JP2000143729A - Active energy ray-curable resin composition containing maleimide derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition with high curing rate, excellent in workability and long-term stability, capable of giving cured products of sufficient mechanical strength and flexibility, and suitable as an optical fiber coating material or the like by including a specific maleimide derivative. SOLUTION: This composition is obtained by including (A) a maleimide derivative of the formula [(m) and (n) are each 0-6, (m+n) being 1-6; R11 and R12 are each an aliphatic or aromatic hydrocarbon chain; G1 and G2 are each an ether linkage, ester linkage, urethane linkage or carbonate linkage; R2 is a (poly)ether coupled chain or (poly)ether residue, (poly)urethane coupled chain or (poly)urethane residue, or the like, with an average molecular weight of 40-100,000, each formed by coupling aliphatic or aromatic hydrocarbon chains or aliphatic or aromatic groups through ether linkages, urethane linkages, or the like] and (B) as necessary, a compound copolymerizable with maleimide group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having excellent active energy ray curability. In particular, the present invention relates to a resin composition for coating an optical fiber and an optical fiber core, a colored core, a unit or an overcoat core coated with a cured product of the composition.

[0002]

2. Description of the Related Art Optical fibers are used immediately after hot melt spinning of glass preforms to protect the surface and maintain strength.
Coated with resin. Usually, on the surface of the optical fiber,
A flexible primary coating (called primary coating material) layer is formed, and a rigid secondary coating (called secondary coating material) layer is formed thereon to manufacture an optical fiber. Further, the wires are colored with ink (called ink) for identification. In order to improve the workability of this optical fiber,
An optical fiber unit is manufactured by arranging one or a plurality of, for example, two, four, or eight strands, and using a binding material (called a unit material) with or without a tension member as a reinforcing material. ing. A unit in which a plurality of units are arranged on a plane is called a tape or a ribbon. There is also a unit composed of eight units in which four units are arranged on a plane and two units are connected with a connecting material (called a binding material). In some cases, the strand is further coated with a resin (overcoat material) to increase the diameter, and used.

[0003] As a primary coating material, a secondary coating material, an ink, a unit material, a binding material, an overcoat material and the like used for coating an optical fiber, a coating layer which is liquid, has a high curing speed, and has a uniform thickness is formed. Active energy ray-curable resins are used because they have the characteristic that they can be used.

[0004] The characteristics required of the coating material for optical fibers are as follows: (1) It is liquid at the time of coating (at room temperature or heated state) and has excellent workability such as applicability, and (2) it has excellent long-term stability. (3) that the curing rate is high; (4) that the cured product has sufficient strength and flexibility; (5)
(6) the cured product has heat resistance, hydrolysis resistance, acid resistance, alkali resistance, oil resistance, light yellowing resistance, heat yellowing resistance,
(7) low hydrogen gas generation, (8) appropriate adhesion to the substrate (optical fiber, active energy ray-curable resin coating layer, etc.), (9) ) The coating layer may be easily peeled off.
In particular, it is particularly desired that the demand for optical fibers is expanding and the curing speed is high.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a cured product having a high curing rate, excellent workability, excellent long-term stability, sufficient strength and flexibility, and a wide range. With little change in physical properties due to temperature change, excellent heat resistance, hydrolysis resistance, acid resistance, alkali resistance, oil resistance, light yellowing resistance, heat yellowing resistance, ultraviolet light resistance, low hydrogen gas generation, moderate In particular, it is an object of the present invention to provide a resin composition suitable as an optical fiber coating material, which has a property of having an adhesive property and a property that a coating layer is appropriately peeled off, and particularly has a high curing rate and a small generation of hydrogen gas.

[0006]

Means for Solving the Problems In view of this situation, the present inventors have conducted intensive studies to solve the above problems, and as a result,
The present invention has been reached. That is, the present invention has found that the above problems can be solved by using a specific maleimide derivative (A), and have completed the present invention.

That is, the present invention provides (1) the general formula (1)

[0008]

Embedded image (1) In the formula, m and n each independently represent an integer of 0 to 6, and m + n is an integer of 1 to 6. R ₁₁ and R
Each ₁₂ independently represents a hydrocarbon chain comprising an aliphatic group and / or an aromatic group. G ₁ and G ₂ each independently represent an ether bond, an ester bond, a urethane bond, or a carbonate bond. R ₂ is a hydrocarbon chain composed of an aliphatic group and / or an aromatic group, or at least one of the aliphatic group and / or the aromatic group selected from the group consisting of an ether bond, an ester bond, a urethane bond and a carbonate bond.
(Poly) ether linking chain or (poly) ether residue (A) having an average molecular weight of 40 to 100,000
-1), (poly) ester linked chain or (poly) ester residue (A-2), (poly) urethane linked chain or (poly)
A urethane residue (A-3) or a (poly) carbonate linking chain or a (poly) carbonate residue (A-
4). The present invention provides an active energy ray-curable resin composition for coating an optical fiber, comprising a maleimide derivative (A) represented by the following formula:

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to an active energy ray-curable resin composition containing the maleimide derivative (A) represented by the above general formula (1).

In the above general formula (1), m and n are
Each independently represents an integer of 0 to 6, and a compound in which m + n is an integer of 1 to 6 is preferable. In particular, m and n are each independently an integer of 1 to 5 and m + n is 2 or more and 6 because they are liquid at room temperature and form a cured film by themselves.
Compounds having the following integers are recommended.

R ₁₁ and R ₁₂ each independently represent a hydrocarbon chain comprising an aliphatic group and / or an aromatic group. Among them, a hydrocarbon bond selected from the group consisting of an alkylene group, a cycloalkylene group, an arylalkylene group and a cycloalkylalkylene group is particularly preferred. Here, the alkylene group may be linear or branched, and the arylalkylene group or the cycloalkyl-alkylene group may be an aryl group or a cycloalkyl group in a main chain or a branched chain, respectively. May be provided. Linear alkylene groups having 1 to 5 carbon atoms and branched alkylene groups having 1 to 5 carbon atoms have good curability and are recommended. Specific examples of R ₁₁ and R ₁₂ include, for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group,
Linear alkylene groups such as nonamethylene group, decamethylene group, undecamethylene group and dodecamethylene group;
Methylethylene group, 1-methyl-trimethylene group, 2-
Branching such as methyl-trimethylene group, 1-methyl-tetramethylene group, 2-methyl-tetramethylene group, 1-methyl-pentamethylene group, 2-methyl-pentamethylene group, 3-methyl-pentamethylene group, neopentyl group An alkylene group having an alkyl group; a cyclopentylene group,
Cycloalkylene group such as cyclohexylene group; main chain or side chain such as benzylene group, 2,2-diphenyl-trimethylene group, 1-phenyl-ethylene group, 1-phenyl-tetraethylene group, 2-phenyl-tetraethylene group An arylalkylene group having an aryl group; a cycloalkyl having a cycloalkyl group in a main chain or a side chain such as a cyclohexylmethylene group, a 1-cyclohexyl-ethylene group, a 1-cyclohexyl-tetraethylene group, or a 2-cyclohexyl-tetraethylene group. -Alkylene group, and the like, but are not limited thereto.

R ₂ is a hydrocarbon chain comprising an aliphatic group or an aromatic group, or at least one bond wherein the aliphatic group or the aromatic group is selected from the group consisting of an ether bond, an ester bond, a urethane bond and a carbonate bond. (Poly) ether linking chains having an average molecular weight of 40 to 100,000 or (poly) ether residues (A-1), (poly)
Ester linking chains or (poly) ester residues (A-2),
(A-4) represents a (poly) urethane linking chain or a (poly) urethane residue or (A-3), a (poly) carbonate or a (poly) carbonate linking chain. R ₂ may be a connecting chain composed of an oligomer or a polymer in which these connecting chains are repeated as one unit and are repeated.

Specific examples of R ₂ include, for example, those represented by R ₁₁ and R ₁₂ as hydrocarbon chains comprising an aliphatic group and / or an aromatic group.

As the straight-chain alkylene group, at least one hydrocarbon group selected from the group consisting of a branched alkylene group, a cycloalkylene group and an aryl group has one or a repeating unit thereof bonded by an ether bond. A connecting chain or a residue (A-) composed of (poly) ether (poly) ol having an average molecular weight of 40 to 100,000.
1): An average molecular weight in which at least one hydrocarbon group selected from the group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group, and an aryl group has one or a repeating unit thereof bonded by an ester bond. Linking chain or residue (A-2-1) composed of 40 to 100,000 (poly) ester (poly) ol: a group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group, and an aryl group. At least one hydrocarbon group selected from the group consisting of one or a repeating unit thereof bonded by an ether bond has an average molecular weight of 40 to 10
0000 (poly) ether (poly) ol and di-hexa-carboxylic acid (hereinafter abbreviated as polycarboxylic acid)
And a linking chain or residue (A-2-2) composed of (poly) carboxylic acid {(poly) ether (poly) ol} ester having a polycarboxylic acid residue at the end obtained by esterification of Average molecular weight in which at least one hydrocarbon group selected from the group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group, and an aryl group has one or a repeating unit thereof bonded by an ether bond and an ester bond. (Poly) carboxylic acid {(poly) ester (poly) ol} ester having 40 to 100,000 (poly) ester (poly) ol and polycarboxylic acid and having a polycarboxylic acid residue at the end. A linking chain or residue (A-2-
3): Average molecular weight in which at least one hydrocarbon group selected from the group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group, and an aryl group has one or a repeating unit thereof bonded by an ether bond. Linking chain or residue (A-5) obtained by opening 100 to 40,000 (poly) epoxides: selected from the group consisting of linear alkylene groups, branched alkylene groups, cycloalkylene groups and aryl groups. At least one hydrocarbon group has one or more repeating units linked by an ether bond, and has an average molecular weight of 40 to 100,000.
A linking chain or residue (A) composed of a (poly) ether (poly) isocyanate obtained by urethane-forming a (poly) ether (poly) ol and an organic (poly) isocyanate
-3-1): at least one hydrocarbon group selected from the group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group, and an aryl group is one or a repeating unit thereof bonded by an ester bond. A linking chain or residue (A-3-) composed of a (poly) ester (poly) isocyanate obtained by urethane-forming a (poly) ester (poly) ol having an average molecular weight of 40 to 100,000 and an organic (poly) isocyanate 2): Average molecular weight in which at least one hydrocarbon group selected from the group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group, and an aryl group has one or a repeating unit thereof bonded by an ether bond. 40-100,00
Examples include, but are not limited to, a connecting chain or a residue (A-4) composed of a carbonic ester of 0 (poly) ether (poly) ol. (A-
2-1), (A-2-2) and (A-2-3) are referred to as a (poly) ester connecting chain or a (poly) ester residue (A-2) in the general formula (1). (A-3-1) and (A-
3-2) is defined as a (poly) urethane linking chain or a (poly) urethane residue (A-2) referred to in the general formula (1).

The (poly) ether (poly) ol constituting the above-mentioned connecting chain or residue (A-1) includes, 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,
Examples of alkylene glycols such as diglycerin, ditrimethylolpropane, and dipentaerythritol, ethylene oxide modified products, propylene oxide modified products, butylene oxide modified products, tetrahydrofuran modified products, etc. Are preferred. Furthermore, the above-mentioned connecting chain (A-
Examples of the (poly) ether (poly) ol constituting 1) include a copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran, a copolymer of ethylene glycol and tetrahydrofuran, polyisoprene glycol, and hydrogenated poly. Examples include, but are not limited to, hydrocarbon polyols such as isoprene glycol, polybutadiene glycol, and hydrogenated polybutadiene glycol, and polyvalent hydroxyl compounds such as polytetramethylene hexaglyceryl ether (tetrahydrofuran modified hexaglycerin). Not something.

The (poly) ester (poly) ol constituting the above-mentioned connecting chain or residue (A-2-1) includes, for example, polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol. Alkylene glycols, or ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol Modified ε-caprolactone, γ-butyrolactone, δ-valerolactone or methyl valerolactone of alkylene glycols; Aliphatic polyester polyol which is an esterified product of an aliphatic dicarboxylic acid such as dicarboxylic acid or dimer acid and a polyol such as neopentyl glycol or methylpentanediol; an aromatic dicarboxylic acid such as terephthalic acid and a polyol such as neopentyl glycol; A polyester polyol such as an aromatic polyester polyol which is an esterified product of a polyhydric hydroxyl group compound such as a polycarbonate polyol, an acrylic polyol, and polytetramethylene hexaglyceryl ether (a tetrahydrofuran modified product of hexaglycerin);
Esterified products of dicarboxylic acids such as fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, and maleic acid; by transesterification reaction between polyhydric hydroxyl group-containing compounds such as glycerin and animal / plant fatty acid esters Examples thereof include, but are not limited to, polyhydric hydroxyl group-containing compounds such as monoglyceride obtained.

Examples of the (poly) carboxylic acid {(poly) ether (poly) ol} ester having a polycarboxylic acid at the terminal constituting the linking chain or the residue (A-2-2) include, for example, succinic acid , Adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, fumaric acid,
Isophthalic acid, itaconic acid, adipic acid, sebacic acid,
Polycarboxylic acids such as maleic acid, trimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid, citric acid, tetrahydrofurantetracarboxylic acid, and cyclohexane bird carboxylic acid are shown in the above (A-1) ( (Poly) carboxylic acid {(poly) ether (poly) ol} ester having a polycarboxylic acid at the end obtained by esterification with (poly) ether (poly) ol, and the like, but are not limited thereto. Absent.

Examples of the (poly) carboxylic acid {(poly) ester (poly) ol} ester in which the terminal constituting the linking chain or residue (A-2-3) is a polycarboxylic acid include, for example, succinic acid , Adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, fumaric acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid, trimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, benzenehexacarboxylic Di-hexa-carboxylic acid such as acid, citric acid, tetrahydrofurantetracarboxylic acid, cyclohexane bird carboxylic acid and the (poly) ester (poly) shown in the above (A-2)
Examples thereof include, but are not limited to, (poly) carboxylic acid {(poly) ester (poly) ol} ester having a polycarboxylic acid terminal obtained by esterification with all.

The (poly) epoxide constituting the above-mentioned connecting chain or residue (A-5) is, 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 or pyromellitic acid Glycols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol, and neopentyl glycol, and polyglycidyl ethers of alkylene oxide-modified products thereof; trimethylolpropane, trimethylolpropane; Methylolethane, glycerin, diglycerin, erythritol, pentaerythritol, sorbitol, 1,4-butanediol, 1,6
Glycidyl ethers of aliphatic polyhydric alcohols such as hexanediol and alkylene oxide modified products thereof; glycidyl esters of carboxylic acids such as adipic acid, sebacic acid, maleic acid and itaconic acid; polyhydric alcohols and polycarboxylic acids; Glycidyl ethers of polyester polyols; copolymers of glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; fats such as glycidyl esters of higher fatty acids, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, and epoxidized polybutadiene Group epoxy resin, and the like, but are not limited thereto.

Examples of the (poly) ether (poly) isocyanate constituting the linking chain or residue (A-3) include methylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, lysine diisocyanate, and dimer. Aliphatic diisocyanate compounds such as acid diisocyanate; 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate;
2,6-tolylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,
Aromatic diisocyanate compounds such as 4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, and 3,3'-dimethylbiphenyl-4,4'-diisocyanate; isophorone diisocyanate;
4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6) diisocyanate, 1,3- (isocyanatomethylene)
(Poly) ether (poly) isocyanate obtained by urethanization reaction of polyisocyanate such as cycloaliphatic diisocyanate such as cyclohexane and (poly) ether (poly) ol, and the like, but are not limited thereto. is not.

Examples of the (poly) ether (poly) ol used for the reaction with the polyisocyanate include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol;
Modified ethylene oxide of alkylene glycols such as propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol And modified products of propylene oxide, butylene oxide, and modified products of tetrahydrofuran. Of these, various modified products of alkylene glycols are preferable. Further, as the (poly) ether (poly) ol used for the reaction with the polyisocyanate, a copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran, a copolymer of ethylene glycol and tetrahydrofuran, polyisoprene glycol, Hydrocarbon polyols such as hydrogenated polyisoprene glycol, polybutadiene glycol and hydrogenated polybutadiene glycol; and polyhydric hydroxyl compounds such as polytetramethylene hexaglyceryl ether (tetrahydrofuran-modified hexaglycerin). It is not limited.

Examples of the (poly) ester (poly) isocyanate constituting the linking chain or residue (A-3-1) include, for example, the polyisocyanate listed for the linking chain (A-1) and (poly) Examples include (poly) ester (poly) isocyanate obtained by urethanation with ester (poly) ol, but are not limited thereto.

Examples of the (poly) ester (poly) ol used for the reaction with the polyisocyanate include ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, and trimethylol. Of alkylene glycols such as propane, pentaerythritol, diglycerin, ditrimethylolpropane, and dipentaerythritol,
ε-caprolactone modified, γ-butyrolactone modified, δ-valerolactone modified, methylvalerolactone modified; aliphatic dicarboxylic acids such as adipic acid and dimer acid, and polyols such as neopentyl glycol and methylpentanediol Aliphatic polyester polyol which is an esterified product; polyester polyol such as an aromatic polyester polyol which is an esterified product of an aromatic dicarboxylic acid such as terephthalic acid and a polyol such as neopentyl glycol; polycarbonate polyol, acrylic polyol, polytetramethylene hexagon Polyhydric hydroxyl compound such as glyceryl ether (tetrahydrofuran modified hexaglycerin), fumaric acid, phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, maleic acid Esterified products with a dicarboxylic acid such as glycerin; and polyhydric hydroxyl group-containing compounds such as monoglyceride obtained by transesterification of a polyvalent hydroxyl-containing compound such as glycerin with a fatty acid ester of an animal or a plant, but are not limited thereto. It is not done.

The (poly) ether (poly) ol constituting the above connecting chain or residue (A-4) includes the above (A-
Examples include (poly) ether (poly) ol described in 1), but are not limited thereto.

(Poly) ether Examples of the compound used for carbonic esterification with (poly) ol include diethyl carbonate, dipropyl carbonate and phosgene.
Further, polycarbonate can be obtained by alternate polymerization of epoxide and carbon dioxide, but is not limited thereto.

Among them, R ₂ has _{2 to} 24 carbon atoms.
Linear alkylene group, a C 2-24 branched alkylene group,
At least one organic group selected from the group consisting of a C2 to C24 alkylene group having a hydroxyl group, a cycloalkylene group, an aryl group and an arylalkylene group is at least one bond selected from the group consisting of an ether bond and an ester bond. Tied average molecular weight 100-100,
000 (poly) ether-linked chains or (poly) ether residues (A-1) or (poly) ester-linked chains or (poly) ester residues (A-2) are preferred. Linear alkylene group having 2 to 2 carbon atoms
A branched alkylene group having 4 or 2 to 24 carbon atoms having a hydroxyl group;
(Poly) ether linking chain or (poly) ether residue having an average molecular weight of 100 to 100,000 comprising a repeating unit containing an alkylene group and / or an aryl group (A-
1) Alternatively, the average molecular weight of a repeating unit containing a straight-chain alkylene group having 2 to 24 carbon atoms, a branched alkylene group having 2 to 24 carbon atoms, an alkylene group having 2 to 24 carbon atoms having a hydroxyl group and / or an aryl group 100-100,00
A (poly) ester linking chain of 0 or a (poly) ester residue (A-2) is preferred.

The curability is excellent, and particularly, the irradiation amount of the ultraviolet ray is 0.1.
1J / cm^TwoIn order to cure below₁₁And R₁₂
Are each independently an alkylene group having 1 to 5 carbon atoms.
G ₁And G_TwoAre each independently -COO- or -OCO
An ester bond represented by-_TwoIs the carbon atom
A straight-chain alkylene group having 2 to 6 carbon atoms, a branch having 2 to 6 carbon atoms
C2-C2 having an alkylene group and / or a hydroxyl group
Average molecule consisting of repeating units containing 6 alkylene groups
An amount of 100-1,000 (poly) ether linked chains or
Derivation of a maleimide which is a (poly) ether residue (A-1)
The use of the body is particularly recommended. Hardened material has sufficient strength
And flexible optical fiber coating composition
Among them, G₁And G_TwoIs a urethane bond, R_Two
Is a straight-chain alkylene group having 2 to 24 carbon atoms,
A branched alkylene group having 2 to 24 children and a carbon having a hydroxyl group;
An alkylene group and / or an aryl group having 2 to 24 atoms
Average molecular weight of 100 to 100,
000 (poly) ether linked chains or (poly) ether
Residue (A-1) (poly) ester connecting chain or (poly)
Stele residue (A-2), (poly) urethane linking chain or
(Poly) urethane residue or (A-3),
-Carbonate connecting chain or (poly) carbonate residue (A-
4) The use of the maleimide derivative (A)
More effective.

The maleimide derivative (A) represented by the general formula (1) of the present invention includes, for example, a maleimide compound (A-a-1) having a carboxyl group and a compound (A-a-2) which reacts with a carboxyl group. Or a maleimide compound having a hydroxyl group (A-b-1)
And a compound (Ab-2) that reacts with a hydroxyl group, using a known technique.

The maleimide compound (A-a-1) having a carboxyl group can be produced, for example, by the following reaction scheme.

[0030]

Embedded image

As shown in the above, from maleic anhydride and primary aminocarboxylic acid (A-a-1-1), a known technique [for example, DH Rich et al.
"Journal of Medical Chemistry (Jour
nal of Medical Chemistry) ", Vol. 18, No. 1004-
1010 (1975)].

The maleimide compound (Ab-1) having a hydroxyl group can be prepared, for example, by the following reaction scheme.

[0033]

Embedded image

As shown in the above formula, from maleimide and formaldehyde, or from the reaction formula

[0035]

Embedded image

As shown in the above, from the maleic anhydride and the primary amino alcohol (Ab-1-1), a known technique (for example, US Pat. No. 2,526,517, JP-A-2-268155) can be used. See, for example).

The primary aminocarboxylic acid (A-a-1-1) used in the above reaction includes, for example, 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-aminocaprylic acid, 2-aminononanoic acid, 4-aminononanoic acid, 9-aminononanoic acid, 2-aminocapric acid, 9-aminocapric acid, 10-aminocapric acid,
2-aminoundecanoic acid, 10-aminoundecanoic acid,
11-aminoundecanoic acid, 2-aminolauric acid, 1
1-aminolauric acid, 12-aminolauric acid, 2-
Aminotridecanoic acid, 13-aminotridecanoic acid, 2-
Amino mystinic acid, 14-amino mystinic acid, 2-aminopentadecanoic acid, 15-aminopentadecanoic acid, 2-
Amino palmitic acid, 16-amino palmitic acid, 2-
Aminoheptadecanoic acid, 17-aminoheptadecanoic acid,
2-aminostearic acid, 18-aminostearic acid,
2-aminoeicosanonic acid, 20-aminoeicosanonic acid, aminocyclohexanecarboxylic acid, aminomethylcyclohexanecarboxylic acid, 2-amino-3-propionic acid, 3-amino-3-phenylpropionic acid, and the like. However, the present invention is not limited to this, and any primary aminocarboxylic acid can be used. Also, lactams such as pyrrolidone, δ-valerolactam and ε-caprolactam can be used.

The primary amino alcohol (Ab-1-1) used in the above reaction includes, for example, 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-4-methylthio-1-butanol, 2
-Amino-1-pentanol, 5-amino-1-pentanol, (1-aminocyclopentane) methanol, 6
-Amino-1-hexanol, 2-amino-1-hexanol, 7-amino-1-heptanol, 2- (2-aminoethoxy) ethanol, N- (2-aminoethyl)
Ethanolamine, 4-amino-1-piperazineethanol, 2-amino-1-phenylethanol, 2-amino-3-phenyl-1-propanol, 1-aminomethyl-1-cyclohexanol, aminotrimethylcyclohexanol, etc. Examples include, but are not limited to, any primary amino alcohol.

Compounds which react with carboxyl groups (Aa
-2) is, for example, one in which at least one hydrocarbon group selected from the group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group and an aryl group is bonded by an ether bond and / or an ester bond. Or having an average molecular weight of 100 or more having a repeating unit thereof
1,000,000 2- to 6-functional polyols or polyepoxides, and the like.

Compounds that react with a hydroxyl group (Ab
-2) is, for example, one in which at least one hydrocarbon group selected from the group consisting of a linear alkylene group, a branched alkylene group, a cycloalkylene group, and an aryl group is bonded by an ether bond and / or an ester bond. Or an average molecular weight of from 100 to 1,
2 to 6 carboxyl groups, ether bonds and / or ester bonds in one molecule of 1,000,000
Hexa-carboxylic acid (A-b-2-1), (poly) isocyanate (A-b-2-2), or carbonate and phosgene (b-2-3).

The reaction between the maleimide compound (A-a-1) having a carboxyl group and the polyol which is one of the compounds (A-a-2) reacting with the carboxyl group is not particularly limited. [For example, CEE
CE Rehberg et al., “Organic
Synthesis Collective Volume (Org. Synth.C
ollective Volume), Vol. III, p. 46 (1955)
)] Can be used to synthesize the maleimide derivative represented by the general formula (1).

This reaction is carried out at room temperature to 1 under normal pressure or reduced pressure.
It is preferable to perform the dehydration in a temperature range of 50 ° C. while using a catalyst. Examples of the catalyst include acid catalysts such as sulfuric acid, phosphoric acid, metasulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and strongly acidic cation exchange resin. The addition amount of the catalyst is preferably in the range of 0.01 to 10% by weight based on the whole charged amount.

In this reaction, an organic solvent azeotropic with water can be used as a reaction solvent. Examples of such an organic solvent include toluene, benzene, butyl acetate, ethyl acetate, diisopropyl ether, dibutyl ether, and the like.

The reaction between the maleimide compound (A-a-1) having a carboxyl group and the polyepoxide, which is one of the compounds (A-a-2) reacting with the carboxyl group, is not particularly limited, but it is well known in the art. [See, for example, Japanese Patent Application Laid-Open No. 4-228529] using the general formula (1)
Can be synthesized.

This reaction is carried out in a temperature range from room temperature to 150 ° C., and it is desirable to use a catalyst. Examples of the catalyst include imidazoles such as 2-methylimidazole, quaternary ammonium salts such as tetramethylammonium chloride, trimethylbenzylammonium chloride and tetramethylammonium bromide, and amines such as trimethylamine, triethylamine, benzylmethylamine and tributylamine. Phosphines such as triphenylphosphine and tricyclohexylphosphine; lauric esters such as dibutyltin laurate; basic alkali metal salts such as potassium acetate, potassium tertiary phosphate, sodium acrylate and sodium methacrylate; sodium methylate And alkali metal alcoholates such as potassium ethylate and anion exchange resins. The addition amount of the catalyst is preferably in the range of 10 to 10,000 ppm based on the whole charged amount.

In this reaction, an organic solvent containing no active hydrogen can be used as a reaction solvent. Such organic solvents include, for example, toluene,
Aromatic hydrocarbons such as ethylbenzene, tetralin, cumene and xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; formate, methyl acetate, ethyl acetate and n-acetic acid
And esters such as butyl.

A maleimide compound (Ab-1) having a hydroxyl group and a compound (Ab-2-1) having a carboxyl group which is one of the compounds (Ab-2) reacting with the hydroxyl group The reaction with is not particularly limited, but known techniques [for example, CE Rehberg, “Org. Synth. Collective Vol.
ume) ", Vol. III, p. 46 (1955)] can be used to synthesize the maleimide derivative represented by the general formula (1).

The reaction is carried out at room temperature to 1 under normal pressure or reduced pressure.
It is preferable to perform the dehydration in a temperature range of 50 ° C. while using a catalyst. Examples of the catalyst include acid catalysts such as sulfuric acid, phosphoric acid, metasulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and a strongly acidic cation exchange resin.
And the like. The addition amount of the catalyst is preferably in the range of 0.01 to 10% by weight based on the whole charged amount.

At this time, an organic solvent azeotropic with water can be used as a reaction solvent. Such organic solvents include, for example, toluene, benzene, butyl acetate, ethyl acetate, diisopropyl ether, dibutyl ether,
And the like.

A maleimide compound (Ab-1) having a hydroxyl group and (poly) isocyanate which is one of the compounds (Ab-2) reacting with the hydroxyl group
The reaction with (A-b-2-2) is not particularly limited,
By a known urethanation reaction, a maleimide derivative represented by the general formula (1) can be synthesized.

This reaction is preferably carried out in a nitrogen atmosphere at a temperature in the range of room temperature to 90 ° C., and a catalyst is preferably used. As the catalyst, for example, organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, tin octylate, dibutyl tin oxide, organic tin compounds such as dibutyl tin laurate, stannous iodide, and the like can be used. . The addition amount of the catalyst is preferably in the range of 10 to 10,000 ppm based on the whole charged amount.

In this reaction, various organic solvents not containing active hydrogen can be used as reaction solvents. Such organic solvents include, for example, aromatic hydrocarbons such as toluene, ethylbenzene, tetralin, cumene and xylene; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; formate, methyl acetate, ethyl acetate, Esters such as n-butyl acetate are exemplified.

A maleimide compound (Ab-1) having a hydroxyl group and a carbonate (Ab-2) which is one of the compounds (Ab-2) reacting with the hydroxyl group
The reaction with -3) is not particularly limited, but the maleimide derivative represented by the general formula (1) can be synthesized by a known transesterification reaction.

The reaction is carried out at room temperature to 1 under normal pressure or reduced pressure.
It is preferable to carry out the reaction while distilling off the alcohol formed in a temperature range of 50 ° C. and use a catalyst. Examples of the catalyst include sulfuric acid, phosphoric acid, metasulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, an acid catalyst such as a strongly acidic cation exchange resin, an organic titanium compound such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; Examples include organotin compounds such as tin octylate, dibutyltin oxide, and dibutyltin laurate; and aluminum alkoxides such as aluminum triisopropoxide. The amount of the catalyst added was 0.1 to the total charge.
The range of 01 to 10% by weight is preferred.

At this time, the reaction solvent may not be used, but an organic solvent which azeotropes with the produced alcohol can be used. Such organic solvents include, for example, toluene,
Examples thereof include benzene, hexane, heptane, butyl acetate, ethyl acetate, diisopropyl ether, dibutyl ether and the like.

In any of the above reactions, it is desirable to use a radical polymerization inhibitor for the purpose of suppressing the radical polymerization of the maleimide group. Examples of the radical polymerization inhibitor include hydroquinone, tert-butylhydroquinone, methoquinone, 2,4-dimethyl-6-te
Phenolic compounds such as rt-butylphenol, catechol, tert-butylcatechol; phenothiazine, p
Amines such as phenylenediamine and diphenylamine; and copper complexes such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate and copper dibutyldithiocarbamate. These polymerization inhibitors can be used alone or in combination of two or more. The amount of the polymerization inhibitor to be added is 10 to 1 with respect to the total charged amount.
A range of 0.00000 ppm is preferred.

Compound (Aa) which reacts with a carboxyl group
Examples of the polyol used as -2) include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol; ethylene glycol, propanediol, propylene glycol, butanediol, butylene glycol, and hexanediol. , Neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, ethylene oxide-modified products of alkylene glycols such as dipentaerythritol, propylene oxide-modified products, butylene oxide-modified products, tetrahydrofuran-modified products, ε- Modified caprolactone, γ
-Butyrolactone modified, δ-valerolactone modified,
Methyl valerolactone modified product;

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 ester reactants 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 and Aromatic polyester polyols which are ester reaction products with polyols such as pentyl glycol; polycarbonate polyols; acrylic polyols; Polyhydric hydroxyl compounds such as tylene hexaglyceryl ether (tetrahydrofuran-modified hexaglycerin); mono- and polyhydric hydroxyl-containing compounds having terminal ether groups of the above polyhydric hydroxyl-containing compounds; and the above-mentioned polyhydric hydroxyl-containing compounds and fumaric acid Polyhydric hydroxyl-containing compounds obtained by esterification with dicarboxylic acids such as phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, and maleic acid; polyhydric hydroxyl compounds such as glycerin; and fatty acid esters of animals and plants And polyhydric hydroxyl group-containing compounds such as monoglyceride obtained by transesterification reaction with the same. Can also be used.

Compound (Aa) which reacts with a carboxyl group
Examples of the polyepoxide used as -2) include, for example, an epichlorohydrin-modified bisphenol-type epoxy resin synthesized from (methyl) epichlorohydrin and bisphenol A, bisphenol F, and their ethylene oxide and propylene oxide modified products; (methyl) epichlorohydrin And hydrogenated bisphenol A,
Epichlorohydrin-modified hydrogenated bisphenol type epoxy resin synthesized from hydrogenated bisphenol F, ethylene oxide, propylene oxide modified product thereof,
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, (poly) propylene glycol, Glycols such as poly) butylene glycol, (poly) tetramethylene glycol and neopentyl glycol, and polyglycidyl ethers of alkylene oxide modified products thereof; trimethylolpropane, trimethylolethane,
Aliphatic polyhydric alcohols such as glycerin, diglycerin, erythritol, pentaerythritol, sorbitol, 1,4-butanediol and 1,6-hexanediol; glycidyl ethers of alkylene oxide modified products thereof; adipic acid, sebacic acid, maleic acid Glycidyl esters of carboxylic acids such as acids and itaconic acids; glycidyl ethers of polyester polyols of polyhydric alcohols and polycarboxylic acids; copolymers of glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; glycidyl esters of higher fatty acids Epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, aliphatic epoxy resins such as epoxidized polybutadiene, and the like.

Compounds having a carboxyl group (Ab-
Examples of the di-hexa-carboxylic acid having 2 to 6 carboxyl groups, ether bond and ester bond in one molecule to be used as 2-1) include fumaric acid, phthalic acid, isophthalic acid, itaconic acid and adipine A dicarboxylic acid such as acid, sebacic acid, maleic acid, succinic acid, adipic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and pyromellitic acid; )

[0061]

Embedded image (2)

(Wherein X ′ represents a dicarboxylic acid residue, Y ′ represents a polyol residue, and n represents an integer of 1 to 5), but is not limited thereto. It is not something to be done.

(Poly) isocyanate compound (Ab-
Examples of 2-2) include aliphatic diisocyanate compounds such as methylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, lysine diisocyanate, and dimer acid diisocyanate;
4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate Isocyanate, 3,
Aromatic diisocyanate compounds such as 3'-dimethylbiphenyl-4,4'-diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4
(Or 2,6) an alicyclic diisocyanate compound such as diisocyanate and 1,3- (isocyanatomethyl) cyclohexane; Diisocyanate compound as a reactant; general formula (3) obtained from the above polyisocyanate and polyol

[0064]

Embedded image OCN—X—NHCOO—Y — (— OCONH—X—NCO) _n (3) (wherein, X represents a polyisocyanate residue, Y represents a polyol residue, and n is an integer of 1 to 5) And a terminal isocyanate compound represented by the following formula:

The polyols usable in the above reaction include, for example, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol; ethylene glycol, propanediol, propylene glycol, butanediol, butylene 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;
A copolymer of ethylene oxide and propylene oxide, a copolymer of propylene glycol and tetrahydrofuran,
A copolymer of ethylene glycol and tetrahydrofuran,
Hydrocarbon polyols such as polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol; aliphatic dicarboxylic acids such as adipic acid and dimer acid, and polyols such as neopentyl glycol and methylpentanediol Aliphatic polyester polyol which is a reactant;
Polyester polyols such as aromatic polyester polyols which are reaction products of an aromatic dicarboxylic acid such as terephthalic acid and a polyol such as neopentyl glycol; polycarbonate polyols, acrylic polyols, polytetramethylene hexaglyceryl ether (of hexaglycerin) Polyhydric hydroxyl compounds such as tetrahydrofuran modified products); mono- and polyhydric hydroxyl-containing compounds having terminal ether groups of the above-mentioned polyhydric hydroxyl-containing compounds; Polyhydric hydroxyl group-containing compounds obtained by esterification with dicarboxylic acids such as acid, adipic acid, sebacic acid, and maleic acid; monoglycols obtained by transesterification between polyhydric hydroxyl compounds such as glycerin and fatty acid esters of animals and plants Polyhydric hydroxyl group-containing compounds such Ceilidh, and the like, but is not limited thereto, as long as 2-6 functional polyol, either can be used.

Examples of the carbonate (Ab-2-3) include carbonates such as dimethyl carbonate, diethyl carbonate and dipropyl carbonate. Incidentally, phosgene, methyl chlorocarbonate, ethyl chlorocarbonate and the like can also be used.

The maleimide derivative represented by the general formula (1) used in the active energy ray-curable resin composition of the present invention can be obtained by the above-described production method. It is not limited to these.

The active energy ray-curable resin composition containing the maleimide derivative (A) of the present invention may be used in combination with a compound (B) having a maleimide group and copolymerizability. Compound (B) having maleimide group and copolymerizability
Is a compound having various unsaturated double bonds. Examples of such a compound include a compound having an acryloyl group or a methacryloyl group (B-
1), a compound having a vinyl ether group (B-2), and a maleimide derivative other than the maleimide derivative (A) (B-
3), (meth) acrylamide derivative (B-4), vinyl carboxylate derivative (B-5), styrene derivative (B-
6) and unsaturated polyester (B-7).

The compound (B-1) having an acryloyloxy group or a methacryloyloxy group is roughly classified as follows:
(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 (Meth) acrylate (B-1-6) having an alicyclic structure (meth)
Examples include acrylate (B-1-7), but are not limited thereto.

(Poly) which can be used in combination with the resin composition of the present invention
Ester (meth) acrylate (B-1-1) is a generic term for (meth) acrylates having one or more ester bonds in the main chain, and is urethane (meth) acrylate (B-
1-2) is a general term for (meth) acrylates having one or more urethane bonds in the main chain, and epoxy acrylate (B-1-3) is a reaction of (meth) acrylic acid with one or more functional epoxides. (Poly) ether (meth) acrylate (B-1-4) is a general term for the (meth) acrylate obtained by the above method.
Alkyl (meth) acrylate or alkylene (meth) acrylate (B-1-5) as a generic term for (meth) acrylates having one or more has a main chain of linear alkyl, branched alkyl, linear alkylene group or branched alkylene group. And a general term for (meth) acrylates which may have a halogen atom and / or a hydroxyl group at a side chain or at a terminal,
The (meth) acrylate having an aromatic ring (B-1-6) is a general term for a (meth) acrylate having an aromatic ring in its main chain or side chain, and is a (meth) acrylate having an alicyclic structure (B-1-). 7) 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.

(Poly) which can be used in combination with the resin composition of the present invention
Examples of the ester (meth) acrylate (B-1-1) include, for example, alicyclic-modified neopentyl glycol (meth) acrylate (“R-62” manufactured by Nippon Kayaku Co., Ltd.).
9 "or" R-644 "), caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth)
Acrylate, ethylene oxide modified succinic acid (meth)
Monofunctional (poly) ester (meth) acrylates such as acrylate and caprolactone-modified tetrahydrofurfuryl (meth) acrylate;

Pivalic acid ester neopentyl glyco-
Rudi (meth) acrylate, caprolactone-modified hydroxypivalic acid ester neopentylglycol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate; 1 mol or more of ε- in 1 mol of trimethylolpropane or glycerin Caprolactone, γ
Mono-, di- or tri (meth) acrylate of triol obtained by adding a cyclic lactone compound such as butyrolactone, δ-valerolactone or methylvalerolactone; 1 mol or more of ε-caprolactone per mol of pentaerythritol or ditrimethylolpropane , Mono-triol obtained by adding a cyclic lactone compound such as γ-butyrolactone, δ-valerolactone or methylvalerolactone,
Di-, tri- or tetra (meth) acrylate; mono-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 dipentaerythritol Or poly (meth) acrylate mono (meth) acrylates or poly (meth) acrylates of polyhydric alcohols such as triols, tetraols, pentaols or hexaols;

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 (B-1-2) which can be used in combination with the resin composition of the present invention comprises a hydroxy compound (B-1-2-1) having at least one (meth) acryloyloxy group. Isocyanate compound (B
-1-2-2).

Examples of the hydroxy compound (B-1-2-1) having at least one (meth) acryloyloxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Hydroxybutyl (meth) acrylate, 3-
Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, Trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate or glycidyl (meth) acrylate- (meth) acrylic acid adduct, 2-hydroxy-3-
Examples include (meth) acrylate compounds having various hydroxyl groups such as phenoxypropyl (meth) acrylate, and ring-opening products of the above-mentioned (meth) acrylate compounds having a hydroxyl group and ε-caprolactone.

Isocyanate compound (B-1-2-2)
As, 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, 3,3'-diethyldiphenyl-4,4 '
Aromatic diisocyanates such as diisocyanate and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate and lysine diisocyanate; One or more burettes of isocyanate monomer or the above diisocyanate compound
Polyisocyanates such as quantified isocyanurates; the above isocyanate compounds and various polyols (B-
And polyisocyanates obtained by a urethanization reaction with 1-2-3).

The polyol (B-1-2-3) used for producing the polyisocyanate includes, for example,
(Poly) alkylene glycols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol; ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, Ethylene oxide modified, propylene oxide modified, butylene oxide modified, tetrahydrofuran modified alkylene glycols such as hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol , Modified ε-caprolactone, modified γ-butyrolactone, modified δ-valerolactone, modified methylvalerolactone, etc.

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 and polyols such as neopentyl glycol; polycarbonate polyols; acrylic polyols; Polyhydric hydroxyl compounds such as methylene hexaglyceryl ether (tetrahydrofuran modified product of hexaglycerin); mono- and polyhydric hydroxyl-containing compounds having terminal ether groups of the above-mentioned polyhydric hydroxyl-containing compounds; and the above-mentioned polyhydric hydroxyl-containing compounds and fumaric acid Polyhydric hydroxyl-containing compounds obtained by esterification with dicarboxylic acids such as phthalic acid, isophthalic acid, itaconic acid, adipic acid, sebacic acid, and maleic acid; polyhydric hydroxyl compounds such as glycerin; and fatty acid esters of animals and plants And a polyvalent hydroxyl group-containing compound such as monoglyceride obtained by transesterification with thiol, but are not limited thereto.

The epoxy (meth) acrylate (B-1-) which can be used in combination with the active energy ray-curable ink of the present invention.
3) is a generic term for (meth) acrylates obtained by reacting monofunctional or higher epoxides with (meth) acrylic acid. Examples of the epoxide (B-1-3-1) which is a raw material of the epoxy (meth) acrylate include (methyl) epichlorohydrin, hydrogenated bisphenol A, hydrogenated bisphenol S, hydrogenated bisphenol F, ethylene oxide, propylene thereof, and the like. Epichlorohydrin-modified hydrogenated bisphenol-type epoxy resin synthesized from an oxide-modified product or the like; alicyclic such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate Epoxy resins; alicyclic epoxides such as epoxy resins containing a heterocycle 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, and 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 .

(Poly) which 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,
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, phenoxyhydroxypropyl (meth) acrylate, phenoxy (poly) ethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) ) Acrylates, monofunctional (poly) ether (meth) acrylates such as 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.

Examples of the alkyl (meth) acrylate or alkylene (meth) acrylate (B-1-5) that can be used in combination with the resin composition of the present invention include, 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-2-hexene (meth) Monofunctional (meth) acrylates such as acrylates;

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 (meth) acrylate (B-1-6) having an aromatic ring which can be used in combination with the resin composition of the present invention includes:
Examples include monofunctional (meth) acrylates such as phenyl (meth) acrylate and benzyl acrylate; diacrylates such as bisphenol A diacrylate, bisphenol F diacrylate, and bisphenol S diacrylate, but are not limited thereto. Not something.

The (meth) acrylate (B-1-7) having an alicyclic structure which can be used in combination with the resin composition of the present invention includes, for example, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate. ) Acrylate, bicycloheptyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentyl di (meth) acrylate, tricyclodecyl (meth) acrylate, bicyclopentenyl (meth) acrylate, norbornyl (meth) acrylate, bicyclooctyl (meth) A) monofunctional (meth) acrylates having an alicyclic structure, such as acrylate, tricycloheptyl (meth) acrylate, and cholesteroid skeleton substituted (meth) acrylate; hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol Di (meth) acrylate such as hydrogenated bisphenol phenol S, di (meth) acrylate of hydrogenated trisphenols, hydrogenated p, p '
Di (meth) acrylates of biphenols; dicyclopentane-based di (meth) acrylates such as "Kayarad R684" (manufactured by Nippon Kayaku Co., Ltd.), tricyclodecane dimethylol di (meth) acrylate, bisphenol fluorene hydroxy (meth) A) polyfunctional (meth) acrylates having a cyclic structure such as acrylate; an alicyclic acrylate having an oxygen atom and / or a nitrogen atom in a structure such as tetrahydrofurfuryl (meth) acrylate or morpholinoethyl (meth) acrylate; And the like, but are not limited thereto.

The compound (B) having an acryloyl group or a methacryloyl group which can be used in combination with the resin composition of the present invention.
As -1), in addition to the above compounds, for example, a reaction product of a (meth) acrylic acid polymer and glycidyl (meth) acrylate or a reaction product of a glycidyl (meth) acrylate polymer and (meth) acrylic acid Poly (meth) acrylic (meth) acrylate; (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate; isocyanuric (meth) acrylate such as tris ((meth) acryloxyethyl) isocyanurate; hexakis [( (Meth) acryloyloxyethyl) cyclotriphosphazene], (meth) acrylate having a polysiloxane skeleton, polybutadiene (meth) acrylate, melamine (meth) acrylate, and the like. Among these compounds having an acryloyl group or a methacryloyl group, a compound having 1 to 6 acryloyl groups or methacryloyl groups in one molecule is preferable.

Next, the compound (B-2) having a vinyl ether group which can be used in combination with the resin composition of the present invention is roughly classified into alkyl vinyl ethers whose other terminal may be substituted with a halogen atom, a hydroxyl group or an amino group. (B-2-
1) a cycloalkyl vinyl ether (B
-2-2), a vinyl ether group is bonded to an alkylene group, and at least one group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aromatic group which may have a substituent, and an ether bond; Monovinyl ether, divinyl ether and polyvinyl ether (B-2) having a structure bonded through at least one bond selected from the group consisting of a urethane bond and an ester bond
-3) and the like, but are not limited thereto.

The alkyl vinyl ether (B-2-1) which can be used in combination with the resin composition of the present invention includes, for example, methyl vinyl ether, hydroxymethyl vinyl ether,
Chloromethyl vinyl ether, ethyl vinyl ether,
2-hydroxyethyl vinyl ether, 2-chloroethyl vinyl ether, diethylaminoethyl vinyl ether, propyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 3-chloropropyl vinyl ether, 3-aminopropyl vinyl ether, isopropyl vinyl ether,
Butyl vinyl ether, 4-hydroxybutyl vinyl ether, isobutyl vinyl ether, 4-aminobutyl vinyl ether, pentyl vinyl ether, isopentyl vinyl ether, hexyl vinyl ether, 1,6-
Hexanediol monovinyl ether, heptyl vinyl ether, 2-ethylhexyl vinyl ether, octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether, isononyl vinyl ether, decyl vinyl ether, isodecyl vinyl ether, dodecyl vinyl ether, isododecyl vinyl ether, tridecyl vinyl ether, isotridecyl vinyl ether,
Pentadecyl vinyl ether, isopentadecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, methylene glycol divinyl ether, ethylene glycol divinyl ether, propylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, cyclohexane Diol divinyl ether,
Examples include, but are not limited to, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, and the like.

The cycloalkyl vinyl ether (B-2-2) which can be used in combination with the resin composition of the present invention includes, for example, cyclopropyl vinyl ether, 2-hydroxycyclopropyl vinyl ether, 2-chlorocyclopropyl vinyl ether, cyclopropylmethyl vinyl ether , Cyclobutyl vinyl ether, 3-hydroxycyclobutyl vinyl ether, 3-chlorocyclobutyl vinyl ether, cyclobutyl methyl vinyl ether, cyclopentyl vinyl ether, 3-hydroxycyclopentyl vinyl ether, 3-chlorocyclopentyl vinyl ether, cyclopentyl methyl vinyl ether, cyclohexyl vinyl ether, 4-hydroxycyclo Hexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-aminosi B hexyl vinyl ether, cyclohexanediol monovinyl ether, cyclohexanedimethanol monovinyl ether, and cyclohexanedicarboxylic methanol divinyl ether, but it is not limited thereto.

A vinyl ether group which can be used in combination with the resin composition of the present invention is bonded to an alkylene group, and at least one selected from the group consisting of an alkyl group which may have a substituent, a cycloalkyl ring and an aromatic ring. And monovinyl ether, divinyl ether and polyvinyl ether (B-2-3) having a structure bonded via at least one bond selected from the group consisting of an ether bond, a urethane bond and an ester bond;

Compound having an ether bond (B-2-3)
Examples of -1) include ethylene glycol methyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol methyl vinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol methyl vinyl ether, triethylene glycol divinyl ether, polyethylene glycol monovinyl ether, and polyethylene glycol. Methyl vinyl ether, polyethylene glycol divinyl ether, propylene glycol methyl vinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol methyl vinyl ether, dipropylene glycol divinyl ether, tripropylene glycol monovinyl ether,
Tripropylene glycol methyl vinyl ether, tripropylene glycol divinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol methyl vinyl ether, polypropylene glycol divinyl ether,

Tetramethylene glycol methyl vinyl ether, di (tetramethylene glycol) monovinyl ether, di (tetramethylene glycol) methyl vinyl ether, di (tetramethylene glycol) divinyl ether, tri (tetramethylene glycol) monovinyl ether, tri (tetramethylene glycol) ) Methyl vinyl ether, tri (tetramethylene glycol) divinyl ether, poly (tetramethylene glycol) monovinyl ether, poly (tetramethylene glycol) methyl vinyl ether, poly (tetramethylene glycol) divinyl ether, 1,6-hexanediol methyl vinyl ether, (Hexamethylene glycol) monovinyl ether, di (hexamethylene glycol) methyl vinyl ether Di (hexamethylene glycol)
Divinyl ether, tri (hexamethylene glycol)
Monovinyl ether, tri (hexamethylene glycol) methyl vinyl ether, tri (hexamethylene glycol) divinyl ether, poly (hexamethylene glycol) monovinyl ether, poly (hexamethylene glycol) methyl vinyl ether, poly (hexamethylene glycol) divinyl ether and the like. Can be

Among the compounds having a vinyl ether group classified into the above (B-2-3), the compound having a urethane bond (B-2--3-2) has at least one compound per molecule.
Monovinyl ether of a (poly) alkylene glycol having two hydroxyl groups (B-2--3-2a) and a compound having at least one isocyanate group in one molecule (B-
It can be obtained by the urethanization reaction of 2-3-2b).

Among these, the monovinyl ether (B-2--3-2a) of (poly) alkylene glycol having at least one hydroxyl group in one molecule includes, for example, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, Polyethylene glycol monovinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxy-2-methylethyl vinyl ether, dipropylene glycol monovinyl ether,
Examples thereof include polypropylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, and 1,6-hexanediol monovinyl ether.

On the other hand, examples of the compound having at least one isocyanate group in one molecule (B-2--3-2b) include, for example, m-isopropenyl-α, α-dimethylbenzyl isocyanate, 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, 3,3'-diethyldiphenyl-
Aromatic isocyanates such as 4,4'-diisocyanate and naphthalene diisocyanate, and fats such as propyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate and lysine diisocyanate And alicyclic isocyanates.

Polyisocyanate raw materials such as one or more dimers or trimers of these isocyanate monomers can be used. Further, two or more isocyanate groups in one molecule of the above isocyanate compounds can be used. The adduct obtained by a urethanization reaction between the compound having the above formula and various alcohols (B-2-3-2c) can also be used.

As the various alcohols (B-2--3-2c) used in the adduct, those having at least one hydroxyl group in one molecule can be used. Although the molecular weight is not particularly limited, it is preferable that the average molecular weight is 100,00.
0 or less. Such alcohols include, for example, methanol, ethanol, propanol,
Isopropanol, butanol, isobutanol, ethylene glycol, 1,3-propylene glycol, 1,
2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,
3-butanediol, 1,4-butanediol, 1,6
-Hexanediol, 1,9-nonanediol, 1,1
0-decanediol, 2,2,4-trimethyl-1,3
-Pentanediol, 3-methyl-1,5-pentanediol, dichloroneopentyl glycol, dibromoneopentyl glycol, neopentylglycol hydroxypivalate, cyclohexane dimethylol, 1,4-cyclohexanediol, spiroglycol, tricyclode Candimethylol, hydrogenated bisphenol A, ethylene oxide added bisphenol A, propylene oxide added bisphenol A, dimethylolpropionic acid, dimethylolbutanoic acid, trimethylolethane, trimethylolpropane, glycerin, 3-methylpentane-1, 3,5-triol, tris (2-hydroxyethyl) isocyanurate and the like can be mentioned.

The alcohols (B-2--3-2c) used in this adduct include polyester polyol (B-2--3-2c-1) and polyether polyol (B-2--3-2c-2). ) And polycarbonate polyols (B-2-3-2c-3).

These alcohols can be used alone or in combination of two or more.

The polyester polyol (B-2--3-2c-1) used in the adduct includes the above-mentioned polyol component (B-2--3-2c) and carboxylic acid (B-2-3-C).
Polyester polyols obtained by the reaction with 3-2c-1b) can also be used. Carboxylic acid (B-2-
As 3-2c-1b), various known and commonly used carboxylic acids or their acid anhydrides can be used. Examples of such carboxylic acids include, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, hetic acid, hymic acid, chlorendic acid, dimer acid, adipic acid, succinic 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, 5-sodium-dimethyl sulfoisophthalate
Or di-lower alkyl esters of 5-sodium-sulfoisophthalic acid such as diethyl ester, orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutaric acid, Examples thereof include melitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexentricarboxylic acid or pyromellitic acid, and acid anhydrides thereof and ester compounds with alcohols such as methanol and ethanol. In addition, lactone polyols obtained by a ring opening reaction between ε-caprolactone and the above-mentioned polyol component can also be used.

As the polyether polyol (B-2--3-2c-2) used in the adduct, known and commonly used ones can be used. Examples of such polyether polyols include, for example, polytetramethylene glycol, propylene oxide-modified polytetramethylene glycol, ethylene oxide-modified polytetramethylene glycol, polypropylene glycol, ether glycols such as polyethylene glycol, and trifunctional or higher polyols as initiators. Examples thereof include polyether polyols formed by ring-opening polymerization of a cyclic ether, but are not limited to those exemplified herein.

The polycarbonate polyol (B-2--3-2c-3) used in the adduct body includes carbonate (B-2--3-2c-3a) and various polyols (B-2
-3-2c-3b). Examples of the carbonate (B-2--3-2c-3a) that can be used here include diphenyl carbonate, bischlorophenyl carbonate,
Dinaphthyl carbonate, phenyl-tolyl-carbonate, phenyl-chlorophenyl-carbonate or 2-tolyl-4-tolyl-carbonate; diaryl- or dialkylcarbonate such as dimethyl carbonate or diethyl carbonate; Not something. Further, the polyol (B-2--3-2c-3) which can be used here
a) As the alcohol (B-2-3-2) described above,
c), polyester polyol (B-2-3-2c-)
1) or polyether polyol (B-2-3-2c-)
2) and the like.

Among the compounds having a vinyl ether group classified into the above (B-2-3), the compound having an ester bond (B-2--3-3) has at least one compound per molecule.
Monovinyl ether of an alkylene glycol having two hydroxyl groups (B-2-3-3-a) and a compound having at least one carboxyl group per molecule (B-2-3-3)
It can be obtained by the esterification reaction of b).

Monovinyl ether of alkylene glycol having at least one hydroxyl group in one molecule (B-2
Examples of -3-3a) include those described above as (B-2--3-2a) of compound (B-2--3-2) having a urethane bond.

As the compound having at least one carboxyl group in one molecule (B-2--3-3b), known carboxylic acids and acid anhydrides thereof can be used.
Such compounds include, for example, formic acid, acetic acid, propionic acid, valeric acid, benzoic acid, maleic acid, fumaric acid,
Itaconic acid, citraconic acid, tetrahydrophthalic acid, hetonic acid, hymic acid, chlorendic acid, dimer acid, adipic acid, succinic acid, alkenylsuccinic 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; 5-sodium-sulfoisophthalic acid Dimethyl-
Or di-lower alkyl esters of 5-sodium-sulfoisophthalic acid such as diethyl ester, orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutaric acid, Menlitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexentricarboxylic acid or pyromellitic acid, or acid anhydrides thereof, and the like. Further, among these carboxylic acids, various alcohols used as an isocyanate adduct of a compound having two or more carboxyl groups in one molecule and the compound having a urethane bond (B-2-3-2) A carboxylic acid obtained by a reaction with (B-2--3-2c) can also be used.

Examples of the maleimide derivative (B-3) other than the maleimide derivative (A) include, for example, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Nn-butylmaleimide, N-tert-butylmaleimide Monofunctional aliphatic maleimides such as N-pentylmaleimide, N-hexylmaleimide, N-laurylmaleimide, 2-maleimidoethyl-ethylcarbonate, 2-maleimidoethyl-isopropylcarbonate, N-ethyl- (2-maleimidoethyl) carbamate Alicyclic monofunctional maleimides such as N-cyclohexylmaleimide; N-phenylmaleimide, N-2-methylphenylmaleimide, N-2-ethylphenylmaleimide, N- (2,6-diethylphenyl) maleimide;
Aromatic monofunctional maleimides such as N-2-chlorophenylmaleimide, N- (4-hydroxyphenyl) maleimide, N-2-trifluoromethylphenylmaleimide; N, N'-methylenebismaleimide, N, N'-ethylene Bismaleimide, N, N'-trimethylenebismaleimide, N, N'-hexamethylenebismaleimide,
Alicyclic bismaleimides such as N, N'-dodecamethylene bismaleimide and 1,4-dimaleimidocyclohexane; N, N '-(4,4'-diphenylmethane) bismaleimide, N, N'-(4,4 '-Diphenyloxy)
Bismaleimide, N, N'-p-phenylenebismaleimide, N, N'-m-phenylenebismaleimide,
N'-2,4-tolylenebismaleimide, N, N'-
2,6-tolylenebismaleimide, N, N '-[4,
Aromatic bismaleimides such as 4′-bis (3,5-dimethylphenyl) methane] bismaleimide and N, N ′-[4,4′-bis (3,5-diethylphenyl) methane] bismaleimide; But not limited thereto.

(Meth) usable in combination with the resin composition of the present invention
As the acrylamide derivative (B-4), for example, N
Monofunctional (meth) acrylamides such as isopropyl (meth) acrylamide, acryloylmorpholine,
Examples include polyfunctional (meth) acrylamides such as methylenebis (meth) acrylamide.

The vinyl carboxylate derivative (B-5) which can be used in combination with the active energy ray-curable resin composition of the present invention includes, for example, vinyl acetate, vinyl cinnamate and the like. Examples of the styrene derivative (B-6) include styrene and divinylstyrene.

The unsaturated polyester (B-7) usable in combination with the active energy ray-curable resin composition of the present invention includes, for example, maleic esters such as dimethyl malate and diethyl malate, dimethyl fumarate, diethyl Fumarate esters such as fumarate, maleic acid,
An esterification reaction product of a polyunsaturated carboxylic acid such as fumaric acid and a polyhydric alcohol is exemplified.

The curable compound which can be used in combination with the active energy ray-curable resin composition of the present invention is not limited to the above-mentioned compounds, but is a compound having copolymerizability with the maleimide group of the maleimide derivative (A). If so, one or more of the compounds can be used in combination without particular limitation.

When the compound (B-1) having an acryloyloxy group or a methacryloyloxy group is used in combination with the active energy ray-curable resin composition containing the maleimide derivative (A) represented by the general formula (1) of the present invention. There is no particular limitation on the combination ratio, but the compound (B-1) 10 having an acryloyloxy group or a methacryloyloxy group
It is preferable to use the maleimide derivative (A) represented by the general formula (1) in a proportion of 5 parts by weight or more with respect to 0 parts by weight. Is particularly preferred.

Compound (B-2) having a vinyl ether group in the active energy ray-curable resin composition containing the maleimide derivative (A) represented by the general formula (1) of the present invention
When used in combination, the proportion of use is not particularly limited, but the maleimide derivative (A) represented by the general formula (1) is 5 parts by weight or more based on 100 parts by weight of the compound (B-2) having a vinyl ether group. It is preferable to use at a ratio of 1
It is particularly preferable to use an equivalent ratio in terms of curing speed and cured film characteristics.

When a maleimide derivative (B-3) other than the maleimide derivative (A) is used in combination with the active energy ray-curable resin composition containing the maleimide derivative (A) of the present invention, there is no particular limitation on the proportion used. But not more than 95% by weight of the total weight in the composition, especially 90% by weight
The following are particularly preferred.

When the composition of the present invention is used as a primary coating material, a homopolymer having a glass transition temperature of 20 ° C. is used as the compound (B) having a maleimide group and copolymerizability.
It is preferable to select a monofunctional compound (B-8) having one group that reacts with the following maleimide. The glass transition temperature is described in a polymer handbook and other documents, a catalog of the compound (B) having a copolymerizability with a maleimide group, and the like. As the monofunctional compound (B-8), specifically,
Lauryl acrylate, isodecyl acrylate, isostearyl acrylate, lauryl alcohol ethoxy acrylate, epoxy stearyl acrylate, 2- (1
-Methyl-4-dimethyl) butyl-5-methyl-7-dimethyloctyl acrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, phenol polyalkoxy acrylate, nonylphenoxyethyl acrylate, nonylphenol ethylene oxide modified acrylate, nonylphenol polypropylene oxide modified acrylate, Butoxy polypropylene glycol acrylate, tetrahydrofurfuryl alcohol lactone-modified acrylate, lactone-modified 2-hydroxyethyl acrylate, 2-ethylhexyl carbitol acrylate, and the like.

Further, in combination with the monofunctional compound (B-8),
Examples of the compound (B) having a maleimide group and a copolymerizability that improve adhesion or curability to glass include 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid dimer, ω-carboxy-polycaprolactone monoacrylate, and tetrahydrofuran. Furyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, isobornyl acrylate, dicyclopentenyloxyalkyl acrylate, dicyclopentenyl acrylate, tricyclodecanyl acrylate, tricyclodecanyloxyethyl acrylate, isobornyloxy Acrylates such as ethyl acrylate, acrylamides such as acryloyl morpholine and diacetone acrylamide, N-vinylpyrrolidone, N-vinyl Examples include N-vinylamides such as lucaprolactam, vinyl ethers such as hydroxybutyl vinyl ether and lauryl vinyl ether, and maleimides such as chlorophenylmaleimide, cyclohexylmaleimide and laurylmaleimide. For the purpose of adjusting the tensile modulus of the cured coating film, a polyfunctional compound (B-9) having two or more groups that react with maleimide described below can also be used.

When the composition of the present invention is used for a secondary coating material, ink, unit material and overcoat material,
Monofunctional compound (B-10) having one group that reacts with maleimide having a homopolymer having a glass transition temperature of 50 ° C. or higher.
It is good to choose. The glass transition temperature is described in a polymer handbook and other documents, a catalog of the compound (B) having a copolymerizability with a maleimide group, and the like. Examples include acrylates such as isobornyl acrylate, dicyclopentenyloxyalkyl acrylate, dicyclopentenyl acrylate, tricyclodecanyl acrylate, tricyclodecanyloxyethyl acrylate, and isobornyloxyethyl acrylate, and acrylamides such as acryloylmorpholine. , N-vinyl pyrrolidone, N-vinyl amides such as N-vinyl caprolactam,
Examples thereof include vinyl ethers such as hydroxybutyl vinyl ether and lauryl vinyl ether, and maleimides such as chlorophenylmaleimide, cyclohexylmaleimide and laurylmaleimide. And / or a polyfunctional compound (B-9) having two or more groups that react with maleimide is preferably used. For example, ethylene glycol di (meth) acrylate, triethylene glycol diacrylate,
Propylene glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, diacrylate of ethylene oxide adduct of bisphenol A, diacrylate of propylene oxide adduct of bisphenol A, tricyclodecane dimethylol diacrylate, 2,
2-di (glycidyloxyphenyl) propane acrylic acid adduct, trimethylolpropane triacrylate,
Pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tris (2-hydroxyethyl)
Triacrylate of isocyanurate, diacrylate of tris (2-hydroxyethyl) isocyanurate,
There are tris (hydroxypropyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane triacrylate and the like. Since the polyfunctional compound (B-9) increases the tensile elasticity of the cured coating film, but decreases the elongation, the polyfunctional compound is preferably used in combination with the monofunctional compound (B-8). Use of the polyfunctional compound (B-9) has an effect of preventing the cured coating film from swelling and deforming due to water absorption. For the purpose of adjusting the tensile modulus to a low value, the above monofunctional compound (B-8) may be used.

In addition to the above components, the resin composition for coating an optical fiber of the present invention may contain, if necessary, urethane (meth) acrylate (B-1-2) and epoxy (meth) acrylate (B-1-3). ) And polyester (meth) acrylate (B-1-4). In particular, when urethane (meth) acrylate (B-1-2) is used, the strength and elongation of the cured coating film can be balanced, which is effective. Urethane (meth) acrylate (B-1-2)
Are effective as those containing an ether bond or an ester bond. The reaction of a polyisocyanate with a (meth) acrylate having an active hydrogen group such as a hydroxyl group is also effective. Urethane (meth) acrylate (B-
The molecular weight, urethane bond concentration, number of (meth) acrylic groups, and molecular skeleton of 1-2) may be changed to design necessary strength and elongation of the cured coating film. It is effective to use not only one kind but two or more kinds.

The active energy ray-curable resin composition of the present invention has a spectral sensitivity unique to 200 to 400 nm, and is irradiated with ultraviolet light or visible light having a wavelength of 180 to 500 nm in the absence of a photopolymerization initiator. 254 nm, 308 nm, 31
Light having a wavelength of 3 nm or 365 nm is effective for curing the active energy ray-curable resin composition of the present invention. Further, the active energy ray-curable resin composition of the present invention can be cured by irradiation with energy rays other than ultraviolet rays or by heat. Further, the active energy ray-curable resin composition of the present invention can be cured in air and / or in an inert gas. As long as a radical active species can be generated as the active energy ray, any energy species such as an electron beam, an ionizing radiation such as an α-ray, a β-ray, and a γ-ray, a microwave, and a high frequency may be used in addition to ultraviolet rays. Infrared rays and laser beams may be used. The selection may be made in consideration of the absorption wavelength of the compound generating the radical active species.

Examples of light sources of ultraviolet or visible light 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, and excimer lamps. Lamps, short arc lamps,
Helium / cadmium laser, argon laser,
Excimer laser and sunlight.

The active energy ray-curable resin composition of the present invention is cured by irradiation of ultraviolet light or visible light in the absence of a photopolymerization initiator. Curing can also be performed by adding a polymerization initiator (C). The photopolymerization initiator (C) can be roughly classified into two types: an intramolecular bond cleavage type (C-1) and an intramolecular hydrogen abstraction type (C-2).

Intramolecular bond cleavage type photopolymerization initiator (C-1)
As, for example, diethoxyacetophenone, 4-
(2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one (“Irgacure 907” manufactured by Ciba-Geigy), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1-
Phenylpropan-1-one (“Darocur 1173” manufactured by Merck), 1-hydroxycyclohexylphenylketone (“Irgacure 18” manufactured by Ciba-Geigy)
4 "), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (" Darocure 1116 "manufactured by Merck), benzyldimethyl ketal (" Irgacure 651 "manufactured by Ciba-Geigy), Oligo {2-hydroxy-2-methyl-1- "4- (1-methylvinyl) phenyl" propane} (Esacure KIP100 manufactured by Lamberti), 4- (2-acryloyl-oxyethoxy) phenyl-2-hydroxy-2 -Propyl ketone (“ZLI3331” manufactured by Ciba-Geigy)
Benzoin derivatives such as acetophenones, benzoin, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin alkyl; a mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone (“Irgacure 500” manufactured by Ciba Geigy);
2,4,6-trimethylbenzoyldiphenylphosphine oxide (“Lucillin TPO” manufactured by BASF) and bisacylphosphine oxide (“C” manufactured by Ciba-Geigy)
GI1700 ") and the like.
Benzyl and benzyl derivatives, methylphenylglyoxyester, 3,3 ′, 4,4 ′,-tetra (t-butylperoxycarbonyl) benzophenone (BTTB manufactured by NOF Corporation) and the like. Examples of the intramolecular hydrogen abstraction type photopolymerization initiator (C-2) include benzophenone, o-
Methyl benzoylbenzoate and alkyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone,
-Benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'-
Benzophenones such as tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4- Thioxanthones such as dichlorothioxanthone, Michler's ketone, aminobenzophenones such as 4,4'-diethylaminobenzophenone, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, etc. There is.

The resin composition of the present invention is cured by irradiation with ultraviolet rays, but it is preferable to use a photosensitizer (C-3) in combination in order to carry out the curing reaction efficiently. As such a photosensitizer (C-3), for example, triethanolamine,
Methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, (2-dimethylamino) ethyl benzoate, 4
-Dimethylaminobenzoate (n-butoxy) ethyl, 4
Amines such as 2-ethylhexyl dimethylaminobenzoate;

The ratio of the photopolymerization initiator (C) used is based on the active energy ray-curable resin composition (A) + (B).
It is preferably in the range of 0.1 to 20.0% by weight.
If the content is more than 20% by weight, ultraviolet rays are prevented from penetrating into the inside of the coating film, resulting in insufficient curing. The compounding amount of the photosensitizer is the active energy ray-curable resin composition (A) +
It is preferably in the range of 0.1 to 20% by weight based on (B). Preferably, it is 0.5 to 10% by weight.
If the content is more than 20% by weight, ultraviolet rays are prevented from penetrating into the inside of the coating film, resulting in insufficient curing. Compositions for coating optical fibers include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) phenyl] -2. -Morpholinopropanone-
1,2-hydroxy-2-methyl-1-phenyl-propan-1-one and derivatives thereof, 4-dimethylaminobenzoate, 1,1-dialkoxyacetophenone, benzophenone and benzophenone derivatives, alkyl benzoylbenzoate, bis (4-dialkylaminophenyl) ketone, benzyl and benzyl derivatives, benzoin and benzoin derivatives, benzoin alkyl ether, 2-hydroxy-2-methylpropiophenone, thioxanthone and thioxanthone derivatives, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6
Photopolymerization initiators such as -trimethylphenyl) -phenylphosphine oxide are preferable because they generate less hydrogen gas. It is effective to use a combination of two or more photopolymerizable initiators having different ultraviolet absorption characteristics. When the lower layer portion is to be cured by overlapping like the primary coating material and the secondary coating material, the photopolymerization initiator (C) contained in each material is used.
It is effective to change the absorption wavelength. An additive (D) may be added to the active energy ray-curable resin composition containing the maleimide derivative (A) of the present invention.

As the additive (D), a saturated compound (D-1) having no unsaturated double bond, a pigment and a dye (D-
2), antioxidant (D-3), ultraviolet absorber (D-
4), light stabilizer (D-5), plasticizer (D-6), non-reactive compound (D-7), chain transfer agent (D-8), thermal polymerization initiator (D-9), anaerobic Polymerization initiator (D-10), polymerization inhibitor (D-11), inorganic filler and organic filler (D-1)
2) Adhesion improvers such as coupling agents (D-13), heat stabilizers, antibacterial / antifungal agents, flame retardants (D-14), matting agents, defoamers, leveling agents, wetting / dispersing. Agents, anti-settling agents, thickeners / anti-sagging agents, anti-segregation agents, emulsifiers, anti-slip / scratch agents, anti-skinning agents, desiccants, anti-fouling agents, anti-static agents, conductive agents (electrostatic aids) ) May be added. In addition, for applications such as paints and coatings, the viscosity can be adjusted by adding an organic solvent or water as needed.In this case, it is necessary to remove the organic solvent or water before curing with active energy rays. preferable.

A saturated compound having no unsaturated double bond (D
As -1), a liquid or solid oligomer or resin having low or no radical reactivity is shown.
Liquid polybutadiene, liquid polybutadiene derivative, liquid chloroprene, liquid polypentadiene, dicyclopentadiene derivative, saturated polyester oligomer, polyether oligomer, liquid polyamide, polyisocyanate oligomer, xylene resin, ketone resin, petroleum resin, fluorine-based oligomer / resin, silicon Oligomers / resins, polysulfide oligomers / resins, cellulose derivatives such as nitrocellulose, benzylcellulose, acetylcellulose, acetylbutylcellulose, vinyl chloride / vinyl acetate copolymer resins, other vinyl chloride copolymer resins, vinylidene chloride or copolymers thereof Polymerized resin, rack or copearl resin, fatty acid modified urethane resin,
Lacquer, oxidized polymer resin such as oil-modified phenolic resin, alkyd resin, amino alkyd resin, epoxy resin / fatty acid ester, epoxy resin, polyurethane resin,
There are acrylic resin, acrylic resin / polyurethane, vinyl resin and the like. These non-reactive oligomers and resins are
It may have a functional group such as a halogen, an epoxy group, an amino group, a hydroxyl group, a thiol group, an amide group, a carboxyl group, a phosphoric acid group and a sulfonic acid group.

As the pigments and dyes (D-2), oil-soluble dyes are suitable because of their excellent solubility, but any pigments and dyes may be used. For example, inorganic pigments such as carbon black, titanium white, miloli blue, and ultramarine blue; metal powder pigments such as brass powder, copper powder, and aluminum powder; monoazo yellow, disazo yellow, isoindolinone yellow, condensed azo yellow, and isoindolin Linone orange, benzimidazolone orange, disazo orange, azo lake red, condensed azo red, quinacridone red, dioxazine violet, phthalocyanine blue, phthalocyanine green,
And organic pigments such as white luster, silica, talc, alumina white, and precipitated barium sulfate. The amount added varies depending on the purpose of use, but is generally used in the range of 0.1 to 30%.

As the antioxidant (D-3), 2,6-
Di-tert-butyl-p-cresol, butylated hydroxyanisole, stearyl-propionate-β- (3,5-
Di -t- butyl-4-hydroxyphenyl), n-octadecyl-3- _{(4-hydroxy-3'} ^{`5 '-} di -
(t-butylphenyl) pyropionate, distearyl (4-hydroxy-3-methyl-5-t-butyl) benzylmalonate, 2,4,6-tri-t-butylphenol, 2,2′-methylene-bis (4 -Methyl-6-
t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), NN-bis-3- (3 ', 5')-di-t-
Butyl-4-hydroxyphenyl) propionylhexamethylenediamine, 1,6 hexanediol bis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2, 2-thio-diethylene-bis- [3- (3,5-di-t-butyl-4-
(Hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-
4-hydroxy-5-methylphenyl) propionyloxyethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,2'-ethylidene-bis- (2,4-di-t- Butylphenol), 1,1,3
-Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,
4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, 1,1,3-tris-
(2-methyl-4-hydroxy-5-t-butylphenylbutane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-di-t-butyl-4-hydroxybenzyl ) Benzene, tris (3,5-di-t-butyl-)
4-hydroxybenzyl) isocyanurate, tris [2- (3 ', 5'-di-t-butyl-4'-hydroxyhydro-cinnamyloxyl) ethyl] isocyanurate, tris- (4-t-butyl- 2,6-di-methyl-3-hydroxybenzyl) isocyanurate,
Tetrakis- [methylene-3- (3 ', 5'-di-t-
Butyl-4'-hydroxy-phenyl) propionate] -methane and other phenolic antioxidants; sulfur-based antioxidants such as dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate; Triphenyl phosphate, diphenyl isdecyl phosphite, tris (nonylphenyl) phosphite, 4,4'-butylidene-bis (3-methyl-6-t phosphite)
-Butylphenyl-ditridecyl) and phosphorus-based antioxidants such as phosphite cyclic neopentanetetraylbis (octadecyl). Phenolic antioxidants are particularly effective.

The compounding amount of the antioxidant (D-3) is 0.1 to 1 with respect to 100 parts by weight of the components (A) and (B).
0 parts by weight, preferably 0.5 to 8 parts by weight.

As the ultraviolet absorber (D-4), 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2 ′ −
Dihydroxy-4-methoxybenzophenone, 2,4-
Dihydroxybenzophenone, 2-hydroxy-4-methoxy-4′-chlorobenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,
2 ', 4,4'-tetradihydroxybenzophenone,
Benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone,
(2′-hydroxy-5-methylphenyl) benzotriazole, 2 (2′-hydroxy-3 ′, 5′-di-t
-Butylphenyl) benzotriazole, 2 (2'-hydroxy-3'-t-butyl-5'-methylphenyl)
Benzotriazole, 2 (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2 (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5
-Chlorobenzotriazole, 2 (2'-hydroxy-
Benzotriazole UV absorbers such as 3 ', 5'-dibutylphenyl) -6-chlorobenzotriazole, and phenylsalicylate UV such as phenylsalicylate, para-t-butylphenylsalicylate, and para-octylphenylsalicylate Absorbers, cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3-diphenylacrylate, methyl-2-carbomethoxy-3- (paramethoxy) -acrylate, nickel- [2,2′-thiobis- ( 4-t-
Octyl) -phenolate] -n-butylamine, nickel dibutyldithiocarbamate, metal complex salt ultraviolet absorbers such as cobalt dicyclohexyldithiophosphate, resorcinol-monobenzoate, 2'-ethyl-hexyl-2-cyanate, 3-phenylcinnamate And other ultraviolet absorbers. Particularly, a benzotriazole type is preferable. The added amount of the ultraviolet absorber (D-4) is based on 100 parts by weight of the component (A) + (B).
0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight.

As the light stabilizer (D-5), bis (1,2,2,6,6-pentamethyl-4-piperidyl) separate, bis (2,2,6,6-tetramethyl-4-) Piperidyl) separate, 2- (3,5-di-t)
Bis (1,2,2,6,6-pentamethyl-4) -butyl-4-hydroxybenzel) -2-n-butylmalonate
-Piperidyl), dimethyl succinate-1- (2-hydroxylethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine hybrid, poly [16- (1,
(1,3,3-tetramethylbutyl) imino-1.3.5
-Triazine-2,4-diyl], [(2,2,6,6
-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], 1- [2- [3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionyloxy) ethyl] -4- [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionyloxy] -2,
2,6,6-tetramethylpiperidine, (mixed 1,2,2,6,6-pentamethyl-4-piperidyl /
Tridecyl) -1,2,3,4-butane tetracarboxylate, mixed [1,2,2,6,6-pentamethyl-4-piperidyl / beta, beta, beta ^'- tetramethyl -
3,9- [2,4,8,10-tetraoxaspiro (5,5) undecashi] diethyl] diethyl 1-1,
2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)
There are hindered amine light stabilizers such as -1,2,3,4-butanetetracarboxylate. The hindered amine-based light stabilizers may be used alone or in combination of two or more. The amount of the light stabilizer (D-5) is based on 100 parts by weight of the components (A) and (B).
0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight.

The resin composition for coating an optical fiber includes a hindered amine light stabilizer (D-5) and an antioxidant (D-
Preferably, 3) is added. In particular, when (A) or (B) having a polyether skeleton is used, a hindered amine light stabilizer (D-5) and an antioxidant (D-3)
By using together, has good heat resistance, light resistance,
A composition that generates less hydrogen can be obtained. As the hindered amine light stabilizer (D-5), bis (1,2,2,6,6-
(Pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6
-Tetramethyl-4-piperidyl) sebacate, tetra (1,2,
2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylic acid ester. Screw (1,2,2,
6,6-Pentamethyl-4-piperidyl) sebacate is preferred. Examples of the antioxidant (D-3) include tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and n-octyl-3- (3,5-di- t-butyl-4
-Hydroxyphenyl) propionate, 4,4'-thiobis
Hindered phenol antioxidants such as (3-methyl-6-t-butylphenol), ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, bis
Examples thereof include sulfur-based antioxidants such as [2-methyl-4- {3-n-alkyl (C ₁₂ or C ₁₄ ) thiopropionyloxy} -5-t-butylphenyl] sulfide. Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane is preferred. The added amount of the hindered amine light stabilizer (D-5) and the antioxidant (D-3) are each preferably in the range of 0.1 to 2% by weight.

Examples of the plasticizer (D-6) include adipic acid compounds such as di- (2-ethylhexyl) adipate and diisodecyl adipate; azelaic acid compounds such as di (2-ethylhexyl) azelate; Phthalates such as diethyl phthalate, dibutyl phthalate, dihexyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, di-n-heptyl phthalate, diisodecyl phthalate, and butylphthalylbutyl glycolate Acid compounds, sebacic acid compounds such as dioctyl sebacate, trimellitic acid compounds such as tris- (2-ethylhexyl) trimellitate, phosphoric acid compounds such as triphenyl phosphate and tricresyl phosphate, and epoxidation Examples include soybean oil, medium molecular weight polyester, and chlorinated paraffin. Non-reactive compounds (D-7) include n-docosan, 2,6,10,14-tetramethylpentadecane,
Examples include eicosan, α-farnesene, squalane, squalene, n-dodecylcyclohexane, stearylcyclohexane, n-dodecylbenzene, o-terphenyl and m-terphenyl.

Examples of the chain transfer agent (D-8) include dodecyl mercaptan, ethyl mercapto acetate, butanediol dithiopropionate, pentaerythritol tetrakis (β-thiopropionate), triethylene glycol dimercaptan and the like. Chain transfer agent (D-
The amount of 8) is 0.001 to 5 parts by weight, preferably 0.01 to 100 parts by weight of the components (A) and (B).
~ 5 parts by weight.

As the thermal polymerization initiator (D-9), 2,4
-Dichlorobenzoyl peroxide, benzoyl peroxide, 1,1-di (t-butylperoxy)-
3,3,5-trimethylcyclohexane, n-butyl-
Peroxides such as 4,4'-di (t-butylperoxy) valerate and dicumyl peroxide; azo compounds such as 7-azobisisobutylnitrile; and tetramethylthiuram disulfide.

The amount of the thermal polymerization initiator (D-9) was 0.001 to 100 parts by weight of the components (A) and (B).
10 to 10 parts by weight, preferably 0.01 to 5 parts by weight.

Examples of the anaerobic polymerization initiator (D-10) include cumene hydroperoxide and t-butyl hydroperoxide. As a polymerization accelerator for anaerobic polymerization, dibenzenesulfonamide, tertiary amine, 1,2,3,4
-Tetrahydroquinoline and the like. Anaerobic polymerization initiator (D
The amount of -10) used in the resin composition (A) + (B)
0.05-5% by weight. Particularly preferably, 0.1 to 3% by weight. The amount of the polymerization accelerator used in the anaerobic polymerization is 0.1 to 10% by weight in the resin composition (A) + (B). Particularly preferably, it is 0.5 to 5% by weight.

Examples of the polymerization inhibitor (D-11) include quinones, nitrosos, and sulfur compounds. For example, hydroquinone, hydroquinone monomethyl ether, p-
Benzoquinone, 2,5-di-tert-butyl-p-benzoquinone, nitrosobenzene, tert-butylhydroquinone, pyrogallol, phenothiazine and the like.
The compounding amount of the polymerization inhibitor (D-11) is the above (A) +
0.001 to 5 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the component (B).

The inorganic filler and the organic filler (D-12)
Generally used to improve mechanical properties such as strength, cushioning, and slipperiness. As the inorganic filler, 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, sulfuric acid Barium, alumina white, zeolite, silica balloon,
There are glass balloons, glass fibers and the like. By adding and reacting a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconate coupling agent, etc. to the inorganic filler, a halogen group, an epoxy group, an amino group, a hydroxyl group, a thiol It may have a functional group such as a group, an amide group, a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Organic fillers include benzoguanamine resin, melamine resin, benzoguanamine / melamine resin, urea resin, silicone resin, low density polyethylene, high density polyethylene, polyolefin resin, ethylene / acrylic acid copolymer, polystyrene, cross-linked polystyrene, polydivinylbenzene , Styrene-divinylbenzene copolymer, acrylic copolymer, cross-linked acrylic resin, polymethyl methacrylate resin, vinylidene chloride resin, fluororesin, nylon 12,
Nylon 11, nylon 6/66, phenolic resin, epoxy resin, urethane resin, polyimide resin and the like.
The organic filler may have a functional group such as a halogen group, an epoxy group, an amino group, a hydroxyl group, a thiol group, an amide group, a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

As the coupling agent (D-13), γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, hexamethyl Silane coupling agent having an amino group such as silazane, γ-glycidoxypropyltrimethoxysilane, silane coupling agent having an epoxy group such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercapto A silane coupling agent having a mercapto group such as propyltrimethoxysilane, a silane coupling agent such as a silane coupling agent having a halogen group such as γ-chloropropyltrimethoxysilane, tetra (2,2-diallyloxymethyl- 1-butyl ) Bis (ditridecyl) phosphite titanate, isopropyldimethacrylisostearoyl titanate, isopropyldiacrylisostearoyl titanate, isopropyltriisostearoyl titanate, bis (dioctyl pyrophosphate)
Titanate coupling agents such as oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tricumylphenyl titanate; aluminum coupling agents such as acetoalkoxy aluminum diisopropylate; acetylacetone / zirconium Zirconium-based coupling agents such as a complex are exemplified. Silane coupling agent (D-
The amount of (13) is 0.001 to 5 parts by weight, preferably 0.0 to 100 parts by weight of the components (A) and (B).
1 to 5 parts by weight.

In the resin composition for coating optical fibers, silane coupling agents (D-13) include γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxy. Addition of silane, γ-acryloyloxypropylmethyldimethoxysilane, or the like can improve the stability of adhesion to glass.

Examples of the flame retardant (D-14) include phosphates such as tricresyl phosphate, cresylphenyl phosphate, octyldiphenyl phosphate, tris (chloroethyl) phosphate, and tris (2,3-dichlorophosphate). Propyl), tris (2,3-dibromopropyl) phosphate, halogenated phosphates such as 2,3-dibromopropyl-2,3-chloropropyl phosphate, chlorinated paraffin, perchloropentacyclodecane, hexa Bromocyclododecane, hexabromobenzene, tetrabromobisphenol A derivatives, low molecular weight halides such as decabromobisphenyl ether, chlorinated polyethylene, brominated polycarbonate, brominated epoxy, brominated polystyrene, brominated polybenzyl acrylate, bromine Polyphenylene oxide, etc. Reactive halides such as high molecular weight halides, brominated epoxies, brominated phenols, brominated phenyl (meth) acrylates, brominated styrenes, tetrabromophthalic anhydride, diallyl brominated phthalates, chloroendoic acids, and phosphorus-containing There are inorganic substances such as polyols, phosphorus-containing polyol polyurethanes, antimony trioxide, sodium antimonate, tin oxide, barium metaborate, red phosphorus, aluminum hydroxide, and magnesium hydroxide.

A silicone compound (D-15) such as silicone oil or modified silicone may be added for the purpose of an antifoaming agent, a leveling agent, an anti-slip agent, and the like.

The modified silicone is a dimethylpolysiloxane (silicone) having an organic group other than a methyl group introduced into a terminal and / or a side chain thereof. The introduced organic group includes an amino group, a hydroxyl group, a carboxyl group, and ( (Meth) acrylic group, alkoxy (meth) acrylic group, glycidyl group, mercapto group, polyether group, phenyl group, alkyl group, higher fatty acid ester group, alkoxy group, fluorine-substituted alkyl group, fluorine-substituted alkoxy group and amino group, hydroxyl group Etc. Among them, long-chain polyether groups,
Alkyl group, higher fatty acid ester group, alkoxy group, fluorine-substituted alkyl group, fluorine-substituted alkoxy group,
It is preferable because it has good compatibility with the components (A) and (B) and provides excellent surface properties. In particular, it is preferable to use a modified silicone containing a glycidyl group, a (meth) acryl group, a hydroxyl group, an ether group, an ester group, a higher fatty acid ester group, a copolymer of ethylene oxide and propylene oxide, a urethane bonding group, and the like.

For the purpose of an antifoaming agent, a leveling agent, an anti-slip agent, etc., an acrylic copolymer, a fluorine surfactant, an acetylene glycol-based surfactant, etc. may be used in addition to the silicone compound. For example, Disparon # 1700-based surface conditioner (Kusumoto Kasei Co., Ltd.), perenol-based acrylic copolymer (Henkel Hakusui Co., Ltd.), Megafac fluorinated surfactant (Dainippon Ink Chemical Industry Co., Ltd.), Dynol 604 acetylene glycol-based surfactant (Air Products Japan K.K.) and the like. The present invention is not limited to the exemplified compounds.

Solvents used as needed include aromatic hydrocarbons such as toluene and xylene, and alcohols such as methanol, ethanol and isopropyl alcohol, and esters such as ethyl acetate, ethyl cellosolve, methyl cellosolve and cellosolve acetate. Ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are exemplified. These solvents may be used alone or in a combination of two or more.

In order to obtain the active energy ray-curable resin composition of the present invention, the above-mentioned components (A), (B), (C) and (D) may be mixed, and the order and method of mixing may be selected. Is not particularly limited. Photopolymerization initiator (C), non-reactive oligomers, pigments and dyes, inorganic fillers, organic fillers, polymerization inhibitors, defoamers, leveling agents, plasticizers, additives such as adhesion improvers such as couplings, etc. (D) is each independently,
(A) may be added, but (B), a part of (B),
Part of (A), part of (A) + (B), part of (A) +
In a part of (B), it may be dissolved in a separate step by operation such as heating or stirring, or dispersed by operation such as stirring or roll dispersion, and then added to the remaining components.

The active energy ray-curable resin composition of the present invention is applied to a substrate, irradiated with an active energy ray, cured, and the cured product is peeled off from the substrate, or the resin is adhered to the substrate. Serve for use. The active energy ray-curable resin composition may be formed into a shaped state without using a substrate, and irradiated with active energy rays to form a cured product.

The active energy ray-curable resin composition of the present invention may be heated to 180 ° C. for a short time and applied or shaped.
If the viscosity of the active energy ray-curable resin composition of the present invention is 23 ° C. and 0.05 to 1,000 Pa · s,
A combination of the heating temperature, the coating method, and the shaping method can be used. Preferably, it is 0.1 to 500 Pa · s. The resin composition for coating an optical fiber is preferably 1 to 15 Pa · s in a method using a coating cup, but may be adjusted according to a coating method.

The thickness of the film to be cured is from the thickness of a monomolecular film to 1
0 cm. When the film is thick, it is important to select the type of energy beam and the compound that absorbs the energy beam and generates a radical species so that the active energy beam reaches the deep part. If the polymerization using active energy rays and the curing using thermal polymerization or / and the curing using anaerobic polymerization are used in combination, it is also possible to cure where energy rays do not reach.

The active energy ray-curable resin composition of the present invention comprises (1) metals such as aluminum, iron and copper, vinyl chloride, acryl, polycarbonate, PET, ABS,
Plastics such as polyethylene, polypropylene, and polystyrene; ceramics such as glass; coating materials and surface treatment agents for various materials such as wood, paper, printing paper, and fibers;
(2) binder, (3) plastic material, (4) F
It is useful for applications such as molding materials such as RP, (5) laminates, (6) adhesives and (7) adhesives.

In particular, it has a high curing rate and generates little hydrogen gas, and is suitable as a coating material for optical fibers.

[0160]

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

(Synthesis Example 1): Synthesis of Maleimidocaproic Acid A 6-aminocaproic acid (65.5 g) and 400 ml of acetic acid were charged into a 1 L three-necked flask equipped with a dropping funnel, a condenser and a stirrer, and stirred at room temperature. A solution consisting of 49.0 g of maleic anhydride and 300 ml of acetic acid was added dropwise from the dropping funnel over 2 hours. After dropping, add 1 more
After stirring was continued for an hour, the reaction was terminated. The resulting precipitate was collected by filtration and recrystallized from methanol to obtain 111 g of maleamic acid N-caproate. Next, 45.8 g of maleamic acid N-caproate, 40.4 g of triethylamine and 500 ml of toluene were charged into a 1 L three-necked flask equipped with a Dean-Stark fractionator and a stirrer while removing generated water. The reaction was continued at reflux temperature for 1 hour. Toluene obtained by distilling toluene from the reaction mixture,
After adjusting the pH to 2 by adding 0.1N hydrochloric acid, the mixture was extracted three times with 100 ml of ethyl acetate. The organic phase was separated, dried by adding magnesium sulfate, and then ethyl acetate was distilled off under reduced pressure. The obtained crude product was recrystallized from water to obtain 19 g of pale yellow crystals of maleimidocaproic acid.

(Synthesis Example 2): Method for synthesizing maleimide acetic acid The same procedure as in Synthesis Example 1 was carried out except that 37.5 g of glycine was used instead of 65.5 g of 6-aminocaproic acid. Was purified by recrystallization from methanol to obtain 36 g of maleimide acetic acid.

(Synthesis Example 3) 2-maleimido-2-methylacetic acid The same procedure as in Synthesis Example 1 was carried out except that 44.5 g of alanine was used instead of 65.5 g of 6-aminocaproic acid. The crude product was purified by recrystallization from methanol to obtain 48 g of 2-maleimido-2-methylacetic acid.

(Synthesis Example 4): Synthesis of N-hydroxymethylmaleimide In a 100-ml eggplant-shaped flask equipped with a cooling tube and a stirrer, 33.3 g of a 36% aqueous formaldehyde solution and 19.4 g of maleimide were charged. Refluxed for 1 hour. After the completion of the reaction, the precipitate formed by concentrating the reaction mixture to about 25 ml was filtered off. About 120
The crystals were recrystallized from ml of 2-propanol to obtain 14.2 g of white crystals of N-hydroxymethylmaleimide.

(Synthesis Example 5): Synthesis of N-hydroxyethylmaleimide 49 g of maleic anhydride and 30.5 g of ethanolamine were dissolved in 150 ml of acetone, respectively, each having a volume of 1 L equipped with a dropping funnel, a condenser and a stirrer. 2 in the neck flask
Equivalent amounts were dropped from the two dropping funnels and stirred under ice cooling. The dropwise addition took 5 hours, followed by stirring for 2 hours. After completion of the reaction, acetone was distilled off under reduced pressure, and the residue was recrystallized from ethyl acetate to obtain 48 g of hydroxyethylmaleamic acid.

Next, a 1 L capacity equipped with a cooling pipe and a stirrer
In a three-necked flask, add hydroxyethylmaleamic acid 3
1.6 g, 204 g of acetic anhydride and 10 g of sodium acetate were added, and the mixture was stirred at 60 ° C. for 5 hours. After the reaction was completed, acetic acid and acetic anhydride were distilled off under reduced pressure, and the residue was extracted with chloroform. The extract was concentrated, and the precipitated crystals were collected by filtration.

Further, a capacity 1 equipped with a cooling pipe and a stirrer
18.3 g of the above crystals, 250 ml of methanol and p-toluenesulfonic acid monohydrate were added to a three-necked L flask, and the mixture was refluxed for 8 hours. After completion of the reaction, methanol was distilled off under reduced pressure, and the residue was washed with dilute alkali alcohol. After drying, the crystals were recrystallized from toluene to obtain 18.3 g of white crystals of N-hydroxyethylmaleimide.

(Synthesis Example 6) 20 g of polytetramethylene glycol having a number average molecular weight of 1,000 and 9.8 g of maleimidocaproic acid obtained in Synthesis Example 1 were placed in a 200-ml eggplant-shaped flask equipped with a Dean-Stark type fractionator. , P-toluenesulfonic acid 1.2 g, 2,6-tert-butyl-p-
Charge 0.06 g of cresol and 15 ml of toluene,
The reaction was continued with stirring for 4 hours while removing the water produced at 40 torr (80 tons). The reaction mixture was dissolved in 200 ml of toluene, and saturated sodium hydrogen carbonate 1
It was washed three times with 00 ml and once with 100 ml of saturated saline. Concentrating the organic phase and formula (4)

[0169]

Embedded image (4) A pale yellow liquid 18 of the maleimide derivative ES1 represented by
g was obtained.

(Synthesis Example 7) In Synthesis Example 6, 20 g of polytetramethylene glycol having a number average molecular weight of 1,000 was used.
In place of the above, polymethylpentanediol adipate having a number average molecular weight of 1,000 (“Kurapol P-1010” manufactured by Kuraray Co., Ltd., polystyrene conversion value by GPC:
(Number average molecular weight 2,700, weight average molecular weight 4,700)
Except that 20 g was used, formula (5) was used in the same manner as in Synthesis Example 6.

[0171]

Embedded image (5) A pale yellow liquid 17 of the maleimide derivative ES2 represented by
g was obtained.

(Synthesis Example 8) In a 100 ml three-necked flask equipped with a condenser and a stirrer, add a bisphenol A epichlorohydrin adduct (Epiclon 840S, manufactured by Dainippon Ink and Chemicals, Inc., converted to polystyrene by GPC: Average molecular weight 465, weight average molecular weight 510)
23.8 g, 2,6-tert-butyl p-cresol 0.
10 g and 0.02 g of 2-methylimidazole were charged, and 29.5 g of maleimidocaproic acid obtained in Synthesis Example 1 was added over 3 hours while stirring at 90 ° C. under a nitrogen stream. After 4 hours, when the acid value becomes almost 0, the reaction is terminated and the formula (6)

[0173]

Embedded image 50 of pale yellow liquid of maleimide derivative ES3 represented by
g was obtained.

(Synthesis Example 9) In Synthesis Example 6, 20 g of polytetramethylene glycol having a number average molecular weight of 1,000 was used.
Pentaerythritol modified with tetra (ethylene oxide) ("PNT-4" manufactured by Nippon Emulsifier Co., Ltd.)
0 ”, polystyrene equivalent value by GPC: number average molecular weight 490, weight average molecular weight 530) Except for using 3.1 g, the formula (7) was obtained in the same manner as in Synthesis Example 7.

[0175]

Embedded image 8. pale yellow liquid of maleimide derivative ES4 represented by (7)
5 g were obtained.

(Synthesis Example 10) The same procedure as in Synthesis Example 6 was repeated, except that 9.8 g of maleimidocaproic acid was used.
20 g of polytetramethylene glycol having a number average molecular weight of 1,000 using 7.0 g of maleimide-2-methylacetic acid
Instead of polytetramethylene glycol having a number average molecular weight of 650 (“PTG650S” manufactured by Hodogaya Chemical Co., Ltd.)
N ", a polystyrene equivalent value by GPC: number-average molecular weight 1,200, weight-average molecular weight 1,600) except that 13 g of formula (8) was used in the same manner as in Synthesis Example 6.

[0177]

Embedded image (8) A pale yellow liquid 19 of the maleimide derivative ES5 represented by
g was obtained. (Synthesis Example 11) In a 200 ml eggplant-shaped flask equipped with a Dean-Stark fractionator, 7.1 g of tetrahydrofurfuryl alcohol (manufactured by Kanto Chemical Co., Ltd.), 14.8 g of maleimide acetic acid, and 0.1 g of p-toluenesulfonic acid were added. 8g,
0.04 g of 2,6-tert-butyl-p-cresol and 15 ml of toluene were charged and 240 torr at 80 ° C.
The reaction was continued while stirring for 4 hours while removing water generated under the conditions described in (1). The reaction mixture was dissolved in 200 ml of toluene and washed three times with 100 ml of saturated sodium bicarbonate and once with 100 ml of saturated saline. Concentrate the organic phase and formula (9)

[0178]

Embedded image (9) 2-maleimidoacetic acid tetrahydrofurfuryl ester (ES6) represented by the following formula was obtained.

(Synthesis Example 12) 8.9 g of isophorone diisocyanate (abbreviated as IPDI), 0.03 g of dibutyltin dilaurate, and 2,6-tert were placed in a 300 ml four-necked flask equipped with a dropping funnel, a condenser and a stirrer. -Butyl-p-cresol 0.06 g and methyl ethyl ketone 10 ml were charged and tetramethylene glycol having a weight average molecular weight of 1,000 ("PTGL1000" manufactured by Hodogaya Chemical Co., Ltd.
Gel permeation chromatography (hereinafter, referred to as
GPC) abbreviated to polystyrene: number average molecular weight 2,100, weight average molecular weight 5,000) 20 g
Was dropped from the dropping funnel over 1 hour. After the NCO% reaches the theoretical value (5.40%), N-hydroxymethylmaleimide (abbreviated as HMMI) at the same temperature under a nitrogen stream.
5.1 g was added over 1 hour, and after 3 hours, the reaction was terminated after confirming that the absorption at 2,250 cm ^-1 derived from isocyanate had disappeared by IR. The reaction mixture is concentrated to obtain the compound of formula (10)

[0180]

Embedded image (10) pale yellow liquid 28 of the maleimide derivative UR1
g was obtained.

(Synthesis Example 13) 2,8.7 g (165 mmol) of 2,4-tolylene diisocyanate (abbreviated as TDI) was charged into a flask equipped with stirring blades, and the mixture was stirred and mixed with polypropylene-tetramethylene glycol (number average molecular weight). 4000, abbreviated as PPTG-4000)
444 g (110 mmol) was charged and the temperature was raised to 60 ° C. while paying attention to heat generation. The reaction was carried out at this temperature for 4 hours, and the NCO% was measured to be 0.98%. Then, 15.5 g (110 mmol) of N-hydroxyethylmaleimide (abbreviated as HEMI) was charged, and the reaction was further performed at this temperature for 4 hours. After confirming that the absorption of NCO has disappeared by infrared absorption spectrum, take out PP.
488 g of a pale yellow liquid of a maleimide derivative UR2 having TG-4000 / TDI / HEMI = 2/3/2 was obtained.

(Synthesis Example 14) In Synthesis Example 13, tetramethylene glycol having a weight average molecular weight of 1,000 was used.
Instead of 9 g, a weight average molecular weight of 1,000 polymethylpentanediol adipate (“Kurapol P-1010” manufactured by Kuraray Co., Ltd .; polystyrene conversion value by GPC: number average molecular weight 2,700, weight average molecular weight 4,70)
0) "Clapol P-1010" / IPDI / HMM in the same manner as in Synthesis Example 12 except that 20 g was used.
25 g of a pale yellow liquid of maleimide derivative UR3 in which I) = 1/2/2 was obtained.

(Synthesis Example 15) In Synthesis Example 13, N-
Instead of 5.1 g of hydroxymethylmaleimide, 8.9 g of β-hydroxyethyl acrylate (abbreviated as HEA)
Except that PPTG- was used in the same manner as in Synthesis Example 12.
492 g of a pale yellow liquid of urethane acrylate UA1 having 4000 / TDI / HEA = 2/3/2 was obtained.

(Synthesis Example 16) In Synthesis Example 12, β-
Except for using 8.9 g of hydroxyethyl acrylate, “PTGL1000” /
25 g of a pale yellow liquid of urethane acrylate UA2 in which IPDI / HEA = 1/2/2 was obtained.

(Example 1) Nonylphenol E was added to 40 parts by weight of the maleimide derivative UR1 synthesized in Synthesis Example 12.
50 parts by weight of O1 mol-modified acrylate ("Aronix M111" manufactured by Toagosei Co., Ltd., abbreviated as NPA), N-
10 parts by weight of vinylpyrrolidone (abbreviated as NVP), 2,
0.1 parts by weight of 4,6-trimethylbenzoyldiphenyl phosphine oxide (abbreviated as "Lucillin TPO" manufactured by FS Japan Co., Ltd.) is mixed uniformly with a dispersion stirrer, and the active energy ray-curable resin is added. A composition was made.

Example 2 20 parts by weight of bisphenol AEO 4 mol-modified diacrylate (abbreviated as "Aronix M210" manufactured by Toagosei Co., Ltd., abbreviated as BPA) were added to 60 parts by weight of urethane acrylate UA2 synthesized in Synthesis Example 12; Bornyl acrylate ("IBXA", manufactured by Osaka Organic Chemical Co., Ltd .; abbreviated as IBA) 10 parts by weight; N-vinylcaprolactam (abbreviated as NVC) 10 parts by weight; 1-hydroxy-cyclohexylphenyl ketone (Ciba Geigy Specialty Co., Ltd.) "Irgacure 184)
0.5 part by weight (hereinafter abbreviated as HCPK) was added, and the mixture was uniformly mixed with a dispersion stirrer to prepare a composition.

(Examples 3 to 6) In the same manner as in Example 1,
A composition was made. (Comparative Example 1) NPA: 50 parts by weight, NV: 40 parts by weight of urethane acrylate UA synthesized in Synthesis Example 15
10 parts by weight of P and 0.1 parts by weight of TPO were added and uniformly mixed with a dispersion stirrer to prepare a composition. Comparative Example 2 A composition was prepared in the same manner as in Comparative Example 1. (Examples 1 to 6) (Comparative Examples 1 and 2)
The results are summarized in Table 1.

[0188]

[Table 1] Table 1

B is a compound having a maleimide group and copolymerizability. NPA: the glass transition temperature of the homopolymer is 17 ° C. This corresponds to the monofunctional compound (B-8) component. BPA: corresponds to the polyfunctional compound (B-9) component. NVP: the glass transition temperature of the homopolymer is 175 ° C. This corresponds to the monofunctional compound (B-10) component. NVC: the glass transition temperature of the homopolymer is 135 ° C. This corresponds to the monofunctional compound (B-10) component. IBX: homopolymer has a glass transition temperature of 94 ° C. This corresponds to the monofunctional compound (B-10) component.

Next, according to the method described below, the viscosity, curability, gel fraction, and
The tensile modulus, tensile elongation at break, and hydrogen generation amount of the cured coating film were measured. 1. Viscosity: The viscosity at 25 ° C. was measured using a B-type viscometer. 2. Curability: The resin compositions for coating optical fibers of Examples and Comparative Examples were smoothly applied on a glass plate to a thickness of 200 μm using a 120 W / cm metal halide lamp under a nitrogen atmosphere. 0.05 J / cm ² and 0.
Apply a 5 J / cm ² irradiation dose to form a cured coating. The tensile modulus of the cured coating film peeled from the glass plate is measured, and the degree of curing is determined by the following equation.

[0191] 3. Gel fraction The resin compositions for coating optical fibers of Examples and Comparative Examples were
On a glass plate, apply a smooth coating to a thickness of 200 μm and use a 120 W / cm metal halide lamp under a nitrogen atmosphere to apply a dose of 0.05 J / cm ² to form a cured coating. I do. The cured coating film (weight; W ¹ ) peeled off from the glass plate was refluxed in methyl ethyl ketone at 80 ° C. for 3 hours, and then dried at 100 ° C. for 1 hour and weighed (weight; W ¹ ).
W ² ) and determine the gel fraction by the following equation.

Gel fraction (%) = (W ¹ −W ² ) / W ¹ × 00

[0193] 4. Tensile modulus of cured coating film The resin composition for coating optical fibers of Examples and Comparative Examples,
On a glass plate, apply a smooth coating to a thickness of 200 μm and use a 120 W / cm metal halide lamp under a nitrogen atmosphere to apply a dose of 0.05 J / cm ² to form a cured coating. I do. The tensile modulus of the cured coating film peeled from the glass plate was measured under a condition of 23 ° C and 50% RH in accordance with JIS-K7113. did. 5. In the same manner as the tensile elongation at break of the cured coating film and the tensile modulus of the cured coating film, a cured coating film peeled from the glass plate was prepared, and JIS-K71 was used at 23 ° C and 50% RH.
According to 13, the tensile elongation at break is measured at a tensile speed of 50 mm / min and a mark length of 25 mm.

6. Hydrogen generation amount Resin compositions for coating optical fibers of Examples and Comparative Examples,
On a glass plate, apply a smooth coating to a thickness of 200 μm and use a 120 W / cm metal halide lamp under a nitrogen atmosphere to apply a dose of 0.05 J / cm ² to form a cured coating. I do. 1 g of the cured coating film peeled off from the glass plate was precisely weighed and sealed in a head space bottle, and then sealed.
After leaving at 00 ° C. for 7 days, the gas in the headspace bottle is sampled with a syringe, and the amount of hydrogen gas contained in this gas is quantified by gas chromatography.
Tables 2 summarize the measurement results of the resin compositions of Examples 1 to 6 and Comparative Examples 1 and 2.

[0195]

[Table 2]

Unit of viscosity: Poise Curing degree:% Gel fraction:% Tensile elastic modulus: kg / mm2 Tensile elongation at break:% Hydrogen generation: μl / g

[0197]

The active energy ray-curable resin composition of the present invention is characterized by having excellent curability, and generates a small amount of hydrogen from a cured product obtained by curing the composition. When used as, it exhibits excellent performance. By using the resin composition for coating an optical fiber of the present invention, an optical fiber core wire, a colored core wire, a unit or an overcoat core wire having excellent reliability can be manufactured at high speed.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02B 6/44 301 G02B 6/44 301A 4J100 (72) Inventor Naoto Shiroshiro 845-Kojikiya, Oaza, Ageo City, Saitama Prefecture 1 Nishiageo housing complex 3-16-408 (72) Inventor Yoshitomo Yonehara 1-1-1 Senari, Sakura-shi, Chiba F-term (reference) 2H050 BB06W BB07W BB14W BB17W BB33W BD02 4G060 AA01 AA03 AC15 CB12 4J011 QA03 QA04 QA08 QA12 QA13 QA14 QA15 QA17 QA19 QA21 QA22 QA23 QA24 QA26 QA32. SA54 SA61 SA62 SA63 SA64 UA01 UA02 UA06 WA03 4J027 AA02 AB13 AB15 AB16 AB18 AB19 AB23 AB24 AB25 AB26 AB29 AB32 AC02 AC03 AC04 AC06 AC 07 AC08 AC09 AD04 AE02 AE03 AE04 AG01 AG02 AG03 AG04 AG13 AG14 AG15 AG23 AG24 AJ08 BA04 BA05 BA07 BA08 BA09 BA11 BA14 BA17 BA20 BA21 BA26 BA27 CA02 CA03 CA04 CA05 CA06 CA07 CA08 CA14 CA16 CA18 CA19 CA24 CA34 CA35 CA03 CC03 CC03 CC03 CC03 CC03 CC03 CC03 CC03 CC03 CC03 CC03 CC03 CC03 CC03 CC03 CD08 4J038 FA011 FA012 FA181 KA03 KA04 PA17 4J100 AG04Q AG08Q AL03Q AL04Q AL05Q AL08Q AL09Q AL66Q AL67Q AM17Q AM21Q AM24Q AM47P AM47Q AM48Q AM55P AM55Q AM59P AR28Q BA02P BA08P BA08Q BA15P BA15Q BA16Q BA22P BA22Q BA29Q BA31Q BA38P BA39P BB01Q BB18Q BC02Q BC03P BC03Q BC04P BC04Q BC07Q BC43P BC43Q BC45Q BC51Q BC53Q BC75Q

Claims (9)

[Claims] 1. A compound of the general formula (1) (1) In the formula, m and n each independently represent an integer of 0 to 6, but m + n represents an integer of 1 to 6. R ₁₁ and R
Each ₁₂ independently represents a hydrocarbon chain comprising an aliphatic group or an aromatic group. G ₁ and G ₂ each independently represent an ether bond, an ester bond, a urethane bond or a carbonate bond. R ₂ is a hydrocarbon chain composed of an aliphatic group or an aromatic group, or an aliphatic group or an aromatic group connected by at least one bond selected from the group consisting of an ether bond, an ester bond, a urethane bond and a carbonate bond. (Poly) ether-linked chain or (poly) ether residue (A-1) having an average molecular weight of 40 to 100,000, (poly)
Ester linking chains or (poly) ester residues (A-2),
(Poly) urethane connecting chain or (poly) urethane residue or (A-3), (poly) carbonate connecting chain or (poly) carbonate residue (A-4). An active energy ray-curable resin composition containing the maleimide derivative (A) represented by｝. 2. R ₁₁ and R ₁₂ are each independently a hydrocarbon chain selected from the group consisting of an alkylene group, a cycloalkylene group, an arylalkylene group and a cycloalkylalkylene group, and G ₁ and G ₂ are Each independently -COO
Or an ester bond represented by -OCO-,
₂ 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 and an ester bond. (Poly) ether-linked chain or (poly) ether residue (A-1) or (poly) ester-linked chain or (poly) ester residue having an average molecular weight of 100 to 100,000 and connected by at least one bond selected from the group consisting of: Group (A
The active energy ray-curable resin composition according to claim 1, which contains the maleimide derivative (A) which is -2). 3. G ₁ and G ₂ are a urethane bond;
₂ is a repeating unit containing a linear alkylene group having 2 to 24 carbon atoms, a branched alkylene group having 2 to 24 carbon atoms, an alkylene group having 2 to 24 carbon atoms having a hydroxyl group and / or an aryl group. Average molecular weight 100-100,
000 (poly) ether linked chains or (poly) ether residues (A-1) (poly) ester linked chains or (poly) ester residues (A-2), (poly) urethane linked chains or (poly) urethane Residue or (A-3), (poly) carbonate linking chain or (poly) carbonate residue (A-
4) The composition according to claim 1, which comprises a maleimide derivative (A). 4. A compound (B) having a copolymerizability with the maleimide derivative (A) according to claim 1 and a maleimide group.
An active energy ray-curable resin composition comprising: 5. The compound (B) having a copolymerizability with a maleimide group is other than the compound (B-1) having an acryloyl group or a methacryloyl group, the compound (B-2) having a vinyl ether group and the maleimide derivative (A). The composition according to claim 4, which is at least one compound selected from the group consisting of a maleimide derivative (B-3). 6. A compound (B) having a copolymerizability between the maleimide derivative (A) according to claim 1 and a maleimide group.
And a photopolymerization initiator (C). 7. The compound (B) having a copolymerizability with a maleimide group is other than the compound (B-1) having an acryloyl group or a methacryloyl group, the compound (B-2) having a vinyl ether group and the maleimide derivative (A). The composition according to claim 6, which is one or more compounds selected from the group consisting of maleimide derivatives (B-3). 8. An active energy ray-curable resin composition for coating an optical fiber according to claim 1. 9. An optical fiber core, a colored core, a unit or an overcoat core coated with a cured product of the composition according to claim 8.