JP2011201803A - Onium borate salt, photoacid generator and photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an onium borate salt which generates a strong acid by optically active energy ray irradiation.SOLUTION: The onium borate salt is represented by formula (1) (wherein A is the group VIA to group VIIA atom having a valence of m; m is an integer of 1 or 2; n is an integer of 0-3; R is a 6-30C aryl group, a 4-30C heterocyclic group, a 1-30C alkyl group, a 2-30C alkenyl group or a 2-30C alkynyl group; D is a structure represented by formula (2); and Xis a counter ion of the onium and at least one thereof is a borate anion).

Description

  The present invention relates to an onium borate salt having a specific structure first, and secondly, cationic photopolymerization by allowing an active energy ray such as light, electron beam or X-ray to act on the photoacid generator. The present invention relates to a photoacid 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 photoacid generator and a cured product obtained by curing the curable composition. Fourthly, the present invention relates to a chemically amplified positive photoresist composition containing the photoacid generator and a method for producing a resist pattern using the same. Fifth, the present invention relates to a chemically amplified negative photoresist composition containing the photoacid generator.

Conventionally, onium salts have been known as photoacid generators (photocation 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 Literature). 1), paints, stereolithography, adhesives, resists, etc.

Photoacid generator curing these cationically polymerizable compounds, BF ₄ as an anion ^{_{-, PF 6 -, AsF 6}} -, SbF 6 - , but containing, cationic polymerization performance differed kind of anion, BF ₄ ^- <PF ₆ ⁻ <AsF ₆ ⁻ <SbF ₆ ⁻ in this order. This corresponds to the strength of the acid generated by decomposition of the photoacid generator upon irradiation with active energy rays (exposure), and the acid strength increases in the order of HBF ₄ ⁻ <HPF ₆ ⁻ <HAsF ₆ ⁻ <HSbF ₆ ^−. . AsF ₆ ^-, SbF ₆ ^- photoacid generator containing the can, As, from toxicity problems of Sb, SbF ₆ in some applications ^- only salts have been used. BF ₄ ^- salt polymerization initiation ability is little, PF ₆ ^- the salts are utilized, PF ₆ ^- salt for polymerization performance is low, SbF ₆ ^- the latter in order to obtain the same degree of polymerization performance and salt It is necessary to add an amount close to 10 times, and the physical properties of the cured product are impaired because the unreacted acid generator, the amount of solvent used in the acid generator, or the decomposition residual amount of the acid generator increases. Moreover, since the amount of HF produced as a by-product due to the decomposition of the acid generator is increased, there is a problem that the base material, equipment and the like are corroded.

As these photoacid generators having improved tetrakis known (pentafluorophenyl) onium salt having the anion borate (see Patent Document 4), SbF ₆ ^- have a close cationic polymerization performance, sub by decomposition Although corrosion due to the generated HF is reduced, the cured product is easy to peel off because of its low adhesion to the substrate. Further, in order to obtain this anion in a high yield, it is either a lithiation reaction at ultra-low temperature (−78 ° C.) or a Grignard reaction using diethyl ether which is a special flammable substance (see Patent Document 3). There was a practical problem because the production cost was high and the anion was expensive.

  In recent years, with the further miniaturization of electronic devices, high-density mounting of semiconductor packages has progressed. Multi-pin thin-film mounting and downsizing of packages, mounting based on two-dimensional and three-dimensional mounting techniques using a flip chip method The density is improved. As connection terminals of such high-density mounting technology, for example, protruding electrodes (mounting terminals) such as bumps protruding on the package, metal posts that connect the rewiring extending from the peripheral terminals on the wafer and the mounting terminals, etc. It is arranged with high accuracy on the substrate.

  As a material used for such high-precision photofabrication, a chemically amplified positive resist composition (Patent Document 4) using an oxime sulfonate compound as an acid generator or a triarylsulfonium salt compound is photoacid-generated. Chemically amplified positive resist compositions (Non-patent Documents 1 and 2, Patent Documents 5 and 6) used as an agent have been proposed. This is because radiation (exposure) generates an acid such as perfluoroalkylsulfonic acid from the photoacid generator, and the heat treatment after the exposure promotes acid diffusion and acid-catalyzed reaction. This is to change the solubility of the resin in alkali, and the base resin that was insoluble before exposure is solubilized by alkali and is called a positive photoresist. However, these resist compositions, particularly when the pattern dimensions are fine, have problems such as poor adhesion to the substrate and pattern collapse when developed with an alkaline developer.

Furthermore, photosensitive polyimide resins having excellent heat resistance and mechanical properties are widely used for surface protective films, interlayer insulating films, and the like used for semiconductor elements of electronic devices (Patent Documents 7, 8, and 9). However, these compositions require a ring-closing step in which heat treatment is performed at a high temperature in order to imidize, the process conditions such as temperature control are complicated, the substrate warps due to film reduction after curing, and the semiconductor due to high temperature There are problems such as deterioration of the element. In order to improve these, a photosensitive resin composition using an alkali-soluble resin having a phenolic hydroxyl group has been proposed (Patent Documents 10 and 11).
Although it is a negative photoresist composition in which an acid is generated from the photoacid generator upon exposure and the reaction between the crosslinking agent and the main resin is promoted to become insoluble in an alkali developer, the triazine photoacid generator is Since the generated acid is hydrochloric acid or odorous acid and easily volatilizes, there is a problem of contaminating the equipment, and the composition using the photoacid generator of oxime sulfonate or triarylsulfonium salt is similar to the above positive resist, There were problems such as pattern collapse and pattern peeling due to poor adhesion to the substrate.

Japanese Patent Laid-Open No. 50-151997 JP-A-6-184170 JP-A-6-247980 JP 2000-66385 A JP 2003-231673 A JP 2002-193925 A JP 54-145794 A Japanese Patent Laid-Open No. 03-186847 Japanese Patent Application Laid-Open No. 08-50354 JP 2008-77057 A WO2008-117619

M.J.O'Brien, J.V.Crivello, SPIE Vol. 920, Advances in Resist Technology and Processing, p42 (1988). H.ITO, SPIE Vol.920, Advances in Resist Technology and Processing, p33, (1988).

In the above background, a first object of the present invention is to provide an onium borate salt having a specific structure that is inexpensive and can be decomposed by irradiation with photoactive energy rays to generate a strong acid.
The second object of the present invention is inexpensive and has high polymerization performance for cationically polymerizable compounds such as epoxy compounds, high catalytic activity for positive resists and negative resist compositions, and excellent adhesion to substrates. It is to provide a new acid generator comprising an onium borate salt having a specific structure.
The third object of the present invention is to provide an energy ray curable composition and a cured product using the acid generator.
The fourth object of the present invention is to provide a chemically amplified positive photoresist composition and a method for producing a resist pattern, which can obtain a resist having good storage stability and excellent adhesion to a substrate. Is to provide.
A fifth object of the present invention is to provide a chemically amplified negative photoresist composition and a method for producing a resist pattern, which can obtain a resist having good storage stability and excellent adhesion to a substrate. Is to provide.

[式（１）中、ＡはVIA族〜VIIA族（ＣＡＳ表記）の原子価mの原子を表し、mは１又は２の整数であり、ｎは０〜３の整数である。ＲはＡに結合している有機基であり、炭素数６〜３０のアリール基、炭素数４〜３０の複素環基、炭素数１〜３０のアルキル基、炭素数２〜３０のアルケニル基又は炭素数２〜３０のアルキニル基を表し、さらにＲはアルキル、ヒドロキシ、アルコキシ、アルキルカルボニル、アリールカルボニル、アルコキシカルボニル、アリールオキシカルボニル、アリールチオカルボニル、アシロキシ、アリールチオ、アルキルチオ、アリール、複素環、アリールオキシ、アルキルスルフィニル、アリールスルフィニル、アルキルスルホニル、アリールスルホニル、アルキレンオキシ、グリシジルオキシ、オキセタニルメチルオキシ、ビニロキシエトキシ、アミノ、シアノ、ニトロの各基及びハロゲンからなる群より選ばれる少なくとも１種で置換されていてもよい。Ｒの個数はｍ＋ｎ（ｍ−１）＋１であり、それぞれ互いに同一であっても異なっていてもよい。また２個以上のＲが互いに直接又はＯ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＮＨ−、−ＮＲ’ −、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、炭素数１〜３のアルキレンもしくはフェニレン基を介して結合し、原子Ａを含む環構造を形成してもよい。ここでＲ’は炭素数１〜５のアルキル基又は炭素数６〜１０のアリール基である。
Ｄは下記一般式（２）で表される構造であり、

式（２）中、Ｅは炭素数１〜８のアルキレン基、炭素数６〜２０のアリーレン基又は炭素数８〜２０の複素環化合物の２価の基を表し、さらにＥは炭素数１〜８のアルキル、炭素数１〜８のアルコキシ、炭素数６〜１０のアリール、ヒドロキシ、シアノ、ニトロの各基及びハロゲンからなる群より選ばれる少なくとも１種で置換されていてもよい。Ｇは−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−ＮＨ−、−ＮＲ’ −、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、炭素数１〜３のアルキレン又はフェニレン基を表す。ａは０〜５の整数である。ａ＋１個のＥ及びａ個のＧはそれぞれ同一であっても異なっていてもよい。ここでＲ’は前記のものと同じ。
X⁻はオニウムの対イオンである。その個数は１分子当りｎ＋１であり、そのうち少なくとも１個は一般式（３）で表されるボレートアニオンであって、残りは他のアニオンであってもよい。
[
（Ｙ）_ｂB（Ar）_４‐b] （３）
一般式（３）において、Ｙは炭素数６〜３０のアリール基又は炭素数４〜３０の複素環基であり、このアリール基又は複素環基は炭素数１〜１２のアルキル基、炭素数３〜６のシクロアルキル基、炭素数１〜６のアルコキシ基、炭素数１〜６のアルキルチオ基、炭素数６〜１２のアリールチオ基、炭素数２〜７のアルキルカルボニル基、炭素数２〜７のアルコキシカルボニル基、フェニル基及びベンゾイル基からなる群より選ばれる少なくとも１種で置換されていてもよく、置換基が複数の場合は、同一でも異なっていても良い。Ａｒは水素原子が少なくとも１つ以上、パーフルオロアルキル、パーフルオロアルコキシ及びハロゲンからなる群より選択される少なくとも１種で置換されたフェニル基を表す。ｂは1〜３の整数である。ｂ個のＹもしくは４−ｂ個のＡｒはそれぞれ同一であっても異なっていてもよい。] 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 photoacid generator satisfying these requirements, and have reached the present invention.
That is, the present invention is an onium borate salt represented by the general formula (1).

[In Formula (1), A represents an atom having a valence m of Group VIA to Group VIIA (CAS notation), m is an integer of 1 or 2, and n is an integer of 0 to 3. R is an organic group bonded to A and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or Represents an alkynyl group having 2 to 30 carbon atoms, and R represents alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy , Alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, glycidyloxy, oxetanylmethyloxy, vinyloxyethoxy, amino, cyano, nitro groups, and at least one selected from the group consisting of halogen It can have. The number of R is m + n (m−1) +1, and may be the same as or different from each other. In addition, two or more R's are each directly or O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ′ —, —CO—, —COO—, —CONH—, carbon number 1 It may be bonded via an alkylene or phenylene group of ˜3 to form a ring structure containing atom A. Here, R ′ is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
D is a structure represented by the following general formula (2),

In the formula (2), E represents a divalent group of an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a heterocyclic compound having 8 to 20 carbon atoms, and E represents 1 to 1 carbon atoms. It may be substituted with at least one selected from the group consisting of 8 alkyls, C 1-8 alkoxys, C 6-10 aryls, hydroxy, cyano, nitro groups and halogens. G is -O -, - S -, - SO -, - SO 2 -, - NH -, - NR '-, - CO -, - COO -, - CONH-, alkylene or phenylene group having 1 to 3 carbon atoms Represents. a is an integer of 0-5. a + 1 E and a G may be the same or different. Here, R ′ is the same as described above.
X ⁻ is a counter ion of onium. The number thereof is n + 1 per molecule, at least one of which is a borate anion represented by the general formula (3), and the other may be another anion.
[
(Y) _b B (Ar) _4-b ] (3)
In General Formula (3), Y is an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms, and the aryl group or heterocyclic group is an alkyl group having 1 to 12 carbon atoms or 3 carbon atoms. -6 cycloalkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, C6-C12 arylthio group, C2-C7 alkylcarbonyl group, C2-C7 It may be substituted with at least one selected from the group consisting of an alkoxycarbonyl group, a phenyl group and a benzoyl group, and when there are a plurality of substituents, they may be the same or different. Ar represents a phenyl group substituted with at least one hydrogen atom and at least one selected from the group consisting of perfluoroalkyl, perfluoroalkoxy and halogen. b is an integer of 1 to 3. b Y or 4-b Ar may be the same or different. ]

  The present invention also provides a photoacid generator containing the onium borate salt described above.

  Moreover, this invention is an energy beam curable composition characterized by containing the said photo-acid generator and a cationically polymerizable compound.

  Furthermore, the present invention is a cured product obtained by curing the energy beam curable composition.

  Furthermore, the present invention provides a chemically amplified positive photoresist composition comprising the photoacid generator and a component (B) which is a resin whose solubility in alkali is increased by the action of an acid. is there.

  Furthermore, the present invention provides a laminating step of laminating a photoresist layer having a film thickness of 10 to 150 μm comprising any one of the above chemically amplified positive photoresist compositions to obtain a photoresist laminate, A method for producing a resist pattern, comprising: an exposure step of selectively irradiating light or radiation with a part; and a development step of developing a photoresist laminate to obtain a resist pattern after the exposure step.

  The present invention further includes a chemically amplified negative photo, comprising the photoacid generator, a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and a crosslinking agent component (G). It is a resist composition.

  Furthermore, the present invention is a cured product obtained by curing any one of the above chemically amplified negative photoresist compositions.

The onium borate salt of the present invention does not contain any toxic element such as arsenic and antimony. Further, the onium borate salt of the present invention is not only excellent in solubility in the cationic polymerizable compound, but the composition comprising these and the cationic polymerizable compound can be heated or active energy rays such as light, electron beam, and X-ray. It has excellent curability by irradiation and does not corrode the substrate and wiring parts because it does not release HF, has good adhesion to the substrate and storage stability, and can be manufactured at low cost. it can.

  The chemically amplified positive photoresist composition and the chemically amplified negative photoresist composition of the present invention have high storage stability, good resist pattern shape, excellent adhesion, and no pattern peeling.

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

In the general formula (1) representing the onium borate salt of the present invention, A represents an atom of VIA group to VIIA (CAS notation), and combines with organic groups R and D to form onium [A ⁺ ]. Of the VIA group to VIIA group atoms, S (sulfur), I (iodine) and Se (selenium) which are excellent in cationic polymerization initiating ability are preferable, and S and I are particularly preferable. m represents the valence of A and is an integer of 1 or 2.

R is an organic group bonded to A, and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or Represents an alkynyl group having 2 to 30 carbon atoms, and these are alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, Substituted with at least one selected from the group consisting of alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, glycidyloxy, oxetanylmethyloxy, vinyloxyethoxy, amino, cyano, nitro groups and halogen It may be. The number of R is m + n (m−1) +1, and may be the same as or different from each other. In addition, two or more R's are each directly or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ′ —, —CO—, —COO—, —CONH—, carbon number A ring structure containing atom A may be formed by bonding via 1 to 3 alkylene or phenylene groups. Here, R ′ is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

Examples of the aryl group having 6 to 30 carbon atoms include monocyclic aryl groups such as phenyl groups and condensed polycyclic rings such as naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, anthraquinone, etc. And a formula aryl group.

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. Is a monocyclic heterocyclic group such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl , Carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl, etc. It is.

Examples of the alkyl group having 1 to 30 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and the like, isopropyl, isobutyl, sec-butyl, tert-butyl, Examples thereof include branched alkyl groups such as isopentyl, neopentyl, tert-pentyl and isohexyl, and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of the alkenyl group having 2 to 30 carbon atoms include vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, and 1-methyl-2- Propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-2-butenyl, Linear or branched such as 3-methyl-2-butenyl, 1,2-dimethyl-1-propenyl, 1-decenyl, 2-decenyl, 8-decenyl, 1-dodecenyl, 2-dodecenyl, 10-dodecenyl Is 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-pentynyl, 2-pentynyl, 3-pentynyl, 4- Pentynyl, 3-methyl-1-butynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-decynyl, 2-decynyl, 8-decynyl, 1-dodecynyl, Examples thereof include linear or branched ones such as 2-dodecynyl and 10-dodecynyl.

無置換のアミノ基並びに炭素数１〜５のアルキル及び／又は炭素数６〜１０のアリールでモノ置換もしくはジ置換されているアミノ基（炭素数１〜５のアルキル基の具体例としてはメチル、エチル、プロピル、ブチル、ペンチルなどの直鎖アルキル基；イソプロピル、イソブチル、sec−ブチル、tert−ブチル、イソペンチル、ネオペンチル、tert−ペンチルなどの分岐アルキル基；シクロプロピル、シクロブチル、シクロペンチルなどのシクロアルキル基が挙げられる。炭素数６〜１０のアリール基の具体例としてはフェニル、ナフチルなどが挙げられる）；シアノ基；ニトロ基；フッ素、塩素、臭素、ヨウ素などのハロゲンなどが挙げられる。 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 The alkyl group may have various substituents, and examples of the substituent include linear alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, okdadecyl Branched alkyl groups having 1 to 18 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl and isohexyl; cycloalkyl having 3 to 18 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl Group; hydroxy group; methoxy, ethoxy, propoxy, isopropoxy, butoxy Linear or branched alkoxy groups having 1 to 18 carbon atoms such as isobutoxy, sec-butoxy, tert-butoxy, hexyloxy, decyloxy, dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyl, 2-methylbutanoyl , 3-methylbutanoyl, octanoyl, decanoyl, dodecanoyl, octadecanoyl, etc., a straight or branched alkylcarbonyl group having 2 to 18 carbon atoms; benzoyl, naphthoyl, etc., an arylcarbonyl group having 7-11 carbon atoms; methoxycarbonyl, ethoxy Carbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, octyloxycarbonyl, tetradecyloxycarbonyl, o Linear or branched alkoxycarbonyl groups having 2 to 19 carbon atoms such as tadecyloxycarbonyl; aryloxycarbonyl groups having 7 to 11 carbon atoms such as phenoxycarbonyl and naphthoxycarbonyl; 7 to 7 carbon atoms such as phenylthiocarbonyl and naphthoxythiocarbonyl 11 arylthiocarbonyl groups; acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octylcarbonyloxy, tetradecylcarbonyloxy, C2-C19 linear or branched acyloxy group such as octadecylcarbonyloxy; phenylthio, 2-methylphenylthio, 3-methylphenylthio, 4-methyl Ruphenylthio, 2-chlorophenylthio, 3-chlorophenylthio, 4-chlorophenylthio, 2-bromophenylthio, 3-bromophenylthio, 4-bromophenylthio, 2-fluorophenylthio, 3-fluorophenylthio, 4-fluoro Phenylthio, 2-hydroxyphenylthio, 4-hydroxyphenylthio, 2-methoxyphenylthio, 4-methoxyphenylthio, 1-naphthylthio, 2-naphthylthio, 4- [4- (phenylthio) benzoyl] phenylthio, 4- [ 4- (phenylthio) phenoxy] phenylthio, 4- [4- (phenylthio) phenyl] phenylthio, 4- (phenylthio) phenylthio, 4-benzoylphenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chloro Enylthio, 4-benzoyl-3-methylthiophenylthio, 4-benzoyl-2-methylthiophenylthio, 4- (4-methylthiobenzoyl) phenylthio, 4- (2-methylthiobenzoyl) phenylthio, 4- (p-methylbenzoyl) Arylthio groups having 6 to 20 carbon atoms such as phenylthio, 4- (p-ethylbenzoyl) phenylthio 4- (p-isopropylbenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio; methylthio, ethylthio, propylthio, isopropylthio Linear or branched alkylthio having 1 to 18 carbon atoms such as butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, etc. Groups: aryl groups having 6 to 10 carbon atoms such as phenyl, tolyl, dimethylphenyl, naphthyl; thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl, indolyl, benzofuranyl, benzothienyl, quinolyl, isoquinolyl, quinoxalinyl , Quinazolinyl, carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthenyl, phenoxazinyl, phenoxathiinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl and the like, a phenoxy, Aryloxy groups having 6 to 10 carbon atoms such as naphthyloxy; methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropyl Linear or branched alkyl having 1 to 18 carbon atoms such as sulfinyl, butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, pentylsulfinyl, isopentylsulfinyl, neopentylsulfinyl, tert-pentylsulfinyl, octylsulfinyl Sulfinyl group; arylsulfinyl group having 6 to 10 carbon atoms such as phenylsulfinyl, tolylsulfinyl, naphthylsulfinyl; methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, Pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, tert-pentylsulfonyl, octylsulfonyl A linear or branched alkylsulfonyl group having 1 to 18 carbon atoms; an arylsulfonyl group having 6 to 10 carbon atoms such as phenylsulfonyl, tolylsulfonyl (tosyl group) and naphthylsulfonyl; an alkyleneoxy group represented by the following general formula (Q represents a hydrogen atom or a methyl group, k is an integer of 1 to 5);

An unsubstituted amino group and an amino group mono- or di-substituted with an alkyl having 1 to 5 carbon atoms and / or an aryl having 6 to 10 carbon atoms (specific examples of alkyl groups having 1 to 5 carbon atoms include methyl, Linear alkyl groups such as ethyl, propyl, butyl and pentyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and tert-pentyl; cycloalkyl groups such as cyclopropyl, cyclobutyl and cyclopentyl Specific examples of the aryl group having 6 to 10 carbon atoms include phenyl and naphthyl); cyano group; nitro group; halogen such as fluorine, chlorine, bromine and iodine.

In addition, two or more R's are each directly or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ′ — (R ′ represents an alkyl group having 1 to 5 carbon atoms or a carbon number. An aryl group having 6 to 10. Specific examples of the alkyl group having 1 to 5 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, etc., isopropyl, isobutyl, sec-butyl, tert-butyl, Branched alkyl groups such as isopentyl, neopentyl, tert-pentyl, etc .; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, etc. Specific examples of aryl groups having 6 to 10 carbon atoms include phenyl, naphthyl and the like), As an example of forming a ring structure containing an atom A by bonding via —CO—, —COO—, —CONH—, an alkylene or phenylene group having 1 to 3 carbon atoms It is possible to include the following.

[A is an atom of Group VIA to Group VIIA (CAS notation), L is —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ′ —, —CO—, —COO— , -CONH-. R ′ is the same as described above. ]

In the general formula (1), m + n (m−1) +1 R bonded to the atom A of the valence m group VIA to VIIA (CAS notation) may be the same or different. , At least one of R, more preferably all of R is an aryl having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms, which may have the substituent.

一般式（２）中のＥはメチレン、エチレン、プロピレンなど炭素数１〜８の直鎖状、分岐状又は環状のアルキレン基；フェニレン、キシリレン、ナフチレン、ビフェニレン、アントラセニレンなどの炭素数６〜２０のアリーレン基；ジベンゾフランジイル、ジベンゾチオフェンジイル、キサンテンジイル、フェノキサチインジイル、チアンスレンジイル、ビチオフェンジイル、ビフランジイル、チオキサントンジイル、キサントンジイル、カルバゾールジイル、アクリジンジイル、フェノチアジンジイル、フェナジンジイルなどの炭素数８〜２０の複素環化合物の２価の基を表す。ここで複素環化合物の２価の基とは複素環化合物の異なる２個の環炭素原子からおのおの１個の水素原子を除いてできる２価の基のことをいう。 D in the general formula (1) is represented by the structure of the following general formula (2),

E in the general formula (2) is a linear, branched or cyclic alkylene group having 1 to 8 carbon atoms such as methylene, ethylene and propylene; and having 6 to 20 carbon atoms such as phenylene, xylylene, naphthylene, biphenylene and anthracenylene. Arylene group: carbon number such as dibenzofurandiyl, dibenzothiophenediyl, xanthenediyl, phenoxathiindiyl, thiensrangeyl, bithiophenediyl, bifuranyl, thioxanthonediyl, xanthonediyl, carbazolediyl, acridinediyl, phenothiazinediyl, phenazinediyl Represents a divalent group of 8-20 heterocyclic compounds. Here, the divalent group of the heterocyclic compound refers to a divalent group formed by removing one hydrogen atom from two different ring carbon atoms of the heterocyclic compound.

The alkylene group, arylene group or divalent group of the heterocyclic compound may have at least one substituent, and specific examples of the substituent include carbon such as methyl, ethyl, propyl, butyl, pentyl, octyl and the like. A linear alkyl group having 1 to 8 carbon atoms; a branched alkyl group having 1 to 8 carbon atoms such as isopropyl, isobutyl, sec-butyl and tert-butyl; a cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl and cyclohexyl; Alkoxy groups having 1 to 8 carbon atoms such as ethoxy, propoxy, butoxy, hexyloxy; aryl groups having 6 to 10 carbon atoms such as phenyl and naphthyl; hydroxy groups; cyano groups; nitro groups or fluorine, chlorine, bromine, iodine, etc. Halogen is mentioned.

G in the general formula (2) is —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ′ — (R ′ is the same as above), —CO—, —COO—. , -CONH-, an alkylene or phenylene group having 1 to 3 carbon atoms. Examples of the alkylene group having 1 to 3 carbon atoms include linear or branched alkylene groups such as methylene, ethylene and propylene.

A in general formula (2) is an integer of 0-5. a + 1 E and a G may be the same as or different from each other.

ａ=１の場合

ａ＝２の場合

ａ=３の場合

A typical example of D represented by the general formula (2) is shown below.
When a = 0

When a = 1

When a = 2

When a = 3

Of these D, the following groups are particularly preferred.

N in the general formula (1) represents the number of repeating units of the [D-A ⁺ R _m-1 ] bond, and is an integer of 0 to 3, preferably 0 or 1.

Preferred examples of the onium ion [A ⁺ ] in the general formula (1) include sulfonium, iodonium, and selenium. Typical examples include the following.

  Examples of sulfonium ions 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) sulfonium, 4- (phenylthio) sulfone Nylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenyldi-p-tolylsulfonium, 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-chlorophenylthio) 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-tolylsulfonium, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldiphenylsulfonium, 4- [4- (benzoylphenylthio) ] Phenyldi-p-tolylsulfonium, 4- [ 4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiantrenium, 5-phenylthiantrenium, 5-tolylthanthrenium, 5- (4-ethoxyphenyl) thiantrenium, 5- (2,4,6-trimethylphenyl) thiantrenium, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium, [4- (2-thioxanthonylthio) phenyl] phenyl Triarylsulfonium such as 2-thioxanthonylsulfonium; diarylsulfonium such as diphenylphenacylsulfonium, diphenyl (4-nitrophenacyl) sulfonium, diphenylbenzylsulfonium, diphenylmethylsulfonium; phenylmethylbenzylsulfone , (4-hydroxyphenyl) methylbenzylsulfonium, (4-methoxyphenyl) methylbenzylsulfonium, (4-acetocarbonyloxyphenyl) methylbenzylsulfonium, (2-naphthyl) methylbenzylsulfonium, (2-naphthyl) methyl [ (1-Ethoxycarbonyl) ethyl] sulfonium, phenylmethylphenacylsulfonium, (4-hydroxyphenyl) methylphenacylsulfonium, (4-methoxyphenyl) methylphenacylsulfonium, (4-acetocarbonyloxyphenyl) methylphenacylsulfonium , (2-naphthyl) methylphenacylsulfonium, (2-naphthyl) octadecylphenacylsulfonium, (9-anthracenyl) methylphenacylsulfonium, etc. Nonarylsulfonium; trialkylsulfonium such as dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octadecylmethylphenacylsulfonium, and the like, which are described in the following documents: Yes.

Regarding triarylsulfonium, U.S. Pat. No. 4,231,951, U.S. Pat. No. 4,256,828, JP-A-7-61964, JP-A-8-165290, JP-A-7-10914, JP-A-7-25922, JP-A-8- 27208, JP-A-8-27209, JP-A-8-165290, JP-A-8-301991, JP-A-9-143212, JP-A-9-278813, JP-A-10-7680, JP-A-10-287463. JP-A-10-245378, JP-A-8-157510, JP-A-10-204083, JP-A-8-245656, JP-A-8-157451, JP-A-7-324069, JP-A-9-268205. JP, 9-278935, JP 2001-288205, JP 11-80118, JP JP-A-10-182825, JP-A-10-330353, JP-A-10-152495, JP-A-5-239213, JP-A-7-333834, JP-A-9-12537, JP-A-8-325259, JP-A-8-160606. JP, 2000-186071 (US Pat. No. 6,368,769), etc .; Regarding diarylsulfonium, JP-A-7-300504, JP-A-64-45357, JP-A-64-29419, etc .; Monoarylsulfonium JP-A-6-345726, JP-A-8-325225, JP-A-9-118663 (US Pat. No. 6,097,753), JP-A-2-196812, JP-A-2-1470, and JP-A-3-237107. JP-A-3-17101, JP-A-6-228086, JP-A-10-152 69, JP-A-7-300505, JP-A-2003-277353, JP-A-2003-277352, etc .; regarding trialkylsulfonium, JP-A-4-308563, JP-A-5-140210, JP-A-5-140209, JP-A-5-230189, JP-A-6-271532, JP-A-58-37003, JP-A-2-178303, JP-A-10-338688, JP-A-9-328506, JP-A-11-228534, Examples include JP-A-8-27102, JP-A-7-333834, JP-A-5-222167, JP-A-11-21307, JP-A-11-35613, and US Pat. No. 6,031,014.

Examples of the iodonium ions include diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxyphenyl). ) Iodonium, [4- (2-hydroxytetradecyloxy) phenyl] phenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium, isobutylphenyl (p-tolyl) iodonium, and the like. 1307 (1977), JP-A-6-184170, U.S. Pat. No. 4,256,828, U.S. Pat.No. 4,351,708, JP-A-56-135519, JP-A-58-38350, JP-A-10-195117, JP-A-2001. -139539 No. 2000, JP-A 2000-510516, JP-A 2000-119306, and the like.

Examples of selenium ions include triphenyl selenium, tri-p-tolyl selenium, tri-o-tolyl selenium, tris (4-methoxyphenyl) selenium, 1-naphthyldiphenyl selenium, tris (4-fluorophenyl) selenium, tri-1- Naphthyl selenium, tri-2-naphthyl selenium, tris (4-hydroxyphenyl) selenium, 4- (phenylthio) phenyl diphenyl selenium,
Triaryl selenium such as 4- (p-tolylthio) phenyldi-p-tolyl selenium; diaryl selenium such as diphenylphenacyl selenium, diphenylbenzyl selenium, diphenylmethyl selenium; phenylmethylbenzyl selenium, (4-hydroxyphenyl) methylbenzyl selenium Monoaryl selenium such as phenylmethylphenacyl selenium, (4-hydroxyphenyl) methyl phenacyl selenium, (4-methoxyphenyl) methyl phenacyl selenium; dimethyl phenacyl selenium, phenacyl tetrahydroselenophenium, dimethyl benzyl selenium, Examples include trialkyl selenium such as benzyltetrahydroselenophenium and octadecylmethylphenacyl selenium. Is, they JP 50-151997, JP 50-151976, are described, for example, JP-A-53-22597.

Among these oniums, preferred are sulfonium and iodonium, and more preferred are [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium, [4- (2-thioxanthonylthio). ) Phenyl] phenyl-2-thioxanthonylsulfonium, triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- { Bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-Fluorophenyl) Ruphonium, 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-tolylsulfonium, 4- [4- (benzoylphenylthio)] phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiantrenium, 5-phenylthiantrenium, diphenylphena Silsulfonium, (4-hydroxy Sulfonium ions such as phenyl) methylbenzylsulfonium, (2-naphthyl) methyl [(1-ethoxycarbonyl) ethyl] sulfonium, (4-hydroxyphenyl) methylphenacylsulfonium and octadecylmethylphenacylsulfonium, and diphenyliodonium, di-p -Tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) ) Iodonium ions such as phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium and 4-isobutylphenyl (p-tolyl) iodonium. Emissions, and the like.
Particularly preferably, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium, [4- ( 2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium.

In the general formula (1) representing the onium borate salt of the present invention, X ⁻ is a counter ion. The number thereof is n + 1 per molecule, at least one of which is a borate anion represented by the general formula (3), and the other may be another anion.
[
(Y) _b B (Ar) _4-b ] (3)
As the other anion, any conventionally known anion may be used. For example, halogen ions such as F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ ; OH ⁻ ; ClO ₄ ⁻ ; FSO ₃ ⁻ and ClSO ₃ ⁻ Sulfonic acid ions such as CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO ₃ ⁻ , C ₆ F ₅ SO ₃ ⁻ and CF ₃ SO ₃ ^— ; sulfate ions such as HSO ₄ ⁻ and SO ₄ ²⁻ ; HCO Carbonate ions such as ₃ ⁻ and CO ₃ ²⁻ ; phosphate ions such as H ₂ PO ₄ ⁻ , HPO ₄ ²⁻ and PO ₄ ³⁻ ; PF ₆ ⁻ , PF ₅ OH ⁻ , PF ₃ (CF _{3 ) 3 -, PF 3 (C} 2 F 5) 3 -, PF 3 (C 3 F 7) 3 - fluorophosphate ions such ^{_{as; BF 4 -, B (C}} 6 F 5) 4 -, B (C ₆ H ₄ CF _{3) 4} ^- borate ions such as; AlCl ₄ ^-; BiF ₆ ^-, and the like It is done. Other examples include fluoroantimonate ions such as SbF ₆ ⁻ and SbF ₅ OH ^−, and fluoroarsenate ions such as AsF ₆ ⁻ and AsF ₅ OH ⁻ , which are not preferred because they contain toxic elements. .

In the borate anion represented by the general formula (3), Y is an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms, and the aryl group or heterocyclic group has 1 to 12 carbon atoms. An alkyl group, a cycloalkyl group having 3 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an arylthio group having 6 to 12 carbon atoms, an alkylcarbonyl group having 2 to 7 carbon atoms, It may be substituted with at least one selected from the group consisting of an alkoxycarbonyl group having 2 to 7 carbon atoms, a phenyl group and a benzoyl group. Specific examples of the substituent are the same as the specific examples of R. A plurality of substituents may be present or unsubstituted. When it has a plurality of substituents, the substituents may be the same or different.

Y is preferably an aryl group having 6 to 30 carbon atoms, particularly preferably a phenyl group, a naphthyl group, or an anthracenyl group, and more preferably a phenyl group.

In the general formula (3), the number b of Y is an integer of 1 to 3, preferably 1 to 2, and particularly preferably 1. The b Ys may be the same or different. An increase in the number of Y 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 formula (3), Ar represents a phenyl group substituted with at least one hydrogen atom and at least one selected from the group consisting of perfluoroalkyl, perfluoroalkoxy and halogen. . 4-b Ar 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 and catalytic ability to resist, Ar is preferably a perfluoroalkyl group or a phenyl group substituted with a fluorine atom.

Specific examples of particularly 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), pentafluoroethyl phenyl group _{(CF 2 CF 3 C 6 H} 4), 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 _{((CF 3 CF 2) 2} C 6 H 2 F) can be mentioned.
Of these, a pentafluorophenyl group (C ₆ F ₅ ) and a fluoro-bis (pentafluoroethyl) phenyl group ((CF ₃ CF ₂ ) ₂ C ₆ H ₂ F) are preferable.

Specific examples of preferred borate anion _{[(C 6 H 5) B} (C 6 F 5) 3] - , and _{[(C 6 H 5) B} (C 6 H 3 (CF 3) 2) 3 3] - is Can be mentioned.

The onium borate of the present invention can be produced by a metathesis method. The metathesis method is, for example, New Experimental Chemistry Lecture 14-I (1978, Maruzen) p-448; Advance
in Polymer Science, 62, 1-48 (1984); New Experimental Chemistry Course 14-III (1978, Maruzen) p1838-1846; Organic Sulfur Chemistry (Synthetic Reaction, 1982, Chemistry), Chapter 8, p237-280; Japan Chemical Journal, 87, (5), 74 (1966)
J. Org. Chem., 32, 2580 (1967);
Tetrahedron Letters, 36, 3437 (1973); Bulletin de la Societe Chimique de France, 1, 228 (1976); Bulletin de la Societe Chimique de France 11, 2571 (1975); Inorg. Chem., 10, 1559 (1971) Chem. Ber., 93, 2729 (1960);
J. Organomet. Chem., 54, 255 (1973); “Organometallic Syntheses”, vol. 1, Academic
Press, P138 (1965); Tetrahedron, 39, 4027 (1983); J. Amer. Chem. Soc., 103, 758 (1981);
J. Chem. Soc., Chem. Commun., 1971, 930 (1971); J. Amer. Chem. Soc., 92, 7207 (1970); JP-A-61-100557, JP-A-5-4996, JP-A-7-82244, JP-A-7-82245, JP-A58-210904, JP-A-6-184170, and the like. First, halogen ion salts of onium such as F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ ; OH ⁻ salt; ClO ₄ ⁻ salt; FSO ₃ ⁻ , ClSO ₃ ⁻ , CH ₃ SO ₃ ⁻ , C ₆ H ₅ SO Salts with sulfonate ions such as ₃ ⁻ and CF ₃ SO ₃ ^— ; salts with sulfate ions such as HSO ₄ ⁻ and SO ₄ ²⁻ ; and carbonate ions such as HCO ₃ ⁻ and CO ₃ ^{2− _{salt; H 2 PO 4 -, HPO}} 4 2-, manufactures and salts with phosphate ions such as PO ₄ ^3-, this Formula alkali metal salts of borate anions represented by (3), to metathesis an alkaline earth metal salt or a quaternary ammonium salt in addition to the aqueous solution containing more than the theoretical amount. Since the salt of the present invention thus produced is separated in the form of crystals or oil, the crystals can be recovered by filtration, and the liquid can be recovered by liquid separation or extraction with a suitable solvent. The onium salt of the present invention thus obtained can be purified by a method such as recrystallization or washing with water or a solvent, if necessary.

The structure of the onium borate thus obtained can be obtained by a general analytical method, for example, each nuclear magnetic resonance spectrum such as ¹ H, ¹³ C, ¹⁹ F, and ¹⁰ B, an infrared absorption spectrum, or an elemental analysis. Can be identified.

As the borate used in the above metathesis reaction, an alkali metal salt is preferable. This alkali metal salt can be produced, for example, by the following reaction.

An ether liquid such as diethyl ether or tetrahydrofuran of Y-MgBr is cooled to room temperature, and borane (wherein X represents a halogen group) is added and reacted at 20 to 65 ° C. for several minutes to several hours (first stage) Reaction of). The reaction mixture is cooled to room temperature, and this reaction solution is added dropwise to a separately prepared Ar-MgBr ether-based solution (diethyl ether, tetrahydrofuran, etc.) and reacted at 20 to 65 ° C. for several minutes to several hours to complete the reaction ( Second stage reaction). The reaction solution is poured into a saturated aqueous solution of an alkali metal bicarbonate, the organic layer is separated, the organic layer is washed with a hydrocarbon solvent (hexane, etc.), and the residue is dried under reduced pressure to remove alkali metal. The borate can be obtained in solid or semi-solid form. If necessary, it is purified by means of sublimation, recrystallization, column chromatography, solvent washing and the like.

The onium borate salt of the present invention may be used alone as a photoacid generator (cationic polymerization initiator), or two or more kinds may be used in combination. Moreover, you may use together with another conventionally well-known photo-acid generator (cationic polymerization initiator). Examples of other photoacid generators (cationic polymerization initiators) include salts of onium ions or transition metal complex ions such as sulfonium, iodonium, selenium, ammonium, phosphonium, and various anions.

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 photoacid generator (cationic polymerization initiator) is used in combination is arbitrary, but the other cationic polymerization initiator is usually 10 to 900 parts by weight with respect to 100 parts by weight of the onium borate salt of the present invention. , Preferably 25 to 400 parts by weight (in the following description, parts represent parts by weight).

The photoacid generator (cationic polymerization initiator) of the present invention may be dissolved in advance in a solvent that does not inhibit cationic polymerization in order to facilitate dissolution in a cationically polymerizable compound. Examples of the solvent include propylene carbonate, Carbonates such as 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 monoacetate, diethylene glycol, diethylene glycol mono Acetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and monomethyl ether of dipropylene glycol monoacetate, Polyhydric alcohols such as no ethyl 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, acetic acid Butyl, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxy- Esters such as ethyl 2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene It is below.
When these solvents are used, the use ratio is usually 15 to 1000 parts, preferably 30 to 500 parts, with respect to 100 parts of the photoacid generator of the present invention.

  The energy beam curable composition in the present invention is composed of the photoacid generator of the present invention and a cationically polymerizable compound.

  Examples of the cationic polymerizable compound include cyclic ethers (epoxides and oxetanes), ethylenically unsaturated compounds (vinyl ether and styrene, etc.), bicycloorthoesters, spiroorthocarbonates and spiroorthoesters (Japanese Patent Laid-Open No. 11-060996). JP-A 09-302269, JP-A 2003-026993, JP-A 2002-206017, JP-A 11-349895, JP-A 10-212343, JP-A 2000-119306, JP-A 10-67812, JP 2000-186071, JP 08-85775, JP 08-134405, JP 2008-20838, JP 2008-20839, JP 2008-20841, JP 2008-26660, JP 2008-26444. , JP 2 07-277327, photopolymer social gathering “Photopolymer Handbook” (1989, Industrial Research Committee), General Technology Center “UV / EB Curing Technology” (1982, General Technology Center), Radtech Study Group “UV. EB Curing Material "(1992, CMC), Technical Information Association," Hardening Failure / Inhibition Causes in UV Curing and Countermeasures "(2003, Technical Information Association), Coloring Materials, 68, (5), 286-293 (1995), fine chemicals, 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.

  Examples of the aliphatic epoxide 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.

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.

  The content of the photoacid generator of the present invention in the energy ray curable composition is preferably 0.05 to 20 parts, more preferably 0.1 to 10 parts, relative to 100 parts of the cationic 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 considering various factors such as the nature of the cationically polymerizable compound, the type of energy beam and the irradiation amount, temperature, curing time, humidity, and coating thickness, and is limited to the above range. Not.

  In the energy beam curable composition of the present invention, if necessary, known additives (sensitizers, pigments, fillers, antistatic agents, flame retardants, antifoaming agents, flow regulators, light stabilizers, An antioxidant, an adhesion-imparting agent, an ion scavenger, a coloring inhibitor, a solvent, a non-reactive resin, a radically polymerizable compound, and the like).

  The energy beam curable composition of the present invention basically does not require a sensitizer, but can contain a sensitizer as necessary to supplement the curability. As such a sensitizer, known sensitizers (JP-A Nos. 11-279212 and 09-183960) can be used, and anthracene {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, and 2,4-diethylthioxanthone}; Phenothiazine {Phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, N Xanthone; naphthalene {1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, 4-methoxy-1-naphthol, etc.}; ketone {dimethoxyacetophenone, Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 4-benzoyl-4′-methyldiphenyl sulfide, etc.}; Carbazole {N-phenylcarbazole, N-ethylcarbazole, poly-N-vinylcarbazole, N-glycidylcarbazole and the like}; chrysene {1,4-dimethoxychrysene and 1,4-di-α-methylbenzyloxychrysene}; Fena And entomene {9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.} and the like.

  When it contains a sensitizer, the content of the sensitizer is preferably 1 to 300 parts, more preferably 5 to 200 parts, relative to 100 parts of the photoacid 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, more preferably 10 to 150,000 parts, with respect to 100 parts of the photoacid 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 it contains a filler, the content of the filler is preferably 50 to 600000 parts, more preferably 300 to 200000 parts, relative to 100 parts of the photoacid 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, more preferably 0.6 to 5000 parts, relative to 100 parts of the photoacid 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 a flame retardant is contained, the content of the flame retardant is preferably 0.5 to 40,000 parts, more preferably 5 to 10,000 parts, with respect to 100 parts of the photoacid 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 Examples thereof include an inhibitor and a phosphorus-based antioxidant.

  When containing an antifoaming agent, a flow regulator, a light stabilizer, an antioxidant, an adhesion promoter, an ion scavenger, or an anti-coloring agent, each content is based on 100 parts of the photoacid generator, The amount is preferably 0.1 to 20000 parts, more preferably 0.5 to 5000 parts.

  The solvent is not particularly 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 photoacid generator can be used.

  In the case of containing a solvent, the content of the solvent is preferably 50 to 2,000,000 parts, more preferably 200 to 500,000 parts with respect to 100 parts of the photoacid 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, more preferably 50 to 150,000 parts, relative to 100 parts of the photoacid 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, more preferably 50 to 150,000 parts with respect to 100 parts of the photoacid 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, more preferably 0.1 to 10 parts, relative to 100 parts of the radical polymerizable compound.

  The energy ray-curable composition of the present invention comprises a cationically polymerizable compound, a photoacid generator and, if necessary, a uniform agent at room temperature (about 20 to 30 ° C.) or optionally under heating (about 40 to 90 ° C.). Can be mixed and dissolved, or further kneaded with three rolls or the like.

The energy ray-curable composition of the present invention can be cured by irradiation with energy rays to obtain a cured product.
As the energy ray, any energy ray may be used as long as it has an energy that induces decomposition of the sulfonium salt of the present invention, but low pressure, medium pressure, high pressure or ultrahigh pressure mercury lamp, metal halide lamp, LED lamp, xenon lamp, carbon arc lamp, Energy rays in the ultraviolet to visible light region (wavelength: about 100 to about 800 nm) obtained from a fluorescent lamp, a semiconductor solid state laser, an argon laser, a He—Cd laser, a KrF excimer laser, an ArF excimer laser, an F ₂ laser, or the like are 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 150. It is also possible to heat and cure at a temperature of several seconds to several hours.

  Specific applications of the energy beam curable composition of the present invention include paints, coating agents, inks, inkjet inks, positive resists, resist films, liquid resists, negative resists, MEMS resists, positive photosensitive materials. , Negative photosensitive material, various adhesives, molding material, casting material, putty, glass fiber impregnating agent, sealing material, sealing material, sealing material, optical semiconductor (LED) sealing material, optical waveguide material, nanoimprint Examples include materials, photofabrication materials, and micro stereolithography materials.

  Since the sulfonium salt of the present invention generates a strong acid when irradiated with light, light for chemically amplified resist materials known in the art (Japanese Patent Application Laid-Open Nos. 2003-267968, 2003-261529, 2002-193925, etc.) is used. It can also be used as an acid generator.

  As the chemically amplified resist material, (1) a two-component chemically amplified positive resist containing, as essential components, a resin that is soluble in an alkali developer by the action of an acid and a photoacid generator; (2) an alkali developer Soluble resin, a three-component chemical amplification type positive resist containing, as essential components, a dissolution inhibitor that becomes soluble in an alkali developer by the action of an acid and a photoacid generator, and (3) acceptable for an alkali developer. A chemically amplified negative resist containing a cross-linking agent that crosslinks the resin by heat treatment in the presence of an acid and an acid and an insoluble in an alkaline developer and a photoacid generator as an essential component is included.

The chemically amplified positive photoresist composition of the present invention is soluble in alkali by the action of the component (A) containing the photoacid generator of the present invention, which is a compound that generates acid upon irradiation with light or radiation, and the acid. It contains the resin component (B) which increases.

  In the chemically amplified positive photoresist composition of the present invention, the component (A) may be used in combination with other conventionally known photoacid 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 photoacid generators, one or more of the group of onium compounds, sulfonimide compounds, diazomethane compounds and oxime sulfonate compounds are preferred.

  When such other conventionally known photoacid generators are used in combination, the ratio of use may be arbitrary, but usually other photoacid generators are 10 to 900 per 100 parts by weight of the total weight of the onium salt. Part by weight, preferably 25 to 400 parts by weight.

  The content of the component (A) is preferably 0.05 to 5% by weight in the solid content of the chemically amplified positive photoresist composition.

<Resin component (B) whose solubility in alkali is increased by the action of acid>
The above-mentioned “resin (B) whose solubility in alkali is increased by the action of an acid” used in the chemically amplified positive photoresist composition for thick film of the present invention (referred to herein as “component (B)”) .) Is at least one resin selected from the group consisting of novolak resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3), or a mixed resin or copolymer thereof.

[Novolac resin (B1)]
As the novolac resin (B1), a resin represented by the following general formula (b1) can be used.

In the general formula (b1), R ^1b represents an acid dissociable, dissolution inhibiting group, R ^2b and R ^3b each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is in parentheses. Represents the number of repeating units in the structure.

Furthermore, ^examples of the acid dissociable, dissolution inhibiting group represented by R ^1b include a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and a cyclic group having 3 to 6 carbon atoms. Are preferably an alkyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

Here, specific examples of the acid dissociable, dissolution inhibiting group represented by R ^1b include methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, isobutoxyethyl. Group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group, tert-butoxycarbonyl group, tert- Examples include butoxycarbonylmethyl group, trimethylsilyl group, and tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene resin (B2)]
As the polyhydroxystyrene resin (B2), a resin represented by the following general formula (b4) can be used.

In the general formula (b4), R ^8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^9b represents an acid dissociable, dissolution inhibiting group, and n represents the number of repeating units of the structure in parentheses. To express.

  The alkyl group having 1 to 6 carbon atoms is a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. The cyclic alkyl group includes a cyclopentyl group and a cyclohexyl group. Etc.

As the acid dissociable, dissolution inhibiting group represented by R ^9b , the same acid dissociable, dissolution inhibiting groups as those exemplified for R ^1b can be used.

  Furthermore, the polyhydroxystyrene resin (B2) can contain other polymerizable compounds as structural units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anionic polymerizable compounds. For example, monocarboxylic acids such as acrylic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid; methyl (meth) acrylate, etc. (Meth) acrylic acid alkyl esters of (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate; vinyl group-containing fragrances such as styrene and vinyltoluene Aliphatic compounds; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride; And the like amide bond-containing polymerizable compounds such as.

[Acrylic resin (B3)]
As the acrylic resin (B3), resins represented by the following general formulas (b5) to (b10) can be used.

In the general formulas (b5) to (b7), R ^{10b to} R ^17b each independently represent a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms. Represents a group, a fluorine atom, a linear fluorinated alkyl group having 1 to 6 carbon atoms or a branched fluorinated alkyl group having 3 to 6 carbon atoms, and ^Xb together with the carbon atom to which it is bonded Forming a hydrocarbon ring having 5 to 20 carbon atoms, Y ^b represents an aliphatic cyclic group or an alkyl group which may have a substituent, n represents the number of repeating units of the structure in parentheses, p is an integer of 0 to 4, and q is 0 or 1.

In General Formula (b8), General Formula (b9), and General Formula (b10), R ^18b , R ^20b, and R ^21b each independently represent a hydrogen atom or a methyl group, and in General Formula (b8), R ^19b is independently of each other a hydrogen atom, a hydroxyl group, a cyano group or a COOR ^23b group (where R ^23b is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a branched group having 3 to 4 carbon atoms). Represents a chain alkyl group or a cycloalkyl group having 3 to 20 carbon atoms.) In the general formula (b10), each R ^22b is independently a monovalent alicyclic group having 4 to 20 carbon atoms. A hydrocarbon group or a derivative thereof, or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms, and at least one of R ^22b is the alicyclic hydrocarbon group or Either its derivatives or any two R ^22b of each other are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the common carbon atom to which each is bonded, and the remaining R ^22b is carbon A linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof is represented.

  Among the components (B), it is preferable to use an acrylic resin (B3).

  Moreover, the polystyrene conversion weight average molecular weight of a component (B) becomes like this. Preferably it is 10000-600000, More preferably, it is 50000-600000, More preferably, it is 230000-550,000. By setting it as such a weight average molecular weight, the resin physical property of a resist becomes excellent.

  Furthermore, the component (B) is preferably a resin having a dispersity of 1.05 or more. Here, the “dispersion degree” is a value obtained by dividing the weight average molecular weight by the number average molecular weight. By setting such a degree of dispersion, the resist plating resistance and resin physical properties are excellent.

  The content of the component (B) is preferably 5 to 60% by weight in the solid text of the chemically amplified positive photoresist composition.

<Alkali-soluble resin (C)>
The chemically amplified positive photoresist composition of the present invention preferably further contains an alkali-soluble resin (hereinafter referred to as “component (C)”) in order to improve the resin physical properties of the resist. . The component (C) is preferably at least one selected from the group consisting of novolak resins, polyhydroxystyrene resins, acrylic resins and polyvinyl resins.

  The content of the component (C) is preferably 5 to 95 parts by weight, and more preferably 10 to 90 parts by weight with respect to 100 parts by weight of the component (B). When the amount is 5 parts by weight or more, the resin physical properties of the resist can be improved, and when the amount is 95 parts by weight or less, there is a tendency that film loss during development can be prevented.

<Acid diffusion control agent (D)>
In the chemically amplified positive photoresist composition for thick film of the present invention, an acid diffusion control agent (D) (in this specification, “component ( D) ").) Is preferably included. As the component (D), a nitrogen-containing compound is preferable, and an organic carboxylic acid, an oxo acid of phosphorus, or a derivative thereof can be further contained as necessary.

  In addition, the chemically amplified positive photoresist composition of the present invention may further contain an adhesion assistant in order to improve the adhesion to the substrate. As the adhesion assistant used, a functional silane coupling agent is preferable.

  The chemically amplified positive photoresist composition of the present invention may further contain a surfactant in order to improve coating properties, antifoaming properties, leveling properties and the like.

  In addition, the chemically amplified positive photoresist composition of the present invention may further contain an acid, an acid anhydride, or a high boiling point solvent in order to finely adjust the solubility in an alkali developer.

  In addition, the chemically amplified positive photoresist composition of the present invention basically does not require a sensitizer, but can contain a sensitizer as necessary to complement the sensitivity. 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 onium salt.

  In addition, an organic solvent can be appropriately blended in the chemically amplified positive photoresist composition of the present invention for viscosity adjustment. Specific examples of the organic solvent include those described above.

  The amount of these organic solvents used is such that the solid layer concentration is such that the film thickness of the photoresist layer obtained by using the chemically amplified positive photoresist composition of the present invention (for example, spin coating method) is 5 μm or more. Is preferably 30% by weight or more.

  The chemical amplification type positive photoresist composition for thick film of the present invention can be prepared, for example, by mixing and stirring each of the above components by a usual method. If necessary, a dissolver, a homogenizer, a three roll mill, etc. You may disperse and mix using a disperser. Moreover, after mixing, you may further filter using a mesh, a membrane filter, etc.

  The chemically amplified positive photoresist composition of the present invention is suitable for forming a photoresist layer having a thickness of usually 5 to 150 μm, more preferably 10 to 120 μm, and still more preferably 10 to 100 μm on a support. ing. In this photoresist laminate, a photoresist layer made of the chemically amplified positive photoresist composition of the present invention is laminated on a support.

  The support is not particularly limited, and a conventionally known one can be used. Examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed. Examples of the substrate include a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, and aluminum, a glass substrate, and the like. In particular, the chemically amplified positive photoresist composition of the present invention can form a resist pattern satisfactorily even on a copper substrate. As a material for the wiring pattern, for example, copper, solder, chromium, aluminum, nickel, gold, or the like is used.

  The said photoresist laminated body can be manufactured as follows, for example. That is, a desired coating film is formed by applying a solution of a chemically amplified positive photoresist composition prepared as described above onto a support and removing the solvent by heating. As a coating method on the support, methods such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, and an applicator method can be employed. The pre-baking conditions of the coating film of the composition of the present invention vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc., but are usually 70 to 150 ° C., preferably 80 to 140 ° C. What is necessary is just about 60 minutes.

  The film thickness of the photoresist layer is usually 5 to 150 μm, preferably 10 to 120 μm, more preferably 10 to 100 μm.

  In order to form a resist pattern using the thus-obtained photoresist laminate, light or radiation, for example, having a wavelength of 300 to 500 nm is applied to the obtained photoresist layer through a mask having a predetermined pattern. Irradiation (exposure) with ultraviolet rays or visible rays may be performed selectively.

Here, the “light” may be light that activates the acid generator to generate an acid, and includes ultraviolet rays, visible rays, and far ultraviolet rays, and “radiation” means X-rays, electron beams, It means an ion beam. As a light or radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon gas laser, an LED lamp, or the like can be used. Moreover, although the amount of radiation irradiation changes with kinds of each component in a composition, a compounding quantity, the film thickness of a coating film, etc., when using an ultrahigh pressure mercury lamp, it is 50-10000 mJ / cm < ² >, for example.

  Then, after the exposure, the diffusion of the acid is promoted by heating using a known method to change the alkali solubility of the exposed photoresist layer. Next, for example, using a predetermined alkaline aqueous solution as a developer, unnecessary portions are dissolved and removed to obtain a predetermined resist pattern.

  The development time varies depending on the type of each component of the composition, the blending ratio, and the dry film thickness of the composition, but it is usually 1 to 30 minutes. Any of these may be used. After the development, washing with running water is performed for 30 to 90 seconds and dried using an air gun or an oven.

  Forming connection terminals such as metal posts and bumps by embedding a conductor such as metal in the non-resist portion (the portion removed with the alkali developer) of the resist pattern thus obtained, for example, by plating. Can do. The plating method is not particularly limited, and various conventionally known methods can be employed. As the plating solution, solder plating, copper plating, gold plating, or nickel plating solution is particularly preferably used. The remaining resist pattern is finally removed using a stripping solution or the like according to a conventional method.

  The chemically amplified positive photoresist composition of the present invention can also be used as a dry film. This dry film has a protective film formed on both sides of a layer made of the chemically amplified positive photoresist composition of the present invention. The thickness of the layer made of the chemically amplified positive photoresist composition is usually 10 to 150 μm, preferably 20 to 120 μm, more preferably 20 to 80 μm. Moreover, a protective film is not specifically limited, The resin film conventionally used for the dry film can be used. As an example, one may be a polyethylene terephthalate film and the other may be one selected from the group consisting of a polyethylene terephthalate film, a polypropylene film, and a polyethylene film.

  The chemical amplification type positive dry film as described above can be produced, for example, as follows. That is, a solution of a chemically amplified positive photoresist composition prepared as described above is applied onto one protective film, and the solvent is removed by heating to form a desired coating film. The drying conditions vary depending on the type of each component in the composition, the blending ratio, the coating film thickness and the like, but are usually 60 to 100 ° C. and about 5 to 20 minutes.

  In order to form a resist pattern using the thus obtained chemically amplified dry film, one protective film of the chemically amplified positive dry film is peeled off and the exposed surface is directed to the support side described above. Then, after laminating on the support to obtain a photoresist layer, after prebaking to dry the resist, the other protective film may be peeled off.

  In the photoresist layer thus obtained on the support, a resist pattern can be formed in the same manner as described above with respect to the photoresist layer formed by coating directly on the support. .

The chemically amplified negative photoresist composition of the present invention comprises a component (E) comprising the photoacid generator of the present invention, which is a compound that generates acid upon irradiation with light or radiation, and an alkali-soluble compound having a phenolic hydroxyl group. A resin (F) and a crosslinking agent (G) are contained.

Component (E) comprising the photoacid generator of the present invention is the same as component (A) described above.
Alkali-soluble resin (F) 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 (F)”) include, for example, novolak resin, polyhydroxystyrene, a copolymer of polyhydroxystyrene, hydroxystyrene and styrene. Copolymer of hydroxystyrene, styrene and (meth) acrylic acid derivative, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, and the like. 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 (F) may be used individually by 1 type, and may mix and use 2 or more types.

Moreover, the phenolic resin (F) 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 (G)
The “crosslinking agent” (hereinafter also referred to as “crosslinking agent (G)”) 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 (F). Examples of the crosslinking agent (G) 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 as a skeleton, An oxirane ring-containing compound, a thiirane ring-containing compound, an oxetanyl group-containing compound, an isocyanate group-containing compound (including a blocked one), and the like can be given.

Of these crosslinking agents (G), 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 (G) 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 (F). When the amount of the crosslinking agent (G) is 1 to 100 parts by weight, the curing reaction proceeds sufficiently, and the resulting cured product has a good pattern shape with high resolution, heat resistance and electrical insulation. 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 (H)
The chemically amplified negative photoresist composition of the present invention further contains crosslinked fine particles (hereinafter also referred to as “crosslinked fine particles (H)”) in order to improve the durability and thermal shock resistance of the resulting cured product. Can be made.

The average particle size of the crosslinked fine particles (H) 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 (H) 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 (H) 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 (H) 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 (F). When the blended amount of the crosslinked fine particles (H) 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 (I)
Further, the chemically amplified negative photoresist composition of the present invention contains an adhesion assistant (hereinafter also referred to as “adhesion assistant (I)”) in order to improve the adhesion to the substrate. Can do.
Examples of the adhesion assistant (I) include functional silane coupling agents 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 (I) 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 (F). 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.

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, sensitizers, 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 its cured product is excellent in electrical insulation, thermal shock, etc. The cured product can be suitably used as a surface protective film, planarizing film, interlayer insulating film material, etc. for electronic components such as semiconductor elements and semiconductor packages.

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 (henceforth this heat processing is called "PEB") is performed, and reaction with a phenol resin (F) and a crosslinking agent (G) 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 (F) and the crosslinking agent (G) 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”.

(Production Example 1) Production of sodium phenyltris (pentafluorophenyl) borate 1.7 parts of magnesium and 26.1 parts of tetrahydrofuran were charged into a deaerated nitrogen-substituted reaction vessel and cooled to 18 ° C in a water bath. 17.3 parts of bromopentafluorobenzene and 26.1 parts of tetrahydrofuran are charged into a dropping funnel and added dropwise so that the internal temperature does not exceed 25 ° C. After completion of dropping, the reaction is continued at 45 ° C. for 2 hours, and then the reaction solution is cooled to 20 ° C. Thereafter, 3.0 parts of dichlorophenylborane is dropped from the dropping funnel so that the system temperature does not exceed 25 ° C. After completion of dropping, the reaction is 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 10.4 parts of sodium phenyltris (pentafluorophenyl) borate as a target product, yield 90% (purity 98 % Or more). The product was identified by ¹ H-NMR, ¹⁹ F-NMR { ¹ H-NMR, d ₆ -dimethylsulfoxide, δ (ppm); 7.20 (2H, d), 6.95 (2H, t), 6.85 (1H, t)}. { ¹⁹ F-NMR, d ₆ -dimethyl sulfoxide, δ (ppm); −125 (6 F, d), −158.5 (3 F, t), −162.5 (6 F, t); internal standard = hexa Fluorobenzene, -159 (6F, s)}. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

(Production Example 2) Production of sodium tetrakis (pentafluorophenyl) borate 1.7 parts of magnesium and 26.1 parts of tetrahydrofuran are charged into a deaerated nitrogen-substituted reaction vessel and cooled to 18 ° C in a water bath. 17.3 parts of bromopentafluorobenzene and 26.1 parts of tetrahydrofuran are charged into a dropping funnel and added dropwise so that the internal temperature does not exceed 25 ° C. After completion of dropping, the reaction is continued at 45 ° C. for 2 hours, and then the reaction solution is cooled to 20 ° C. Thereafter, 2.4 parts of boron trifluoride diethyl ether complex is dropped from the dropping funnel so that the system temperature does not exceed 25 ° C. The reaction is continued at 65 ° C. for 12 hours after completion of the dropwise addition.
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 give 5.8 parts of the target product, sodium tetrakis (pentafluorophenyl) borate, yield 40% (purity 98 % Or more). The product was identified by ^{19 F-NMR {19 F-} NMR, d 6 - dimethyl sulfoxide, δ (ppm); - 128 (8F, d), - 158 (4F, t), - 162.5 (8F, t); internal standard = hexafluorobenzene, −159 (6F, s)}. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 1 Synthesis of 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate 2.0 parts of diphenylsulfoxide, 1.5 parts of diphenylsulfide, and 7.0 parts of methanesulfonic acid were charged. After mixing uniformly, 1.3 parts of acetic anhydride was added dropwise. After reacting at 40-50 ° C. for 5 hours, it was cooled to room temperature. The reaction solution was neutralized with an aqueous potassium hydroxide solution, dropped into a container containing 61.0 parts of a 10% by weight aqueous solution of phenyltris (pentafluorophenyl) borate, and stirred well at room temperature for 1 hour. 20 parts of toluene was added for extraction, the aqueous layer was separated, and the organic layer was washed with 20 parts of water three times. The solvent was distilled off from the organic layer, and 10 parts of toluene was added to the resulting yellow residue to dissolve it. In order to remove impurities such as unreacted raw materials and by-products, 44 parts of hexane was added to this toluene solution, and the mixture was allowed to stand after stirring well at 10 ° C. for 1 hour. Since the solution was separated into two layers, the upper layer was removed by liquid separation. When 25 parts of hexane was added to the remaining lower layer and mixed well at room temperature, pale yellow crystals were precipitated. This was filtered off and dried under reduced pressure to obtain 7.2 parts of 4- (phenylthio) phenyldiphenylsulfonium phenyltris (pentafluorophenyl) borate (yield 75%, purity 98% or more).
The product was identified by ¹ H-NMR and ¹⁹ F-NMR { ¹ H-NMR: d ₆ -dimethylsulfoxide, δ (ppm); 7.72-7.87 (12H, m), 7.54-7 .63 (5H, m), 7.42 (2H, d, 7.20 (2H, d), 6.95 (2H, t), 6.85 (1H, t)} { ¹⁹ F-NMR: d ₆ -dimethylsulfoxide, δ (ppm); -125 (6F, d), -158.5 (3F, t), -162.5 (6F, t); internal standard = hexafluorobenzene, -159 (6F , S)} In addition, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared spectroscopic analysis (KBr tablet method).

Example 2 Synthesis of [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate (1) Synthesis of 4- (phenylthio) biphenyl 4-Bromobiphenyl 3 0.0 part, 1.7 parts of thiophenol, 2.5 parts of sodium tert-butoxide, 0.15 part of tetrakistriphenylphosphine palladium and 64.3 parts of 1-butanol were uniformly mixed and reacted at 120 ° C. for 2 hours. It was. 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) Synthesis of [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluorophenyl) borate 55% of 4-[(phenyl) sulfinyl] biphenyl synthesized in (2) And 2.0 parts of a mixture containing 45% of 4- (phenylthio) biphenyl, 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 were mixed uniformly 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 is dissolved in 27 parts of dichloromethane, charged into 61.0 parts of a 10% by weight aqueous solution of phenyl tris (pentafluorophenyl) sodium borate, and stirred at room temperature (about 25 ° C.) for 3 hours. After washing with water three times by a liquid separation operation, the solution was transferred to a rotary evaporator and the solvent was distilled off, whereby [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium phenyltris (pentafluoro). Phenyl) borate was obtained in 88% yield. The product was identified by ¹ H-NMR and ¹⁹ F-NMR {d6-dimethylsulfoxide, δ (ppm) 8.1 (2H, d), 7.6-8.0 (17H, m), 7. 3-7.6 (8H, m)} 7.20 (2H, d), 6.95 (2H, t), 6.85 (1H, t)}. { ¹⁹ F-NMR, d ₆ -dimethyl sulfoxide, δ (ppm); −125 (6 F, d), −158.5 (3 F, t), −162.5 (6 F, t); internal standard = hexa Fluorobenzene, -159 (6F, s)}. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Example 3 Synthesis of [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate (1) Synthesis of 2- (phenylthio) thioxanthone 2-chloro 11.0 parts of thioxanthone, 4.9 parts of thiophenol, 2.5 parts of potassium hydroxide and 162 parts of N, N-dimethylformamide were uniformly mixed and reacted at 130 ° C. for 9 hours. 25 ° C.) and poured into 200 parts of distilled water to precipitate the product. 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) Synthesis of [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris (pentafluorophenyl) borate 4.3 parts of 2- (phenylthio) thioxanthone synthesized in (1) While stirring 4.5 parts of 2-[(phenyl) sulfinyl] thioxanthone synthesized in (2), 4.1 parts of acetic anhydride and 110 parts of acetonitrile at 40 ° C., 2.4 parts of trifluoromethanesulfonic acid was added thereto. After slowly dropping and reacting at 40 to 45 ° C. for 1 hour, the reaction solution was cooled to room temperature (about 25 ° C.), poured into 150 parts of distilled water, extracted with chloroform, and the pH of the aqueous phase was medium. Washed with water until sex. 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, whereby [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium triflate (triflate = trifluoromethanesulfonic acid anion). ) This triflate was dissolved in 212 parts of dichloromethane and charged into 180.0 parts of a 10% by weight aqueous solution of phenyltris (pentafluorophenyl) sodium borate, and then stirred at room temperature (about 25 ° C.) for 2 hours. 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 obtain [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonylsulfonium phenyltris. (Pentafluorophenyl) borate was obtained with a yield of 95%. The product was identified by ¹ H-NMR and ¹⁹ F-NMR {d6-dimethylsulfoxide, δ (ppm) 8.72 (1H, s), 8.54 (1H, s), 8.46 (2H, d), 8.27 (1H, d), 7.76-8.10 (14H, m), 7.60-7.69 (4H, m), 7.20 (2H, d), 6.95 (2H, t), 6.85 (1H, t)}. { ¹⁹ F-NMR, d ₆ -dimethyl sulfoxide, δ (ppm); −125 (6 F, d), −158.5 (3 F, t), −162.5 (6 F, t); internal standard = hexa Fluorobenzene, -159 (6F, s)}. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

(Example 4) Synthesis of di-p-tolylodonium phenyltris (pentafluorophenyl) borate (1) Synthesis of di-p-tolyliodonium chloride 6.4 parts of ice and 20 parts of sulfuric acid were charged in a reaction vessel, and 20 ° C. Cooled to. Next, 30 parts of glacial acetic acid was charged, and 41 parts of ammonium persulfate was added at 25 ° C. or lower. After the mixture was cooled to 15 ° C., a mixture of 21.8 parts of 4-iodotoluene and 36.8 parts of toluene was added dropwise over 2 hours while maintaining the liquid temperature at 20 ° C. After stirring at 20 ° C. for 15 hours, 135 parts of 35% by weight brine was added, and the precipitated solid product was filtered off and washed with saturated brine and then with water. Furthermore, after washing with toluene and hexane, it was dried under reduced pressure. Recrystallization from acetone gave 15.9 parts of di-p-tolyliodonium chloride as pale yellow crystals (yield 46%).
(2) Synthesis of di-p-tolylodonium phenyltris (pentafluorophenyl) borate 2.8 parts of the di-p-tolyliodonium chloride obtained above was dissolved in 38 parts of methanol, and this was dissolved in phenyltris (pentafluorophenyl). ) When dripped into a container containing 61 parts of a 10% by weight aqueous solution of sodium borate and stirred for 3 hours at room temperature, a slightly viscous oil separated. The supernatant was removed and 20 parts of diethyl ether was dissolved in the oily substance, followed by washing with 20 parts of water three times, and then 75 parts of hexane was added to the organic layer to precipitate a white solid. This was filtered off, washed with hexane, and then dried under reduced pressure to obtain 6.3 parts of di-p-tolyliodonium phenyltris (pentafluorophenyl) borate (yield 78%, purity 98% or more).
The product was identified by ¹ H-NMR, ¹⁹ F-NMR { ¹ H-NMR: d ₆ -dimethyl sulfoxide, δ (ppm); 7.80 (4H, d), 7.40 (4H, d), 7.20 (2H, d), 6.95 (2H, t), 6.85 (1H, t) 2.45 (6H, s). ¹⁹ F-NMR: d ₆ -dimethyl sulfoxide, δ (ppm); -125 (6F, d), -158.5 (3F, t), -162.5 (6F, t); internal standard substance = hexafluoro Benzene, -159 (6F, s)}. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

Comparative Example 1 Synthesis of 4- (phenylthio) phenyldiphenylsulfonium tetrakis (pentafluorophenyl) borate 61.0 parts of a 10% by weight aqueous solution of phenyltris (pentafluorophenyl) borate was added to tetrakis (pentafluorophenyl) borane. 4- (phenylthio) phenyldiphenylsulfonium tetrakis (pentafluoro) in the same manner as in Example 1 except that 56.0 parts of a 10% by weight aqueous solution of lithium acid and the number of water washings after extraction with toluene were changed from 3 to 10 times. Phenyl) borate 5.3 parts was obtained (yield 62%, purity 98% or more). The product was identified by ¹ H-NMR and ¹⁹ F-NMR { ¹ H-NMR: d ₆ -dimethylsulfoxide, δ (ppm); 7.72-7.87 (12H, m), 7.54-7 .63 (5H, m), 7.42 (2H, d)} {19 F-NMR: d 6 - dimethyl sulfoxide, δ (ppm); - 128 (8F, d), - 158 (4F, t), −162.5 (8F, t); internal standard = hexafluorobenzene, −159 (6F, s)}. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

(Comparative Example 2) CPI-110A {4- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, manufactured by San Apro Corporation} was used as a comparative sulfonium salt.

(Comparative Example 3) CPI-110P {4- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, manufactured by San Apro Corporation} was used as a comparative sulfonium salt.

Comparative Example 4 Synthesis of di-p-tolyliodonium tetrakis (pentafluorophenyl) borate 61.0 parts of a 10% by weight aqueous solution of phenyltris (pentafluorophenyl) borate lithium was added to tetrakis (pentafluorophenyl) lithium borate. Di-p-tolyliodonium tetrakis (pentafluorophenyl) borate 6 in the same manner as in Example 3 except that 56.0 parts of a 10% by weight aqueous solution of the product and the number of water washing after extraction with toluene were changed from 3 times to 10 times. 0.0 part was obtained (yield 75%, purity 98% or more).
The product was identified by ¹ H-NMR, ¹⁹ F-NMR { ¹ H-NMR: d ₆ -dimethylsulfoxide, δ (ppm); 7.80 (4H, d), 7.40 (4H, d), 2.45 (6H, s). ¹⁹ F-NMR: d ₆ -dimethyl sulfoxide, δ (ppm); -128 (8F, d), -158 (4F, t), -162.5 (8F, t); internal standard = hexafluorobenzene, -159 (6F, s)}. Further, absorption of BC bond was confirmed in the vicinity of 980 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

(Comparative Example 5) Synthesis of di-p-tolyliodonium hexafluoroantimonate 61.0 parts of a 10 wt% aqueous solution of phenyltris (pentafluorophenyl) lithium borate was added to a 5 wt% aqueous solution of potassium hexafluoroantimonate. In the same manner as in Example 3 except that 20 parts of diethyl ether was replaced with 20 parts of ethyl acetate in 0 part, 3.7 parts of di-p-tolyliodonium hexafluoroantimonate was obtained (yield: 85%, Purity 98% or more). The product was confirmed by ¹ H-NMR. { ¹ H-NMR: d ₆ -dimethyl sulfoxide, δ (ppm); 7.80 (4H, d), 7.40 (4H, d), 2.45 (6H, s)}. Further, absorption of Sb—F bond was confirmed in the vicinity of 650 cm ⁻¹ by infrared absorption spectroscopic analysis (KBr tablet method).

[Evaluation of cationic polymerizability]
(Preparation of energy beam curable composition)
The photoacid generators of the present invention and comparative examples are blended in the amounts shown in Table 1 (solvent-1 (propylene carbonate), sensitizer (2,4-diethylthioxanthone), epoxide (3, 4-Epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, Dow Chemical Co., Ltd., UVR-6110)) was uniformly mixed to prepare an energy ray curable composition.

<Evaluation of photosensitivity (photocurability)>
The energy ray-curable composition obtained above was applied to a polyethylene terephthalate (PET) film with an applicator (40 μm). 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

<Adhesion evaluation>
Cello tape (registered trademark) was applied in the range of 2 cm × 1 cm of the cured film prepared in the above-described photosensitivity test, strongly pressed, peeled off perpendicularly to the cured film, and the subsequent state was visually observed. The same operation was repeated 5 times and evaluated according to the following criteria.
(Criteria)
◎: The cured film does not peel off from the substrate at all 5 times ○: Slightly peeled off only once in 5 times Δ: Slightly peeled off 2 times or more out of 5 times or larger once Things that peel off ×
: Most peeled 2 times or more out of 5 times

<Solubility evaluation>
Cyclohexanedimethanol divinyl ether (1,4-bis [(vinyloxy) methyl]), which is a cationically polymerizable compound, was added to 1 part of a 50 wt% propylene carbonate solution of various onium salts obtained in Examples 1 to 4 and Comparative Examples 1 to 5. Cyclohexane, manufactured by ISP Co., Ltd., trade name, RAPI-CURE CHVE) and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (same as above) in addition to 20 parts each and after stirring uniformly at room temperature, according to the following criteria Solubility was evaluated.
(Criteria)
Appearance ○: Uniform, transparent Δ: Haze or turbidity ×: White turbidity or salt separated

<Storage stability evaluation>
50 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (same as above) were added to 1.5 parts of a 50 wt% propylene carbonate solution of various onium salts obtained in Examples 1 to 4 and Comparative Examples 1 to 5. And uniformly mixed. The viscosity immediately after preparation of this composition and after storage for 1 month at 80 ° C. was measured at 25 ° C. and evaluated according to the following criteria. In addition, the thing whose cation part is di-p-tolyl iodonium (DTI) measured the same thing about the thing after a 5-day preservation | save at 70 degreeC, and evaluated storage stability.
(Criteria)
Change in viscosity after storage ○: Less than twice the initial viscosity Δ: More than twice the initial viscosity ×: Gelation (solidification)

<Hydrolytic evaluation (quantification of amount of HF by-produced by hydrolysis)>
1 part of various onium salts obtained in Examples 1 to 4 and Comparative Examples 1 to 5 were charged into a pressure-resistant SUS container made of interior Teflon (registered trademark), 25 parts of water (ultra pure water) was added, and sealed at 160 ° C. Heated for 3 days. After cooling to room temperature, the supernatant was collected, the amount of F ions was quantified by ion chromatography, and the concentration of F ions in water added first was calculated, and evaluated according to the following criteria. The results are shown in Table 2.
(Evaluation criteria)
F ion concentration in water after heating test after 160 ° C. × 3 days ○: 100 ppm or less Δ: 100 to less than 1000 ×: 1000 ppm or more

* 1: PTDS; 4- (phenylthio) phenyldiphenylsulfonium * 2: BPTBPS; [4- (4-biphenylthio) phenyl] -4-biphenylylphenylsulfonium * 3: TXTPTXS; [4- (2-thioxanthoni Ruthio) phenyl] phenyl-2-thioxanthonylsulfonium * 4: DTI; di-p-tolyliodonium
* 5: CHVE: cyclohexanedimethanol divinyl ether (1,4-bis [(vinyloxy) methyl] cyclohexane, manufactured by ISP, trade name, RAPI-CURE CHVE)
* 6: EP; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by DOW, trade name, UVR-6110)
* 7: Evaluation results after 70 ° C x 5 days

From Table 2, the onium borate obtained by the present invention is excellent in cationic polymerization initiating ability with respect to an epoxy resin, has good compatibility with a cationic polymerizable monomer, and the obtained cured film has excellent adhesion to a substrate. I understand that. Moreover, it is understood that the storage stability of the curable composition containing them is excellent, and the borate of the present invention is excellent in hydrolysis resistance and does not release free F ions.

[Evaluation of Positive Photoresist Composition]
<Preparation of sample for evaluation>
As shown in Table 3, 1 part by weight of component (A) which is a photoacid generator, 2,4-diethylthioxanthone as a sensitizer, and resin 40 represented by the following chemical formula (Resin-1) as resin component (B) As a resin component (C), 60 parts by weight of a novolak resin obtained by addition condensation of m-cresol and p-cresol in the presence of formaldehyde and an acid catalyst were used as solvent-2 (propylene glycol monomethyl ether acetate). And a positive photoresist composition (Examples P1 to P4) having a solid content concentration of 40% by weight was prepared.
Moreover, the comparative example was similarly performed by the compounding quantity shown in Table 3, and the positive photoresist composition (Comparative Examples P1-P4) was prepared.

<Sensitivity evaluation>
The positive resist compositions prepared in Examples P1 to P4 and Comparative Examples P1 to P4 were spin-coated on a silicon wafer substrate, and then dried to obtain a photoresist layer having a thickness of about 20 μm. This resist layer was pre-baked at 130 ° C. for 6 minutes using a hot plate. After pre-baking, pattern exposure (i-line) was performed using TME-150RSC (manufactured by Topcon Corporation), and post-exposure heating (PEB) was performed at 75 ° C. for 5 minutes using a hot plate. Thereafter, a development process for 5 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 15 μm line and space (L & S) pattern. Further, below that, the minimum exposure amount at which no residue of this pattern was observed, that is, the minimum essential exposure amount (corresponding to the sensitivity) necessary for forming the resist pattern was measured.

<Pattern shape evaluation (Lb / La)>
By the above operation, the lower side dimension La and the upper side dimension Lb of the cross section of the 15 μm L & S pattern formed on the silicon wafer substrate were measured using a scanning electron microscope, and the pattern shape was judged according to the following criteria.
○: 0.85 ≦ Lb / La ≦ 1
X: Lb / La <0.85

<Storage stability evaluation>
In addition, using the chemically amplified positive resist composition prepared above, the photosensitivity (sensitivity) was evaluated as described above immediately after preparation and after storage for 1 month at 40 ° C., and the storage stability was determined according to the following criteria. It was judged.
○: Sensitivity change after 1 month storage at 40 ° C is less than 5% of the sensitivity immediately after preparation ×: Sensitivity change after storage at 40 ° C for 1 month is 5% or more of the sensitivity immediately after preparation

<Pattern formation evaluation (peelability)>
By the above operation, a 7 μm L & S pattern was formed on the silicon wafer substrate, and the degree of pattern peeling was visually observed.
○: No peeling at all in the pattern ×: No resist pattern is formed, part of the pattern is peeled off, or the pattern falls down

Table 4 shows the results obtained under the above conditions.

  As shown in Table 4, the chemically amplified positive photoresist compositions of Examples P1 to P4 were used in a 7 μm L & S pattern evaluation, compared to the case where a conventional photoacid generator was used as in Comparative Examples P1 to P4. It was also found that the pattern formability (peelability) was excellent.

[Evaluation of negative photoresist composition]
<Preparation of sample for evaluation>
As shown in Table 5, 1 part by weight of component (E) which is a photoacid generator, 2,4-diethylthioxanthone as a sensitizer, and p-hydroxystyrene / styrene = 80 / as a component (F) which is a phenol resin. 100 parts by weight of a copolymer (Mw = 10000) consisting of 20 (molar ratio) as a component (G) which is a crosslinking agent, hexamethoxymethylmelamine (trade name “Nicalak MW-390” manufactured by Sanwa Chemical Co., Ltd.) As a component (H) which is 20 parts by weight of crosslinked fine particles, a copolymer (average particle size) of butadiene / acrylonitrile / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 64/20/8/6/2 (% by weight) 10 parts by weight of a diameter = 65 nm, Tg = −38 ° C., and component (I) as an adhesion assistant, γ-glycidoxypropyltrimethoxysilane ( A negative photoresist composition of the present invention (Examples N1 to N4) obtained by uniformly dissolving 5 parts by weight of a product name “S510” manufactured by Rosso Co., Ltd. in 145 parts by weight of solvent-3 (ethyl lactate) Was prepared.
Moreover, the comparative example was similarly performed by the compounding quantity shown in Table 5, and the positive photoresist composition (Comparative Examples N1-N4) was prepared.

<Sensitivity evaluation>
Each composition was spin-coated on a silicon wafer substrate, and then heat-dried at 110 ° C. for 3 minutes using a hot plate to obtain a resin coating film having a thickness of about 20 μm. Then, pattern exposure (i line | wire) 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 15 μm line and space pattern. Further, the minimum essential exposure amount (corresponding to the sensitivity) necessary for forming a pattern having a remaining film ratio of 95% or more indicating the ratio of the remaining film before and after development was measured.

<Pattern shape evaluation (Lb / La)>
By the above operation, the lower side dimension La and the upper side dimension Lb of the cross section of the 15 μm L & S pattern formed on the silicon wafer substrate were measured using a scanning electron microscope, and the pattern shape was judged according to the following criteria.
○: 0.85 ≦ Lb / La ≦ 1
X: Lb / La <0.85

<Storage stability evaluation>
In addition, using the chemically amplified negative resist composition prepared above, the photosensitivity (sensitivity) was evaluated as described above immediately after preparation and after storage for 1 month at 40 ° C., and the storage stability was determined according to the following criteria. It was judged.
○: Sensitivity change after 1 month storage at 40 ° C is less than 5% of the sensitivity immediately after preparation ×: Sensitivity change after storage at 40 ° C for 1 month is 5% or more of the sensitivity immediately after preparation

<Pattern formation evaluation (peelability)>
By the above operation, a 7 μm L & S pattern was formed on the silicon wafer substrate, and the degree of pattern peeling was visually observed.
○: No peeling at all in the pattern ×: No resist pattern is formed, part of the pattern is peeled off, or the pattern falls down

Table 6 shows the results obtained under the above conditions.

  As shown in Table 6, the chemically amplified positive photoresist compositions of Examples N1 to N4 were used in a 7 μm L & S pattern evaluation, compared to the case of using a conventional photoacid generator as in Comparative Examples N1 to N4. It was also found that the pattern formability (peelability) was excellent.

The onium borate salt of the present invention includes paints, coating agents, inks, inkjet inks, 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 (permanent film materials such as surface protection films for semiconductor elements, interlayer insulation films, planarization films, etc.), resists for MEMS, photosensitive materials, various adhesives, molding materials, casting materials, putty, glass fibers It is suitably used as a photoacid generator for use in impregnating agents, sealing materials, sealing materials, encapsulating materials, optical semiconductor (LED) encapsulating materials, nanoimprint materials, photofabrication, micro stereolithography materials, and the like.

Claims (23)

An onium borate salt represented by the general formula (1).

[In Formula (1), A represents an atom having a valence m of Group VIA to Group VIIA (CAS notation), m is an integer of 1 or 2, and n is an integer of 0 to 3. R is an organic group bonded to A and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or Represents an alkynyl group having 2 to 30 carbon atoms, and R represents alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy , Alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, glycidyloxy, oxetanylmethyloxy, vinyloxyethoxy, amino, cyano, nitro groups, and at least one selected from the group consisting of halogen It can have. The number of R is m + n (m−1) +1, and may be the same as or different from each other. In addition, two or more R's are each directly or —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ′ —, —CO—, —COO—, —CONH—, carbon number It may be bonded via 1 to 3 alkylene or phenylene groups to form a ring structure containing atom A. Here, R ′ is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
D is a structure represented by the following general formula (2),

In the formula (2), E represents a divalent group of an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a heterocyclic compound having 8 to 20 carbon atoms, and E represents 1 to 1 carbon atoms. It may be substituted with at least one selected from the group consisting of 8 alkyls, C 1-8 alkoxys, C 6-10 aryls, hydroxy, cyano, nitro groups and halogens. G is -O -, - S -, - SO -, - SO 2 -, - NH -, - NR '-, - CO -, - COO -, - CONH-, alkylene or phenylene group having 1 to 3 carbon atoms Represents. a is an integer of 0-5. a + 1 E and a G may be the same or different. Here, R ′ is the same as described above.
X ⁻ is a counter ion of onium. The number thereof is n + 1 per molecule, at least one of which is a borate anion represented by the general formula (3), and the other may be another anion.
[
(Y) _b B (Ar) _4-b ] (3)
In General Formula (3), Y is an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms, and the aryl group or heterocyclic group is an alkyl group having 1 to 12 carbon atoms or 3 carbon atoms. -6 cycloalkyl group, C1-C6 alkoxy group, C1-C6 alkylthio group, C6-C12 arylthio group, C2-C7 alkylcarbonyl group, C2-C7 It may be substituted with at least one selected from the group consisting of an alkoxycarbonyl group, a phenyl group and a benzoyl group, and when there are a plurality of substituents, they may be the same or different. Ar represents a phenyl group substituted with at least one hydrogen atom and at least one selected from the group consisting of perfluoroalkyl, perfluoroalkoxy and halogen. b is an integer of 1 to 3. b Y or 4-b Ar may be the same or different. ] The onium borate salt according to claim 1, wherein A is S (sulfur) or I (iodine). At least one of R is an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms, and these are alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthio Carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, glycidyloxy, oxetanylmethyloxy, vinyloxyethoxy, amino, cyano, nitro groups The onium borate salt according to claim 1 or 2, which may be substituted with at least one selected from the group consisting of halogen and halogen. R is an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms, and these are alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl , Acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, glycidyloxy, oxetanylmethyloxy, vinyloxyethoxy, amino, cyano, nitro and The onium borate salt according to claim 1, which may be substituted with at least one selected from the group consisting of halogens, and may be the same or different from each other. The onium borate salt according to any one of claims 1 to 4, wherein D is at least one group selected from the following group.

The onium borate salt according to any one of claims 1 to 5, wherein n is 0 or 1. The onium ion of general formula (1) is [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium, [4- (2-thioxanthonylthio) phenyl] phenyl-2-thioxanthonyl Sulfonium, triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy)] Phenyl] sulfonio} phenyl] sulfide, bis {4- [bis (4-fluorophenyl) sulfonio] phenyl} sulfide, 4- (4-benzoyl-2-chlorophenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-Benzoylphenylthio) phenyldipheny Rusulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene- 2-yldiphenylsulfonium, 2-[(di-p-tolyl) sulfonio] thioxanthone, 2-[(diphenyl) sulfonio] thioxanthone, 4- [4- (4-tert-butylbenzoyl) phenylthio] phenyldi-p-tolyl Sulfonium, 4- (4-benzoylphenylthio) phenyldiphenylsulfonium, 5- (4-methoxyphenyl) thiantrenium, 5-phenylthiantrenium, diphenylphenacylsulfonium, (4-hydroxyphenyl) methylbenzylsulfonium, ( 2-naphthyl) methyl [ (1-Ethoxycarbonyl) ethyl] sulfonium, (4-hydroxyphenyl) methylphenacylsulfonium, octadecylmethylphenacylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4- Methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4-decyloxy) phenyliodonium, [4- (2-hydroxytetradecyloxy) phenyl] phenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium Or the onium borate salt of Claim 1 or 2 which is 4-isobutylphenyl (p-tolyl) iodonium. In the borate anion represented by the general formula (3), Y 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 any one of claims 1 to 7, which is phenyl substituted by an atom. The onium borate salt according to claim 8, wherein Y is a phenyl group, a naphthyl group or an anthracenyl group. The onium borate salt according to claim 8 or 9, wherein Ar is a pentafluorophenyl or bis (trifluoromethyl) phenyl group. The onium borate salt according to any one of claims 8 to 10, wherein b is 1 in the borate anion represented by the general formula (3). Borate anion represented by the general formula (3) _{[(C 6 H 5) B} (C 6 F 5) 3] -, or _{[(C 6 H 5) B} (C 6 H 3 (CF 3) 2) The onium borate salt according to claim 8, which is ₃ ] ^- . It consists of at least 1 sort (s) chosen from the onium borate salt in any one of Claims 1-12, The photo-acid generator characterized by the above-mentioned. An energy ray-curable composition comprising the photoacid generator according to claim 13 and a cationically polymerizable compound. A cured product obtained by curing the energy beam curable composition according to claim 14.   A chemical amplification type positive photo, comprising: a component (A) comprising the photoacid generator according to claim 13; and a component (B) which is a resin whose solubility in alkali is increased by the action of an acid. Resist composition.   The component (B) comprises at least one resin selected from the group consisting of a novolak resin (B1), a polyhydroxystyrene resin (B2), and an acrylic resin (B3). Chemically amplified positive photoresist composition.   The chemically amplified positive photoresist composition according to claim 16 or 17, further comprising an alkali-soluble resin (C) and an acid diffusion controller (D).   A laminating step of laminating a photoresist layer having a film thickness of 10 to 150 μm comprising the chemically amplified positive photoresist composition according to any one of claims 16 to 18 on a support; A method for producing a resist pattern, comprising: an exposure step of selectively irradiating light or radiation to a photoresist laminate, and a development step of developing the photoresist laminate after the exposure step to obtain a resist pattern .   A chemical amplification comprising a component (E) comprising the photoacid generator according to claim 13, a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and a crosslinking agent component (G). Type negative photoresist composition.   21. The chemically amplified negative photoresist composition according to claim 20, further comprising a crosslinked fine particle component (H).   The chemically amplified negative photoresist composition according to claim 21, further comprising an adhesion assistant component (I). A cured product obtained by curing the chemically amplified negative photoresist composition according to any one of claims 20 to 22.