JP2003002928A - Resin composition and its cured material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition curable with a practical amount of light irradiation without a photo-polymerization initiator, or using it by a smaller amount than that used conventionally, and the cured material. SOLUTION: This resin composition is composed of (A) a maleimide derivative which is a reaction product of (c) 2-isocyanateethyl methacrylate with (I) a reaction product of (a) a maleimide group-containing monocarboxylic acid with (b) a compound having at least one epoxy group in one molecule, and as an optional component, (B) a polymerizable compound other than the component (A).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to various coating materials, surface treatment agents, molding materials, laminated plates, adhesives, adhesives,
Regarding a novel active energy ray-curable resin composition useful for printing inks, binders, and the like, more specifically, a photopolymerization initiator is not used, or a practical irradiation dose even when used in a smaller amount than the conventional amount. The present invention relates to a novel resin composition which is cured by ultraviolet rays and a cured product thereof.

[0002]

2. Description of the Related Art Resin compositions which are polymerized by active energy rays such as ultraviolet rays and visible rays have an advantage of rapid curing and are widely used in paints, printing inks, adhesives, coating agents and the like. However, the conventional active energy ray-curable compositions do not initiate polymerization by themselves, and thus it is necessary to use a photopolymerization initiator in combination. If the amount of the photopolymerization initiator added is increased, the curing proceeds rapidly, so that the amount added tends to be large.

Further, in a cured product of an active energy ray-curable composition containing a photopolymerization initiator, an unreacted photopolymerization initiator or a decomposition product of the photopolymerization initiator remains. When light or heat acts on the cured product, the cured product may turn yellow or generate a bad odor. In addition, a cured product of an active energy ray-curable composition containing a photopolymerization initiator is not suitable for use as a food packaging material because the unreacted photopolymerization initiator and the like bleed when left in water or the like. It was suitable.

In order to improve the drawbacks of the active energy curable composition containing these photopolymerization initiators, an active energy ray curable composition containing no photopolymerization initiator is disclosed in JP-A-6-298817. A photopolymerization method using a maleimide compound as an electron acceptor via a charge transfer complex formed in combination with an electron donor is disclosed.

Furthermore, "Polymer Materials Science and Engineering (Polymer M
materials Science and Engi
72) pp. 470-472 (19)
1995) and "4th Fusion UV Technology Seminar", pp. 43-77 (1996), a method of using a maleimide derivative as an electron acceptor and vinyl ether as an electron donor is reported. In these documents, a photopolymerizable composition composed of a combination of 1,4-bis (vinyloxymethyl) cyclohexane and cyclohexylmaleimide, or 4-hydroxy, is shown as a compound exhibiting polymerizability in the absence of a photopolymerization initiator. Photopolymerizable compositions comprising a combination of butyl vinyl ether and hydroxyalkyl maleimide are described. However, these compositions had a problem that a cured coating film was not formed although the reaction proceeded.

On the other hand, "Polymer preprints (Poly
Mer Preprints) ", Vol. 37, No. 2, 34
Pages 8 to 349 (1996) include 1,6-hexanediol diacrylate and polyethylene glycol # 40.
N, N'-4,9 as a polymerization initiator of 0 diacrylate
Maleimides such as -dioxa-1,12-bismaleimido dodecane are disclosed. However, these maleimides have problems that they are often solid and their solubility in acrylate is poor.

[0007]

The object of the present invention is to use a specific maleimide derivative (A) so that no photopolymerization initiator is used, or a practical irradiation is possible even when the amount used is smaller than the conventional amount. Provided are a novel resin composition which is cured by a certain amount of ultraviolet rays and which is cured by a liquid active energy ray at room temperature, and a cured product thereof.

[0008]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present inventors have been able to solve the above-mentioned problems by using the novel resin composition containing the specific maleimide derivative (A). The inventors have found that the above can be achieved and completed the present invention. That is, the present invention provides (1) a reaction product (I) of a maleimide group-containing monocarboxylic acid (a) and a compound (b) having at least one epoxy group in one molecule, and 2-isocyanate ethyl methacrylate (c). A) a resin composition comprising a maleimide derivative (A) which is a reaction product of the above) and a polymerizable compound other than the component (A) as an optional component, (2) the polymerizable compound (B) is (meth) acryloyl The resin composition according to (1), which is one or more compounds selected from the group consisting of compounds having a group, a vinyl ether group or an N-vinyl group, and (3) a compound having a (meth) acryloyl group is a (poly) ester. (Meth) acrylate (B-1-1), urethane (meth) acrylate (B-1-2), epoxy (meth) acrylate (B-1-3), (poly) ether (meth
Acrylate (B-1-4), alkyl (meth) acrylate or alkylene (meth) acrylate (B-1-
5), (meth) acrylate having an aromatic ring (B-1-
6) and a (meth) acrylate having an alicyclic structure (B-
The resin composition according to (2), which is one or more compounds selected from the group consisting of 1-7), and (4) a compound having a vinyl ether group, in which the other end may be substituted with a halogen atom or a hydroxyl group. Vinyl ether (B-2-
1), a cycloalkyl vinyl ether which may be substituted on the other end with a halogen atom or a hydroxyl group (B-2-
2), at least one selected from the group consisting of an alkyl group, a cycloalkyl group, and an aromatic group in which a vinyl ether group is bonded to an alkylene group and further having a substituent, an ether bond, a urethane bond, and an ester bond. One or more compounds selected from the group consisting of monovinyl ethers, vinyl ethers and polyvinyl ethers (B-2-3) having a structure in which they are bonded via at least one bond selected from the group consisting of (3) The resin composition described above, (5) containing a photopolymerization initiator (C) (1)
To the resin composition according to any one of (4),
(6) A cured product of the resin composition according to any one of (1) to (5).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention comprises a maleimide group-containing monocarboxylic acid (a) and at least 1 in the molecule.
With a compound (b) having one epoxy group (I)
And a maleimide derivative (A) which is a reaction product of 2-isocyanatoethyl methacrylate (c) and a polymerizable compound (B) other than the component (A) as an optional component.

Specific examples of the maleimide group-containing monocarboxylic acid (a) include, firstly,

[0011]

[Chemical 1]

As shown by the formula (1), a known technique [for example, D.
DH Rich et al. "Journal
Of Medical Chemistry (Journal o
f Medical Chemistry) "18th
Vol. 1004-1010 (1975)], compound (a-1), secondly, a maleimide compound having a hydroxyl group and a compound having one acid anhydride group in the molecule. The half-esterified compound (a-2) and the like can be mentioned.

Examples of the maleimide compound having a hydroxyl group include those represented by the reaction formula

[0014]

[Chemical 2]

As shown by the formula, maleimide and formaldehyde, or a reaction formula

[0016]

[Chemical 3]

As shown in (1), it can be synthesized from maleic anhydride and a primary amino alcohol using a known technique (see, for example, US Pat. No. 2,526,517, JP-A-2-268155). it can.

Examples of the primary aminocarboxylic acid used in the above reaction include asparagine, alanine, β-alanine, arginine, isoleucine, glycine, glutamine, tryptophan, threonine, valine, phenylalanine, homophenylalanine, α-methyl-phenylalanine. , Lysine, leucine, cycloleucine, 3-
Aminopropionic acid, α-aminobutyric acid, 4-aminobutyric acid, aminovaleric acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 2-aminocaprylic acid, 3-aminocaprylic acid, 6-aminocaprylic acid, 8-amino Caprylic acid,
Examples thereof include 9-aminononanoic acid, 2-aminocapric acid, 9-aminocapric acid, 15-aminopentadecanoic acid, 2-aminopalmitic acid, 16-aminopalmitic acid, but are not limited thereto.

Examples of the primary amino alcohol used in the above reaction include 2-aminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-
Amino-3-phenyl-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 2-
Amino-3-methyl-1-butanol, 2-amino-thiomethylthio-1-butanol, 2-amino-1-pentanol, (1-aminocyclopentane) methanol, 6
Examples thereof include, but are not limited to, -amino-1-hexanol, 7-amino-1-heptanol, 2- (2-aminoethoxy) ethanol, and the like.

Specific examples of the compound having one acid anhydride group in the molecule include maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride and methyl-hexahydroanhydride. Examples thereof include phthalic acid and methyl-tetrahydrophthalic anhydride.

The half-esterified product (a-2) is
It can be obtained by reacting one chemical equivalent of a hydroxyl group in the maleimide compound having a hydroxyl group with about one chemical equivalent of an anhydride group in a compound having one acid anhydride group in the molecule. The reaction temperature is preferably 60 to 100 ° C., and the reaction time is preferably 1 to 10 hours. At the time of reaction, an organic solvent can be used if necessary.

Specific examples of the compound (b) having at least one epoxy group in one molecule include tert-butyl glycidyl ether, phenyl glycidyl ether,
Glycidyl (meth) acrylate, 9,10-epoxystearyl (meth) acrylate, methylglycidyl (meth) acrylate,

[0023]

[Chemical 4]

(CYCLO manufactured by Daicel Chemical Industries, Ltd.)
MER A200)

[0025]

[Chemical 5]

(CYCLO manufactured by Daicel Chemical Industries, Ltd.)
Monofunctional epoxy compounds (b) such as MER M100)
-1), bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol methane type epoxy resin, brominated epoxy resin, bixylenol type epoxy resin, biphenol type Polyfunctional glycidyl ethers such as epoxy resin (b
-2), 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 1-epoxyethyl-3,4
Examples thereof include alicyclic epoxy compounds (b-3) such as epoxycyclohexane, and heterocyclic epoxy compounds (b-4) such as triglycidyl isocyanurate.

The reaction of the maleimide group-containing monocarboxylic acid (a) with the compound (b) having at least one epoxy group in one molecule is solvent-free, solvents such as, for example,
Acetone, ethyl methyl ketone, cyclohexanone and other ketones, benzene, toluene, xylene, tetramethylbenzene and other aromatic hydrocarbons, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triketone Glycol ethers such as ethylene glycol dimethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, etc. , Cyclic esters such as γ-butyrolactone, petroleum ether , Petroleum naphtha, a petroleum solvent or the like, such as Sorubensonafusa can be preferably used. Further, a compound having a (meth) acryloyl group described later can be preferably used.

During the reaction, it is preferable to use a catalyst for promoting the reaction, and the amount of the catalyst used is 0.1 to 10% by weight based on the reactant. Specific examples of the catalyst are
Triethylamine, benzyldimethylamine, 2-methylimidazole, triethylammonium chloride,
Examples thereof include benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, chromium octanoate, zirconium octanoate and the like.

A polymerization inhibitor may be used during the reaction for the purpose of preventing polymerization. Specific examples of the polymerization inhibitor include P-
Methoxyphenol, hydroquinone, methylhydroquinone, phenothiazine and the like can be mentioned. The amount of the polymerization inhibitor used is 0.05 to 3% by weight based on the reaction product.

With respect to the reaction ratio of the above-mentioned components (a) and (b), it is preferable to react about 1 equivalent of the carboxylic acid in the component (b) with respect to 1 equivalent of the epoxy group in the component (a). The reaction temperature is preferably 70 to 150 ° C, and the reaction time is 5 to 5
0 hours is preferred.

The 2-isocyanatoethyl methacrylate (c) used in the present invention can be easily obtained from the market. For example, Showa Denko KK product name, Karens MOI, etc. can be mentioned.

The maleimide derivative (A) of the present invention is a hydroxyl group in the reaction product (I) obtained by reacting the above-mentioned components (a) and (b) with the isocyanate of 2-isocyanate ethyl methacrylate (c). It can be obtained by reacting a group. Reactants (I) and (c)
The reaction ratio of the components is preferably such that 0.1 to 1.1 equivalents of isocyanate groups in the component (c) are reacted with 1 equivalent of hydroxyl groups in the reaction product (I), and particularly preferably 0.5.
~ 1.0 equivalent. The reaction temperature is preferably 40 to 100 ° C., and the reaction time is preferably 0.5 to 15 hours. In the resin composition of the present invention, a polymerizable compound (B) other than the component (A) can be used as an optional component. Specific examples of the polymerizable compound (B) include (meth) acryloyl group-containing compounds, vinyl ether group-containing compounds, and N-
Examples thereof include compounds having a vinyl group, maleimide compounds other than the component (A), (meth) acrylamide compounds, and unsaturated polyesters.

(Meth) that can be used in combination with the resin composition of the present invention
Compounds having an acryloyl group are roughly classified into (poly)
Ester (meth) acrylate (B-1-1); Urethane (meth) acrylate (B-1-2); Epoxy (meth) acrylate (B-1-3); (Poly) ether (meth) acrylate (B- 1-4); alkyl (meth) acrylate or alkylene (meth) acrylate (B-1-5); (meth) acrylate having an aromatic ring (B-1-6); (meth) acrylate having an alicyclic structure ( B-1-7) and the like, but the invention is not limited thereto.

(Poly) that can be used in combination with the resin composition of the present invention
The ester (meth) acrylate (B-1-1) is a generic term for (meth) acrylate having one or more ester bonds in the main chain and is a urethane (meth) acrylate (B-.
1-2) is a general term for (meth) acrylates having one or more urethane bonds in the main chain, and is epoxy (meth)
Acrylate (B-1-3) is a general term for (meth) acrylate obtained by reacting a monofunctional or higher functional epoxy compound with (meth) acrylic acid, and is a (poly) ether (meth) acrylate (B-1- 4) is a general term for (meth) acrylate having at least one ether bond in the main chain, and alkyl (meth) acrylate or alkylene (meth) acrylate (B-1-5) is a straight-chain alkyl having a main chain. , Branched alkyl, and (meth) acrylate (B-1-6) having an aromatic ring as a general term for (meth) acrylate which may have a halogen atom and / or a hydroxyl group at a straight chain or at a terminal are the main chains. Or, as a general term for (meth) acrylates having an aromatic ring in the side chain, (meth) acrylate (B-1-7) having an alicyclic structure means that the main chain or side chain has an acid as a structural unit. As a general term that also contain an atom or a nitrogen atom having a good alicyclic structure-containing (meth) acrylate is used, respectively.

(Poly) that can be used in combination with the resin composition of the present invention
Examples of the ester (meth) acrylate (B-1-1) include caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth ) Acrylate, monofunctional (poly) ester (meth) acrylates such as caprolactone modified tetrahydrofurfuryl (meth) acrylate; hydroxypivalic acid ester neopentyl glycol di (meth) acrylate, caprolactone modified hydroxypivalic acid ester neopentyl glycol di ( (Meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate; 1 mol or more of ε- per 1 mol of trimethylolpropane or glycerin
Mono-, di- or tri (meth) acrylate of triol obtained by adding a cyclic lactone compound such as caprolactone, γ-butyrolactone, δ-valerolactone;

1 mol or more of ε-caprolactone per 1 mol of pentaerythritol or ditrimethylolpropane,
Mono-, di-, tri- or tetra (meth) acrylate of triol obtained by adding a cyclic lactone compound such as γ-butyrolactone and δ-valerolactone; 1 mol or more of ε-caprolactone and γ-butyrolactone per 1 mol of dipentaerythritol , A monool of triol obtained by adding a cyclic lactone compound such as δ-valerolactone, or a mono (meth) acrylate of polyhydric alcohol such as triol, tetraol, pentaol or hexaol of poly (meth) acrylate, or poly (Meth) acrylate;

(Poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, 3-methyl-1,5
-Diol components such as pentanediol and hexanediol and maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, dimer acid, sebacic acid, azelaic acid, 5-sodium (Meth) acrylate of polyester polyol which is a reaction product of polybasic acids such as sulfoisophthalic acid and their anhydrides; the diol component and polybasic acids and their anhydrides and ε-caprolactone, γ-
Examples thereof include, but are not limited to, polyfunctional (poly) ester (meth) acrylates such as (meth) acrylate of a cyclic lactone-modified polyester diol composed of butyrolactone, δ-valerolactone and the like.

The urethane (meth) acrylate (B-1-2) usable in combination with the resin composition of the present invention is a hydroxy compound (B-1-2) having at least one (meth) acryloyl group and an isocyanate compound. (B-1-
It is a general term for (meth) acrylates obtained by the reaction with 2-).

As the hydroxy compound (B-1-2) having at least one (meth) acryloyl group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, 4-hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, Examples thereof include (meth) acrylate compounds having various hydroxyl groups such as 2-hydroxy-3-phenoxypropyl (meth) acrylate, and ring-opening reaction products of the above-mentioned (meth) acrylate compounds having hydroxyl groups and ε-caprolactone.

Isocyanate compound (B-1-2)
As, for example, P-phenylene diisocyanate,
m-Phenylene diisocyanate, P-xylene diisocyanate, m-xylene diisocyanate, 2,4-
Aromatic diisocyanates such as tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexyl methane diisocyanate, hydrogenated xylene diisocyanate, Aliphatic or alicyclic diisocyanates such as norbornene diisocyanate and lysine diisocyanate;
Examples include polyisocyanates such as one or more burettes of isocyanate monomers or isocyanates obtained by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by urethanization reaction between the above isocyanate compounds and the above polyol compounds.

The epoxy (meth) acrylate (B-1-3) that can be used in combination with the resin composition of the present invention is obtained by reacting an epoxy resin containing a monofunctional or higher epoxy group with (meth) acrylic acid. Is a general term for (meth) acrylates. Examples of the epoxy resin used as a raw material for the epoxy (meth) acrylate include the compound (b-4) having an epoxy group described above.

(Poly) that can be used in combination with the resin composition of the present invention
Examples of the ether (meth) acrylate (B-1-4) include butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate,
Epichlorohydrin-modified butyl (meth) acrylate,
Dicyclopentenyloxyethyl (meth) acrylate,
Monofunctional (poly) ether (meth) acrylates such as 2-ethoxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate;

Alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate; ethylene oxide and Propylene oxide copolymers, propylene glycol-tetrahydrofuran copolymers, polyisoprene glycols, hydrogenated polyisoprene glycols, polybutadiene glycols, hydrogenated polybutadiene glycols and other polyhydric hydroxyl compounds such as hydrocarbon-based polyols (meth) Polyfunctional (meth) acrylates derived from acrylic acid; neopentyl glycol 1
Di (meth) acrylate of diol in which 1 mole or more of a cyclic ether such as ethylene oxide, propylene oxide, butylene oxide is added to a mole;

Di (meth) acrylates of alkylene oxide modified products of bisphenols such as bisphenol A, bisphenol F and bisphenol S; hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S
Alkylene oxide-modified di (meth) acrylate of hydrogenated bisphenols such as trimethylolpropane or glycerin, 1 mol or more of ethylene oxide,
A mono-, di- or tri (meth) acrylate of triol obtained by adding a cyclic ether compound such as propylene oxide or butylene oxide;

1 mol or more of ethylene oxide per 1 mol of pentaerythritol or ditrimethylolpropane,
Mono-, di-, tri- or tetra (meth) acrylate of triol to which cyclic ether compound such as propylene oxide and butylene oxide is added; 1 mol or more of cyclic ether compound such as ethylene oxide, propylene oxide and butylene oxide per 1 mol of dipentaerythritol Examples thereof include polyfunctional (poly) ether (meth) acrylates such as 3- to 6-functional (meth) acrylates of hexaol added with.

Examples of the alkyl (meth) acrylate or alkylene (meth) acrylate (B-1-5) that can be used in the resin composition of the present invention include octyl (meth) acrylate, isooctyl (meth) acrylate and decyl ( Monofunctional (meth) acrylates such as (meth) acrylate and dodecyl (meth) acrylate;

Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate,
1,4-butanediol di (meth) acrylate, 1,
6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate,
1,9-nonanediol di (meth) acrylate, 1,
Hydrocarbon diol di (meth) acrylates of 10-decanediol di (meth) acrylate;

Trimethylolpropane mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate
Acrylate (hereinafter, “poly” is used as a general term for polyfunctional such as di, tri, tetra, etc.), mono (meth) acrylate or poly (meth) acrylate of glycerin, mono- or poly (meth) acrylate of pentaerythritol, ditri. Methylol propane mono or poly (meta)
Acrylate, triol such as dipentaerythritol mono- or poly (meth) acrylate, tetraol,
Mono- or poly (meth) acrylates of polyhydric alcohols such as hexaol;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4
-Hydroxyl group-containing (meth) acrylates such as hydroxybutyl (meth) acrylate; and the like.

As the (meth) acrylate (B-1-6) having an aromatic ring which can be used in combination with the resin composition of the present invention,
For example, monofunctional (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;
Examples thereof include, but are not limited to, di (meth) acrylates such as bisphenol A di (meth) acrylate and bisphenol F di (meth) acrylate.

Examples of the (meth) acrylate (B-1-7) having an alicyclic structure which can be used in combination with the resin composition of the present invention include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate and isobornyl (meth). Monofunctional (meth) acrylates having an alicyclic structure such as acrylate and dicyclopentenyl (meth) acrylate; Di (meth) acrylate of hydrogenated bisphenols such as hydrogenated bisphenol A and hydrogenated bisphenol F; tricyclodecanedi Examples include polyfunctional (meth) acrylates having a cyclic structure such as methylol di (meth) acrylate; alicyclic (meth) acrylates having an oxygen atom in the structure such as tetrafurfuryl (meth) acrylate, and the like. However, it is not limited to this.

As the compound having a (meth) acryloyl group which can be used in combination with the resin composition of the present invention, in addition to the above-mentioned compounds, for example, a reaction of a (meth) acrylic acid polymer with glycidyl (meth) acrylate Or a poly (meth) acrylic polymer (meth) acrylate such as a reaction product of a glycidyl (meth) acrylate polymer and (meth) acrylic acid; dimethylaminoethyl (meth)
(Meth) acrylate having amino group such as acrylate; isocyanuric (meth) acrylate such as tris ((meth) acryloxyethyl) isocyanurate; (meth) acrylate having polysiloxane skeleton; polybutadiene (meth) acrylate; melamine (meth) ) Acrylate and the like can also be used.

Next, the compounds having a vinyl ether group which can be used in combination with the resin composition of the present invention are roughly classified, and an alkyl vinyl ether (B-2-1) in which the other end may be substituted with a halogen atom or a hydroxyl group, Cycloalkyl vinyl ether (B-2-2) which may be substituted with a halogen atom or a hydroxyl group at the other end, an alkyl group which has a vinyl ether group bonded to an alkylene group, and which may further have a substituent, a cycloalkyl group And a mono-, di-, or polyvinyl ether having a structure in which at least one group selected from the group consisting of, and an aromatic group is bonded to each other through at least one bond selected from the group consisting of an ether bond, a urethane bond, and an ester bond. (B-2-3), and the like, but are not limited to these.

The above-mentioned alkyl vinyl ether (B-2-
As 1), for example, hydroxymethyl vinyl ether, chloromethyl vinyl ether, hydroxyethyl vinyl ether, 2-chloroethyl vinyl ether, 1,
4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 4-hydroxybutyl vinyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether and the like can be mentioned, but not limited thereto.

Cycloalkyl vinyl ether (B
Examples of -2-2) include, but are not limited to, 2-hydroxycyclopropyl vinyl ether, cyclohexyl vinyl ether, cyclohexane dimethanol mono- or divinyl ether, cyclohexane diol mono- or divinyl ether, and the like.

Examples of the mono-, di- and polyvinyl ethers (B-2-3) include compounds having an ether bond (B-2-3-) and compounds having a urethane bond (B-2-3-). , A compound having an ester bond (B-2-3-), and the like. Examples of the compound (B-2-3-) having an ether bond include ethylene glycol methyl vinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol methyl vinyl ether,
Examples include dipropylene glycol divinyl ether and ditetramethylene glycol divinyl ether.

Compound having urethane bond (B-2-3
-) Is a monovinyl ether (m) of (poly) alkylene glycol having one hydroxyl group in one molecule.
And a compound (n) having at least one isocyanate group in one molecule can be obtained by a urethanization reaction.

Among these, examples of the monovinyl ether (m) of (poly) alkylene glycol having one hydroxyl group in one molecule include 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether,
Examples thereof include polyethylene glycol monovinyl ether.

On the other hand, the compound (n) containing at least one isocyanate group in one molecule is, for example,
The above-mentioned isocyanate compound (B-1-2) and the like can be mentioned.

A compound having an ester bond (B-2-3
-) Is the dehalogenation of the compound (liter) having the monovinyl ether (m) of (poly) alkylene glycol having one hydroxyl group in one molecule and at least one carboxylic acid halide in one molecule. It can be obtained by an esterification reaction with hydrogen.

Examples of the compound (liter) having at least one carboxylic acid halide in one molecule include known carboxylic acid halides such as carboxylic acid chloride and bromide. Specific examples of the carboxylic acid include acetic acid, propionic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, dimer acid, sebacic acid, tetrahydrophthalic acid and azelaic acid.

Next, N which can be used in combination with the resin composition of the present invention
Examples of the compound having a vinyl group include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide and the like.

Examples of the maleimide compound other than the component (A) that can be used in combination with the resin composition of the present invention include N-n-butylmaleimide, N-tert-butylmaleimide, N-hexylmaleimide, 2 -Maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-
Monofunctional aliphatic maleimides such as propyl carbonate, N-ethyl- (2-maleimidoethyl) carbamate;
Alicyclic monofunctional maleimides such as N-cyclohexylmaleimide; Aliphatic bismaleimides such as N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, and bis (2-maleimidoethyl) carbonate 1,4-dimaleimidocyclohexane, isophorone bisurethane bis (N-
Alicyclic bismaleimides such as ethylmaleimide); maleimide compounds obtained by esterification of maleimideacetic acid and polytetramethylene glycol; carboxy of maleimide compounds by esterification of maleimidecaproic acid and tetraethylene oxide adduct of pentaerythritol. Examples thereof include (poly) ester (poly) maleimide compounds obtained by esterifying a maleimide derivative with various (poly) ols, but are not limited thereto.

(Meth) that can be used in combination with the resin composition of the present invention
Examples of the acrylamide compound include monofunctional (meth) acrylamides such as acryloylmorpholine and N-isopropyl (meth) acrylamide; and polyfunctional (meth) acrylamides such as methylenebis (meth) acrylamide.

As the unsaturated polyester which can be used in combination,
Examples thereof include maleic acid esters such as dimethyl maleate and diethyl maleate; esterification reaction products of polyunsaturated carboxylic acids such as maleic acid and fumaric acid, and polyhydric alcohols.

The polymerizable compound (B) that can be used in the resin composition of the present invention is not limited to the above-mentioned compounds, but any compound having a copolymerizability with the component (A) can be used. There are no particular restrictions on the type or compounds of multiple types,
Can be used together.

In the resin composition of the present invention, the ratio of the components (A) and (B) used is not particularly limited, but the ratio (B) to 100 parts by weight of the component (A) is not limited. )
It is preferable to use 0 to 1000 parts by weight of the component.
It is particularly preferred to use ˜500 parts by weight.

The resin composition of the present invention is cured by irradiation with ultraviolet rays or visible rays in the absence of a photopolymerization initiator, but in order to carry out the curing reaction more efficiently, a known conventional photopolymerization initiator is used. (C) can be added and cured.
The photopolymerization initiator (C) can be roughly classified into two types, an intramolecular bond cleavage type and an intramolecular hydrogen abstraction type.

Examples of the intramolecular bond cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal and 1- (4-isopropylphenyl). ) -2-Hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-
Hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenone series such as morpholinophenyl) -butanone;
Benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; acylphosphine oxides such as 2,4,6-trimethylbenzoindiphenylphosphine oxide; benzyl and methylphenylglyoxyester.

On the other hand, as the intramolecular hydrogen abstraction type photopolymerization initiator, for example, benzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, benzophenone compounds such as acryl and benzophenone; 2-isopropylthioxanthone, 2,4 A thioxanthone system such as diethoxythioxanthone or 2-chlorothioxanthone;
Aminobenzophenone compounds such as 4,4′-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, camphorquinone and the like can be mentioned.

When the photopolymerization initiator is used, the compounding amount is
The range of 0.01 to 10.00% by weight in the resin composition is preferable.

The resin composition obtained in the present invention is cured by irradiation with ultraviolet rays or visible rays in the absence of a photopolymerization initiator, but a photopolymerization accelerator is added in order to carry out the curing reaction more efficiently. It can also be used together.

Examples of such a photopolymerization accelerator include triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl ester, 4-dimethylaminobenzoic acid ethyl ester and 4-dimethylaminobenzoic acid. Examples include amines such as isoamyl ester.

When the photopolymerization accelerator is used, the compounding amount is
The range of 0.01 to 10.00% by weight in the resin composition is preferable.

Further, the resin composition obtained in the present invention is a non-reactive compound, an inorganic filler, an organic filler, a coupling agent, a tackifier, a defoaming agent, a leveling agent, a plasticizer depending on the use. , Antioxidants, ultraviolet absorbers, flame retardants, pigments, dyes and the like can be appropriately used.

Specific examples of the non-reactive compound include:
Liquid or solid oligomer or resin with low or no reactivity, alkyl (meth) acrylate copolymer, epoxy resin, liquid polybutadiene, dicyclopentadiene derivative, saturated polyester oligomer, xylene resin, polyurethane Examples thereof include, but are not limited to, polymers, ketone resins, diallyl phthalate polymers (dap resins), petroleum resins, rosin resins, fluorine-based oligomers and silicon-based oligomers.

Examples of the above-mentioned inorganic filler include silicon dioxide, silicon oxide, calcium carbonate, calcium silicate,
Magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide, zinc sulfate, aluminum hydroxide, aluminum oxide, glass, mica, barium sulfate, alumina white, zeolite, silica balloon, glass balloon and the like can be mentioned. To these inorganic fillers, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, etc. are added and reacted by a method such as a halogen group, an epoxy group, a hydroxyl group, a thiol group. It is also possible to have a functional group of the group.

Examples of the organic filler include benzoguanamine resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, acrylic copolymer, polymethylmethacrylate resin, Examples thereof include fluororesin, nylon 12, nylon 6/66, phenol resin, epoxy resin, urethane resin, and polyimide resin.

As the silane coupling agent, for example,
γ-glycidoxypropyltrimethoxysilane or γ-
A silane coupling agent such as chloropropyltrimethoxysilane, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate,
Examples thereof include titanate coupling agents such as bis (dioctyl pyrophosphate) ethylene titanate; aluminum coupling agents such as acetoalkoxyaluminum diisopropylate; zirconium coupling agents such as acetylacetone-zirconium complex.

The tackifier, defoaming agent, leveling agent, plasticizer, antioxidant, ultraviolet absorber, flame retardant, pigment and dye that can be used in the resin composition of the present invention are known and commonly used. Any material can be used without particular limitation as long as its curability and resin properties are not impaired.

In order to obtain the resin composition of the present invention, the above-mentioned components may be mixed, and the order and method of mixing are not particularly limited.

The resin composition of the present invention requires substantially no solvent, but examples thereof include ketones such as methyl ethyl ketone and methyl isobutyl ketone, acetic acid esters such as ethyl acetate and butyl acetate, benzene, toluene and xylene. It is also possible to dilute and use the resin composition of the present invention with other commonly used organic solvents such as aromatic hydrocarbons.

The resin composition of the present invention is 180 to 500 n
It can be polymerized by irradiating ultraviolet rays or visible rays having a wavelength of m. It can also be cured by irradiation with energy rays other than ultraviolet rays or by heat.

Examples of light sources of ultraviolet rays or visible rays having a wavelength of 180 to 500 nm include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, chemical lamps, black light lamps, mercury-xenon lamps, excimers. Lamp, short arc lamp,
Examples include helium / cadmium laser, argon laser, excimer laser, and sunlight.

The resin composition of the present invention is used in inks, metals such as aluminum, iron and copper, vinyl chloride, acrylic, polycarbonate, polyethylene terephthalate, polyethylene and polypropylene and other plastics, glass and other ceramics, wood, paper and printing paper. As various coating materials for fibers, etc., they are useful for applications such as surface treatment agents, binders, plastic materials, molding materials, laminated plates, adhesives and pressure-sensitive adhesives. More specific uses include planographic ink,
Ink fields such as flexo ink, gravure ink, screen ink, gloss field, paper coating field, wood coating field, beverage can coating or printing ink field, soft packaging film coating agent, printing ink or adhesive , Thermal paper, coating film for thermal film, printing ink, adhesive, pressure-sensitive adhesive or optical fiber coating agent.

[0086]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the scope of these Examples.

(Synthesis Example of Maleimide Derivative (A)) Synthesis Example 1 Bisphenol A diglycidyl ether (manufactured by Tohto Kasei Co., Ltd., YD-8125, epoxy equivalent 173) 34
6 g, maleimidocaproic acid 400.9 g, P-methoxyphenol 0.4 g, and triphenylphosphine 1.5
Then, the reaction is terminated when the acid value of the reaction solution reaches 1.0 (mgKOH / g) and the reaction solution is cooled to 60 ° C. Next, 155 g of 2-isocyanatoethyl methacrylate was added dropwise to this reaction solution over 3 hours, and then the reaction was carried out for about 5 hours until the isocyanate groups disappeared, to obtain a maleimide derivative (A-1) as a pale yellow, highly viscous liquid. Weight average molecular weight is about 2000 (GP
According to the C method).

Synthesis Example 2 182 g of a compound having the following structural formula (manufactured by Daicel Chemical Industries Ltd., product name CYCLOMER A200)

[0089]

[Chemical 6]

Then, 211 g of maleimidocaproic acid, 0.2 g of P-methoxyphenol and 0.15 g of 2-methylimidazole were charged and reacted at 90 ° C. for about 9 hours. When the acid value became 0.5 or less, the reaction was terminated. Then, after cooling the reaction solution to 60 ° C., 155 g of 2-isocyanatoethyl methacrylate was added dropwise in about 3 hours, and then the reaction was carried out for about 5 hours until the isocyanate group disappeared. A pale-yellow transparent liquid maleimide derivative of the following structural formula (A-2) was obtained. It was confirmed by MS measurement that the product had the following structural formula with a molecular weight of 548.

[0091]

[Chemical 7]

[0092]

Examples 1 to 5 and Comparative Examples 1 to 4 The resin compositions of the present invention were blended and dissolved according to the blending composition of Table 1 to prepare. The prepared resin composition was evaluated for UV curability, gel fraction of cured coating and pencil hardness according to the following evaluation methods, and the results are summarized in Table 1.

(1) Ultraviolet curability: Each resin composition was applied onto a glass plate so that the film thickness after curing was 50 μm, and then 80 w / cm high pressure mercury lamp (eye graphics ( Manufactured by K.K.), the lamp height is 8 cm,
Ultraviolet rays were irradiated under the condition of a conveyor speed of 10 m / min, and the number of times of irradiation required to make the coating film surface tack-free was evaluated. The UV irradiation dose per time is about 80 mJ / c.
It was m ² .

(2) Gel Fraction: A coating film was prepared by passing under the lamp three times under the above curing conditions. The cured coating film (weight: W ₁ ) peeled from the glass plate was refluxed in methyl ethyl ketone at 80 ° C. for 3 hours, dried at 100 ° C. for 1 hour, and then weighed (weight: W ₂ ) to give a gel fraction (%). ) = W ₂ ÷ W ₁
× 100 was obtained.

(3) Surface hardness: A coating film was prepared in the same manner as in the above gel fraction evaluation, and the pencil hardness was measured according to JIS K-5400.

Table 1 Examples Comparative Examples 1 2 3 4 5 1 ^{* 3} 2 ^{* 4} 3 4 Reaction product (A-1) obtained in Synthesis Example 1 100-70-70----〃 2 〃 (A -2)-50-70-----KAYARAD DPHA ^* 1-20 30------70 trimethylolpropane triacrylate---30-----KAYARAD PEG400DA ^{* 2} ----30-- 50-N-tert-butylmaleimide-----100---N, N'-4,9-dioxa-1,12-bismaleimidododecane-30----100 50-N-ethylmaleimide-- ------30 UV curability (times) 1 1 2 2 2>10> 10 6> 10 Gel fraction (%) 96.5 97.5 98.4 97.7 97.1 0 0 46.2 0 Pencil hardness HB 2H 3H 2H H--< 4B-

Note) * 1 KAYARAD DPHA: a mixture of dipentaerythritol penta and hexaacrylate manufactured by Nippon Kayaku Co., Ltd. * 2 KAYARAD PEG400DA: Polyethylene glycol diacrylate manufactured by Nippon Kayaku Co., Ltd. * 3 Comparative Example 1: Irradiation with ultraviolet rays was carried out under the same conditions as in Example, but even after irradiation with 10 times, liquid state was maintained and curing was not carried out. * 4 Comparative Example 2: N, N'-4,9-dioxy-1,1
2-Bismaleimido dodecane was solid at room temperature and could not be evenly coated on glass. Therefore, this compound was applied as a chloroform solution, and the solvent was evaporated to form a yellowish white coating film. This coating film was irradiated with ultraviolet rays under the same conditions as in Example, but the coating film was not cured even after 10 irradiations, and the gel fraction of the coating film was 0%.

From the results shown in Table 1, the resin composition of the present invention can be easily cured by irradiation with ultraviolet rays to form a uniform and transparent coating film, even though no photopolymerization initiator is used. Is clear.

[0100]

Industrial Applicability The novel resin composition of the present invention cures at a practical light irradiation amount even in the absence of a photopolymerization initiator,
Moreover, a coating film having a high gel fraction can be formed.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J027 AB01 AC02 AC03 AE01 AE02                       AG01 BA07 BA13 BA26 BA28                       CB03 CB10 CC04 CC05 CD08                 4J100 AK51Q AL03Q AL08Q AL09Q                       AL63Q AL67P AM43Q AM47P                       BA03Q BA08Q BA21Q BC43Q                       CA04 FA03 JA01

Claims (6)

[Claims] 1. A reaction product of a maleimide group-containing monocarboxylic acid (a) with a compound (b) having at least one epoxy group in one molecule (I) and a reaction product of 2-isocyanatoethyl methacrylate (c). And a polymerizable compound (B) other than the component (A) as an optional component. 2. The resin composition according to claim 1, wherein the polymerizable compound (B) is at least one compound selected from the group consisting of compounds having a (meth) acryloyl group, a vinyl ether group or an N-vinyl group. 3. A compound having a (meth) acryloyl group is a (poly) ester (meth) acrylate (B-1-).
1), urethane (meth) acrylate (B-1-2),
Epoxy (meth) acrylate (B-1-3), (poly) ether (meth) acrylate (B-1-4), alkyl (meth) acrylate or alkylene (meth) acrylate (B-1-5), aromatic ring The resin composition according to claim 2, wherein the resin composition is one or more compounds selected from the group consisting of (meth) acrylate (B-1-6) having a group and (meth) acrylate (B-1-7) having an alicyclic structure. object. 4. A compound having a vinyl ether group, an alkyl vinyl ether (B-2-1) in which the other end may be substituted with a halogen atom or a hydroxyl group, and a cycloalkyl in which the other end may be substituted with a halogen atom or a hydroxyl group. Alkyl vinyl ether (B-2-2), at least one selected from the group consisting of an alkyl group which has a vinyl ether group bonded to an alkylene group, and which may further have a substituent, a cycloalkyl group and an aromatic group, and an ether. 1 selected from the group consisting of monovinyl ether, divinyl ether and polyvinyl ether (B-2-3) having a structure in which they are bonded via at least one bond selected from the group consisting of a bond, a urethane bond and an ester bond. The resin composition according to claim 2, which is one or more compounds. 5. The resin composition according to claim 1, which contains a photopolymerization initiator (C). 6. A cured product of the resin composition according to claim 1.