KR20150032746A - Curing agent for episulfide compounds, curable composition, cured product of episulfide compound, and method for curing episulfide compound - Google Patents

Abstract

일반식 (1) 중,
X₁는, 예를 들면, 산소 원자이며, X₂, 및 X₃는, 예를 들면, 수소 원자이다. R₁는 예를 들면, 메틸기이며, R2, 및 R3는 모두 존재하지 않는다. R4, R5, R6, R7, R8, 및 R9는 예를 들면, 모두 수소 원자이다. R10는 예를 들면, 메틸기이다. B는, 염기이다.A curing agent for a photobase-generating type episulfide compound, which is excellent in base generation efficiency and does not cause outgas, is provided. The curing agent for an episulfide compound of the present invention is composed of a compound represented by the following general formula (1).
(Formula 1)

In the general formula (1)
X ₁ is, for example, an oxygen atom, and X ₂ and X ₃ are, for example, hydrogen atoms. R ₁ is, for example, a methyl group, and both R2 and R3 are not present. R4, R5, R6, R7, R8, and R9 are, for example, all hydrogen atoms. R10 is, for example, a methyl group. B is a base.

Description

TECHNICAL FIELD The present invention relates to a curing agent for an episulfide compound, a curing composition, and a cured product of an episulfide compound and a cured composition for an episulfide compound,

The present invention relates to a curing agent for an episulfide compound, a curing composition and an episulfide compound, and more particularly to a curing agent for a photobase-generating type episulfide compound, a curing composition containing such a curing agent and an episulfide compound, To a cured product of an episulfide compound. The present invention also relates to a curing method for curing an episulfide compound with such a curing agent.

A resin cured product obtained by curing an episulfide compound with a curing agent is excellent in heat resistance, moisture resistance, transparency and refractive index, and can be applied to a wide variety of applications because it is an excellent resin cured product. In particular, it can be advantageously used in applications such as semiconductor encapsulants, electrical and electronic fields such as electrical insulating materials, and optical materials such as resins for lenses.

Examples of the curing agent for the episulfide compound include general bases as curing agents for anion curing compounds such as 1,3-bis (aminomethyl) cyclohexane and 1,8-diazabicyclo [5.4.0] However, since the reactivity is very high, there is a problem that the curable composition containing the episulfide compound and the curing agent has poor storage stability and pot life is very short. Therefore, the use of a nucleating agent has been proposed as a means for carrying out a curing reaction promptly by external stimulation with good storage stability of the curable composition.

As the base generator, there can be mentioned, for example, the photobase generator described in Patent Document 1. [ However, the photobase generator of Patent Document 1 has a limitation on the base that can be generated, and it is difficult to adjust the base strength. In addition, there is a drawback that the base generation efficiency due to the action of light is low, and the reaction for generating a base is difficult to be performed quickly.

On the other hand, a base generator having a high base generation efficiency is disclosed in Patent Document 2, for example. However, this base generating agent simultaneously generates outgas because it accompanies a decarboxylation reaction when a base is generated by light irradiation. For this reason, out gas generated may remain in the cured film as bubbles, and in this case, there is a fear that the hardened film strength is lowered.

Therefore, a photobase generator that does not generate outgas is disclosed in, for example, Patent Document 3. However, even in this photocatalyst, the base generation efficiency is still not satisfactory with respect to the high performance required in recent years, and further improvement of the photocatalyst is required.

(Patent Document 1) JP 2005-264156 A (Patent Document 2) JP 2009-280785 A (Patent Document 3) JP 2009-80452 A

In the present invention, a curing agent for a photobase-generating type episulfide compound, which is excellent in base generation efficiency and does not cause outgas formation under the above-mentioned background and has excellent storage stability in the case of using a curable composition, and a curing agent for an episulfide compound , A cured product of an episulfide compound cured by the curing agent, and a curing method.

Accordingly, the present inventors have conducted intensive studies in view of such circumstances, and as a result, they have found that by using a compound represented by the following general formula (1), it is possible to generate bases more efficiently than conventional photobase generators, And that the curing composition containing the curing agent and the episulfide compound has good storage stability, and thus the present invention has been accomplished.

That is, the present invention has the following structures [1] to [6].

[1] A curing agent for an episulfide compound, comprising a compound represented by the following general formula (1).

(Formula 1)

In the general formula (1)

X ₁ , X ₂ and X ₃ are each independently any one atom or group selected from the group consisting of a hydrogen atom, an oxygen atom, an alkylene group having 1 to 3 carbon atoms, a sulfur atom, a sulfonyl group, and a silanol group. R 1, R 2, and R 3 are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 3 to 20 carbon atoms, an oxygen atom, a nitrogen atom, A monocyclic, bicyclic or tricyclic heteroaryl group having 3 to 15 carbon atoms including a hetero atom, a monocyclic, a dicyclic or tricyclic cycloalkyl group having 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom A monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including 1 to 5 heteroatoms selected from the group consisting of hydrogen, Two or more groups selected from the group consisting of R 1, R 2, and R 3 may combine to form a cyclic structure, and the cyclic structure may be substituted with one or two or more heteroatoms selected from the group consisting of oxygen atom, nitrogen atom, . However, when X ₁ , X ₂ , and X ₃ are hydrogen atoms or silanol groups, R1, R2, and R3 are not present.

R4, R5, R6, R7, R8 and R9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, A monocyclic, bicyclic or tricyclic heteroaryl group having from 3 to 15 carbon atoms and containing from 1 to 5 hetero atoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, A monocyclic, bicyclic or tricyclic cycloalkyl group, and a monocyclic, bicyclic or tricyclic heterocycloalkyl group of 3 to 15 carbon atoms containing 1 to 5 hetero atoms selected from the group consisting of a hetero atom, a nitrogen atom and a sulfur atom Lt; / RTI > is an atom or group selected from the group consisting of R4 and R6 or R6 and R9 may be taken together to form an unsaturated bond together with an existing carbon-carbon bond.

R10 represents a carbon number including 1 to 5 hetero atoms selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 3 to 20 carbon atoms, an oxygen atom, A cycloalkyl group having from 3 to 15 carbon atoms, a monocyclic, bicyclic or tricyclic heteroaryl group having from 3 to 15 carbon atoms, a monocyclic, a dicyclic or tricyclic cycloalkyl group having from 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom Is a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including a hetero atom.

B is a base.

[2] The curing agent for an episulfide compound according to the above [1], wherein in the general formula (1), R 4, R 5, R 6, R 7, R 8 and R 9 are all hydrogen atoms and R ₁₀ is a methyl group.

[3] The curing agent for an episulfide compound according to [1] or [2], wherein the episulfide compound is an episulfide compound having an episulfide equivalent of 50 to 2,000.

[4] A curable composition containing a curing agent for an episulfide compound and an episulfide compound according to any one of [1] to [3].

[5] A cured product of an episulfide compound, wherein an episulfide compound is cured by a curing agent for an episulfide compound according to any one of [1] to [3].

[6] A method of curing an episulfide compound, which is cured by reacting an episulfide compound with a compound represented by the following general formula (1).

(Formula 1)

X ₁ , X ₂ and X ₃ are each independently selected from the group consisting of a hydrogen atom, an oxygen atom, an alkylene group having 1 to 3 carbon atoms, a sulfur atom, a sulfonyl group, and a silanol group One atom or group.

R 1, R 2, and R 3 are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 3 to 20 carbon atoms, an oxygen atom, a nitrogen atom, A monocyclic, bicyclic or tricyclic heteroaryl group having 3 to 15 carbon atoms including a hetero atom, a monocyclic, a dicyclic or tricyclic cycloalkyl group having 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom Or a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including 1 to 5 hetero atoms, Two or more groups selected from the group consisting of R 1, R 2, and R 3 may combine to form a cyclic structure, and the cyclic structure may be substituted with one or two or more heteroatoms selected from the group consisting of oxygen atom, nitrogen atom, . However, when X1, X2, and X3 are hydrogen atoms or silanol groups, R1, R2, and R3 are not present.

R4, R5, R6, R7, R8 and R9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silanol group, an alkyl group having 1 to 20 carbon atoms, a monocyclic group having 3 to 20 carbon atoms, Or a monocyclic, bicyclic or tricyclic heteroaryl group having 3 to 15 carbon atoms containing 1 to 5 hetero atoms selected from the group consisting of a triple ring aryl group, an oxygen atom, a nitrogen atom and a sulfur atom, , A bicyclic or tricyclic cycloalkyl group, and a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including 1 to 5 hetero atoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom Lt; / RTI > is an atom or group selected from the group consisting of R4 and R6 or R6 and R9 may be taken together to form an unsaturated bond together with an existing carbon-carbon bond.

R10 represents a carbon number including 1 to 5 hetero atoms selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 3 to 20 carbon atoms, an oxygen atom, A cycloalkyl group having from 3 to 15 carbon atoms, a monocyclic, bicyclic or tricyclic heteroaryl group having from 3 to 15 carbon atoms, a monocyclic, a dicyclic or tricyclic cycloalkyl group having from 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom Is a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including a hetero atom.

B is a base.

According to the curing agent for an episulfide compound of the present invention, since the base generation efficiency is excellent and outgas is not generated when the episulfide compound is cured, the curing of the episulfide compound can be carried out quickly, An effect that the bubble does not remain is obtained. Further, the curing composition containing the curing agent and the episulfide compound of the present invention has an excellent storage stability and can secure a sufficient working time.

Hereinafter, the present invention will be described in detail. Further, in the present invention, the curing agent for an episulfide compound includes not only a function as a curing agent but also a function as a curing accelerator (curing auxiliary).

[Curing agent for episulfide compound]

The curing agent for an episulfide compound of the present invention is characterized by being composed of a compound represented by the following general formula (1).

(Formula 1)

The basic structure parts that contribute to the generation of the base (B) of the chemical structure represented by the above general formula (1), and the structure portion, particularly carboxylate groups (-COO-) and the ethylenic double bond (C = CH ₂ ) Directly contribute to the cyclization-type nucleation mechanism.

That is, the structural moiety in the general formula (1) is a characteristic moiety that generates a base (B) as an active species by light irradiation (hν) to cure the episulfide compound efficiently as shown below.

R _{1 to} R ₁₀ and X _{1 to} X ₃ in the formula (1) are optional substituents attached to the basic skeleton as a characteristic moiety, and they are a substituent which inhibits the base generation mechanism according to the present invention or hardens the episulfide compound , It may be any substituent in nature. However, in the present invention to a particular to the R1~R10, and X ₁ ~X ₃ deliberately.

X ₁ , X ₂ , and X ₃ each independently represent a hydrogen atom, an oxygen atom, an alkylene group having 1 to 3 carbon atoms, a sulfur atom, a sulfonyl group, and a silanol group Lt; 2 > is an atom or a group selected from the group consisting of

X _1, X _2, and X ₃ is the case when the non-hydrogen atom or a silanol group, an oxygen atom In other words, any one of an alkylene group, a sulfur atom, and a sulfonyl group having a carbon number of 1~3, X _1, X _2, and each R1, R2, and R3 corresponding to the X ₃ are, each independently, an alkyl group of 1 to 20 carbon atoms, monocyclic ring of 3 to 20 carbon atoms, consisting of bicyclic or tricyclic aryl group, an oxygen atom, a nitrogen atom and a sulfur atom , A monocyclic, bicyclic or tricyclic heteroaryl group having 3 to 15 carbon atoms, a monocyclic ring having 3 to 15 carbon atoms, a dicyclic or tricyclic cycloalkyl group containing 1 to 5 hetero atoms selected from the group consisting of oxygen, nitrogen A monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including 1 to 5 hetero atoms selected from the group consisting of an oxygen atom, an oxygen atom and a sulfur atom. When X ₁ , X ₂ , and X ₃ are hydrogen atoms or silanol groups, R1, R2, and R3 are not present.

Two or more groups selected from the group consisting of R 1, R 2, and R 3 may be bonded to form a cyclic structure, and the cyclic structure may be substituted with one or two or more heteroatoms selected from the group consisting of oxygen atom, nitrogen atom, .

In the present invention, the aryl group means a cyclic unsaturated compound, for example, an unsaturated three-membered ring or a five-membered ring.

A halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silanol group, an alkyl group having 1 to 20 carbon atoms, a monocyclic ring having 3 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, A monocyclic, bicyclic or tricyclic heteroaryl group having from 3 to 15 carbon atoms and containing from 1 to 5 hetero atoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, a cycloalkyl group having from 3 to 15 carbon atoms A monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including 1 to 5 hetero atoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, Lt; 2 > is an atom or a group selected from the group consisting of R4 and R6 or R6 and R9 may be taken together to form an unsaturated bond together with an existing carbon-carbon bond.

R10 represents a carbon number including 1 to 5 hetero atoms selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 3 to 20 carbon atoms, an oxygen atom, A cycloalkyl group having from 3 to 15 carbon atoms, a monocyclic, bicyclic or tricyclic heteroaryl group having from 3 to 15 carbon atoms, a monocyclic, a dicyclic or tricyclic cycloalkyl group having from 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom Is a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including a hetero atom.

Examples of the alkyl group having 1 to 20 carbon atoms include a straight chain or branched alkyl group such as methyl, ethyl, propyl and isopropyl groups.

Examples of the monocyclic, bicyclic or tricyclic aryl group having 3 to 20 carbon atoms include a phenyl group, a benzyl group, a tolyl group, a naphthyl group, a phenanthryl group and an anthracenyl group. The number of carbon atoms is preferably 4 to 18, 15 is more preferable.

Examples of the monocyclic, bicyclic or tricyclic heteroaryl group having 3 to 15 carbon atoms including 1 to 5 heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom include furanyl, benzofuranyl, thienyl, Naphthyridyl, carbazolyl, and the like, and the number of carbon atoms in the alkyl group is preferably from 1 to 10, more preferably from 1 to 10, more preferably from 1 to 10, Is preferably 3 to 14, more preferably 3 to 13. The number of heteroatoms is preferably from 1 to 4, and may contain heteroatoms of different kinds.

Examples of the monocyclic, bicyclic or tricyclic cycloalkyl group having 3 to 15 carbon atoms include cyclopropyl, cyclohexyl, cycloheptyl, etc. The number of carbon atoms is preferably from 3 to 14, more preferably from 3 to 13.

Examples of the monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including 1 to 5 heteroatoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom include tetrahydrofuranyl, tetrahydropyranyl, tetra Methylpyrrolidyl, etc. The number of carbon atoms is preferably from 3 to 14, more preferably from 3 to 13. The number of heteroatoms is preferably from 1 to 4, and may contain heteroatoms of different kinds.

Examples of the halogen atom include an iodine atom, a bromine atom, a chlorine atom and a fluorine atom.

In the cation structure moiety in the general formula (1), B is a base, and examples thereof include the following amine compounds. But are not limited to, methylamine, ethylamine, propylamine, hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, ethylenediamine, 1,3-propanediamine, Aliphatic primary amine compounds such as amine;

Alicyclic primary amine compounds such as cyclohexylamine, 1,3- (bisaminoethyl) cyclohexane, diaminocyclohexane, isophoronediamine, etc., benzylamine, aniline, metaphenylene diamine, Aromatic primary amine compounds;

Aliphatic secondary amine compounds such as dimethylamine, diethylamine, dibutylamine, dihexylamine, dioctylamine, dioctylamine and ethylmethylamine;

Alicyclic secondary amine compounds such as aziridine, azetidine, pyrrolidine, piperidine, norbornane dimethylamine and 1,3-bis (4-piperidyl) propane;

Aromatic secondary amine compounds such as benzylmethylamine, diphenylamine and dibenzylamine;

Diethylamine, triethylamine, tributylamine, trihexylamine, trioctylamine, tridecylamine, ethyldiisopropylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] -7-undecene DBU), 1,5,7-triazabicyclo [4.4.0] deca-5-ene (TBD), 1,4-diazabicyclo [2.2.0] octane, phosphazene base compound;

Pyridine-based compounds such as pyridine, 2,4,6-trimethylpyridine and 2,6-di (t-butyl) pyridine, imidazole compounds such as imidazole, 2-methylimidazole, 2-undecylimidazole, Imidazole compounds such as imidazole, 2-ethyl-4-methylimidazole and 1-benzyl-2-methylimidazole, aromatic compounds such as triphenylamine, methyldiphenylamine, diethylaniline and tribenzylamine Tertiary amine compounds.

Among them, an aliphatic tertiary amine compound or an aromatic tertiary amine compound is preferably used because it contains a small amount when it is used as a curing agent, and among these, 1,8-diazabicyclo [5.4.0] -7- Undecene (DBU), 1,5,7-triazabicyclo [4.4.0] deca-5-ene (TBD), phosphazene base, imidazole and 2-methylimidazole.

In the general formula (1), R4, R5, R6, R7, R8 and R9 are all hydrogen atoms and R10 is a methyl group, that is, a compound represented by the following general formula (2) is preferable.

(Formula 2)

X ₁ , X ₂ , X ₃ , R 1, R 2, and R 3 in the general formula (2) are the same as those in the general formula (1).

In the anionic structural part of the compound represented by the general formula (2), one of X ₁ is an oxygen atom, X _2, and X ₃ are both a hydrogen atom, R ₁ alkyl group of 1 to 20 carbon atoms, and, X _1, and X ₂ is all a hydrogen atom, X ₃ is an oxygen atom, and R ₃ is an alkyl group having 1 to 20 carbon atoms, and X ₁ is an oxygen atom, X ₂ and X ₃ are all hydrogen atoms and R ₁ is a methyl group , And it is more preferable that both X ₁ and X ₂ are hydrogen atoms, X ₃ is an oxygen atom, and R ₃ is a methyl group. Further, in the cation structure portion, the base B is preferably selected from the group consisting of 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), 1,5,7-triazabicyclo [4.4.0] deca- (TBD), phosphazene base, imidazole, 2-methylimidazole, and the like.

The compound represented by the general formula (1) can be produced by employing a known method. For example, it can be produced by the method described in Japanese Patent Application Laid-Open No. 250996/1990.

The episulfide compound to be cured by the curing agent for the episulfide compound of the present invention is a monofunctional episulfide compound or one having at least one episulfide group in one molecule and can be prepared by reacting various known epoxy resins with thiocyanates, In the presence of an appropriate solvent to replace the oxygen atom of the epoxy group with the sulfur atom. When the oxygen atom of the epoxy group is substituted with sulfur atom, the oxygen atom of all the epoxy groups may be substituted with a sulfur atom or the oxygen atom of some epoxy groups may be substituted with a sulfur atom.

Among them, typical episulfide compounds include the following.

(1) bisphenol type obtained by glycidylating bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S and tetrabromobisphenol A A bisphenol type episulfide resin in which an epoxy resin is again thioglysed;

(2) Nucleophilic addition products of bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S and tetrabromobisphenol A A hydrogenated bisphenol type episulfide resin in which a hydrogenated bisphenol type epoxy resin obtained by glycidylation is again thioglysed;

(3) An epoxy resin obtained by glycidylating other divalent phenols such as biphenol, dihydroxynaphthalene, dihydroxyanthracene, and 9,9-bis (4-hydroxyphenyl) fluorene, with thioglycidyl Dilated episulfide resins;

(4) Synthesis of 1,1,1-tris (4-hydroxyphenyl) methane and 4,4- (1- (4- (1- (4- hydroxyphenyl) An episulfide resin obtained by further glycidylating a trisphenol such as bisphenol into a thioglycidylated epoxy resin;

(5) an episulfide resin obtained by glycidylating tetracene phenols such as 1,1,2,2-tetraquis (4-hydroxyphenyl) ethane and thioglycidylating an epoxy resin obtained therefrom;

(6) A novolac epoxy resin obtained by glycidylating phenol novolak, cresol novolak, bisphenol A novolac, brominated phenol novolac, brominated bisphenol A novolak, etc., Sulfide resin;

(7) an aliphatic ether-type episulfide resin obtained by glycidylating a polyhydric alcohol such as glycerin or polyethylene glycol and then glycidylating an aliphatic ether-type epoxy resin;

(8) an ether ester type episulfide resin obtained by glycidylating a hydroxycarboxylic acid such as p-oxybenzoic acid or? -Oxynaphthoic acid and thiolizing an ether ester type epoxy resin;

(9) an ester-type episulfide resin obtained by glycidylating a polycarboxylic acid such as phthalic acid or terephthalic acid and then thioglycidylating the ester-type epoxy resin;

(10) amine type epoxy resins obtained by glycidylating amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, amine type epoxy resins obtained by thioglycidylating triglycidyl isocyanurate and the like Episulfide resin;

(11) thioglycidyl polyamides of polyalkylene polyamines such as diethylenetriamine and triethylenetetramine with dicarboxylic acids such as adipic acid;

(12) 3,4-epithiocyclohexylmethyl-3 ', 4'-epithiocyclohexanecarboxylate, bis- (3,4-epithiocyclohexyl) adipate, 1,2- Alicyclic episulfide such as vinyl cyclohexane;

(13) a silicone-modified episulfide resin obtained by reacting an organopolysiloxane with an episulfide resin or a phenol novolac type episulfide resin;

(14) episulfide compounds such as thioglycidyl methacrylate, 3,4-epithicyclohexylmethyl methacrylate, propylene sulfide, and cyclohexane sulfide, and polymers thereof;

(15) Episulfide compounds such as bis (2,3-epithiopropyl) sulfide and bis (2,3-epithiopropylthio) ethane and bis (5,6-epithio-3-thiohexane) sulfide; .

And one kind of episulfide compound selected from these episulfide compounds or a mixture of two or more kinds of episulfide compounds can be used.

These episulfide compounds are appropriately selected depending on the use of the cured product.

(2), (10), (12), (14), and (12) in the above-described episulfide compounds of the above (2) 15), the episulfide compounds of the above (3) and (13) in the organic EL element encapsulant and the episulfide compound of the above (2), (10), (12) , And the episulfide compounds (1), (3) and (6) are preferably used for the insulating material for a printed wiring board.

The episulfide compound preferably has an episulfide equivalent (average molecular weight per episulfide group) of 50 to 2,000, more preferably 50 to 1,800. When the episulfide equivalent is too small, it is difficult to control the reaction at the time of curing. On the other hand, if the episulfide equivalent is too large, compatibility with the curing agent for the episulfide compound or the solvent tends to decrease. In addition, the episulfide equivalent of the episulfide compound can be calculated by gel permeation chromatography and the number of episulfide functional groups of the compound.

[Curable composition]

The curable composition of the present invention is characterized by containing a curing agent for the episulfide compound of the present invention and the above-mentioned episulfide compound.

The content of the curing agent for the episulfide compound in the curable composition of the present invention is preferably 0.1 to 60 parts by weight, more preferably 0.5 to 50 parts by weight, and more preferably 1 to 40 parts by weight based on 100 parts by weight of the episulfide compound. By weight. When the content of the curing agent is too small, it tends to be difficult to rapidly react the episulfide compound. On the other hand, if the content is too large, the curing agent itself tends to lower the solubility of the episulfide compound and tends to be costly disadvantageous.

In the curable composition of the present invention, a base proliferating agent capable of generating a base proliferatively by the action of a base is added in an amount of usually 1 to 40 parts by weight, preferably 5 to 20 parts by weight per 100 parts by weight of the episulfide compound May be included. The sensitizer may be contained in an amount of usually 1 to 30 parts by weight, preferably 2 to 20 parts by weight, based on 100 parts by weight of the episulfide compound.

The curable composition of the present invention may contain a solvent as required. Examples of such a solvent include aromatic hydrocarbon compounds such as toluene, saturated or unsaturated hydrocarbon compounds such as hexane and heptane, ethers such as diethyl ether and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, , Alcohols such as ethanol and isopropyl alcohol, halogen solvents such as chloroform, and the like. One type of solvent selected from these solvents, or a mixed solvent obtained by mixing two or more kinds of solvents can be used.

In the curable composition of the present invention, the content of the solvent can be appropriately selected so as to be uniformly coated, for example, when the curable composition is applied onto a predetermined substrate and the layer is formed by the curable composition.

The curing agent for the episulfide compound of the present invention may also be used as a curing accelerator. In this case, for example, the following known curing agents are used as the curing agent.

Acid anhydrides, aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride and pyromellitic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl and methylene tetra anhydride Cyclic aliphatic acid anhydrides such as hydrophthalic acid, dodecenyl succinic anhydride, and anhydrous trialkyltetrahydrophthalic acid, and those in which oxygen atoms are substituted with sulfur atoms.

Polyhydric phenols; novolac products of divalent phenols such as catechol resol, hydroquinone, bisphenol F, bisphenol A, bisphenol S, biphenol, phenol novolacs, cresol novolacs and bisphenol A, Methanes, aralkyl polyphenols, dicyclopentadiene polyphenols, etc., and those in which these oxygen atoms are substituted with sulfur atoms.

These curing agents may be used alone or in combination of two or more. The use ratio of the curing agent is usually 0.01 to 200 parts by weight, preferably 10 to 100 parts by weight, per 100 parts by weight of the episulfide compound.

The content of the curing accelerator (curing agent of the present invention) is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the episulfide compound.

Further, with respect to 100 parts by weight of the known curing agent, the curing accelerator (curing agent of the present invention) is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight.

The curable composition of the present invention may contain various additives as appropriate within the range not hindering the objects and effects of the present invention. Examples of such additives include fillers, pigments, dyes, labeling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, dispersing aids, surface modifiers, plasticizers, plasticizers, source inhibitors, curing accelerators, And the like. These additives may be used alone or in combination of two or more.

Various curable monomers, oligomers or synthetic resins may be added to the curable composition of the present invention for the purpose of improving the properties of the cured product which may be placed on the final coat, adhesive layer, molded product, and the like. For example, a diluent for an epoxy resin such as monoepoxy, a typical aromatic and alicyclic epoxy resin, a phenol resin, an alkyd resin, a melamine resin, a fluororesin, a vinyl chloride resin, an acrylic resin, a silicone resin, Species, or a combination of two or more species. These blend ratios are not particularly limited so long as they do not impair the inherent properties of the curable composition of the present invention and are usually 100 parts by weight or less, particularly preferably 50 parts by weight or less, based on 100 parts by weight of the episulfide compound.

The curable composition of the present invention is prepared by physically mixing a curing agent for an episulfide compound of the present invention, an episulfide compound, and optional components by known means and conditions.

As a method of mixing the curing agent for an episulfide compound and an episulfide compound of the present invention, for example, a predetermined amount of a curing agent and an episulfide compound and optional components are kneaded using a roll kneader, a kneader, an extruder or the like Method.

[Curing method of episulfide compound]

In the present invention, the episulfide compound can be cured by allowing the compound represented by the general formula (1) to act. For example, the curing agent for the episulfide compound of the present invention and the curable composition containing the episulfide compound can be cured by light irradiation or heating.

By action of light or heat, a base is generated in the curable composition of the present invention, the episulfide compound is cured by polymerization, and a cured product of the episulfide compound is formed.

When the curable composition of the present invention is cured by irradiation with ultraviolet rays, it can be cured by irradiating ultraviolet rays with an accumulated dose of 10 to 10,000 mJ / cm 2, preferably 10 to 8000 mJ / cm 2. The output wavelength is preferably an ultraviolet ray having a light emission distribution with a wavelength of 400 nm or less.

The ultraviolet ray source used for ultraviolet ray irradiation is not particularly limited as long as it can output a wavelength in the vicinity of 256 to 365 nm. For example, a high pressure mercury lamp, a metal halide lamp, a high power metal halide lamp, a xenon lamp, , And various known ones can be used. Among them, a high-pressure mercury lamp and a metal halide lamp are preferably used.

In the curing reaction by ultraviolet ray irradiation, since it is easy to be inhibited by oxygen, the atmosphere at the time of ultraviolet irradiation preferably has an oxygen concentration of 3% or less, more preferably 0.5% or less, and particularly preferably 0.3% or less.

In the curable composition of the present invention, the polymerization reaction proceeds at room temperature after irradiation with ultraviolet rays. However, in order to efficiently cure the composition, it is preferable to conduct the heat treatment. The heat treatment conditions may be appropriately determined depending on various conditions such as illuminance, cumulative dose, type of base generated from the photobase generator to be used, kind of base curable compound, and the heating temperature is usually 30 to 200 Deg.] C, preferably 40 to 150 [deg.] C, and particularly preferably 50 to 130 [deg.] C. The heating time is usually 10 seconds to 1 day, preferably 60 seconds to 360 minutes, particularly preferably 5 minutes to 120 minutes.

Since the curable composition of the present invention contains the curing agent for the episulfide compound and the episulfide compound of the present invention, the reaction between the base generated from the curing agent and the episulfide compound or the like progresses successively, and the curing rate and reaction efficiency Is excellent, and curing is performed quickly. In addition, since no outgas is generated when the episulfide compound is cured, an effect that bubbles do not remain in the cured product can be obtained. The curable composition of the present invention having such an effect can be suitably used for, for example, highly sensitive photocurable materials and resist materials (pattern forming materials).

The cured product of the episulfide compound cured by the curing agent for the episulfide compound of the present invention is widely used as a member in the field where the properties such as heat resistance, dimensional stability, and insulation are considered to be effective. For example, An electronic ejection layer such as a printing ink, a sealant for sealing an organic EL or an LED and an adhesive, a polarizer adhesive, a color filter, an organic EL, and a light ejection film, a display substrate, a flexible display substrate, a film for a flexible display, , A hologram, an optical member, or a building material, and is widely used as an electronic component, an interlayer insulating film, a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, A substrate, a flexible display substrate, a film for a flexible display, a semiconductor device, an electronic component, an interlayer insulating film, The coated film, as gwanghoe, gwanghoe parts, the anti-reflection film, holographic, optical element or the like building members are provided. The pattern or the like formed as a cured product has heat resistance and insulation and can be used as a transparent encapsulant, a color filter, a display substrate, a flexible display substrate, a film for a flexible display, an electronic component, a semiconductor device, It can be advantageously used as a coating film, an optical circuit, an optical circuit component, an antireflection film, other optical members or electronic members.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In the examples, "% " and " part "

[Synthesis Example 1]

Synthesis of 8-bromo-7-methoxy-3,4-dihydro-2H-naphthalen-1-one (i)

(0.11 mol) of 7-methoxy-3,4-dihydro-2H-naphthalen-1-one, 23.14 g (0.13 mol) of N-bromosuccinimide and 200 ml of acetonitrile I added. The entire reactor was shielded from light and the reaction was carried out at room temperature for 30 hours. After completion of the reaction, the reaction solution was washed three times with 300 ml of water and then concentrated to obtain a defective product. The resulting impure product was purified by silica gel column chromatography (ethyl acetate / hexane = 1/7 (volume ratio)) to obtain 8-bromo-7-methoxy-3,4-dihydro- 23.28 g of on (i) was obtained. The yield was 83%.

[Synthesis Example 2]

Synthesis of 8-bromo-1-ethylidene-7-methoxy-1,2,3,4-tetrahydronaphthalene (ii)

In a 500 ml reactor, 37.28 g (0.10 mol) of ethyltriphenylphosphonium bromide, 8.64 g (0.08 mol) of t-butoxy gallium and 90 ml of tetrahydrofuran were added to the reactor, and the mixture was stirred at room temperature for 1 hour. Subsequently, a solution of 20.15 g (0.08 mol) of 8-bromo-7-methoxy-3,4-dihydro-2H-naphthalen-1-one (i) obtained in Synthetic Example 1 in tetrahydrofuran , And the mixture was reacted at room temperature for 16 hours after completion of dropwise addition. After completion of the reaction, diluted hydrochloric acid was added to the reaction mixture, and the mixture was washed three times with 200 ml of dichloromethane. The obtained organic layer was concentrated, 700 ml of hexane was added to the concentrate, and the mixture was stirred for 30 minutes. Subsequently, the precipitated crystals were removed by filtration, and the resulting solution was concentrated to obtain a defective product.

The resulting impure product was purified by silica gel column chromatography (ethyl acetate / hexane = 1/5 (volume ratio)) to obtain 8-bromo-1-ethylidene 7-methoxy- 16.36 g of tetrahydronaphthalene (ii) was obtained. The yield was 79%.

[Synthesis Example 3]

Synthesis of " 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (iii)

In a nitrogen atmosphere, 1.46 g (0.06 mol) of magnesium and 80 ml of tetrahydrofuran were added to a 500 ml reactor, and the mixture was stirred at room temperature for 10 minutes. Subsequently, a solution of 8.55 g (0.03 mol) of the 8-bromo-1-ethylidene-7-methoxy-1,2,3,4-tetrahydronaphthalene (ii) obtained in Synthesis Example 2 in tetrahydrofuran And the mixture was heated to reflux for 1 hour. After the completion of the heating and refluxing, the reaction solution was poured into a large amount of dry ice (approximately 500 g), and left until the dry ice sublimated. Then, diluted hydrochloric acid was added to the reaction solution, and the mixture was washed three times with 200 ml of dichloromethane. The obtained organic layer was concentrated to obtain a defect product.

The obtained impure product was purified by silica gel column chromatography (ethyl acetate / hexane = 1/5 (volume ratio)) to obtain 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene- 4.53 g of carboxylic acid (iii) was obtained. The yield was 61%.

[Production Example 1]

Synthesis of " 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid diazabicyclo [

(4.3 mmol) of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (iii) obtained in Synthesis Example 3, 1,8 -Diazabicyclo [5.4.0] -7-undecene and 250 ml of diethyl ether were added, and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the solvent was removed under reduced pressure to obtain 1.38 g of the following 8-ethylidene 2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid diazabicyclo [ . The yield was 83%.

[Production Example 2]

Synthesis of " 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid triazabicyclodecane salt "

1.00 g (4.3 mmol) of the 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (iii) obtained in Synthesis Example 3, , 0.60 g (4.3 mmol) of 7-triazabicyclo [4.4.0] deca-5-ene and 10 ml of diethyl ether were added, and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the precipitated crystals were collected by filtration to obtain the following 8-ethylidene 2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid triazabicyclo dececane salt as 1.47 g. The yield was 92%.

[Production Example 3]

Synthesis of " 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid spazene base salt "

In a 200 ml reactor, 0.80 g (3.4 mmol) of 8-ethylidene 2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (iii) obtained in Synthesis Example 3, g (3.4 mmol) of diethyl ether and 100 ml of diethyl ether, and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the solvent was removed under reduced pressure to obtain 1.41 g of the following 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxysulfospan base salt Respectively. The yield was 100%.

[Production Example 4]

Synthesis of " 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid imidazole salt "

 1.9 g (8.4 mmol) of 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (iii) obtained in Synthesis Example 3, 0.57 g (8.4 mmol) of triethylamine and 500 ml of diethyl ether, and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the precipitated crystals were collected by filtration to obtain 1.72 g of the following 8-ethylidene-2-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid imidazole salt Respectively. The yield was 68%.

[Synthesis Example 4]

Synthesis of 8-bromo-5-methoxy-3,4-dihydro-2H-naphthalen-1-one (iv)

(0.11 mol) of 5-methoxy-3,4-dihydro-2H-naphthalen-1-one, 23.14 g (0.13 mol) of N-bromosuccinimide and 200 ml of acetonitrile I added. The whole reactor was shielded from light and the reaction was carried out at room temperature for 48 hours. After completion of the reaction, the reaction solution was washed three times with 300 ml of water and then concentrated to obtain a defective product.

The resulting impure product was purified by silica gel column chromatography (ethyl acetate / hexane = 1/7 (volume ratio)) to obtain 8-bromo-5-methoxy-3,4-dihydro- 25.98 g of on (iv) was obtained. The yield was 89%.

[Synthesis Example 5]

Synthesis of 8-bromo-1-ethylidene 5-methoxy-1,2,3,4-tetrahydronaphthalene (v)

In a nitrogen atmosphere, 37.28 g (0.10 mol) of ethyltriphenylphosphonium bromide, 8.64 g (0.08 mol) of t-butoxygallium and 90 ml of tetrahydrofuran were added to a 500 ml reactor, and the mixture was stirred at room temperature for 1 hour. Subsequently, a solution of 20.15 g (0.08 mol) of 8-bromo-5-methoxy-3,4-dihydro-2H-naphthalen-1-one (iv) obtained in Synthetic Example 4 in tetrahydrofuran , And the mixture was reacted at room temperature for 16 hours after completion of dropwise addition. After completion of the reaction, diluted hydrochloric acid was added to the reaction mixture, and the mixture was washed three times with 200 ml of dichloromethane. The obtained organic layer was concentrated, 700 ml of nucleic acid was added to the concentrate, and the mixture was stirred for 30 minutes. Subsequently, the precipitated crystals were removed by filtration, and the resulting solution was concentrated to obtain a defective product.

The resulting impure product was purified by silica gel column chromatography (ethyl acetate / hexane = 1/5 (volume ratio)) to obtain 8-bromo-1-ethylidene-5-methoxy-1,2,3,4 -Tetrahydronaphthalene (v) was obtained in an amount of 13.78 g. The yield was 65%.

[Synthesis Example 6]

Synthesis of " 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (vi)

Under a nitrogen atmosphere, 1.46 g (0.06 mol) of magnesium and 80 ml of tetrahydrofuran were added to a 500 ml reactor, and the mixture was stirred at room temperature for 10 minutes. Subsequently, a solution of 8.55 g (0.03 mol) of 8-bromo-1-ethylidene 5-methoxy-1,2,3,4-tetrahydronaphthalene (v) obtained in Synthetic Example 5 in 40 ml of tetrahydrofuran was reacted And the mixture was heated under reflux for 1 hour. After the completion of the heating and refluxing, the reaction solution was poured into a large amount of dry ice (approximately 500 g), and left until the dry ice sublimated. Then, diluted hydrochloric acid was added to the reaction solution, and the mixture was washed three times with 200 ml of dichloromethane. The obtained organic layer was concentrated to obtain a defect product.

The resulting impure product was purified by silica gel column chromatography (ethyl acetate / hexane = 1/5 (volume ratio)) to obtain 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene- To obtain 4.00 g of carboxylic acid (vi). The yield was 54%.

[Production Example 5]

Synthesis of " 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid diazabicyclo [

1.00 g (4.3 mmol) of 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (vi) obtained in Synthesis Example 6, 1,8 -Diazabicyclo [5.4.0] -7-undecene and 250 ml of diethyl ether were added, and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the solvent was removed under reduced pressure to obtain 1.67 g of the following 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid diazabicyclo [ Respectively. The yield was 100%.

[Production Example 6]

Synthesis of 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid triazabicyclo dececane salt A 200 ml reactor was charged with 8-ethylidene- 0.31 g (1.3 mmol) of 4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (vi), 1,5,5-triazabicyclo [4.4.0] deca- (1.3 mmol) and 120 ml of diethyl ether were added, and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the reaction mixture was precipitated and the crystals were collected by filtration to obtain 0.34 g of 8-ethylidene-4-methoxy-5,6,7, -tetrahydronaphthalene-1-carboxylic acid triazabicyclo dececane g. The yield was 69%.

[Production Example 7]

Synthesis of " 8-ethylidene 4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid spazene base salt "

In a 200 ml reactor, 0.23 g (1.0 mmol) of the 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid (vi) obtained in Synthesis Example 6, (1.0 mmol) of diethyl ether and 50 ml of diethyl ether, and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the solvent was removed under reduced pressure to obtain 0.40 g of the following 8-ethylidene-4-methoxy-5,6,7,8-tetrahydronaphthalene-1-carboxylic acid triazabicyclo dececane salt Respectively. The yield was 97%.

[Comparative Production Example 1]

Synthesis of " 2- (3-benzoylphenyl) propionic acid diazabicyclo [

(11.8 mmol) of 2- (3-benzoylphenyl) propionic acid, 1.80 g (11.8 mmol) of 1,8-diazabicyclo [5.4.0] -7- undecene, And the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the solvent was removed under reduced pressure to obtain 4.96 g of the following 2- (3-benzoylphenyl) propionic acid diazabicyclo-undecene salt. The yield was 100%.

[Comparative Preparation Example 2]

Synthesis of " 2- (3-benzoylphenyl) propionic acid triazabicyclodecane salt "

1.00 g (3.9 mmol) of 2- (3-benzoylphenyl) propionic acid, 0.55 g (3.9 mmol) of 1,5,7-triazabicyclo [4.4.0] deca- 150 ml of ethyl ether was added and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the solvent was removed under reduced pressure to obtain 1.73 g of 2- (3-benzoylphenyl) propionic acid triazabicyclo dececane salt shown below. The yield was 100%.

[Examples 1 to 7 and Comparative Examples 1 and 2]

The following evaluations were carried out using the compounds prepared in Preparation Examples 1 to 7 as the curing agents of Examples 1 to 7 and the compounds prepared in Comparative Preparation Examples 1 and 2 as the curing agents of Comparative Examples 1 and 2.

[Evaluation Items]

(1) Measurement of insolubilization rate (base generation efficiency)

8 parts of a curing agent and 100 parts of chloroform were mixed with 100 parts of a hydrogenated bisphenol A type episulfide resin (manufactured by Mitsubishi Chemical Corporation, YL-7007) to prepare a homogeneous solution. The thus prepared solution was coated on a non-alkali glass using a bar coater (No. 20), and pre-baked at 50 ° C for 5 minutes. Ultraviolet rays of an exposure amount of 928 mJ / cm < 2 > were irradiated in 365 nm conversion using a metal halide lamp at a temperature shown in Table 1 for 40 minutes to obtain a cured film. The obtained cured film was immersed in chloroform for 30 seconds, taken out from chloroform, and dried. The insolubilization ratio was determined by the weight difference between the cured films before and after immersion in chloroform. The results are shown in Table 1.

(2) Confirmation of occurrence of bubbles

8 parts of a curing agent was mixed with 100 parts of a hydrogenated bisphenol A type episulfide resin (YL-7007, manufactured by Mitsubishi Chemical Corporation). The mixed solution was defoamed on a deaerator to prepare a sample. The prepared sample was placed in a form of a silicon spacer having a thickness of 2 mm, sandwiched between two pieces of alkali-free glass through a release film, and irradiated with ultraviolet rays at an exposure amount of 2145 mJ / cm 2 in terms of 365 nm using a metal halide lamp. Subsequently, the substrate was heat-treated at the temperature shown in Table 1 for 1 hour, and then a plate-shaped cured product of about 2 mm in thickness was obtained. With respect to the obtained cured product, the presence or absence of bubbles was visually confirmed. The results are shown in Table 1.

In Example 6, a cured film was not obtained, except that the nucleus-hydrogenated bisphenol A type episulfide resin was changed to a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828).

[Comparative Example 4]

The same procedure as in Example 6 was carried out except that the nucleus-hydrogenated bisphenol A type episulfide resin was changed to a nucleus hydrogenated bisphenol A type epoxy resin (YX8000 manufactured by Mitsubishi Chemical Corporation), but a cured film could not be obtained .

From the results shown in Table 1, it can be seen that the curing agent for the episulfide compound of the present invention is equivalent to the conventional curing agents shown in Comparative Examples 1 and 2, and the curing of the episulfide compound can be carried out rapidly have. In addition, unlike the conventional curing agents shown in Comparative Examples 1 and 2, in the curing agent for an episulfide compound of the present invention, outgas is not generated when the episulfide compound is cured, so that no bubbles remain in the cured film The effect can be obtained. Further, from the results of Comparative Examples 3 and 4, it can be seen that the curing agent of the present invention is particularly excellent in curability against the episulfide compound.

The storage stability test was carried out as follows.

[Storage stability test]

The curable compositions shown in Examples 8 and 9 and Comparative Examples 5 and 6 were prepared and when the viscosity reached twice the initial viscosity using a B-type clay system (manufactured by BROOKFIELD, DV-II + Pro) at 25 ° C Was measured, and the time was evaluated as storage stability.

[Example 8]

8 parts of the curing agent of Production Example 5 and 16 parts of chloroform were mixed with 100 parts of the hydrogenated bisphenol A type episulfide resin to prepare a curing composition. The time until the viscosity of this curable composition became twice the initial viscosity at 25 캜 was measured and the storage stability was evaluated. The results are shown in Table 2.

[Example 9]

8 parts of the curing agent of Production Example 6 and 16 parts of chloroform were mixed with 100 parts of the hydrogenated bisphenol A type episulfide resin to prepare a curing composition. The time until the viscosity of this curable composition became twice the initial viscosity at 25 캜 was measured and the storage stability was evaluated. The results are shown in Table 2.

[Comparative Example 5]

3 parts of 1,8-diazabicyclo [5.4.0] -7-undecene and 16 parts of chloroform were mixed with 100 parts of the hydrogenated bisphenol A type episulfide resin to prepare a curing composition. The time until the viscosity of this curable composition became twice the initial viscosity at 25 캜 was measured and the storage stability was evaluated. The results are shown in Table 2.

[Comparative Example 6]

3 parts of 1,5,7-triazabicyclo [4.4.0] deca-5-ene and 16 parts of chloroform were mixed with 100 parts of the hydrogenated bisphenol A type episulfide resin to prepare a curable composition. The storage stability was evaluated by measuring the time until the viscosity of the curable composition became twice the initial viscosity at 25 캜. The results are shown in Table 2.

From the results shown in Table 2, it can be seen that the storage stability of the curable composition using the curing agent for the episulfide compound of the present invention is far superior to that in the case where an alkaline compound generally used as a conventional curing agent is used as a curing agent.

Although the present invention has been described in detail with reference to specific embodiments, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application (Japanese Patent Application No. 2012-159536) filed on July 18, 2012, the content of which is incorporated herein by reference.

The curing agent for an episulfide compound of the present invention is useful as a curing agent in the field of electronic materials in particular because it is excellent in base generation efficiency and does not cause generation of outgas and has excellent storage stability in the case of using a curable composition. In addition, the episulfide compound cured by the curing agent for an episulfide compound of the present invention is useful as an element such as an optical member or an electronic member which is required to have properties such as heat resistance, dimensional stability, Do.

Claims (6)

A curing agent for an episulfide compound, comprising a compound represented by the following general formula (1).
(Formula 1)

In the general formula (1)
X ₁ , X ₂ and X ₃ are each independently any one atom or group selected from the group consisting of a hydrogen atom, an oxygen atom, an alkylene group having 1 to 3 carbon atoms, a sulfur atom, a sulfonyl group, and a silanol group. R 1, R 2, and R 3 are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 3 to 20 carbon atoms, an oxygen atom, a nitrogen atom, A monocyclic, bicyclic or tricyclic heteroaryl group having 3 to 15 carbon atoms including a hetero atom, a monocyclic, a dicyclic or tricyclic cycloalkyl group having 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom A monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including 1 to 5 heteroatoms selected from the group consisting of hydrogen, Two or more groups selected from the group consisting of R 1, R 2, and R 3 may combine to form a cyclic structure, and the cyclic structure may be substituted with one or two or more heteroatoms selected from the group consisting of oxygen atom, nitrogen atom, . However, when X ₁ , X ₂ , and X ₃ are hydrogen atoms or silanol groups, R1, R2, and R3 are not present.
R4, R5, R6, R7, R8 and R9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, A monocyclic, bicyclic or tricyclic heteroaryl group having from 3 to 15 carbon atoms and containing from 1 to 5 hetero atoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, A monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms containing 1 to 5 hetero atoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom, Lt; / RTI > is an atom or group selected from the group consisting of R ₄ and R ₆ or R ₆ and R ₉ may be combined to form an unsaturated bond together with an existing carbon-carbon bond.
R10 represents a carbon number including 1 to 5 hetero atoms selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 3 to 20 carbon atoms, an oxygen atom, A cycloalkyl group having from 3 to 15 carbon atoms, a monocyclic, bicyclic or tricyclic heteroaryl group having from 3 to 15 carbon atoms, a monocyclic, a dicyclic or tricyclic cycloalkyl group having from 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom Is a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including a hetero atom.
B is a base. The method according to claim 1,
R4, R5, R6, R7, R8, and R9 are both hydrogen atoms and R10 is a methyl group. The method according to claim 1 or 2,
A curing agent for an episulfide compound wherein the episulfide compound is an episulfide compound having an episulfide equivalent of 50 to 2,000. A curable composition containing the curing agent for an episulfide compound according to any one of claims 1 to 3 and an episulfide compound. An episulfide compound is a cured product of an episulfide compound which is cured by the curing agent for an episulfide compound according to any one of claims 1 to 3. A method of curing an episulfide compound, wherein the episulfide compound is cured by reacting a compound represented by the following general formula (1).
(Formula 1)

X ₁ , X ₂ and X ₃ are each independently selected from the group consisting of a hydrogen atom, an oxygen atom, an alkylene group having 1 to 3 carbon atoms, a sulfur atom, a sulfonyl group, and a silanol group One atom or group.
R 1, R 2, and R 3 are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 3 to 20 carbon atoms, an oxygen atom, a nitrogen atom, A monocyclic, bicyclic or tricyclic heteroaryl group having 3 to 15 carbon atoms including a hetero atom, a monocyclic, a dicyclic or tricyclic cycloalkyl group having 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom Or a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including 1 to 5 hetero atoms, Two or more groups selected from the group consisting of R 1, R 2, and R 3 may combine to form a cyclic structure, and the cyclic structure may be substituted with one or two or more heteroatoms selected from the group consisting of oxygen atom, nitrogen atom, . However, when X ₁ , X ₂ , and X ₃ are hydrogen atoms or silanol groups, R1, R2, and R3 are not present.
R4, R5, R6, R7, R8 and R9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silanol group, an alkyl group having 1 to 20 carbon atoms, a monocyclic group having 3 to 20 carbon atoms, Or a monocyclic, bicyclic or tricyclic heteroaryl group having 3 to 15 carbon atoms containing 1 to 5 hetero atoms selected from the group consisting of a triple ring aryl group, an oxygen atom, a nitrogen atom and a sulfur atom, , A bicyclic or tricyclic cycloalkyl group, and a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including 1 to 5 hetero atoms selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom Lt; / RTI > is an atom or group selected from the group consisting of R4 and R6 or R6 and R9 may be taken together to form an unsaturated bond together with an existing carbon-carbon bond.
R10 represents a carbon number of 1 to 5 hetero atoms selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a monocyclic, bicyclic or tricyclic aryl group having 3 to 20 carbon atoms, an oxygen atom, a nitrogen atom, A cycloalkyl group having from 3 to 15 carbon atoms, a monocyclic, bicyclic or tricyclic heteroaryl group having from 3 to 15 carbon atoms, a monocyclic, a dicyclic or tricyclic cycloalkyl group having from 3 to 15 carbon atoms, and an oxygen atom, a nitrogen atom and a sulfur atom Is a monocyclic, bicyclic or tricyclic heterocycloalkyl group having 3 to 15 carbon atoms including a hetero atom.
B is a base.