a dicyclopentanyl group, and a dicyclopentenyl group are preferable because of excellent solvent resistance of the cured film.

Examples of aromatic groups include phenyl, tolyl, xylyl, cumenyl and cumyl groups of monocyclic aromatic hydrocarbon groups, and naphthyl, anthryl and phenanthryl groups of condensed polycyclic aromatic hydrocarbon groups. Preferred examples thereof include a biphenyl group (phenylphenyl group) and a terphenyl group of an aromatic hydrocarbon group composed of a plurality of monocycles.
As the aromatic group in the component (C), a phenyl group, a phenylphenyl group or a p-cumylphenyl group is preferable because of excellent solvent resistance of the cured film.

  As an ethylenically unsaturated group, vinyl bonds, such as a vinyl group, an allyl group, and a styryl group, (meth) acrylolyl group, etc. are mentioned, A (meth) acryloyl group is preferable.

  As the component (C), (meth) acrylate is preferable.

  Specific examples of the (meth) acrylate having an alicyclic group include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecane dimethylol (meth) acrylate, dicyclopentanyl (meth) ) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like.

Specific examples of the (meth) acrylate having an aromatic group include phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, phenoxy (polyalkyleneoxy) (meth) acrylate, which contains a phenyl group as an aromatic group, Phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate (adduct of phenylglycidyl ether and (meth) acrylic acid) and the like;
(Meth) acrylates of alkylphenol alkylene oxide adducts such as (meth) acrylates of nonylphenol ethylene oxide adducts;
O-phenylphenoxyethyl (meth) acrylate, m-phenylphenoxyethyl (meth) acrylate, p-phenylphenoxyethyl (meth) acrylate, o-phenylphenoxypropyl (meth) acrylate containing a phenylphenyl group as an aromatic group M-phenylphenoxypropyl (meth) 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 and the like; and p-cumylphenoxyethyl (meth) acrylate, p-cumylphenoxypropyl (meth) acrylate, p-cumylphenoxy (polyalkyleneoxy (meth)) containing p-cumylphenyl group as an aromatic group ) Acrylate, p-cumylphenyl (meth) acrylate, and the like.
In the above compound, “polyalkyleneoxy” means a compound having 2 to 10 repeating alkylene oxide units such as ethylene oxide and propylene oxide.

  Examples of the compound having a heterocyclic ring include (meth) acrylate having a maleimide group such as tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, and (meth) acrylolyloxyethyl hexahydrophthalimide.

  Examples of the component (C) other than (meth) acrylate include styrene, N-vinyl carbazole, vinyl naphthalene, vinyl phenyl ether, and allyl phenyl ether.

As the component (C), a compound having an aromatic group and a (meth) acryloyl group or / and a compound having an alicyclic group and a (meth) acryloyl group are preferable.
As the compound having an aromatic group and a (meth) acryloyl group, phenylphenyl group-containing (meth) acrylate, cumyl group-containing (meth) acrylate or / and phenyl group-containing (meth) acrylate are preferable. Furthermore, phenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, acrylate of p-cumylphenol ethylene oxide adduct, and o-phenylphenoxyethyl acrylate are more preferable.
As the compound having an alicyclic group and a (meth) acryloyl group in the component (C), a cyclohexyl group-containing (meth) acrylate, an isobornyl group-containing (meth) acrylate, a tricyclodecane group-containing (meth) acrylate or / and di A cyclopentenyl group-containing (meth) acrylate is preferred. Furthermore, cyclohexyl (meth) acrylate isobornyl (meth) acrylate, tricyclodecane dimethylol (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate are more preferable.

The ratio of (C) component is 5-65 weight% in the total amount of a sclerosing | hardenable component, Preferably it is 30-55 weight%.
When the proportion of component (C) is less than 5% by weight, the flexibility of the cured film becomes insufficient, and the cured film may be peeled off due to substrate deformation such as bending. When the proportion of the component (C) exceeds 65% by weight, the solvent resistance of the cured film is deteriorated, peeling due to dissolution or swelling of the cured film occurs, the tack of the cured film surface becomes strong, and a cured film is formed. There is a risk that the ease of handling of the member may be impaired.

4). Component (D) The component (D) is a compound having an ethylenically unsaturated group and is a compound other than the components (A) to (C), and a compound having two or more (meth) acryloyl groups is essential. It is a compound included as a component .
(D) A component is a component mix | blended as needed for the purpose of adjusting the viscosity of a composition, various physical properties of a cured film, etc.
Examples of the ethylenically unsaturated group include a (meth) acryloyl group, a vinyl group, and an allyl group. Among these, a (meth) acryloyl group is preferable because of excellent copolymerizability with other components.

(D) The ratio of a component is 0.5 to 40 weight% in the total amount of a sclerosing | hardenable component, Preferably it is 0.5 to 30 weight%.
When the ratio of (D) component exceeds 40 weight%, there exists a problem that it becomes impossible to make compatible adhesiveness and solvent resistance which are the characteristics of a composition.

As the component (D), a compound containing two or more ethylenically unsaturated groups in the molecule [hereinafter referred to as “component (D1)”] and a compound containing one ethylenically unsaturated group in the molecule [Hereinafter referred to as “component (D2)”].

First, the component (D1) will be described.
By including the component (D1), the solvent resistance of the resulting cured film can be improved.

  As the component (D1), a compound having two (meth) acryloyl groups [hereinafter referred to as “bifunctional (meth) acrylate”] and [hereinafter referred to as “trifunctional or higher (meth) acrylate”] are preferable.

  Specific examples of the bifunctional (meth) acrylate include 1,6-hexanediol di (meth) acrylate, nonanediol diacrylate, polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, and tetramethylene glycol. Di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) ) Di (meth) acrylates of alkylene oxide adducts of acrylate and bisphenol A, and the like.

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

  Among these compounds, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are more preferable.

  In addition, as the component (D1), oligomers other than the component (A) can be used, and examples thereof include epoxy (meth) acrylate and polyester (meth) acrylate.

  Component (D1) is commercially available. Specifically, Toronsei Mfg. Co., Ltd. Aronix M-305 (a mixture of pentaerythritol tri and tetraacrylate), M-309 (trimethylolpropane triacrylate), M-310 ( Trimethylolpropane propylene oxide modified (3 mol) triacrylate), M-315 (isocyanuric acid ethylene oxide modified tritriacrylate), M-320 (trimethylolpropane propylene oxide modified (6 mol) triacrylate), M-350 (tri Methylolpropane ethylene oxide modified triacrylate), M-360 (trimethylolpropane ethylene oxide modified (6 mol) triacrylate), M-402 (dipentaerythritol penta and hexaacrylate mixed) Things), M-404 (dipentaerythritol pentaacrylate and hexaacrylate mixture), M-408 (ditrimethylolpropane tetraacrylate), M-450 (pentaerythritol and tetraacrylate mixture), and the like.

(D1) As a ratio of a component, 0.5-30 weight% is preferable in a sclerosing | hardenable component total amount, More preferably, it is 1-10 weight%.
By making the proportion of the component (D1) 0.5% by weight or more, the solvent resistance of the cured film can be improved, and by making the proportion of the component (D1) 30% by weight or less, to the substrate It is possible to improve the adhesion of the substrate, prevent the cured film from becoming too hard, and follow the deformation of the substrate such as bending.

  The component (D2) is appropriately blended for the purpose of adjusting secondary performance such as glass transition temperature, water permeability, water absorption, etc., of the cured film depending on the purpose and usage.

  Examples of the ethylenically unsaturated group include a (meth) acryloyl group, a vinyl group, and an allyl group. Among these, a (meth) acryloyl group is preferable because of excellent copolymerizability with other components.

As the component (D2), 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”).
Monofunctional (meth) acrylates include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate and lauryl acrylate;
Monofunctional (meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate;
Monofunctional (meth) acrylates having alkoxyalkyl groups such as ethyl carbitol (meth) acrylate and alkyl carbitol (meth) acrylate such as 2-ethylhexyl carbitol (meth) acrylate;
Such as 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane Examples include alkoxysilyl group-containing (meth) acrylates; and glycidyl (meth) acrylates.
Examples of the vinyl compound include N-vinylcaprolactam and N-vinylpyrrolidone.

  (D2) is preferably an alkyl carbitol (meth) acrylate among the aforementioned compounds.

  The content ratio of the component (D2) is preferably 0 to 40% by weight and more preferably 30% by weight or less in the total amount of the curable component. When the proportion of the component (D2) exceeds 40% by weight, the resulting cured film tends to swell with respect to the organic solvent and may be easily peeled off.

5. Other components The composition of the present invention comprises the above components (A) to (D) as essential components, but various components usually used as a coating agent are blended depending on the purpose and application. Can do.
Preferable components include (E) component (photo radical polymerization initiator). Besides these, polyisocyanate compounds, photo acid generators, silane coupling agents, antioxidants, ultraviolet absorbers, light stabilizers. , Tackifiers, thiol compounds, plasticizers, fillers, fluorescent agents and / or dyes.

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 (E) The component (E) is a radical photopolymerization initiator.
The component (E) 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 necessary to add the component (E).

Specific examples of the 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-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.
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)-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.

  (E) As for the content rate of a component, 0.1-20 weight part is preferable with respect to 100 weight part of sclerosing | hardenable component total amount, More preferably, it is 1-10 weight part. (E) By making the ratio of a component into 0.1 weight part or more, the photocurability of a composition can be made favorable and it can be excellent in adhesiveness, and a cured film can be made into 20 weight part or less. The internal curability can be improved, and the adhesion to the substrate can be improved.

2) Polyisocyanate compound The polyisocyanate compound is irradiated with active energy rays to form a cured layer, and then the polyisocyanate compound is further reacted with the hydrophilic group of the component (B). Solvent properties can be greatly improved. In the polymerization of a compound having an ethylenically unsaturated group by irradiation with active energy rays, when the crosslinking component is increased, the solvent resistance is improved, but there is a problem that the adhesiveness is reduced due to stress concentration at the interface, Since the polyisocyanate compound can gradually increase the cross-linking density after the cured film is formed, it has an effect of facilitating compatibility between adhesion and solvent resistance.

The polyisocyanate compound needs to have a plurality of isocyanates in one molecule.
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, Examples include trimethylolpropane tris (tolylene diisocyanate) adduct and isophorone diisocyanate. The organic polyisocyanate is preferably an organic diisocyanate.

  Polyisocyanate compounds are commercially available, manufactured by Nippon Polyurethane Co., Ltd., Coronate L, Coronate T-65, Coronate T-80, Coronate T-100, Millionate MT, Millionate MR, etc., manufactured by Asahi Kasei Chemicals Co., Ltd. Examples include Duranate series, TPA-100, TKA-100, MFA-75B, MHG-80B, TLA-100, TSA-100, TSS-100, TSE-100, and 24A-100.

  The content rate of a polyisocyanate compound is 0.1-20 weight% with respect to the total amount of a sclerosing | hardenable component, Preferably it is 0.5-10 weight%. By making the content ratio of the polyisocyanate compound 0.1% by weight or more, the solvent resistance of the cured film layer is improved, and by making it 20% by weight or less, it contributes to the improvement of the adhesion to the base material (B It is possible to prevent the hydrophilic group of the component from being greatly reduced by the reaction with the isocyanate and the adhesion of the cured film to be lowered.

3) 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 ⁻ . Particularly preferable are PF ₆ ⁻ and B (C ₆ F _{5) 4} ^- it is.

The photo acid generator is commercially available, and examples thereof include the following compounds.
Examples of the aromatic sulfonium salt include Dow Chemical Co., Ltd., Cyracure UVI-6922 and UVI-6974, Asahi Denka Kogyo Co., Ltd., Adekaoptomer SP-150, SP-152, SP-170, and SP-172, San Apro Co., Ltd. CPI-100P, CPI-101A, etc. are mentioned.
Examples of the aromatic iodonium salt 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. .

  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.

4) 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-mercaptopropylmethyldi Tokishishiran, 3-mercaptopropyltrimethoxysilane, and the like.

What is necessary is just to set suitably the mixing | blending ratio of a silane coupling agent according to the objective, 0.1-10 weight part is preferable with respect to 100 weight part of curable components total, More preferably, it is 1-5 weight part.
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.

5) 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. 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.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphites and triaryl phosphites. 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 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.

What is necessary is just to set suitably as a mixture ratio of antioxidant according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable components, More preferably, it is 0.1-1 weight part. .
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.

6) 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.
What is necessary is just to set suitably the mixture ratio of a light stabilizer according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of total curable components, More preferably, it is 0.1-1 weight part. . 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.

7) Ultraviolet absorber An ultraviolet absorber is mix | blended in order to improve the light resistance of a cured film.
Examples of the ultraviolet absorber include triazine ultraviolet absorbers such as TINUVIN400, TINUVIN405, TINUVIN460, and TINUVIN479 manufactured by BASF, and benzotriazole ultraviolet absorbers such as TINUVIN900, TINUVIN928, and TINUVIN1130.
What is necessary is just to set suitably as a compounding ratio of a ultraviolet absorber according to the objective, 0.01-5 weight part is preferable with respect to 100 weight part of sclerosing | hardenable components total, More preferably, it is 0.1-1 weight part. is there. When the blending ratio is 0.01 parts by weight or more, the light resistance of the cured film can be made favorable, while by making it 5 parts by weight or less, the curability of the composition is excellent. be able to.

8) Tackifier A 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, 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 compounding ratio of a tackifier according to the objective, and 5-100 weight part is preferable with respect to 100 weight part of curable components total. 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.

9) 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) 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, 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.

10) 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 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.

11) 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 the multi-walled carbon nanotube 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.

12) 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 base material, after coating the composition on the base material, 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 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. 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 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 and the dye, if the amount is too large, the curability of the composition may be deteriorated when ultraviolet rays or visible rays are used as active energy rays. .
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.

13) 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 in order to prevent these 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, DISPERBYK manufactured 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-P104Y , 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. 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, AF-1005, NAF-250 etc. can be mentioned, but it is not limited to these.

  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.

6). Active energy ray-curable coating agent composition As a method for producing the composition of the present invention, the above components (A) to (D) are produced by stirring and mixing the other components as required according to a conventional method. can do. However, when a polyisocyanate compound is used, since the reaction with the component (B) proceeds by mixing, it is preferable to additionally mix the polyisocyanate compound immediately before use.
In this case, heating can be performed as necessary. The heating temperature may be appropriately set according to the composition to be 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, in terms of dialkyl carbonate content: cyclic carbonate content.

7). 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 metal substrates.
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 on 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 on the base material may be selected according to the use of the base material and the coated material, but is preferably 1 to 100 μm, more preferably 5 to 40 μm. It is.

  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, 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.

8). 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.
In this case, 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 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.

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 insulation coating layer hardened | cured on the desired film-like 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. In the following examples, “parts” means parts by weight.

1. Examples 1 to 28, Comparative Examples 1 to 7 (Production of active energy ray-curable coating agent composition)
The components 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 coating agent compositions.

  The numbers in Tables 1 to 5 mean the number of copies. The abbreviations in Tables 1 to 5 are as follows.

1) (A) component OT-1501: polyether-based urethane acrylate, Mw: 3,000 [Aronix OT-1501 manufactured by Toagosei Co., Ltd.]
M-1200: Polyester urethane acrylate, Mw: 5,000 [Aronix M-1200, manufactured by Toagosei Co., Ltd.]
* ABTO-003: Polycarbonate urethane acrylate, Mw: 10,000 [ABTO-003, manufactured by Negami Kogyo Co., Ltd.]
TGSA: Polyurethane acrylate urethane skeleton containing aromatics, Mw: 10,210 (Negami Kogyo Co., Ltd. Art Resin TGSA-001)
UN6060: Polyurethane skeleton urethane acrylate containing aromatic, Mw: 6,000, but this component contains 30 wt% of (C) component phenoxyethyl acrylate (Negami Kogyo Art Resin UN -6060P)
UN1255: Polyurethane acrylate containing an aromatic polyester, Mw: 8,000 (Art Resin UN-1255 manufactured by Negami Kogyo Co., Ltd.)
OT-1001: Polyester urethane acrylate, Mw: 40,000, manufactured by Toagosei Co., Ltd., trade name Aronix OT-1001 (however, IBXA is contained as a diluent at 50 wt%)
UN9200: Polycarbonate urethane acrylate, Mw: 1,500, manufactured by Negami Kogyo Co., Ltd., trade name Art Resin UN-9200A
KY-303: polyether-based urethane acrylate, Mw: 15,000 (KY-303 manufactured by Negami Kogyo Co., Ltd.)

2) Component (B) DMAA: N, N-dimethylacrylamide [manufactured by Kojin DMAA]
ACMO: acryloylmorpholine [ACMO manufactured by Kojin Co., Ltd.]
-HEAA: N-hydroxyethylacrylamide [ACMO manufactured by Kojin Co., Ltd.]
HBA: 4-hydroxybutyl acrylate [Osaka Organic Chemical Industry Co., Ltd. 4-HBA]
MAA: methacrylic acid [GE-110 manufactured by Mitsubishi Gas Chemical Co., Ltd.]
P-2M: 2-methacryloyloxyethyl acid phosphate [Kyoeisha Chemical Co., Ltd. light ester P-2M]
M-5300: ω-carboxy-polycaprolactone (average caprolactone addition mole number ≈ 2) monoacrylate [Aronix M-5300 manufactured by Toagosei Co., Ltd.]
M-5400: phthalic acid monohydroxyethyl acrylate [Toagosei Co., Ltd. Aronix M-5400]
M-5700: 2-hydroxy-3-phenoxypropyl acrylate [Aronix M-5700 manufactured by Toagosei Co., Ltd.]
-HPA: 2-hydroxypropyl acrylate [Osaka Organic Chemical Co., Ltd. 2-HPA]
HPMA: 2-hydroxypropyl methacrylate [Kyoeisha Chemical Co., Ltd. light ester HOP]

3) Component (C) M-106: o-phenylphenoxyethyl acrylate [Aronix M-106, manufactured by Toagosei Co., Ltd.]
POA: phenoxyethyl acrylate [Aronix M-100 manufactured by Toagosei Co., Ltd.]
BzMA: benzyl methacrylate [Kyoeisha Chemical Co., Ltd. light ester BZ]
M-101A: acrylate of phenol ethylene oxide adduct (average number of moles of added ethylene oxide ≈ 2) [Aronix M-101A manufactured by Toagosei Co., Ltd.]
-IBXA: Isobornyl acrylate [IBXA manufactured by Osaka Organic Chemical Industry Co., Ltd.]
THFA: Tetrahydrofurfuryl acrylate [Osaka Organic Chemical Co., Ltd. Viscoat # 150]
DCPA: tricyclodecane dimethylol diacrylate [Kyoeisha Chemical Co., Ltd. light acrylate DCP-A]
FA-512: dicyclopentenyloxyethyl acrylate [manufactured by Hitachi Chemical Co., Ltd., FA-512AS]

4) Component (D1) 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: Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture [Aronix M-402 manufactured by Toagosei Co., Ltd.]
M-313: Mixture of bis (2-acryloyloxyethyl) isocyanurate and tris (2-acryloyloxyethyl) isocyanurate [Aronix M-313 manufactured by Toagosei Co., Ltd.]

5) Component (D2) # 190: Ethyl carbitol acrylate [Biscoat 190 manufactured by Osaka Organic Chemical Industry Co., Ltd.]
KBM: 3-methacryloxypropyltrimethoxysilane [KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.]

6) Component (E) 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)
Irg379: 2-dimethylamino-2- (4-methyl-benzyl) -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)
Irg369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (IRGACURE369 manufactured by BASF)
・ TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (DAROCUR TPO manufactured by BASF)

7) Other ingredients
◆ Fluorescent brightener・ OB: 2,5-thiophenezyl bis (5-tert-butyl-1,3-benzoxazole (UVITEX OB manufactured by BASF)
◆ Thiol compound TMTP: Trimethylolpropane tristhiopropionate [manufactured by Sakai Chemical Co., Ltd. Trimethylolpropane tristhiopropionate (TMTP)]
◆ Polyisocyanate compound / COL45: Polyisocyanate consisting of a reaction product of tolylene diisocyanate and trimethylolpropane [Coronate L-45, manufactured by Nippon Polyurethane Co., Ltd.]
P301: polyisocyanate comprising a reaction product of hexamethylene diisocyanate and trimethylolpropane [Duranate P301-75E manufactured by Asahi Kasei Chemicals Corporation]
◆ Photoacid generator CPI: propylene carbonate solution of diphenyl [4- (phenylthio) phenyl] sulfonium = hexafluorophosphate and thiodi-p-phenylenebis (diphenylsulfonium) = bis (hexafluorophosphate) ) CPI-100P]
Irg250: propylene carbonate solution of iodonium, (4-methylphenyl) [4- (2-methylpropyl) phenyl] -hexafluorophosphate (1-) (IRGACURE250 manufactured by BASF)

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 used and 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).
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.

1) Evaluation method
(1) The cured film surface of the initial adhesion test specimen was cut with an X mark with a cutter, and a cello tape (registered trademark) manufactured by Nichiban Co., Ltd. was pasted thereon and peeled off by hand for evaluation. The adhesion was evaluated according to the following two levels.
○: A cured film remained on the surface of 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 cured film was peeled off by wind pressure.

(4) Solvent resistance: Insulating property A tester was applied to the surface of the cured film of the test specimen after the appearance was evaluated and the non-coated portion of the aluminum foil, and the electrical conductivity was examined, and evaluated according to the following two levels.
◯: There was no conduction and good insulation was maintained.
X: Conductivity was recognized.

2) Evaluation results The compositions of Examples 1 to 28, which are the compositions of the present invention, have excellent cured film adhesion to the substrate and followability to deformation, and substrate adhesion after immersion in an organic solvent. It was also excellent in insulation.
On the other hand, the compositions of Comparative Examples 1 and 4 and 7 that do not contain the component (B) have adhesion to the substrate, followability to deformation, substrate adhesion after immersion in an organic solvent, and insulating properties. Neither was satisfactory. The composition of Comparative Example 3 not containing the component (B) was excellent in followability to deformation, but was not satisfactory in adhesion to the substrate, adhesion to the substrate after immersion in an organic solvent, and insulation. there were.
Although the compositions of Comparative Examples 2 and 6 that do not contain the component (C) are excellent in adhesion to the substrate, the composition of Comparative Example 2 is not satisfactory in the followability to deformation. None of the compositions of the same 6 could satisfy the substrate adhesion and insulation after immersion in an organic solvent.
The composition of Comparative Example 5 containing no component (A) was excellent in adhesion to the substrate and followability to deformation, but could not satisfy the substrate adhesion or insulation after immersion in an organic solvent.
Furthermore, a flashlight NS365HBS (manufactured by Nitride Semiconductor Co., Ltd.) provided with a 365 nm UV-LED on a substrate with a cured film formed using the composition of Example 13 and 23 containing an optical brightener When the irradiation was performed, 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.

3. Examples 29 to 32 (Production of active energy ray-curable coating agent 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. 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 -Specific surface area (JISK6217) determined by the BET formula (hereinafter referred to as “# 3050”) was used.
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 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 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)

An active energy ray-curable metal base coating composition containing the following components (A) to (D) in the following proportions as a curable component.
(A) Urethane (meth) acrylate having a weight average molecular weight of 1,000 to 60,000: 5 to 50% by weight in the total amount of curable components
(B) Compound having a hydrophilic group and one ethylenically unsaturated group: 5 to 45% by weight in the total amount of the curable component
(C) have a cyclic hydrocarbon group and one ethylenically unsaturated group, a compound having no hydrophilic group, (B) other than the component compounds: 5 to 65 in the curable composition the total amount weight%,
(D) A compound having an ethylenically unsaturated group, which is a compound other than the components (A) to (C) and includes a compound having two or more (meth) acryloyl groups as an essential component : Curability 0.5 to 40% by weight in the total amount of ingredients The active energy ray-curable metal substrate coating composition according to claim 1, wherein the component (A) is a reaction product of a polyol, an organic polyisocyanate, and a hydroxyl group-containing (meth) acrylate. The component (B) is one or more selected from the group consisting of a compound having a hydroxyl group and a (meth) acryloyl group, a compound having a carboxyl group and a (meth) acryloyl group, and a compound having an amide group and a (meth) acryloyl group. The active energy ray hardening-type coating material composition for metal base materials of Claim 1 or Claim 2. The coating composition for an active energy ray-curable metal substrate according to claim 3, wherein the compound having a hydroxyl group and a (meth) acryloyl group in the component (B) contains a hydroxyalkyl (meth) acrylate. The active energy ray-curable coating material composition for a metal substrate according to claim 3, wherein the compound having a carboxyl group and a (meth) acryloyl group in the component (B) contains (meth) acrylic acid. The compound having an amide group and a (meth) acryloyl group in component (B) is (meth) acryloylmorpholine, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide or / and N-hydroxyethyl. The coating composition for an active energy ray-curable metal substrate according to claim 3, comprising (meth) acrylamide. The component (C) includes a compound having an aromatic group and a (meth) acryloyl group or / and a compound having an alicyclic group and a (meth) acryloyl group. An active energy ray-curable metal base material coating agent composition. The compound having an aromatic group and a (meth) acryloyl group in the component (C) includes phenylphenyl group-containing (meth) acrylate, cumyl group-containing (meth) acrylate or / and phenyl group-containing (meth) acrylate. The coating composition for active energy ray-curable metal substrate according to the above. The compound having an alicyclic group and a (meth) acryloyl group in the component (C) is a cyclohexyl group-containing (meth) acrylate, isobornyl group-containing (meth) acrylate, tricyclodecane group-containing (meth) acrylate, and / or dicyclohexane. The coating composition for an active energy ray-curable metal substrate according to claim 7, comprising a pentenyl group-containing (meth) acrylate. Additionally, (E) a photo-radical polymerization initiator, active energy ray-curable metal according to any one of claims 1 to 9 comprising 0.1 to 20 wt% of the curable components total amount A coating composition for a substrate . Furthermore, the coating agent composition for active energy ray hardening-type metal base materials of any one of Claims 1-10 containing a fluorescent agent, a pigment | dye, and / or a pigment. 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. radiation-curable metal substrate coating composition according to any one of 1 to claim 11. The coating composition for an active energy ray-curable metal substrate according to any one of claims 1 to 12, wherein the metal substrate is a film-like substrate. The metal substrate is aluminum, The active energy ray hardening-type coating material composition for metal substrates of any one of Claims 1-13 . The metal substrate surface, according to claim 1 metal substrate having a cured film cured film is formed of a radiation-curable metal substrate coating composition according to any one of claims 14. Applying the coating composition for active energy ray-curable metal substrate according to any one of claims 1 to 14 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. The method for producing a metal substrate having a cured film according to claim 16 , wherein the metal substrate is a film-like metal substrate. The method for producing a metal substrate having a cured film according to claim 16 or 17 , wherein the metal substrate is aluminum. 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. Cured film cured by irradiation of active energy rays, after immersion for 24 hours at 25 ° C. to dialkyl carbonate and cyclic carbonate mixed organic solvent, not peeled from the metal substrate, any one of claims 16 to claim 19 A method for producing a metal substrate having the cured film according to item 1. The active energy ray-curable metal substrate coating composition includes 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,
Method for producing a metal substrate having a cured film according to any one of claims 16 to claim 20.