JP2017222621A - Onium borate salt, acid generator, curable resin composition and cured body prepared therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an onium borate salt and the like having cationic polymerizing performance and crosslinking reacting performance.SOLUTION: An onium borate salt contains onium borate salt (OB1) represented by general formula (1) and onium borate salt (OB2) represented by general formula (2), where the content of (OB2) in (OB1) and (OB2) is 0.01-4 wt.% [(R)-E][(R)B(Ar)](1), [(R)-E][(OH)(R)B(Ar)](2) [in formulae (1) and (2), E represents an n-valence element of Group VIA to Group VIIA (CAS notation) and n is an integer of 1 or 2; Ris an organic group bonded to E; Ris an organic group bonded to B (boron) and b is an integer of 1 to 3; and Ar represents a substituted phenyl group and b is an integer of 1 to 3].SELECTED DRAWING: None

Description

  The present invention relates firstly to an onium borate salt having a specific structure, and secondly, an acid generator, more specifically, an active energy ray such as heat, light, electron beam, or X-ray is allowed to act on the cationic polymerizability. The present invention relates to an acid generator containing an onium borate salt having a specific structure suitable for curing a compound. Thirdly, the present invention relates to a curable composition containing the acid generator and a cured product obtained by curing the curable composition. Fourthly, the present invention relates to a chemically amplified negative photoresist composition containing the photoacid generator and a cured product obtained by curing the composition.

Conventionally, onium salts such as iodonium and sulfonium salts are known as cationic polymerization initiators for curing a cationically polymerizable compound such as an epoxy compound by irradiation with active energy rays such as heat, light, or an electron beam (Patent Documents 1 to 3). 10).
These onium salts are also referred to as acid generators because they generate acid upon irradiation with heat or active energy rays, and are also used in resists and photosensitive materials (Patent Documents 11 to 13).

By the way, the cationic polymerization initiator (acid generator) described in these specifications contains BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF ₆ ⁻ as anions. Curing performance and cross-linking reaction performance by an acid catalyst differ depending on the type of anion, and improve in the order of BF ₄ ⁻ <PF ₆ ⁻ <AsF ₆ ⁻ <SbF ₆ ⁻ . However, the polymerization and crosslinking performance good AsF ₆ ^-, SbF ₆ ^- cationic polymerization initiator containing (acid generating agent), As, use applications are limited from toxicity problems of Sb, SbF ₆ ^- salt stereolithography It is only used for limited purposes. Therefore, in general, PF ₆ poor polymerization or crosslinking performance ^- the salts are utilized, PF ₆ ^- salt, for example, SbF ₆ ^- to obtain the cure rate comparable to salt, the latter 10 times more It is necessary to add the amount of unreacted initiator (acid generator), the amount of solvent used as necessary to dissolve the initiator (acid generator), or the residual amount of initiator decomposition product. Therefore, there is a problem that the physical properties of the cured product are impaired and the amount of HF produced as a by-product due to decomposition of the initiator increases, so that the base material, equipment, and the like are easily corroded. Thus free of toxic metals, SbF ₆ ^- cationic polymerization initiator having a cationic polymerization initiating ability comparable to salt has been strongly desired.

For members that require optical properties, such as displays, optical waveguides, and optical lenses, the transparency of the cured product cured by irradiation with active energy rays such as heat, light, or electron beam, the heat resistance test, and the cured product after the moisture resistance test Transparency is important. In addition, paint, coating agent, ink, inkjet ink, resist film, liquid resist, negative resist, MEMS resist, negative photosensitive material, various adhesives, molding material, casting material, putty, glass fiber impregnating agent, Members such as sealants, sealing agents, sealants, optical semiconductor (LED) sealants, optical waveguide materials, nanoimprint materials, stereolithography, and micro stereolithography materials, ACF (anisotropic conductive film), This is an application that requires corrosion resistance against the remaining strong acid.

The present inventors do not contain toxic metals, SbF ₆ ^- cationic polymerization initiator having a cationic polymerization performance and crosslinking reaction performance comparable to salts (acid generator), a fluorinated alkyl phosphoric acid onium salt-based acid generator (Patent Document 14) has been proposed, but the cured product using this product has a problem that transparency is lowered because it causes corrosion and coloring of resins and the like due to strong fluorinated alkylphosphoric acid remaining after the heat test. Therefore, application to the members that require the above optical characteristics has not progressed.

Further, free of toxic metals, SbF ₆ ^- as a cationic polymerization initiator having a cationic polymerization performance and crosslinking reaction performance comparable to salt (acid generator), tetrakis (pentafluorophenyl) borate an onium salt having an anion (Patent Literature 15) is known, but the cured product using this material is particularly deteriorated in transparency because it causes corrosion and coloring of resins and the like due to strong acid HB (C ₆ F ₅ ) ₄ remaining after the heat test. There is a problem, and the application to the members that require the above optical characteristics has not progressed.

The present inventors do not contain toxic metals, SbF ₆ ^- cationic polymerization initiator having a cationic polymerization performance and crosslinking reaction performance comparable to salts (acid generator), borate-based acid generator (Patent Document 16) It has been proposed that a cured product using this product is reported to have high transparency without being colored after the heat resistance test (Patent Document 17). However, there was no description about the influence which the by-product contained in an acid generator has on curability and transparency.

Japanese Patent Laid-Open No. 50-151997 JP 50-158680 A JP-A-2-178303 JP-A-2-178303 US Patent 4069054 U.S. Pat. No. 4,450,360 US Pat. No. 4,576,999 U.S. Pat. No. 4,640,967 Canadian Patent 1274646 European Published Patent No. 203829 JP 2002-193925 A JP 2001-354669 A JP 2001-294570 A WO2005-116038 JP 2000-66385 A JP 2011-201803 A Japanese Patent Application No. 2013-93502

In the above background, the first object of the present invention is to contain a toxic metal, have a cationic polymerization performance and a crosslinking reaction performance higher than tetrakis (pentafluorophenyl) borate salt, and a cured product using the same. In particular, there is no strong acid remaining after the heat test, so there is no corrosion of the member, and there is no problem of transparency deterioration due to the corrosion of the resin. The onium borate salt (acid generator) is also provided. It is to provide a heat or energy ray curable composition and a cured product using a generator.
The second object of the present invention is to provide a chemically amplified negative photoresist composition and a cured product using the acid generator.

As a result of intensive studies to solve the above problems, the present inventors have found that a specific onium borate salt is an excellent acid generator that satisfies these requirements, and have reached the present invention.
That is, the present invention is an onium borate salt including an onium borate salt (OB1) represented by the following general formula (1) and an onium borate salt (OB2) represented by the following general formula (2), (OB1 ) And (OB2) is an onium borate salt having a content of (OB2) in the range of 0.01 to 4% by weight.

_{^{[(R 1) n + 1}} -E] + [(R 2) b B (Ar) 4-b] - (1)

_{^{[(R 1) n + 1}} -E] + [(OH) (R 2) b B (Ar) 3-b] - (2)

[In the formulas (1) and (2), E represents an element having a valence of n from VIA group to VIIA group (CAS notation), and n is an integer of 1 or 2;
R ¹ is an organic group bonded to E, and (n + 1) R ^{1 s} may be the same or different from each other, and two or more R ¹ may be directly or —O—, — S -, - SO -, - SO 2 -, - NH -, - CO -, - COO -, - CONH-, may form a ring structure containing an element E through an alkylene group or a phenylene group;
R ² is an organic group bonded to B (boron), b is an integer of 1 to 3, and b R ^{2 s} may be the same or different;
Ar represents a phenyl group substituted with at least one selected from the group consisting of perfluoroalkyl, perfluoroalkoxy and halogen, and Ar may be the same or different. ]

Moreover, this invention is an acid generator characterized by containing the said onium borate salt.

Moreover, this invention is a heat | fever or energy beam curable composition characterized by containing the said acid generator and a cationically polymerizable compound.

Moreover, this invention is a hardening body obtained by hardening the said heat | fever or energy beam curable composition.

The present invention also includes a component (A) comprising the acid generator, a component (B) which is an alkali-soluble resin having a phenolic hydroxyl group, and a cross-linking agent component (C). It is a negative photoresist composition.

The present invention also provides a cured product obtained by curing the above chemically amplified negative photoresist composition.

Onium borate salt of the present invention do not contain high elemental toxicity such as Sb, SbF ₆ ^- it has a cationic polymerization performance and crosslinking reaction performance comparable to the case of using a salt containing the onium borate salt A cured product obtained by curing a heat or energy ray curable composition by irradiation with active energy rays such as heat or ultraviolet rays does not leave a strong acid, so the transparency does not deteriorate due to corrosion of the resin, and optical characteristics (transparency) Is good.
In addition, a cured product obtained by curing a chemically amplified negative photoresist composition containing the onium borate salt by irradiation with active energy rays such as ultraviolet rays does not leave strong acid, so that transparency does not deteriorate due to corrosion of the resin. Optical properties (transparency) are good.

  Hereinafter, embodiments of the present invention will be described in detail.

The onium borate salt of the present invention is represented by the above general formulas (1) and (2).
E in the formula (1) and the formula (2) represents an element having a valence of n from Group VIA to Group VIIA (CAS notation), and is combined with the organic group R ¹ to form an onium ion [E +]. Among the elements of Group VIA to VIIA, S (sulfur) or I (iodine) excellent in cationic polymerization performance and crosslinking reaction performance is preferable, and the corresponding onium ions are sulfonium and iodonium. n represents the valence of the element E and is an integer of 1 or 2.

R ^{1 in} Formula (1) and Formula (2) represents an organic group bonded to E, and may be the same or different. Examples of the organic group for R ¹ include aryl groups having 6 to 30 carbon atoms, heterocyclic groups having 4 to 30 carbon atoms, alkyl groups having 1 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, and 2 to 30 carbon atoms. These include alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, aryl It may be substituted with at least one selected from the group consisting of sulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups and halogen.

In the above, aryl groups having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl group and biphenylyl group, and naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, anthraquinone And a condensed polycyclic aryl group such as

Examples of the heterocyclic group having 4 to 30 carbon atoms include cyclic groups containing 1 to 3 hetero atoms such as oxygen, nitrogen and sulfur, which may be the same or different. Are monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl A condensed polycyclic heterocyclic group such as carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl It is below.

Examples of the alkyl group having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl, okdadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, etc. And a cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
Examples of the alkenyl group having 2 to 30 carbon atoms include linear, branched, etc. such as vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 1-methyl-1-propenyl. Can be mentioned.
Further, examples of the alkynyl group having 2 to 30 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl and 1-methyl-2-propynyl. And straight chain or branched ones.

The aryl group having 6 to 30 carbon atoms, the heterocyclic group having 4 to 30 carbon atoms, the alkyl group having 1 to 30 carbon atoms, the alkenyl group having 2 to 30 carbon atoms, or the alkynyl group having 2 to 30 carbon atoms is at least 1 It may have a kind of substituent, and examples of the substituent include a linear alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, okdadecyl; isopropyl, isobutyl, sec-butyl, tert-butyl A branched alkyl group having 1 to 18 carbon atoms; a cycloalkyl group having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; a hydroxy group; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, straight-chain or branched alkoxy groups having 1 to 18 carbon atoms such as tert-butoxy and dodecyloxy; C2-C18 linear or branched alkylcarbonyl groups such as pionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl; benzoyl, naphthoyl, etc. Arylcarbonyl group; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, etc., a straight or branched alkoxycarbonyl group having 2 to 19 carbon atoms; phenoxy Aryloxycarbonyl groups having 7 to 11 carbon atoms such as carbonyl and naphthoxycarbonyl; arylthiocarbonyl groups having 7 to 11 carbon atoms such as phenylthiocarbonyl and naphthoxythiocarbonyl; A linear or branched acyloxy group having 2 to 19 carbon atoms such as xyl, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octadecylcarbonyloxy; phenylthio, biphenylylthio, Methylphenylthio, chlorophenylthio, bromophenylthio, fluorophenylthio, hydroxyphenylthio, methoxyphenylthio, naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [4- (phenylthio) phenoxy] phenylthio, 4 -[4- (phenylthio) phenyl] phenylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-chlorophenylthio, 4-benzoyl-methyl Thiophenylthio, 4- (methylthiobenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio, etc. arylthio groups having 6 to 20 carbon atoms; methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, dodecylthio, etc. Straight or branched alkylthio group having 1 to 18 carbon atoms; aryl group having 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl, naphthyl; thienyl, furanyl, pyranyl, xanthenyl, chromanyl, isochromanyl, xanthonyl, thioxanthonyl, dibenzofuran A heterocyclic group having 4 to 20 carbon atoms such as nyl; an aryloxy group having 6 to 10 carbon atoms such as phenoxy and naphthyloxy; methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, octylsulfur A linear or branched alkylsulfinyl group having 1 to 18 carbon atoms such as nyl; an arylsulfinyl group having 6 to 10 carbon atoms such as phenylsulfinyl, tolylsulfinyl, naphthylsulfinyl; methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl A linear or branched alkylsulfonyl group having 1 to 18 carbon atoms such as octylsulfonyl; an arylsulfonyl group having 6 to 10 carbon atoms such as phenylsulfonyl, tolylsulfonyl (tosyl group) and naphthylsulfonyl; an alkyleneoxy group; a cyano group; Nitro group; halogen such as fluorine, chlorine, bromine and iodine.

In addition, two or more R ¹ groups may be bonded to each other directly or —O—, —S—, —SO—, —SO ₂ —, —NH—, —CO—, —COO—, —CONH—, an alkylene group, or a phenylene group. A ring structure containing the element E may be formed through.

Examples of the sulfonium ion include conventionally known ones. Specific examples thereof include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris (4-methoxyphenyl) sulfonium, 1-naphthyldiphenylsulfonium. 2-naphthyldiphenylsulfonium, tris (4-fluorophenyl) sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris (4-hydroxyphenyl) sulfonium, 4- (phenylthio) phenyldiphenylsulfonium, 4- (P-tolylthio) phenyldi-p-tolylsulfonium, 4- (4-methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenylbis (4-fluorophenyl) s Phonium, 4- (phenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenyldi-p-tolylsulfonium, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium, [ 4- (2-thioxanthonylthio) phenyl] diphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide Bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methylphenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methoxyphenyl) sulfonio ] Phenyl} sulfide, 4- (4-benzoyl-2-chloro) Phenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenylsulfonium, 4- (4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- ( 4-benzoylphenylthio) phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia- 9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) Phenylthio] phenyldi-p-tolylsulfur Honium, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldiphenylsulfonium, 4- [4- (benzoylphenylthio)] phenyldi-p-tolylsulfonium, 4- [4- (benzoylphenylthio)] Phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiaanthrhenium, 5-phenylthiaanthrhenium, 5-tolylthiaanthrhenium, 5- (4-ethoxyphenyl) thiaanthrhenium, 5- (2,4,6 -Triarylsulfonium such as trimethylphenyl) thiaanthrhenium, [4- (4-acetyl) phenylthio] phenyldiphenylsulfonium; diphenylphenacylsulfonium, diphenyl4-nitrophenacylsulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium Diarylsulfonium such as nium; phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-hydroxyphenyl-methyl-1-naphthylmethylsulfonium, 4-hydroxyphenyl-methyl-4-nitrobenzylsulfonium, 4-acetoxyphenylbenzyl Methylsulfonium, 4-hydroxyphenyldimethylsulfonium, 4-acetoxyphenyldimethylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxy Carbonyl) ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethyl Enacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4-acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfonium, 2-naphthyloctadecylphenacylsulfonium, 9-anthracenylmethylphenacylsulfonium, etc. Monoarylsulfonium; trialkylsulfonium such as dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octadecylmethylphenacylsulfonium, and the like.

Examples of iodonium ions include conventionally known ions, and specific examples thereof include diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, and (4-octyl). Oxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium and 4-isobutylphenyl (p-tolyl) iodonium And iodonium ions.

In the borate anion represented by the general formulas (1) and (2), R ² is an organic group bonded to B (boron), b is an integer of 1 to 3, and b R ² are respectively They may be the same or different. Examples of the organic group for R ² include an aryl group having 6 to 30 carbon atoms and a heterocyclic group having 4 to 30 carbon atoms, and these include alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl. , Arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogen It may be substituted with at least one.

R ² is preferably an aryl group having 6 to 30 carbon atoms and a heterocyclic group having 4 to 30 carbon atoms which may have a substituent, and more preferably, from the viewpoint of acid generation efficiency and thermal stability. Is a group selected from the group consisting of a phenyl group, a methylphenyl group, a methoxyphenyl group, a dimethylphenyl group, a naphthyl group and an anthracenyl group, and particularly preferably a phenyl group.

In the general formulas (1) and (2), the number b of R ² is an integer of 1 to 3, preferably 1 to 2, and particularly preferably 1. The b R ^{2 s} may be the same or different. When the number of R ² is increased, it is not preferable because of a decrease in cationic polymerization initiating ability and a reduction in catalytic ability to resist.

In the borate anion represented by the general formulas (1) and (2), Ar represents a phenyl group substituted with at least one selected from the group consisting of perfluoroalkyl, perfluoroalkoxy and halogen, preferably , Ar is a perfluoroalkyl group and phenyl substituted with a fluorine atom. b is an integer of 1 to 3, and 4-b Ars may be the same or different.
Here, the perfluoroalkyl group has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of perfluoroalkyl groups include linear perfluoroalkyl groups such as trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, perfluoropentyl, perfluorooctyl; heptafluoroisopropyl, nonafluoroisobutyl, nonafluoro Branched perfluoroalkyl groups such as -sec-butyl and nonafluoro-tert-butyl; and perfluorocycloalkyl groups such as perfluorocyclopropyl, perfluorocyclobutyl, perfluorocyclopentyl, and perfluorocyclohexyl.
Here, the perfluoroalkoxy group has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples of perfluoroalkoxy groups include linear perfluoroalkoxy groups such as trifluoromethoxy, pentafluoroethoxy, heptafluoropropoxy, nonafluorobutoxy, perfluoropentyloxy, perfluorooctyloxy; heptafluoroisopropoxy, nonafluoro Examples thereof include branched perfluoroalkoxy groups such as isobutoxy, nonafluoro-sec-butoxy and nonafluoro-tert-butoxy.
Examples of the halogen include fluorine, chlorine, bromine and iodine.
From the viewpoint of cationic polymerization performance, Ar is preferably a perfluoroalkyl group and a phenyl group substituted with a fluorine atom.

Specific examples of preferable Ar include a pentafluorophenyl group (C ₆ F ₅ ), a trifluorophenyl group (C ₆ H ₂ F ₃ ), a tetrafluorophenyl group (C ₆ HF ₄ ), and a trifluoromethylphenyl group (CF ₃ C ₆ H ₄ ), bis (trifluoromethyl) phenyl group ((CF ₃ ) ₂ C ₆ H ₃ ), pentafluoroethylphenyl group (CF ₂ CF ₃ C ₆ H), bis (pentafluoroethyl) phenyl group ( (CF ₂ CF ₃ ) ₂ C ₆ H ₃ ), fluoro-trifluoromethylphenyl group (CF ₃ C ₆ H ₃ F), fluoro-bis (trifluoromethyl) phenyl group ((CF ₃ ) ₂ C ₆ H ₂ F), fluoro - pentafluoroethyl phenyl group _{(CF 3 CF 2 C 6 H} 3 F), fluoro - bis (pentafluoroethyl) phenyl group (( _{F 3 CF 2) 2 C 6} H 2 F) , and the like.
Among these, a pentafluorophenyl (C ₆ F ₅ ) group and a bis (trifluoromethyl) phenyl group are more preferable, and a pentafluorophenyl group is particularly preferable.

Specific examples of preferred borate anions of the general formula (1) include [CH ₃ (C ₆ H ₄ ) B (C ₆ F ₅ ) ₃ ] ^— , [(C ₆ H ₅ ) B (C ₆ F ₅ ) ₃ ]. ^— , [CH ₃ (C ₆ H ₄ ) B ((CF ₃ ) ₂ C ₆ H ₃ ) ₃ ] ^— , [(C ₆ H ₅ ) B ((CF ₃ ) ₂ C ₆ H ₃ ) ₃ ] ^— Particularly preferred is [(C ₆ H ₅ ) B (C ₆ F ₅ ) ₃ ] ^- .

The onium borate salt of the general formula (1) used in the present invention can be produced according to Patent Documents 16 and 17.

Specific examples of preferred borate anions of the general formula (2) include [(OH) CH ₃ (C ₆ H ₄ ) B (C ₆ F ₅ ) ₂ ] ^— , [(OH) (C ₆ H ₅ ) B (C ₆ F ₅ ) ₂ ] ^— , [(OH) CH ₃ (C ₆ H ₄ ) B ((CF ₃ ) ₂ C ₆ H ₃ ) ₂ ] ^— , [(OH) (C ₆ H ₅ ) B ((CF ₃ ) ₂ C ₆ H ₃ ) ₂ ] ^— , and [(OH) (C ₆ H ₅ ) B (C ₆ F ₅ ) ₂ ] ^— is particularly preferable.

The sodium borate salt, which is an anion raw material of the onium borate salt of the general formula (2) of the present invention, reacts with moisture in the reaction system when producing the sodium borate salt which is the anionic raw material of the general formula (1). Is a by-product generated in

The onium borate salt of this invention may be used independently as an acid generator (cationic polymerization initiator), and may use 2 or more types together. Moreover, you may use together with another conventionally well-known acid generator (cationic polymerization initiator). Examples of the other acid generator (cationic polymerization initiator) include salts of onium ions such as sulfonium, iodonium, selenium, ammonium, phosphonium or transition metal complex ions and various anions.

The content of (OB2) in the onium borate salt (OB1) represented by the general formula (1) and the onium borate salt (OB2) represented by the general formula (2) is 0.01 to 4% by weight, Preferably it is 0.01 to 2 weight%. When it exceeds 4% by weight, the curability decreases. When it is 0.01% by weight or less, the transparency of the cured product is lowered.

An example of the general formula (2) is hydroxyphenylbis (pentafluorophenyl) borate salt. This borate salt is a by-product generated when synthesizing the onium borate salt of the general formula (1) (anion is [(C ₆ H ₅ ) B (C ₆ F ₅ ) ₃ ] ⁻ )). (It can be synthesized by a known method (Patent Documents 16 and 17).)
Borane ([(C ₆ H ₅ ) B (C ₆ F ₅ ) ₂ ]), which is an intermediate when synthesizing the sodium borate salt that is an anion raw material of the onium borate salt of the general formula (1), is present in the reaction system. Since it reacts with a small amount of water and a hydroxyphenylbis (pentafluorophenyl) borate salt is by-produced, the hydroxyphenylbis (pentafluorophenyl) borate salt is unavoidably contained as a by-product.
Therefore, the borate anion salt containing the hydroxyphenylbis (pentafluorophenyl) borate salt and the onium salt are subjected to salt exchange to obtain a mixture of the formulas (1) and (2) of the present invention.

¹ H-NMR, ¹³ C-NMR, ¹⁹ F-NMR, and high performance liquid chromatograph (HPLC) are used as the method for analyzing the impurity amount of the onium borate salt defined in the present invention. The measurement conditions of ¹ H-NMR, ¹³ C-NMR, and ¹⁹ F-NMR are as follows. Equipment: AL-300 (manufactured by JEOL), solvent: dimethyl sulfoxide. HPLC measurement conditions are as follows. Equipment: Model name (L-2130), manufacturer (Hitachi), column: (Ph-3) manufacturer (GL Sciences Inc), moving bed: methanol: water: sodium perchlorate monohydrate = 600: 68: 20 : Solution, detector: UV (210 nm), injection volume 10 μl, column temperature 40 ° C.

The ratio in the case of using two or more onium borate salts of the present invention in combination is arbitrary and is not limited.
The use ratio when other acid generator (cationic polymerization initiator) is used in combination may be arbitrary, but usually 100 parts by weight of the onium borate salt of the present invention is 10 to 900 parts by weight of the other cationic polymerization initiator, Preferably it is 25-400 weight part.

  In the case of using an acid generator containing an onium borate salt represented by the general formulas (1) and (2), in order to facilitate dissolution in a cationically polymerizable compound or a chemically amplified negative resist composition, It may be dissolved in a solvent that does not inhibit the crosslinking reaction.

  Solvents include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; ethylene glycol, ethylene glycol Polyhydric alcohols such as monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether And derivatives thereof; cyclic ethers such as dioxane 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, 2- Such as methyl hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. Esters: aromatic hydrocarbons such as toluene and xylene.

  When using a solvent, the usage-amount of a solvent has preferable 15-1000 weight part with respect to 100 weight part of acid generators, More preferably, it is 30-500 weight part. The solvent to be used may be used independently or may use 2 or more types together.

  The acid generator containing the onium borate salt (OB1) represented by the general formula (1) and the onium borate salt (OB2) represented by the general formula (2) of the present invention, and a cationically polymerizable compound The alkali metal content in the heat or energy beam curable composition is preferably 1.5 ppm or less from the viewpoint of coloring of the cured product.

Cationic polymerizable compounds that are constituents of heat or energy ray curable compositions include cyclic ethers (such as epoxides and oxetanes), ethylenically unsaturated compounds (such as vinyl ethers and styrene), bicycloorthoesters, spiroorthocarbonates and spiro. Examples include orthoesters and the like {JP-A-11-060996, JP-A-09-302269, JP-A-2003-026993, JP-A-2002-206017, JP-A-11-349895, JP-A-10-212343, JP 2000-119306, JP 10-67812, JP 2000-186071, JP 08-85775, JP 08-134405, JP 2008-20838, JP 2008-20839, JP 2008- 20841, JP 20 8-26660, Japanese Patent Application Laid-Open No. 2008-26644, Japanese Patent Application Laid-Open No. 2007-277327, Photopolymer Social Meeting “Photopolymer Handbook” (1989, Industrial Research Committee), General Technology Center “UV / EB Curing Technology” (1982, Comprehensive Technology Center), Radtech Study Group “UV / EB Curing Materials” (1992, CMC), Technical Information Association “UV Curing Failure / Inhibition Causes and Countermeasures” (2003, Technical Information Association), Color material, 68, (5), 286-293 (1995), fine chemical, 29, (19), 5-14 (2000), etc.}.

  As the epoxide, known ones can be used, and aromatic epoxides, alicyclic epoxides and aliphatic epoxides are included.

  Examples of the aromatic epoxide include glycidyl ethers of monovalent or polyvalent phenols (phenol, bisphenol A, phenol novolac and compounds obtained by adducting these alkylene oxides) having at least one aromatic ring.

  As the alicyclic epoxide, a compound obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, etc.) Is mentioned.

  Aliphatic epoxides include aliphatic polyhydric alcohols or polyglycidyl ethers of this alkylene oxide adduct (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), aliphatic polybasic acids. Examples thereof include polyglycidyl esters (such as diglycidyl tetrahydrophthalate) and epoxidized products of long chain unsaturated compounds (such as epoxidized soybean oil and epoxidized polybutadiene).

As oxetane, known ones can be used. For example, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3- Oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, oxetanylsilsesquioxetane, phenol novolac oxetane, etc. Is mentioned.

  As the ethylenically unsaturated compound, known cationic polymerizable monomers and the like can be used, and include aliphatic monovinyl ether, aromatic monovinyl ether, polyfunctional vinyl ether, styrene, and cationic polymerizable nitrogen-containing monomer.

  Examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.

  Examples of the aromatic monovinyl ether include 2-phenoxyethyl vinyl ether, phenyl vinyl ether and p-methoxyphenyl vinyl ether.

  Examples of the polyfunctional vinyl ether include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.

  Examples of styrene include styrene, α-methylstyrene, p-methoxystyrene, and p-tert-butoxystyrene.

  Examples of the cationic polymerizable nitrogen-containing monomer include N-vinylcarbazole and N-vinylpyrrolidone.

  Bicycloorthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2.2.2] octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo. -[2.2.2] octane and the like.

  Examples of the spiro ortho carbonate include 1,5,7,11-tetraoxaspiro [5.5] undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5.5] undecane. It is done.

  Spiro orthoesters include 1,4,6-trioxaspiro [4.4] nonane, 2-methyl-1,4,6-trioxaspiro [4.4] nonane and 1,4,6-trioxas. Examples include pyro [4.5] decane.

Furthermore, polyorganosiloxane having at least one cationic polymerizable group in one molecule can be used (Japanese Patent Laid-Open No. 2001-348482, Japanese Patent Laid-Open No. 2000-281965, Japanese Patent Laid-Open No. 7-242828, JP-A-2008-195931, Journal of Polym. Sci., Part A, Polym. Chem., Vol. 28, 497 (1990)).
These polyorganosiloxanes may be linear, branched or cyclic, or a mixture thereof.

Of these cationically polymerizable compounds, epoxide, oxetane and vinyl ether are preferable, epoxide and oxetane are more preferable, and alicyclic epoxide and oxetane are particularly preferable. Moreover, these cationically polymerizable compounds may be used alone or in combination of two or more.

  Content of acid generator containing onium borate salt (OB1) represented by general formula (1) and onium borate salt (OB2) represented by general formula (2) in the heat or energy beam curable composition Is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. Within this range, the polymerization of the cationically polymerizable compound is further sufficient, and the physical properties of the cured product are further improved. This content is determined by taking into consideration various factors such as the nature of the cationically polymerizable compound, heating temperature, time, energy ray type and irradiation amount, temperature, curing time, humidity, and coating thickness. It is not limited to the above range.

  In the heat or energy ray curable composition of the present invention, known additives (sensitizers, pigments, fillers, antistatic agents, flame retardants, antifoaming agents, flow regulators, light stabilizers, if necessary) Agents, antioxidants, adhesion promoters, ion scavengers, anti-coloring agents, solvents, non-reactive resins and radical polymerizable compounds).

  As the sensitizer, known sensitizers (JP-A-11-279212 and JP-A-09-183960) can be used, and anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene. , 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; thioxanthone {thioxanthone, 2 -Methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, etc.}; phenothiazine {phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, N-phenylphenol 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 and N-glycidylcarbazole and the like}; chrysene {1,4-dimethoxychrysene and 1,4-di-α-methylbenzyloxychrysene and the like}; phenanthrene {9 -Hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.}.

  When the sensitizer is contained, the content of the sensitizer is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, with respect to 100 parts of the acid generator.

  Known pigments can be used as the pigment, and examples include inorganic pigments (such as titanium oxide, iron oxide, and carbon black) and organic pigments (such as azo pigments, cyanine pigments, phthalocyanine pigments, and quinacridone pigments).

  When the pigment is contained, the content of the pigment is preferably 0.5 to 400,000 parts by weight, more preferably 10 to 150,000 parts by weight with respect to 100 parts of the acid generator.

  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 600,000 parts by weight, more preferably 300 to 200,000 parts by weight with respect to 100 parts of the acid generator.

  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 parts by weight, more preferably 0.6 to 5000 parts by weight with respect to 100 parts of the acid generator.

  As the flame retardant, known flame retardants can be used. Inorganic flame retardant {antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide , Magnesium hydroxide, calcium aluminate, etc.}; bromine flame retardant {tetrabromophthalic anhydride, hexabromobenzene, decabromobiphenyl ether, etc.}; and phosphate ester flame retardant {tris (tribromophenyl) phosphate, etc.} It is done.

  When the flame retardant is contained, the content of the flame retardant is preferably 0.5 to 40000 parts by weight, more preferably 5 to 10000 parts by weight with respect to 100 parts of the acid generator.

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 and the like can be used. Ultraviolet absorbing stabilizers {benzotriazole, benzophenone, salicylate, cyanoacrylate and derivatives thereof}; radical scavenging stabilizers {hindered amines, etc.}; and quenching And a type stabilizer {nickel complex etc.}.
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.
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 Inhibitors and phosphorus-based antioxidants may be mentioned, but they are hardly effective in preventing coloring during a heat resistance test at high temperatures.

  When an antifoaming agent, a flow control agent, a light stabilizer, an antioxidant, an adhesion promoter, an ion scavenger, or a coloring inhibitor is contained, each content is 0 with respect to 100 parts of the acid generator. 0.1 to 20000 parts by weight is preferable, and 0.5 to 5000 parts by weight is more preferable.

  The solvent is not limited as long as it can be used for dissolving the cationic polymerizable compound and adjusting the viscosity of the energy ray-curable composition, and those mentioned as the solvent for the acid generator can be used.

  When the solvent is contained, the content of the solvent is preferably 50 to 2,000,000 parts by weight, more preferably 200 to 500,000 parts by weight with respect to 100 parts of the acid generator.

  Non-reactive resins include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, hydrogenated styrene butadiene block copolymer, and (meth) acrylic ester co-polymer. Examples include coalescence and polyurethane. The number average molecular weight of these resins is preferably 1,000 to 500,000, and more preferably 5,000 to 100,000 (the number average molecular weight is a value measured by a general method such as GPC).

  When the non-reactive resin is contained, the content of the non-reactive resin is preferably 5 to 400000 parts by weight, more preferably 50 to 150,000 parts by weight with respect to 100 parts of the acid generator.

  When a non-reactive resin is contained, it is desirable to dissolve the non-reactive resin in a solvent in advance in order to facilitate dissolution of the non-reactive resin with the cationic polymerizable compound.

  As radically polymerizable compounds, known {Photopolymer social gathering “Photopolymer Handbook” (1989, Industrial Research Committee), General Technology Center “UV / EB Curing Technology” (1982, General Technology Center), Radtech Research The radical-polymerizable compounds of the “UV / EB Curing Materials” (1992, CMC) edited by the Society and the “Technical Information Association” “Hardening Failure / Inhibition Causes and Countermeasures for UV Curing” (2003, Technical Information Association)} Monofunctional monomers, bifunctional monomers, polyfunctional monomers, epoxy (meth) acrylates, polyester (meth) acrylates and urethane (meth) acrylates can be used.

  When the radically polymerizable compound is contained, the content of the radically polymerizable compound is preferably 5 to 400000 parts by weight, more preferably 50 to 150,000 parts by weight with respect to 100 parts of the acid generator.

  When a radically polymerizable compound is contained, it is preferable to use a radical polymerization initiator that initiates polymerization by heat or light in order to increase the molecular weight of the compound by radical polymerization.

  As the radical polymerization initiator, known radical polymerization initiators can be used, thermal radical polymerization initiators (organic peroxides, azo compounds, etc.) and photo radical polymerization initiators (acetophenone initiators, benzophenone initiators, Michler ketone-based initiator, benzoin-based initiator, thioxanthone-based initiator, acylphosphine-based initiator, etc.).

  When the radical polymerization initiator is contained, the content of the radical polymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts of the radical polymerizable compound. .

  The heat or energy beam curable composition of the present invention comprises a cationically polymerizable compound, an acid generator and, if necessary, an additive at room temperature (about 20 to 30 ° C.) or optionally heated (about 40 to 90 ° C.), It can be mixed and dissolved uniformly, or can be prepared by kneading with a three-roll.

The heat or energy beam curable composition of the present invention can be cured by heating or irradiation with energy rays to obtain a cured product.
Any energy ray may be used as long as it has an energy that induces decomposition of the acid generator, but a low-pressure, medium-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, LED lamp, xenon lamp, carbon arc lamp, fluorescent lamp. An energy beam in the ultraviolet to visible light region (wavelength: about 100 to about 800 nm) obtained from a semiconductor solid laser, an argon laser, a He—Cd laser, a KrF excimer laser, an ArF excimer laser, an F ₂ laser, or the like is preferable. In addition, the radiation which has high energy, such as an electron beam or an X-ray, can also be used for an energy beam.

  The irradiation time of the energy beam is affected by the energy beam intensity and the energy beam permeability to the energy beam curable composition, but about 0.1 to 10 seconds is sufficient at room temperature (about 20 to 30 ° C.). It is. However, it may be preferable to spend more time when energy beam permeability is low or when the energy beam curable composition is thick. Most energy ray-curable compositions are cured by cationic polymerization 0.1 seconds to several minutes after irradiation with energy rays, but if necessary, after irradiation with energy rays, room temperature (about 20 to 30 ° C.) to 200. It is also possible to heat and cure at a temperature of several seconds to several hours.

  Specific applications of the heat or energy ray curable composition of the present invention include paints, coating agents, various coating materials (hard coat, anti-stain coating, anti-fogging coating, anti-touch coating, optical fiber, etc.), Adhesive tape backside treatment agent, release coating material for adhesive labels (release paper, release plastic film, release metal foil, etc.), printing plate, dental materials (dental compound, dental composite) ink, inkjet ink , Positive resists (formation of connection terminals and wiring patterns for manufacturing electronic components such as circuit boards, CSPs, MEMS elements, etc.), resist films, liquid resists, negative resists (surface protective films such as semiconductor elements, interlayer insulating films, flat surfaces) Permanent film materials such as chemical film), MEMS resists, positive photosensitive materials, negative photosensitive materials, various adhesives (for various electronic components) Fixing agent, HDD adhesive, pickup lens adhesive, FPD functional film (deflection plate, antireflection film, etc.) adhesive, holographic resin, FPD material (color filter, black matrix, partition material, Photo spacers, ribs, alignment films for liquid crystals, sealants for FPDs, etc.), optical members, molding materials (for building materials, optical components, lenses), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials , Encapsulant, optical semiconductor (LED) encapsulant, optical waveguide material, nanoimprint material, photofabrication material, and micro stereolithography material, etc. Especially, the obtained cured product is less colored and excellent in transparency. Therefore, it is optimal for optical applications.

Since the acid generator containing the onium borate salt (OB1) represented by the general formula (1) and the onium borate salt (OB2) represented by the general formula (2) generates a strong acid even by light irradiation, It can also be used as a known acid generator for chemically amplified resist materials (JP 2003-267968 A, JP 2003-261529 A, JP 2002-193925 A, etc.).

  Chemically amplified resist materials include resins that are soluble in an alkaline developer, chemicals that contain a crosslinking agent and an acid generator that crosslink the resin by heat treatment in the presence of an acid and make it insoluble in an alkaline developer. Amplified negative resist is included.

The chemically amplified negative photoresist composition of the present invention is represented by the onium borate salt (OB1) represented by the general formula (1) and the general formula (2), which are compounds that generate an acid upon irradiation with light or radiation. A component (A) comprising an acid generator containing an onium borate salt (OB2), a component (B) which is an alkali-soluble resin having a phenolic hydroxyl group, and a crosslinking agent component (C), and (OB1) And the content of (OB2) in (OB2) is 0.01 to 4% by weight.
The alkali metal content in the chemically amplified negative photoresist composition is preferably 1.3 ppm or less from the viewpoint of coloring of the cured product.

  In the chemically amplified negative photoresist composition of the present invention, the component (A) may be used in combination with other conventionally known acid generators. Examples of other acid generators include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, and nitrobenzyl compounds. In addition, organic halides, disulfone and the like can be mentioned.

  As other conventionally known acid generators, one or more selected from the group of onium compounds, sulfonimide compounds, diazomethane compounds and oxime sulfonate compounds are preferable.

  When such other conventionally known acid generators are used in combination, the ratio of use may be arbitrary, but usually in the onium borate salt (OB1) and the general formula (2) represented by the general formula (1). The other acid generator is 10 to 900 parts by weight, preferably 25 to 400 parts by weight with respect to 100 parts by weight of the total weight of the acid generator including the onium borate salt (OB2).

  The content of the component (A) is preferably 0.01 to 10% by weight in the solid content of the chemically amplified positive photoresist composition.

Alkali-soluble resin (B) having phenolic hydroxyl group
Examples of the “alkali-soluble resin having a phenolic hydroxyl group” in the present invention (hereinafter referred to as “phenol resin (B)”) include, for example, novolak resin, polyhydroxystyrene, a copolymer of polyhydroxystyrene, hydroxystyrene and styrene. Copolymer, hydroxystyrene, copolymer of styrene and (meth) acrylic acid derivative, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, phenolic hydroxyl group A polyimide resin or the like is used. Among these, novolac resin, polyhydroxystyrene, copolymer of polyhydroxystyrene, copolymer of hydroxystyrene and styrene, copolymer of hydroxystyrene, styrene and (meth) acrylic acid derivative, phenol-xylylene glycol Condensed resins are preferred. In addition, these phenol resin (B) may be used individually by 1 type, and may mix and use 2 or more types.

Further, the phenol resin (B) may contain a phenolic low molecular compound as a part of the component.
Examples of the phenolic low molecular weight compound include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, and the like.

Cross-linking agent (C)
The crosslinking agent (C) in the present invention is not particularly limited as long as it acts as a crosslinking component (curing component) that reacts with the phenol resin (B). Examples of the crosslinking agent (C) include a compound having at least two or more alkyl etherified amino groups in the molecule, a compound having at least two or more alkyl etherified benzenes in the molecule, Examples thereof include oxirane ring-containing compounds, thiirane ring-containing compounds, oxetanyl group-containing compounds, isocyanate group-containing compounds (including blocked compounds), vinyl ether group-containing compounds, and the like.

Among these crosslinking agents (C), compounds having at least two alkyl etherified amino groups in the molecule and oxirane ring-containing compounds are preferred. Furthermore, it is more preferable to use a compound having at least two alkyl etherified amino groups in the molecule and an oxirane ring-containing compound in combination.

The blending amount of the crosslinking agent (C) in the present invention is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the phenol resin (B). When the amount of the crosslinking agent (C) is 1 to 100 parts by weight, the curing reaction proceeds sufficiently, and the resulting cured product has a high resolution and good pattern shape, and is heat resistant and electrically insulating. It is preferable because of its excellent properties.
When the compound having an alkyl etherified amino group and the oxirane ring-containing compound are used in combination, the content ratio of the oxirane ring-containing compound is the sum of the compound having an alkyl etherified amino group and the oxirane ring-containing compound being 100. In the case of weight%, it is preferably 50% by weight or less, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight.
In this case, the obtained cured film is preferable because it is excellent in chemical resistance without impairing high resolution.

Cross-linked fine particles (D)
The chemically amplified negative photoresist composition of the present invention may further contain crosslinked fine particles (D) in order to improve the durability and thermal shock resistance of the resulting cured product.
The crosslinked fine particle (D) is not particularly limited as long as the glass transition temperature (Tg) of the polymer constituting the crosslinked fine particle is 0 ° C. or lower, but a crosslinkable monomer having two or more unsaturated polymerizable groups (hereinafter referred to as “crosslinked monomer”). , Simply referred to as “crosslinking monomer”) and one or more “other monomers” selected so that the Tg of the crosslinked fine particles (D) is 0 ° C. or less. preferable.
In particular, two or more other monomers are used in combination, and at least one of the other monomers has a functional group other than a polymerizable group such as a carboxyl group, an epoxy group, an amino group, an isocyanate group, or a hydroxyl group. It is preferable.

Examples of the crosslinkable monomer include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and polyethylene glycol. Examples include compounds having a plurality of polymerizable unsaturated groups such as di (meth) acrylate and polypropylene glycol di (meth) acrylate. Of these, divinylbenzene is preferred.

The crosslinkable monomer used in producing the crosslinked fine particles (D) is preferably 1 to 20% by weight, more preferably 1 to 10%, based on 100% by weight of all monomers used for copolymerization. % By weight, particularly preferably 1 to 5% by weight.

Examples of the other monomer include diene compounds such as butadiene, isoprene, dimethylbutadiene, chloroprene, 1,3-pentadiene, (meth) acrylonitrile, α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-methoxyacrylonitrile. , Α-ethoxyacrylonitrile, crotonic acid nitrile, cinnamic acid nitrile, itaconic acid dinitrile, maleic acid dinitrile, fumaric acid dinitrile and other unsaturated nitrile compounds, (meth) acrylamide, dimethyl (meth) acrylamide, N, N′- Methylenebis (meth) acrylamide, N, N′-ethylenebis (meth) acrylamide, N, N′-hexamethylenebis (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N- (2-H Roxyethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, unsaturated amides such as crotonic acid amide, cinnamic acid amide, methyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid such as ethyl, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate Esters, styrene, α-methylstyrene, o-methoxystyrene, p-hydroxystyrene, p-isopropenylphenol and other aromatic vinyl compounds, bisphenol A diglycidyl ether, glycol diglycidyl ether and (meth) acrylic Acid, hydroxy Epoxy (meth) acrylate obtained by reaction with alkyl (meth) acrylate and the like, and urethane (meth) acrylates obtained by reaction of hydroxyalkyl (meth) acrylate and polyisocyanate, glycidyl (meth) acrylate, (meth ) Epoxy group-containing unsaturated compounds such as allyl glycidyl ether, (meth) acrylic acid, itaconic acid, succinic acid-β- (meth) acryloxyethyl, maleic acid-β- (meth) acryloxyethyl, phthalic acid-β -Unsaturated acid compounds such as (meth) acryloxyethyl and hexahydrophthalic acid-β- (meth) acryloxyethyl, amino group-containing unsaturated compounds such as dimethylamino (meth) acrylate and diethylamino (meth) acrylate, hydroxy Ethyl (meth) acrylate, Examples thereof include hydroxyl group-containing unsaturated compounds such as hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.

Among these other monomers, butadiene, isoprene, (meth) acrylonitrile, (meth) acrylic acid alkyl esters, styrene, p-hydroxystyrene, p-isopropenylphenol, glycidyl (meth) acrylate, (meth) acrylic Acid, hydroxyalkyl (meth) acrylates and the like are preferable.

In the production of the crosslinked fine particles (D), it is preferable that at least one diene compound, specifically butadiene, is used as the other monomer. Such a diene compound is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, particularly preferably 40 to 70% by weight based on 100% by weight of the total monomers used for copolymerization.
When the diene compound such as butadiene is copolymerized in an amount of 20 to 80% by weight with respect to 100% by weight of the total monomer as another monomer, the crosslinked fine particles (D) become rubber-like soft fine particles, resulting in a cured product. Cracks can be prevented from occurring in the film, and a cured film having excellent durability can be obtained.

The crosslinked fine particles (D) may be used singly or in combination of two or more.

The average particle size of the crosslinked fine particles (D) is usually 30 to 500 nm, preferably 40 to 200 nm, more preferably 50 to 120 nm.
The method for controlling the particle size of the crosslinked fine particles (D) is not particularly limited. For example, when the crosslinked fine particles are synthesized by emulsion polymerization, the number of micelles during emulsion polymerization is controlled by the amount of the emulsifier used, and the particle size is controlled. Can be controlled.
The average particle diameter of the crosslinked fine particles (D) is a value measured by diluting a dispersion of crosslinked fine particles according to a conventional method using a light scattering flow distribution measuring device or the like.

The amount of the crosslinked fine particles (D) is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the phenol resin (B). When the blended amount of the crosslinked fine particles (D) is 0.5 to 50 parts by weight, the compatibility or dispersibility with other components is excellent, and the thermal shock resistance and heat resistance of the resulting cured film are improved. be able to.

Adhesion aid (E)
Moreover, in order to improve the adhesiveness with a base material, the chemical amplification type negative photoresist composition of this invention can be made to contain an adhesion assistant.
Examples of the adhesion assistant include a functional silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group.

The compounding amount of the adhesion assistant is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, with respect to 100 parts by weight of the phenol resin (B). A blending amount of the adhesion aid of 0.2 to 10 parts by weight is preferable because it is excellent in storage stability and good adhesion can be obtained.

Solvent Further, the chemically amplified negative photoresist composition of the present invention may contain a solvent for improving the handleability of the resin composition and adjusting the viscosity and storage stability.
The solvent is not particularly limited, but specific examples include those described above.

  Further, the chemically amplified negative photoresist composition of the present invention can contain a sensitizer if necessary. As such a sensitizer, conventionally known ones can be used, and specific examples thereof include those described above.

  The amount of these sensitizers used is 5 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the total weight of the acid generator.

Other Additives In addition, the chemically amplified negative photoresist composition of the present invention can contain other additives as necessary so as not to impair the characteristics of the present invention. Examples of such other additives include inorganic fillers, quenchers, leveling agents and surfactants.

The method for preparing the chemically amplified negative photoresist composition of the present invention is not particularly limited, and can be prepared by a known method. It can also be prepared by stirring a sample bottle with each component in it and completely plugged on the wave rotor.

The cured product in the present invention is obtained by curing the chemically amplified negative photoresist composition.
The above-mentioned chemically amplified negative photoresist composition according to the present invention has a high residual film ratio and excellent resolution, and the cured product has an electrical insulating property, thermal shock property, heat resistant colorability (transparency). The cured product is preferably used as a surface protection film, planarization film, interlayer insulating film material, etc. for electronic components such as semiconductor elements, semiconductor packages and displays that require transparency. Can do.

In order to form the cured product of the present invention, first, the chemically amplified negative photoresist composition according to the present invention is used as a support (a silicon wafer with a resin-coated copper foil, a copper-clad laminate, a metal sputtered film, Coating onto an alumina substrate and the like, and drying to volatilize the solvent and the like to form a coating film. Then, it exposes through a desired mask pattern, heat processing (this heat processing is hereafter called "PEB") is performed, and reaction with a phenol resin (B) and a crosslinking agent (C) is accelerated | stimulated. Subsequently, it develops with an alkaline developing solution, A desired pattern can be obtained by melt | dissolving and removing an unexposed part. Furthermore, a cured film can be obtained by performing a heat treatment in order to develop insulating film characteristics.

As a method of applying the resin composition to the support, for example, a coating method such as a dipping method, a spray method, a bar coating method, a roll coating method, or a spin coating method can be used. The thickness of the coating film can be appropriately controlled by adjusting the coating means and the solid content concentration and viscosity of the composition solution.
Examples of radiation used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, h-line steppers, i-line steppers, gh-line steppers, and ghi-line steppers, electron beams, and laser beams. . The exposure amount is appropriately selected depending on the light source used, the resin film thickness, and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the resin film thickness is about 100 to 50000 J / m 2 when the resin film thickness is 1 to 50 μm.

After the exposure, the PEB treatment is performed to promote the curing reaction of the phenol resin (B) and the crosslinking agent (C) by the generated acid. The PEB condition varies depending on the blending amount of the resin composition, the used film thickness, and the like, but is usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes. Thereafter, development is performed with an alkaline developer, and a desired pattern is formed by dissolving and removing unexposed portions. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method. The development conditions are usually 20 to 40 ° C. and about 1 to 10 minutes.

Furthermore, in order to sufficiently develop the characteristics as an insulating film after development, the film can be sufficiently cured by heat treatment. Such curing conditions are not particularly limited, but the composition can be cured by heating at a temperature of 50 to 250 ° C. for about 30 minutes to 10 hours depending on the use of the cured product. Moreover, in order to fully advance hardening and to prevent the deformation | transformation of the obtained pattern shape, it can also heat in two steps, for example, at the temperature of 50-120 degreeC in a 1st step, 5 minutes-2 It can also be cured by heating for about an hour and further heating for about 10 minutes to 10 hours at a temperature of 80 to 250 ° C. Under such curing conditions, a general oven, an infrared furnace, or the like can be used as a heating facility.

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

Example 1 Synthesis of diphenyl [4- (phenylthio) phenyl] sulfonium phenyltris (pentafluorophenyl) borate (content 96%) and diphenyl [4- (phenylthio) phenyl] sulfonium hydroxyphenylbis (pentafluorophenyl) borate ( (1) Sodium phenyltris (pentafluorophenyl) borate (content 96%) and hydroxyphenylbis (pentafluorophenyl) sodium borate (content) 4% Production A reaction vessel purged with deaerated nitrogen was charged with 1.7 parts of magnesium and 26.1 parts of tetrahydrofuran, and cooled to 18 ° C. in a water bath. 17.3 parts of bromopentafluorobenzene and 26.1 parts of tetrahydrofuran were charged into a dropping funnel and dropped so that the internal temperature did not exceed 25 ° C. After completion of dropping, the reaction was continued at 45 ° C. for 2 hours, and then the reaction solution was cooled to 20 ° C. Thereafter, 3.0 parts of dichlorophenylborane was dropped from the dropping funnel so that the internal temperature did not exceed 25 ° C. After completion of dropping, the reaction was continued at 65 ° C. for 2 hours to complete the reaction.
This solution is added to 50 parts of a saturated aqueous sodium hydrogen carbonate solution, the organic layer is separated, the aqueous layer is washed twice with 10 parts of ethyl acetate, and the resulting ethyl acetate layer is added to the previously separated organic layer. added. The organic layer was removed, and the residue was washed twice with hexane, and the residue was dried under reduced pressure to obtain sodium phenyltris (pentafluorophenyl) borate (content 96%) and hydroxyphenylbis (by-product) ( 10.4 parts of a mixture of sodium pentafluorophenyl) borate (content 4%) were obtained with a yield of 90% (based on dichlorophenylborane). The product was identified by ^{1 H-NMR, 19 F-} NMR.
(2) Synthesis of diphenyl [4- (phenylthio) phenyl] sulfonium phenyltris (pentafluorophenyl) borate (content 96%) and diphenyl [4- (phenylthio) phenyl] sulfonium hydroxyphenylbis (pentafluorophenyl) borate ( Synthesis of a mixture having a content of 4%) 1.6 parts of diphenyl sulfoxide, 1.5 parts of diphenyl sulfide, 2.4 parts of acetic anhydride, 1.44 parts of trifluoromethanesulfonic acid and 13.0 parts of acetonitrile are mixed uniformly. The reaction was carried out at 6 ° C. for 6 hours. The reaction solution was cooled to room temperature (about 25 ° C.), poured into 60 parts of distilled water, extracted with 60 parts of dichloromethane, and washed with water until the pH of the aqueous layer became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a brown liquid product. To this was added 20 parts of ethyl acetate and dissolved in a 60 ° C. water bath, 60 parts of hexane was added and stirred, cooled to 5 ° C., allowed to stand for 30 minutes, and the supernatant was removed twice. The product was washed. This was transferred to a rotary evaporator and the solvent was distilled off to obtain diphenyl [4- (phenylthio) phenyl] sulfonium triflate (triflate = trifluoromethanesulfonic acid anion).
(Double decomposition method)
Dissolve this triflate in 45 parts of dichloromethane and add to an aqueous solution prepared with 4.2 parts of the sodium borate salt synthesized in (1) and 37.8 parts of water, then stir at room temperature (about 25 ° C.) for 3 hours. The dichloromethane layer was washed three times with water by a liquid separation operation, then transferred to a rotary evaporator, and the solvent was distilled off to diphenyl [4- (phenylthio) phenyl] sulfonium phenyltris (pentafluorophenyl) borate ( A mixture of 96% content) and diphenyl [4- (phenylthio) phenyl] sulfonium hydroxyphenylbis (pentafluorophenyl) borate (4% content) was obtained.

Example 2 Diphenyl [4- (phenylthio) phenyl] sulfonium phenyltris (pentafluorophenyl) borate (content 98%) and diphenyl [4- (phenylthio) phenyl] sulfonium hydroxyphenylbis (pentafluorophenyl) borate (content) The onium borate salt synthesized in Example 1 was recrystallized (dissolved in dichloromethane, charged with isobutanol as a poor solvent, and the precipitated yellow solid was filtered) once and dried. Diphenyl [4- (phenylthio) phenyl] sulfonium phenyltris (pentafluorophenyl) borate (content 98%) and diphenyl [4- (phenylthio) phenyl] sulfonium hydroxyphenylbis (pentafluorophenyl) vole To give a mixture of (content 2%).

Example 3 Diphenyl [4- (phenylthio) phenyl] sulfonium phenyltris (pentafluorophenyl) borate (content 99.99%) and diphenyl [4- (phenylthio) phenyl] sulfonium hydroxyphenylbis (pentafluorophenyl) borate ( Synthesis of the mixture having a content of 0.01% The onium borate salt synthesized in Example 1 was recrystallized (dissolved in dichloromethane, charged with isobutanol as a poor solvent, and the precipitated yellow solid was filtered) twice. And drying, diphenyl [4- (phenylthio) phenyl] sulfonium phenyltris (pentafluorophenyl) borate (content 99.99%) and diphenyl [4- (phenylthio) phenyl] sulfonium hydroxyphenylbis (pentafluoro) Phenyl) to give a mixture of borate (content 0.01%).

Example 4 [4- (4-Biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate (content 96%) and [4- (4-biphenylylthio) phenyl]- Synthesis of a mixture of 4-biphenylylphenylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 4%) (1) Synthesis of 4- (phenylthio) biphenyl 4-bromobiphenyl 3.0 parts, thiophenol 1.7 Parts, 2.5 parts of sodium-t-butoxide, 0.15 parts of tetrakistriphenylphosphine palladium and 64.3 parts of 1-butanol were uniformly mixed and reacted at 120 ° C. for 2 hours. The reaction solution was cooled to room temperature (about 25 ° C.) and then filtered. The filtrate was transferred to a rotary evaporator and the solvent was distilled off to obtain a reddish brown crystalline product. This was dissolved in 70 parts of dichloromethane, 50 parts of a saturated aqueous sodium hydrogen carbonate solution was added, washed three times by liquid separation, and the dichloromethane layer was washed with 70 parts of distilled water until the pH became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a brown crystalline product. To this was added 20 parts of hexane, dispersed in hexane with an ultrasonic cleaner, allowed to stand for about 15 minutes, and then the operation of removing the supernatant was repeated three times to wash the resulting solid, and the solvent was removed with a rotary evaporator. By leaving, brown crystalline 4- (phenylthio) biphenyl was obtained in a yield of 84%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 7.6 to 7.7 (4H, m), 7.3 to 7.5 (10H, m)}.
(2) Synthesis of a mixture containing 4-[(phenyl) sulfinyl] biphenyl and 4- (phenylthio) biphenyl 2.0 parts of 4- (phenylthio) biphenyl synthesized in (1), 8.0 parts of acetonitrile, and 0. 037 parts and 0.43 part of 30% aqueous hydrogen peroxide were mixed uniformly and reacted at 65 ° C. for 3 hours. After cooling the reaction solution to room temperature (about 25 ° C.), 30 parts of dichloromethane was added and washed with liquid separation operation with 40 parts of distilled water until the pH became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a mixture containing 55% of brown liquid 4-[(phenyl) sulfinyl] biphenyl and 45% of 4- (phenylthio) biphenyl. After isolation by column chromatography (eluent: ethyl acetate / hexane = 1/1: volume ratio), the product was identified by ¹ H-NMR. ¹ H-NMR data of 4-[(phenyl) sulfinyl] biphenyl: {d6-dimethylsulfoxide, δ (ppm) 7.7 to 7.9 (4H, m), 7.3 to 7.6 (10H, m )}. The content was calculated from the peak area ratio by HPLC analysis of the mixture.
(3) [4- (4-Biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate (content 96%) and [4- (4-biphenylylthio) phenyl]- Synthesis of a mixture of 4-biphenylylphenylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 4%) (2) 55% 4-[(phenyl) sulfinyl] biphenyl and 4- (phenylthio) biphenyl 2.0 parts of a mixture containing 45%, 0.24 parts of 4- (phenylthio) biphenyl synthesized in (1), 1.2 parts of acetic anhydride, 0.72 parts of trifluoromethanesulfonic acid, and 6.5 parts of acetonitrile. The mixture was uniformly mixed and reacted at 60 ° C. for 2 hours. The reaction solution was cooled to room temperature (about 25 ° C.), poured into 30 parts of distilled water, extracted with 30 parts of dichloromethane, and washed with water until the pH of the aqueous layer became neutral. The dichloromethane layer was transferred to a rotary evaporator and the solvent was distilled off to obtain a brown liquid product. After adding 10 parts of ethyl acetate and dissolving in a 60 ° C. water bath, adding 30 parts of hexane, stirring, and allowing to stand in a refrigerator (about 5 ° C.) for 30 minutes, and then removing the supernatant twice. And the product was washed. This was transferred to a rotary evaporator and the solvent was distilled off to obtain [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium triflate (triflate = trifluoromethanesulfonic acid anion).
(Double decomposition method)
This triflate was dissolved in 27 parts of dichloromethane and charged into an aqueous solution prepared with 6.1 parts of the sodium borate salt synthesized in (1) of Example 1 and 54.9 parts of water, and then room temperature (about 25 ° C.). And the dichloromethane layer was washed three times with water by a liquid separation operation, and then transferred to a rotary evaporator, and the solvent was distilled off to thereby remove [4- (4-biphenylylthio) phenyl] -4- Biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate (content 96%) and [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 4%) of the mixture was obtained.

Example 5 [4- (4-Biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate (content 98%) and [4- (4-biphenylylthio) phenyl]- Synthesis of a mixture of 4-biphenylylphenylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 2%) The onium borate salt synthesized in Example 4 was recrystallized (dissolved in dichloromethane, isobutanol being a poor solvent) The resulting yellow solid is filtered once) and dried to give [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate (containing 98%) and [4- (4-biphenylylthio) phenyl] -4- A mixture of biphenylylphenylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 2%) was obtained.

Example 6 [4- (4-Biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate (content 99.99%) and [4- (4-biphenylylthio) phenyl Synthesis of a mixture of 4-biphenylylphenylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 0.01%) The onium borate salt synthesized in Example 4 was recrystallized (dissolved in dichloromethane, poor solvent The isobutanol is added and the precipitated yellow solid is filtered twice) and dried to give [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl). ) Borate (content 99.99%) and [4- (4-biphenylylthio) ) Phenyl] -4-biphenylylphenylsulfonium A mixture of hydroxyphenylbis (pentafluorophenyl) borate (content 0.01%) was obtained.

Example 7 [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate (content 96%) and [4- (2-thioxanthonylthio) Phenyl] phenyl-2-thioxanthonylsulfonium Synthesis of a mixture of hydroxyphenylbis (pentafluorophenyl) borate (content 4%) (1) Synthesis of 2- (phenylthio) thioxanthone 2-chlorothioxanthone 11.0 parts, thio After 4.9 parts of phenol, 2.5 parts of potassium hydroxide and 162 parts of N, N-dimethylformamide were uniformly mixed and reacted at 130 ° C. for 9 hours, the reaction solution was cooled to room temperature (about 25 ° C.), The product was deposited in 200 parts of distilled water. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. The product was purified by column chromatography (eluent: toluene / hexane = 1/1: volume ratio) to give 2- (phenylthio) thioxanthone in a yield of 45%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.43 (1H, d), 8.25 (1H, s), 7.75-7.90 (3H, m ), 7.66 (1H, d), 7.60 (1H, t), 7.42-7.46 (5H, m)}.
(2) Synthesis of 2-[(phenyl) sulfinyl] thioxanthone While stirring 11.2 parts of 2- (phenylthio) thioxanthone synthesized in (1), 215 parts of acetonitrile and 0.02 part of sulfuric acid at 40 ° C, After 4.0 parts of 30% hydrogen peroxide aqueous solution was gradually added dropwise and reacted at 40 to 45 ° C. for 14 hours, the reaction solution was cooled to room temperature (about 25 ° C.) and poured into 200 parts of distilled water. The product precipitated out. This was filtered, and the residue was washed with water until the pH of the filtrate became neutral, and then the residue was dried under reduced pressure to obtain a yellow powdery product. The product was purified by column chromatography (eluent: ethyl acetate / toluene = 1/3: volume ratio) to give 2-[(phenyl) sulfinyl] thioxanthone in a yield of 83%. The product was identified by ¹ H-NMR {d6-dimethylsulfoxide, δ (ppm) 8.75 (1H, s), 8.45 (1H, d), 8.01 (2H, d), 7. 75-7.85 (4H, m), 7.53-7.62 (4H, m)}.
(3) [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate (content 96%) and [4- (2-thioxanthonylthio) Phenyl] phenyl-2-thioxanthonylsulfonium Hydroxyphenylbis (pentafluorophenyl) borate (content 4%) Synthesis of mixture (1) 2- (phenylthio) thioxanthone 4.3 parts, (2) While stirring 4.5 parts of synthesized 2-[(phenyl) sulfinyl] thioxanthone, 4.1 parts of acetic anhydride and 110 parts of acetonitrile at 40 ° C., 2.4 parts of trifluoromethanesulfonic acid was gradually added dropwise thereto. After reacting at 40 to 45 ° C. for 1 hour, the reaction solution is cooled to room temperature (about 25 ° C.) and distilled water 150 The solution was put into a portion, extracted with chloroform, and washed with water until the pH of the aqueous phase became neutral. After the chloroform phase was transferred to a rotary evaporator and the solvent was distilled off, 50 parts of toluene was added, dispersed in toluene with an ultrasonic cleaner, allowed to stand for about 15 minutes, and then the supernatant was removed three times to produce The washed solid was washed. Subsequently, the solid was transferred to a rotary evaporator and the solvent was distilled off to obtain [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium triflate (triflate = trifluoromethanesulfonic acid anion). )
(Double decomposition method)
This triflate was dissolved in 212 parts of dichloromethane and charged into an aqueous solution prepared with 18.0 parts of the sodium borate salt synthesized in (1) of Example 1 and 162 parts of water, and then 2% at room temperature (about 25 ° C.). After stirring for 3 hours, the dichloromethane layer was washed three times with water by a liquid separation operation, and then transferred to a rotary evaporator to distill off the solvent, whereby [4- (2-thioxanthonylthio) phenyl] phenyl-2- Thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate (content 96%) and [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium hydroxyphenylbis (pentafluorophenyl) borate ( A mixture with a content of 4%) was obtained.

Example 8 [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate (content 98%) and [4- (2-thioxanthonylthio) Phenyl] phenyl-2-thioxanthonylsulfonium Synthesis of a mixture of hydroxyphenylbis (pentafluorophenyl) borate (content 2%) The onium borate salt synthesized in Example 7 was recrystallized (dissolved in dichloromethane, poor solvent The isobutanol is added and the precipitated yellow solid is filtered once) and dried to give [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris (penta Fluorophenyl) borate (content 98%) and [4- (2-thi Oxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium Hydroxyphenylbis (pentafluorophenyl) borate (content 2%) was obtained.

Example 9 [4- (2-Thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate (content 99.99%) and [4- (2-thioxanthoniton Ruthio) phenyl] phenyl-2-thioxanthonylsulfonium Synthesis of a mixture of hydroxyphenylbis (pentafluorophenyl) borate (content 0.01%) The onium borate salt synthesized in Example 7 was recrystallized (dissolved in dichloromethane). [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium by drying twice by adding isobutanol as a poor solvent and filtering the precipitated yellow solid) Phenyltris (pentafluorophenyl) borate (content 99.99%) ) And [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 0.01%).

Example 10 4-Isopropylphenyl (p-tolyl) iodonium phenyltris (pentafluorophenyl) borate (content 96%) and 4-isopropylphenyl (p-tolyl) iodonium hydroxyphenylbis (pentafluorophenyl) borate (content) 4%) Mixture of 4-isopropylphenyl (p-tolyl) iodonium chloride in 10 parts of water while stirring and dispersing 4.2 parts of the sodium borate salt synthesized in Example 1 (1) An aqueous solution prepared with 37.8 parts of water and 45 parts of dichloromethane were added with stirring, and the mixture was stirred and mixed at room temperature (about 25 ° C.) for 3 hours. The dichloromethane layer was washed three times with water by a liquid separation operation, then transferred to a rotary evaporator, and the solvent was distilled off to give 4-isopropylphenyl (p-tolyl) iodonium phenyltris (pentafluorophenyl) borate (content ratio) 96%) and 4-isopropylphenyl (p-tolyl) iodonium hydroxyphenylbis (pentafluorophenyl) borate (content 4%).

Example 11 4-Isopropylphenyl (p-tolyl) iodonium phenyltris (pentafluorophenyl) borate (content 98%) and 4-isopropylphenyl (p-tolyl) iodonium hydroxyphenylbis (pentafluorophenyl) borate (content) The onium borate salt synthesized in Example 10 was recrystallized (dissolved in dichloromethane, charged with isobutanol as a poor solvent, and the precipitated yellow solid was filtered) once and dried. 4-isopropylphenyl (p-tolyl) iodonium phenyltris (pentafluorophenyl) borate (content 98%) and 4-isopropylphenyl (p-tolyl) iodonium hydroxyphenylbis (pentafluorophenyl) borate (content) 2 ) To give a mixture of.

Example 12 4-Isopropylphenyl (p-tolyl) iodonium phenyltris (pentafluorophenyl) borate (content 99.99%) and 4-isopropylphenyl (p-tolyl) iodonium hydroxyphenylbis (pentafluorophenyl) borate ( Synthesis of the mixture having a content of 0.01%) The onium borate salt synthesized in Example 10 was recrystallized (dissolved in dichloromethane, charged with isobutanol as a poor solvent, and the precipitated yellow solid was filtered) twice. By performing and drying, 4-isopropylphenyl (p-tolyl) iodonium phenyltris (pentafluorophenyl) borate (content 99.99%) and 4-isopropylphenyl (p-tolyl) iodonium hydroxyphenylbis (pentafluoro) Phenyl) To give a mixture of rate (0.01% content).

Example 13 4-hydroxyphenylmethylbenzylsulfonium A mixture of phenyltris (pentafluorophenyl) borate (content 96%) and 4-hydroxyphenylmethylbenzylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 4%) Synthesis 2.1 parts of 4-hydroxyphenylmethylbenzylsulfonium chloride was dispersed in 10 parts of water with stirring, and adjusted with 4.2 parts of the sodium borate salt synthesized in (1) of Example 1 and 37.8 parts of water. The aqueous solution and 45 parts of dichloromethane were added with stirring, and the mixture was stirred and mixed at room temperature (about 25 ° C.) for 3 hours. The dichloromethane layer was washed three times with water by a liquid separation operation, then transferred to a rotary evaporator, and the solvent was distilled off to give 4-hydroxyphenylmethylbenzylsulfonium phenyltris (pentafluorophenyl) borate (content 96%) And 4-hydroxyphenylmethylbenzylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 4%) was obtained.

Example 14 4-Hydroxyphenylmethylbenzylsulfonium Phenyltris (pentafluorophenyl) borate (content 98%) and 4-hydroxyphenylmethylbenzylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 2%) The onium borate salt synthesized in Synthesis Example 13 was recrystallized (dissolved in dichloromethane, charged with isobutanol as a poor solvent, and the precipitated yellow solid was filtered) once and dried to give 4-hydroxy Mixture of phenylmethylbenzylsulfonium phenyltris (pentafluorophenyl) borate (content 98%) and 4-hydroxyphenylmethylbenzylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 2%) To obtain things.

Example 15 4-hydroxyphenylmethylbenzylsulfonium phenyltris (pentafluorophenyl) borate (content 99.99%) and 4-hydroxyphenylmethylbenzylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 0.01%) The onium borate salt synthesized in Example 13 was recrystallized (dissolved in dichloromethane, charged with isobutanol as a poor solvent, and the precipitated yellow solid was filtered) twice and dried. 4-hydroxyphenylmethylbenzylsulfonium phenyltris (pentafluorophenyl) borate (content 99.99%) and 4-hydroxyphenylmethylbenzylsulfonium hydroxyphenylbis (pentafluorophenyl) borate To give a mixture of content 0.01%).

Comparative Example 1 Synthesis of a mixture of diphenyl [4- (phenylthio) phenyl] sulfonium phenyltris (pentafluorophenyl) borate (content 100%) The onium borate salt synthesized in Example 1 was recrystallized (dissolved in dichloromethane, Diphenyl [4- (phenylthio) phenyl] sulfonium phenyltris (pentafluorophenyl) borate (content: 100%) was performed three times by adding isobutanol, which is a poor solvent, and filtering the precipitated yellow solid, and drying. )

Comparative Example 2 Synthesis of [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate (100% content)
The onium borate salt synthesized in Example 4 was recrystallized (dissolved in dichloromethane, charged with isobutanol as a poor solvent, and the precipitated yellow solid was filtered) three times, and dried to obtain a content of 100%. [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate was obtained.

Comparative Example 3 Synthesis of [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate (100% content)
The onium borate salt synthesized in Example 7 was recrystallized (dissolved in dichloromethane, charged with isobutanol as a poor solvent, and the precipitated yellow solid was filtered) three times, and dried to obtain a content of 100%. [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate was obtained.

Comparative Example 4 Synthesis of 4-isopropylphenyl (p-tolyl) iodonium phenyltris (pentafluorophenyl) borate (content 100%)
The onium borate salt synthesized in Example 10 was recrystallized (dissolved in dichloromethane, charged with isobutanol as a poor solvent, and the precipitated yellow solid was filtered) three times, and dried to obtain a content of 100%. 4-isopropylphenyl (p-tolyl) iodonium phenyltris (pentafluorophenyl) borate was obtained.

Comparative Example 5 Synthesis of 4-hydroxyphenylmethylbenzylsulfonium phenyltris (pentafluorophenyl) borate (content 100%)
The onium borate salt synthesized in Example 13 was recrystallized (dissolved in dichloromethane, charged with isobutanol as a poor solvent, and the precipitated yellow solid was filtered) three times, and dried to obtain a content of 100%. 4-hydroxyphenylmethylbenzylsulfonium phenyltris (pentafluorophenyl) borate was obtained.

Comparative Example 6 Synthesis of diphenyl [4- (phenylthio) phenyl] sulfonium phenyltris (pentafluorophenyl) borate (content 90%) and diphenyl [4- (phenylthio) phenyl] sulfonium hydroxyphenylbis (pentafluorophenyl) borate ( (1) Sodium phenyltris (pentafluorophenyl) borate (content 90%) and hydroxyphenylbis (pentafluorophenyl) sodium borate (content 10%) Production A deaerated nitrogen-substituted reaction vessel was charged with 1.7 parts of magnesium and 26.1 parts of tetrahydrofuran and cooled to 18 ° C. in a water bath. 17.3 parts of bromopentafluorobenzene and 26.1 parts of tetrahydrofuran were charged into a dropping funnel and dropped so that the internal temperature did not exceed 25 ° C. After completion of dropping, the reaction was continued at 45 ° C. for 2 hours, and then the reaction solution was cooled to 20 ° C. Thereafter, 3.0 parts of dichlorophenylborane was dropped from the dropping funnel so that the internal temperature did not exceed 25 ° C. After the completion of dropping, 0.1 part of water was added and the reaction was continued at 65 ° C. for 2 hours to complete the reaction.
This solution is added to 50 parts of a saturated aqueous sodium hydrogen carbonate solution, the organic layer is separated, the aqueous layer is washed twice with 10 parts of ethyl acetate, and the resulting ethyl acetate layer is added to the previously separated organic layer. added. The organic layer was removed, and the residue was washed twice with hexane, and the residue was dried under reduced pressure to obtain sodium phenyltris (pentafluorophenyl) borate (content 90%) and hydroxyphenylbis (by-product) ( 10.0 parts of a mixture of sodium pentafluorophenyl) sodium borate (content 10%) was obtained in a yield of 87% (based on dichlorophenylborane). The product was identified by ¹ H-NMR and ¹⁹ F-NMR.
(2) Synthesis of diphenyl [4- (phenylthio) phenyl] sulfonium phenyltris (pentafluorophenyl) borate (content 90%) and diphenyl [4- (phenylthio) phenyl] sulfonium hydroxyphenylbis (pentafluorophenyl) borate ( Synthesis of a mixture having a content of 10%) “An aqueous solution prepared with 4.2 parts of the sodium borate salt synthesized in (1) of Example 1 and 37.8 parts of water” in Example 1 was used. The compound was synthesized in the same manner except that the aqueous solution was adjusted with 4.2 parts of the sodium borate salt synthesized in 1) and 37.8 parts of water.

Comparative Example 7 [4- (4-Biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate (content 90%) and [4- (4-biphenylylthio) phenyl]- Synthesis of a mixture of 4-biphenylylphenylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 10%) Example 4 “6.1 parts of sodium borate salt synthesized in (1) of Example 1 and water 54 Was prepared in the same manner except that “the aqueous solution prepared in 9 parts” was changed to “the aqueous solution prepared in 6.1 parts of sodium borate salt and 54.9 parts of water synthesized in (1) of Comparative Example 6”.

Comparative Example 8 [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate (content 90%) and [4- (2-thioxanthonylthio) Phenyl] phenyl-2-thioxanthonylsulfonium Synthesis of a mixture of hydroxyphenylbis (pentafluorophenyl) borate (content 10%) Example 7 “Sodium borate salt 18.0 synthesized in (1) of Example 1” This was synthesized in the same manner except that the aqueous solution adjusted with 162 parts of water and 162 parts of water was changed to “the aqueous solution adjusted with 18.0 parts of the sodium borate salt synthesized in (1) of Comparative Example 6 and 162 parts of water”.

Comparative Example 9 4-Isopropylphenyl (p-tolyl) iodonium phenyltris (pentafluorophenyl) borate (content 90%) and 4-isopropylphenyl (p-tolyl) iodonium hydroxyphenylbis (pentafluorophenyl) borate (content) 10%) of the mixture of Example 10 “the aqueous solution prepared with 4.2 parts of the sodium borate salt synthesized in (1) of Example 1 and 37.8 parts of water” was used as “(1) of Comparative Example 6”. This was synthesized in the same manner except that the aqueous solution was adjusted with 4.2 parts of the sodium borate salt and 37.8 parts of water.

Comparative Example 10 4-Hydroxyphenylmethylbenzylsulfonium Phenyltris (pentafluorophenyl) borate (content 90%) and 4-hydroxyphenylmethylbenzylsulfonium hydroxyphenylbis (pentafluorophenyl) borate (content 10%) “Sodium borate salt synthesized in (1) of Comparative Example 6” in Synthesis Example 13 “Aqueous solution prepared with 4.2 parts of sodium borate salt synthesized in (1) of Example 1 and 37.8 parts of water” The synthesis was performed in the same manner except that the aqueous solution was adjusted to 4.2 parts and 37.8 parts of water.

Comparative Example 11 Synthesis of diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate 4.2 parts of sodium borate salt synthesized in (1) of Example 1 and 37.8 parts of water This was synthesized in the same manner except that “the aqueous solution prepared in step 1” was changed to “50 parts of 10% tetrakis (pentafluorophenyl) borate aqueous solution”.

Comparative Example 12 Synthesis of 4-isopropylphenyl (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate 4.2 parts of sodium borate salt synthesized in (1) of Example 1 and 37.8 parts of water This was synthesized in the same manner except that “the aqueous solution prepared in step 1” was changed to “50 parts of 10% tetrakis (pentafluorophenyl) borate aqueous solution”.

Comparative Example 13 Synthesis of 4-hydroxyphenylmethylbenzylsulfonium tetrakis (pentafluorophenyl) borate Example 13 “Adjusted with 4.2 parts of sodium borate salt synthesized in (1) of Example 1 and 37.8 parts of water This was synthesized in the same manner except that the “aqueous solution” was changed to “50 parts of 10% tetrakis (pentafluorophenyl) borate aqueous solution”.

Comparative Example 14 CPI-110A {diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, manufactured by San Apro Corporation} was used as a comparative sulfonium salt.

Comparative Example 15 Synthesis of 4-isopropylphenyl (p-tolyl) iodonium hexafluoroantimonate Example 13 “Adjusted with 4.2 parts of sodium borate salt synthesized in (1) of Example 1 and 37.8 parts of water This was synthesized in the same manner except that the “aqueous solution” was changed to “35 parts of a 10% potassium hexafluoroantimonate aqueous solution”.

Comparative Example 16 Synthesis of 4-hydroxyphenylmethylbenzylsulfonium hexafluoroantimonate Example 13 “Aqueous solution prepared with 4.2 parts of sodium borate salt synthesized in (1) of Example 1 and 37.8 parts of water” Was synthesized in the same manner except that was changed to “35 parts of 10% potassium hexafluoroantimonate aqueous solution”.

Comparative Example 17 CPI-110P {diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, manufactured by San Apro Corporation} was used as a comparative sulfonium salt.

Comparative Example 18 Synthesis of 4-isopropylphenyl (p-tolyl) iodonium hexafluorophosphate Example 13 “Aqueous solution prepared with 4.2 parts of sodium borate salt synthesized in Example 1 and 37.8 parts of water” The compound was synthesized in the same manner except that it was changed to “30 parts of 10% potassium hexafluorophosphate aqueous solution”.

Comparative Example 19 Synthesis of 4-hydroxyphenylmethylbenzylsulfonium hexafluorophosphate Example 13 “An aqueous solution prepared by 4.2 parts of sodium borate salt synthesized in (1) of Example 1 and 37.8 parts of water” was prepared. The compound was synthesized in the same manner except that it was changed to “30 parts of 10% potassium hexafluorophosphate aqueous solution”.

[Evaluation]
(Preparation of heat and energy ray curable composition)
Examples, Comparative Example Acid Generator, Solvent-1 (Propylene Carbonate), Sensitizer (2,4-Diethylthioxanthone), Epoxide (3,4-Epoxycyclohexylmethyl-3,4-) as Cationic Polymerizable Compound Examples C1 to C15 and Comparative Examples which are heat or energy ray curable compositions of the present invention are obtained by uniformly mixing epoxycyclohexanecarboxylate, manufactured by Daicel Chemical Industries, Ltd., Celoxide 2021P) in the blending amounts shown in Table 1. HC1 to HC19 were adjusted.

<Evaluation of photosensitivity (photocurability)>
Examples C1 to C12 and Comparative Examples HC1 to HC4, HC6 to HC9, HC11, HC12, HC14, HC15, HC17, and HC18, which are the energy beam curable compositions of the present invention described above, are made of polyethylene terephthalate (PET) with an applicator (40 μm). ) Applied to film. The PET film was irradiated with ultraviolet light having a wavelength limited by a filter using an ultraviolet irradiation device. In addition, the filter used together 365 filters (The filter made from an iGraphics Co., Ltd. which cuts light less than 365 nm), and L-34 (The filter made from Kenko Optical Co., Ltd. cuts light less than 340 nm). After irradiation, the coating hardness after 40 minutes was measured with pencil hardness (JIS K5600-5-4: 1999) and evaluated according to the following criteria (the coating thickness after curing was about 40 μm).
(Criteria)
◎: Pencil hardness is 2H or more ○: Pencil hardness is H to B
(Triangle | delta): Pencil hardness is 2B-4B
×: There is liquid to tack, and pencil hardness cannot be measured

(Ultraviolet light irradiation conditions)
・ Ultraviolet irradiation device: Belt conveyor type UV irradiation device (manufactured by Eye Graphics Co., Ltd.)
・ Lamp: 1.5kW high-pressure mercury lamp ・ Filter: 365 filter (manufactured by Eye Graphics Co., Ltd.)
L-34 (manufactured by Kenko Optical Co., Ltd.)
Illuminance (measured with a 365 nm head illuminometer): 145 mW / cm ²
-Integrated light quantity (measured with a 365 nm head illuminometer): 300 mJ / cm ²

<Heat resistance (yellowing) test-1>
Examples C1 to C12 and Comparative Examples HC1 to HC4, HC6 to HC9, HC11, HC12, HC14, HC15, HC17, and HC18, which are the energy beam curable compositions of the present invention, are formed on a slide glass with an applicator Application was at 25 μm. The slide glass after the application was irradiated with ultraviolet rays using an ultraviolet irradiation device.
(Ultraviolet light irradiation conditions)
・ Ultraviolet irradiation device: Belt conveyor type UV irradiation device (manufactured by Eye Graphics Co., Ltd.)
Lamp: 1.5 kW high-pressure mercury lamp Illuminance (measured with a 365 nm head illuminometer): 190 mW / cm ²
Integrated light quantity (measured with a 365 nm head illuminometer): 800 mJ / cm ²
After curing for 30 minutes at room temperature, after-curing at 120 ° C. for 30 minutes on a hot plate, a sample for a heat resistance test was prepared.
This sample was heated on a hot plate adjusted to 240 ° C. for 15 minutes, and the hue of the coating film was visually evaluated. The evaluation criteria are as follows.

(Evaluation criteria)
A: Colorless (no yellowing of the coating film)
○: Light yellow to yellow ×: Brown

* 1: DPTS; diphenyl [4- (phenylthio) phenyl] sulfonium * 2: BPTBPS; [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium * 3: TXTPTXS; [4- (2- Thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium * 4: IPTI; 4-isopropylphenyl (p-tolyl) iodonium * 5: Onium salt of formula (2). The anion is (OH) (C ₆ H ₅ ) B (C ₆ F ₅ ) ₂
Content of (OB2) in (OB1) and (OB2)

<Evaluation of heat sensitivity (thermosetting)>
Examples C13 to C15 and Comparative Examples HC5, HC10, HC13, HC16, and HC19, which are the energy beam curable compositions of the present invention, were applied to a polyethylene terephthalate (PET) film with an applicator (40 μm). After coating, it was heated on a hot plate at 100 ° C. for 5 minutes, and the coating film hardness immediately after heating was measured with pencil hardness (JIS K5600-5-4: 1999) and evaluated according to the following criteria (coating after curing) The film thickness is about 40 μm).
(Criteria)
◎: Pencil hardness is 2H or more ○: Pencil hardness is H to B
(Triangle | delta): Pencil hardness is 2B-4B
×: There is liquid to tack, and pencil hardness cannot be measured

<Heat resistance (yellowing) test-2>
Examples C13 to C15 and Comparative Examples HC5, HC10, HC13, HC16, and HC19, which are the energy beam curable compositions of the present invention, were applied onto a slide glass with a film thickness of 25 μm using an applicator.
This sample was heated and cured on a hot plate adjusted to 240 ° C. for 15 minutes, and the hue of the coating film was visually evaluated. The evaluation criteria are as follows.

(Evaluation criteria)
A: Colorless (no yellowing of the coating film)
○: Light yellow to yellow ×: Brown

* 5: Onium salt of formula (2). The anion is (OH) (C ₆ H ₅ ) B (C ₆ F ₅ ) ₂
Content of (OB2) in (OB1) and (OB2) * 6: HPMBS; 4-hydroxyphenylmethylbenzylsulfonium

From Tables 2 and 3, it can be seen that the curable composition using the onium borate salt of the present invention is excellent in cationic polymerization initiating ability and excellent in heat resistance (yellowing).

<Preparation of negative photoresist composition and its evaluation>
As shown in Table 4, 1 part by weight of the component (A) that is an acid generator and the component (B) that is a phenol resin are copolymers (Mw) composed of p-hydroxystyrene / styrene = 80/20 (molar ratio). = 10,000) is 100 parts by weight, and the component (C) is a cross-linking agent. Hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd., trade name “Nicalak MW-390”) is 20 parts by weight, and the component is cross-linked fine particles As (D), a copolymer comprising butadiene / acrylonitrile / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 64/20/8/6/2 (% by weight) (average particle size = 65 nm, Tg = −38 ° C.) 10 parts by weight of component (E) as an adhesion assistant, 5 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Chisso, trade name “S510”) Examples N1 to N9 and Comparative Examples HN1 to HN8, which are negative photoresist compositions of the present invention, were uniformly dissolved in 145 parts by weight of solvent-2 (ethyl lactate).

<Evaluation of UV curability (negative resist)>
Examples N1 to N9 and Comparative Examples HN1 to HN8, which are the above-described negative photoresist compositions of the present invention, were spin-coated on a silicon wafer substrate, and then heated and dried at 110 ° C. for 3 minutes using a hot plate. A resin coating film having a film thickness of about 20 μm was obtained. Then, pattern exposure (i line | wire; 500 mJ / cm < ² >) was performed using TME-150RSC (made by Topcon Corporation), and the post-exposure heating (PEB) for 3 minutes was performed at 110 degreeC with the hotplate. Thereafter, a development process for 2 minutes was performed by an immersion method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, washed with running water, and blown with nitrogen to obtain a 50 μm line and space pattern. The remaining film ratio indicating the ratio of the remaining film before and after development was measured. The evaluation criteria are as follows.
(Criteria)
◎: Remaining film ratio is 90% or more ○: Remaining film ratio is 80% or more and less than 90% △: Remaining film ratio is 70% or more and less than 80% ×: Remaining film ratio is less than 70%

<Heat resistance (yellowing) test-3>
Table 5 shows the results of heating the patterned silicon substrate obtained by the UV curability evaluation on a hot plate adjusted to 200 ° C. for 15 minutes and visually evaluating the hue of the pattern portion. The evaluation criteria are as follows.
(Evaluation criteria)
A: Colorless (no yellowing of the coating film)
○: Light yellow to yellow ×: Brown

* 1: DPTS; diphenyl [4- (phenylthio) phenyl] sulfonium * 2: BPTBPS; [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium * 3: TXTPTXS; [4- (2- Thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium * 5: Onium salt of formula (2). The anion is (OH) (C ₆ H ₅ ) B (C ₆ F ₅ ) ₂
Content of (OB2) in (OB1) and (OB2)

From Table 5, it can be seen that the chemically amplified negative photoresist composition using the onium borate salt of the present invention is excellent in UV curing performance and heat resistance (yellowing).

From the results of Tables 2, 3 and 5, the curable composition using the onium borate salt and the chemically amplified negative photoresist composition of the present invention have a good UV curing performance and a cured product after a heat test. Since it is highly transparent (not easily yellowed), it can be seen that it is useful as a member that requires optical characteristics such as a display, an optical waveguide, and an optical lens.

The curable composition of the present invention is used for paints, coating agents, various coating materials (hard coats, antifouling coating materials, antifogging coating materials, touch-proof coating materials, optical fibers, etc.), back surface treatment agents for adhesive tapes, and adhesive labels. Release coating material for release sheets (release paper, release plastic film, release metal foil, etc.), printing plate, dental material (dental compound, dental composite) ink, inkjet ink, positive resist (circuit board, CSP, Connection terminals and wiring pattern formation for manufacturing electronic components such as MEMS elements), resist films, liquid resists, negative resists (permanent film materials such as surface protective films for semiconductor elements, interlayer insulating films, planarization films, etc.), Resists for MEMS, positive photosensitive materials, negative photosensitive materials, various adhesives (temporary fixing agents for various electronic components, HDD adhesives, pickup lenses Adhesives, functional films for FPD (adhesives for deflection plates, antireflection films, etc.), holographic resins, FPD materials (color filters, black matrix, barrier rib materials, photo spacers, ribs, alignment films for liquid crystals, FPD sealants, etc.), optical members, molding materials (for building materials, optical components, lenses), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, sealing materials, optical semiconductors (LEDs) It is suitably used for a sealing material, an optical waveguide material, a nanoimprint material, an optical fabrication material, a micro stereolithography material, and the like.

Claims (11)

An onium borate salt containing an onium borate salt (OB1) represented by the following general formula (1) and an onium borate salt (OB2) represented by the following general formula (2), in (OB1) and (OB2) An onium borate salt having an (OB2) content of 0.01 to 4% by weight.

_{^{[(R 1) n + 1}} -E] + [(R 2) b B (Ar) 4-b] - (1)

_{^{[(R 1) n + 1}} -E] + [(OH) (R 2) b B (Ar) 3-b] - (2)

[In the formulas (1) and (2), E represents an element having a valence of n from VIA group to VIIA group (CAS notation), and n is an integer of 1 or 2;
R ¹ is an organic group bonded to E, and (n + 1) R ^{1 s} may be the same or different from each other, and two or more R ¹ may be directly or —O—, — S -, - SO -, - SO 2 -, - NH -, - CO -, - COO -, - CONH-, may form a ring structure containing an element E through an alkylene group or a phenylene group;
R ² is an organic group bonded to B (boron), b is an integer of 1 to 3, and b R ^{2 s} may be the same or different;
Ar represents a phenyl group substituted with at least one selected from the group consisting of perfluoroalkyl, perfluoroalkoxy and halogen, and when there are a plurality of Ars, they may be the same or different. ] In the general formulas (1) and (2), R ² is an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms which may have a substituent, and Ar is a perfluoroalkyl group or fluorine The onium borate salt according to claim 1, which is phenyl substituted by an atom. The onium according to claim 1, wherein, in the general formulas (1) and (2), R ² is a group selected from the group consisting of a phenyl group, a methylphenyl group, a methoxyphenyl group, a dimethylphenyl group, a naphthyl group, and an anthracenyl group. Borate salt. The onium borate salt according to any one of claims 1 to 3, wherein, in the general formulas (1) and (2), Ar is a pentafluorophenyl group or a bis (trifluoromethyl) phenyl group. In general formula (1) and (2), b is 1, The onium borate salt in any one of Claims 1-4. In the general formula (1), a borate anion represented by [(R ² ) _b B (Ar) _4-b ] ⁻ is [CH ₃ (C ₆ H ₄ ) B (C ₆ F ₅ ) ₃ ] ⁻ , [ _{(C 6 H 5) B (} C 6 F 5) 3] -, [CH 3 (C 6 H 4) B ((CF 3) 2 C 6 H 3) 3] - or _{[(C 6 H} 5) B ((CF ₃ ) ₂ C ₆ H ₃ ) ₃ ] ^—
In the general formula ^{(2), [(OH)} (R 2) b B (Ar) 3-b] - borate anion represented by the _{[(OH) CH 3 (C} 6 H 4) B (C 6 F 5 ^{_{) 2] -, [(OH}} ) (C 6 H 5) B (C 6 F 5) 2] -, [(OH) CH 3 (C 6 H 4) B ((CF 3) 2 C 6 H 3) _2] ^- or _{[(OH) (C 6 H} 5) B ((CF 3) 2 C 6 H 3) 2] - onium borate salt according to any one of claims 1 to 5 is. It consists of at least 1 sort (s) chosen from the onium borate salt in any one of Claims 1-6, The acid generator characterized by the above-mentioned.   A heat or energy beam curable composition comprising the acid generator according to claim 7 and a cationically polymerizable compound. A cured product obtained by curing the heat or energy beam curable composition according to claim 8. A chemically amplified negative photoresist comprising a component (A) comprising the acid generator according to claim 7, a component (B) which is an alkali-soluble resin having a phenolic hydroxyl group, and a crosslinking agent component (C). Composition. A cured product obtained by curing the chemically amplified negative photoresist composition according to claim 10.