JP2002161106A - Photo-curable colored composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photo-curable colored composition to be cured by practical light intensity and irradiation dose, to minimize problems such as bad odor and discoloration. SOLUTION: The photo-curable colored composition containing a polyfunctional maleimido compound, a polymerizable compound having an acryloyl group or a methacryloyl group, a photopolymerization initiator of phosphine oxide type and a colorant is characterized by very low loading of the photopolymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable coloring composition using a maleimide derivative which is cured by irradiation with active energy rays. This composition is used for printing inks, paints and the like.

[0002]

2. Description of the Related Art An active energy ray-curable composition which is polymerized by an active energy ray such as ultraviolet light or visible light cures quickly, and inks and paints using the composition hardly use a diluting solvent, so that there are few volatile substances. It has advantages such as low energy cost, etc., and has been growing rapidly in recent years. However, these usually require the combined use of a photopolymerization initiator and the like. Generally, in a cured product in which a large amount of a photopolymerization initiator is added, an unreacted photopolymerization initiator or a decomposition product of the photopolymerization initiator often remains, and light or heat acts on the cured product. In this case, there is a problem that the cured product is yellowed or generates a bad smell. Further, these cured products containing a large amount of the photopolymerization initiator are unsuitable for use as food packaging materials because unreacted photopolymerization initiators and the like bleed when left in water or the like.

In order to improve the disadvantages of the photocurable resin compositions containing these photopolymerization initiators, Japanese Patent Application Laid-Open No. H11-1244 has been proposed.
No. 03 proposes a curable resin composition containing a maleimide derivative as a photocurable composition containing no photopolymerization initiator. Odor by not using photopolymerization initiator,
Solved problems such as burnt colors. However, these methods have a problem that, in applications using a coloring agent, the curing speed is low and the strength of the cured coating film is low.

Further, JP-A-2000-160086 discloses a radiation-curable printing ink composition containing a photocurable compound containing a specific maleimide derivative, a compound containing an acryloyl group or a methacryloyl group, and a photopolymerization initiator. was suggested. However, even in this composition,
In order to obtain good curability, use of a photopolymerization initiator exceeding 2 parts by weight was essential.

[0005]

An object of the present invention is to provide a photocurable coloring composition which can be cured with practical light intensity and light irradiation amount while minimizing problems such as bad smell and burning. To provide things.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result,
In a photocurable coloring composition containing an acryloyl group or a methacryloyl group-containing polymerizable compound, a phosphine oxide-based photopolymerization initiator, and a coloring agent, the use of a very small amount of a photopolymerization initiator solves the above problem. They have found that they can be solved and have completed the present invention.

That is, the present invention provides (1) a polyfunctional maleimide compound, (2) a polymerizable compound having an acryloyl group or a methacryloyl group, (3) a phosphine oxide-based photopolymerization initiator, and (4) a colorant. And a colorant containing a photocurable coloring composition. Above all, a photocurable colored composition in which the molar ratio of the unsaturated bond between (1) the maleimide compound and (2) the polymerizable compound having an acryloyl group or a methacryloyl group is 30/70 to 99.8 / 0.2. And (3) a photocurable coloring composition containing 0.01 to 2% by weight of a phosphine oxide-based photopolymerization initiator.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The maleimide compound used in the present invention is not particularly limited, and any known and commonly used one can be used. However, from the viewpoint of curability, a polyfunctional maleimide compound having two or more functional groups is preferred. The polyfunctional maleimide compound may have any structure, for example, a compound represented by the general formula (II)
The following can be used.

[0009]

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(Wherein, n represents an integer of 2 or more, R3 represents a hydrocarbon bond which may contain an ester bond, a urethane bond, or an ether bond. R3 may be linear or branched; Further, it may contain a substituent such as a halogen group, a hydroxyl group, a carboxyl group, or an amino group.
R4 and R5 each independently represent a hydrogen atom, a halogen atom,
A substituent represented by a lower alkyl group or a substituent formed by linking lower alkyl groups by an ester bond. )

In the above general formula (II), n is an integer represented by 2 or more, preferably 2 to 6.
R3 represents a hydrocarbon bond such as, for example, an alkylene group, a cycloalkylene group, an aryl group, an arylalkylene group, or a cycloalkylalkylene group. Even when these organic groups are used alone, for example, an ester bond, a urethane bond, an ether bond A bonding group such as a bond may be included. R3
May be linear or branched, and may contain a substituent such as a halogen group, a hydroxyl group, a carboxyl group, or an amino group. R4 and R5 each independently represent a hydrogen atom, a halogen atom, a substituent represented by a lower alkyl group such as a methyl group or an ethyl group, or a substituent formed by linking a lower alkyl group by an ester bond. The lower alkyl group may be linear or branched, and may contain a halogen group, an amino group, or the like.

Among them, a maleimide compound represented by the following general formula (I) is more preferred.

[0013]

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In the general formula (I), m and n each independently represent an integer of 1 to 5, wherein m + n is an integer of 6 or less.

R11 and R12 each independently represent a hydrocarbon bond selected from the group consisting of an alkylene group, a cycloalkylene group, an arylalkylene group and a cycloalkylalkylene group. Here, the alkyl group may have a branched chain, and the arylalkylene group or the cycloalkyl-alkylene group may have an aryl group or a cycloalkyl group in the main chain or the branched chain, respectively.

Examples of such a group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group,
Linear alkylene groups such as pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group and dodecamethylene group; propylene group, 1-methyl-trimethylene group, 2-methyl -Alkyl branches such as trimethylene group, 1-methyl-tetramethylene group, 2-methyl-tetramethylene group, 1-methyl-pentamethylene group, 2-methyl-pentamethylene group, 3-methyl-pentamethylene group, neopentyl group, etc. An alkylene group having a chain;

Cyclopentylene, cyclohexylene, cyclohexylmethylene, 1-cyclohexyl-
Ethylene group, 1-cyclohexyl-tetraethylene group,
A cycloalkylene group or a cycloalkyl-alkylene group having a cycloalkyl group in a main chain or a side chain such as a 2-cyclohexyl-tetraethylene group; a benzylene group;
2,2-diphenyl-trimethylene group, 1-phenyl-
Examples include, but are not limited to, aryl groups having an aryl group in the main chain or side chain, such as an ethylene group, a 1-phenyl-tetraethylene group, and a 2-phenyl-tetraethylene group, and an arylalkylene group. .

G1 and G2 each independently represent an ester bond or a urethane bond. Among them, an ester bond has higher reactivity and is more preferable.

R2 is a group in which at least one organic group selected from the group consisting of a linear alkylene group, a branched alkylene group, an alkylene group having a hydroxyl group, a cycloalkylene group, an aryl group, an arylalkylene group and an isocyanuric group is an ether bond; (Poly) ether-linked chain, (poly) ester-linked chain, or
Represents a (poly) urethane linking chain. R2 may be a connecting chain composed of an oligomer or polymer in which these connecting chains are repeated as one unit. Among them, a (poly) ether connecting chain and a (poly) ester connecting chain have high reactivity and are more preferable.

The connecting chain representing R2 has a number average molecular weight of 10
There is no particular limitation as long as it is not more than 000, but if it is not less than 200, it becomes liquid and easily mixes with other components when preparing a composition such as an ink, which is more preferable.

Specific examples of the connecting chain representing R2 include: (a) a linear alkylene group having 1 to 24 carbon atoms, a branched alkylene group having 1 to 24 carbon atoms, a cycloalkylene group and an aryl group. A linking chain comprising at least one hydrocarbon group selected from the group consisting of: a (poly) ether (poly) ol residue having one or a repeating unit thereof bonded by an ether bond;

(B) at least one hydrocarbon group selected from the group consisting of a linear alkylene group having 1 to 24 carbon atoms, a branched alkylene group having 1 to 24 carbon atoms, a cycloalkylene group and an aryl group; Having one or their repeating units linked by an ester bond (poly)
A linking chain composed of ester (poly) ol residues;

(C) at least one hydrocarbon group selected from the group consisting of a linear alkylene group having 1 to 24 carbon atoms, a branched alkylene group having 1 to 24 carbon atoms, a cycloalkylene group and an aryl group; Having one or their repeating units linked by an ether bond (poly)
Obtained by esterifying an ether (poly) ol with a polycarboxylic acid such as a carboxylic acid or a hexacarboxylic acid,
A connecting chain composed of (poly) carboxylic acid {(poly) ether (poly) ol} ester having a polycarboxylic acid residue at the end;

(D) at least one hydrocarbon group selected from the group consisting of a linear alkylene group having 1 to 24 carbon atoms, a branched alkylene group having 2 to 24 carbon atoms, a cycloalkylene group and an aryl group; The terminal is a polycarboxylic acid residue obtained by esterifying a (poly) ester (poly) ol having one or a repeating unit thereof bonded by an ether bond and an ester bond with a polycarboxylic acid (polycarboxylic acid residue) ) A linking chain composed of carboxylic acid {(poly) ester (poly) ol} ester;

(E) at least one hydrocarbon group selected from the group consisting of a linear alkylene group having 1 to 24 carbon atoms, a branched alkylene group having 1 to 24 carbon atoms, a cycloalkylene group, and an aryl group; Having one or their repeating units linked by an ether bond (poly)
(Poly) ether (poly) obtained by urethanizing ether (poly) ol and (poly) isocyanate
A linking chain composed of urethane;

(F) at least one hydrocarbon group selected from the group consisting of a linear alkylene group having 1 to 24 carbon atoms, a branched alkylene group having 1 to 24 carbon atoms, a cycloalkylene group and an aryl group; A (poly) ester (poly) ol having one or a repeating unit thereof bonded by an ether bond and / or an ester bond,
(Poly) isocyanate obtained by urethanization,
A linking chain composed of (poly) ester (poly) urethane;

(G) at least one hydrocarbon group selected from the group consisting of a linear alkylene group having 1 to 24 carbon atoms, a branched alkylene group having 1 to 24 carbon atoms, a cycloalkylene group and an aryl group; Having one or their repeating units linked by an ether bond (poly)
A linking chain obtained by ring-opening an epoxide; and the like. Of course, it is not limited to these examples.

Specific examples of the (poly) ether (poly) ol constituting the linking chain (a) include, for example,
Polyethylene glycol, polypropylene glycol,
Polyalkylene glycols such as polybutylene glycol and polytetramethylene glycol, ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin,
Modified ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran of alkylene glycols such as trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, and dipentaerythritol;

Carbonization of ethylene oxide and propylene oxide copolymers, propylene glycol and tetrahydrofuran copolymers, ethylene glycol and tetrahydrofuran copolymers, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol, etc. Hydrogen-based polyols,
And polyhydric hydroxyl compounds such as polytetramethylene hexaglyceryl ether (tetrahydrofuran-modified hexaglycerin). Among these, various modified products of alkylene glycols are more preferable.

As the (poly) ester (poly) ol constituting the linking chain (b), specifically, for example,
Polyethylene glycol, polypropylene glycol,
Polyalkylene glycols such as polybutylene glycol and polytetramethylene glycol, ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol,
Modified ε-caprolactone, modified γ-butyrolactone, modified δ-valerolactone, modified methylvalerolactone of alkylene glycols such as diglycerin, ditrimethylolpropane, dipentaerythritol;

Aliphatic polyester polyol which is a reaction product of an aliphatic dicarboxylic acid such as adipic acid or dimer acid with a polyol such as neopentyl glycol or methylpentanediol; an aromatic dicarboxylic acid such as terephthalic acid and neopentyl glycol Aromatic polyester polyol which is a reaction product with polyol; polyhydric hydroxyl compound such as polycarbonate polyol, acrylic polyol, polytetramethylene hexaglyceryl ether (modified tetrahydrofuran of hexaglycerin), and fumaric acid, phthalic acid, isophthalic acid, itacone Polyhydric hydroxyl group-containing compounds obtained by esterification with dicarboxylic acids such as acid, adipic acid, sebacic acid and maleic acid; transesterification between polyhydric hydroxyl group-containing compounds such as glycerin and animal / plant fatty acid esters Polyhydric hydroxyl group-containing compound such as monoglyceride obtained by response; and the like.

The (poly) carboxylic acid {(poly) ether (poly) ol} ester constituting the linking chain (c) is specifically exemplified by, for example, succinic acid, adipic acid, phthalic acid, hexahydro Dicarboxylic acids such as phthalic acid, tetrahydrophthalic acid, pyromellitic acid, fumaric acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, and maleic acid, and the (poly) ether (poly) ol shown in (a) (Poly) ether (poly) carboxylic acid obtained by esterification and the like.

The (poly) carboxylic acid {(poly) ester (poly) ol} ester constituting the linking chain (d) is specifically exemplified by, for example, succinic acid, adipic acid, phthalic acid, hexahydroacid Dicarboxylic acids such as phthalic acid, tetrahydrophthalic acid, pyromellitic acid, fumaric acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, and maleic acid, and the (poly) ester (poly) ol shown in (b) (Poly) ester (poly) carboxylic acid obtained by esterification, etc. are mentioned.

Specific examples of the (poly) ether (poly) urethane constituting the linking chain (e) include methylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, lysine diisocyanate, and the like. Aliphatic diisocyanate compounds such as dimer acid diisocyanate; 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate;
6-tolylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4'-
Diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-
Aromatic diisocyanate compounds such as 4,4'-diisocyanate;

Isophorone diisocyanate, 4,4'-
(Poly) isocyanates such as alicyclic diisocyanates such as methylene bis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, and 1,3- (isocyanatomethylene) cyclohexane; (Poly) ether (poly) urethane compounds obtained by urethanation with an ether polyol are exemplified. As the (poly) ester (poly) urethane constituting the linking chain (f), the (poly) isocyanate shown in the above (e) and (b)
(Poly) ether (poly) urethane compounds obtained by urethanation with the polyester polyol shown in (1).

The (poly) epoxide constituting the linking chain (g) is specifically, for example, synthesized from (methyl) epichlorohydrin, bisphenol A or bisphenol F and its ethylene oxide or propylene oxide modified products. Epichlorohydrin-modified bisphenol-type epoxy resin; epichlorohydrin-modified hydrogenated bisphenol-type epoxy resin synthesized from (methyl) epichlorohydrin and hydrogenated bisphenol A, hydrogenated bisphenol F, their ethylene oxide-modified products, propylene oxide-modified products, etc. , Epoxy novolak resin; reaction product of phenol, biphenol and the like with (methyl) epichlorohydrin; aromatic epoxy resin such as glycidyl ester of terephthalic acid, isophthalic acid and pyromellitic acid; Poly) ethylene glycol,
Glycols such as (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol, neopentyl glycol and the like, and polyglycidyl ethers of alkylene oxide modified products thereof;

Trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol,
Aliphatic polyhydric alcohols such as pentaerythritol, sorbitol, 1,4-butanediol and 1,6-hexanediol, and glycidyl ethers of alkylene oxide modified products thereof; adipic acid, sebacic acid, maleic acid, itaconic acid, etc. Glycidyl ester; glycidyl ether of polyester polyol of polyhydric alcohol and polycarboxylic acid, copolymer of glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate, glycidyl ester of higher fatty acid, epoxidized linseed oil, epoxidized large Examples include aliphatic epoxy resins such as soybean oil, epoxidized castor oil, and epoxidized polybutadiene.

In a coloring composition such as an ink, general formula (I)
Since the maleimide compound represented by has an ether bond, an ester bond, a urethane bond, and the like in the molecule, it is easy to give an affinity between the coloring agent and the vehicle and to easily control the ink characteristics. In particular, when a pigment is used as a coloring agent, the wetting with the pigment is very important, and the degree of freedom of design for imparting good wettability to the compound is wide and preferred.

Examples of polyfunctional maleimide compounds other than those represented by the general formula (I) include, for example, N,
N'-ethylene dimaleimide, N, N'-hexamethylene dimaleimide, N, N'-dodecamethylene dimaleimide, N, N'-m-phenylenedimaleimide, N, N
'-P-phenylenedimaleimide, N, N'-(oxydi-p-phenylene) dimaleimide, N, N '-(methylenedi-p-phenylene) dimaleimide, N, N'-
2,4-tolylene dimaleimide, N, N′-2,6-tolylene dimaleimide, N, N′-dimaleimide, N,
N'-m-xylylene dimaleimide, N, N'-p-xylylene dimaleimide, N, N'-oxydipropylene dimaleimide, ethylenedioxy-bis-N-ethylmaleimide, N, N'-p, p '-Diphenylsulfone bismaleimide, N, N'-p, p'-diphenylether bismaleimide, N, N'-dicyclohexylmethanebismaleimide, N, N'-(3,3'-dichloro-
p, p'-bisphenylene) bismaleimide, 1,1,
1,3,3,3-hexafluoro-2,2-bis (4-
Maleimidophenyl) propane, 1,1,1,3,3
3-hexafluoro-2,2-bis [4- (4-maleimidophenoxy) phenyl] propane and the like.

Further, as the maleimide compound of the present invention,
Of course, a monofunctional maleimide compound can be used, but since the curability is slightly inferior, the polymerizable compound having an acryloyl group or a methacryloyl group used in combination is preferably a polyfunctional compound. As the monofunctional maleimide compound, specifically, maleimide, N-methylmaleimide, N
-Ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, Nt-butylmaleimide, N-
Cyclohexylmaleimide, N-phenylmaleimide,
N-chlorophenylmaleimide, N-methylphenylmaleimide, N-bromophenylmaleimide, N-naphthylmaleimide, N-laurylmaleimide, N-hydroxyethylmaleimide, N-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, N-carboxyphenyl Maleimide, N-nitrophenylmaleimide, and the like.

Next, the polymerizable compound (2) having an acryloyl group or a methacryloyl group used in the present invention will be described.

The polymerizable compound having an acryloyl group or a methacryloyl group used in the present invention is, for example, (poly) ester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, (poly) ether (Meth) acrylate, alkyl (meth) acrylate or alkylene (meth) acrylate, (meth) acrylate having an aromatic ring, (meth) acrylate having an alicyclic structure, and the like,
It is not limited to these.

The (poly) ester (meth) acrylate that can be used in the present invention is a general term for a (meth) acrylate having one or more ester bonds in the main chain, and the urethane (meth) acrylate is a urethane (meth) acrylate in the main chain. Epoxy acrylate, as a generic term for (meth) acrylates having one or more bonds, refers to (poly) ether (meth) acrylate as a generic term for (meth) acrylates obtained by reacting (meth) acrylic acid with one or more functional epoxides. ) Acrylate is a generic term for (meth) acrylates having one or more ether bonds in the main chain, and alkyl (meth) acrylate or alkylene (meth) acrylate is a main chain having a linear alkyl, a branched alkyl, a linear alkylene. Group or branched alkylene group having a halogen atom and / or a hydroxyl group on the side chain or terminal. (Meth) acrylate having an aromatic ring as a generic name of (meth) acrylates which may be used is a (meth) acrylate having an alicyclic structure as a generic name of (meth) acrylates having an aromatic ring in a main chain or a side chain. Is used as a general term for a (meth) acrylate having an alicyclic structure which may contain an oxygen atom or a nitrogen atom in a constitutional unit in a main chain or a side chain.

The (poly) ester (meth) acrylate usable in the present invention includes, for example, alicyclic modified neopentyl glycol (meth) acrylate (“R-629” or “R-629” manufactured by Nippon Kayaku Co., Ltd.). 644 "), caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, and caprolactone-modified tetrahydrofurfuryl (meth) acrylate. Functional (poly) ester (meth) acrylates; pivalic acid ester neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalic acid ester neopentyl glycol di (meth) acrylate,
Epichlorohydrin-modified phthalic acid di (meth) acrylate;

Trimethylolpropane or glycerin 1
Mono-, di- or tri (meth) acrylate of triol obtained by adding a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone to at least one mole; pentaerythritol or ditrimethylol Mono, di, tri or tetra (meth) acrylate of triol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone to 1 mol of propane; Triol mono- or poly (meth) acrylate triol, tetra-triol obtained by adding 1 mol or more of a cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone to 1 mol of pentaerythritol Oar, penta Lumpur or mono (meth) of a polyhydric alcohol such as hexanol acrylate or poly (meth) acrylate;

Diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, (poly) pentanediol, (poly) methylpentanediol and (poly) hexanediol And maleic acid, fumaric acid, succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, heptic acid, hymic acid, chlorendic acid, dimer acid, alkenyl succinic acid, Sebacic acid, azelaic acid, 2,2,4-trimethyladipic acid, 1,
4-cyclohexanedicarboxylic acid, terephthalic acid, 2-
Sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, shu (Meth) acrylates of polyester polyols composed of polybasic acids such as acid, malonic acid, glutanic acid, trimellitic acid, and pyromellitic acid; the diol component, polybasic acid, ε-caprolactone, γ-butyrolactone, and δ-valerolactone Or polyfunctional (poly) ester (meth) acrylates such as (meth) acrylate of a cyclic lactone-modified polyester diol composed of methyl valerolactone, but is not limited thereto.

The urethane (meth) acrylate usable in the present invention is a general term for (meth) acrylate obtained by reacting a hydroxy compound having at least one (meth) acryloyl group with an isocyanate compound.

The hydroxy compound having at least one (meth) acryloyl group includes, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy Butyl (meta)
Acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexane dimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropanedi (meth) acrylate, trimethylolethanedi ( (Meth) acrylate, pentaerythritol tri (meth) acrylate or glycidyl (meth) acrylate- (meth) acrylic acid adduct, 2-hydroxy-3-phenoxypropyl (meth)
Examples include (meth) acrylate compounds having various hydroxyl groups such as acrylate, and ring-opening products of the above-mentioned (meth) acrylate compounds having a hydroxyl group and ε-caprolactone.

As the isocyanate compound, for example,
p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 ′
-Diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,
Aromatic diisocyanates such as 3'-diethyldiphenyl-4,4'-diisocyanate and naphthalene diisocyanate; such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate and lysine diisocyanate Diisocyanates having an aliphatic or alicyclic structure; polyisocyanates such as one or more burettes of isocyanate monomers or isocyanurates obtained by trimerizing the diisocyanate compound; obtained by a urethanization reaction between the isocyanate compound and various polyols Polyisocyanate, and the like.

Examples of the polyol used for producing the polyisocyanate include (poly) alkylene glycols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, and (poly) tetramethylene glycol; Ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol,
Alkylene glycols such as diglycerin, ditrimethylolpropane and dipentaerythritol, ethylene oxide-modified, propylene oxide-modified, butylene oxide-modified, tetrahydrofuran-modified, ε-caprolactone-modified, γ-butyrolactone-modified, δ-
Modified valerolactone, modified methylvalerolactone and the like;

Copolymers such as ethylene oxide and propylene oxide copolymers, propylene glycol and tetrahydrofuran copolymers, ethylene glycol and tetrahydrofuran copolymers, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, and hydrogenated polybutadiene glycol Hydrogen-based polyols; aliphatic polyester polyols which are esterification products of aliphatic dicarboxylic acids such as adipic acid and dimer acid with polyols such as neopentyl glycol and methylpentanediol; aromatic dicarboxylic acids such as terephthalic acid Aromatic polyester polyols, which are esterification products of phenol with polyols such as neopentyl glycol;

Polycarbonate polyols; Acrylic polyols; Polyhydric hydroxyl compounds such as polytetramethylene hexaglyceryl ether (modified tetrahydrofuran of hexaglycerin); Mono- and polyhydric hydroxyl groups at the terminal ether groups of the above polyhydric hydroxyl-containing compounds Compound; a polyhydric hydroxyl group-containing compound obtained by esterification of the above polyhydric hydroxyl group-containing compound with a dicarboxylic acid such as fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, and maleic acid; Examples thereof include, but are not limited to, polyhydric hydroxyl group compounds such as monoglycerides obtained by transesterification of fatty acid esters of animals and plants.

The epoxy (meth) acrylate that can be used in the present invention is a general term for (meth) acrylate obtained by reacting a monofunctional or higher epoxide with (meth) acrylic acid. Examples of the epoxide (A-3-1) serving as a raw material of the epoxy (meth) acrylate include (methyl) epichlorohydrin, hydrogenated bisphenol A, hydrogenated bisphenol S, hydrogenated bisphenol F, and ethylene oxide and propylene oxide modified thereof. Epichlorohydrin-modified hydrogenated bisphenol-type epoxy resin synthesized from a product or the like; alicyclic epoxy resin such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate An alicyclic epoxide such as an epoxy resin containing a hetero ring such as triglycidyl isocyanurate;

Epichlorohydrin-modified bisphenol type epoxy resin synthesized from (methyl) epichlorohydrin and bisphenol A, bisphenol S, bisphenol F, ethylene oxide and propylene oxide modified products thereof; phenol novolak type epoxy resin; cresol novolak type epoxy resin Epoxidized products of various dicyclopentadiene-modified phenol resins obtained by reacting dicyclopentadiene with various phenols; epoxidized products of 2,2 ', 6,6'-tetramethylbiphenol, aromatic epoxides such as phenylglycidyl ether ;

(Poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol,
(Poly) glycidyl ethers of glycols such as (poly) tetramethylene glycol and neopentyl glycol; (poly) glycidyl ethers of glycols modified with alkylene oxide; trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol, Pentaerythritol, sorbitol,
Alkylene-type epoxides such as (poly) glycidyl ether of aliphatic polyhydric alcohol such as 1,4-butanediol and 1,6-hexanediol; (poly) glycidyl ether of alkylene oxide-modified aliphatic polyhydric alcohol;

Glycidyl esters of carboxylic acids such as adipic acid, sebacic acid, maleic acid and itaconic acid; glycidyl ethers of polyester polyols of polyhydric alcohols and polycarboxylic acids; glycidyl (meth) acrylate, methyl glycidyl (meth) Copolymers of acrylates, including, but not limited to, glycidyl esters of higher fatty acids, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, and aliphatic epoxy resins such as epoxidized polybutadiene .

Examples of the (poly) ether (meth) acrylate usable in the present invention include butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, epichlorohydrin-modified butyl (meth) acrylate, and dicyclopentenyl. Roxyethyl (meth) acrylate, 2-ethoxyethyl (meth)
Acrylate, ethyl carbitol (meth) acrylate, 2-methoxy (poly) ethylene glycol (meth)
Acrylate, methoxy (poly) propylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, phenoxy hydroxypropyl (meth) acrylate, phenoxy (poly) ethylene glycol (meth) acrylate, Monofunctional (poly) ether (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol / polypropylene glycol mono (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 Propylene oxide copolymer, propylene glycol and tetrahydrofuran copolymer, ethylene glycol and tetrahydrofuran copolymer, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, hydrocarbon polyols such as hydrogenated polybutadiene glycol, A polyvalent hydroxyl compound such as polytetramethylene hexaglyceryl ether (tetrahydrofuran-modified hexaglycerin); Polyfunctional (meth) acrylates derived from crylic acid; di (meth) acrylates of diols obtained by adding one or more moles of a cyclic ether such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mole of neopentyl glycol )
Acrylate;

Di (meth) acrylate of alkylene oxide-modified bisphenols such as bisphenol A, bisphenol F and bisphenol S; alkylene oxide of hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S Modified di (meth) acrylate; Trisphenol alkylene oxide modified di (meth) acrylate; Hydrogenated trisphenol alkylene oxide modified di (meth) acrylate; p, p'-biphenol alkylene Oxide-modified di (meth) acrylate; hydrogenated biphenol alkylene oxide-modified di (meth) acrylate; p, p'-dihydroxybenzophenone alkylene oxide-modified di (meth) acrylate; trimethylo Trimethylolpropane or glycerin 1 mole to 1 mole or more of ethylene oxide, propylene oxide, a triol obtained by adding the butylene oxide and / or such a cyclic ether compound of tetrahydrofuran mono-, di- or tri (meth) acrylate;

Triol mono, di, tri or tetra (meth) obtained by adding one or more moles of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mole of pentaerythritol or ditrimethylolpropane Acrylates: Triol mono- or poly (meth) acrylate triols, tetraols, pentaols obtained by adding one or more moles of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mole of dipentaerythritol Monofunctional (poly) ether (meth) acrylates or polyfunctional (poly) ether (meth) acrylates of polyhydric alcohols such as all and hexaol, but are not limited thereto. Not shall.

The alkyl (meth) acrylate or alkylene (meth) acrylate usable in the present invention includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (Meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (Meth) acrylate,

Isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, pentadecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate , Stearyl (meth) acrylate,
Neryl (meth) acrylate, geranyl (meth) acrylate, farnesyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate, trans-
Monofunctional (meth) acrylates such as 2-hexene (meth) acrylate;

Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate,
1,2-butylene glycol di (meth) acrylate,
1,3-butylene 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,
Di (meth) acrylates of hydrocarbon diols of 10-decanediol di (meth) acrylate;

Mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane
Acrylate (hereinafter, "poly" is used as a generic term for polyfunctional such as di, tri, tetra, etc.), glycerin mono (meth) acrylate or poly (meth) acrylate, pentaerythritol mono (meth) acrylate or poly (meth) A) mono (meth) acrylate or poly (meth) acrylate of acrylate, ditrimethylolpropane, mono (meth) acrylate of dipentaerythritol or mono (meth) acrylate of poly (meth) acrylate (Meth) acrylates or poly (meth) acrylates;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4
Hydroxy-containing (meth) acrylates such as -hydroxybutyl (meth) acrylate and 3-chloro-2-hydroxyethyl (meth) acrylate; 2,3-dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate, ethylene oxide (Meth) acrylates having a bromine atom such as modified tribromophenyl (meth) acrylate and ethylene oxide-modified tetrabromobisphenol A di (meth) acrylate;

Trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, dodecafluoroheptyl (meth) acrylate, hexadecafluorononyl (meth) Acrylate, hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (Meth) acrylate, 3- (perfluoro-5-
Methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) acrylate,
(Meth) acrylates having a fluorine atom, such as 3- (perfluoro-8-methyldecyl) -2-hydroxypropyl (meth) acrylate, and the like,
It is not limited to these.

The aromatic ring-containing (meth) acrylate usable in the present invention includes, for example, phenyl (meth)
Monofunctional (meth) acrylates such as acrylate and benzyl acrylate; diacrylates such as bisphenol A diacrylate, bisphenol F diacrylate and bisphenol S diacrylate, but are not limited thereto.

The (meth) acrylate having an alicyclic structure usable in the present invention includes, for example, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate, bicycloheptyl (meth) acrylate, isobornyl (Meth) acrylate, bicyclopentyl di (meth) acrylate, tricyclodecyl (meth) acrylate, bicyclopentenyl (meth) acrylate, norbornyl (meth) acrylate, bicyclooctyl (meth) acrylate, tricycloheptyl (meth) acrylate,
Monofunctional (meth) acrylates having an alicyclic structure, such as cholesteroid skeleton-substituted (meth) acrylates;

Di (meth) acrylates of hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S, di (meth) acrylate of hydrogenated trisphenols, hydrogenated p, p'-biphenol Class of di (meth) acrylates; "Kayarad R68
4 "(manufactured by Nippon Kayaku Co., Ltd.) such as dicyclopentane-based di (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, and bisphenol fluorenedihydroxy (meth) acrylate. A) acrylates; alicyclic acrylates having an oxygen atom and / or a nitrogen atom in the structure thereof, such as tetrahydrofurfuryl (meth) acrylate and morpholinoethyl (meth) acrylate, but are not limited thereto. is not.

The compound having an acryloyl group or a methacryloyl group that can be used in the present invention may be, for example, a reaction product of a (meth) acrylic acid polymer and glycidyl (meth) acrylate or glycidyl ( Poly (meth) acrylic (meth) acrylate such as a reaction product of (meth) acrylate polymer and (meth) acrylic acid; (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate; tris ((meth) acrylic) Isocyanuric (meth) acrylates such as (roxyethyl) isocyanurate; phosphazene (meth) acrylates such as hexakis [((meth) acryloylethyl) cyclotriphosphazene]; (meth) acrylates having a polysiloxane skeleton; polybutadiene (meth) Acrylate; melamine (meth) acrylates may also be used.

Among these compounds having an acryloyl group or a methacryloyl group, compounds having 1 to 6 acryloyl groups or methacryloyl groups in one molecule are preferable.

In the present invention, the molar ratio of the unsaturated bond between the maleimide compound and the polymerizable compound having an acryloyl group or a methacryloyl group is from 30/70 to 99.8 /.
They can be combined in the range of 0.2, preferably in the range of 50/50 to 99.5 / 0.5. These unsaturated bond ratios have an optimum range for each compound. If the ratio of the polymerizable compound having an acryloyl group or a methacryloyl group exceeds this range, the curability is undesirably reduced. Also, when the amount is small, the desired curability cannot be obtained. In the present invention, a polymerizable compound having an acryloyl group or a methacryloyl group is an essential component, and without such a component, no curability is exhibited.

The (3) phosphine oxide-based photopolymerization initiator used in the present invention is specifically, for example,
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,6-dimethylbenzoyl-diphenyl-phosphine oxide, 2,6-dimethoxybenzoyl-diphenyl-phosphine oxide, benzoyl-diphenyl-phosphine oxide; 2,4,6
-Trimethylbenzoyl-methoxy-phenyl-phosphine oxide; 2,6-dimethylbenzoyl-methoxy-phenyl-phosphine oxide, 2,6-dimethoxybenzoyl-methoxy-phenyl-phosphine oxide;

2,4,6-trimethylbenzoyl-ethoxy-phenyl-phosphine oxide, 2,6-dimethylbenzoyl-ethoxy-phenyl-phosphine oxide, 2,6-dimethoxybenzoyl-ethoxy-phenyl-phosphine oxide; 2,4 , 6-Trimethylbenzoyl-dimethoxy-phosphine oxide;
2,4,6-trimethylbenzoyl-bis (4-methoxyphenyl) phosphine oxide, 2,6-dimethylbenzoyl-bis (4-methoxyphenyl) phosphine oxide, 2,6-dimethoxybenzoyl-bis (4
-Methoxyphenyl) phosphine oxide; 2,4,
6-trimethylbenzoyl-4-methoxyphenyl-phenyl-phosphine oxide, 2,6-dimethylbenzoyl-4-methoxyphenyl-phenyl-phosphine oxide, 2,6-dimethoxybenzoyl-4-methoxyphenyl-phenyl-phosphine oxide;

2,4,6-trimethylbenzoyl-dicyclohexyl-phosphine oxide, 2,6-dimethylbenzoyl-dicyclohexyl-phosphine oxide, 2,6-dimethoxybenzoyl-dicyclohexyl-phosphine oxide; 2,4,6-trimethylbenzoyl- Bis (2-methylpropyl) phosphine oxide; 2,4,6-trimethylbenzoyl-bis (4-
Pentyloxyphenyl) phosphine oxide, 2,
6-dimethylbenzoyl-bis (4-pentyloxyphenyl) phosphine oxide, 2,6-dimethoxybenzoyl-bis (4-pentyloxyphenyl) phosphine oxide; 2,4,6-trimethylbenzoyl-
Methyl-isopropyloxy-phosphine oxide;
Benzoyl-diethoxy-phosphine oxide; benzoyl-bis (2,4,6-trimethylphenyl) phosphine oxide;

Bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide, bis (2,6-
Dimethylbenzoyl) phenyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) phenyl-
Phosphine oxide; bis (2,4,6-trimethylbenzoyl) -2-methoxyphenyl-phosphine oxide, bis (2,6-dimethylbenzoyl) -2-methoxyphenyl-phosphine oxide, bis (2,6
-Dimethoxybenzoyl) -2-methoxyphenyl-phosphine oxide; bis (2,4,6-trimethylbenzoyl) -2-methylpropyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) -2-methylpropyl-phosphine oxide , Bis (2,6-diethoxybenzoyl) -2-methylpropyl-phosphine oxide, bis (2,6-dibutoxybenzoyl)
-2-methylpropyl-phosphine oxide,

Bis (2,6-dimethylbenzoyl) -2
-Methylpropyl-phosphine oxide, bis (2,
4-dimethoxy-6-methylbenzoyl) -2-methylpropyl-phosphine oxide, bis (2-methoxy-benzoyl) -2-methylpropyl-phosphine oxide, bis (2-ethoxy-6-methoxybenzoyl) -2-methyl Propyl-phosphine oxide; bis (2,4,6-trimethylbenzoyl) -1-methylpropyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) -1-methylpropyl-phosphine oxide, bis (2,6-di Ethoxybenzoyl)-
1-methylpropyl-phosphine oxide, bis (2,6-dibutoxybenzoyl) -1-methylpropyl-phosphine oxide, bis (2,6-dimethylbenzoyl) -1-methylpropyl-phosphine oxide, bis (2-methoxy) -Benzoyl) -1-methylpropyl-phosphine oxide, bis (2-ethoxy-
6-methoxybenzoyl) -1-methylpropyl-phosphine oxide; bis (2,4,6-trimethylbenzoyl) -2,4,4-trimethylpentyl-phosphine oxide, bis (2,6-dimethoxybenzoyl)
-2,4,4-trimethylpentyl-phosphine oxide, bis (2,6-dimethylbenzoyl) -2,4
4-trimethylpentyl-phosphine oxide, bis (2,4-dibutoxy-6-methylbenzoyl) -2,
4,4-trimethylpentyl-phosphine oxide;

Bis (2,4,6-trimethylbenzoyl) butyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) butyl-phosphine oxide,
Bis (4-dibutoxy-2,6-dimethylbenzoyl)
Butyl-phosphine oxide, bis (2,6-dimethylbenzoyl) butyl-phosphine oxide, bis (4-methoxy-2,6-dimethylbenzoyl) butyl-phosphine oxide, bis (2-ethyl-4-methoxy-6-methyl) Benzoyl) butyl-phosphine oxide, bis (2-methyl-4-methoxy-6-propylbenzoyl) butyl-phosphine oxide, bis (2,4-dibutoxy-6-methylbenzoyl) -butyl-phosphine oxide,

(2,4,6-trimethylbenzoyl)
(2,6-dimethoxybenzoyl) butyl-phosphine oxide; bis (2,4,6-trimethylbenzoyl) -1,1-dimethylethyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) -1,1-
Dimethylethyl-phosphine oxide, bis (2,6
-Dimethylbenzoyl) -1,1-dimethylethyl-phosphine oxide; bis (2,4,6-trimethylbenzoyl) cyclohexyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) cyclohexyl-
Phosphine oxide, bis (2,6-dimethylbenzoyl) cyclohexyl-phosphine oxide; bis (2,4,6-trimethylbenzoyl) octyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) octyl-phosphine oxide, bis (2 , 6-
Dimethoxybenzoyl) octadecyl-phosphine oxide; and the like, but is not limited thereto.

In the present invention, the content of the photopolymerization initiator can be used in the range of 0.01 to 2% by weight, preferably in the range of 0.05 to 1.5% by weight. In the present invention, it is characteristic that a phosphine oxide-based photopolymerization initiator is used as an essential component, and good curing becomes possible by using a small amount of these. Further, since sufficient curability is obtained within the above-mentioned range, the addition of 2% by weight or more is unnecessary, and an excessive amount of the initiator remains in the coating film after curing, and the odor and extract It is not preferable because it causes.

Further, other known and commonly used photopolymerization initiators can be used in combination. Other photopolymerization initiators that can be used in the present invention, for example, diethoxyacetophenone,
2-hydroxy-2-methyl-1-phenylpropane-
1-one, benzyldimethyl ketal, 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
Acetophenones such as-(4-morpholinophenyl) -butanone; benzoin, benzoin methyl ether,
Benzoins such as benzoin isopropyl ether;
An intramolecular bond-cleavable photopolymerization initiator such as benzyl and methylphenylglyoxyester;

Benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-
Benzoyl-4'-methyl-diphenyl sulfide,
Benzophenones such as acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4-dimethyl Thioxanthones such as thioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; Michler's ketone, 4,4'-
Aminobenzophenones such as diethylaminobenzophenone; and intramolecular hydrogen abstraction type photopolymerization initiators such as 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone and camphorquinone. However, the present invention is not limited to these.

In the photocurable coloring composition of the present invention,
In the structure, the colorant is an essential component, and a general-purpose colorant such as carbon black, an organic pigment, an inorganic pigment, or a dye is used.

As the carbon black, known carbon blacks such as furnace black, acetylene black and channel black are used.
n7000, Raven5750, Raven525
0, Raven5000 ULTRAII, Raven3
500, Raven2500 ULTRA, Raven2
000, Raven 1500, Raven 1255, R
aven1250, Raven1200, Raven1
190ULTRAII, Raven1170, Rave
n1080ULTRA, Raven1060ULTR
A, Raven 790ULTRA, Raven 780U
LTRA, Raven760ULTRA (all manufactured by Columbian Carbon Co., Ltd.), Rega1400R, Reg
a1330R, Rega1660R, MogulL, M
onarch700, Monarch800, Mona
rch880, Monarch900, Monarch
1000, Monarch1100, Monarch1
300, Monarch 1400 (all manufactured by Cabot Corporation),

Color Black FW1, Col
or Black FW2, Color Black
FW2V, Color Black 18, Color
Black FW200, Color Black
S160, Color Black S170, Pri
ntex 35, Printex U, Printex
V, Printex 140U, Printex 14
0V, SpecialBlack 4, Special
Black 4A, Special Black
No. 5, Special Black 6 (above, manufactured by Degussa), 25, NO. 33, NO. 40, no.
47, no. 52, no. 900, No. 2300, M
CF-88, MA7, MA8, MA100, MA600
(Above, manufactured by Mitsubishi Chemical Corporation), and the like, but not limited thereto.

Examples of the organic pigment include azo pigments; polycyclic pigments such as phthalocyanine pigments, perylene pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments; nitro pigments and nitroso pigments. I. Pigment Blue-1, C.I. I.
Pigment Blue-2, C.I. I. Pigmen
tBlue-3, C.I. I. Pigment Blue-
15, C.I. I. Pigment Blue-15: 1,
C. I. Pigment Blue-15: 3, C.I.
I. Pigment Blue-15: 34, C.I. I.
Pigment Blue-16, C.I. I. Pigme
nt Blue-22, C.I. I. Pigment Bl
ue-60, C.I. I. Pigment Red-5,
C. I. Pigment Red-7, C.I. I. Pig
Ment Red-12, C.I. I. Pigment R
ed-48, C.I. I. Pigment Red-48:
1, C.I. I. Pigment Red-57, C.I. I.
Pigment Red-57: 1, C.I. I. Pigm
ent Red-112, C.I. I. Pigment R
ed-122, C.I. I. Pigment Red-12
3, C.I. I. Pigment Red-146, C.I. I.
Pigment Red-168, C.I. I. Pigme
nt Red-184, C.I. I. Pigment Re
d-202,

C. I. Pigment Yellow-
1, C.I. I. Pigment Yellow-2, C.I.
I. Pigment Yellow-3, C.I. I. Pi
gment Yellow-12, C.I. I. Pigme
nt Yellow-13, C.I. I. Pigment
Yellow-14, C.I. I. Pigment Yel
low-16, C.I. I. Pigment Yellow
-17, C.I. I. Pigment Yellow-7
3, C.I. I. Pigment Yellow-74,
C. I. Pigment Yellow-75, C.I.
I. Pigment Yellow-83, C.I. I. P
pigment yellow-93, C.I. I. Pigm
ent Yellow-95, C.I. I. Pigment
Yellow-97, C.I. I. Pigment Ye
low-98, C.I. I. Pigment Yellow
-114, C.I. I. Pigment Yellow-1
28, C.I. I. Pigment Yellow-12
9, C.I. I. Pigment Yellow-151,
C. I. Pigment Yellow-154, and the like, but not limited thereto.

Examples of the inorganic pigment include, but are not limited to, titanium dioxide, zinc sulfide, titanium black, ultramarine, navy blue, molybdenum red, and titanium yellow. Further, specific color pigments such as red, green, and brown, metallic luster pigments such as gold and silver, and plastic pigments may be used.

As the dye, direct pigments, acidic pigments, basic dyes, disperse dyes, direct dyes and the like are used. For example, as the direct dye, for example, C.I. I. Direct Black-2, -4, -9, -17, -19, -22,-
32, -80, -154, -168, -171, -19
4, C.I. I. Direct Blue-1, -2, -8, -2
2, -34, -78, -86, -112, -165,-
199, -200, -207, -236, C.I. I. Direct Red-1, -2, -8, -15, -20, -3
3, -51, -62, -75, -87, -101, -1
10, -189, -227, C.I. I. Direct Yellow-1, -2, -4, -8, -11, -26, -27,-
28, -33, -34, -41, -44, -48, -5
8, -86, -87, -88, -135, -142,-
144 and the like.

Examples of the acidic pigment include C.I. I. Acid Black-1, -2, -7, -9, -16, -2
4, -26, -31, -48, -52, -63, -7
4, -107, -112, -121, -156, -17
2, -194, -208, C.I. I. Acid Blue-
1, -7, -9, -15, -22, -23, -40,-
55, -62, -78, -81, -90, -102,-
111, -185, -249, -254, C.I. I. Acid Red-1, -4, -8, -13, -21, -3
7, -51, -87, -92, -110, -144,-
180, -249, -257, C.I. I. Acid Yellow-1, -3, -4, -7, -18, -19, -23,
-38-42, -53, -61, -78, -122 and the like.

The basic dyes include, for example, C.I. I. Basic Blue-5, -7, -9, -26, C.I. I. Basic Red-1, -13, C.I. I. Basic Yellow-2, -11, and -51.

Examples of the disperse dye include C.I. I. Disperse Blue-56, -60, -73, -87, -1
13, -128, -143, -158, -165, -1
65: 1, -165: 2, -176, -183, -19
8, -201, -214, -224, -257, -26
6, -287, -354, -365, C.I. I. Disperse Red -54, -60, -72, -86, -91,
-111, -126, -134, -143, -159,
-164, -177, -181, -204, -221,
-239, -240, -258, -277, -283,
-311, -323, -343, -356, -362,
C. I. Disperse Yellow-5, -42, -54,
-64, -79, -82, -93, -100, -11
9, -122, -160, -184: 1, -198,-
204, -224, and -237.

The oily dyes include, for example, C.I. I. Solvent Black-3, -7, 27, -29, -34,
C. I. Solvent Blue-2, -11, -70, C.I.
I. Solvent Red-1, -3, -8, -18, -2
4, -43, -51, -72, -132, -218,
C. I. Solvent Yellow-14, -16, -19,
-29, -56, -82, -162 and the like.

These coloring agents may be used alone or in combination of two or more. In general, the content of these coloring agents is appropriately changed depending on the use or the like. In the composition of the present invention, these coloring agents are contained in the range of 1 to 50% by weight. Is preferred.

In summary, the composition of the present invention comprises 25 to 99.9% by weight of a maleimide compound and 0.1 to 50% by weight of a polymerizable compound having an acryloyl group or a methacryloyl group. Phosphine oxide-based photopolymerization initiator in an amount of 0.01 to 2% by weight, and a colorant in an amount of 1 to 5%.
It is preferably contained in the range of 0% by weight. More preferably, the maleimide compound is 30 to 99% by weight, and the polymerizable compound having an acryloyl group or a methacryloyl group is 0.2 to 0.2% by weight.
-40% by weight, phosphine oxide-based photopolymerization initiator in the range of 0.05-1.5% by weight, and colorant in the range of 1-50% by weight.

Further, the photocurable coloring composition of the present invention may contain a non-reactive compound, an inorganic filler, an organic filler, a tackifier, an antifoaming agent, a leveling agent, a plasticizer,
An antioxidant, an ultraviolet absorber, a flame retardant, and the like can be appropriately used in combination.

The non-reactive compounds include those having low reactivity,
Alternatively, it is a liquid or solid oligomer or resin having no reactivity, and is an alkyl (meth) acrylate copolymer,
Epoxy resin, liquid polybutadiene, liquid polybutadiene derivative, liquid chloroprene, liquid polypentadiene,
Dicyclopentadiene derivatives, saturated polyester oligomers, polyether oligomers, liquid polyamides, polyisocyanate oligomers, xylene resins, ketone resins, petroleum resins, rosin resins, fluorine oligomers, silicon oligomers, polysulfide oligomers, and the like. However, the present invention is not limited to this.

The inorganic and organic fillers are generally
It is used to improve mechanical properties such as strength, cushioning, and slipperiness. Known inorganic fillers include, for example, silicon dioxide, silicon oxide, calcium carbonate,
Calcium silicate, magnesium carbonate, magnesium oxide, talc, kaolin clay, calcined clay, zinc oxide,
Examples include, but are not limited to, zinc sulfate, aluminum hydroxide, aluminum oxide, glass, mica, barium sulfate, alumina white, zeolite, silica balloons, glass balloons, and the like.

Examples of the organic filler include, for example, benzoguanamine resin, silicone resin, low-density polyethylene, high-density polyethylene, polyolefin resin, ethylene-acrylic acid copolymer, polystyrene, cross-linked polystyrene, polydivinylbenzene, and styrene. -Divinylbenzene copolymer, acrylic copolymer, crosslinked acrylic resin, polymethyl methacrylate resin, vinylidene chloride resin, fluororesin, nylon 12, nylon 11,
Examples include, but are not limited to, nylon 6/66, phenolic resin, epoxy resin, urethane resin, polyimide resin, and the like.

In addition, any of tackifiers, defoamers, leveling agents, plasticizers, antioxidants, ultraviolet absorbers, and flame retardants which are known and commonly used impair their curability and resin properties. It can be used without any particular restrictions as long as it does not exist.

To obtain the active energy ray-curable composition of the present invention, the above-mentioned components may be mixed, and the order and method of mixing are not particularly limited.

The photocurable coloring composition of the present invention has a wavelength of 30.
The polymerization can be carried out by irradiating ultraviolet light or visible light of 0 to 500 nm. Wavelength 300-500n
As a light source of ultraviolet or visible light of m, for example,
High pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, chemical lamp, black light lamp, xenon lamp, mercury-xenon lamp, electrodeless lamp, excimer lamp, short arc lamp, helium / cadmium laser, argon laser, excimer laser, sun Light. Further, the photocurable coloring composition of the present invention can be cured in air and / or in an inert gas.

When the photocurable coloring composition of the present invention is applied to printing inks and other paints, it is instantaneously cured and dried by irradiation with light such as ultraviolet rays to obtain an excellent cured film without color burn. be able to.

[0104]

EXAMPLES Hereinafter, 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. First, synthesis examples of the maleimide compounds MA to MC used in the examples will be described.

(Synthesis Example 1) Synthesis of Maleimide Compound MA In a 200 ml eggplant-shaped flask equipped with a Dean-Stark type fractionator, a polypropylene glycol having a number average molecular weight of 400 (“Sanix PP- 400 ") 8 g, maleimidoacetic acid 6.8 g, p
-1.2 g of toluenesulfonic acid, 0.06 g of 2,6-tert-butyl-p-cresol and 15 ml of toluene
And stirred for 4 hours while removing water produced at 240 torr and 80 ° C. to continue the reaction. The reaction mixture was dissolved in 200 ml of toluene, three times with 100 ml of saturated sodium bicarbonate, and 100 ml of saturated saline.
Washed once with ml. The organic phase was concentrated to obtain a maleimide compound MA.

(Synthesis Example 2) Synthesis of Maleimide Compound MB In Synthesis Example 1, instead of 6.8 g of maleimide acetic acid,
Instead of 9.8 g of maleimidocaproic acid and 8 g of polypropylene glycol having a number average molecular weight of 400, polytetramethylene glycol having a number average molecular weight of 250 (B.A.
"Poly (THF)" manufactured by SF Japan
250 ", polystyrene equivalent value by GPC: number average molecular weight 440, weight average molecular weight 470), except that 5 g of maleimide compound MB was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 3) Synthesis of Maleimide Compound MC In Synthesis Example 1, polytetramethylene glycol having a number average molecular weight of 650 (“PTG650SN” manufactured by Hodogaya Chemical Co., Ltd.) was used instead of 8 g of polypropylene glycol having a number average molecular weight of 400. , GPC value in terms of polystyrene: number average molecular weight 1,200, weight average molecular weight 1,60
0) A maleimide compound MC was obtained in the same manner as in Synthesis Example 1 except that 13 g was used.

(Synthesis Example 4) Synthesis of Maleimide Compound MD A known method using maleic anhydride and a terminally aminated polypropylene glycol having a number average molecular weight of 400 (“Jeffamine D-400” manufactured by Mitsui Chemicals, Inc.) US
P244444, USP4171302, JP51-
40078, EP213933, etc.) to obtain a maleimide compound MD.

<Example 1> 80 parts by weight of the maleimide compound MA obtained in Synthesis Example 1 was added to SR-454 (E product of Sartomer).
2 parts by weight of O-modified trimethylolpropane triacrylate, Irgacure 819 (a radical photopolymerization initiator manufactured by Ciba Specialty Chemicals: bis (2,4,6)
1 part by weight of trimethylbenzoyl) -phenylphosphine oxide) and 18 parts by weight of Carbon Raven 1060 (carbon black manufactured by Mitsubishi Chemical Corporation) were mixed and kneaded to obtain a photocurable colored composition (maleimide group / unsaturated bond ratio). =
94/6). Take 0.075 ml of the obtained photocurable coloring composition into a dropper, apply it to polyester tack paper with an RI tester (manufactured by Hoei Seiko Co., Ltd.), and apply the 160 W / cm metal halide lamp (eye・ Graphics Co., Ltd.) and cured (film thickness: about 1.5 μm). At this time, the conveyor speed at which a cured film could be formed was 60 m / min.

<Example 2> 70 parts by weight of the maleimide compound MB obtained in Synthesis Example 2 was mixed with SR-454 (Sartomer E
5 parts by weight of O-modified trimethylolpropane triacrylate, Irgacure 819 (a radical photopolymerization initiator manufactured by Ciba Specialty Chemicals: bis (2,4,6)
-Trimethylbenzoyl) -phenylphosphine oxide) 0.5 parts by weight, Fastgen Blue TG
25 parts by weight of RL (Cyanine Pigment manufactured by Dainippon Ink and Chemicals, Inc.) were mixed and kneaded to obtain a photocurable coloring composition (maleimide group / unsaturated bond ratio = 86/14). 0.075 ml of the obtained photocurable coloring composition was added to a dropper.
Take it, and apply it to polyester tack paper by RI tester (manufactured by Hoei Seiko Co., Ltd.).
It was irradiated with a 0 W / cm metal halide lamp (manufactured by Eye Graphics Co., Ltd.) and cured (thickness: about 1.5 μm).
m). At this time, the conveyor speed at which a cured film could be formed was 50 m / min.

Example 3 68 parts by weight of the maleimide compound MC obtained in Synthesis Example 3 was used, and Aronix M-400 (dipentaerythritol hexaacrylate manufactured by Toagosei Co., Ltd.) was used.
7 parts by weight, Lucirin TPO (BASF radical photopolymerization initiator: 2,4,6-trimethylbenzoyldiphenylphosphine oxide) 1 part by weight, Fast
25 parts by weight of gen Blue TGR-L (Cyanine pigment manufactured by Dainippon Ink and Chemicals, Inc.) were mixed and kneaded,
A photocurable colored composition was obtained (maleimide group / unsaturated bond ratio = 66/34). Take 0.075 ml of the obtained photocurable coloring composition into a dropper, apply it to polyester tack paper with an RI tester (manufactured by Hoei Seiko Co., Ltd.), and apply the 160 W / cm metal halide lamp (eye・ Graphics Co., Ltd.) and cured (film thickness: about 1.5 μm). At this time, the conveyor speed at which a cured film could be formed was 60 m / min.

<Example 4> 92 parts by weight of the maleimide compound MD obtained in Synthesis Example 4, Aronix M-400 (dipentaerythritol hexaacrylate manufactured by Toagosei) 8
Parts by weight, Irgacure 819 (a radical photopolymerization initiator manufactured by Ciba Specialty Chemicals: bis (2,4,
6-trimethylbenzoyl) -phenylphosphine oxide) 1 part by weight, Fastgen Blue TGR
-L (Cyanine pigment manufactured by Dainippon Ink and Chemicals, Inc.)
25 parts by weight were mixed and kneaded to obtain a photocurable colored composition (maleimide group / unsaturated bond ratio = 79/21). 0.075 ml of the obtained photocurable coloring composition was placed in a dropper, which was then spread on polyester tack paper with an RI tester (manufactured by Hoei Seiko Co., Ltd.), and the developed product was filled with 160
Irradiated with a W / cm metal halide lamp (manufactured by Eye Graphics Co., Ltd.) and cured (thickness: about 1.5 μm)
m). At this time, the conveyor speed at which the cured film could be formed was 50 m / min, but the surface of the cured film was slightly roughened due to insufficient fluidity of the ink. <Example 5> 55 parts by weight of N, N'-p, p'-diphenylether bismaleimide, Aronix TO-14
50 (polyester acrylate manufactured by Toagosei), Irgacure 819 (radical photopolymerization initiator manufactured by Ciba Specialty Chemicals: bis (2,4,6)
-Trimethylbenzoyl) -phenylphosphine oxide) 1 part by weight, Fastgen Blue TGR-
L (Cyanine pigment manufactured by Dainippon Ink and Chemicals, Inc.) 2
0 parts by weight were mixed and kneaded to obtain a photocurable colored composition.
0.075 m of the obtained photocurable coloring composition was added to a dropper.
After the color is spread on polyester tack paper by an RI tester (manufactured by Hoei Seiko Co., Ltd.) and the volatile solvent is dried, a 160 W / cm metal halide lamp (I Graphics Co., Ltd.) Was irradiated and cured. At this time, the conveyor speed at which a cured film could be formed was 15 m / min. In addition, the surface of the cured film was roughened due to insufficient fluidity of the ink.

<Comparative Example 1> 80 parts by weight of the maleimide compound MA obtained in Synthesis Example 1 was mixed with SR-454 (Sartomer E
2 parts by weight of O-modified trimethylolpropane triacrylate) and 18 parts by weight of Carbon Raven 1060 (Carbon Black manufactured by Mitsubishi Chemical Corporation) were mixed and kneaded to obtain a photocurable colored composition (maleimide group / unsaturated bond ratio =). 94 /
6). The obtained photocurable coloring composition was added to a dropper in an amount of 0.0
A 75 ml sample was spread on polyester tack paper with an RI tester (manufactured by Hoei Seiko Co., Ltd.), and the developed product was irradiated with a 160 W / cm metal halide lamp (manufactured by Eye Graphics Co., Ltd.) and cured. (Thickness: about 1.5 μm). At this time, the conveyor speed is 5m / m
It did not cure in.

<Comparative Example 2> 75 parts by weight of the maleimide compound MB obtained in Synthesis Example 2 was mixed with Irgacure 819 (a radical photopolymerization initiator manufactured by Ciba Specialty Chemicals:
1 part by weight of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, Fastgen B
25 parts by weight of lue TGR-L (Cyanine pigment manufactured by Dainippon Ink and Chemicals, Inc.) were mixed and kneaded to obtain a photocurable coloring composition. 0.075 ml of the obtained photocurable coloring composition was placed in a dropper and spread on polyester tack paper with an RI tester (manufactured by Hoei Seiko Co., Ltd.).
The developed product was irradiated with a 160 W / cm metal halide lamp (manufactured by I-Graphics Co., Ltd.) to be cured (film thickness: about 1.5 μm). At this time, it did not cure at a conveyor speed of 5 m / min.

<Comparative Example 3> 30 parts by weight of the maleimide compound MB obtained in Synthesis Example 2 was mixed with SR-454 (Sartomer E
O-modified trimethylolpropane triacrylate) 45
Parts by weight, Irgacure 819 (a radical photopolymerization initiator manufactured by Ciba Specialty Chemicals: bis (2,4,
6-trimethylbenzoyl) -phenylphosphine oxide) 1 part by weight, Fastgen Blue TGR
-L (Cyanine pigment manufactured by Dainippon Ink and Chemicals, Inc.)
Was mixed and kneaded to obtain a photocurable colored composition (maleimide group / unsaturated bond ratio = 23/77). 0.075 ml of the obtained photocurable coloring composition was added to a dropper.
Take it, and apply it to polyester tack paper by RI tester (manufactured by Hoei Seiko Co., Ltd.).
It was irradiated with a 0 W / cm metal halide lamp (manufactured by Eye Graphics Co., Ltd.) and cured (thickness: about 1.5 μm).
m). At this time, it did not cure at a conveyor speed of 5 m / min.

<Comparative Example 4> 68 parts by weight of the maleimide compound MC obtained in Synthesis Example 3 was used, and Aronix M-400 (dipentaerythritol hexaacrylate manufactured by Toagosei) was used.
7 parts by weight, 1 part by weight of EAB (radical photopolymerization initiator: 44'-diethylaminobenzophenone manufactured by Hodogaya Chemical), 25 parts by weight of Fastgen Blue TGR-L (Cyanine pigment manufactured by Dainippon Ink and Chemicals, Inc.)
Was mixed and kneaded to obtain a photocurable colored composition (maleimide group / unsaturated bond ratio = 66/34). 0.075 ml of the obtained photocurable coloring composition was placed in a dropper,
Developed on polyester tack paper with an I tester (manufactured by Hoei Seiko Co., Ltd.), and then used a 160 W / cm metal halide lamp (manufactured by Eye Graphics Co., Ltd.)
And cured (film thickness: about 1.5 μm). At this time, it did not cure at a conveyor speed of 5 m / min.

[0117]

The photocurable coloring composition of the present invention minimizes problems such as odor, color burn, and bleed (amount of extract) due to a residual photopolymerization initiator, and has practical light intensity and light irradiation amount. To cure.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 299/02 C08F 299/02 F-term (Reference) 4J011 PA03 PA07 PA13 PA22 PB25 PC02 QA03 QA19 QA26 QA39 QB14 QB16 QB19 QB24 SA06 SA21 SA25 SA31 SA36 SA46 SA49 SA64 UA01 WA02 WA05 4J027 AB03 AB10 AB23 AB24 AB25 AC02 AC03 AC04 AC06 AE02 AE04 AG02 AG03 AG04 AG22 AG33 AJ08 BA03 BA07 BA08 BA09 BA10 BA11 BA12 BA19 BA20 BA26 BA27 BA28 4Q08 AL04 AL08 AL08Q AL09Q AL11Q AL62Q AL66Q AM54P AM59P BA02P BA03P BA03Q BA08Q BA15P BA16P BA21Q BA29P BA38P BA38Q BA39Q BB00P BC03Q BC04Q BC07Q BC43Q BC54Q CA04 JA01 JA07

Claims (7)

[Claims] (1) a polyfunctional maleimide compound,
A photocurable coloring composition comprising (2) a polymerizable compound having an acryloyl group or a methacryloyl group, (3) a phosphine oxide-based photopolymerization initiator, and (4) a coloring agent. (1) The polyfunctional maleimide compound is a maleimide compound represented by the general formula (I): (In the formula, m and n each independently represent an integer of 1 to 5, and m + n is 6 or less. R11 and R12 each independently represent an alkylene group, a cycloalkylene group, an arylalkylene group, and a cycloalkyl group. Represents a hydrocarbon bond selected from the group consisting of alkylalkylene groups, and G1 and G
2 independently represents an ester bond or a urethane bond. R2 is a group in which at least one organic group selected from the group consisting of a linear alkylene group, a branched alkylene group, an alkylene group having a hydroxyl group, a cycloalkylene group, an aryl group and an arylalkylene group is an ether bond, an ester bond, and a urethane bond. A number average molecular weight of 100,0 linked by at least one bond selected from the group consisting of
And represents a (poly) ether connecting chain, a (poly) ester connecting chain or a (poly) urethane connecting chain of 00 or less. The photocurable colored composition according to claim 1, wherein 3. The molar ratio of the unsaturated bond between (1) the maleimide compound and (2) the polymerizable compound having an acryloyl group or a methacryloyl group is from 30/70 to 99.8 /.
The photocurable coloring composition according to claim 1, wherein the value is 0.2. 4. A (1) maleimide compound, (2) a polymerizable compound having an acryloyl group or a methacryloyl group, 0.01 to 2% by weight of (3) a phosphine oxide-based photopolymerization initiator, The photocurable coloring composition according to any one of claims 1 to 3, further comprising a coloring agent. 5. The photocurable coloring composition according to claim 1, wherein (2) the polymerizable compound having an acryloyl group or a methacryloyl group has an average functional group number of 1 to 6. (2) The polymerizable compound having an acryloyl group or a methacryloyl group is (poly) ester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, (poly) ether (meth) acrylate, The compound is at least one compound selected from the group consisting of alkyl (meth) acrylate, alkylene (meth) acrylate, (meth) acrylate having an aromatic ring, and (meth) acrylate having an alicyclic structure. The photocurable colored composition according to any one of the above. 7. The method of claim 1, wherein (1) the maleimide compound is 25-99.
9% by weight, (2) 0.1 to 50% by weight of a polymerizable compound having an acryloyl group or a methacryloyl group, (3) 0.01 to 2% by weight of a phosphine oxide-based photopolymerization initiator, (4) coloring The photocurable coloring composition according to any one of claims 1 to 6, wherein the composition contains 1 to 50% of an agent.