JP2014205624A - Onium borate-based acid generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acid generator and the like containing no toxic metal, having sufficient cationic polymerization performance and crosslinking performance, giving sufficient reliability particularly in electric characteristics (insulation reliability) of a cured product that uses the acid generator.SOLUTION: The acid generator contains an onium borate expressed by general formula (1) shown below. A thermally curable or active energy ray-curable composition is provided, which comprises the above acid generator and a cationic polymerizable compound. A chemically amplified negative photoresist composition is provided, which comprises a component (A) comprising the above acid generator, a component (B) that is an alkali-soluble resin having a phenolic hydroxyl group, and a crosslinking agent component (C).

Description

The present invention firstly relates to an acid generator, and more particularly to an onium borate salt acid generator.
Secondly, the present invention relates to a heat or active energy ray-curable composition containing the acid generator and a cured product obtained by curing the composition.
Thirdly, the present invention relates to a chemically amplified negative photoresist composition containing the acid generator and a cured product obtained by curing the composition.

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

By the way, the cationic polymerization initiator (acid generator) described in these specifications contains BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ as anions. Curing performance and cross-linking reaction performance with an acid catalyst differ depending on the type of anion, and improve in the order of BF ₄ ⁻ <PF ₆ ⁻ <AsF ₆ ⁻ <SbF ₆ ⁻ . However, the polymerization and crosslinking performance good _AsF ⁶ -, SbF ₆ ^- cationic polymerization initiator containing (acid generating agent), As, use applications are limited from toxicity problems of Sb, SbF ₆ ^- salt stereolithography It is only used for limited purposes. Therefore, in general, PF 6 poor polymerization or crosslinking performance ^_- the salts are utilized, PF 6 ^_- salt, for example, SbF 6 ^_- to obtain the cure rate comparable to salt, the latter 10 times more It is necessary to add an amount of unreacted initiator (acid generator), the amount of solvent used to dissolve the initiator (acid generator) or the decomposition of the initiator (acid generator) as necessary Since the remaining amount of the product increases, the physical properties of the cured product may be impaired. Further, in common with these anions, HF is produced as a by-product due to decomposition of the initiator (acid generator). Particularly in electronic materials and semiconductor materials, this is an important problem in electrical characteristics (insulation reliability). There is a need for a cationic polymerization initiator (acid generator) that can provide sufficient reliability even in such applications.

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

In the above background, the first object of the present invention is to contain no toxic metal, have sufficient cationic polymerization performance and cross-linking reaction performance, and cured products using this have particularly electrical characteristics (insulation reliability). It is to provide an acid generator (cationic polymerization initiator) that can provide sufficient reliability.
The second object of the present invention is to provide a heat or active energy ray-curable composition and a cured product using the acid generator.
A third object of the present invention is to provide a chemically amplified negative photoresist composition and a cured product using the acid generator.

The present inventor has found an acid generator suitable for the above purpose.
That is, this invention is an acid generator characterized by including the onium borate salt represented by following General formula (1).

[In Formula (1), R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 18 carbon atoms or Ar, provided that at least one is Ar,
Ar is an aryl group having 6 to 14 carbon atoms (not including the carbon number of the following substituents), wherein some of the hydrogen atoms in the aryl group are alkyl groups having 1 to 18 carbon atoms and halogen atoms are Substituted alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group having 6 to 14 carbon atoms, nitro group, hydroxyl group, cyano group, -OR ⁶ alkoxy or aryloxy group ^represented, acyl group represented by R 7 ^CO-, acyloxy group represented by R 8 COO-, alkylthio group or arylthio group represented by -SR ^{9, -NR} 10 ^{R 11} May be substituted with an amino group represented by
R ^{6 to} R ⁹ are each an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms,
R ¹⁰ and R ¹¹ are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms;
E represents an element having a valence of n from Group 15 to Group 17 (IUPAC notation),
n is an integer of 1 to 3,
R ⁵ is an organic group bonded to E, the number of R ⁵ is n + 1, and (n + 1) R ^{5 s} may be the same or different from each other, and two or more R ⁵ are Ring structure containing element E directly or each other through —O—, —S—, —SO—, —SO ₂ —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group May be formed. ]

  The present invention is also a heat or active energy ray-curable composition comprising the above acid generator and a cationic polymerizable compound, and a cured product obtained by curing these.

  The present invention also provides a chemical amplification comprising the component (A) comprising the above acid generator, the component (B) which is an alkali-soluble resin having a phenolic hydroxyl group, and the crosslinking agent component (C). Type negative photoresist composition and a cured product obtained by curing these.

The acid generator of the present invention does not contain a highly toxic element such as Sb, has sufficient cationic polymerization performance and crosslinking reaction performance, and a composition using this is used as active energy such as heat and ultraviolet rays. The cured product cured by irradiation with radiation has good electrical characteristics (insulation reliability).

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

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

[In Formula (1), R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 18 carbon atoms or Ar, provided that at least one is Ar,
Ar is an aryl group having 6 to 14 carbon atoms (not including the carbon number of the following substituents), wherein some of the hydrogen atoms in the aryl group are alkyl groups having 1 to 18 carbon atoms and halogen atoms are Substituted alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group having 6 to 14 carbon atoms, nitro group, hydroxyl group, cyano group, -OR ⁶ alkoxy or aryloxy group ^represented, acyl group represented by R 7 ^CO-, acyloxy group represented by R 8 COO-, alkylthio group or arylthio group represented by -SR ^{9, -NR} 10 ^{R 11} May be substituted with an amino group represented by
R ^{6 to} R ⁹ are each an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms,
R ¹⁰ and R ¹¹ are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms;
E represents an element having a valence of n from Group 15 to Group 17 (IUPAC notation),
n is an integer of 1 to 3,
R ⁵ is an organic group bonded to E, the number of R ⁵ is n + 1, and (n + 1) R ^{5 s} may be the same or different from each other, and two or more R ⁵ are Ring structure containing element E directly or each other through —O—, —S—, —SO—, —SO ₂ —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group May be formed. ]

In general formula (1), as the alkyl group having 1 to 18 carbon atoms in R ^{1 to} R ⁴ , a linear alkyl group (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2- Ethylhexyl and 1,1,3,3-tetramethylbutyl), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.).
From the viewpoint of catalytic activity in the cationic polymerization reaction, those substituted with a halogen atom, a nitro group or a cyano group are preferred, and those substituted with a fluorine atom are more preferred.

In general formula (1), as the aryl group having 6 to 14 carbon atoms (not including the carbon number of the following substituents) in R ^{1 to} R ⁴ , a monocyclic aryl group (such as phenyl), a condensed polycycle Monocyclic heterocycles such as formula aryl groups (naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl and naphthoquinolyl) and aromatic heterocyclic hydrocarbon groups (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, phenoxathiniini , Chromanyl, isochromanyl, coumarinyl, dibenzothienyl, Kisantoniru, Chiokisantoniru, dibenzofuranyl, etc. fused polycyclic heterocyclic ring).
As the aryl group, in addition to the above, a part of hydrogen atoms in the aryl group is an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 8 carbon atoms substituted by a halogen atom, and an alkenyl having 2 to 18 carbon atoms. Group, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, an alkoxy group represented by —OR ⁶ or an aryloxy group, and R ⁷ CO—. It may be substituted with an acyl group, an acyloxy group represented by R ⁸ COO—, an alkylthio group or arylthio group represented by —SR ⁹ , an amino group represented by —NR ¹⁰ R ¹¹ , or a halogen atom.

In the above substituent, the alkenyl group having 2 to 18 carbon atoms may be a linear or branched alkenyl group (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1- Methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, etc.), cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl) and An arylalkenyl group (styryl, cinnamyl, etc.) is mentioned.

In the above substituent, the alkynyl group having 2 to 18 carbon atoms is a linear or branched alkynyl group (ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl- 2-propynyl, 1,1-dimethyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 3-methyl-1-butynyl, 1-decynyl , 2-decynyl, 8-decynyl, 1-dodecynyl, 2-dodecynyl and 10-dodecynyl) and arylalkynyl groups (phenylethynyl etc.).

In the above substituent, the alkyl group having 1 to 8 carbon atoms substituted by a halogen atom may be a linear alkyl group (trifluoromethyl, trichloromethyl, pentafluoroethyl, 2,2,2-trichloroethyl, 2,2, 2-trifluoroethyl, 1,1-difluoroethyl, heptafluoro-n-propyl, 1,1-difluoro-n-propyl, 3,3,3-trifluoro-n-propyl, nonafluoro-n-butyl, 3 , 3,4,4,4-pentafluoro-n-butyl, perfluoro-n-pentyl, perfluoro-n-octyl, etc.), branched alkyl groups (hexafluoroisopropyl, hexachloroisopropyl, hexafluoroisobutyl, nonafluoro- tert-butyl, etc.), cycloalkyl groups (pentafluorocyclopropyl, nonaf) Orosi black butyl, perfluorocyclopentyl and perfluorocyclohexyl, etc.) and bridged cyclic alkyl group (perfluoro adamantyl, etc.).

In the above substituents, an alkoxy group represented by —OR ⁶ , an acyl group represented by R ⁷ CO—, an acyloxy group represented by R ⁸ COO—, an alkylthio group represented by —SR ⁹ , —NR ¹⁰ the amino group represented by R ^11, include alkyl groups having 1 to 8 carbon atoms as R ⁶ to R ^11, include alkyl groups having 1 to 8 carbon atoms among the alkyl groups mentioned specifically .

In the above substituent, an aryloxy group represented by -OR ⁶ , an acyl group represented by R ⁷ CO-, an acyloxy group represented by R ⁸ COO-, an arylthio group represented by -SR ⁹ , -NR ^As R ^{6 to} R ¹¹ of the amino group represented by ¹⁰ R ¹¹ , an aryl group having 6 to 14 carbon atoms can be mentioned, and specifically, the above aryl group having 6 to 14 carbon atoms can be mentioned.

Examples of the alkoxy group represented by —OR ⁶ include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, neo-pentoxy and 2- Examples include methylbutoxy.
Examples of the aryloxy group represented by —OR ⁶ include phenoxy and naphthoxy.
Examples of the acyl group represented by R ⁷ CO— include acetyl, propanoyl, butanoyl, pivaloyl and benzoyl.
Examples of the acyloxy group represented by R ⁸ COO— include acetoxy, butanoyloxy and benzoyloxy.
Examples of the alkylthio group represented by —SR ⁹ include methylthio, ethylthio, butylthio, hexylthio, cyclohexylthio and the like.
Examples of the arylthio group represented by —SR ⁹ include phenylthio and naphthylthio.
Examples of the amino group represented by —NR ¹⁰ R ¹¹ include methylamino, ethylamino, propylamino, dimethylamino, diethylamino, methylethylamino, dipropylamino, dipropylamino and piperidino.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Among these substituents, from the viewpoint of catalytic activity in the cationic polymerization reaction, a C1-C8 alkyl group substituted with a halogen atom, a halogen atom, a nitro group, or a cyano group is preferable, and a C1-C8 group substituted with a fluorine atom. Of these, an alkyl group and a fluorine atom are more preferred.

R ⁵ in formula (1) represents an organic group bonded to E and may be the same or different. Examples of R ⁵ include an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and an alkynyl group having 2 to 18 carbon atoms. Alkyl group having 1 to 18 carbon atoms, alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group having 6 to 14 carbon atoms, nitro group, hydroxyl group, cyano group, alkoxy represented by —OR ⁶ A group or an aryloxy group, an acyl group represented by R ⁷ CO—, an acyloxy group represented by R ⁸ COO—, an alkylthio group or an arylthio group represented by —SR ⁹ , and represented by —NR ¹⁰ R ¹¹ It may be substituted with an amino group or a halogen atom.

As the aryl group having 6 to 14 carbon atoms, the alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, and the alkynyl group having 2 to 18 carbon atoms in the organic group, R in the general formula (1) It may be the same as those described in ¹ to R ^4.

Further, two or more R ⁵ groups may be bonded directly to each other or —O—, —S—, —SO—, —SO ₂ —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group. A ring structure containing the element A may be formed through the intermediate structure.

E in the formula (1) represents an element having a valence n of Group 15 to Group 17 (IUPAC notation), and forms an onium ion [E ⁺ ] by combining with an organic group R ⁵ . Among the elements of group 15 to group 17, preferred are O (oxygen), N (nitrogen), P (phosphorus), S (sulfur) or I (iodine), and the corresponding onium ions are oxonium, ammonium, Phosphonium, sulfonium, iodonium. Among these, ammonium, phosphonium, sulfonium, and iodonium that are stable and easy to handle are preferable, and sulfonium and iodonium that are excellent in cationic polymerization performance and crosslinking reaction performance are more preferable.
n represents the valence of the element E and is an integer of 1 to 3.

Specific examples of the oxonium ion include trimethyloxonium, diethylmethyloxonium, triethyloxonium, oxonium such as tetramethylenemethyloxonium; 4-methylpyrrinium, 2,4,6-trimethylpyrrinium, 2,6 -Pyririnium such as di-tert-butylpyrrinium and 2,6-diphenylpyrrinium; chromium and isochromenium such as 2,4-dimethylchromenium and 1,3-dimethylisochromenium.

Specific examples of ammonium ions include tetraalkylammonium such as tetramethylammonium, ethyltrimethylammonium, diethyldimethylammonium, triethylmethylammonium, tetraethylammonium; N, N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidi Pyrrolidinium such as N, N, N-diethylpyrrolidinium; N, N′-dimethylimidazolinium, N, N′-diethylimidazolinium, N-ethyl-N′-methylimidazolinium, 1,3 4-trimethylimidazolinium, imidazolinium such as 1,2,3,4-tetramethylimidazolinium; tetrahydropyrimidinium such as N, N′-dimethyltetrahydropyrimidinium; N, N′-dimethylmol Such as holinium Piperidinium such as N, N′-diethylpiperidinium; Pyridinium such as N-methylpyridinium, N-benzylpyridinium, N-phenacylpyridium; Imidazolium such as N, N′-dimethylimidazolium; N -Quinolium such as methyl quinolium, N-benzyl quinolium, N-phenacyl quinolium; isoquinolium such as N-methylisoquinolium; thiazonium such as benzyl benzothiazonium, phenacyl benzothiazonium; benzyl acridium And acridium such as phenacyl acridium.

Specific examples of phosphonium ions include tetraarylphosphonium such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis (2-methoxyphenyl) phosphonium, tetrakis (3-methoxyphenyl) phosphonium, tetrakis (4-methoxyphenyl) phosphonium. Triarylphosphonium such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, triphenylbutylphosphonium; triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium , Tetraalkyl such as tributylphenacylphosphonium Suhoniumu and the like.

Specific examples of the sulfonium ion 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-tolyl Sulfonium, 4- (4-methoxyphenylthio) phenylbis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (phenylthio) pheny Bis (4-methoxyphenyl) sulfonium, 4- (phenylthio) phenyldi-p-tolylsulfonium, [4- (4-biphenylylthio) phenyl] -4-biphenylylphenylsulfonium, [4- (2-thioxanthoni Ruthio) phenyl] diphenylsulfonium, bis [4- (diphenylsulfonio) phenyl] sulfide, bis [4- {bis [4- (2-hydroxyethoxy) phenyl] sulfonio} phenyl] sulfide, bis {4- [bis ( 4-fluorophenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methylphenyl) sulfonio] phenyl} sulfide, bis {4- [bis (4-methoxyphenyl) sulfonio] phenyl} sulfide, 4- ( 4-Benzoyl-2-chlorophenylthio) phenylbis (4-fluoro Phenyl) sulfonium, 4- (4-benzoyl-2-chlorophenylthio) phenyldiphenylsulfonium, 4- (4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium, 4- (4-benzoylphenylthio) phenyldiphenyl Sulfonium, 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- (9-oxo-9H-thioxanthen-2-yl) thiophenyl-9-oxo -9H-thioxanthen-2-ylfe Rusulfonium, 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) thiaanthrhenium, 5-phenylthiaanthrhenium, 5-tolylthia Triarylsulfonium such as anthrenium, 5- (4-ethoxyphenyl) thiaanthrhenium, 5- (2,4,6-trimethylphenyl) thiaanthrhenium; diphenylphenacylsulfonium, diphenyl-4-nitrophenacylsulfonium, diphenyl Benzylsulfo Diarylsulfonium such as nium, diphenylmethylsulfonium; phenylmethylbenzylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 4-methoxyphenylmethylbenzylsulfonium, 4-acetocarbonyloxyphenylmethylbenzylsulfonium, 4-hydroxyphenyl (2-naphthylmethyl) ) Methylsulfonium, 2-naphthylmethylbenzylsulfonium, 2-naphthylmethyl (1-ethoxycarbonyl) ethylsulfonium, phenylmethylphenacylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, 4-methoxyphenylmethylphenacylsulfonium, 4- Acetocarbonyloxyphenylmethylphenacylsulfonium, 2-naphthylmethylphenacylsulfo Monoarylsulfonium such as um, 2-naphthyloctadecylphenacylsulfonium, 9-anthracenylmethylphenacylsulfonium; dimethylphenacylsulfonium, phenacyltetrahydrothiophenium, dimethylbenzylsulfonium, benzyltetrahydrothiophenium, octadecylmethylphena And trialkylsulfonium such as silsulfonium.

Specific examples of iodonium ions include diphenyliodonium, di-p-tolyliodonium, bis (4-dodecylphenyl) iodonium, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium, bis (4- Examples include iodonium ions such as decyloxy) phenyliodonium, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium, 4-isopropylphenyl (p-tolyl) iodonium and 4-isobutylphenyl (p-tolyl) iodonium.

Preferred examples of the anion structure of the acid generator represented by the general formula (1) include those represented by the following chemical formulas (A-1) to (A-5).

  The onium borate salt (acid generator) represented by the formula (1) is dissolved in a solvent that does not inhibit polymerization or crosslinking reaction in advance in order to facilitate dissolution in a cationically polymerizable compound or a chemically amplified negative resist composition. You may keep it.

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

  When a solvent is used, the use ratio of the solvent is preferably 15 to 1000 parts by weight, more preferably 30 parts per 100 parts by weight of the onium borate salt (acid generator) represented by the formula (1) of the present invention. -500 parts by weight. The solvent to be used may be used independently or may use 2 or more types together.

  The heat or active energy ray-curable composition (hereinafter referred to as curable composition) of the present invention comprises the acid generator and a cationically polymerizable compound.

Examples of the cationic polymerizable compound that is a constituent of the curable composition include cyclic ethers (epoxides and oxetanes), ethylenically unsaturated compounds (vinyl ether and styrene, etc.), bicycloorthoesters, spiroorthocarbonates, spiroorthoesters, and the like. {(For example, as the cationic polymerizable compound component in the active energy ray-curable composition, JP-A-11-060996, JP-A-09-302269, JP-A-2003-026993, JP-A-2002-206017, JP-A-11-349895, JP-A-10-212343, JP-A-2000-119306, JP-A-10-67812, JP-A-2000-186071, JP-A-08-85775, JP-A-08-134405, Special Open 2008-20838, JP 2 08-20839, JP 2008-20841, JP 2008-26660, JP 2008-26644, JP 2007-277327, 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 Materials" (1992, CMC), Technical Information Association "UV Curing Failure / Inhibition Causes "Countermeasures" (2003, Technical Information Association), coloring materials, 68, (5), 286-293 (1995), fine chemicals, 29, (19), 5-14 (2000), etc. These are heat. It can be used as a cationically polymerizable compound component in the curable composition.}.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The content of the onium borate salt (acid generator) represented by the formula (1) of the present invention in the curable composition is preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound, More preferably, it is 0.1-10 weight part. 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 depends on various factors such as the nature of the cationically polymerizable compound, the type of active energy rays and the irradiation amount (when using active energy rays), heating temperature, curing time, humidity, and coating thickness. It is determined by considering and is not limited to the above range.

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

  As the sensitizer, known sensitizers (JP-A-11-279212 and JP-A-09-183960) can be used, such as benzoquinone {1,4-benzoquinone, 1,2-benzoquinone, etc.}; naphthoquinone { 1,4-naphthoquinone, 1,2-naphthoquinone, etc.}; anthraquinone {2-methylanthraquinone, 2-ethylanthraquinone, etc.}, 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-ethylthioxanthate , 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone}; phenothiazine {phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, N-phenylphenothiazine, etc.}; xanthone; naphthalene {1-naphthol, 2 -Naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, 1,4-dihydroxynaphthalene, 4-methoxy-1-naphthol and the like}; ketone {dimethoxyacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 4-benzoyl-4′-methyldiphenyl sulfide and the like}; carbazole {N-phenylcarbazol N-ethylcarbazole, poly-N-vinylcarbazole and N-glycidylcarbazole etc.}; chrysene {1,4-dimethoxychrysene and 1,4-di-α-methylbenzyloxychrysene etc.}; phenanthrene {9-hydroxyphenanthrene , 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.}.

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

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

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

  As the filler, known fillers can be used, such as fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate and lithium aluminum silicate. Can be mentioned.

When the filler is contained, the content of the filler is preferably 50 to 600,000 parts by weight, more preferably 300 to 200,000 parts by weight with respect to 100 parts of the acid generator.

  As the conductive particles, known conductive particles can be used. Metal particles such as Ni, Ag, Au, Cu, Pd, Pb, Sn, Fe, Ni, and Al, and plated metal obtained by further metal plating the metal particles Particles, plated resin particles obtained by metal plating on resin particles, and particles of a conductive material such as carbon can be used.

  When the conductive particles are contained, the content of the conductive particles is preferably 50 to 30000 parts by weight, and more preferably 100 to 20000 parts by weight with respect to 100 parts of the acid generator.

  As the antistatic agent, known antistatic agents can be used, and examples include nonionic antistatic agents, anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents, and polymeric antistatic agents. .

  When the antistatic agent is contained, the content of the antistatic agent is preferably 0.1 to 20000 parts by weight, more preferably 0.6 to 5000 parts by weight with respect to 100 parts of the acid generator.

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

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

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

As the flow control agent, known flow control agents can be used, and examples thereof include hydrogenated castor oil, polyethylene oxide, organic bentonite, colloidal silica, amide wax, metal soap, and acrylate polymer.
As the light stabilizer, a known light stabilizer or the like can be used, and an ultraviolet absorbing stabilizer {benzotriazole, benzophenone, salicylate, cyanoacrylate, and derivatives thereof}; radical scavenging stabilizer {hindered amine, 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 an antifoaming agent, a flow control agent, a light stabilizer, an antioxidant, an adhesion promoter, an ion scavenger, or a coloring inhibitor is contained, each content is 0 with respect to 100 parts of the acid generator. 0.1 to 20000 parts by weight is preferable, and 0.5 to 5000 parts by weight is more preferable.

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

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

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

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

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

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

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

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

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

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

  The curable composition of the present invention comprises a cationically polymerizable compound, an acid generator, and optionally an additive, which are uniformly mixed and dissolved at room temperature (about 20 to 30 ° C.) or optionally heated (about 40 to 90 ° C.). Or can be prepared by kneading with three rolls or the like.

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

The irradiation time of the energy beam is affected by the energy beam intensity and the energy beam permeability to the energy beam curable composition, but about 0.1 to 10 seconds is sufficient at room temperature (about 20 to 30 ° C.). It is. However, it may be preferable to spend more time when energy beam permeability is low or when the energy beam curable composition is thick. Most energy ray-curable compositions are cured by cationic polymerization 0.1 seconds to several minutes after irradiation with energy rays, but if necessary, after irradiation with energy rays, room temperature (about 20 to 30 ° C.) to 250. It is also possible to heat and cure at a temperature of several seconds to several hours.

Among the curable compositions of the present invention, the thermosetting composition can generate an acid from an acid generator by heating, and a cationically polymerizable compound can be polymerized or crosslinked to obtain a cured product. The temperature required for curing is not particularly limited as long as curing proceeds sufficiently and does not deteriorate the substrate, but is preferably 50 ° C to 300 ° C, more preferably 60 ° C to 250 ° C. Although the heating time varies depending on the heating temperature, several minutes to several hours are preferable in terms of productivity.

Here, the base material is a material for applying or filling the curable composition of the present invention, and known materials can be used as appropriate. For example, resin films such as PET film, polypropylene film, polyimide film, metal foils such as aluminum foil, substrates such as glass, copper, and aluminum, devices, light-emitting diode elements, transistors, integrated circuits, and the like are also used as substrates in the present invention. Elements or circuits that are included or formed on the substrate described above are also included in the substrate of the present invention.

  Specific applications of the curable composition of the present invention include paints, coating agents, various coating materials (hard coats, antifouling coatings, antifogging coatings, touchproof coatings, optical fibers, etc.), and the back of adhesive tapes. Treatment agent, Release coating material for release sheet for adhesive labels (release paper, release plastic film, release metal foil, etc.), printing plate, dental material (dental compound, dental composite) ink, inkjet ink, positive resist (Connecting terminals and wiring pattern formation for manufacturing electronic parts such as circuit boards, CSPs, and MEMS elements), resist films, liquid resists, negative resists (semiconductor elements and transparent electrodes for FPD (ITO, IZO, GZO), etc.) Protective film, interlayer insulating film, permanent film material such as planarization film), MEMS resist, positive photosensitive material, negative photosensitive material, each Adhesives (temporary fixing agents for various electronic parts, HDD adhesives, pickup lens adhesives, FPD functional film (deflecting plates, antireflection films, etc.) adhesives, circuit forming and semiconductor sealing insulating films , Anisotropic conductive adhesive (ACA), film (ACF), paste (ACP), etc., holographic resin, FPD material (color filter, black matrix, partition material, photospacer, rib, alignment film for liquid crystal, FPD Sealing materials, etc.), optical members, molding materials (for building materials, optical components, lenses), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, flip chips, COF and other chip sealing materials , CSP or BGA packaging encapsulant, optical semiconductor (LED) encapsulant, optical waveguide material, nanoimprint material, photofabrication, and micro photofabrication Use materials and the like, in particular resulting cured product is excellent in electrical characteristics (insulating reliability), it is ideal for electronic components and circuit forming material applications.

  Since the acid generator of the present invention generates a strong acid even when irradiated with light, the chemical amplification type known in the art (JP 2003-267968 A, JP 2003-261529 A, JP 2002-193925 A, etc.) is known. It can also be used as an acid generator for resist materials.

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

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

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

  When such other conventionally known acid generators are used in combination, the ratio of use may be arbitrary, but the other acid generator is usually 10 to 900 parts by weight with respect to 100 parts by weight of the acid generator of the present invention. The amount is preferably 25 to 400 parts by weight.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The cured product in the present invention is obtained by curing the chemically amplified negative photoresist composition.
The above-mentioned chemically amplified negative photoresist composition according to the present invention has a high residual film ratio and excellent resolution, and the cured product has an electrical insulating property, thermal shock property, heat resistant colorability (transparency). The cured product can be suitably used as a semiconductor element, a transparent electrode for display, a surface protective film, a planarizing film, an interlayer insulating film material, etc. for electronic components such as semiconductor packages and displays. .

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, and heat processing (henceforth this heat processing is called "PEB") is performed, and reaction with a phenol resin (B) and a crosslinking agent (C) is accelerated | stimulated. Subsequently, it develops with an alkaline developing solution, A desired pattern can be obtained by melt | dissolving and removing an unexposed part. Furthermore, a cured film can be obtained by performing a heat treatment in order to develop insulating film characteristics.

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

After the exposure, the PEB treatment is performed to promote the curing reaction of the phenol resin (B) and the crosslinking agent (C) by the generated acid. The PEB condition varies depending on the blending amount of the resin composition, the used film thickness, etc., 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 and a comparative example are given and this invention is demonstrated concretely, this invention is not limited by this. In addition, the part in each example shows a weight part.

[Production Example 1] Synthesis of sodium tetrakis (3,4,5-trifluorophenyl) borate 3.5 parts (0.025 mol) of boron trifluoride ether complex was added to a nitrogen-substituted four-necked reaction vessel, and tetrahydrofuran was further added. 100 mL was added and stirred. This was cooled to −20 ° C., and 100 mL of 1.0 mol L ⁻¹ 3,4,5-trifluorophenyllithium tetrahydrofuran solution prepared from 3,4,5-trifluorobromobenzene and n-butyllithium was gradually added thereto. It was dripped. The temperature was raised to room temperature, and the reaction was further continued for 6 hours. To this solution was added 100 mL of saturated aqueous sodium hydrogen carbonate solution, the organic layer was separated, the solvent was removed, the resulting residue was washed twice with hexane, and dried under reduced pressure to obtain the desired product.

[Production Example 2] Synthesis of sodium phenyltris (pentafluorophenyl) borate 6.4 parts (0.012 mol) of trispentafluorophenylborane (manufactured by Aldrich) was added to a nitrogen-substituted four-necked reaction vessel, and further 100 mL of tetrahydrofuran Added and stirred. This was cooled to -20 ° C., and 12 mL of phenylmagnesium bromide 1.0 mol L- ¹ tetrahydrofuran solution prepared from bromobenzene by a conventional method was gradually added dropwise thereto. The temperature was raised to room temperature, and the reaction was further continued for 2 hours. To this solution was added 100 mL of saturated aqueous sodium hydrogen carbonate solution, the organic layer was separated, the solvent was removed, the resulting residue was washed twice with hexane, and dried under reduced pressure to obtain the desired product.

[Production Example 3] Synthesis of sodium n-butyltris (pentafluorophenyl) borate In Production Example 2, 12 mL of phenylmagnesium bromide 1.0 molL- ¹ tetrahydrofuran solution and 6 mL of n-lithium 2.0 molL- ¹ cyclohexane solution (Aldrich) The product was synthesized according to the method described in Production Example 2 except that the target product was obtained.

[Example 1] Synthesis of compound AG-1 (1) Synthesis of intermediate (a) 16 parts of diphenyl sulfoxide, 15 parts of diphenyl sulfide, 24 parts of acetic anhydride, 1.44 parts of trifluoromethanesulfonic acid and 130 parts of acetonitrile are homogeneously mixed. Mix and react at 40 ° C. for 6 hours. The reaction solution was cooled to room temperature (about 25 ° C.), poured into 600 parts of distilled water, extracted with 600 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 200 parts of ethyl acetate and dissolving in a water bath at 60 ° C, adding 600 parts of hexane, stirring, cooling to 5 ° C, allowing to stand for 30 minutes, and then removing the supernatant twice, The product was washed. This was transferred to a rotary evaporator and the solvent was distilled off to obtain intermediate (a) as a pale yellow solid.

(2) Synthesis of Compound AG-1 Intermediate (a) 5.5 parts is dissolved in 100 parts of dichloromethane, and 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) and 100 parts of ion-exchanged water are added thereto at room temperature. Stir for 6 hours. The organic layer was washed 5 times with 100 parts of ion-exchanged water and the organic layer was concentrated, and then the residue was subjected to silica gel column chromatography to obtain a white solid. This solid was confirmed to be AG-1 by H-NMR and F-NMR. The structure of Compound AG-1 is shown in Table 1.

Example 2 Synthesis of Compound AG-2 Sodium tetrakis (3,5-bistrifluoromethylphenyl) borate (Aldrich) instead of 10 parts of lithium tetrakispentafluoroborate (Aldrich) in Example 1- (2) A white solid was obtained in the same manner as in Example 1- (2) except that the amount was 10 parts. This solid was confirmed to be AG-2 by 1 H-NMR. The structure of Compound AG-2 is shown in Table 1.

Example 3 Synthesis of Compound AG-3 Example 1 except that 7 parts of the compound synthesized in Production Example 1 was used instead of 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) in Example 1- (2). A white solid was obtained in the same manner as (2). This solid was confirmed to be AG-3 by 1 H-NMR. The structure of Compound AG-3 is shown in Table 1.

Example 4 Synthesis of Compound AG-4 Example 1 except that 7 parts of the compound synthesized in Production Example 2 was used instead of 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) in Example 1- (2). A white solid was obtained in the same manner as (2). This solid was confirmed to be AG-4 by 1 H-NMR. The structure of Compound AG-4 is shown in Table 1.

Example 5 Synthesis of Compound AG-5 Example 1 except that 7 parts of the compound synthesized in Production Example 2 was used instead of 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) in Example 1- (2). A white solid was obtained in the same manner as (2). This solid was confirmed to be AG-5 by 1 H-NMR. The structure of Compound AG-5 is shown in Table 1.

Example 6 Synthesis of Compound AG-6 (1) Synthesis of Intermediate (b) In Example (1) -1, 16 parts of diphenyl sulfoxide and 4-[(phenyl) sulfinyl] biphenyl instead of 15 parts of diphenyl sulfide A yellow solid was obtained in the same manner as in Example (1) -1, except that 22 parts and 23 parts of 4- (phenylthio) biphenyl were used.

(2) Synthesis of Compound AG-6 Same as Example (1) -2, except that 5.5 parts of intermediate (a) was changed to 7.1 parts of intermediate (b) in Example (1) -2. To give a yellow solid. This solid was confirmed to be AG-6 by H-NMR and F-NMR. The structure of Compound AG-6 is shown in Table 1.

[Example 7] Synthesis of compound AG-7 Sodium tetrakis (3,5-bistrifluoromethylphenyl) borate (Aldrich) instead of 10 parts of lithium tetrakispentafluoroborate (Aldrich) in Example 6- (2) A yellow solid was obtained in the same manner as in Example 6- (2) except that the amount was 10 parts. This solid was confirmed to be AG-7 by 1 H-NMR. The structure of Compound AG-7 is shown in Table 1.

[Example 8] Synthesis of Compound AG-8 Example 6 except that 7 parts of the compound synthesized in Production Example 2 was used instead of 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) in Example 6- (2). A yellow solid was obtained in the same manner as (2). This solid was confirmed to be AG-8 by 1 H-NMR. The structure of Compound AG-8 is shown in Table 1.

[Example 9] Synthesis of compound AG-9 (1) Synthesis of intermediate (c) In Example (1) -1, 16 parts of diphenyl sulfoxide and 2-[(phenyl) sulfinyl] thioxanthone instead of 15 parts of diphenyl sulfide A yellow solid was obtained in the same manner as in Example (1) -1, except that 27 parts and 26 parts of 2- (phenylthio) thioxanthone were used.

(2) Synthesis of Compound AG-9 Same as Example (1) -2, except that 5.5 parts of intermediate (a) was changed to 8.3 parts of intermediate (c) in Example (1) -2. To give a yellow solid. This solid was confirmed to be AG-9 by H-NMR and F-NMR. The structure of Compound AG-9 is shown in Table 1.

[Example 10] Synthesis of compound AG-10 Sodium tetrakis (3,5-bistrifluoromethylphenyl) borate (manufactured by Aldrich) instead of 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) in Example 9- (2) A yellow solid was obtained in the same manner as in Example 9- (2) except that the amount was 10 parts. This solid was confirmed to be AG-10 by 1 H-NMR. The structure of Compound AG-10 is shown in Table 1.

[Example 11] Synthesis of Compound AG-11 Example 6-Except for Example 9- (2) except that 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) was used and 7 parts of the compound synthesized in Production Example 2 were used. A yellow solid was obtained in the same manner as (2). This solid was confirmed to be AG-11 by 1 H-NMR. The structure of Compound AG-11 is shown in Table 1.

[Example 12] Synthesis of compound AG-12 2 parts of 4-hydroxyphenylmethylbenzylsulfonium chloride was dispersed in 100 parts of water with stirring, and 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) and 100 parts of dichloromethane were added thereto. Stir and mix at room temperature (about 25 ° C.) for 3 hours. The dichloromethane layer was washed 5 times with water by a liquid separation operation, then transferred to a rotary evaporator and the solvent was distilled off to obtain a white solid. This solid was confirmed to be AG-12 by 1 H-NMR. The structure of Compound AG-12 is shown in Table 1.

Example 13 Synthesis of Compound AG-13 Except that 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) was replaced with 10 parts of sodium tetrakis (3,5-bistrifluoromethylphenyl) borate (manufactured by Aldrich) in Example 12. A white solid was obtained in the same manner as in Example 12. This solid was confirmed to be AG-13 by 1 H-NMR. The structure of Compound AG-13 is shown in Table 1.

Example 14 Synthesis of Compound AG-14 The same procedure as in Example 12 was carried out except that 2 parts of 4-hydroxyphenylmethylbenzylsulfonium chloride was changed to 3.4 parts of 4-hydroxyphenyl- (2-naphthylmethyl) -methylsulfonium chloride. A pale yellow solid was obtained in the same manner as in Example 12. This solid was confirmed to be AG-14 by 1 H-NMR. The structure of Compound AG-14 is shown in Table 1.

Example 15 Synthesis of Compound AG-15 Except that in Example 13, 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) was replaced with 10 parts of sodium tetrakis (3,5-bistrifluoromethylphenyl) borate (manufactured by Aldrich). A pale yellow solid was obtained in the same manner as in Example 13. This solid was confirmed to be AG-15 by 1 H-NMR. The structure of Compound AG-15 is shown in Table 1.

Example 16 Synthesis of Compound AG-16 4-Isopropylphenyl (p-tolyl) iodonium chloride (4 parts) was dispersed in 10 parts of water with stirring, to which 10 parts of lithium tetrakispentafluoroborate (Aldrich), dichloromethane 100 Add the portion with stirring and stir and mix at room temperature (about 25 ° C.) for 3 hours. The dichloromethane layer was washed 5 times with water by a liquid separation operation, then transferred to a rotary evaporator and the solvent was distilled off to obtain a white solid. This solid was confirmed to be AG-16 by 1 H-NMR. The structure of Compound AG-16 is shown in Table 1.

Example 17 Synthesis of Compound AG-17 Except that in Example 16, 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) was changed to 10 parts of sodium tetrakis (3,5-bistrifluoromethylphenyl) borate (manufactured by Aldrich). A white solid was obtained in the same manner as in Example 16. This solid was confirmed to be AG-17 by 1 H-NMR. The structure of Compound AG-17 is shown in Table 1.

Comparative Example 1 Synthesis of Compound H-1 Same as Example 9 except that 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) was changed to 2.5 parts of potassium hexafluorophosphate in Example 1- (2). A white solid was obtained. This solid was confirmed to be H-1 by H-NMR and F-NMR. The structure of Compound H-1 is shown in Table 1.

Comparative Example 2 Synthesis of Compound H-2 A white solid was obtained in the same manner as in Comparative Example 1 except that 2.5 parts of potassium hexafluorophosphate was changed to 3.5 parts of potassium hexafluoroantimonate in Comparative Example 1. . This solid was confirmed to be H-2 by H-NMR and F-NMR. The structure of Compound H-2 is shown in Table 1.

[Comparative Example 3] Synthesis of Compound H-3 Yellowish white solid in the same manner as in Example 12 except that 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) was changed to 2.5 parts of potassium hexafluorophosphate. Got. This solid was confirmed to be H-3 by H-NMR and F-NMR. The structure of Compound H-3 is shown in Table 1.

Comparative Example 4 Synthesis of Compound H-4 A yellowish white solid was obtained in the same manner as in Comparative Example 3 except that 2.5 parts of potassium hexafluorophosphate was changed to 3.5 parts of potassium hexafluoroantimonate in Comparative Example 3. It was. This solid was confirmed to be H-4 by H-NMR and F-NMR. The structure of Compound H-4 is shown in Table 1.

[Comparative Example 5] Synthesis of Compound H-5 A white solid was prepared in the same manner as in Example 16 except that 10 parts of lithium tetrakispentafluoroborate (manufactured by Aldrich) was replaced with 2.5 parts of potassium hexafluorophosphate. Obtained. This solid was confirmed to be H-5 by H-NMR and F-NMR. The structure of Compound H-5 is shown in Table 1.

Comparative Example 6 Synthesis of Compound H-6 A white solid was obtained in the same manner as in Comparative Example 5, except that 2.5 parts of potassium hexafluorophosphate was changed to 3.5 parts of potassium hexafluoroantimonate. . This solid was confirmed to be H-6 by H-NMR and F-NMR. The structure of Compound H-6 is shown in Table 1.

In Table 1, cations (CA-1 to CA-6) are represented by the following chemical formulas.

<Preparation of energy ray curable composition and insulation reliability evaluation>
Epoxide (Celoxide 2021P, manufactured by Daicel Chemical Industries, Ltd.), which is a cationic polymerizable compound, and acid generators (AG-1 to AG-11, AG-16 and AG-17, H-1, H-2, H-5) , H-6) and a solvent (propylene carbonate) were uniformly mixed in the blending amounts shown in Table 2 to prepare energy ray curable compositions (Examples 18 to 30, Comparative Examples 7 to 10).

An evaluation wiring board obtained by processing a copper surface of a printed wiring board substrate in which a 12 μm thick copper foil is laminated on a glass epoxy substrate into a comb electrode having a line / space of 50 μm / 50 μm by etching. Was applied at a film thickness of 20 μm with an applicator.
Heating was performed at 100 ° C. for 10 minutes on a hot plate, and ultraviolet light was irradiated using an ultraviolet irradiation device equipped with a heat ray cut filter (manufactured by Eye Graphics Co., Ltd.).

(Ultraviolet light irradiation conditions)
・ Ultraviolet irradiation device: Belt conveyor type UV irradiation device (manufactured by Eye Graphics Co., Ltd.)
Lamp: 1.5 kW high-pressure mercury lamp Illuminance (measured with a 365 nm head illuminometer): 190 mW / cm ²
Integrated light quantity (measured with a 365 nm head illuminometer): 800 mJ / cm ²

After curing at room temperature for 30 minutes after irradiation, this substrate was put into a migration evaluation system (manufactured by Espec Corp.) and treated for 200 hours under conditions of a temperature of 120 ° C., a humidity of 85%, and an applied voltage of 5V. Thereafter, the resistance value (Ω) was measured, and the change in insulation of the upper cured film was confirmed.

(Evaluation criteria)
A: Insulation retention up to 99%
○: Insulation retention ~ 90%
×: Insulation retention <90%

A similar test was performed on aluminum wiring boards, and the results are summarized in Table 2.

<Preparation of thermosetting composition and insulation reliability evaluation>
Table 3 shows acid generators (AG-12 to AG-15, H-3 to H-4) and solvents (propylene carbonate) to epoxide (Celoxide 2021P, manufactured by Daicel Chemical Industries, Ltd.) which is a cationic polymerizable compound. A thermosetting composition (Examples 31 to 34, Comparative Examples 11 to 12) was prepared by uniformly mixing at the indicated blending amounts.

An evaluation wiring board obtained by processing a copper surface of a printed wiring board substrate in which a 12 μm thick copper foil is laminated on a glass epoxy substrate into a comb electrode having a line / space of 50 μm / 50 μm by etching. Was applied at a film thickness of 20 μm with an applicator.
After heating and curing on a hot plate at 120 ° C. for 30 minutes, this substrate is put into a migration evaluation system (manufactured by Espec Corp.), and the temperature is 120 ° C., the humidity is 85%, and the applied voltage is 5V. For 200 hours. Thereafter, the resistance value (Ω) was measured, and the change in insulation of the upper cured film was confirmed.

(Evaluation criteria)
A: Insulation retention up to 99%
○: Insulation retention ~ 90%
×: Insulation retention <90%

Similar tests were performed on aluminum wiring boards, and the results are summarized in Table 3.

<Preparation of negative photoresist composition and its evaluation>
As shown in Table 4, a copolymer (Mw) consisting of 1 part by weight of the component (A) that is an acid generator and the component (B) that is a phenol resin is p-hydroxystyrene / styrene = 80/20 (molar ratio). = 10,000) is 100 parts by weight, and the component (C) is a cross-linking agent. As (D), a copolymer comprising butadiene / acrylonitrile / hydroxybutyl methacrylate / methacrylic acid / divinylbenzene = 64/20/8/6/2 (% by weight) (average particle size = 65 nm, Tg = −38 ° C.) 5 parts by weight of γ-glycidoxypropyltrimethoxysilane (trade name “S510”, manufactured by Chisso Corporation) as component (E) which is an adhesion assistant Solvent -2 homogeneously dissolved in ethyl lactate () 145 parts by weight, the negative photoresist composition of the present invention (Examples 35-36, Comparative Examples 7-8) were prepared.

<Evaluation of UV curability (negative resist)>
Each composition was spin-coated on a copper substrate, and then heated and 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; ² J / cm < ² >) was performed using TME-150RSC (made by Topcon Corporation), and the post-exposure heating (PEB) for 3 minutes was performed at 110 degreeC with the hotplate. Thereafter, a development process for 2 minutes was performed by an immersion method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, washed with running water, and blown with nitrogen to obtain a 50 μm line and space pattern. About the obtained pattern, the residual film ratio which shows the ratio of the residual film before and behind image development was measured. Further, this substrate was put into a migration evaluation system (manufactured by ESPEC Corp.) and treated for 200 hours under the conditions of a temperature of 120 ° C., a humidity of 85%, and an applied voltage of 5V. Thereafter, the resistance value (Ω) was measured to confirm the change in the insulating property of the resist film.
The results are shown in Table 4.

From the results of Tables 2 to 4, the active energy ray-curable composition and the negative resist composition using the acid generator of the present invention have good UV curing performance / thermosetting performance and electrical properties of the cured product ( Insulation reliability is high, so it is useful as a member that requires electrical reliability, such as various protective materials such as surface protective films such as semiconductor elements, interlayer insulation films, and permanent film materials such as planarization films. I know that there is.

Paints, coating agents, various coating materials (hard coat, anti-stain coating, anti-fogging coating, touch-resistant coating, optical fiber, etc.), adhesive tape back treatment, adhesive label release sheet (release paper, release plastic film) , Release metal foil etc.) release coating material, printing plate, dental material (dental compound, dental composite) ink, ink jet ink, positive resist (circuit board, CSP, MEMS element, etc.) Terminals, wiring pattern formation, etc.), resist films, liquid resists, negative resists (surface protective films such as semiconductor elements and FPD transparent electrodes (ITO, IZO, GZO), permanent film materials such as interlayer insulation films, planarization films, etc. Etc.), MEMS resist, positive photosensitive material, negative photosensitive material, various adhesives (temporary fixing agent for various electronic parts, HDD contact) Agent, pickup lens adhesive, FPD functional film (deflecting plate, antireflection film, etc.) adhesive, circuit forming and semiconductor sealing insulating film, anisotropic conductive adhesive (ACA), film (ACF) ), Paste (ACP), etc.), holographic resin, FPD material (color filter, black matrix, partition wall material, photospacer, rib, liquid crystal alignment film, FPD sealant, etc.), optical member, molding material (building material) , Optical components, lenses), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, flip chip, chip sealing materials such as COF, package sealing materials such as CSP or BGA, optical semiconductors (LED) It is suitably used for sealing materials, optical waveguide materials, nanoimprint materials, photofabrication, micro stereolithography materials, and the like.

Claims (6)

An acid generator comprising an onium borate salt represented by the following general formula (1).

[In Formula (1), R ^{1 to} R ⁴ are each independently an alkyl group having 1 to 18 carbon atoms or Ar, provided that at least one is Ar,
Ar is an aryl group having 6 to 14 carbon atoms (not including the carbon number of the following substituents), wherein some of the hydrogen atoms in the aryl group are alkyl groups having 1 to 18 carbon atoms and halogen atoms are Substituted alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group having 6 to 14 carbon atoms, nitro group, hydroxyl group, cyano group, -OR ⁶ alkoxy or aryloxy group ^represented, acyl group represented by R 7 ^CO-, acyloxy group represented by R 8 COO-, alkylthio group or arylthio group represented by -SR ^{9, -NR} 10 ^{R 11} May be substituted with an amino group represented by
R ^{6 to} R ⁹ are each an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms,
R ¹⁰ and R ¹¹ are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms;
E represents an element having a valence of n from Group 15 to Group 17 (IUPAC notation),
n is an integer of 1 to 3,
R ⁵ is an organic group bonded to E, the number of R ⁵ is n + 1, and (n + 1) R ^{5 s} may be the same or different from each other, and two or more R ⁵ are Ring structure containing element E directly or each other through —O—, —S—, —SO—, —SO ₂ —, —NH—, —CO—, —COO—, —CONH—, an alkylene group or a phenylene group May be formed. ] The acid generator according to claim 1, wherein E is S, I, N, or P.   A heat or active energy ray-curable composition comprising the acid generator according to claim 1 or 2 and a cationically polymerizable compound.   A cured product obtained by curing the curable composition according to claim 3.   A chemical comprising a component (A) comprising the acid generator according to claim 1 or 2, a component (B) which is an alkali-soluble resin having a phenolic hydroxyl group, and a crosslinking agent component (C). Amplified negative photoresist composition. A cured product obtained by curing the chemically amplified negative photoresist composition according to claim 5.