TW201920117A - Composition and cured product - Google Patents

Abstract

The purpose of the present invention is to provide: a composition suitable as a curable composition; and a cured product of said composition, wherein a cured product having excellent curability, exemplified by heat resistance etc., can be obtained from the composition. Provided is a composition containing a compound represented by formula (1). In formula (1), Xm + represents an m-valent counter cation, R1 represents an aromatic group which may have a substituent, R2 represents an alkylene group which may have a substituent, R3 represents a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfonic acid ester group, a phosphino group, a phosphinyl group, a phosphonic acid ester group, or an organic group, m represents an integer of 1 or more, n represents an integer of 0-3, and R2 may combine with R1 to form a ring structure.

Description

Composition and hardened material

The present invention relates to a preferable composition as a curable composition, and a cured product of the above composition.

A hardening composition containing a hardening compound such as an epoxy compound and a hardener or a hardening catalyst is widely used in various applications such as adhesive applications, sealing applications for various electronic parts, and matrix forming applications for fiber-reinforced composite materials. This curable composition is required to further improve the curability (for example, the heat resistance of the obtained cured product) (for example, Patent Document 1).

On the other hand, Patent Document 2 describes an imidazole compound having a specific structure that provides a metal surface treatment liquid excellent in the effect of suppressing migration or oxidation of the wiring surface.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2016-074890
[Patent Document 2] International Publication No. 2016/031928

[Problems to be solved by the invention]

This invention is made in view of the said subject of the prior art, and an object is to provide the composition which is excellent in hardenability exemplified by the heat resistance of the obtained hardened | cured material, and which is preferable as a hardenable composition, and the hardened | cured material of the said composition.
[Technical means to solve the problem]

The present inventors have found that, under the same or different conditions, a novel compound having a plurality of residues in the molecule that promotes the hardening of the composition can improve the heat resistance of the obtained hardened material and the like. Hardenability, thus completing the present invention.

A first aspect of the present invention is a composition including a compound represented by the following formula (1).
[Chemical 1]

(In the formula (1), X ^{m +} represents an m-valent counter cation, R ¹ represents an aromatic group which may have a substituent, R ² represents an alkylene group which may have a substituent, and R ³ represents a halogen atom, a hydroxyl group, a mercapto group, Thio, silane, silanol, nitro, nitroso, sulfonate, phosphine, phosphine, phosphonate, or organic, m is an integer of 1 or more, n is 0 or more and (Integers up to 3, R ² can be bonded to R ¹ to form a ring structure)
A second aspect of the present invention is a hardened material, which is a hardened material of the composition of the first aspect.
[Effect of the invention]

The composition of the present invention is excellent in hardenability as exemplified by the heat resistance of the obtained hardened product, and is preferably a hardenable composition.
According to the present invention, a cured product having excellent heat resistance can be provided.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments, and can be implemented by appropriately adding changes within the scope of the object of the present invention.
In addition, in this specification, "~" means the above to the following, unless otherwise stated.

≪Composition≫
<The compound represented by the following formula (1)>
The composition of a 1st aspect contains the compound represented by following formula (1).
[Chemical 2]

(In the formula (1), X ^{m +} represents an m-valent counter cation, R ¹ represents an aromatic group which may have a substituent, R ² represents an alkylene group which may have a substituent, and R ³ represents a halogen atom, a hydroxyl group, a mercapto group, Thio, silane, silanol, nitro, nitroso, sulfonate, phosphine, phosphine, phosphonate, or organic, m is an integer of 1 or more, n is 0 or more and (Integers up to 3, R ² can be bonded to R ¹ to form a ring structure)

The m-valent counter cation X ^{m + is} preferably an acyclic or cyclic nitrogen-containing aliphatic cation, a nitrogen-containing aromatic cation, or a metal cation. m is preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, and even more preferably 1.
As the cyclic nitrogen-containing aliphatic cation, a hetero atom (for example, an oxygen atom, a sulfur atom, etc.) other than a nitrogen atom may be contained as an atom constituting the ring.
The acyclic or cyclic nitrogen-containing aliphatic cation is preferably represented by any one of the following formulae (2) to (4).
[Chemical 3]

(In the formula (2), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkenyl group which may have a substituent, and an alkyne which may have a substituent. Group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a heterocyclic group which may have a substituent, at least two selected from R ¹¹ to R ¹⁴ may be linked to form a ring)

In the formula (2), the alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms. Specific examples of the alkyl group which may have a substituent include methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, and n-octadecane Isopropyl, isopropyl, isobutyl, second butyl, third butyl, 1-ethylpentyl, trifluoromethyl, 2-ethylhexyl, benzamidinemethyl, 1-naphthylmethyl Methyl, 2-naphthylmethyl, 4-methylthiobenzylmethyl, 4-phenylthiobenzylmethyl, 4-dimethylaminobenzylmethyl, 4- Cyanobenzylmethyl, 4-methylbenzylmethyl, 2-methylbenzylmethyl, 3-fluorobenzylmethyl, 3-trifluoromethylbenzylmethyl, and 3-nitro benzamidine methyl and the like.
The cycloalkyl group which may have a substituent is preferably a cycloalkyl group having 5 to 30 carbon atoms. Specific examples of the cycloalkyl group which may have a substituent include a cyclopentyl group and a cyclohexyl group.

The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms. Specific examples of the alkenyl group which may have a substituent include a vinyl group, an allyl group, and a styryl group.
The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms. Specific examples of the alkynyl group which may have a substituent include an ethynyl group, a propynyl group, and a propargyl group.
The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms. Specific examples of the aryl group which may have a substituent include phenyl, biphenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 9-phenanthryl, 1-fluorenyl, and 5-thick Tetraphenyl, 1-indenyl, 2-fluorenyl, 9-fluorenyl, bitriphenyl, bitetraphenyl, ortho, m- and p-tolyl, xylyl, ortho, m- and p-cumenyl, 2,4,6-trimethylphenyl, benzocyclopentadienyl, binaphthyl, bitrinaphthyl, bitetranaphthyl, cycloheptatrienyl, biphenylene, dicyclopentadiene acene Base, allenyl fluorenyl, fluorenyl, vinyl anthracenyl, propenyl naphthyl, fluorenyl, anthracenyl, bianthryl, bitrianthryl, bitetrathryl, anthraquinone, phenanthryl, diphenylene Phenyl, fluorenyl, Base, fused tetraphenyl, benzyl, fluorenyl, fluorenyl, pentaphenyl, fused pentaphenyl, stretched tetraphenyl, hexaphenyl, fused hexaphenyl, ruthenium, succinyl, stretched trinaphthyl , Heptyl, fused heptyl, fluoranthene, and uranyl.

The aralkyl group which may have a substituent is preferably an aralkyl group having 7 or more and 20 or less carbon atoms. Specific examples of the aralkyl group which may have a substituent include benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, 2-α-naphthylethyl, and 2-β- Naphthylethyl and the like.
The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Specific examples of the aralkyl group which may have a substituent include thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thienyl, furyl, pyranyl, Isobenzofuranyl, benzopiperanyl, Methyl, phenanthryl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyryl, pyrimidinyl, daphyl, indolyl, isoindolyl, 3H-indolyl, indyl Indolyl, 1H-indazolyl, purinyl, 4H-quinyl, isoquinolinyl, quinolinyl, fluorenyl, naphthyridinyl, quinolinolyl, quinazolinyl, fluorinyl, pyridinyl , 4aH-carbazolyl, carbazolyl, β-carolinyl, morphinyl, acridinyl, Pyridinyl, morpholinyl, morphinyl, phenanthrene, isothiazolyl, morphinyl, isoxazolyl, furazinyl, morphinyl, isopropyl base, Base, pyrrolidinyl, pyrrolinyl, imidazolinyl, imidazolinyl, pyrazolidyl, pyrazolinyl, piperidinyl, piperidyl, indololinyl, isoindolinyl, Pyridyl, phosphono, and 9-oxosulfur Base etc.

The alkyl group which may have a substituent, the cycloalkyl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, the aryl group which may have a substituent, and the aralkyl group which may have a substituent Alternatively, a hydrogen atom of a heterocyclic group which may have a substituent may be further substituted with another substituent.

Examples of such a substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a cyano group, a nitro group, an alkoxy group (methoxy, ethoxy, and tertiary butoxy) Groups, etc.), aryloxy groups (phenoxy, p-tolyloxy, etc.), organic oxycarbonyl groups (methoxycarbonyl, butoxycarbonyl, phenoxycarbonyl, vinyloxycarbonyl, and aryloxycarbonyl Etc.), fluorenyl (ethoxy, propionyl, and benzyloxy, etc.), fluorenyl (ethenyl, benzyl, isobutylfluorenyl, propenyl, methacryl) , And methoxysulfamoyl, etc.), alkylthio (methylthio, and third butylthio, etc.), arylthio (phenylthio, and p-tolylthio, etc.), alkyl Methylamino (methylamino, cyclohexylamino, etc.), dialkylamino (dimethylamino, diethylamino, phosphono, piperidinyl, etc.), arylamino (phenylamine Group, p-tolylamino, etc.), alkyl (methyl, ethyl, third butyl, and dodecyl, etc.), aryl (phenyl, p-tolyl, xylyl, cumenyl, Naphthyl, anthracenyl, and phenanthryl, etc.), hydroxyl, carbonyl, sulfonamido, Fluorenyl, mercapto, sulfo, methanesulfonyl, p-toluenesulfonyl, amine, nitroso, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphonic acid subunit, phosphonic acid group , Alkylsulfonyl, arylsulfonyl, trialkylammonium, dimethylsulfonium ion, and triphenylbenzylmethylsulfonium ion.

In formula (2), when at least two members selected from R ¹¹ to R ¹⁴ are linked to form a ring, examples of the linking group include an alkylene group, a cycloalkylene group, or a divalent group formed by linking them. base. The number of carbon atoms in the linking group is preferably 1 or more and 10 or less. A ring formed by at least two members selected from R ¹¹ to R ¹⁴ may contain an oxygen atom as an atom constituting the ring.

(R ²¹ ) ₂ N ⁺ = C (NR ²² ₂ ) ₂ (3)
(In the formula (3), R ²¹ each independently represents a hydrogen atom, an alkyl group, or a cycloalkyl group, and R ²² each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, and -C (= NR ²³ ) -NR ²³ ₂ (3 R ²³ are each independently a hydrogen atom, an alkyl group or a cycloalkyl group), or = C (-NR ²⁴ ₂ ) ₂ (4 R ²⁴ are each independently a hydrogen atom or an organic group))

The alkyl group for R ²¹ to R ²³ is preferably an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, and second butyl. Base, third butyl, and 1-ethylpentyl.
The cycloalkyl group as R ²¹ to R ²³ is preferably a cycloalkyl group having 5 or more and 30 or less carbon atoms. Specific examples of cycloalkyl include cyclopentyl and cyclohexyl.
Examples of the organic group related to R ²⁴ include an alkyl group, a cycloalkyl group, an aralkyl group, and an aryl group.
Examples of the cation represented by the formula (3) include 1,2-diisopropyl-3- [bis (dimethylamino) methylene] phosphonium cation, 1-methylbisphosphonium cation, and 1-n Butylbisfluorene cation, 1- (2-ethylhexyl) bisfluorene cation, 1-n-octadecylbisfluorene cation, 1,1-dimethylbisfluorene cation, 1,1-diethylbisfluorene Cation, 1-cyclohexylbisphosphonium cation, 2-ethyl-1,1,3,3-tetramethylphosphonium cation, 1-benzylphosphonium cation, 1,3-dibenzylphosphonium cation, 1-benzyl -2,3-dimethylphosphonium cation, and 1-phenylphosphonium cation. Among these cations, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] fluorene cation is preferred.

[Chemical 4]

(In formula (4), R ³¹ independently represents a hydrogen atom or an organic group, and s represents an integer of 2 or more and 6 or less)
Examples of the organic group related to R ³¹ include an alkyl group, a cycloalkyl group, an aralkyl group, and an aryl group. The alkyl group, the cycloalkyl group, the aralkyl group, and the aryl group may each have a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a cyano group, a nitro group, an alkoxy group (a methoxy group, an ethoxy group, and a third butoxy group). Etc.), aryloxy (phenoxy, p-tolyloxy, etc.), organic oxycarbonyl (methoxycarbonyl, butoxycarbonyl, phenoxycarbonyl, vinyloxycarbonyl, and aryloxycarbonyl, etc.) ), Fluorenyl (ethenyl, propionyl, and benzyloxy, etc.), fluorenyl (ethenyl, benzyl, isobutylfluorenyl, acrylfluorenyl, methacrylfluorenyl, And methoxythiomethyl, etc.), alkylthio (methylthio, and third butylthio, etc.), arylthio (phenylthio, and p-tolylthio, etc.), alkyl Amine group (methylamino group, and cyclohexylamino group, etc.), dialkylamino group (dimethylamino group, diethylamino group, phosphono group, piperidinyl group, etc.), arylamino group (phenylamino group , And p-tolylamino, etc.), alkyl (methyl, ethyl, third butyl, and dodecyl, etc.), aryl (phenyl, p-tolyl, xylyl, cumenyl, Naphthyl, anthracenyl, and phenanthryl, etc.), hydroxyl, carbonyl, sulfonamido, Fluorenyl, mercapto, sulfo, methanesulfonyl, p-toluenesulfonyl, amine, nitroso, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphonic acid subunit, phosphonic acid group , Alkylsulfonyl, arylsulfonyl, trialkylammonium, dimethylsulfonium ion, and triphenylbenzylmethylsulfonium ion.
s is preferably an integer of 3 or more and 5 or less, and more preferably 3 or 4.

The nitrogen-containing aromatic cation related to the counter cation X ^{m +} is preferably a cation represented by any one of the following formulae (5) to (13).
[Chemical 5]

(Wherein R ^H and R each independently represent a hydrogen atom or an alkyl group,
R ⁴¹ , R ⁴³ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁵⁰ , R ^51, and R ⁵² each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an olefin Or alkynyl,
R ⁴² , R ⁴⁴ and R ⁴⁹ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group, and R ⁴¹ to R ⁵² may be independently substituted with a halogen atom, a cyano group or a nitro group ,
R ⁴¹ and R ⁴² may be bonded to each other to form a ring, at least two R ⁴¹ may be bonded to each other to form a ring, R ⁴³ and R ⁴⁴ may be bonded to each other to form a ring, and two R ⁴³ may be bonded to each other to form a ring , At least 2 R ⁴⁵ may be bonded to each other to form a ring, at least 2 R ⁴⁶ may be bonded to each other to form a ring, at least 2 R ⁴⁷ may be bonded to each other to form a ring, R ⁴⁸ and R ⁴⁹ may be bonded to each other and Form a ring, at least two R ⁴⁸ may be bonded to each other to form a ring, at least two R ⁵⁰ may be bonded to each other to form a ring, at least two R ⁵¹ may be bonded to each other to form a ring, and at least two R ⁵² may be bonded to each other To form a ring)

Examples of the halogen atom for R ⁴¹ to R ⁵² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The alkyl group related to R ^H and R ⁴¹ to R ⁵² may be a linear alkyl group or a branched alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.
Specific examples of the alkyl group for R ^H and R ⁴¹ to R ⁵² include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, and third Butyl, n-pentyl, isopentyl, third pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl-n-hexyl, n-nonyl, n-decyl, n-undecyl, n-decyl Dialkyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl alkyl.

The cycloalkyl group for R ⁴¹ to R ⁵² is preferably a cycloalkyl group having 5 to 30 carbon atoms. Specific examples of cycloalkyl include cyclopentyl and cyclohexyl.
The alkenyl group for R ⁴¹ to R ⁵² is preferably an alkenyl group having 2 or more and 10 or less carbon atoms. Specific examples of the alkenyl group include a vinyl group, an allyl group, and a styryl group.
The alkynyl group for R ⁴¹ to R ⁵² is preferably an alkynyl group having 2 or more and 10 or less carbon atoms. Specific examples of the alkynyl group include ethynyl, propynyl, and propargyl.

In the case where m is an integer of 2 or more, the acyclic or cyclic nitrogen-containing aliphatic cation concerning the counter cation X ^{m + with} respect to the valence of ^{m is} preferably any one of the following formulae (14) to (16) The cation represented.
[Chemical 6]

(In the above formula, each of R ^H independently represents a hydrogen atom or an alkyl group, R ⁵³ and R ⁵⁵ each independently represent an alkyl group or a cycloalkyl group, and R ⁵⁴ represents an alkylene group, a cycloalkylene group, or a combination thereof. Into a divalent group, R ⁵⁶ represents an alkylene group, and R ⁵³ to R ⁵⁶ may be independently substituted with a halogen atom, a cyano group, or a nitro group. At least two R ⁵³ may be bonded to each other to form a ring. R ⁵³ and R ⁵⁴ can be bonded to each other to form a ring, 2 R ⁵⁵ can be bonded to each other to form a ring)
Specific examples and preferred examples of R ^H include the same as the specific examples and preferred examples described above.
Examples of the alkyl group related to R ^H and R ⁵³ to R ⁵⁵ include the same groups as the specific examples and preferred examples described above as the alkyl group related to R ^H and R ⁴¹ to R ⁵² .
Examples of the cycloalkyl group for R ⁵³ to R ⁵⁵ include the same groups as the specific examples and preferred examples described above as the cycloalkyl group for R ⁴¹ to R ⁵² .
Examples of the alkylene group for R ⁵⁶ include alkylene groups having 1 to 5 carbon atoms, and examples include methylene, ethylidene, propylidene, and butylyl.

In the case where m is an integer of 2 or more, examples of the nitrogen-containing aromatic cation related to the counter cation X ^{m +} of the valence of ^m include a 2,2-bipyridinium skeleton and a 3,3-bipyridinium skeleton in the molecule. , 4,4-bipyridinium skeleton, 2,2-bipyridinium skeleton, 4,4-biquinolinium skeleton, 4,4-biisoquinolinium skeleton, 4- [2- (4-pyridinium ) Vinyl] pyridinium skeleton or 4- [4- (4-pyridinyl) phenyl] pyridinium skeleton having more than two valent cations.

As the metal cation related to the counter cation X ^{m +} , a cation of a metal atom selected from the group consisting of a typical metal element, a transition metal element, and a semi-metal element, or a cation including an atomic group of the above metal atom is preferred.
Examples of the above-mentioned typical metal elements include alkali metal elements (metal elements including elements other than hydrogen in group 1 of the periodic table, such as sodium and potassium), alkaline earth metal elements (metal elements including elements of group 2 of the periodic table, such as Magnesium), metal elements including elements of Group 12 of the periodic table (e.g. zinc), metal elements including elements of Group 13 of the periodic table other than boron (e.g. aluminum), elements including elements other than carbon and silicon of the Periodic Table 14 Metal elements (e.g., tin), metal elements (e.g., antimony) containing elements other than nitrogen, phosphorus, and arsenic in Group 15 of the periodic table; Elemental metal elements (such as rhenium).
Examples of the transition metal element include metal elements (for example, rhenium) containing elements of Groups 3 to 11 of the periodic table.
Examples of the semi-metal element include boron, silicon, arsenic, selenium, and tellurium.
Examples of the cation containing an atomic group of the metal atom include an atomic group containing both a metal atom and a non-metal atom, and specific examples include [ZrO] ²⁺ , [(C ₂ H ₅ O) Al] ²⁺ , And [(nC ₄ H ₉ ) ₂ Sn-O-Sn (nC ₄ H ₉ ) ₂ ] ²⁺ and the like.

In the formula (1), R ¹ represents an aromatic group which may have a substituent. The aromatic group which may have a substituent may be an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent.

The type of the aromatic hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. The aromatic hydrocarbon group may be a monocyclic aromatic group, may be formed by condensing two or more aromatic hydrocarbon groups, or may be formed by bonding two or more aromatic hydrocarbon groups through a single bond. As an aromatic hydrocarbon group, a phenyl group, a naphthyl group, a biphenyl group, an anthracenyl group, and a phenanthryl group are preferable.

The type of the aromatic heterocyclic group is not particularly limited as long as the object of the present invention is not impaired. The aromatic heterocyclic group may be a monocyclic group or a polycyclic group. The aromatic heterocyclic group is preferably pyridyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, benzoxazolyl, benzo Thiazolyl and benzimidazolyl.

Examples of the substituent which the phenyl, polycyclic aromatic hydrocarbon group, or aromatic heterocyclic group may have include a halogen atom, a hydroxyl group, a mercapto group, a thio group, a silane group, a silanol group, a nitro group, a nitroso group, and a Sulfonic acid group, sulfonic acid group, sulfonic acid ester group, phosphine group, phosphine group, phosphonic acid group, phosphonate group, amine group, ammonium group, and organic group. When a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.

When the substituent of the aromatic group is an organic group, examples of the organic group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be any of linear, branched, and cyclic. The organic group is usually monovalent, but may form a bivalent or higher organic group when a cyclic structure is formed.

When the aromatic group has a substituent on an adjacent carbon atom, the two substituents bonded to the adjacent carbon atom may also be bonded to form a cyclic structure. Examples of the cyclic structure include an aliphatic hydrocarbon ring or an aliphatic ring containing a hetero atom.

When the substituent of the aromatic group is an organic group, the bond contained in the organic group is not particularly limited as long as the effect of the present invention is not impaired, and the organic group may include an oxygen atom, a nitrogen atom, and a silicon atom And other heteroatomic bonds. Specific examples of the bond containing a hetero atom include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, a amide bond, and an amine bond (-NR ^A- : R ^A represents a hydrogen atom or a Valent organic group) carbamate bond, imide bond (-N = C (-R ^B )-, -C (= NR ^B )-: R ^B represents a hydrogen atom or a monovalent organic group), Carbonate bond, sulfonyl bond, sulfinyl bond, and azo bond.

As a bond containing a hetero atom that an organic group may have, from the viewpoint of the heat resistance of the imidazole compound represented by formula (1), an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond,醯 Amine bond, amine bond (-NR ^A- : R ^A represents a hydrogen atom or a monovalent organic group) carbamate bond, imine bond (-N = C (-R ^B )-, -C (= NR ^B )-: R ^B represents a hydrogen atom or a monovalent organic group), a carbonate bond, a sulfonyl bond, and a sulfinyl bond.

When the organic group is a substituent other than a hydrocarbon group, the kind of the substituent other than the hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired. Specific examples of the substituent other than the hydrocarbon group include a halogen atom, a hydroxyl group, a mercapto group, a thio group, a cyano group, an isocyano group, a cyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, Silyl, silanol, alkoxy, alkoxycarbonyl, amine, monoalkylamine, dialkylaluminum, monoarylamine, diarylamine, carbamoyl, thiamine Formamidine, nitro, nitroso, carboxylate, fluorenyl, fluorenyl, sulfinate, sulfonate, phosphine, phosphinyl, phosphonate, alkyl ether, Alkenyl ether group, alkyl sulfide group, alkenyl sulfide group, aryl ether group, and aryl sulfide group. The hydrogen atom contained in the substituent may be substituted with a hydrocarbon group. The hydrocarbon group contained in the substituent may be any of linear, branched, and cyclic.

As a substituent of a phenyl group, a polycyclic aromatic hydrocarbon group, or an aromatic heterocyclic group, an alkyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and carbon are preferable. An alkoxy group having 1 or more and 12 or less, an aryloxy group having 1 or more and 12 or less carbon atoms, an arylamino group having 1 or more and 12 or less carbon atoms, and a halogen atom.

As R ¹ , a compound represented by formula (1) can be synthesized inexpensively and easily, and the above compound has good solubility in water or an organic solvent, and phenyl and furan which may each have a substituent are preferred. And thienyl.

In the formula (1), R ² is an alkylene group which may have a substituent. The substitution which the alkylene group may have is not specifically limited within the range which does not impair the objective of this invention. Specific examples of the substituent which the alkylene group may have include a hydroxyl group, an alkoxy group, an amine group, a cyano group, and a halogen atom. The alkylene group may be a linear alkylene group or a branched alkylene group, and is preferably a linear alkylene group. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 or more and 20 or less, preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less. The number of carbon atoms of the alkylene group does not include carbon atoms of a substituent bonded to the alkylene group.

The alkoxy group as a substituent bonded to the alkylene group may be a linear alkoxy group or a branched alkoxy group. The number of carbon atoms of the alkoxy group as a substituent is not particularly limited, but is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and even more preferably 1 or more and 3 or less.

The amine group as a substituent bonded to the alkylene group may be a monoalkylamine group or a dialkylamine group. The alkyl group contained in the monoalkylamino group or the dialkylamino group may be a linear alkyl group or a branched alkyl group. The number of carbon atoms of the alkyl group contained in the monoalkylamino group or the dialkylamino group is not particularly limited, but is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, particularly preferably 1 or more and 3 or less.

Specific examples of preferred alkylene groups for R ² include methylene, ethane-1,2-diyl, n-propane-1,3-diyl, n-propane-2,2-diyl, and n-butyl. Alkane-1,4-diyl, n-pentane-1,5-diyl, n-hexane-1,6-diyl, n-heptane-1,7-diyl, n-octane-1,8-di Base, n-nonane-1,9-diyl, n-decane-1,10-diyl, n-undecane-1,11-diyl, n-dodecane-1,12-diyl, n-deca Triane-1,13-diyl, n-tetradecane-1,14-diyl, n-pentadecan-1,15-diyl, n-hexadecane-1,16-diyl, n-heptadecane -1,17-diyl, n-octadecane-1,18-diyl, n-nonadecane-1,19-diyl, and n-icosane-1,20-diyl.

R ³ is a halogen atom, a hydroxyl group, a mercapto group, a thio group, a silane group, a silanol group, a nitro group, a nitroso group, a sulfonate group, a phosphine group, an phosphine group, a phosphonate group, or an organic group, and n is An integer from 0 to 3. When n is an integer of 2 or more and 3 or less, a plurality of R ³ may be the same or different.

When R ³ is an organic group, the organic group is the same as the organic group which the aromatic group may have as a substituent with respect to R ¹ .

When R ³ is an organic group, the organic group is preferably an alkyl group, an aromatic hydrocarbon group, and an aromatic heterocyclic group. The alkyl group is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. The aromatic hydrocarbon group is preferably a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, and a phenanthryl group, more preferably a phenyl group and a naphthyl group, and particularly preferably a phenyl group. The aromatic heterocyclic group is preferably pyridyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, benzoxazolyl, benzo Thiazolyl and benzimidazolyl are more preferably furanyl and thienyl.

In the case where R ³ is an alkyl group, the bonding position of the alkyl group on the imidazole ring is preferably any of the 2-, 4-, and 5-positions, and more preferably the 2-position. In the case where R ³ is an aromatic hydrocarbon group and an aromatic heterocyclic group, the bonding position based on these imidazoles is preferably the 2-position.

Among the compounds represented by the formula (1), the compounds represented by the following formula (1-1) are preferred because they can be synthesized inexpensively and easily and have excellent solubility in water or organic solvents. And more preferably a compound represented by the formula (1-1) and R ² is a methylene group.

[Chemical 7]

(In formula (1-1), X, R ² , R ³ , m, and n have the same meanings as in formula (1), and R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are each independently a hydrogen atom and a halogen atom. , Hydroxyl, mercapto, thio, silyl, silanol, nitro, nitroso, sulfinyl, sulfo, sulfonate, phosphine, phosphinyl, phosphonic, phosphonate , Amine, ammonium, or organic groups, but at least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ is a group other than a hydrogen atom; R ⁴ , R ⁵ , R ⁶ , R ⁷ and at least two of R ⁸ can be bonded to form a cyclic structure; R ² can be bonded to R ⁶ to form a cyclic structure)

When R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are organic groups, the organic group is the same as the organic group which R ¹ in the formula (1) has as a substituent. In terms of the solubility of the above-mentioned compound in a solvent, R ⁴ , R ⁵ , R ⁶ , and R ^{7 are} preferably a hydrogen atom.

Among them, it is preferred that at least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ is the following substituent, and it is particularly preferred that R ⁸ is the following substituent. When R ⁸ is a substituent described below, R ⁴ , R ⁵ , R ⁶ , and R ^{7 are} preferably a hydrogen atom.
-OR ⁹
(R ⁹ is a hydrogen atom or an organic group)

When R ⁹ is an organic group, the organic group is the same as the organic group as a substituent that R ¹ in Formula (1) has. R ^{9 is} preferably an alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

Among the compounds represented by the formula (1-1), preferred are compounds represented by the following formula (1-1-1).
[Chemical 8]

(In formula (1-1-1), X, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ , m and n are divided by R ⁴ , R ⁵ , R ⁶ , R ⁷ , and (At least one of R ⁸ is other than a hydrogen atom, and has the same meaning as formula (1))

In the compound represented by the formula (1-1-1), it is preferred that at least one of R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ is a base represented by the above-OR ⁹ , and it is particularly preferred. R ⁸ is a base represented by -OR ⁹ . When R ⁸ is a base represented by -OR ⁹ , R ⁴ , R ⁵ , R ⁶ , and R ^{7 are} preferably a hydrogen atom.

Preferred specific examples of the compound represented by the formula (1) include the following compounds.
[Chemical 9]

[Chemical 10]

[Chemical 11]

(content)
The content of the compound represented by the formula (1) in the composition is not particularly limited. The content of the compound represented by the above formula (1) in the above composition is preferably 1% by mass or more and 80% by mass or less, more preferably 2% by mass or more and 40% by mass with respect to the entire composition (excluding the solvent). % Or less, more preferably 3% by mass or more and 30% by mass or less, and particularly preferably 3% by mass or more and 15% by mass or less.

(Production method of the compound represented by the formula (1))
The method for producing the compound represented by the formula (1) is not particularly limited. For example, the compound represented by the following formula (10) and a salt capable of forming an m-valent counter cation X ^{m +} can be formed on the basis of a solvent. The neutralization reaction is performed in the absence or presence of the compound to produce the compound represented by the formula (1).
[Chemical 12]

(In formula (10), R ¹ , R ² , R ³ and n have the same meanings as in formula (1), and specific examples and preferred examples are also the same.)

The salt group capable of forming an m-valent counter cation X ^{m +} is preferably an acyclic or cyclic nitrogen-containing aliphatic compound, a nitrogen-containing aromatic compound, or a metal atom or an atomic group containing the above metal atom.
The salt group capable of forming an m-valent counter cation X ^{m +} is more preferably a non-cyclic or cyclic nitrogen-containing aliphatic cation represented by any one of the above formulae (2) to (4), the above formula The nitrogen-containing aromatic cation represented by any one of (5) to (13), the nitrogen-containing aliphatic cation represented by any one of the above formulae (14) to (16), or selected from a typical metal element and a transition A cation of a metal atom in a group consisting of a metal element and a semi-metal element or a salt group of a cation including an atomic group of the above metal atom.

Examples of a method for neutralizing the compound represented by the above formula (10) with the above salt in a solvent include heating or non-heating, for example, a compound represented by the above formula (10) and a polar solvent in a polar solvent. The method of mixing the above-mentioned bases.
Examples of the polar solvent include alcohols, and specific examples include methanol, ethanol, propanol, isopropanol, butanol, and tertiary butanol.
The compound represented by the formula (10) and the salt group may be dissolved in the solvent and mixed under heating. The heating temperature is, for example, 40 ° C or higher, preferably 50 ° C or higher, and more preferably 55 ° C or higher. The upper limit of the temperature during heating is not particularly limited, but it is preferably below the boiling point of the solvent.
Without heating, the compound represented by the above formula (10) or the above-mentioned base may be difficult to dissolve in a solvent. In this case, as the salt formation proceeds, the amount of insoluble matter in the reaction solution can be reduced.

The method for neutralizing the compound represented by the formula (10) and the salt based on the absence of a solvent is not particularly limited as long as it is a method for bringing the compound represented by the formula (10) into contact with the base. . As a specific method, for example, a method of mixing the compound represented by the above formula (10) as an individual with the individual or liquid as a base at a normal temperature using a mortar or the like can be mentioned.

The ratio (molar ratio) of the compound represented by the formula (10) to the base is not particularly limited. When the mole number of the compound represented by the formula (10) is M1, m is provided. When the molar number of the above-mentioned base of the valence counter cation X ^{m +} is set to M2, the value of M1 / (M2 / m) is preferably 20/80 to 80/20, and more preferably 30/70 to 70/30.

In addition, salt exchange can also be performed by mixing a compound represented by the above formula (1) in which X ^{m +} is a sodium cation and a potassium cation, and a salt group that can form an m-valent counter cation X ^{m +} other than sodium and potassium cations. Thus, a compound represented by the above formula (1) in which X ^{m +} is a sodium cation and a potassium cation is produced.

<Hardening compound>
The composition of the first aspect preferably contains a curable compound.
The hardening compound is not particularly limited as long as it can be stably present in the composition before performing a hardening operation such as heating or exposure, and various hardening compounds known before can be used.

The hardening compound is preferably selected from a group having an ethylene oxide ring or an oxetane ring in terms of providing a hardened product having excellent stability or hardening reactivity and good heat resistance. At least one compound in the group consisting of a compound and a vinyl ether compound is more preferably a compound having an ethylene oxide ring or an oxetane ring.
Among the compounds having an ethylene oxide ring or oxetane ring, a compound having an ethylene oxide ring is preferable in terms of being inexpensive and easily available, or in terms of more excellent curing reactivity, that is, A compound having an epoxy group (hereinafter, also simply referred to as "epoxy compound").

The epoxy compound is not particularly limited as long as it has an epoxy group. The epoxy compound may be selected from various compounds having epoxy groups previously formulated in the curable composition. The compound having an epoxy group may be a low-molecular compound having an epoxy group as a non-polymer, or may be a polymer having an epoxy group. In the following, the epoxy compound is described in order of a non-polymer having an epoxy group and a polymer having an epoxy group.

(Non-polymer with epoxy group)
As the non-polymer having an epoxy group, it can be appropriately selected from various polymerized epoxy compounds previously formulated in a curable composition. Preferred examples of the epoxy compound include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AD epoxy resin, naphthalene epoxy resin, And bifunctional epoxy resins such as biphenyl epoxy resins; glycidyl ester epoxy resins such as dimer acid glycidyl esters and triglycidyl esters; tetraglycidylamino diphenylmethane, triglycidyl Glycidylamine-type epoxy resins such as p-aminophenol, tetraglycidyl metaxylylenediamine, and tetraglycidylbisaminomethylcyclohexane; heterocyclic epoxy such as triglycidyl isocyanurate Resin; Resorcinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, trihydroxyphenylmethane triglycidyl ether, glycerol triglycidyl ether, 2- [4- (2,3-epoxypropylene Oxy) phenyl] -2- [4- [1,1-bis [4- (2,3-glycidoxy) phenyl] ethyl] phenyl] propane, and 1,3-bis [ 4- [1- [4- (2,3-glycidoxy) phenyl] -1- [4- [1- [4- (2,3-glycidoxy) phenyl] -1 -Methylethyl] phenyl] ethyl] phenoxy] -2-propanol and other trifunctional epoxy resins; tetrahydroxyphenylethane tetraglycidyl Ethers, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, tetraglycidyl biphenyl and tetrafunctional type epoxy resins and the like.

In the case where the composition of the first aspect is a curable composition, the cured product formed by using the curable composition is also preferably an aliphatic ring containing no aromatic group in terms of excellent mechanical properties. Oxygen compound. Among the aliphatic epoxy compounds, an aliphatic epoxy compound having an alicyclic epoxy group is preferred in terms of providing a cured product excellent in transparency and hardness.
Specific examples of the aliphatic epoxy compound having an alicyclic epoxy group include 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane. -Methyl-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3 ', 4'-Epoxy-6'-methylcyclohexanecarboxylic acid 3,4-epoxy-6-methylcyclohexyl ester, ε-caprolactone modified 3', 4'-cyclo Oxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester, trimethylcaprolactone modified 3 ', 4'-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester, β -Methyl-δ-valerolactone modified 3 ', 4'-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester, methylenebis (3,4-epoxycyclohexane) , Ethylene glycol bis (3,4-epoxycyclohexylmethyl) ether, ethylene glycol bis (3,4-epoxycyclohexanecarboxylate), epoxycyclohexahydrophthalate dioctyl Ester, and epoxy-2-hexaethyl phthalate di-2-ethylhexyl ester, epoxy resin having a triepoxycyclodecyl group, or compounds represented by the following formulae (A1) to (A5). Among specific examples of these alicyclic epoxy compounds, in terms of providing a hardened material having excellent transparency and high hardness, the alicyclic ring represented by the following formulae (A1) to (A4) is preferred. The oxygen compound is more preferably an alicyclic epoxy compound represented by the following formulae (A1) to (A2). These alicyclic epoxy compounds may be used alone or as a mixture of two or more kinds.

[Chemical 13]

(In the formula (A1), Z is selected from the group consisting of a single bond, -O -, - O-CO -, - S -, - SO -, - SO 2-, -CH 2 -, - C (CH 3) 2 - , -CBr _2- , -C (CBr ₃ ) _2- , -C (CF ₃ ) _2- , and -R ^a19 -O-CO-, the divalent group, R ^a19 is 1 carbon atom For alkylene groups above and below 8, R ^a1 to R ^a18 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group)

[Chemical 14]

(In the formula (A2), R ^a1 to R ^a18 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group; R ^a2 and R ^a10 may be bonded to each other; R ^a13 and R ^a16 may be Bond to each other to form a ring; m ^a1 is 0 or 1)

The alicyclic epoxy compound represented by the formula (A2) is preferably a compound represented by the following formula (A2-1), which corresponds to a compound in which m ^a1 is 0 in the formula (A2).
[Chemical 15]

(In the formula (A2-1), R ^c1 to R ^c12 are a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group; R ^a2 and R ^a10 may be bonded to each other to form a ring)

[Chemical 16]

(In the formula (A3), R ^a1 to R ^a10 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group; R ^a2 and R ^a8 may be bonded to each other)

[Chemical 17]

(In the formula (A4), R ^a1 to R ^a12 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group; R ^a2 and R ^a10 may be bonded to each other)

[Chemical 18]

(In the formula (A5), R ^a1 to R ^a12 are each independently a group selected from the group consisting of a hydrogen atom, a halogen atom, and an organic group)

In the formula (A1), R ^a19 is an alkylene group having 1 to 8 carbon atoms, and is preferably a methylene group or an ethylene group.

In the formulae (A1) to (A5), when R ^a1 to R ^a18 are organic groups, the organic group is not particularly limited within a range that does not impair the object of the present invention, and may be a hydrocarbon group or a carbon atom and a halogen atom. The formed base may also be a base containing a hetero atom such as a carbon atom and a hydrogen atom and a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom.

The organic group is preferably a hydrocarbon group, a group composed of a carbon atom, a hydrogen atom, and an oxygen atom, a halogenated hydrocarbon group, a group composed of a carbon atom, an oxygen atom, and a halogen atom, and a carbon atom, a hydrogen atom, and an oxygen atom. And halogen atoms. When the organic group is a hydrocarbon group, the hydrocarbon group may be an aromatic hydrocarbon group, an aliphatic hydrocarbon group, or a group including an aromatic skeleton and an aliphatic skeleton. The number of carbon atoms of the organic group is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and even more preferably 1 or more and 5 or less.

Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-pentyl, n-hexyl, and n-heptyl , N-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, Chain alkyl groups such as n-heptadecyl, n-octadecyl, n-decadecyl, and n-icosyl; vinyl, 1-propenyl, 2-n-propenyl (allyl), 1 -Alkenyl groups such as n-butenyl, 2-n-butenyl, and 3-n-butenyl; cycloalkyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl; Phenyl, o-tolyl, m-tolyl, p-tolyl, α-naphthyl, β-naphthyl, biphenyl-4-yl, biphenyl-3-yl, biphenyl-2-yl, anthracene Aryl groups such as phenyl and phenanthryl; aralkyl groups such as benzyl, phenethyl, α-naphthylmethyl, β-naphthylmethyl, α-naphthylethyl, and β-naphthylethyl.

Specific examples of the halogenated hydrocarbon group are: chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl, and perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl And halogenated chain alkyl groups such as perfluorodecyl; 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,4-dichlorocyclohexyl, 2-bromocyclohexyl, 3-bromocyclo Hexyl and 4-bromocyclohexyl and other halogenated cycloalkyl groups; 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2-bromophenyl, 3-bromophenyl, 4- Halogenated aryl groups such as bromophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl; 2-chlorophenylmethyl, 3-chlorophenylmethyl, 4-chlorophenylmethyl, Halogenated aromatic compounds such as 2-bromophenylmethyl, 3-bromophenylmethyl, 4-bromophenylmethyl, 2-fluorophenylmethyl, 3-fluorophenylmethyl, 4-fluorophenylmethyl alkyl.

Specific examples of the group consisting of a carbon atom, a hydrogen atom, and an oxygen atom are: hydroxy chain alkyl groups such as methylol, 2-hydroxyethyl, 3-hydroxyn-propyl, and 4-hydroxyn-butyl; Hydroxycycloalkyl such as 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, and 4-hydroxycyclohexyl; 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2,3-dihydroxyphenyl Hydroxyaryl groups such as 2,4-dihydroxyphenyl, 2,5-dihydroxyphenyl, 2,6-dihydroxyphenyl, 3,4-dihydroxyphenyl, and 3,5-dihydroxyphenyl ; Hydroxyaralkyl groups such as 2-hydroxyphenylmethyl, 3-hydroxyphenylmethyl, and 4-hydroxyphenylmethyl; methoxy, ethoxy, n-propoxy, isopropoxy, n- Butoxy, isobutoxy, second butoxy, third butoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyl Oxy, n-decoxy, n-undecyloxy, n-tridecyloxy, n-tetradecyloxy, n-pentadecyloxy, n-hexadecyloxy, n-heptadecanyloxy, Chain alkoxy groups such as n-octadecyloxy, n-nonadecanyloxy, and n-icocosyloxy; vinyloxy, 1-propylene Chain alkenyloxy groups such as oxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, 2-n-butenyloxy, and 3-n-butenyloxy; phenoxy , O-tolyloxy, m-tolyloxy, p-tolyloxy, α-naphthyloxy, β-naphthyloxy, biphenyl-4-yloxy, biphenyl-3-yloxy, biphenyl Aryloxy groups such as 2-yloxy, anthracenyloxy, and phenanthryloxy; benzyloxy, phenethyloxy, α-naphthylmethoxy, β-naphthylmethoxy, α-naphthyl Aryloxy groups such as ethoxy and β-naphthylethoxy; methoxymethyl, ethoxymethyl, n-propoxymethyl, 2-methoxyethyl, 2-ethoxy Ethyl, 2-n-propoxyethyl, 3-methoxy-n-propyl, 3-ethoxy-n-propyl, 3-n-propoxy-n-propyl, 4-methoxy-n-butyl, 4 -Alkoxyalkyl groups such as ethoxy n-butyl and 4-n-propoxy n-butyl; methoxymethoxy, ethoxymethoxy, n-propoxymethoxy, 2-methyl Ethoxyethoxy, 2-ethoxyethoxy, 2-n-propoxyethoxy, 3-methoxy-n-propoxy, 3-ethoxy-n-propoxy, 3-n-propoxy N-propoxy, 4-methoxy-n-butoxy, 4-ethoxy Alkoxy alkoxy such as n-butoxy and 4-n-propoxy n-butoxy; alkane such as 2-methoxyphenyl, 3-methoxyphenyl, and 4-methoxyphenyl Oxyaryl groups; alkoxyaryloxy groups such as 2-methoxyphenoxy, 3-methoxyphenoxy, and 4-methoxyphenoxy; formamyl, ethenyl, and propionyl Aliphatic fluorenyl groups such as methyl, butylfluorenyl, pentamyl, hexyl, heptyl, octyl, nonyl, and decyl; benzyl, α-naphthyl, and β-naphthyl Aromatic fluorenyl groups such as methoxy; methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-pentoxycarbonyl, n-hexylcarbonyl, n-heptyloxycarbonyl, n-octyloxycarbonyl Chain alkoxycarbonyl groups such as n-nonoxycarbonyl and n-decoxycarbonyl; aryloxycarbonyl groups such as phenoxycarbonyl, α-naphthyloxycarbonyl, and β-naphthyloxycarbonyl; methylamino Aliphatic fluorene such as ethoxyl, propylpyroxy, butylpyroxy, pentylpyroxy, hexamethylpyroxy, heptyloxy, octyloxy, nonyloxy, and decyloxy Oxybenzyloxy, α-naphthylmethyloxy, and β-naphthylmethyloxy An aromatic acyl group.

R ^a1 to R ^a18 are each independently preferably a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. In particular, in terms of excellent mechanical properties, it is more preferable that the hardened material obtained by using the composition is R ^a1 to R ^a18 each being a hydrogen atom.

Formula (A2) ~ (A5), the same as R ^a1 ~ R ^a18 of the formula ^{(A1) R a1 ~ R a18} . The cases where R ^a2 and R ^a10 are bonded to each other in Formula (A2) and (A4), the cases where R ^a13 and R ^a16 are bonded to each other in Formula (A2), and R ^a2 and R ^a2 and Examples of the divalent group formed when R ^{a8 is} bonded to each other include -CH ₂ -and -C (CH ₃ ) _2- .

Specific examples of preferred compounds among the alicyclic epoxy compounds represented by the formula (A1) include the following formulae (A1-a), (A1-b), and (A1-b) Alicyclic epoxy compounds, or 2,2-bis (3,4-epoxycyclohexane-1-yl) propane [= 2,2-bis (3,4-epoxycyclohexyl) propane], etc. .
[Chemical 19]

Specific examples of preferred compounds among the alicyclic epoxy compounds represented by the formula (A2) include alicyclic epoxy compounds represented by the following formula (A2-a) and (A2-b) .
[Chemical 20]

Specific examples of the preferable compound among the alicyclic epoxy compounds represented by the formula (A3) include S-spiro [3-oxatricyclo [3.2.1.0 ^2,4 ] octane-6,2'- Ethylene oxide] and so on.
Specific examples of preferred compounds among the alicyclic epoxy compounds represented by the formula (A4) include 4-vinylcyclohexene dioxide, dipentene dioxide, limonene dioxide, and 1-methyl group. -4- (3-methyloxiran-2-yl) -7-oxabicyclo [4.1.0] heptane and the like.
Specific examples of the preferable compound among the alicyclic epoxy compounds represented by the formula (A5) include 1,2,5,6-diepoxycyclooctane and the like.

(Polymer with epoxy group)
The polymer having an epoxy group may be a polymer obtained by polymerizing a monomer having an epoxy group or a monomer mixture containing a monomer having an epoxy group, or it may be, for example, an epoxy having an epoxy group such as epichlorohydrin. A polymer obtained by introducing an epoxy group into a polymer containing a reactive functional group such as a hydroxyl group, a carbonyl group, or an amine group. Further, a local oxide of a polymer having an unsaturated aliphatic hydrocarbon group in a side chain such as 1,2-polybutadiene can also be favorably used as a polymer having an epoxy group. The local oxide includes an epoxy group generated by oxidation of an unsaturated bond contained in a side chain.

In terms of easy acquisition, preparation, and easy adjustment of the amount of epoxy groups in the polymer, as the polymer having an epoxy group, it is preferable to use a monomer having an epoxy group or a monomer containing an epoxy group. A polymer obtained by polymerizing a monomer mixture of a polymer and a local oxide of a polymer having an unsaturated aliphatic hydrocarbon group in a side chain.

(Polymer having an epoxy group or a polymer containing a monomer mixture of the monomer having an epoxy group)
Among the polymers having an epoxy group, in terms of ease of preparation or coating properties of the curable composition to a substrate, a homopolymer of a (meth) acrylate having an epoxy group, Or copolymers of (meth) acrylates with epoxy groups and other monomers.

The (meth) acrylate having an epoxy group may be a (meth) acrylate having a chain aliphatic epoxy group, or may be a (meth) acrylate having an alicyclic epoxy group as described below. The (meth) acrylate having an epoxy group may contain an aromatic group. In terms of the transparency of the cured product formed using the curable composition, among the (meth) acrylates having an epoxy group, an aliphatic (methyl group) having a chain aliphatic epoxy group is preferred. ) Acrylate or aliphatic (meth) acrylate having an alicyclic epoxy group, more preferably an aliphatic (meth) acrylate having an alicyclic epoxy group.

Examples of the (meth) acrylate containing an aromatic group and having an epoxy group include 4-glycidoxyphenyl (meth) acrylate and 3-glycidoxyphenyl (meth) acrylate , 2-glycidyloxyphenyl (meth) acrylate, 4-glycidyloxyphenyl methyl (meth) acrylate, 3-glycidyloxyphenyl methyl (meth) acrylate, and (formyl) Group) 2-glycidyloxyphenyl methyl acrylate and the like.

Examples of the aliphatic (meth) acrylate having a chain aliphatic epoxy group include an alkylene oxide (meth) acrylate and an alkylene oxide alkyl (meth) acrylate. The (meth) acrylic acid ester in which the oxy group (-O-) in the ester group (-O-CO-) is bonded to a chain aliphatic epoxy group. The (chain) aliphatic epoxy group which this (meth) acrylic acid ester has may contain one or several oxygen group (-O-) in a chain. The number of carbon atoms of the chain aliphatic epoxy group is not particularly limited, but is preferably 3 or more and 20 or less, more preferably 3 or more and 15 or less, and even more preferably 3 or more and 10 or less.

Specific examples of the aliphatic (meth) acrylate having a chain aliphatic epoxy group include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and (methyl) ) Epoxy alkyl (meth) acrylates such as 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl (meth) acrylate; 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxy-n-propyl (meth) acrylate, 4-glycidyl-n-butyl (meth) acrylate, 5-glycidyl-n-hexyl (meth) acrylate, (meth) acrylic acid 6 -An alkylene oxide (meth) acrylate such as glycidyloxy-n-hexyl.

Specific examples of the aliphatic (meth) acrylate having an alicyclic epoxy group include compounds represented by the following formulae (a2-1) to (a2-15). Among these, compounds represented by the following formulae (a2-1) to (a2-5) are preferred, and compounds represented by the following formulae (a2-1) to (a2-3) are more preferred.

[Chemical 21]

[Chemical 22]

[Chemical 23]

In the above formula, R ^a20 represents a hydrogen atom or a methyl group, R ^a21 represents a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, R ^a22 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n1 represents An integer from 0 to 10. R ^{a21 is} preferably a linear or branched alkylene, such as methylene, ethylidene, propylidene, tetramethylene, ethylidene, pentamethylene, and hexamethylene base. As R ^a22 , for example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, and cyclohexyl are preferable.

As the polymer having an epoxy group, any of a homopolymer of a (meth) acrylate having an epoxy group and a copolymer of a (meth) acrylate having an epoxy group and other monomers can be used. The content of the unit derived from the (meth) acrylate having an epoxy group in the polymer having an epoxy group is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 80% by mass or more, It is particularly preferably 90% by mass or more, and most preferably 100% by mass.

In the case where the polymer having an epoxy group is a copolymer of a (meth) acrylate having an epoxy group and another monomer, examples of the other monomer include unsaturated carboxylic acids and those having no epoxy group. (Meth) acrylates, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds can be used alone or in combination of two or more. In terms of the storage stability of the hardenable composition or the chemical resistance of the hardened material formed from the hardenable composition to alkali, etc., the (meth) acrylate having an epoxy group and other monomers The copolymer is preferably free of units derived from an unsaturated carboxylic acid.

Examples of unsaturated carboxylic acids include (meth) acrylic acid; (meth) acrylamide; butenoic acid; maleic acid, fumaric acid, methyl maleic acid, methyl Fumaric acid, itaconic acid, anhydrides of these dicarboxylic acids.

Examples of the (meth) acrylate having no epoxy group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and amyl (meth) acrylate Linear or branched alkyl (meth) acrylates, such as the third octyl (meth) acrylate, chloroethyl (meth) acrylate, 2,2-dimethylhydroxy (meth) acrylate Propyl ester, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, and furfuryl (meth) acrylate; containing alicyclic skeleton (Meth) acrylate. In the (meth) acrylate which does not have an epoxy group, it is preferable that it contains the (meth) group which has a alicyclic skeleton from the point of the transparency of the hardened | cured material formed using a hardenable composition. Acrylate.

In the (meth) acrylic acid ester containing a group having an alicyclic skeleton, the alicyclic group constituting the alicyclic skeleton may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a noryl group, an isoyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

Examples of the (meth) acrylate containing a group having an alicyclic skeleton include compounds represented by the following formulae (a3-1) to (a3-8). Among these, compounds represented by the following formulae (a3-3) to (a3-8) are preferred, and compounds represented by the following formulae (a3-3) or (a3-4) are more preferred.

[Chemical 24]

In the above formula, R ^a23 represents a hydrogen atom or a methyl group, R ^a24 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 or more and 6 or less carbon atoms, and R ^a25 represents a hydrogen atom or 1 or more and 5 or less carbon atoms. alkyl. R ^{a24 is} preferably a single bond, linear or branched alkylene, such as methylene, ethylidene, propylidene, tetramethylene, ethylidene, pentamethylene, Hexamethylene. R ^{a25 is} preferably a methyl group or an ethyl group.

Examples of (meth) acrylamide include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N -Dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N -Meth (meth) acrylamide and the like.

Examples of allyl compounds include allyl acetate, allyl hexanoate, allyl octoate, allyl laurate, allyl palmitate, allyl stearate, and allyl benzoate. Esters, allyl acetoacetate, allyl lactate and other allyl esters; allyloxy ethanol and so on.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, and chloroethyl vinyl. Ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylamino ethyl vinyl ether, Alkyl vinyl ethers such as diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl toluene ether, vinyl chlorophenyl ether, Vinyl aromatic ethers such as vinyl-2,4-dichlorophenyl ether, vinylnaphthalene ether, and vinyl anthracene ether.

Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloroacetate, Vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl phenylacetate, ethyl acetate, vinyl lactate, β-phenylbutyrate, vinyl benzoate, water Vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthalate and the like.

Examples of styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, and butylbenzene Ethylene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene, ethoxymethylstyrene Isoalkylstyrene; alkoxystyrene such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; chlorostyrene, dichlorostyrene, and trichlorobenzene Ethylene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4-fluoro Halostyrene such as -3-trifluoromethylstyrene.

(Local oxide of polymer having unsaturated aliphatic hydrocarbon group in side chain)
The polymer having an unsaturated aliphatic hydrocarbon in the side chain is not particularly limited. In terms of easy availability or synthesis, it is preferably 1,2-polybutadiene having a vinyl group in the side chain. By locally oxidizing 1,2-polybutadiene, an epoxidized polybutadiene having an ethylene oxide group and a vinyl group in a side chain can be obtained. The ratio of ethylene oxide groups in such epoxidized polybutadiene is preferably 10 mol% or more and 70 mol% or less, more preferably, relative to the total mol number of the ethylene oxide group and the vinyl group. 10 mol% or more and 50 mol% or less, more preferably 10 mol% or more and 40 mol% or less. As the epoxidized polybutadiene, JP-100 and JP-200 commercially available from Japan Soda Co., Ltd. can be favorably used.

The molecular weight of the polymer having an epoxy group described above is not particularly limited as long as it does not impair the object of the present invention. It is preferably 3,000 or more and 30,000 or less, and more preferably 10,000 or less in terms of mass average molecular weight in terms of polystyrene. Above 5,000 and below 15,000.

(Vinyl ether compound)
As the curable compound, a vinyl ether compound or the like can also be used.
The vinyl ether compound is not particularly limited as long as it is an organic compound containing one or more vinyl ether groups in the molecule. The monovalent or polyvalent organic group as the mother core of the vinyl ether group bond may be a hydrocarbon group or an organic group containing a hetero atom. Examples of the hetero atom include O, S, N, P, and a halogen atom.

As the vinyl ether compound, in terms of ease of synthesis or acquisition, or transparency or mechanical properties of the cured product, a vinyl ether compound containing one vinyl ether group or two containing two vinyl ether groups is preferred. The vinyl ether compound is more preferably a divinyl ether compound.

Specific examples of the monovinyl ether compound include ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, and n-decyl ethylene. Ethers, cyclohexyl vinyl ether, 2-ethyl n-hexyl vinyl ether, 2-methoxyethyl vinyl ether, and alkyl vinyl ethers or alkoxy alkyl vinyl ethers such as 2-ethoxyethyl vinyl ether; 2-vinyloxyethanol, 2-vinyloxypropanol, 3-vinyloxypropanol, 2-vinyloxybutanol, 4-vinyloxybutanol, 6-vinyloxyhexanol, 2- ( (Ethyleneoxyethoxy) ethanol, 2- (ethyleneoxyethoxyethoxy) ethanol, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol Monoethylene ether, tripropylene glycol monovinyl ether, and polypropylene glycol monovinyl ether, such as aliphatic vinyl ethers containing hydroxyl groups; 1-chloro-2-vinyloxyethane, 1-chloro-3-vinyloxypropane, 1- Chloro-4-vinyloxy-n-butane, 1-chloro-6-vinyloxy-n-hexane, 1-chloro-2- (vinyloxyethoxy) -n-propane, 1-chloro-2- (vinyloxy Ethoxy) propane and 1-chloro-2- (vinyloxy (Ethoxyethoxy) ethane and other vinyl ethers containing halogens; vinyl phenyl ether, 4-vinyloxytoluene, 3-vinyloxytoluene, 2-vinyloxytoluene, 1-vinyloxy-4-chloro Benzene, 1-vinyloxy-3-chlorobenzene, 1-vinyloxy-2-chlorobenzene, 1-vinyloxy-2,3-dimethylbenzene, 1-vinyloxy-2,4-di Methylbenzene, 1-vinyloxy-2,5-dimethylbenzene, 1-vinyloxy-2,6-dimethylbenzene, 1-vinyloxy-3,4-dimethylbenzene, 1 -Vinyloxy-3,5-dimethylbenzene, 1-vinyloxynaphthalene, 2-vinyloxynaphthalene, 4-vinyloxy-1,1'-biphenyl, 3-vinyloxy-1, Aromatic vinyl ethers such as 1'-biphenyl, 2-vinyloxy-1,1'-biphenyl, benzyl vinyl ether, 6-vinyloxynaphthyl, and 5-vinyloxynaphthyl.

Specific examples of the divinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, and dipropylene glycol. Divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol divinyl ether, 1,3-propylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,5-pentanediol divinyl ether, 1,6 -Chain aliphatic divinyl ethers such as hexanediol divinyl ether, 1,8-octanediol divinyl ether, and 1,10-decanediol divinyl ether; 1,4-cyclohexanediol diethylene Ether, 1,4-cyclohexanedimethanol divinyl ether, and 2-vinyloxy-5- (vinyloxymethyl) -7-oxabicyclo [2.2.1] heptane, etc. Vinyl ether; 1,4-divinyloxybenzene, 1,3-divinyloxybenzene, 1,2-divinyloxybenzene, 1,4-divinyloxynaphthalene, 1,3-divinyloxy Naphthalene, 1,2-Divinyloxynaphthalene, 1,5-Divinyloxynaphthalene, 1,6-Divinyloxynaphthalene, 1,7-Divinyloxynaphthalene, 1,8-Divinyloxy Naphthalene, 2,3-divinyloxynaphthalene, 2,6-divinyloxynaphthalene, 2,7-divinyloxynaphthalene, 4,4'-divinyloxybiphenyl, 3,3'- two Vinyloxybiphenyl, 2,2'-divinyloxybiphenyl, 3,4'-divinyloxybiphenyl, 2,3'-divinyloxybiphenyl, 2,4'-divinyloxy Dibiphenyl, bisphenol A divinyl ether, 1,4-benzenedimethanol divinyl ether, 1,3-benzenedimethanol divinyl ether, 1,2-benzenedimethanol divinyl ether, and naphthalene-1,4 -Aromatic divinyl ether such as bismethanol divinyl ether.

Among the vinyl ether compounds, compounds represented by the following formula are preferred.
[Chemical 25]

(Content of hardening compound)
The content of the curable compound in the composition of the first aspect with respect to the total mass of components other than the organic solvent in the composition is, for example, 40% by mass or more and 98% by mass or less, preferably 45% by mass or more and 96 mass% or less, more preferably 50 mass% or more and 95 mass% or less.

(Polymerization initiator)
The composition of the first aspect may or may not contain a polymerization initiator. The polymerization initiator is not particularly limited, and a conventionally known photopolymerization initiator may be used.
The content of the polymerization initiator is not particularly limited. The content of the polymerization initiator is preferably 0.5 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the solid matter component of the composition of the first aspect.

(Polymerizable compound)
The composition of the first aspect may or may not contain a polymerizable compound, and examples of the polymerizable compound include a monofunctional monomer and a polyfunctional monomer.
Examples of the monofunctional monomer include (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (methyl) Acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-hydroxymethyl (Meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, methyl maleic acid, methyl Maleic anhydride, butenoic acid, 2-acrylamido-2-methylpropanesulfonic acid, tertiary butylacrylamidosulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate , Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Ester, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloxy-2-hydroxypropyl phthalate , Glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylic acid , Glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, phthalic acid derivatives Semi- (meth) acrylate and so on. These monofunctional monomers can be used alone or in combination of two or more.

On the other hand, examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and propylene glycol di (Meth) acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate Base) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol Di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2- Bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, (methyl) 2-hydroxy-3- (meth) acrylic acid oxypropyl acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglylation Glyceryl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, (meth) acrylic acid Urethane (ie toluene diisocyanate); reactants of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and 2-hydroxyethyl (meth) acrylate; methylenebis (methyl) ) Polyacrylamide, (meth) acrylamide methylene ether; polyfunctional monomers such as polycondensates of polyhydric alcohols and N-methylol (meth) acrylamide, or tripropylenemethylene formaldehyde. These polyfunctional monomers can be used alone or in combination of two or more kinds.

The content of the polymerizable compound is not particularly limited. The content of the polymerizable compound is preferably 1% by mass or more and 70% by mass or more, more preferably 3% by mass or more and 50% by mass or less, and more preferably 5% by mass relative to the solid content of the composition of the first aspect. % To 30% by mass.

(Organic solvents)
The composition of the first aspect may or may not contain an organic solvent. Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono (Poly) alkylene glycol monoalkanes such as n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether Ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (Poly) alkylene glycol monoalkyl ether acetates such as esters, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Other ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, etc. Acid alkyl esters; ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Ethyl ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, N-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate , Other ethyl esters such as ethyl acetate, ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; N-methyl-2-pyrrolidone, N, N-dimethylformamidine Amine, N, N-dimethylacetamide, N, N-dimethylisobutylamidine, N, N-diethylacetamide, N, N-diethylformamide, N- Methyl caprolactam, 1,3-dimethyl-2-imidazolidinone, pyridine, and nitrogen-containing polar organic solvents such as N, N, N ', N'-tetramethylurea and the like.
In addition, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isopentanone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, and Polyols such as ethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether, and the like Derivatives; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl ethyl acetate, ethyl acetate Ethyl acetate, ethyl pyruvate, ethyl ethoxylate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxyl Ethyl-2-methylpropanoate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. Esters; aromatic hydrocarbons such as toluene and xylene.
These organic solvents can be used alone or in combination of two or more.

The content of the organic solvent is not particularly limited. The content of the organic solvent is preferably such that the solid component concentration of the composition of the first aspect is 1% by mass or more and 50% by mass or less, and more preferably the solid component concentration of the composition of the first aspect is 5 mass The amount is not less than 30% by mass and not more than 30% by mass.

(Other ingredients)
The above-mentioned composition may optionally contain various resins or additives. Examples of the resin include an alkali-soluble resin and a resin that improves the solubility in a developing solution (an alkaline developing solution or a solvent developing solution) by exposure or heating. Moreover, it may be a thing which has an ethylenically unsaturated group, and may be a thing which does not have an ethylenically unsaturated group. Examples of the additives include colorants, dispersants, sensitizers, hardening accelerators, fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anticoagulants, thermal polymerization inhibitors, defoamers, and interfacial activity. Agent.
The content of the resin may be appropriately adjusted, for example, in a range of 10% by mass or more and 90% by mass or less with respect to the entire composition except the solvent of the composition of the first aspect, and preferably 20% by mass or more and 80% by mass. Mass% or less.
The addition amounts of various additives may be appropriately adjusted, for example, in the range of 0.001% by mass or more and 60% by mass or less with respect to the entire composition except the solvent in the first aspect, preferably 0.1% by mass or more and 5% by mass. %the following.

(Method for preparing composition of the first aspect)
The composition of the first aspect is prepared by mixing the above components with a blender. Furthermore, the prepared composition of the first aspect may be filtered using a membrane filter or the like so that the composition becomes uniform.
(use)
The composition of the first aspect is preferably a curable composition.
In the case where the composition of the first aspect is a curable composition, the temperature and time when the composition is cured are not particularly limited as long as the curing is sufficiently performed. For example, the composition may be at a temperature of 100 ° C or higher and 160 ° C or lower. The composition is hardened at a temperature of about 3 minutes to about 10 minutes. Furthermore, the above-mentioned composition can be hardened at a low temperature, and can also be hardened at a high temperature.
The composition of the first aspect can be used as a composition for forming a protective film, an antistatic film, an interlayer insulating film, a flat film, and an insulating film for forming electronic components such as liquid crystal display elements, integrated circuit elements, and solid-state imaging elements.

≪hardened matter≫
The hardened material of the second aspect is a hardened material of the composition of the first aspect.
The hardened product of the second aspect can be used as a protective film, an antistatic film, an interlayer insulating film, a flat film, and an insulating film for electronic parts such as liquid crystal display elements, integrated circuit elements, and solid-state imaging elements.
When the cured product is a film, the thickness is preferably 10 nm or more and 30,000 nm or less, more preferably 50 nm or more and 1500 nm or less, and even more preferably 100 nm or more and 1000 nm or less.
[Example]

Hereinafter, the present invention will be described in more detail based on examples. The invention is not limited by these examples.

[Synthesis Example 1] Synthesis 1 of the compound represented by the above formula (1)
[Chemical 26]

In a 50 ml three-necked flask, compound A (2.00 g, 8.12 mmol) and methanol (20 g) were added. After replacing the inside of the flask with nitrogen, the flask was heated at 60 ° C. in a water bath to dissolve Compound A in methanol. Next, diazabicycloundecene (DBU; 1.24 g, 8.12 mmol) was added dropwise according to the above scheme, and Compound A and DBU were reacted at 60 ° C. for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature (25 ° C). Thereafter, the solvent was distilled off from the reaction liquid using a rotary evaporator, whereby a compound (Compound 1) represented by the above formula (1) was obtained. (Yield = 3.27 g, yield = 95%, yellow viscous liquid)
¹ H-NMR (deuterated DMSO, 400 MHz): cation δ (ppm) = 3.48 (CH ₂ , 2H), 3.40 (CH ₂ , 2H), 3.15 (CH ₂ , 2H), 2.65 (CH ₂ , 2H) , 1.82 (CH ₂ , 2H), 1.70-1.45 (CH ₂ , 6H),
Anion δ (ppm) = 7.70 (CH, 1H), 7.22 (Ph, 2H), 7.15 (CH, 1H), 6.85 (Ph, 2H), 6.80 (CH, 1H), 5.63 (CH, 1H), 3.70 ( CH ₃ , 3H), 2.85-2.65 (CH ₂ , 2H)

[Synthesis Example 2] Synthesis 2 of the compound represented by the above formula (1)
[Chemical 27]

In a 50 ml three-necked flask, compound A (2.00 g, 8.12 mmol) and methanol (20 g) were added. After replacing the inside of the flask with nitrogen, the flask was heated at 60 ° C. in a water bath to dissolve Compound A in methanol. Next, according to the above scheme, diazabicyclononene (DBN; 1.11 g, 8.12 mmol) was added dropwise, and the compound A and DBN were reacted at 60 ° C. for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature. Thereafter, the solvent was distilled off from the reaction liquid using a rotary evaporator, whereby a compound (Compound 2) represented by the above formula (1) was obtained. (Yield = 2.91 g, yield = 90%, yellow viscous liquid)
¹ H-NMR (deuterated DMSO, 400 MHz): cation δ (ppm) = 3.55 (CH ₂ , 2H), 3.40-3.25 (CH ₂ , 4H), 2.81 (CH ₂ , 2H), 2.00 (CH ₂ , 2H), 1.88 (CH ₂ , 2H)
Anion δ (ppm) = 7.70 (CH, 1H), 7.22 (Ph, 2H), 7.15 (CH, 1H), 6.85 (Ph, 2H), 6.80 (CH, 1H), 5.63 (CH, 1H), 3.70 ( CH ₃ , 3H), 2.85-2.65 (CH ₂ , 2H)

[Synthesis Example 3] Synthesis 3 of the compound represented by the formula (1)
[Chemical 28]

In a 50 ml three-necked flask, compound A (2.00 g, 8.12 mmol) and methanol (20 g) were added. After replacing the inside of the flask with nitrogen, the flask was heated at 60 ° C. in a water bath to dissolve Compound A in methanol. Next, imidazole (IM; 0.55 g, 8.12 mmol) was added, and Compound A and IM were reacted at 60 ° C for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature. Thereafter, the solvent was distilled off from the reaction liquid using a rotary evaporator, whereby a compound (compound 3) represented by the above formula (1) was obtained. (Yield = 2.43 g, yield = 95%, white solid)
¹ H-NMR (deuterated DMSO, 400 MHz): cation δ (ppm) = 7.03 (CH, 2H), 7.65 (CH, 1H)
Anion δ (ppm) = 7.86 (CH, 1H), 7.35 (3H), 6.99 (3H), 5.70 (CH, 1H), 3.71 (CH ₃ , 3H), 3.35-3.16 (CH ₂ , 2H)

For the compound A monomer, the imidazole monomer, and the obtained compound 3 of the raw materials, an X-ray diffraction measuring device (manufactured by Rigaku Co., Ltd .; the brand name "Full-automatic horizontal multipurpose X-ray diffraction measuring device SmartLab") was used. ), The X-ray diffraction pattern was measured under the following conditions. The obtained compound 3 exhibited a reflection pattern different from that of each of the monomers of the raw material. Therefore, it was determined that the compound 3 was not a simple mixture but a salt.
Use of X-rays: CuKα rays from a rotating counter-cathode X-ray generation source, 45 kV-200 mA
Scanning speed (2θ): 4.0 ° / min
Divergent slit: (2/3) °
Scattering slit: (2/3) °
Other conditions are set according to the standard conditions of package measurement "general measurement> general (concentration method)".

[Synthesis Example 4] Synthesis 4 of the compound represented by the formula (1)
[Chemical 29]

In a 20 ml round bottom flask, add compound A (1.60 g, 6.50 mmol) and tetrahydrofuran (3 g). After replacing the inside of the round bottom flask with nitrogen, the mixture was heated at 60 ° C. in an oil bath to dissolve compound A in tetrahydrofuran. Next, according to the above scheme, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca-5-ene (MTBD; 1.00 g, 6.50 mmol) was added dropwise to bring compound A and MTBD at 60 The reaction was carried out at 30 ° C for 30 minutes. After the reaction was completed, the reaction solution was cooled to room temperature. Thereafter, the solvent was distilled off from the reaction liquid using a rotary evaporator, whereby a compound (Compound 4) represented by the above formula (1) was obtained. (Yield = 2.5 g, yield = 95%, yellow viscous liquid)
¹ H-NMR (deuterated DMSO, 500 MHz): cation δ (ppm) = 9.20 (NH, 1H), 3.27-3.22 (6H), 3.17-3.15 (2H), 2.90 (CH3, 3H), 1.92-1.89 (2H), 1.81-1.79 (2H)
Anion δ (ppm) = 7.67 (CH, 1H), 7.21 (2H), 7.12 (1H), 6.84 (2H), 6.79 (1H), 5.62 (CH, 1H), 3.71 (CH ₃ , 3H), 2.73- 2.61 (CH ₂ , 2H)

[Synthesis Example 5] Synthesis 5 of the compound represented by the formula (1)
[Chemical 30]

In a 20 ml round bottom flask were added compound A (1.50 g, 6.09 mmol) and methanol (9 g). After replacing the inside of the round bottom flask with nitrogen, the mixture was heated at 60 ° C. in an oil bath to dissolve Compound A in methanol. Next, according to the above scheme, 1,5,7-triazabicyclo [4,4,0] deca-5-ene (TBD; 0.85 g, 6.09 mmol) was added dropwise to react Compound A with TBD at 60 ° C 30 minutes. After the reaction was completed, the reaction solution was cooled to room temperature. Thereafter, the solvent was distilled off from the reaction liquid using a rotary evaporator, thereby obtaining the compound (Compound 5) represented by the above formula (1). (Yield = 2.2 g, yield = 95%, yellow solid)
¹ H-NMR (deuterated DMSO, 500 MHz): cation δ (ppm) = 10.48 (NH, 2H), 3.22-3.17 (4H), 3.10-3.07 (4H), 1.86-1.81 (4H)
Anion δ (ppm) = 7.71 (CH, 1H), 7.25 (2H), 7.17 (1H), 6.86 (2H), 6.80 (1H), 5.65 (CH, 1H), 3.71 (CH ₃ , 3H), 2.87- 2.73 (CH ₂ , 2H)

[Synthesis Example 6] Synthesis 6 of the compound represented by the formula (1)
[Chemical 31]

In a 20 ml round bottom flask were added compound A (1.50 g, 6.09 mmol) and methanol (9 g). After replacing the inside of the round bottom flask with nitrogen, the mixture was heated at 60 ° C. in an oil bath to dissolve Compound A in methanol. Next, according to the above scheme, 1,1,3,3-tetramethylguanidine (TMG; 0.7 g, 6.09 mmol) was added dropwise, and the compound A and TMG were reacted at 60 ° C for 30 minutes. After the reaction was completed, the reaction solution was cooled to room temperature. Thereafter, the solvent was distilled off from the reaction liquid using a rotary evaporator, whereby a compound (compound 6) represented by the above formula (1) was obtained. (Yield = 2.2 g, yield = 100%, yellow solid)
¹ H-NMR (deuterated DMSO, 500 MHz): cation δ (ppm) = 2.84 (6H)
Anion δ (ppm) = 7.67 (CH, 1H), 7.21 (2H), 7.12 (1H), 6.85 (2H), 6.79 (1H), 5.62 (CH, 1H), 3.71 (CH ₃ , 3H), 2.28- 2.64 (CH ₂ , 2H)

[Synthesis Example 7] Synthesis 7 of the compound represented by the formula (1)
[Chemical 32]

In a 20 ml round bottom flask were added compound A (1.00 g, 4.06 mmol) and methanol (9 g). After replacing the inside of the round bottom flask with nitrogen, the mixture was heated at 60 ° C. in an oil bath to dissolve Compound A in methanol. Next, according to the above procedure, imine-tris (dimethylamino) phosphorane (0.72 g, 4.06 mmol) was added dropwise, and compound A and imino-tris (dimethylamino) phosphorane were added at 60 ° C. Reaction for 30 minutes. After the reaction was completed, the reaction solution was cooled to room temperature. Thereafter, the solvent was distilled off from the reaction liquid using a rotary evaporator, thereby obtaining a compound (Compound 7) represented by the above formula. (Yield = 1.7 g, yield = 98%, yellow solid)
¹ H-NMR (deuterated DMSO, 500 MHz): cation δ (ppm) = 2.63 (9H), 2.61, 9H),
Anion δ (ppm) = 7.65 (CH, 1H), 7.18 (2H), 7.10 (1H), 6.84 (2H), 6.84 (1H), 5.61 (CH, 1H), 3.71 (CH ₃ , 3H), 2.28- 2.64 (CH ₂ , 2H)

[Preparation of composition]
The composition of Example 1 and Comparative Example 1 was prepared by mixing the following epoxy compound, the compound represented by Formula (1), and the comparative compound at the mixing ratios (parts by mass) shown in Table 1 below.
[Table 1]
[Chemical 33]

[Evaluation of heat resistance]
The compositions of Example 1 and Comparative Example 1 were used for heat resistance evaluation.
The compositions of Example 1 and Comparative Example 1 were applied to a glass substrate and heated at 200 ° C. (5 minutes) to obtain a cured film having a film thickness of 1 μm.
After the obtained cured film was temporarily cooled to room temperature, the temperature was raised from room temperature to 200 ° C again to confirm the state of the film.
The hardened film of Comparative Example 1 began to melt at about 140 ° C, but the hardened film of Example 1 did not melt and did not appear in observations using a differential scanning calorimeter (trade name: DSC-50, manufactured by Shimadzu Corporation). Because of the endothermic peak, it is considered that a cured film having good heat resistance is obtained.

Claims (5)

A composition comprising a compound represented by the following formula (1), (In the formula (1), X ^{m +} represents an m-valent counter cation, R ¹ represents an aromatic group which may have a substituent, R ² represents an alkylene group which may have a substituent, and R ³ represents a halogen atom, a hydroxyl group, a mercapto group, Thio, silane, silanol, nitro, nitroso, sulfonate, phosphine, phosphine, phosphonate, or organic, m is an integer of 1 or more, n is 0 or more and An integer of 3 or less, R ² may be bonded to R ¹ to form a cyclic structure). The composition as claimed in claim 1, which further comprises a compound having an epoxy group. The composition as claimed in claim 1 or 2, which is a hardenable composition. The composition of claim 1 or 2, wherein the m-valent counter cation X ^{m + is an} acyclic or cyclic nitrogen-containing aliphatic cation, a nitrogen-containing aromatic cation, or a metal cation. A hardened material which is a hardened material of the composition according to any one of claims 1 to 4.