JP2016204636A - Zwitterion type borate salt and curable resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a borate salt excellent in stability and excellent in solubility to a curable resin or a polymerizable monomer when blended with the curable resin or the polymerizable monomer.SOLUTION: A zwitterion type borate salt represented by the general formula (1) and curable resin composition containing the zwitterion type borate salt and a curable compound are used. In general formula (1), Y is preferably a group represented by the general formula (2) or a group represented by the general formula (3), Ris preferably an aryl group having 6 to 18 carbon atoms. The curable compound is a compound (J) having two or more glycidyl groups in a molecule and, preferably, further contains a compound (K) having two or more active hydrogen-containing groups in a molecule or acid anhydride (L).SELECTED DRAWING: None

Description

  The present invention relates to zwitterionic borate salts. More specifically, materials and materials that are cured by heating or light irradiation, such as products and members that form a pattern or the like using the difference in solubility in the developer between the exposed and unexposed areas when cured by light irradiation (for example, electronic Parts, optical products, optical component forming materials, layer forming materials, adhesives, etc.) and the like, and a curable resin composition excellent in low-temperature curability comprising the same .

A curable composition comprising a thermosetting resin such as an epoxy resin and a crosslinking agent is used as an electric / electronic material such as an IC sealing material, and an anion curing catalyst such as imidazole or amidine is used as a catalyst for curing. Therefore, a catalyst having excellent curability has to be stored refrigerated in order to ensure stability.
As an anion latent catalyst excellent in curability and storage stability, an amphoteric borate salt having a phosphonium cation and a boron anion in one molecule is known as a borate salt (see Patent Document 1).

  However, the borate salt described in Patent Document 1 has low solubility in a curable resin or a polymerizable monomer when mixed with a curable resin or a polymerizable monomer, or imidization by a cyclization reaction into a photosensitive polyimide. In order to sufficiently advance the reaction, heating at a temperature of 300 ° C. or higher is required, and the occurrence of cracks in the polyimide film sometimes becomes a problem.

JP 2000-128912 A

  An object of the present invention is to provide a borate salt that is excellent in stability and has excellent solubility in a curable resin or a polymerizable monomer when blended with a curable resin or a polymerizable monomer, and at a lower temperature than before. It is to provide a curable resin composition having a good pattern forming property due to the progress of the reaction.

As a result of intensive studies to solve the above problems, the present inventor has found a new borate salt.
That is, this invention is a curable resin composition containing the zwitterionic borate salt represented by the general formula (1) and the zwitterionic borate salt and a curable compound.
[In formula (1), each R ¹ is independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or an aralkyl group having 7 to 24 carbon atoms. Or an aryl group having 6 to 18 carbon atoms or a group in which at least one hydrogen atom of these groups has an oxygen atom, a group having a sulfur atom, a group having a nitrogen atom, or a halogeno group, ⁺ Is a group having a tetravalent covalently bonded nitrogen atom, B ⁻ is an anionic boron atom, and Y is a divalent organic group that bonds a tetravalent covalently bonded nitrogen atom and an anionic boron atom that A ⁺ has. It is. ]

  The borate salt obtained by the present invention is excellent in storage stability and solubility when blended with a curable resin or a polymerizable monomer, and exhibits excellent curability when cured by heating or light irradiation, and includes such curability. The resin composition has an excellent pattern forming property because the reaction proceeds at a temperature lower than conventional ones.

  The borate salt of the present invention is represented by the general formula (1).

Each R ¹ is independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aralkyl group having 7 to 24 carbon atoms, or an alkyl group having 6 to 18 carbon atoms. An aryl group or at least one hydrogen atom of these groups is a group having an oxygen atom, a group having a sulfur atom, a group having a nitrogen atom or a group substituted with a halogeno group, and A ⁺ is a tetravalent covalently bonded nitrogen A group having an atom, B ⁻ is an anionic boron atom, and Y is a divalent organic group for bonding a tetravalent covalently bonded nitrogen atom and an anionic boron atom of A ⁺ .

  Examples of the alkyl group having 1 to 18 carbon atoms include linear alkyl groups (methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-decyl group). Group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, etc.), branched alkyl group (isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, tert-pentyl group, isohexyl group, 2-ethylhexyl group and 1,1,3,3-tetramethylbutyl group), cycloalkyl group (cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc.) and bridged cyclic Examples thereof include an alkyl group (such as a norbornyl group, an adamantyl group, and a pinanyl group). Of these, methyl, ethyl, n-butyl, n-hexyl, n-octyl, isopropyl, sec-butyl, tert-butyl, neopentyl are preferred from the viewpoint of availability of raw materials. , A cyclopentyl group and a cyclohexyl group.

  Examples of the alkenyl group having 2 to 18 carbon atoms include linear or branched alkenyl groups (vinyl group, allyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 2-methyl-1-propenyl group and 2-methyl-2-propenyl group), cycloalkenyl groups (2-cyclohexenyl group and 3- Cyclohexenyl group, etc.) and arylalkenyl groups (styryl group, cinnamyl group, etc.). Among these, a vinyl group, an allyl group, a 1-propenyl group, a 1-butenyl group, a 3-cyclohexenyl group, a styryl group, and a cinnamyl group are preferable from the viewpoint of easy availability of raw materials.

Examples of the alkynyl group having 2 to 18 carbon atoms include linear or branched alkynyl groups (ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl 2-propynyl group, 1,1-dimethyl-2-propynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 3-methyl -1-butynyl group, 1-hexynyl group, 1-decynyl group, 2-decynyl group, 8-decynyl group, 1-dodecynyl group, 2-dodecynyl group and 10-dodecynyl group) and arylalkynyl groups (phenylethynyl group) Etc.). Among these, 1-propynyl group, 1-butynyl group, 1-hexynyl group and phenylethynyl group are preferable from the viewpoint of easy availability of raw materials.

  Examples of the aryl group having 6 to 18 carbon atoms include monocyclic aryl groups (such as phenyl groups), condensed polycyclic aryl groups (such as naphthyl group, anthracenyl group, phenanthrenyl group, anthraquinolyl group, fluorenyl group, and naphthoquinolyl group), aromatic Heterocyclic hydrocarbon groups [monocyclic heterocyclic hydrocarbon groups (thienyl group, furanyl group, pyranyl group, pyrrolyl group, oxazolyl group, thiazolyl group, pyridyl group, pyrimidyl group and pyrazinyl group, etc.) and condensed polycyclic heterocycles Ring hydrocarbon group (indolyl group, benzofuranyl group, isobenzofuranyl group, benzothienyl group, isobenzothienyl group, quinolyl group, isoquinolyl group, quinoxalinyl group, quinazolinyl group, carbazolyl group, acridinyl group, phenothiazinyl group, phenazinyl group , Xanthenyl group, thiantenyl group, Nokisajiniru group, phenoxathiinyl group, chromanyl group, isochromanyl group, coumarinyl group, dibenzothienyl group, Kisantoniru group, Chiokisantoniru group and dibenzofuranyl group)], and the like. Among them, from the viewpoint of availability of raw materials, phenyl group, naphthyl group, anthracenyl group, thienyl group, pyridyl group, indolyl group, quinolyl group, quinoxalinyl group, carbazolyl group, xanthenyl group, thiantenyl group, coumarinyl group, A xanthonyl group and a thioxanthonyl group.

  Examples of the aralkyl group having 7 to 24 carbon atoms include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylpropyl group, 2-phenylpropyl group, 3-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 9-anthracenylmethyl group, 9-anthracenylethyl group, 2-thanthrenylethyl group, 3-thioxanthonylmethyl group, 3-thioxanthonylethyl group, 3-carbazolyl And a rumethyl group and a 3-carbazolylethyl group. Of these, from the viewpoint of easy availability of raw materials, benzyl group, 2-phenylethyl group, 2-phenylpropyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 9-anthracenylmethyl group, 2 -Thiantenylethyl group, 3-thioxanthonylmethyl group and 3-carbazolylethyl group.

Among these groups, a group having a sulfur atom, a group having an oxygen atom, a group having a nitrogen atom, and a halogeno group among those having a sulfur atom replacing at least one hydrogen atom of these groups, a group having a sulfur atom, a group having an oxygen atom, and a nitrogen atom As the group having nitro group (—NO ₂ ), hydroxyl group (—OH), cyano group (—CN), amino group (—NH ₂ ), C 1-8 alkoxy group, C 6-14 carbon group, An aryloxy group, an acyl group having 2 to 15 carbon atoms, an acyloxy group having 2 to 15 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an arylthio group having 6 to 14 carbon atoms, and a substituted amino group having 1 to 28 carbon atoms. Can be mentioned.

Examples of the alkoxy group having 1 to 8 carbon atoms, which is a group having an oxygen atom replacing a hydrogen atom, include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a sec-butoxy group, and a tert. -Butoxy group, n-pentoxy group, iso-pentoxy group, neo-pentoxy group, 2-methylbutoxy group and the like.
Examples of the aryloxy group having 6 to 14 carbon atoms include a phenoxy group and a naphthoxy group.

Examples of the acyl group having 2 to 15 carbon atoms, which is a group having an oxygen atom replacing a hydrogen atom, include an acyl group having an alkyl group having 1 to 8 carbon atoms and an acyl group having an aryl group having 6 to 14 carbon atoms. Can be mentioned.
Examples of the acyl group having an alkyl group having 1 to 8 carbon atoms include an acetyl group, a propanoyl group, a butanoyl group and a pivaloyl group. Examples of the acyl group having an aryl group having 6 to 14 carbon atoms include a benzoyl group. Can be mentioned.

Examples of the acyloxy group having 2 to 15 carbon atoms, which is a group having an oxygen atom replacing a hydrogen atom, include an acyloxy group having an alkyl group having 1 to 8 carbon atoms and an acyloxy group having an aryl group having 6 to 14 carbon atoms. Can be mentioned.
Examples of the acyloxy group having an alkyl group having 1 to 8 carbon atoms include an acetoxy group and a butanoyloxy group. Examples of the acyloxy group having an aryl group having 6 to 14 carbon atoms include a benzoyloxy group.

As a C1-C8 alkylthio group which is a group which has a sulfur atom which substitutes a hydrogen atom, a methylthio group, an ethylthio group, a butylthio group, a hexylthio group, a cyclohexylthio group, etc. are mentioned.
Examples of the arylthio group having 6 to 14 carbon atoms include a phenylthio group and a naphthylthio group.

  Preferred examples of the substituted amino group having 1 to 28 carbon atoms, which is a group having a nitrogen atom for substituting a hydrogen atom, include dialkylamino groups (dimethylamino group, diethylamino group, methyl group to which an alkyl group having 1 to 8 carbon atoms is bonded. An ethylamino group, a dipropylamino group, a dibutylamino group, etc.), an alkylamino group to which an alkyl group having 1 to 8 carbon atoms is bonded (methylamino group, ethylamino group, propylamino group, hexylamino group, cyclohexylamino group, etc.) And a cyclic amino group (piperidino group, morpholino group, etc.) to which a divalent hydrocarbon group having 2 to 8 carbon atoms is bonded.

  Examples of the halogeno group that replaces a hydrogen atom include a fluoro group, a chloro group, a bromo group, and an iodo group.

Among these groups having an oxygen atom, a group having a sulfur atom, a group having a nitrogen atom, and a halogeno group, the group substituting for a hydrogen atom has 1 to 8 carbon atoms from the viewpoint of solvent solubility of the zwitterionic borate salt. An alkoxy group, an aryloxy group having 6 to 14 carbon atoms, an alkylthio group having 1 to 8 carbon atoms, an arylthio group having 6 to 14 carbon atoms, a substituted amino group having 1 to 28 carbon atoms, a fluoro group, a chloro group, and a bromo group; preferable.
More preferably, it is an alkylamino group having 1 to 4 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, or an alkyl group having 1 to 8 carbon atoms, and a divalent carbonization. A cyclic amino group to which a hydrogen group is bonded, a fluoro group, a chloro group and a bromo group, particularly preferably a methoxy group, an ethoxy group, an n-butoxy group, a phenoxy group, a naphthoxy group, a methylthio group, an ethylthio group, a butylthio group, a phenylthio group Group, naphthylthio group, dimethylamino group, diethylamino group, dibutylamino group, piperidino group, morpholino group, fluoro group, chloro group and bromo group.

A ⁺ represents a group having a tetravalent covalently bonded nitrogen atom, and examples thereof include the following.

Ammonio group (ammonio group, butylammonio group, octylammonio group, dimethylammonio group, triethylammonio group, diisopropylethylammonio group, phenyldimethylammonio group, etc.);
Pyrrolidinio group (N-methylpyrrolidinio group, N-methyl-2,5-dimethylpyrrolidinio group, N-ethylpyrrolidinio group, etc.);
Piperidinio groups (N-methylpiperidinio group, N-methyl-2,6-dimethylpiperidinio group, N-ethyl-2,2,6,6-tetramethylpiperidinio group, etc.);
Quinuclidinio groups (such as quinuclidinio groups and 3-hydroxyquinuclidinio groups);
Morpholinio group (N-methylmorpholinio group etc.);
Imidazolinio groups (N-methylimidazolinio group, N-ethylimidazolinio group, etc.)
;
Amidinio group (N-methyltetrahydropyrimidinio group, 1,8-diazabicyclo [5.4.0] -7-undecenio group, 1,5-diazabicyclo [4.3.0] -5-nonenio group, etc.);
Guanidio group (pentamethyl guanidio group and 2-tert-butyl-1,1,3,3-tetramethylguanio group, 1,5,7-triazabicyclo [4.4.0] -5 Decenio group, 7-methyl-1,5,7-triazabicyclo [4.4.0] -5-decenio group, etc.);
An imidazolio group (N-methylimidazolio group, N-ethylimidazolio group and the like);
Thiazonio group (benzothiazonio group, etc.);
Pyridinio group (pyridinio group, 4,4-dimethylaminopyridinio group, 4-octylpyridinio group, etc.);
A quinolinio group (such as a quinolinio group);
Isoquinolinio group (isoquinolinio group etc.);
Acridio group (acridio group etc.).

  Among these ammonium groups, an ammonio group, an alkylammonio group (such as a butylammonio group, an octylammonio group, a dimethylammonio group, a triethylammonio group, a diisopropylethylammonio group and a phenyldimethylammonio group), a pyrrolidinio group ( N-methylpyrrolidinio group, N-methyl-2,5-dimethylpyrrolidinio group, N-ethylpyrrolidinio group, etc.), piperidinio group (N-methylpiperidinio group, N-methyl-2,6) -Dimethylpiperidinio group and N-ethyl-2,2,6,6-tetramethylpiperidinio group), quinuclidinio group (such as quinuclidinio group and 3-hydroxyquinuclidinio group), morpholinio group (N- Methylmorpholinio group), imidazolinio group (N-methylimidazolinio group and N-ethyl) Midazolinio group, etc.), amidinio group (N-methyltetrahydropyrimidinio group, 1,8-diazabicyclo [5.4.0] -7-undecenio group and 1,5-diazabicyclo [4.3.0] -5 Noneniio group, etc.), guaniodio group (pentamethylguaniodio group and 2-tert-butyl-1,1,3,3-tetramethylguaniodio group, 1,5,7-triazabicyclo [4.4. 0] -5-decenio group, 7-methyl-1,5,7-triazabicyclo [4.4.0] -5-decenio group), imidazolio group (N-methylimidazolio group and N-ethylimidazo) Rio group etc.) are preferred.

Y is a divalent organic group that bonds the tetravalent covalently bonded nitrogen atom of A ⁺ and the anionic boron atom.
Examples of the divalent organic group include an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 2 to 18 carbon atoms, an alkynylene group having 2 to 18 carbon atoms, an aralkylene group having 7 to 24 carbon atoms, and these hydrocarbon groups. Groups in which at least one hydrogen atom is substituted with a group having an oxygen atom (hydroxy group, alkoxy group, aryloxy group, ester group, etc.), groups substituted with a group having a sulfur atom (mercapto group, alkylthio group, arylthio group) Groups, thioester groups, sulfoxide groups, sulfonyl groups, etc.), nitrogen-containing groups (amino groups, amide groups, urea groups, etc.) or halogeno groups (fluoro groups, chloro groups, bromo groups, iodo groups, etc.) Groups in which some of the carbon atoms of these groups and these hydrocarbon groups have oxygen atoms (ether groups, keto groups, ester groups, etc.), Group (an imino group, an amido group, and a urea group, etc.) having an atom group having or sulfur atom (thioether group, a sulfide group, a sulfoxide group, sulfonyl group and a thioester group, etc.) and the like.

Examples of the alkylene group having 1 to 18 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a 2-methylpropylene group, a hexylene group, an octylene group, a dodecylene group, an octadecylene group, and a cyclohexane-1,4-diyl group. , Cyclopentane-1,1-diyl group, bicyclo [2.2.1] -2,5-heptylene group and bicyclo [2.2.2] -2,3
-An octylene group etc. are mentioned.

  Examples of the group in which at least one hydrogen atom of the alkylene group having 1 to 18 carbon atoms is substituted with a group having an oxygen atom include a methoxymethylene group, a 1-methoxyethylene group, a 2-butoxypropylene group, and 3,3-dimethoxy. Butylene group, 2-methyl-3-ethoxypropylene group, 3-acetoxyhexylene group, 4-pivaloyloxyoctylene group, 6-hydroxydodecylene group, 2-phenoxyoctadecylene group and 2,3- And ethoxy-cyclohexane-1,4-diylene group.

  Examples of the group in which at least one hydrogen atom of the alkylene group having 1 to 18 carbon atoms is substituted with a group having a sulfur atom include a methylthiomethylene group, a 1-ethylthioethylene group, a 2-phenylthiopropylene group, 3, 3 -A dithiocyclohexyl butylene group, a 2-methylsulfonylpropylene group, a 3-acetylthiohexylene group, a 4-phenylsulfenyloctylene group, a 6-mercaptododecylene group, a 2-phenylthiooctadecylene group, and the like.

  Examples of the group in which at least one hydrogen atom of the alkylene group having 1 to 18 carbon atoms is substituted with a group having a nitrogen atom include an acetamidomethylene group, a 1-dimethylaminoethylene group, a 2-dicyclohexylaminopropylene group, and a 6-aminododecylene. Group, 2-methylureido octadecylene group and the like.

  Examples of the group in which at least one hydrogen atom of the alkylene group having 1 to 18 carbon atoms is substituted with a halogeno group include a difluoromethylene group, a 1,2-dichloroethylene group, a 3-bromocyclohexane-1,4-diylene group, and 2 -An iodomethyl propylene group etc. are mentioned.

Examples of the group in which some of the carbon atoms of these alkylene groups are substituted with a group having an oxygen atom include 2-oxapropylene group, 3-oxapropylene group, 5-methyl-5-azaoctylene group, 3,6- Dioxaoctylene group, 3,6,9-trioxaundecyl group and 3-oxo-1-butylene group, methylenecarboxyethylene group (—CH ₂ COOC ₂ H ₄ —), 6-oxododecylene group, etc. The group substituted with a group having a nitrogen atom includes a 2-azapropylene group, a methylenecarbamoylethylene (—CH ₂ CONHC ₂ H ₄ —) group and a diethylene ureylene group (—C ₂ H ₄ NHCONHC ₂ H ₄ — As the group substituted with a group having a sulfur atom, 2-thiapropylene group, 4-thiahexylene group, methylene Ruhonirumechiren group _{(-CH 2 SO 2 CH 2 -} ) and ethylene sulfinyl propylene _{(-C 2 H 4 SOC 3 H} 6 -) and the like.

  Examples of the alkenylene group having 2 to 18 carbon atoms include vinylene group, propenylene group, 1-butenylene group, 2-methylpropenylene group, 1-hexenylene group, 2-hexenylene group, 1-octenylene group and 1-dodecenylene group. 1-octadecenylene group, 2-cyclohexene-1,4-diyl group, 2-cyclopentene-1,1-diyl group, bicyclo [2.2.1] -2-heptene-2,5-diyl group and bicyclo [2.2.2] -5-octene-2,3-diyl group and the like.

  Examples of the group in which at least one hydrogen atom of the alkenylene group having 2 to 18 carbon atoms is substituted with a group having an oxygen atom include 1-methoxyethenylene group, 2-butoxypropenylene group, 3,3-dimethoxy-1 -Butenylene group, 2-methyl-3-ethoxypropenylene group, 3-acetoxy-1-hexenylene group, 4-pivaloyloxy-1-octenylene group, 6-hydroxy-1-dodecenylene group, 2-phenoxy-1-octadecenylene Group and a 5,6-ethoxy-2-cyclohexene-1,4-diyl group.

  Examples of the group in which at least one hydrogen atom of the alkenylene group having 2 to 18 carbon atoms is substituted with a group having a sulfur atom include 1-methylthioethenylene group, 1-ethylthiopropenylene group, 2-phenylthiopropenylene Group, 3,3-dithiocyclohexyl-1-butenylene group, 2-methylsulfonylpropenylene group, 3-acetylthio-1-hexenylene group, 4-phenylsulfenyl-1-octenylene group, 6-mercapto-2-dodecenylene Group and 2-phenylthio-1-octadecenylene group.

  Examples of the group in which at least one hydrogen atom of the alkenylene group having 2 to 18 carbon atoms is substituted with a group having a nitrogen atom include an acetamidoethenylene group, a 1-dimethylaminoethenylene group, a 2-dicyclohexylaminopropenylene group, Examples include 6-amino-1-dodecenylene group and 2-methylureido-1-octadecenylene group.

  Examples of the group in which at least one hydrogen atom of the alkenylene group having 2 to 18 carbon atoms is substituted with a halogeno group include 1,2-difluoroethenyl group, 1,2-dichloroethenyl group, 3-bromo-2-cyclohexene Examples include -1,4-diyl group and 2-iodomethylpropenylene group.

Examples of the group in which a part of carbon atoms of these alkenylene groups are substituted with a group having an oxygen atom include 3-oxabutenylene group, 3-oxa-1-hexenylene group, 3,6-dioxa-1-octenylene group 3,6,9-trioxa-1-undecenylene group, 3-oxo-1-butenylene group, propenylene carboxyethylene group (—CH═CHCH ₂ COOC ₂ H ₄ —), and 6-oxo-1-dodecenylene group Examples of the group substituted with a group having a nitrogen atom include a 3-azabutenylene group, a 5-methyl-5-aza-1-octenylene group, and a methylenecarbamoylethenylene (—CH ₂ CONHCH═CH—) group. And dietenylene ureylene group (—CH═CHNHCONHCH═CH—) and the like, and substituted with a group having a sulfur atom The 3-Chiabuteniren group, 4-thia-1-to Kiseniren groups, et tennis Ren sulfonyl methylene group _{(-CH = CHSO 2 CH 2 -} ) and d tennis sulfide sulfonyl propylene group _{(-CH = CHSOC 3 H 6 -} ) , etc. Is mentioned.

  Examples of the alkynylene group having 2 to 18 carbon atoms include ethynylene group, propynylene group, 1-butynylene group, 2-methylpropynylene group, 1-hexynylene group, 2-hexynylene group, octynylene group, 3-octynylene group, 1 -Dodecynylene group, 1-octadecynylene group, etc. are mentioned.

  Examples of the group in which at least one hydrogen atom of the alkynylene group having 2 to 18 carbon atoms is substituted with a group having an oxygen atom include a butoxypropynylene group, a 3,3-dimethoxy-1-butynylene group, an ethoxypropynylene group, A 3-acetoxy-1-hexynylene group, a 4-pivaloyloxy-1-octynylene group, a 6-hydroxy-1-dodecynylene group, a 3-phenoxy-1-octadecylene group, and the like can be given.

  Examples of the group in which at least one hydrogen atom of the alkynylene group having 2 to 18 carbon atoms is substituted with a group having a sulfur atom include 3-ethylthiopropynylene group, 3-phenylthiopropynylene group, 3,3-dithio Cyclohexyl-1-butynylene group, methylsulfonylpropynylene group, 3-acetylthio-1-hexynylene group, 4-phenylsulfenyl-1-octynylene group, 6-mercapto-3-dodecynylene group and 4-phenylthio-1-octadecynylene Groups and the like.

Examples of the group in which at least one hydrogen atom of the alkynylene group having 2 to 18 carbon atoms is substituted with a group having a nitrogen atom include an acetamidopropynylene group, 1-dimethylaminopropylenylene group, dicyclohexylaminopropynylene group, 6 -Amino-1-dodecynylene group, 3-methylureido-1-octadecynylene group, and the like.

  Examples of the group in which at least one hydrogen atom of the alkynylene group having 2 to 18 carbon atoms is substituted with a halogeno group include a difluoropropynylene group, a dichloropropenylene group, a 3-bromo-1-hexynylene group, and 3-iodomethyl- 1-butynylene group etc. are mentioned.

Examples of the group in which a part of carbon atoms of these alkynylene groups are substituted with a group having an oxygen atom include 3-oxabutynylene group, 3-oxa-1-hexynylene group, and 3,6-dioxa-1-octynylene group , 3,6,9-trioxa-1-undecynylene group, 6-oxo-1-dodecynylene group, propynylenecarboxyethylene group (—C≡CCH ₂ COOC ₂ H ₄ —) and the like, and a group having a nitrogen atom Examples of the group substituted with 3-azabutynylene, 5-methyl-5-aza-1-octynylene, methylenecarbamoylethynylene (—CH ₂ CONHC≡C—) and dipropynylene ureylene (—C ≡CCH ₂ NHCONHCH ₂ C≡C-) and the like, and as the radicals substituted by a sulfur atom, 3- Chiabuchiniren group 4-thia-1 to Kishiniren group, ethynylene sulfonyl methylene group (-C≡CSO ₂ CH ₂ -) and ethynylene sulfide sulfonyl propylene (-C≡CSOC ₃ H ₆ -) and the like.

  Examples of the aralkylene group having 7 to 24 carbon atoms include p-phenylenemethylene group, m-phenylenemethylene group, p-phenyleneethylene group, m-phenyleneethylene group, p-phenylene-methylmethylene group, 3,5-dimethyl-1 -Methylene-1,4-phenylene group, p-phenylenedimethylmethylene group, p-phenylene-hexylene group, p-biphenylenemethylene group, naphthalene-4-methylene-1,4-diyl group, naphthalene-6-methylene- 2,6-diyl group, naphthalene-5-butylene-1,5-diyl group, anthracene-9-methylene-9,10-diyl group and anthracene-9-ethylene-9,10-diyl group, and aromatic ring A group partially substituted with an oxygen atom, a sulfur atom or a nitrogen atom (thiophene-2-methylene-2,5-diyl group, Lysine-2-methylene-2,6-diyl group, a xanthene-1-methylene-1,4-diyl group).

  Examples of the group in which at least one hydrogen atom of the aralkylene group having 7 to 24 carbon atoms is substituted with a group having an oxygen atom include a 3-methoxy-1,4-phenylene-4-methylene group, 4-acetoxy-1, 3-phenylene-3-ethylene group, α, α-dimethoxy-1,4-phenylene-4-methylene group, 1,4-diethoxyanthracene-9-methylene-9,10-diyl group and 1,4-dimethoxy Anthracene-9-ethylene-9,10-diyl group and a group in which a part of the aromatic ring is substituted with an oxygen atom, a sulfur atom or a nitrogen atom (3,4-dibutoxythiophene-2-methylene-2,5- Diyl group, 4-acetoxypyridine-2-methylene-2,6-diyl group, 6-methoxyxanthene-1-methylene-1,4-diyl group, etc.).

  Examples of the group in which at least one hydrogen atom of the aralkylene group having 7 to 24 carbon atoms is substituted with a group having a sulfur atom include α, α-dithioethylene-p-phenylene-hexylene group, 3-methylsulfanyl-1 , 4-phenylene-4-methylene group, 3-methylsulfonyl-1,4-phenylene-4-ethylene group, 2-methylthionaphthalene-4-methylene-1,4-diyl group, 3,4-methylthionaphthalene-6 -Methylene-2,6-diyl group and 4-mercaptonaphthalene-5-butylene-1,5-diyl group and a group in which a part of the aromatic ring is substituted with an oxygen atom, a sulfur atom or a nitrogen atom (3-phenylthio Thiophene-2-methylene-2,5-diyl group, 4-methanesulfanylpyridine-2-methylene-2,6-diyl group, 6-butylthioxan Ten-1-methylene-1,4-diyl group, etc.).

  Examples of the group in which at least one hydrogen atom of the aralkylene group having 7 to 24 carbon atoms is substituted with a group having a nitrogen atom include 4-dimethylamino-1,3-phenylene-3-methylene group and 3-methylthio-1 , 4-phenylene-4-ethylene group and a group in which a part of the aromatic ring is substituted with oxygen atom, sulfur atom or nitrogen atom (3-dimethylaminothiophene-2-methylene-2,5-diyl group, 4-pyrrole Zircyridine-2-methylene-2,6-diyl group, 6-dibutylaminoxanthene-1-methylene-1,4-diyl group) and the like.

  Examples of the group in which at least one hydrogen atom of the aralkylene group having 7 to 24 carbon atoms is substituted with a halogeno group include 4-bromo-1,3-phenylene-3-methylene group, 4-chloro-1,3-phenylene -3-methylene group, 4-fluoro-1,3-phenylene-3-methylene group and 2,3,5,6-tetrafluoro-1,3-phenylene-3-methylene group and part of the aromatic ring is oxygen Groups substituted with an atom, sulfur atom or nitrogen atom (3-bromothiophene-2-methylene-2,5-diyl group, 4-chloropyridine-2-methylene-2,6-diyl group, 6-fluoroxanthene- 1-methylene-1,4-diyl group, etc.).

  Examples of the group in which a part of carbon atoms of the aralkylene group having 7 to 24 carbon atoms are substituted with oxygen atom, sulfur atom and nitrogen atom include p-phenyleneoxymethylene group, p-phenylenethiomethylene group, p-phenylene- N-methylaminomethylene group, m-phenyleneoxymethylene group, p-phenylene-α-oxoethylene group, m-phenylenethioethylene group, p-phenylenecarbonyloxy-methylmethylene group, p-phenylenesulfonylmethylene group, p- Phenylene-5-oxohexylene group, p-biphenylene-amimethylene group, naphthalene-4-ureylenemethylene-1,4-diyl group, naphthalene-6-carbomethylene-2,6-diyl group, naphthalene-5 (3-Oxabutylene) -1,5-diyl group, anthracene-9-carbomethyl Down-9,10-diyl group, and anthracene-9-carbonitrile ethylene-9,10-diyl group, and the like.

  Y is preferably a group in which a part of carbon atoms of an aralkylene group having 7 to 24 carbon atoms and an aralkylene group having 7 to 24 carbon atoms is substituted with a group having an oxygen atom, and an aralkylene group having 7 to 24 carbon atoms. Further, a group in which a part of carbon atoms of the aralkylene group having 7 to 24 carbon atoms is substituted with a keto group is more preferable.

  Examples of the group in which a part of carbon atoms of the aralkylene group having 7 to 24 carbon atoms and the aralkylene group having 7 to 24 carbon atoms are substituted with a keto group include the group represented by the following general formula (2) and the following general formula The group represented by (3) is preferred.

[In General Formula (2), Y ¹ is an alkylene group having 1 to 18 carbon atoms, Ar is an arylene group, and at least one hydrogen atom of Ar has an alkyl group or oxygen atom having 1 to 8 carbon atoms. And a group having a sulfur atom, or a halogeno group. ]

[In General Formula (3), Y ¹ is an alkylene group having 1 to 18 carbon atoms, Ar is an arylene group, and at least one hydrogen atom of Ar has an alkyl group or oxygen atom having 1 to 8 carbon atoms. And a group having a sulfur atom, or a halogeno group. ]

In the general formulas (2) and (3), Y ¹ is an alkylene group having 1 to 18 carbon atoms, and the alkylene group having 1 to 18 carbon atoms may be an alkylene group having 1 to 18 carbon atoms exemplified as the above Y. The same can be mentioned.
Ar is an arylene group, and includes a phenylene group, a naphthylene group, an anthrylene group, and the like, and at least one hydrogen atom of Ar is a group having an alkyl group having 1 to 8 carbon atoms, an oxygen atom, or a group having a sulfur atom. Alternatively, it may be substituted with a halogeno group.
Preferred examples of Ar include p-phenylene group, m-phenylene group, p-biphenylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, naphthalene-1,5-diyl group, anthracene -9,10-diyl group, 3-methoxy-1,4-phenylene group, 4-acetoxy-1,3-phenylene group, 3-methylsulfanyl-1,4-phenylene group, 3-methylsulfonyl-1,4 -Phenylene group, 2-methoxynaphthalene-1,4-diyl group, 3,4-dihydroxynaphthalene-2,6-diyl group, 4-mercaptonaphthalene-1,5-diyl group, 4-dimethylamino-1,3 -Phenylene group, 3-methylthio-1,4-phenylene group, 4-bromo-1,3-phenylene group, 4-chloro-1,3-phenylene group, 4-fluoro group Oro-1,3-phenylene group and 2,3,5,6-tetrafluoro-1,3-phenylene group.

  Of the groups represented by the general formula (2), preferred are p-phenylenemethylene group, m-phenylenemethylene group, p-phenyleneethylene group, m-phenyleneethylene group, p-phenylene-methylmethylene group, 3 , 5-dimethyl-1-methylene-1,4-phenylene group, p-phenylenedimethylmethylene group, p-phenylene-butylene group, p-phenylene-hexylene group, p-biphenylenemethylene group, naphthalene-4-methylene- 1,4-diyl group, naphthalene-6-methylene-2,6-diyl group, naphthalene-5-butylene-1,5-diyl group, anthracene-9-methylene-9,10-diyl group and anthracene-9- Ethylene-9,10-diyl group, 4-methoxy-1,3-phenylene-3-methylene group, 4-acetoxy-1,3 Phenylene-3-ethylene group, α, α-dimethoxy-1,4-phenylene-4-methylene group, 1,4-diethoxyanthracene-9-methylene-9,10-diyl group and 1,4-dimethoxyanthracene- 9-ethylene-9,10-diyl group, α, α-dithioethylene-p-phenylene-hexylene group, 3-methylsulfanyl-1,4-phenylene-4-methylene group, 3-methylsulfonyl-1,4 -Phenylene-4-ethylene group, 2-methoxynaphthalene-4-methylene-1,4-diyl group, 3,4-dihydroxynaphthalene-6-methylene-2,6-diyl group and 4-mercaptonaphthalene-5-butylene -1,5-diyl group, 4-dimethylamino-1,3-phenylene-3-methylene group, 3-methylthio-1,4-phenylene-4-e Tylene group, 4-bromo-1,3-phenylene-3-methylene group, 4-chloro-1,3-phenylene-3-methylene group, 4-fluoro-1,3-phenylene-3-methylene group and 2, A 3,5,6-tetrafluoro-1,3-phenylene-3-methylene group may be mentioned.

  Of the groups represented by the general formula (3), preferred are p-phenylene-α-oxoethylene group, p-phenylene-α-oxobutylene group, p-phenylenecarbonyloxy-methylmethylene group, p-phenylene. -5-oxohexylene group, p-biphenylene-α oxoethylene group, p-phenylene-α-oxo-phenylethylene group, naphthalene-6-carbomethylene-2,6-diyl group, anthracene-9-carbomethylene- Examples include 9,10-diyl group and anthracene-9-carboethylene-9,10-diyl group.

  The borate salt of the present invention can be produced by a known method such as the following method 1 and method 2.

Method 1: For the borate salt intermediate (D1) having a leaving group, the amine compound (A ¹ ) corresponding to the group (A ⁺ ) having a tetravalent covalently bonded nitrogen atom is added in a solvent or without using a solvent. How to react.
Method 2: A compound (G) having a leaving group is reacted with a borate salt intermediate (D2) having an amino group (A ² ) corresponding to a group (A ⁺ ) having a tetravalent covalently bonded nitrogen atom in a solvent. Or the method of making it react without using a solvent.

Method 1 is a method in which an amine compound (A ¹ ) corresponding to a cation (A ⁺ ) is reacted with a borate salt intermediate (D1) having a leaving group in a solvent or without using a solvent. The reaction formula (1) can be used.

In the reaction formula (1), A ⁺ , R ¹ and Y are the same as those in the general formula (1), Z is a leaving group, and A ¹ is a group having a tetravalent covalently bonded nitrogen atom (A ⁺ ). The corresponding amine compound, M ⁺ is a metal cation. Incidentally, the leaving group in the present invention is combined with Y, binding to Y when reacted with A ¹ means a group which cleaves disconnected.

  Leaving groups include halogeno groups (such as chloro and bromo groups), sulfonyloxy groups (such as trifluoromethylsulfonyloxy and p-toluenesulfonyloxy groups), and acyloxy (such as acetoxy and trifluoromethylcarbonyloxy groups). From the viewpoint of ease of production, a halogeno group is preferable.

The borate salt intermediate (D1) having a leaving group can be synthesized by a known method (the method described in Journal of Polymer Science: Part A: Polymer Chemistry, vol 34, 2817 (1996), etc.), and the corresponding leaving group alkyl It can be obtained by reacting an organometallic compound or aralkyl organometallic compound with an alkylboron compound, arylboron compound or boron halide compound in an organic solvent. As the alkyl organometallic compound and the aralkyl organometallic compound, lithium compounds such as alkyl lithium and aralkyl lithium, and magnesium compounds (Grignard reagent) such as alkyl magnesium halide and aralkyl magnesium halide are preferably used.

  The reaction conditions of the alkyl boron compound, aryl boron compound or boron halide compound and the alkyl or aralkyl organometallic compound are -80 ° C to 100 ° C, preferably -50 ° C to 50 ° C, most preferably -30 ° C to 30 ° C. It is. As the organic solvent to be used, hydrocarbons (hexane, heptane, toluene, xylene, etc.), cyclic ethers (tetrahydrofuran, dioxane, etc.) and chlorinated solvents (chloroform, dichloromethane, etc.) are preferably used.

The metal cation (M ⁺ ) of the borate salt intermediate (D1) obtained above is preferably an alkali metal cation from the viewpoints of stability and solubility. Of these, a sodium cation, a potassium cation, and a lithium cation are more preferable. In the case of reacting with a Grignard reagent, it is preferable to perform metal exchange during or after the reaction by adding sodium hydrogen carbonate, sodium chloride, potassium chloride, lithium chloride, sodium bromide, potassium bromide, lithium bromide or the like.

  In the borate salt intermediate (D1), when the α-position carbon of the alkyl group substituted with the aromatic ring group is halogenated (preferably brominated), a halogen (preferably bromine) is used as the halogenation method. Alternatively, a method using N-bromosuccinimide combined with a radical generator is simple and preferable (4th edition, Experimental Chemistry Course 19, edited by the Chemical Society of Japan, p422).

The amine compound (A ¹ ) is added to the borate salt intermediate (D1) by addition of a residue obtained by removing the leaving group from the borate salt intermediate (D1), whereby the zwitterionic borate salt of the present invention is added. Becomes a group (A ⁺ ) having a tetravalent covalently bonded nitrogen atom.
As the amine compound (A ¹ ), ammonia, alkylamine (such as butylamine, octylamine, dimethylamine, triethylamine, diisopropylethylamine, dicyclohexylamine, and phenyldimethylamine);
Pyrrolidine (N-methylpyrrolidine, N-methyl-2,5-dimethylpyrrolidine, N-ethylpyrrolidine, etc.);
Piperidine (N-methylpiperidine, N-methyl-2,6-dimethylpiperidine and N-ethyl-2,2,6,6-tetramethylpiperidine, etc.);
Quinuclidine (such as quinuclidine and 3-hydroxyquinuclidine);
Morpholine (such as N-methylmorpholine);
Imidazolines (such as N-methylimidazoline and N-ethylimidazoline);
Amidine (N-methyltetrahydropyrimidine, 1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter referred to as DBU) and 1,5-diazabicyclo [4.3.0] -5-nonene (hereinafter referred to as DBU) DBN)));
Guanidine (pentamethylguanidine and 2-tert-butyl-1,1,3,3-tetramethylguanidine, 1,5,7-triazabicyclo [4.4.0] -5-decene, 7-methyl-1 , 5,7-triazabicyclo [4.4.0] -5-decene, etc.);
Imidazole (N-methylimidazole, N-ethylimidazole, etc.);
Thiazole (benzothiazole, etc.);
Pyridine; (pyridine, 4-4-dimethylaminopyridine, 4-octylpyridine, etc.); quinoline (quinoline, etc.);
Isoquinoline (such as isoquinoline);
Examples include acridine (acridine and the like).

Among these, amine compounds (A ¹ ) include ammonia, alkylamines (butylamine, octylamine, dimethylamine, triethylamine, diisopropylethylamine, phenyldimethylamine, etc.), N-alkylpyrrolidines (N-methylpyrrolidine, N-methyl- 2,5-dimethylpyrrolidine and N-ethylpyrrolidine), N-alkylpiperidine (N-methylpiperidine, N-methyl-2,6-dimethylpiperidine and N-ethyl-2,2,6,6-tetramethylpiperidine) ), Quinuclidine (such as quinuclidine and 3-hydroxyquinuclidine), N-alkylmorpholine (such as N-methylmorpholine), N-alkylimidazoline (such as N-methylimidazoline and N-ethylimidazoline), amidine (N-methyl) Trahydropyrimidine, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene), guanidine (pentamethylguanidine and 2-tert- Butyl-1,1,3,3-tetramethylguanidine, 1,5,7-triazabicyclo [4.4.0] -5-decene, 7-methyl-1,5,7-triazabicyclo [4 4.0] -5-decene, etc.) and N-alkylimidazoles (N-methylimidazole, N-ethylimidazole, etc.) are preferred.

Method 1 may be carried out in a solvent or without using a solvent, but is preferably carried out in a solvent from the viewpoint of suppressing side reactions.
Solvents used in Method 1 include hydrocarbons (hexane, heptane, toluene, xylene, etc.), nitriles (acetonitrile, propionitrile, etc.), alcohols (methanol, propanol, etc.), water, ketones (acetone, methyl ethyl ketone, and methyl isobutyl ketone). Etc.), amides (N, N-dimethylformamide, N-methylpyrrolidone, etc.), chlorinated solvents (chloroform, dichloromethane, etc.) and the like.
These solvents may be used alone or in combination of two or more.

In Method 1, the conditions for carrying out the addition reaction between the amine compound (A ¹ ) and the borate salt intermediate (D1) are as follows: in the presence of the borate salt intermediate (D1), the amine compound (A ¹ ) or amine compound (A It is preferable to add dropwise a solution prepared by dissolving ¹ ) in the above solvent. Speed in the case of dropping, from the viewpoint of suppression of side reactions, 0.1～20ML / min as the amine compound ^{(A 1)} (more preferably 0.5 to 10 / min) is preferred.
In Method 1, the ratio between the borate salt intermediate (D1) and the amine compound (A ¹ ) is preferably such that the molar ratio is 0.6 to 1.5 from the viewpoint of suppressing side reactions. 0.8 to 1.2 is more preferable. The reaction between the borate salt intermediate (D1) and the amine compound (A ¹ ) is usually −20 ° C. to 150 ° C., preferably −10 ° C. to 100 ° C., most preferably 0 ° C. to 70 ° C. from the viewpoint of suppressing side reactions. It is.

In Method 2, a compound (G) having a leaving group is added to a borate salt intermediate (D2) having an amino group (A ² ) corresponding to a group (A ⁺ ) having a tetravalent covalently bonded nitrogen atom in a solvent. Or without using a solvent, and can be represented by the following reaction formula (2).

In the reaction formula (2), A ⁺ , R ¹ and Y are the same as those in the general formula (1), Z is a leaving group, and A ² is a group having a tetravalent covalently bonded nitrogen atom (A ⁺ ). It is a corresponding amino group, E is a functional group that becomes a constituent component of a group (A ⁺ ) having a tetravalent covalently bonded nitrogen atom by reacting with A ^2, and M ⁺ is a metal cation.

The compound (G) is represented by EZ in the reaction formula (2), and is added to the amino group (A ² ) of the leaving group (Z) and the borate salt intermediate (D2) to add a tetravalent covalent bond. It consists of a functional group (E) which is a constituent component of a group (A ⁺ ) having a nitrogen atom.
By the reaction between the compound (G) and the borate salt intermediate (D2), the functional group (E), which is a residue obtained by removing the leaving group from the compound (G), has an amino group ( It becomes a group (A ⁺ ) having a tetravalent covalently bonded nitrogen atom which is added to A ² ) and which the zwitterionic borate salt of the present invention has.

Examples of the leaving group (Z) include halogeno groups (chloro group, bromo group, iodide group, etc.), sulfonyloxy groups (trifluoromethylsulfonyloxy group, methanesulfonyloxy group, p-toluenesulfonyloxy group, etc.) and acyloxy ( An acetoxy group and a trifluoromethylcarbonyloxy group).
Preferable examples of the functional group (E) include an alkyl group having 1 to 18 carbon atoms and an aralkyl group having 7 to 30 carbon atoms from the viewpoint of reactivity with the amino group (A ² ).

From the viewpoint of reactivity and the like, preferred compounds (G) include methyl bromide, methyl iodide, dimethyl sulfate, methyl methanesulfonate, methyl p-toluenesulfonate, ethyl bromide, diethyl sulfate, butyl bromide, and benzyl. Bromide, benzyl chloride, 1-bromomethylnaphthalene, 2-chloromethylnaphthalene, chloroethylbenzene, α-bromoacetone, α
-Chlorobenzophenone and α-bromoethylbenzene.

The amino group (A ² ) is a constituent component of a group (A ⁺ ) having a tetravalent covalently bonded nitrogen atom that the borate salt intermediate (D2) has, and at least one hydrogen atom in the amine compound (A ¹ ) And a monovalent amino group that is a residue obtained by removing one hydrogen atom from an amine compound having a hydrogen atom.
Among them, amino group (A ² ) includes amino group (NH ₂ ), alkylamino group (butylamino group, octylamino group, dimethylamino group, etc.), pyrrolidino group (pyrrolidino group, 2,5-dimethylpyrrolidino group, etc.) ), Piperidino group (piperidino group, 2,6-dimethylpiperidino group and 2,2,6,6-tetramethylpiperidino group etc.), quinuclidino group (quinuclidino group and 3-hydroxyquinuclidino group etc.) , Morpholino group, imidazolino group (2-methylimidazolino group and imidazolino group etc.), amidino group (tetrahydropyrimidino group etc.), guanidino group (tetramethylguanidino group and 1,5,7-triazabicyclo [4. 4.0] -5-decenyl group and the like, and imidazolino groups (such as imidazolino group and 2-methylimidazolino group) are preferable.

The metal cation (M ⁺ ) of the borate salt intermediate (D2) is the same as the borate salt intermediate (D1), and the preferred one is also the same.

A borate salt intermediate (D2) having an amino group (A ² ) can be obtained by a known method, and can be obtained by using the same method as the borate salt intermediate (D1). The reaction conditions for (D2) and compound (G) are the same as the reaction conditions for borate salt intermediate (D1) and amine compound (A ¹ ), and the preferred reaction conditions are also the same.

The zwitterionic borate salt of the present invention can be obtained by further isolating the borate salt from the reaction mixture obtained in the above-mentioned method 1 and method 2.
Isolation can be performed by a known method, and after concentrating an organic solvent solution containing a zwitterionic borate salt as necessary, a poor solvent of the zwitterionic borate salt is added to precipitate the zwitterionic borate salt. A method of isolating and a method of isolating a zwitterionic borate salt from an organic solvent solution containing the zwitterionic borate salt by a chromatographic method can be used.

  In the method of depositing and isolating zwitterionic borate salt by adding a poor solvent, the chain ether, the hydrocarbon solvent and the ester solvent (such as ethyl acetate and butyl acetate) are used as the poor solvent. I can do it.

In the method of precipitating and isolating the zwitterionic borate salt by adding a poor solvent, when the zwitterionic borate salt is an oil, the isolated oil is separated from the organic solvent solution by a decantation method, etc. A zwitterionic borate salt can be obtained by distilling off the organic solvent contained in the oil.
When the zwitterionic borate salt is a solid, the precipitated solid is separated from the organic solvent solution by a decantation method or the like, and the organic solvent contained in the solid is distilled off to obtain the zwitterionic borate salt. .

  In the case of isolating zwitterionic borate salt by chromatographic method, the zwitterionic borate salt is obtained by distilling off the organic solvent from the organic solvent solution containing the zwitterionic borate salt obtained after the separation operation. be able to.

  When the zwitterionic borate salt isolated by the above method is a solid, it may be recrystallized by a known method.

The zwitterionic borate salt of the present invention is a latent basic catalyst (a catalyst that does not have a catalytic action before irradiation with light, but does not have a catalytic action during storage, or has no catalytic action during storage. Can be applied to a catalyst that exhibits the action of a base catalyst).
For example, a curable resin composition comprising a curable resin or a polymerizable monomer that accelerates curing with a base, the zwitterionic borate salt of the present invention, and, if necessary, a solvent and / or an additive is easily configured. It can be cured by heat or light irradiation. Such a curable resin composition is excellent in storage stability because it contains the zwitterionic borate salt of the present invention.
As an example of a curing method, a curable resin composition containing the zwitterionic borate salt of the present invention is irradiated with light (also referred to as light irradiation) to generate a base, thereby promoting a curing reaction and curing. You can get things.
In the present invention, light irradiation means irradiation with active energy rays such as radiation, X-rays, electron beams, ultraviolet rays and visible rays.
In addition, you may heat as needed in the case of hardening reaction. Or hardening reaction can be accelerated | stimulated by heating the curable resin composition containing the zwitterionic borate salt of this invention, and hardened | cured material can be obtained.

  The curable resin composition of the present invention contains the zwitterionic borate salt and a curable compound.

The curable compound is not limited as long as it is a curable compound that is cured by the zwitterionic borate salt, and includes a curable urethane compound {(poly) isocyanate and a curing agent (polyol, thiol, etc.). Etc.}, curable epoxy compounds {curable compounds comprising (poly) epoxides and curing agents [acid anhydrides, carboxylic acids, (poly) epoxides, thiols, etc.], curable compounds comprising epichlorohydrin and carboxylic acids, etc.} , Curable acrylic compounds [(meth) acrylic monomers and / or (meth) acrylic oligomers and curing agents (such as thiol, malonate and acetylacetonate)], polysiloxane (cured and crosslinked) Curable compound to be polysiloxane), curable polyamide compound (Am), and poly Examples include a mid compound.
Among them, a curable epoxy compound and a curable polyamide compound (Am) are preferable, and the curable epoxy compound includes a compound (J) having two or more glycidyl groups in the molecule and two or more in the molecule. More preferably, it is a curable compound comprising the compound (K) or acid anhydride (L) having an active hydrogen-containing group, and the curable polyamide compound (Am) is a repeating unit represented by the general formula (4). The polyamide resin (Am1) and / or the polyamide resin (Am2) having a repeating unit represented by the general formula (5) is more preferable.
In the above and the following, when referring to both and / or “acrylate” and “methacrylate”, when referring to “(meth) acrylate” and “acryl” and / or “methacryl”, “(meth) acryl” May be described respectively.

[In General Formula (4), (V) represents a tetravalent organic group, and (W) represents a divalent organic group. ]

[In General Formula (5), (V) represents a tetravalent organic group, (W) represents a divalent organic group, and X represents a hydroxyl group, a mercapto group, or an amino group. ]

As a curable compound contained in the curable resin composition of the present invention, a compound (J) having two or more glycidyl groups and a compound (K) having two or more active hydrogen-containing groups in the molecule or an acid anhydride When used in a curable compound comprising (L), the compound (J) having two or more glycidyl groups in the molecule includes bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and fat. Examples thereof include cyclic epoxy resins. In addition to these, a phenol novolac type epoxy resin, a heterocyclic epoxy resin, a hydrogenated bisphenol A type epoxy resin, a hydrogenated bisphenol F type epoxy resin, an aliphatic epoxy resin, a spiro ring-containing epoxy resin, and the like can also be used. Further, a thiirane compound similar to the glycidyl group in which the oxygen atom of the epoxy group is substituted with a sulfur atom can also be used.
These can be used individually or in mixture of 2 or more types.

Examples of the active hydrogen group possessed by the compound (K) having two or more active hydrogen-containing groups in the molecule include OH group, SH group, NH ₂ group and NHR group. The compound (K) is preferably a compound having at least two functional groups selected from the group consisting of OH group, SH group, NH ₂ group and NHR group. Note that R contained in the NHR group is a monovalent organic group bonded to a nitrogen atom.

Among the compounds (K), examples of the compound having an OH group include phenol resins and polyfunctional alcohols.
Examples of the phenolic resins include phenol novolac resins, xylylene novolac resins, bisphenol A novolac resins, triphenylmethane novolac resins, biphenyl novolac resins, and dicyclopentadiene phenol novolac resins.
Examples of the polyfunctional alcohols include alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, mannitol, glucose, hydroquinone and glycidol, and adducts of these alkylene oxides (such as ethylene oxide and propylene oxide). It is done.

  Among the compounds (K), examples of the compound having an SH group include thiophenols and polyfunctional thiols, such as trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, ethylene glycol bisthioglyco. 1,4-butanediol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, di (2-mercaptoethyl) ether, ethanedithiol, 1,4-butanedithiol, 1, 6-hexanedithiol, 1,4-dimercaptobenzene, 1,3,5-trimercaptomethylbenzene, 4,4′-thiodibenzenethiol, 2,4,6-trimercapto-s-triazine, 2-dibutyl Amino-4,6-dimercapto s-triazine, other terminal thiol group-containing polyether, terminal thiol group-containing polythioether, thiol compound obtained by reaction of epoxy compound and hydrogen sulfide, and thiol having terminal thiol group obtained by reaction of polythiol compound and epoxy compound Compounds and the like.

Among the compounds (K), examples of the compound having an NH ₂ group and an NHR group include aromatic polyamines and aliphatic polyamines. Specifically, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, Trimethylyl to xylenediamine, 2-methylpentamethylenediamine, aliphatic amines such as diethylaminopropylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornenediamine, 1,2-diaminocyclohexane Examples include isoalicyclic amines, diaminodiphenylmethane, metaphenylenediamine, and diaminodiphenylsulfone.

  As the acid anhydride (L), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, methylnorbornane- 2,3-dicarboxylic anhydride, tetraalkyltetrahydrophthalic anhydride, methylcyclohexenetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride Products, ethylene glycol bis (trimellitic anhydride) ester, glycerin bis (trimellitic anhydride) ester monoacetate, dodecenyl succinic anhydride and chlorendic anhydride.

  When the curable compound is a curable epoxy compound, the content of the zwitterionic borate salt contained in the curable resin composition of the present invention is cured from the viewpoint of curing speed and stability of the curable composition. The content is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the total weight of the active compound.

  When the curable compound is a curable epoxy compound, the total content of the curable compound contained in the curable resin composition of the present invention is based on the total weight of the curable composition from the viewpoint of the physical properties of the cured product. The amount is preferably 5 to 99% by weight, more preferably 10 to 60% by weight.

Curability comprising a compound (J) having two or more glycidyl groups in the molecule and a compound (K) or acid anhydride (L) having two or more active hydrogen-containing groups in the molecule as the curable compound. When using the compound, the content of the compound (K) is preferably 0.5 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the compound (J) from the viewpoint of the physical properties of the cured product according to the purpose. More preferably, it is 0.7-1.2 equivalent.
The content of the acid anhydride (L) is preferably from 0.7 to 1.5 equivalents, more preferably from 1 equivalent of the epoxy group of the compound (J), from the viewpoint of the physical properties of the cured product according to the purpose. 0.8 to 1.2 equivalents.

  Among the curable compounds contained in the curable resin composition of the present invention, a curable polyamide compound (Am) which is a preferable curable compound is obtained by reacting a polycarboxylic acid (or an acid anhydride thereof) with a polyamine. It is a thermosetting compound having repeating units bonded by repeating amide bonds.

  Of the curable polyamide compound (Am), more preferred is a polyamide resin (Am1) having a repeating unit represented by the general formula (4).

  In the general formula (4), (V) is a tetravalent organic group, and (W) is a divalent organic group.

  Examples of the tetravalent organic group (V) include a residue obtained by removing four hydrogen atoms from an aromatic ring of an aromatic compound (benzene, naphthalene, pyridine, thiophene, etc.), an alicyclic compound (cyclobutane, cyclopentane). And a residue obtained by removing four hydrogen atoms from the cyclic structure of norbornane, etc., a residue obtained by removing two hydrogen atoms from the aromatic ring of the aromatic compound, and a cyclic structure of the alicyclic compound. Two residues selected from residues excluding two hydrogen atoms, each directly or an ether group, a sulfide group, a phenylene group, a biphenylene group, an alkylene group having 1 to 8 carbon atoms, and a carbon number of 1 substituted by fluorine Groups of 8 to 8 alkylene groups, sulfone groups, sulfoxide groups, disulfide groups or ketone groups. Among these, (V) includes a residue obtained by removing 4 hydrogen atoms from benzene, a residue obtained by removing 4 hydrogen atoms from naphthalene, a residue obtained by removing 4 hydrogen atoms from cyclobutane, and a residue obtained by removing 4 hydrogen atoms from cyclopentane. Residues from which 2 hydrogen atoms have been removed from benzene, residues from which 2 hydrogen atoms have been removed from naphthalene, residues from which 2 hydrogen atoms have been removed from cyclobutane, and cyclohexane Two residues selected from the group consisting of residues obtained by removing two hydrogen atoms from pentane are substituted directly or by an ether group, sulfide group, sulfone group, keto group, alkylene group having 1 to 8 carbon atoms or fluorine. A group bonded with an alkylene group having 1 to 8 carbon atoms is preferred.

(W) that is a divalent organic group includes a residue obtained by removing two hydrogen atoms bonded to the aromatic ring of the aromatic compound, and two hydroxyl groups from the cyclic structure of the alicyclic compound. Two residues selected from a removed residue, a residue obtained by removing one hydrogen atom from the aromatic ring of the aromatic compound, and a residue obtained by removing one hydrogen atom from the alicyclic compound; Bonded to each other directly or through an ether group, sulfide group, phenylene group, biphenylene group, alkylene group having 1 to 8 carbon atoms, alkylene group having 1 to 8 carbon atoms substituted by fluorine, sulfone group, sulfoxide group, disulfide group or keto group It is a group.
Among them, a residue obtained by removing two hydrogen atoms from benzene, a residue obtained by removing two hydrogen atoms from naphthalene, a residue obtained by removing two hydrogen atoms from cyclobutane, and two hydrogen atoms from cyclopentane. Excluded residue, residue obtained by removing two hydrogen atoms from norbornane, 1 from benzene
Residues obtained by removing one hydrogen atom, residues obtained by removing one hydrogen atom from naphthalene, residues obtained by removing one hydrogen atom from cyclobutane, residues obtained by removing one hydrogen atom from cyclopentane, and Two residues selected from the group consisting of residues obtained by removing one hydrogen atom from norbornane are substituted directly or by an ether group, sulfide group, sulfone group, keto group, alkylene group having 1 to 8 carbon atoms or fluorine. Preferred is a group bonded with alkylene having 1 to 8 carbon atoms.

  The polyamide resin (Am1) is usually called a polyamic acid and can be obtained by reacting a tetracarboxylic dianhydride (T1) with a diamino compound (E1).

Examples of the tetracarboxylic dianhydride (T1) include alicyclic tetracarboxylic acids having 4 to 18 carbon atoms and acid anhydrides of aromatic tetracarboxylic acids having 6 to 30 carbon atoms, and 4 to 18 carbon atoms. As the alicyclic tetracarboxylic acid, cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, norbornanetetracarboxylic acid, 3,3 Examples include ', 4,4'-dicyclohexyltetracarboxylic acid. Examples of the aromatic tetracarboxylic acid having 6 to 30 carbon atoms include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3, 3 ′, 4,4′-benzophenonetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propanetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanetetra Carboxylic acid, 2,2-bis {4- (3,4-dicarboxyphenoxy) phenyl} hexafluoropropanetetracarboxylic acid, 2,2-bis {4- (3,4-dicarboxyphenoxy) phenyl} propanetetra Examples thereof include carboxylic acid and 3,3 ′, 4,4′-tetracarboxydiphenyltetramethyldisiloxane.
Preferred examples of the tetracarboxylic dianhydride (T1) include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- Diphenylsulfonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propanetetracarboxylic dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropanetetracarboxylic dianhydride, 2,2-bis {4- (3,4-dicarboxyphenoxy) phenyl} hexafluoropropanetetracarboxylic dianhydride 2,2-bis {4- (3,4-dicarboxyphenoxy) phenyl} propanetetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride And 1,2,3,4-cyclopentane tetracarboxylic acid dianhydride. These may be used alone or in combination of two or more.

  Examples of the diamino compound (E1) include aliphatic amine compounds having 4 to 18 carbon atoms, aromatic diamine compounds having 6 to 30 carbon atoms, p-phenylenediamine, tetramethyl-1,4-phenylenediamine, p -Xylenediamine, 2,4-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenylmethane, 4,4'-diamino Diphenyl sulfide, 4,4′-diaminodicyclohexylmethane, 1,5-diaminonaphthalene, 2,2-bis (4- (p-aminophenoxy) phenyl) propane, 2,2-bis (4-aminophenyl) hexafluoro Propane, 2,3-diaminopyridine, hexamethylenediamine Bis (aminomethyl) norbornane and acetoguanamine, and the like. These may be used alone or in combination of two or more.

  Of the curable polyamide compound (Am), a polyamide resin (Am2) having a repeating unit represented by the general formula (5) is more preferable.

  In the general formula (5), (V) which is a tetravalent organic group includes (V) included in the general formula (4) in which four hydrogen atoms removed from an aromatic ring or a cyclic structure are adjacent to each other. Residues that are a combination of two hydrogen atoms and residues obtained by removing two hydrogen atoms adjacent to each other from an aromatic ring or cyclic structure directly or ether group, sulfide group, sulfone group, keto group, carbon number A group bonded by an alkylene group having 1 to 8 carbon atoms or an alkylene group having 1 to 8 carbon atoms substituted by fluorine is preferable.

  In the general formula (5), (W) which is a divalent organic group is the same as that in the general formula (4), and preferred ones are also the same.

In formula (5), X is a hydroxyl group, a mercapto group or an amino group (NH _2).

  When the repeating unit represented by the general formula (5) is further subjected to a dehydration condensation reaction, when X is a hydroxyl group, polybenzoxazole is represented, when X is a mercapto group, polybenzothioxazole is represented, and X is an amino group. In this case, polybenzimidazole is obtained.

  Polyamide resin (Am2) is dicarboxylic acid, dicarboxylic acid halide or dicarboxylic ester) [Hereinafter, dicarboxylic acid, dicarboxylic acid halide or dicarboxylic ester is referred to as dicarboxylic acid derivative (T2). And a diaminodihydroxy compound (E2), a diaminodimercapto compound (E3), or a tetraamino compound (E4).

Examples of the dicarboxylic acid derivative (T2) include dicarboxylic acid derivatives of 6 to 30 carbon dicarboxylic acids. Examples of the dicarboxylic acid having 6 to 30 carbon atoms include terephthalic acid, 4,4′-dicarboxydiphenyl ether, benzophenone-4,4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and 2,2′-biphenyldicarboxylic acid. 4,4′-dicarboxydiphenylsulfone, 2,2′-bis (4-carboxyphenyl) propane, 2,2′-bis (4-carboxyphenyl) hexafluoropropane, 2,6-naphthalenedicarboxylic acid, bis (4-Carboxyphenyl) methane, 1,10-bis (4-carboxyphenoxy) decane, ethylene glycol bis (4-carboxyphenyl) ether and the like.
Preferred examples of the dicarboxylic acid derivative include terephthalic acid, 4,4′-dicarboxydiphenyl ether, benzophenone-4,4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 2,2′-biphenyldicarboxylic acid, 4 , 4′-dicarboxydiphenylsulfone, 2,2′-bis (4-carboxyphenyl) propane, 2,2′-bis (4-carboxyphenyl) hexafluoropropane, 2,6-naphthalenedicarboxylic acid, bis (4 -Carboxyphenyl) methane, 1,10-bis (4-carboxyphenoxy) decane, ethylene glycol bis (4-carboxyphenyl) ether, and acid chlorides, acid bromides, and esterified compounds having 1 to 8 carbon atoms. It is done. These may be used alone or in combination of two or more.

  Examples of the diaminodihydroxy compound (E2) include diaminodihydroxy compounds having 6 to 18 carbon atoms, such as 2,4-diaminoresorcinol, 2,2′-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2′-bis (3-amino-4-hydroxyphenyl) propane, 3,4′-diamino-4,3′-dihydroxydiphenylsulfone, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3 , 3′-diamino-4,4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxy-6,6′-trifluoromethylbiphenyl, 1,3-diamino-4,6-dihydroxybenzene 2,6-diamino-3,7-dihydroxynaphthalene, bis (3-amino-4-hydroxyphene) Le) ketone, bis (3-amino-4-hydroxyphenyl) sulfide, bis (3-hydroxy-4-aminophenyl) include those such as methane is known, it is possible to use one or more of these.

  Examples of the diaminodimercapto compound (E3) include diaminodimercapto compounds having 6 to 18 carbon atoms, such as 2,2′-bis (4-amino-3-mercaptophenyl) hexafluoropropane, 2,2′-. Bis (4-amino-3-mercaptophenyl) propane, 3,4′-diamino-4,3′-dimercaptodiphenyl sulfone, 3,3′-diamino-4,4′-dimercaptobiphenyl, 3,3 ′ -Diamino-4,4'-dimercapto 2,2'-trifluoromethylbiphenyl, 1,3-diamino-4,6-dimercaptodifluorobenzene, 1,4-diamino-3,6-dimercaptobenzene, 2, 7-diamino-3,6-dimercaptonaphthalene, bis (3-amino-4-mercaptophenyl) ketone, bis (3-amino-4-me Known examples include captophenyl) sulfide, bis (3-amino-4-mercaptophenyl) ether, bis (3-mercapto-4-aminophenyl) sulfone, bis (3-mercapto-4-aminophenyl) methane, and the like. One or more of these can be used.

  Examples of the tetraamino compound (E4) include tetraamino compounds having 6 to 18 carbon atoms, such as 1,2,4,5-tetraaminobenzene, 1,2,5,6-tetraaminonaphthalene, 2,3. , 6,7-tetraaminonaphthalene, 3,3′-diaminobenzidine, 3,3 ′, 4,4′-tetraaminodiphenylmethane, 3,3 ′, 4,4′-tetraaminodiphenylethane, 3,3 ′ , 4,4′-tetraaminodiphenyl ether, 3,3 ′, 4,4′-tetraaminodiphenyl thioether, 3,3 ′, 4,4′-tetraaminodiphenyl sulfone, and the like. More than seeds can be used.

Polyamide resins (Am1) and (Am2) may be prepared by known methods (for example, patent literature; JP-A-60-223824, JP-A-10-168173, non-patent literature; J. Polymer. Sci., A-1). 3, p 1373 (1965), etc.) using tetracarboxylic dianhydride (T1) or dicarboxylic acid derivative (T2) [hereinafter referred to as a polycarboxylic acid derivative (T) component. ] And a diamino compound (E1) or a diaminodihydroxy compound (E2), a diaminodimercapto compound (E3) or a tetraamino compound (E4) [hereinafter referred to as a polyhetero compound (E) component. ] Can be obtained by reacting.
In the reaction for obtaining the polyamide resins (Am1) and (Am2), it is preferable to react the polycarboxylic acid derivative (T) component and the polyhetero compound (E) component in an organic solvent.
A specific method for reacting the polycarboxylic acid derivative (T) component with the polyhetero compound (E) component is obtained by dissolving at least one polyhetero compound (E) component in an organic solvent. Examples include a method in which at least one polycarboxylic acid derivative (T) component is added to the obtained solution and the mixture is stirred at a temperature of 0 to 100 ° C. for 1 to 60 hours.

When the reaction between the polycarboxylic acid derivative (T) component and the polyhetero compound (E) component is performed in an organic solvent, examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butylactone, N,
N-dimethylacetamide, dimethyl sulfoxide, 2-methoxyethanol, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1 1,3-butylene glycol acetate, 1,3-butylene glycol acetate, cyclohexanone, cyclopentanone, tetrahydrofuran and mixtures thereof can be used.
In the reaction of the polycarboxylic acid derivative (T) component and the polyhetero compound (E) component, in a reaction solution comprising the polycarboxylic acid derivative (T) component, the polyhetero compound (E) component, and an organic solvent to be used if necessary. The total weight of the polycarboxylic acid derivative (T) component and the polyhetero compound (E) component contained in is preferably 1% by weight or more, more preferably 5 to 80% with respect to the total weight of the reaction solution. % By weight, particularly preferably 10 to 60% by weight.
When an organic solvent is used in the reaction of the polycarboxylic acid derivative (T) component and the polyhetero compound (E) component, the amount of the organic solvent used is preferably 99% by weight or less, more preferably 20%, based on the weight of the reaction solution. To 95% by weight, particularly preferably 40% to 90% by weight.

  The polycarboxylic acid derivative (T) component and the polyhetero compound (E) component are preferably reacted so that the molar ratio {(T) component / (E) component} is 0.8 to 1.2, It is more preferable to make it react so that it may become 0.95-1.0. When the molar ratio of the (T) component and the (E) component is less than 0.8 equivalent or more than 1.2 equivalent, the molecular weight may be low and it may be difficult to form a film (film).

  The reaction mixture obtained by reacting the polycarboxylic acid derivative (T) component and the polyhetero compound (E) component may be used as it is as the curable resin composition of the present invention. Am1) and (Am2) may be isolated and used. As a method for isolating the polyamide resins (Am1) and (Am2) from the reaction mixture, the reaction mixture is poured into a poor solvent (water, methanol, isopropanol, etc.) for the polyamide resins (Am1) and (Am2) to form a polyamide resin ( Examples thereof include a method in which Am1) and (Am2) are precipitated and separated by filtration, washing, drying, and the like.

  When the curable compound contained in the curable resin composition of the present invention is a curable amide compound (Am), the content of the zwitterionic borate salt contained in the curable resin composition of the present invention is the photosensitive resin composition. The amount is preferably 1 to 20% by weight based on the weight of the product, more preferably 3 to 15% by weight, and particularly preferably 5 to 10% by weight.

  When the curable polyamide compound (Am) is included as the curable compound, the curable polyamide compound (Am) contained in the curable resin composition of the present invention [preferably a polyamide having a repeating structure represented by the general formula (4) The total weight of the resin (Am1) and / or the polyamide resin (Am2) having a repeating structure represented by the general formula (5)] is preferably 1 to 100% by weight based on the weight of the curable resin composition. Preferably it is 5 to 80 weight%, Most preferably, it is 10 to 60 weight%.

The curable resin composition in the present invention may further contain a solvent. Solvents include monoalcohols (methanol, ethanol, normal propanol, isopropanol, butanol, geraniol, linalool, citronellol, etc.), carbonate solvents (propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.) ), Ketone solvents (acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, etc.), polyhydric alcohol solvents (ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, etc.) and derivatives thereof (ethylene glycol monoacetate, Diethylene glycol monoacetate, propylene glycol monoacetate and dipropylene glycol Monoacetate and polyhydric alcohol solvents such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether and / or monophenyl ether), cyclic ether solvents (tetrahydrofuran, dioxane and 1,8-cineol etc.), esters Solvents (ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate , Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate Beauty 3-methyl-3-methoxybutyl acetate, etc.) and aromatic hydrocarbon solvents (toluene, xylene and mesitylene), and the like.
These may be used alone or in combination of two or more.
Further, glycidyl ethers such as phenyl glycidyl ether and methyl glycidyl ether having one glycidyl group in the molecule, and alkylene oxides such as oxetane, styrene oxide, and cyclohexene oxide can be used as a solvent. These glycidyl ethers and alkylene oxides are called reactive diluents.

  The content of the solvent is preferably 99% by weight or less, more preferably 95% by weight or less, more preferably 3 to 95% by weight based on the total weight of the curable resin composition including the solvent, from the viewpoint of blending stability. Is particularly preferred, more preferably 1 to 90% by weight, particularly preferably 5 to 90% by weight, and most preferably 5 to 80% by weight.

  When hardening by light irradiation, it is preferable to contain a sensitizer (H) further according to the kind (wavelength) of the light source to be used.

As the sensitizer (H), known sensitizers (JP-A Nos. 11-279212 and 09-183960) can be used, and anthracene (anthracene, 9,10-dibutoxyanthracene, 9,10) can be used. -Dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene and 9,10-dipropoxyanthracene), pyrene, 1,2-benzanthracene, perylene, tetracene, coronene, thioxanthone ( Thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone and 2,4-diethylthioxanthone), phenothiazine (phenothiazine, N-methylphenothiazine, N-ethylphenothiazine and N- Phenyphenothiazine), xanthone, naphthalene (1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, 4-methoxy-1-naphthol, etc.), ketone (dimethoxyacetophenone, di Ethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 4-benzoyl-4′-methyldiphenyl sulfide, etc.), carbazole (N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole, etc.), chrysene (1,4-dimethoxychrysene, 1,4-di-α-methylbenzyloxychrysene, etc.), phenanthre (9-hydroxy phenanthrene, 9-methoxy phenanthrene, 9-hydroxy-10-methoxy-phenanthrene and 9-hydroxy-10-ethoxy phenanthrene, etc.) and the like.
Among the colorants listed below, a colorant having photosensitivity to the wavelength of light to be irradiated (particularly, visible light region 400 to 830 nm; see JISZ8120) can be used as a sensitizer.

  The content of the sensitizer (H) is preferably 1 to 20% by weight, more preferably 3 to 15% by weight, particularly preferably 5 to 10% by weight based on the curable resin composition. From the viewpoint, the content is preferably 1 to 500% by weight, more preferably 10 to 300% by weight, based on the weight of the zwitterionic borate salt.

  In the curable resin composition of the present invention, colorants (pigments, etc.), inorganic fine particles (metal oxide particles, metal particles, etc.), dispersants, antifoaming agents, leveling agents are further added as additives depending on the intended use. , Thixotropy imparting agent (also called flow regulator), slip agent, flame retardant, antistatic agent, ion scavenger, antioxidant, adhesion imparting agent, anti-coloring agent and light stabilizer (ultraviolet absorption type and quenching type) Etc.) and the like.

As the colorant, known pigments conventionally used in paints and inks can be used, inorganic pigments (titanium oxide, iron oxide, carbon black, etc.), organic pigments (azo pigments, cyanine pigments, phthalocyanine pigments, and the like) And quinacridone pigments) and dyes.
When the pigment is contained, the content of the pigment is preferably 0.5 to 400,000 weight percent, more preferably 10 to 150,000 weight percent based on the weight of the zwitterionic borate salt.

  In addition to titanium oxide, iron oxide and carbon black, examples of inorganic pigments include yellow lead, zinc yellow, bitumen, barium sulfate, cadmium red, zinc white, bengara, alumina, calcium carbonate, ultramarine, graphite and titanium black. It is done.

  Among organic pigments, azo pigments include soluble azo pigments (β-naphthol, β-oxynaphthoic acid anilide, acetoacetate anilide, pyrazolone, etc.) and insoluble azo pigments (β-naphthol, β-oxynaphthoyl). Acid-based, β-oxynaphthoic acid-based anilide-based, acetoacetate-anilide-based monoazo, acetoacetate-anilide-based disazo and pyrazolone-based), and phthalocyanine pigments include copper phthalosinine blue, halogenated copper phthalocyanine blue, sulfonated copper Examples include phthalocyanine blue and metal-free phthalocyanine. In addition to these, polycyclic or heterocyclic compounds such as isocindolinone, dioxazine, perinone, and perylene can be used as the organic pigment.

  As dyes, yellow dyes include phenols, naphthols, anilines, pyrazolones, pyridones, or open-chain active methylene compounds having a coupling component as an aryl or heteryl azo dye, open-chain active methylene compounds as a coupling component And methine dyes such as azomethine dyes, benzylidene dyes and monomethine oxonol dyes, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, quinophthalone dyes, nitro, nitroso dyes, acridine dyes and acridinone dyes.

  For magenta dyes, phenols, naphthols, anilines, pyrazolones, pyridones, pyrazolotriazoles, ring-closing active methylene compounds or heterocycles (pyrrole, imidazole, thiophene and thiazole derivatives, etc.) are used as coupling components. Aryl or heteryl azo dyes, azomethine dyes having a pyrazolone or pyrazolotriazole as a coupling component, arylidene dyes, styryl dyes, merocyanine dyes such as merocyanine dyes and oxonol dyes, diphenylmethane dyes, triphenylmethane dyes and xanthene dyes Examples thereof include carbonium dyes, quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes.

  As cyan dyes, azomethine dyes such as indoaniline dyes and indophenol dyes, polymethine dyes such as cyanine dyes, oxonol dyes and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes and xanthene dyes, phthalocyanine dyes, anthraquinone dyes Examples of the coupling component include phenols, naphthols, anilines, pyrrolopyrimidinone or pyrrolotriazinone derivatives, aryl or heteryl azo dyes (such as CI Direct Blue 14), and indigo / thioindigo dyes.

  The particle diameter of the colorant is preferably from 0.01 μm to 2.0 μm, more preferably from 0.01 μm to 1.0 μm, from the viewpoint of the sharpness of the coating film.

  Although the addition amount of a coloring agent is not specifically limited, It is preferable that it is 1 to 60 weight% based on the total weight of curable resin composition.

When a pigment is used, it is preferable to add a pigment dispersant in order to improve the dispersibility and the storage stability of the curable resin composition.
Pigment dispersants manufactured by Big Chemie (Anti-Terra-U, Disperbyk-101, 103, 106, 110, 161, 162, 164, 166, 167, 168, 170, 174, 182, 184, 2020, etc.) ), Pigment dispersants manufactured by Ajinomoto Fine Techno Co. (Ajisper PB711, PB821, PB814, PN411, PA111, etc.), pigment dispersants manufactured by Lubrizol (Solspers 5000, 12000, 3)
2000, 33000, 39000, etc.). These pigment dispersants may be used alone or in combination of two or more. Although the addition amount of a pigment dispersant is not specifically limited, It is preferable to use in the range of 0.1 to 10 weight% in the photosensitive composition.

  The curable resin composition of the present invention contains inorganic fine particles (such as metal oxide particles or metal particles) as additives, and can be used, for example, for forming green sheets and electrode layers of ceramic electronic components.

  The metal oxide particles are used when forming the dielectric layer, and examples thereof include titanium oxide, aluminum oxide, barium titanate, calcium zirconate, niobium oxide and lead zirconate titanate, and preferably barium titanate. It is. Aluminum oxide, silicon oxide, titanium oxide and the like are used when forming a coating layer for protecting the substrate.

  The particle diameter of the metal oxide particles is preferably 0.01 μm to 2.0 μm, more preferably 0.01 μm to 1.0 μm as an average particle diameter from the viewpoint of dielectric constant.

The metal powder is a noble metal and a base metal used when forming the conductor layer, and specific examples thereof include palladium, nickel, copper, silver, and gold, with palladium, nickel, and copper being preferred.
The average particle diameter of the metal powder is preferably 0.01 μm to 10 μm.

The inorganic fine particles are also used as a filler for the curable resin composition. As the filler, known fillers can be used, such as fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate and lithium aluminum silicate. Can be mentioned.
When the filler is contained, the content of the filler is preferably 50 to 600000% by weight, more preferably 300 to 200000% by weight, based on the weight of the zwitterionic borate salt.

As the antistatic agent, known antistatic agents can be used, and examples include nonionic antistatic agents, anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents, and polymeric antistatic agents. .
When the antistatic agent is contained, the content of the antistatic agent is preferably 0.1 to 20000% by weight, more preferably 0.6 to 5000% by weight, based on the weight of the zwitterionic borate salt.

As the flame retardant, a known flame retardant can be used.
Known flame retardants include inorganic flame retardants (antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide and aluminate. Calcium, etc.), bromine flame retardants (tetrabromophthalic anhydride, hexabromobenzene, decabromobiphenyl ether, etc.), phosphate ester flame retardants [tris (tribromophenyl) phosphate, etc.] and the like.
When the flame retardant is contained, the content of the flame retardant is preferably 0.5 to 40000% by weight, more preferably 5 to 10000% by weight, based on the weight of the zwitterionic borate salt.

  As the antifoaming agent, known antifoaming agents can be used, such as alcohol defoaming agents, metal soap defoaming agents, phosphate ester defoaming agents, fatty acid ester defoaming agents, polyether defoaming agents, and silicone defoaming agents. And mineral oil defoaming agents.

  As the flow control agent, known flow control agents can be used, and examples thereof include hydrogenated castor oil, polyethylene oxide, organic bentonite, colloidal silica, amide wax, metal soap, and acrylate polymer.

  As the light stabilizer, known light stabilizers can be used, UV absorbing stabilizers (benzotriazole, benzophenone, salicylate, cyanoacrylate and derivatives thereof), radical scavenging stabilizers (hindered amine, etc.) and quenching types. Stabilizers (nickel complex etc.) etc. are mentioned.

  As the antioxidant, known antioxidants can be used, and examples include phenolic antioxidants (monophenolic, bisphenolic and polymeric phenolic), sulfur antioxidants and phosphorus antioxidants. It is done.

  As the adhesion-imparting agent, a known adhesion-imparting agent can be used, and examples thereof include a coupling agent, a silane coupling agent, and a titanium coupling agent.

Preferable adhesion promoters are γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, Examples include urea propyltriethoxysilane, tris (acetylacetonate) aluminum, and acetylacetate aluminum diisopropylate.
The content in the case of using the adhesion imparting agent is preferably 0 to 20% by weight, more preferably 1 to 15% by weight, and particularly preferably 5 to 10% by weight based on the total weight of the curable resin composition. .

  As the ion scavenger, known ion scavengers can be used, and organic aluminum (alkoxyaluminum, phenoxyaluminum, etc.) and the like can be mentioned.

  Known anti-coloring agents can be used as the anti-coloring agent. In general, antioxidants are effective. Phenol type antioxidants (monophenol type, bisphenol type and high molecular phenol type, etc.), sulfur type oxidation Examples thereof include an inhibitor and a phosphorus-based antioxidant.

  As the leveling agent and slip agent, known ones can be used.

  When an antifoaming agent, a flow regulator, a light stabilizer, an antioxidant, an adhesion-imparting agent, an ion scavenger or an anti-coloring agent is contained, each content is based on the weight of the zwitterionic borate salt. 0.1 to 20000% by weight, more preferably 0.5 to 5000% by weight.

  The curable resin composition of the present invention comprises a zwitterionic borate salt, a curable compound, a sensitizer (H) used if necessary, a colorant used if necessary, metal oxide particles used if necessary, metal particles used if necessary, A method of uniformly mixing a solvent to be used if necessary and a cohesion imparting agent to be used if necessary using a known stirring and mixing device (a mixing container with a stirrer, a paint shaker, etc.) and a known kneader (a ball mill and a three-roll mill) Etc.) and the like. The uniform mixing temperature and kneading temperature are usually 10 ° C to 40 ° C, preferably 20 ° C to 30 ° C.

  The curable resin composition of the present invention can be cured by heating to obtain a cured product. The heating temperature is preferably 50 ° C to 180 ° C.

The curable resin composition of the present invention can be cured by light irradiation (irradiation with actinic rays in the ultraviolet to visible light region, preferably 360 nm to 830 nm) to obtain a cured product.
The light source may be any light source as long as it has energy that induces the decomposition of the zwitterionic borate salt of the present invention, such as a low pressure, medium pressure, high pressure or ultrahigh pressure mercury lamp, metal halide lamp, high power metal halide lamp, etc. Latest trends in EB curing technology, edited by Radtech Research Group, CMC Publishing, 138, 2006), LED lamp, xenon lamp, carbon arc lamp, fluorescent lamp, semiconductor solid-state laser, argon laser, He-Cd laser, KrF excimer laser ArF excimer laser, F ₂ laser, or the like. Note that radiation having high energy such as an electron beam or an X-ray can be used.

  Heating may be performed for the purpose of diffusing the base generated from the zwitterionic borate salt during and / or after irradiation with actinic rays. The heating temperature is usually 30 ° C to 200 ° C, preferably 35 ° C to 150 ° C, more preferably 40 ° C to 120 ° C.

The curable resin composition of the present invention is preferably used for applications in which a pattern is formed by coating on a substrate (silicon wafer, ceramic and aluminum substrate) and irradiating with light.
The pattern is formed by first applying the composition to a suitable substrate, prebaking at 60 to 120 ° C., drying the coating film, curing it by irradiating the desired pattern shape with light, and further unexposed areas. And a method of obtaining a pattern by dissolving and removing.

  Examples of the coating method include spin coating using a spin coater, spray coating using a spray coater, dipping, printing, and roll coating.

  The curable resin composition of the present invention can be used for pattern formation by an exposure development method. In pattern formation using the curable resin composition of the present invention, examples of the developer include an aqueous alkali solution or an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or a surfactant to an alkaline aqueous solution. Examples of the alkali include inorganic alkalis (sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia), primary amines (such as ethylamine and n-propylamine), and secondary amines (diethylamine and di-n-). Propylamine, etc.), tertiary amines (such as triethylamine and methyldiethylamine), amino alcohols (such as dimethylethanolamine and triethanolamine) and quaternary ammonium salts (such as tetramethylammonium hydroxide and tetraethylammonium hydroxide). .

As a method for dissolving and removing the unexposed portion, a method used as a normal developing method can be used, and examples thereof include spray, paddle, immersion, and ultrasonic methods.
In pattern formation using the curable resin composition of the present invention, the pattern formed by development can be further rinsed (washed). Distilled water can be used as the rinse liquid. Next, the pattern excellent in heat resistance can be obtained by performing heat processing (usually 120-450 degreeC).

  The cured product of the curable resin composition of the present invention can be used for electronic parts such as semiconductor devices and multilayer wiring boards, specifically, surface protective films, interlayer insulating films, and multilayer wiring boards in semiconductor devices. It can be used to form an interlayer insulating film in the inside. It can also be used for color filter protective films, organic EL insulating films, liquid crystal alignment films, optical lens protective films, and optical circuit materials.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not intending to be limited to this. Unless otherwise specified, “%” means “% by weight”.

<Production Example 1: Synthesis of triphenylborane>
Fourth Edition Experimental Chemistry Course 24 [Organic Synthesis VI (Hetero Element / Typical Metal Element Compound)] Triphenylborane was synthesized according to the method described on page 78 of the Chemical Society of Japan.
<Production Example 2: Synthesis of tri (2-naphthyl) borane Tri (2-naphthyl) borane was synthesized by the same method as described above.
<Production Example 3: Synthesis of tri (p-fluorophenyl) borane Tri (p-fluorophenyl) borane was synthesized by the same method as described above.
<Production Example 4: Synthesis of tri (m-chlorophenyl) borane Tri (m-chlorophenyl) borane was synthesized by the same method as described above.

<Production Example 5: Synthesis of borate salt used in Comparative Example 1>
The borate salt (d-1) used for the comparative example 1 represented by following Chemical formula (1) was synthesize | combined by the method of Unexamined-Japanese-Patent No. 2000-128912.

<Production Example 6: Synthesis of polyamide resin (P1-1)>
In a reaction vessel, 10.0 g of 4,4′-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry) was dissolved in 100 g of dimethylacetamide, and 10.9 g of pyromellitic dianhydride was gradually added dropwise thereto in an ice bath. The reaction was allowed to proceed for 16 hours at room temperature. The mixture after the reaction was added little by little to 300 g of methanol under stirring, and the resulting precipitate was collected by filtration. Further, the obtained solid was washed three times with 50 mL of methanol. The washed solid was dried under reduced pressure to obtain a polyamide resin (P1-1).

<Production Example 7: Synthesis of polyamide resin (P1-2)>
10.0 g of 4,4′-diaminodiphenyl ether (Tokyo Kasei) was changed to 7.7 g of bis (aminomethyl) norbornane (Tokyo Kasei), and 10.9 g of pyromellitic dianhydride was changed to 1,2,3, A polyamide resin (P1-2) was obtained in the same manner as in Production Example 6 except that 4-cyclobutanetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry) was changed to 9.8 g.

<Production Example 8: Synthesis of polyamide resin (P1-3)>
5.0 g of 4,4′-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry) and 8.3 g of 2,2-bis (4-aminophenyl) hexafluoropropane (manufactured by Tokyo Chemical Industry) The mixture was changed to a mixture, and the same procedure as in Production Example 6 was carried out except that 10.9 g of pyromellitic dianhydride was changed to 16.1 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride. P1-3) was obtained.

<Production Example 9: Synthesis of polyamide resin (P2-1)>
In a reaction vessel, 10.6 g of 4,6-diaminoresorcinol dihydrochloride (manufactured by Tokyo Chemical Industry) was dissolved in 200 g of dimethylacetamide, and 14.8 g of 4,4′-di (chloroformyl) diphenyl ether and 22 g of triethylamine were added thereto. . The mixture was reacted at room temperature for 20 hours, and the mixture after the reaction was poured little by little into 500 g of water with stirring, and the resulting precipitate was collected by filtration. Furthermore, the obtained solid was washed 3 times with 50 mL of water. The washed solid was dried under reduced pressure to obtain a polyamide resin (P2-1).

<Production Example 10: Synthesis of polyamide resin (P2-2)>
The same procedure as in Production Example 9 was carried out except that 10.6 g of 4,6-diaminoresorcinol dihydrochloride was changed to 12.9 g of 2,2′-bis (3-amino-4-hydroxyphenyl) propane, and a polyamide resin (P2- 2) was obtained.

<Production Example 11: Synthesis of polyamide resin resin (P2-3)>
10.6 g of 4,6-diaminoresorcinol dihydrochloride, 12.3 g of 1,4-diamino-3,6-dimercaptobenzene dihydrochloride (manufactured by Tokyo Chemical Industry), 4,4′-di (chloroformyl) diphenyl ether 14 The same operation as in Production Example 9 was carried out except that .8 g was changed to 12.4 g of 4,4′-biphenyldicarboxylic acid dichloride (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a polyamide resin (P2-3).

<Production Example 12: Synthesis of polyamide resin (P2-4)>
The same procedure as in Production Example 9 was carried out except that 10.6 g of 4,6-diaminoresorcinol dihydrochloride (manufactured by Tokyo Chemical Industry) was changed to 10.7 g of 3,3′-benzidine (manufactured by Wako Pure Chemical Industries), and a polyamide resin was obtained. (P2-4) was obtained.

<Production Example 13: Synthesis of polyamide resin (P2-5)>
10.6-g of 4,6-diaminoresorcinol dihydrochloride, 5.3 g of 4,6-diaminoresorcinol dihydrochloride (manufactured by Tokyo Kasei) and 1,4-diamino-3,6-dimercaptobenzene dihydrochloride (Tokyo Kasei) (Product made) Except changing to a mixture with 6.1g, operation similar to manufacture example 9 was performed and the polyamide resin (P2-5) was obtained.

<Production Example 14: Synthesis of base generator used in Comparative Example 3>
A base generator (d-3) used in Comparative Example 3 represented by the following chemical formula (2) was synthesized by the method described in JP-A-2007-119766.

<Production Example 15: Synthesis of base generator used in Comparative Example 4>
A base generator (d-4) used in Comparative Example 4 represented by the following chemical formula (3) was synthesized by the method described in JP-A-2007-262276.

<Production Example 16: Synthesis of base generator used in Comparative Example 5>
A base generator (d-5) used in Comparative Example 5 represented by the following chemical formula (4) was synthesized by the method described in Non-Patent Document 1.

Example 1: Synthesis of 4- (N-methylmorphoniomethyl) phenyltriphenylborate
(1) Synthesis of intermediate (A10): triphenyl (p-tolyl) borate potassium salt To a reaction vessel, 6.1 g of triphenylborane obtained in Production Example 1 and 100 mL of THF were added and cooled to −10 ° C. Thereto, 30 mL of 4-tolylmagnesium bromide THF solution (1.0 mol / L) prepared by a conventional method was added dropwise over 1 hour. After completion of the dropwise addition, the reaction was further performed at room temperature for 10 hours. The THF was distilled off, 100 mL of saturated aqueous potassium carbonate solution was added thereto, and extraction was further performed with 200 mL of ethyl acetate. The organic layer (ethyl acetate) was distilled off to obtain a light brown solid. Recrystallization was performed with methanol-ether to obtain 8.4 g of a white solid. The yield based on the theoretical yield calculated from triphenylborane used in the reaction was 90%.
This white solid was confirmed to be an intermediate (A10) by 1H-NMR.
(2) Intermediate (A11): Synthesis of 4-bromomethylphenyltriphenylborate potassium salt 7.1 g of N-bromosuccinimide (manufactured by Wako Pure Chemical Industries, Ltd.), 7.4 g of intermediate (A10), 200 mL of carbon tetrachloride and 0.8 g of AIBN (azobisisobutyronitrile) were added, and the reaction was performed at 80 ° C. for 8 hours. After the reaction, filtration was performed at room temperature, and the filtrate was concentrated to obtain a brown solid. It was dissolved in 100 mL of ethyl acetate, washed 5 times with 100 mL of water, and the organic layer was concentrated. Purification was performed by silica gel column chromatography to obtain 7.2 g of a pale yellow solid. The yield based on the theoretical yield calculated from the intermediate (A10) used in the reaction was 80%.
It was confirmed by 1H-NMR that this pale yellow solid was an intermediate (A11).
(3) Synthesis of 4- (N-methylmorphoniomethyl) phenyltriphenylborate 4.5 g of intermediate (A11) and 100 mL of chloroform were added to a reaction vessel and dissolved. Thereto was gradually added 1.5 g of N-methylmorpholine (manufactured by Tokyo Chemical Industry). After making it react at 60 degreeC for 6 hours, it wash | cleaned 5 times with 100 mL of water. The organic layer (chloroform) was concentrated, and 200 mL of methanol was added thereto. The resulting solid was filtered and dried to obtain 3.5 g of a pale yellow solid. The yield based on the theoretical yield calculated from the intermediate (A11) used in the reaction was 80%. It was confirmed by 1H-NMR that the pale yellow solid was 4- (N-methylmorphoniomethyl) phenyltriphenylborate [borate salt (A-1)], which was the target product. The purity calculated by high performance liquid chromatography (hereinafter referred to as HPLC) under the following conditions was 98%.
<HPLC conditions>
LaChrom7000 manufactured by Hitachi High-Technologies Corporation
Developing solvent: methanol / water / sodium perchlorate = 87/10/3 (weight ratio)
Column: Inert Sil Ph-3 manufactured by GL Sciences Inc.
Column temperature: 40 ° C. Flow rate: 1.0 mL / min Detector: UV detector (254 nm)

<Example 2: Synthesis of 4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyltriphenylborate>
The same procedure as in Example 1 was carried out except that 1.5 g of N-methylmorpholine (manufactured by Tokyo Chemical Industry) was changed to 2.3 g of DBU (manufactured by San Apro) in Example 1, and 4- (1,8-diazabicyclo [5. 4.0] -7-undecenium-8-yl) methylphenyltriphenylborate [borate salt (A-2)] was obtained (yield 82%, purity 95%).

<Example 3: Synthesis of 4- (α-tributylammonioethyl) phenyltriphenylborate>
(1) Intermediate (A30): Synthesis of potassium 4-ethylphenyltriphenylborate In the synthesis of intermediate (A10), 4-tolylmagnesium bromide THF solution (1.0 mol / L) was converted to 4-ethylphenylmagnesium bromide. Except having changed to the THF solution (1.0 mol / L), it carried out similarly to the synthesis | combination of intermediate body (A10), and obtained intermediate body (A30).
(2) Intermediate (A31): Synthesis of 4- (α-bromoethyl) phenyltriphenylborate potassium salt In the synthesis of intermediate (A11), 7.4 g of intermediate (A10) was converted to 7.7 g of intermediate (A30). The intermediate (A31) was obtained in the same manner as the synthesis of the intermediate (A11) except that the intermediate (A31) was changed.
(3) Synthesis of 4- (α-tributylammonioethyl) phenyltriphenylborate 4.5 g of intermediate (A11) is changed to 4.7 g of intermediate (A31), and 1.5 g of N-methylmorpholine (produced by Tokyo Chemical Industry) Was performed in the same manner as in Example 1 except that 2.8 g of tributylamine (manufactured by Tokyo Chemical Industry) was changed to obtain 4- (α-tributylammonioethyl) phenyltriphenylborate [borate salt (A-3)]. (Yield 80%, purity 95%).

<Example 4: Synthesis of 4- (1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium-3-yl) ethylphenyltriphenylborate>
(1) Intermediate (A40): Synthesis of 4-bromoethylphenyltriphenylborate potassium salt To a reaction vessel, 8.2 g of 4- (bromoethyl) bromobenzene (manufactured by Aldrich) and 200 mL of THF were added, and in a dry ice acetone bath- Cooled to 78 ° C. 20 mL of n-butyllithium hexane solution (1.6 mol / L, manufactured by Wako Pure Chemical Industries, Ltd.) was added at -70 ° C. After stirring for 10 minutes, 100 mL of triphenylborane THF solution (0.25 mol / L, manufactured by Aldrich) was added dropwise over 2 hours. After completion of dropping, the reaction was further carried out at room temperature for 5 hours. The THF was distilled off, 100 mL of saturated aqueous potassium carbonate solution was added thereto, and extraction was further performed with 200 mL of ethyl acetate. The organic layer (ethyl acetate) was distilled off to obtain a light brown solid. Recrystallization was performed with methanol-ether to obtain 10.5 g of a white solid. The yield based on the theoretical yield calculated from triphenylborane used in the reaction was 90%.
This white solid was confirmed to be an intermediate (A40) by 1H-NMR.
(2) Synthesis of 4- (1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium-3-yl) ethylphenyltriphenylborate 4.5 g of intermediate (A11) is converted to intermediate (A40) Implemented except that 4.7 g was changed from 1.5 g of N-methylmorpholine (manufactured by Tokyo Chemical Industry) to 1.7 g of 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine (manufactured by Wako Pure Chemical Industries). Performed in the same manner as in Example 1, and was 4- (1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium-3-yl) ethylphenyltriphenylborate [borate salt (A-4)]. (Yield 80%, purity 95%).

Example 5 Synthesis of 4- {α- (triethylammonio) acetyl} phenyltriphenylborate>
(1) Intermediate (A50): Synthesis of 2- (4-bromophenyl) -2-methyl-1,3-dioxane 10 g of 4-bromoacetophenone, 50 mL of toluene, 30 g of ethylene glycol in a reaction vessel equipped with a Dean-Stark apparatus. Then, 0.2 g of p-toluenesulfonic acid was added and reacted under reflux for 6 hours. After the reaction, toluene was distilled off. The residue was dissolved in 100 mL of ethyl acetate, washed 3 times with 100 mL of water, and the organic layer (ethyl acetate) was concentrated. This was purified by silica gel column chromatography to obtain a white solid. The yield based on the theoretical yield calculated from 4-bromoacetophenone used in the reaction was 95%. It was confirmed by 1H-NMR that the white solid was 2- (4-bromophenyl) -2-methyl-1,3-dioxane, which was the target product.
(2) Intermediate (A51): Synthesis of (1-methyl-2,5-dioxacyclopentyl) phenyltriphenylborate potassium salt In the synthesis of intermediate (A40), 4-bromoethylbromobenzene (manufactured by Aldrich) was used as an intermediate. The intermediate (A51) was obtained in the same manner as the synthesis of the intermediate (A40) except that the amount was changed to 7.5 g of the body (A50).
(3) Intermediate (A52): Synthesis of 4- (α-bromoacetyl) phenyltriphenylborate potassium salt 9.9 g of carbon tetrabromide (manufactured by Wako Pure Chemical Industries), 6.7 g of intermediate (A51) Acetone 50 mL was charged. After cooling to 0 ° C., 50 mL of an acetone solution of 7.9 g of triphenylphosphine (manufactured by Tokyo Chemical Industry) was added little by little. After stirring for 1 hour, the mixture was further stirred at room temperature for 6 hours. The reaction solution was added to 500 mL of hexane, and the resulting solid was filtered to obtain an intermediate (A52).
(4) Synthesis of 4- {α- (triethylammonio) acetyl} phenyltriphenylborate In Example 1, 4.5 g of the intermediate (A11) was changed to 4.8 g of the intermediate (A52), N-methylmorpholine (Tokyo Kasei) (Manufactured) The same procedure as in Example 1 was carried out except that 1.5 g was changed to 1.5 g of triethylamine, and 4- {α- (triethylammonio) acetyl} phenyltriphenylborate [borate salt (A-5)] was obtained. Obtained (yield 88%, purity 97%).

Example 6 Synthesis of 4- (7-Methyl-1,5,7-triazabicyclo- [4.4.0] -5-decenium-5-yl) phenyltriphenylborate>
In Example 1, 1.5 g of N-methylmorpholine (manufactured by Tokyo Chemical Industry) was converted to 2.3 g of 7-methyl-1,5,7-triazabicyclo- [4.4.0] -5-decene (manufactured by Tokyo Chemical Industry). The procedure was carried out in the same manner as in Example 1 except that 4- (7-methyl-1,5,7-triazabicyclo- [4.4.0] -5-decenium-5-yl) phenyltriphenyl was used. Borate [borate salt (A-6)] was obtained (yield 82%, purity 95%).

Example 7 Synthesis of 4- (1-ethylimidazolinium-3-yl) methylphenyltriphenylborate
The same procedure as in Example 1 was conducted except that 1.5 g of N-methylmorpholine (manufactured by Tokyo Chemical Industry) was changed to 1.4 g of 1-ethylimidazole (manufactured by Tokyo Chemical Industry) in Example 1, and 4- (1-ethylimidazo Linium-3-yl) methylphenyltriphenylborate [borate salt (A-7)] was obtained (yield 90%, purity 95%).

<Example 8: Synthesis of 4- (1,5-diazabicyclo [4.3.0] -5-nonenium-5-yl) butyltriphenylborate>
(1) Preparation of 4-chlorobutylmagnesium bromide 2.9 g of magnesium (shaved, manufactured by Wako Pure Chemical Industries, Ltd.) and 5 mL of ether were added to a reaction vessel equipped with a reflux tube. The 4-chlorobutyl bromide (product made from Tokyo Chemical Industry) 17.1g ether solution (40 mL) was dripped, keeping at 35 to 40 degreeC there. After the dropwise addition, the mixture was further refluxed for 1 hour, cooled to room temperature, and then added with 55 mL of ether to obtain a 4-chlorobutylmagnesium bromide ether solution (1.0 mol / L).
(2) Intermediate 80: Synthesis of 4-chlorobutyltriphenylborate potassium salt In the synthesis of intermediate (A10), 4-tolylmagnesium bromide THF solution (1.0 mol / L) was converted to 4-chlorobutylmagnesium bromide ether solution. Except having changed to (1.0 mol / L), it carried out similarly to the synthesis | combination of intermediate body (A10), and obtained intermediate body (A80).
(3) Synthesis of 4- (1,5-diazabicyclo [4.3.0] -5-nonenium-5-yl) butyltriphenylborate In Example 1, 4.5 g of the intermediate (A11) A80) The same procedure as in Example 1 was carried out except that 1.5 g of N-methylmorpholine (manufactured by Tokyo Chemical Industry) was changed to 1.9 g of DBN (manufactured by San Apro), and 4- (1,5-diazabicyclo) [4.3.0] -5-Nonenium-5-yl) butyltriphenylborate [borate salt (A-8)] was obtained (yield 90%, purity 95%).

Example 9 Synthesis of 4- (1-ethylimidazolinium-3yl) methylphenyltri (2-naphthyl) borate
The same procedure as in Example 1 was carried out except that 6.1 g of triphenylborane in Example 1 was changed to 9.8 g of tri (2-naphthyl) borane obtained in Production Example 2, and 4- (1-ethylimidazolium) was obtained. Nimo-3yl) methylphenyltri (2-naphthyl) borate [borate salt (A-9)] was obtained (yield 88%, purity 95%).

Example 10 Synthesis of 4- (1-ethylimidazolinium-3-ylmethyl) phenyltri (p-fluorophenyl) borate>
The same procedure as in Example 1 was carried out except that 6.1 g of triphenylborane was changed to 7.4 g of tri (p-fluorophenyl) borane obtained in Production Example 3, and 4- (1-ethylimidazo Linium-3-yl) methylphenyltri (p-fluorophenyl) borate [borate salt (A-10)] was obtained (yield 87%, purity 95%).

<Example 11: Synthesis of 4- (2-tert-butyl-tetramethylguanidinium-2-yl) methylphenyltriphenylborate>
The same procedure as in Example 1 was carried out except that 1.5 g of N-methylmorpholine (manufactured by Tokyo Chemical Industry) was changed to 2.5 g of 2-tert-butyl-tetramethylguanidine (manufactured by Aldrich) in Example 1, and 4- ( 2-tert-butyl-tetramethylguanidinium-2-yl) methylphenyltriphenylborate [borate salt (A-11)] was obtained (yield 82%, purity 95%).

<Example 12: Synthesis of 3- (quinuclidinio) methylphenyltris (m-chlorophenyl) borate>
(1) Synthesis of Intermediate (A110) In the synthesis of Intermediate (A10), 4-tolylmagnesium bromide THF solution (1.0 mol / L) was changed to 3-tolylphenylmagnesium bromide THF solution (1.0 mol / L). The intermediate (A110) was obtained in the same manner as the synthesis of the intermediate (A10) except that 6.1 g of triphenylborane was changed to 8.6 g of tris (m-chlorophenyl) borane.
(2) Intermediate (A111): Synthesis of 3-bromomethylphenyltris (m-chlorophenyl) borate potassium salt In the synthesis of intermediate (A11), 7.4 g of intermediate (A10) was converted to intermediate (A110) 7. The intermediate (A111) was obtained in the same manner as the synthesis of the intermediate (A11) except that the amount was changed to 4 g.
It was confirmed by 1H-NMR that the pale yellow solid was an intermediate (A111).
(3) Synthesis of 3- (quinuclidinio) methylphenyltris (m-chlorophenyl) borate In Example 1, 4.5 g of intermediate (A11) was converted to 5.5 g of intermediate A (111), N-methylmorpholine (manufactured by Tokyo Chemical Industry) ) The same procedure as in Example 1 was carried out except that 1.5 g was changed to 1.7 g of quinuclidine (manufactured by Tokyo Chemical Industry), and 3- (quinuclidinio) methylphenyltris (m-
Chlorophenyl) borate [borate salt (A-12)] was obtained (yield 77%, purity 95%).

Example 13 Synthesis of 4- (triethylammoniomethyl) phenyltriphenylborate
(1) Synthesis of intermediate (A130) In a reaction vessel, 25 g of 4-bromobenzyl bromide was dissolved in 50 mL of THF, and 8 g of diethylamine was gradually added thereto. After stirring at room temperature for 5 hours, extraction was performed twice with 50 mL of ethyl acetate, and the organic layer was concentrated. The residue was purified by silica gel column chromatography to obtain intermediate (130).
(2) Synthesis of Intermediate (A131) In the synthesis of Intermediate (A10), Grignard reagent prepared by a conventional method using 4-tolylmagnesium bromide THF solution (1.0 mol / L) as intermediate (A130) as a raw material. Except having changed to (THF solution, 1.0 mol / L), it carried out similarly to the synthesis | combination of the intermediate body (A10) in Example 1, and obtained the intermediate body (A131).
(3) Synthesis of 4- (triethylammoniomethyl) phenyltriphenylborate 4.4 g of intermediate (A131) and 100 mL of THF were added to the reaction vessel, and 1.3 g of ethyl bromide was added dropwise thereto at 10 ° C. After dropping, the mixture was stirred at room temperature for 8 hours, and the organic solvent was distilled off. The residue was washed 5 times with 100 mL of water and dissolved in a small amount of acetone. This was recrystallized from diethyl ether to obtain 3.8 g of a pale yellow solid (yield 87%, purity 97%). It was confirmed by 1H-NMR that the pale yellow solid was 4- (triethylammoniomethyl) phenyltriphenylborate [borate salt (A-13)], which was the target product.

Example 14 Synthesis of 4- (1-Butylimidazoliomethyl) phenyltriphenylborate
(1) Synthesis of intermediate (A140) In the synthesis of intermediate (A130), except that 8 g of diethylamine was changed to 7.5 g of imidazole (manufactured by Tokyo Chemical Industry), the same procedure as in the synthesis of intermediate (A130) was performed. A body (A140) was obtained.
(2) Synthesis of intermediate (A141) In the synthesis of intermediate (A131), Grignard reagent (THF solution, 1.0 mol / L) prepared by a conventional method from intermediate (A130) was used as intermediate (A140). The intermediate (A141) was obtained in the same manner as the synthesis of the intermediate (A131) except that the Grignard reagent (THF solution, 1.0 mol / L) prepared by a conventional method was used as a raw material.
(3) Synthesis of 4- (1-butylimidazoliomethyl) phenyltriphenylborate In Example 13, 4.4 g of the intermediate (A131) was changed to 4.4 g of the intermediate (A141), and ethyl bromide 1. The same procedure as in Example 13 was carried out except that 3 g was changed to 1.6 g of butyl bromide, and 4- (1-butylimidazoliomethyl) phenyltriphenylborate [borate salt (A-14)] was obtained. Rate 90%, purity 96%).

<Example 15: Synthesis of synthesis of 4- (N-methylmorphoniomethyl) phenyltriphenylborate>
(1) Synthesis of intermediate (A150) In the synthesis of intermediate (A131), Grignard reagent (THF solution, 1.0 mol / L) prepared by a conventional method from intermediate (A130) was converted to 4- (morpholinomethyl). The intermediate (A150) was prepared in the same manner as the intermediate (A131) except that the Grignard reagent (THF solution, 1.0 mol / L) prepared in a conventional manner from bromobenzene (manufactured by Wako Pure Chemical Industries) was used. Got.
(2) Synthesis of 4- (N-methylmorphoniomethyl) phenyltriphenylborate In Example 13, 4.4 g of the intermediate (A131) was changed to 4.6 g of the intermediate (A150), and ethyl bromide 1 The same procedure as in Example 13 was conducted except that .3 g was changed to 1.7 g of methyl iodide to obtain 4- (N-methylmorphoniomethyl) phenyltriphenylborate [borate salt (A-15)]. (Yield 93%, purity 98%).

Example 16 Synthesis of 4- (4- {1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl} butanoyl) phenyltriphenylborate
(1) Synthesis of intermediate (A160):
In the synthesis of intermediate (A50), except that 10 g of 4-bromoacetophenone is changed to 13.1 g of 1- (4-bromophenyl) 4-chlorobutanone (manufactured by Aldrich), the same as the synthesis of intermediate (A50) The intermediate (A160) was obtained.
(2) Synthesis of intermediate (A161) In the synthesis of intermediate (A51), intermediate (A51) was synthesized except that 7.5 g of intermediate (A50) was changed to 9.5 g of intermediate (A160). In the same manner, an intermediate (A161) was obtained.
(3) Synthesis of 4- (4- {1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl} butanoyl) phenyltriphenylborate In Example 5, intermediate (A52) 4. The same procedure as in Example 5 was carried out, except that 5 g was changed to 4.7 g of intermediate (A161) and 1.5 g of triethylamine was changed to 2.3 g of DBU, and 4- (4- {1,8-diazabicyclo [5.4. 0] -7-undecenium-8-yl} butanoyl) phenyltriphenylborate [borate salt (A-16)] was obtained (yield 90%, purity 94%).

<Example 17: Synthesis of 6- (α- {1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl} acetyl) -2-naphthyltriphenylborate>
(1) Synthesis of intermediate (A170):
In the synthesis of intermediate (A50), the same procedure as in the synthesis of intermediate (A50) was conducted except that 10 g of 4-bromoacetophenone was changed to 12.5 g of 6-bromo-2-acetonaphthone (manufactured by Aldrich). A170) was obtained.
(2) Synthesis of intermediate (A171) In the synthesis of intermediate (A51), intermediate (A51) was synthesized except that 7.5 g of intermediate (A50) was changed to 9.1 g of intermediate (A170). In the same manner, an intermediate (A171) was obtained.
(3) Synthesis of Intermediate (A172) In the synthesis of Intermediate (A52), except that 6.7 g of Intermediate (A51) is changed to 7.4 g of Intermediate (A171), the same as the synthesis of Intermediate (A52) To obtain an intermediate (A172).
(4) Synthesis of 6- (α- {1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl} acetyl) -2-naphthyltriphenylborate In Example 5, the intermediate (A52 ) 4.5 g was changed to 5.3 g of intermediate (A172) and 1.5 g of triethylamine was changed to 2.3 g of DBU, and the same procedure as in Example 5 was carried out, and 6- (α- {1,8-diazabicyclo [5 4.0] -7-undecenium-8-yl} acetyl) -2-naphthyltriphenylborate [borate salt (A-17)] (yield 88%, purity 95%).

Example 18 Synthesis of 4- {α- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) acetyl} -p-biphenyltriphenylborate>
(1) Synthesis of intermediate (A180):
In the synthesis of intermediate (A50), except that 10 g of 4-bromoacetophenone was changed to 13.8 g of 4 ′-(4-bromophenyl) acetophenone (manufactured by Aldrich), it was carried out in the same manner as the synthesis of intermediate (A50), An intermediate (A180) was obtained.
(2) Synthesis of intermediate (A181) In the synthesis of intermediate (A51), intermediate (A51) was synthesized except that 7.5 g of intermediate (A50) was changed to 9.9 g of intermediate (A180) In the same manner, an intermediate (A181) was obtained.
(3) Synthesis of Intermediate (A182) In the synthesis of Intermediate (A52), except that 6.7 g of Intermediate (A51) is changed to 7.8 g of Intermediate (A181), the same as the synthesis of Intermediate (A52) To obtain an intermediate (A182).
(4) Synthesis of 4- {α- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) acetyl} -p-biphenyltriphenylborate In Example 5, the intermediate (A52 ) 4.5 g was changed to 5.6 g of intermediate (A182) and 1.5 g of triethylamine was changed to 2.3 g of DBU. 4.0] -7-undecenium-8-yl) acetyl} -p-biphenyltriphenylborate [borate salt (A-18)] (yield 87%, purity 90%).

Example 19 Synthesis of 3- {α- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) acetyl} -4-fluorophenyltriphenylborate>
(1) Synthesis of intermediate (A190):
The intermediate (A50) was synthesized in the same manner as the intermediate (A50) except that 10 g of 4-bromoacetophenone was changed to 10.9 g of 3-bromo-4-fluoroacetophenone (manufactured by Tokyo Chemical Industry). A body (A190) was obtained.
(2) Synthesis of intermediate (A191) In the synthesis of intermediate (A51), intermediate (A51) was synthesized except that 7.5 g of intermediate (A50) was changed to 8.1 g of intermediate (A190). In the same manner, an intermediate (A191) was obtained.
(3) Synthesis of Intermediate (A192) In the synthesis of Intermediate (A52), except that 6.7 g of Intermediate (A51) was changed to 6.9 g of Intermediate (A191), the same as Synthesis of Intermediate (A52) To obtain an intermediate (A192).
(4) Synthesis of 3- {α- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) acetyl} -4-fluorophenyltriphenylborate In Example 5, the intermediate ( A52) 4.5 g was changed to 5 g of intermediate (A192) and 1.5 g of triethylamine was changed to 2.3 g of DBU, and the same procedure as in Example 5 was carried out, and 3- {α- (1,8-diazabicyclo [5. 4.0] -7-undecenium-8-yl) acetyl} -4-fluorophenyltriphenylborate [borate salt (A-19)] (yield 82%, purity 96%).

Example 20 Synthesis of 4- {α-phenyl-α- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) acetyl} -phenyltriphenylborate>
(1) Synthesis of intermediate (A200):
In the synthesis of the intermediate (A50), except that 10 g of 4-bromoacetophenone was changed to 13.8 g of 4-bromo-α-phenylacetophenone (manufactured by Aldrich), the intermediate (A50) was synthesized. A200).
(2) Synthesis of intermediate (A201) In the synthesis of intermediate (A51), intermediate (A51) was synthesized except that 7.5 g of intermediate (A50) was changed to 9.9 g of intermediate (A200). In the same manner, an intermediate (A201) was obtained.
(3) Synthesis of intermediate (A202) In the synthesis of intermediate (A52), the same as synthesis of intermediate (A52), except that 6.7 g of intermediate (A51) was changed to 7.8 g of intermediate (A201). To obtain an intermediate (A202).
(4) Synthesis of 4- {α-phenyl-α- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) acetyl} -phenyltriphenylborate In Example 5, intermediate (A52) 4.5 g was changed to 5.6 g of the intermediate (A202) and 1.5 g of triethylamine was changed to 2.3 g of DBU, and the same procedure as in Example 5 was carried out, and 4- {α-phenyl-α- (1 , 8-diazabicyclo [5.4.0] -7-undecenium-8-yl) acetyl} -phenyltriphenylborate [borate salt (A-20)] (yield 89%, purity 94%).

Example 21 Synthesis of 4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methyl-1-naphthyltriphenylborate
(1) Synthesis of intermediate (A210):
In the synthesis of the intermediate (A10), the intermediate (A10) was changed except that the 4-tolylmagnesium bromide THF solution was changed to a 4-methyl-1-naphthylmagnesium bromide THF solution (1.0 mol / L) which can be prepared by a conventional method. ) To give an intermediate (A210).
(2) Synthesis of Intermediate (A211) Synthesis of Intermediate (A11) except that 7.4 g of Intermediate (A10) was changed to 8.4 g of Intermediate (A210) in the synthesis of Intermediate (A11). In the same manner, an intermediate (A211) was obtained.
(3) Synthesis of 4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methyl-1-naphthyltriphenylborate In Example 1, 4.5 g of intermediate (A11) 4- (1,8-diazabicyclo [5.4.0] -7-undecenium) was carried out in the same manner as in Example 1 except that 5 g of the intermediate (A211) and 1.5 g of triethylamine were changed to 2.3 g of DBU. -8-yl) methyl-1-naphthyltriphenylborate [borate salt (A-21)] was obtained (yield 87%, purity 97%).

Example 22 Synthesis of 9- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methyl-10-anthryltriphenylborate>
(1) Synthesis of intermediate (A220):
In the synthesis of the intermediate (A10), the intermediate (A) except that the 4-tolylmagnesium bromide THF solution is changed to a 9-methyl-10-anthrylmagnesium bromide THF solution (1.0 mol / L) that can be prepared by a conventional method The intermediate (A220) was obtained in the same manner as the synthesis of A10).
(2) Synthesis of intermediate (A221) In the synthesis of intermediate (A11), intermediate (A11) was synthesized except that 7.4 g of intermediate (A10) was changed to 9.4 g of intermediate (A220). In the same manner, an intermediate (A221) was obtained.
(3) Synthesis of 9- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methyl-10-anthryltriphenylborate In Example 1, intermediate (A11) 4. 9- (1,8-diazabicyclo [5.4.0]-was carried out in the same manner as in Example 1 except that 5 g was changed to 5.5 g of intermediate (A221) and 1.5 g of triethylamine was changed to 2.3 g of DBU. 7-Undecenium-8-yl) methyl-10-anthryltriphenylborate [borate salt (A-22)] was obtained (yield 76%, purity 97%).

<Example 23: Synthesis of 3-fluoro-4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyltriphenylborate>
(1) Synthesis of intermediate (A230):
In the synthesis of the intermediate (A10), the intermediate (A) except that the 4-tolylmagnesium bromide THF solution is changed to a 9-methyl-10-anthrylmagnesium bromide THF solution (1.0 mol / L) that can be prepared by a conventional method. The intermediate (A230) was obtained in the same manner as in the synthesis of A10).
(2) Synthesis of intermediate (A231) In the synthesis of intermediate (A11), intermediate (A11) was synthesized except that 7.4 g of intermediate (A10) was changed to 7.8 g of intermediate (A230). In the same manner, an intermediate (A231) was obtained.
(3) Synthesis of 3-fluoro-4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyltriphenylborate In Example 1, intermediate (A11) 4. The same procedure as in Example 1 was carried out, except that 5 g was changed to 4.7 g of intermediate (A231) and 1.5 g of triethylamine was changed to 2.3 g of DBU, and 3-fluoro-4- (1,8-diazabicyclo [5.4] was obtained. 0.0] -7-undecenium-8-yl) methylphenyltriphenylborate [borate salt (A-23)] (yield 88%, purity 91%).

<Example 24: Synthesis of 4-methoxy-3- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyltriphenylborate>
(1) Synthesis of intermediate (A240):
In the synthesis of intermediate (A10), except that 4-tolyl magnesium bromide THF solution was changed to 4-methoxy-3-methylphenyl magnesium bromide THF solution (1.0 mol / L) that can be prepared by a conventional method, The intermediate (A240) was obtained in the same manner as the synthesis of A10).
(2) Synthesis of intermediate (A241) In the synthesis of intermediate (A11), intermediate (A11) was synthesized except that 7.4 g of intermediate (A10) was changed to 8.1 g of intermediate (A240). In the same manner, an intermediate (A241) was obtained.
(3) Synthesis of 4-methoxy-3- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyltriphenylborate In Example 1, intermediate (A11) 4. The same procedure as in Example 1 was carried out except that 5 g was changed to 4.8 g of intermediate (A241) and 1.5 g of triethylamine was changed to 2.3 g of DBU, and 4-methoxy-3- (1,8-diazabicyclo [5.4] was obtained. 0.0] -7-undecenium-8-yl) methylphenyltriphenylborate [borate salt (A-24)] (yield 70%, purity 90%).

Example 25 Synthesis of 4- (α-phenyl-α- {1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl}) methylphenyltriphenylborate>
(1) Synthesis of intermediate (A250):
In the synthesis of intermediate (A10), the 4-tolylmagnesium bromide THF solution is changed to a 4- (α-chloro-α-phenyl) methylphenylmagnesium bromide THF solution (1.0 mol / L) that can be prepared by a conventional method. The intermediate (A250) was obtained in the same manner as in the synthesis of the intermediate (A10).
(2) Synthesis of 4- (α-phenyl-α- {1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl}) methylphenyltriphenylborate In Example 1, the intermediate ( A11) The same procedure as in Example 1 was carried out except that 4.5 g of the intermediate (A250) was changed to 4.8 g and triethylamine 1.5 g was changed to DBU 2.3 g, and 4- (α-phenyl-α- {1, 8-Diazabicyclo [5.4.0] -7-undecenium-8-yl}) methylphenyltriphenylborate [borate salt (A-25)] was obtained (yield 81%, purity 94%).

Example 26 Synthesis of 4- (4- {1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl}) butylphenyltriphenylborate>
(1) Synthesis of intermediate (A260):
A reaction vessel was charged with 30 g of potassium hydroxide and 150 mL of ethylene glycol, and potassium hydroxide was dissolved at 150 ° C. At 100 ° C., 40 g of 1- (4-bromophenyl) -4-chlorobutanone (manufactured by Aldrich) was charged, and 12 g of hydrazine monohydrate (manufactured by Tokyo Chemical Industry) was added dropwise thereto. After dropping, the mixture was reacted at 100 ° C. for 8 hours, cooled, and poured into 300 mL of water. Extraction was performed with 200 mL of dichloromethane, and the dichloromethane layer was further washed with water 5 times. The organic layer (dichloromethane) was concentrated and purified by silica gel column chromatography to obtain an intermediate (A260).
(2) Synthesis of intermediate (A261):
In the synthesis of the intermediate (A10), the intermediate (A) except that the 4-tolylmagnesium bromide THF solution was changed from the intermediate (A260) to a Grignard reagent (THF solution, 1.0 mol / L) that can be prepared by a conventional method. The intermediate (A261) was obtained in the same manner as the synthesis of A10).
(3) Synthesis of 4- (4- {1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl}) butylphenyltriphenylborate In Example 1, intermediate (A11) 4. The same procedure as in Example 1 was carried out except that 5 g was changed to 4.5 g of the intermediate (A261) and 1.5 g of triethylamine was changed to 2.3 g of DBU, and 4- (4- {1,8-diazabicyclo [5.4. 0] -7-undecenium-8-yl}) butylphenyltriphenylborate [borate salt (A-26)] was obtained (yield 77%, purity 91%).

Example 27 Synthesis of 4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyltris (sec-butyl) borate>
(1) Synthesis of Intermediate (A270) In the synthesis of Intermediate (40), 8.2 g of 4- (bromoethyl) -bromobenzene was changed to 6.4 g of 4-bromobenzyl chloride (manufactured by Tokyo Chemical Industry), and triphenyl Except that 100 mL of borane THF solution (0.25 mol / L) was changed to 25 mL of tris (sec-butyl) borane THF solution (1.0 mol / L, manufactured by Aldrich), the same procedure as in the synthesis of intermediate (40) was performed. A body (A270) was obtained.
(2) Synthesis of 4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyltris (sec-butyl) borate In Example 1, intermediate (A11) 4. The same procedure as in Example 1 was carried out except that 5 g was changed to 3.5 g of intermediate (A270) and 1.5 g of triethylamine was changed to 2.3 g of DBU, and 4- (1,8-diazabicyclo [5.4.0]- 7-Undecenium-8-yl) methylphenyltris (sec-butyl) borate [borate salt (A-27)] was obtained (yield 56%, purity 94%).

Example 28 Synthesis of 4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyl-diethyl-3-pyridylborate>
(1) Synthesis of Intermediate (A280) In the synthesis of Intermediate (270), the triphenylborane THF solution (0.25 mol / L) was changed to one obtained by dissolving 3.7 g of 3-pyridyldiethylborane in 100 mL of THF. The intermediate (A280) was obtained in the same manner as in the synthesis of the intermediate (270).
(2) Synthesis of 4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyl-diethyl-3-pyridylborate In Example 27, intermediate (A270) 3. 4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyl, which was carried out in the same manner as in Example 27 except that 5 g was changed to 3.1 g of intermediate (A280). -Diethyl-3-pyridyl borate [borate salt (A-28)] was obtained (yield 78%, purity 95%).

Example 29 Synthesis of 4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyl-trispentafluorophenylborate>
(1) Synthesis of Intermediate (A290) In the synthesis of Intermediate (270), 12.8 g of triphenylborane THF solution (0.25 mol / L) and trispentafluorophenylborane (Aldrich) were dissolved in 100 mL of THF. The intermediate (A290) was obtained in the same manner as in the synthesis of the intermediate (270) except that the intermediate (A290) was changed.
(2) Synthesis of 4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyl-trispentafluorophenylborate In Example 27, intermediate (A270) 3.5 g Was performed in the same manner as in Example 27, except that 4- (1,8-diazabicyclo [5.4.0] -7-undecenium-8-yl) methylphenyl- Trispentafluorophenyl borate [borate salt (A-29)] was obtained (yield 74%, purity 98%).

<Examples 30-58, Comparative Examples 1-2>
Zwitterionic borate salts obtained in Examples 1 to 29, comparative borate salt (d-1) and comparative borate salt (d-2) obtained in Production Example 5 [tetraphenylborate of DBU derivative] The following compositions were uniformly mixed using a salt (product name: U-CAT 5002, manufactured by San Apro) to prepare curable resin compositions (thermosetting resin composition and photocurable resin composition), respectively. .
(Thermosetting resin composition)
Bisphenol A type epoxy resin (JER-828; manufactured by Mitsubishi Chemical) 100g
Acid anhydride (HN5500E; manufactured by Hitachi Chemical) 90g
Borate salt 5g
(Photocurable resin composition)
Bisphenol A type epoxy resin (JER-828; manufactured by Mitsubishi Chemical) 100g
Acid anhydride (HN5500E; manufactured by Hitachi Chemical) 90g
Borate salt 5g
Sensitizer (diethylthioxanthone; manufactured by Tokyo Chemical Industry) 5g

  The zwitterionic borate salt (A) obtained in Examples 1 to 29, the borate salt for comparison (d-1) and the borate salt for comparison (d-2) obtained in Production Example 5 are curable resins. In order to confirm the effect when used as a curing accelerator for the composition, solubility, storage stability, thermosetting and photocuring properties were evaluated by the following methods, and the results are shown in Table 1.

(Solubility)
The thermosetting resin composition was visually observed to confirm the presence or absence of insoluble matter.
There is no insoluble matter.

(Storage stability)
The thermosetting resin composition was stored in a constant temperature machine at 40 ° C., and the number of days that reached twice the initial viscosity was compared.
> 2 weeks ..., 1-2 weeks ..., 3-6 days ..., <3 days ..., <1 day XX
The viscosity was measured at 25 ° C. using a rotary viscometer: Viscole Pro L (manufactured by Funkilab).

(Thermosetting)
After the thermosetting resin composition is uniformly applied to a glass substrate (100 mm × 100 mm) with a bar coater, it is heated on a hot plate heated to 150 ° C. for 30 minutes, and the coated surface is touched with a finger to check for surface tack. It was confirmed.
No tack ・ ・ ○ 、 With tack ・ ×

(Light curing)
Using a belt conveyor type UV irradiation device (I Graphics Co., Ltd., ECS-151U) using a high pressure mercury lamp as a light source, uniformly applying a photocurable resin composition to a glass substrate (100 mm × 100 mm) with a bar coater, Perform exposure [using a filter that transmits light with a wavelength of 300 to 450 nm (Eye Graphics Co., Ltd., 365 filter)] so that the exposure amount is 1000 mJ / cm 2 (integrated light amount at 365 nm), and touch the coated surface with your finger The presence or absence of surface tack was confirmed.
No tack ・ ・ ○ 、 With tack ・ ×

  From the results in Table 1, it can be seen that the zwitterionic borate salt of the present invention is superior in curability and storage stability as compared with the borate salt for comparison.

<Examples 59 to 76 and Comparative Examples 3 to 5>
Among the zwitterionic borate salts (A-1) to (A-28) obtained in Examples 1 to 28, the zwitterionic borate salts listed in Table 2 or the base generator (d-3) for comparison (D-5), polyamide resins (P1-1) to (P2-5) obtained in Production Examples 6 to 13, solvents (S-1) to (S-3), and a sensitizer (H -1) or (H-2), respectively, using the number of parts shown in Table 2 and stirring uniformly at room temperature for 3 hours to create a curable resin composition, and the resulting curable resin composition The residual probability after heating and pattern formation were evaluated by the following method, and the results are shown in Table 2.

  In Table 2, solvent (S-1) represents dimethylacetamide, solvent (S-2) represents N-methylpyrrolidone, and sensitizer (H-1) represents 4,4′-dimethylaminobenzophenone. And sensitizer (H-2) represents 2,4-diethylthioxanthone.

[Test method: film ratio after heating]
The curable resin composition prepared on the silicon substrate was spin-coated so as to have a final film thickness of 10 μm, and then dried on a hot plate adjusted to 100 ° C. for 15 minutes. Half of the dried silicon substrate was shielded with a mask, and then exposed with an i-line (365 nm) exposure device at an exposure amount of 1000 mJ / cm. The heating temperature after exposure was changed from 160 ° C to 250 ° C. The heating time was 15 minutes. After the heating, development was performed by immersing the silicon substrate in a 2% NaOH aqueous solution. The development time was the time until the light-shielded part (unexposed part) was completely dissolved.
After completion of development, washing was carried out, and the residual film ratio was calculated from the film thickness before exposure and the film thickness after development of the exposed portion. The results are shown in Table 2. The higher the residual rate, the more the cyclization reaction is progressing.

[Test method: Pattern formation]
In the case where the curable resin composition is applied to a semiconductor protective film or a printed circuit board protective film, it is preferable that a finer pattern can be formed.
The curable resin composition was spin-coated on a silicon substrate to a final film thickness of 3 μm, and then dried on a hot plate adjusted to 100 ° C. for 15 minutes.
A stripe-shaped photomask that can form a pattern composed of a line (L) that is a hardened portion and a space (S) that is an uncured portion, and a plurality of photomasks having different line widths and space widths is used for each i. It exposed with the exposure amount of 1000 mJ / cm with the line | wire (365 nm) exposure machine (TME-150RSC (made by Topcon Corporation)). After exposure, the film was further heated at 150 ° C. for 5 minutes, and then developed using a 2% aqueous NaOH solution. After developing, washing with water, and heating at 200 ° C. for 15 minutes, among the photomasks that can form a stripe pattern corresponding to the photomask, the line width of the photomask having the smallest line width and space width The space width is shown in Table 2 as the minimum L / S of the pattern. A smaller value means that a finer pattern can be formed and the pattern formability is better.

From Table 2, the curable resin composition of the present invention has a good residual film ratio of 80% or more at a heating temperature of 200 ° C., and the line width and space width in pattern forming property are thin and good at 5 to 10 μm. The comparative photosensitive resin composition had a remaining film ratio of about 70% even at a heating temperature of 250 ° C., and the line width and space width were 15 to 20 μm. Further, defects such as partial defects were observed during pattern formation.
As seen in this example, by using the curable resin composition of the present invention, the cyclization reaction proceeds even at 200 ° C., which is lower than the conventional temperature, and a high heat resistant resin such as polyimide can be obtained. I understand. Therefore, it is particularly useful for a protective film of a semiconductor component and a printed circuit board that cannot withstand a heating process at a high temperature.

  The zwitterionic borate salt of the present invention is excellent in storage stability and solubility when blended with a curable resin or a polymerizable monomer, and exhibits excellent curability when cured by heating or light irradiation. Furthermore, imidization proceeds at a lower temperature than before, and a photosensitive resin composition having good pattern forming properties can be obtained. When cured by light irradiation, products and members that form patterns, etc. (for example, electronic components (semiconductor protective film, insulating film, printed circuit board protective film, etc.), optical products, optical component forming materials, layer forming materials, or adhesives Etc.) or a thermosetting composition comprising a thermosetting resin and a cross-linking agent is suitably used for electrical / electronic materials such as IC sealing materials.

Claims (7)

A zwitterionic borate salt represented by the general formula (1).
[In General Formula (1), each R ¹ is independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, or an aralkyl having 7 to 24 carbon atoms. A group or an aryl group having 6 to 18 carbon atoms, or a group in which at least one hydrogen atom of these groups has an oxygen atom, a group having a sulfur atom, a group having a nitrogen atom or a halogeno group, A ⁺ is a group having a tetravalent covalently bonded nitrogen atom, B ⁻ is an anionic boron atom, and Y is a divalent organic that bonds the tetravalent covalently bonded nitrogen atom and anionic boron atom of A ^+. It is a group. ] The zwitterionic borate salt according to claim 1, wherein Y is a group represented by the following general formula (2) or a group represented by the general formula (3).
[In General Formula (2), Y ¹ is an alkylene group having 1 to 18 carbon atoms, Ar is an arylene group, and at least one hydrogen atom of Ar is an alkyl group having 1 to 8 carbon atoms and an oxygen atom. And a group having a sulfur atom, or a halogeno group. ]
[In General Formula (3), Y ¹ is an alkylene group having 1 to 18 carbon atoms, Ar is an arylene group, and at least one hydrogen atom of Ar is an alkyl group having 1 to 8 carbon atoms and an oxygen atom. And a group having a sulfur atom, or a halogeno group. ] The zwitterionic borate salt according to claim 1 or 2, wherein R ¹ is an aryl group having 6 to 18 carbon atoms.   A curable resin composition comprising the zwitterionic borate salt according to claim 1 and a curable compound. A curable compound comprising a curable compound comprising a compound (J) having two or more glycidyl groups in the molecule and a compound (K) or acid anhydride (L) having two or more active hydrogen-containing groups in the molecule. And a curable compound which is a polyamide resin (Am1) having a repeating unit represented by the general formula (4) and / or a polyamide resin (Am2) having a repeating unit represented by the general formula (5). The curable resin composition of Claim 4 containing the at least 1 sort (s) of curable compound chosen from these.
[In General Formula (4), (V) represents a tetravalent organic group, and (W) represents a divalent organic group. ]
[In General Formula (5), (V) represents a tetravalent organic group, (W) represents a divalent organic group, and X represents a hydroxyl group, a mercapto group, or an amino group. ]   Furthermore, the curable resin composition of Claim 4 or 5 containing a sensitizer (H).   The hardened | cured material of the curable composition of any one of Claims 4-6.