JP2012022227A - Energy ray-curable composition containing iodonium alkyl fluorophosphate-based photoacid generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an energy ray-curable composition and a cured product using an iodonium salt-based photoacid generator containing no element of high toxicity such as Sc and having high sensitivity (excellent in cationic polymerization performance) to active energy rays such as UV rays.SOLUTION: The energy ray-curable composition comprises an iodonium alkyl fluorophosphate salt-based photoacid generator expressed by general formula (1) and a cationic polymerizable compound. In formula (1), R1 represents an organic group bonded to I (iodine); Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms; b represents the number of alkyl groups and an integer of 1 to 5; and b of Rf may be identical or different from one another.

Description

In the present invention, first, a specific fluorinated alkyl phosphate iodonium salt is used as a photoacid generator suitable for curing a cationically polymerizable compound by applying an active energy ray such as light, electron beam or X-ray. The present invention relates to an energy beam curable composition to be contained and a cured product obtained by curing the composition.
Secondly, 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.
Thirdly, the present invention relates to a chemically amplified negative photoresist composition containing the photoacid generator.

Conventionally, iodonium salts are known as cationic polymerization initiators that cure cationically polymerizable compounds such as epoxy compounds by irradiation with active energy rays such as heat, light, and electron beams (Patent Documents 1 to 10).
Moreover, since these iodonium salts generate | occur | produce an acid by a heat | fever or active energy ray irradiation, they are also called an acid generator and are used also for a resist and a photosensitive material (patent documents 11-13).

By the way, the cationic polymerization initiators described in these specifications contain BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ as anions, but the cationic polymerization initiating ability varies depending on the type of anion. BF ₄ ⁻ <PF ₆ ⁻ <AsF ₆ ⁻ <SbF ₆ ⁻ . However, the polymerization initiator ability good AsF ₆ ^-, SbF ₆ ^- cationic polymerization initiator containing the, As, limited use applications from toxicity problems of Sb, SbF ₆ ^- applications salts is limited, such as stereolithography It is only used in. Therefore, in general, PF ₆ polymerization initiation ability is poor ^- the salts are utilized, PF ₆ ^- salt, for example, SbF ₆ ^- to obtain the cure rate comparable to salt, the latter 10 times more The amount of unreacted initiator, the solvent used as needed to dissolve the initiator or the decomposition product of the initiator is increased, and the physical properties of the cured product are impaired. In addition, since the amount of HF produced as a by-product due to the decomposition of the initiator increases, there is a problem that the base material, equipment and the like are easily corroded. Thus free of toxic metals, SbF ₆ ^- cationic polymerization initiator having a cationic polymerization initiating ability comparable to salt has been strongly desired.

In recent years, with the further miniaturization of electronic devices, high-density mounting of semiconductor packages has progressed, and multi-pin thin film mounting and miniaturization of packages, mounting based on flip-chip 2D and 3D mounting technology. The density is improved. As a material used for such high-precision photofabrication, there is a positive photosensitive resin composition using an oxime sulfonate compound as an acid generator (Patent Document 14). This is because the acid is generated from the photoacid generator by irradiation (exposure), and the diffusion of the acid and the acid catalytic reaction are promoted by the heat treatment after the exposure, thereby improving the solubility of the base resin in the resin composition in the alkali. The base resin that was insoluble in alkali before exposure is solubilized in alkali, and is called a positive photoresist.
Furthermore, a photosensitive resin composition using an alkali-soluble resin having a phenolic hydroxyl group and a triazine photoacid generator has been proposed for a surface protective film, an interlayer insulating film, etc. used in a semiconductor element of an electronic device (patent) References 15 and 16). This is because an acid is generated from the photoacid generator upon exposure, and the reaction between the crosslinking agent and the alkali-soluble resin is promoted to become insoluble in the developer. This is called a negative photoresist.
In both photoresist compositions, the acid generated by light irradiation undergoes a catalytic reaction. The stronger the acid, the higher the efficiency, but the strong acid anions AsF ₆ ⁻ and SbF ₆ ⁻ have toxicity problems as described above. There is no use.

As photoacid generators to meet this challenge, tetrakis but (pentafluorophenyl) onium salt having the anion borate (Patent Document 17) is proposed, the polymerization initiating ability to cationic polymerizable compound of this compound PF ₆ ^- the Although it is superior to those using anions, it is inferior to those using SbF ₆ ⁻ as anions, and further improvement is desired.

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 JP 2000-66385 A JP 2008-77057 A WO2008-117619 JP-A-6-184170

In the above background, the first object of the present invention is to contain no highly toxic elements such as Sb and to be highly sensitive to active energy rays such as ultraviolet rays (excellent cationic polymerization performance).
It is to provide an energy ray curable composition and a cured body using an iodonium salt photoacid generator.
A second object of the present invention is a chemically amplified positive photoresist composition that does not contain a highly toxic element such as Sb and that can provide a resist that is highly sensitive to active energy rays such as ultraviolet rays. And a method for producing a resist pattern.
A third object of the present invention is a chemically amplified negative photoresist composition that does not contain a highly toxic element such as Sb and that can provide a resist that is highly sensitive to active energy rays such as ultraviolet rays. And providing a cured body.

The present inventor has found an energy ray curable composition suitable for the above-mentioned purpose.
That is, the present invention is an energy beam curable composition comprising a fluorinated alkyl phosphate iodonium salt photoacid generator represented by the following general formula (1) and a cationically polymerizable compound.

[In Formula (1), R1 represents an organic group bonded to I (iodine), and Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. b shows the number and is an integer of 1-5. The b Rf's may be the same or different. ]

The energy ray-curable composition of the present invention does not contain a highly toxic element such as Sb, and is highly sensitive to active energy rays such as ultraviolet rays (excellent cationic polymerization performance).
The cured product of the present invention is highly safe because it does not contain highly toxic elements such as Sb.
The chemically amplified positive photoresist composition and the chemically amplified negative photoresist composition of the present invention do not contain a highly toxic element such as Sb, and are highly sensitive to active energy rays such as ultraviolet rays (cationic polymerization). The performance is excellent) and the resist pattern shape is good.

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

The fluorinated alkyl phosphate iodonium salt photoacid generator of the present invention is represented by the following general formula (1).

[In Formula (1), R1 represents an organic group bonded to I (iodine), and Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. b shows the number and is an integer of 1-5. The b Rf's may be the same or different. ]

R1 in Formula (1) represents the organic group couple | bonded with I, and may be same or different. R1 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 an alkynyl group having 2 to 30 carbon atoms. Which are alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, It may be substituted with at least one selected from the group consisting of arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups and halogen.

In the above, the aryl group having 6 to 30 carbon atoms includes monocyclic aryl groups such as phenyl groups and condensed naphthyl, anthracenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthacenyl, benzanthracenyl, anthraquinolyl, fluorenyl, naphthoquinone, anthraquinone, etc. And a polycyclic 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. Are monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl A condensed polycyclic heterocyclic group such as carbazolyl, acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thianthenyl, phenoxazinyl, phenoxathinyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl It is below.

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

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

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.

In the fluorinated alkyl fluorophosphate anion represented by the formula (1), Rf represents an alkyl group substituted with a fluorine atom, and preferably has 1 to 4 carbon atoms. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl; and cyclopropyl, cyclobutyl, cyclopentyl, Examples thereof include a cycloalkyl group such as cyclohexyl, and the ratio of the hydrogen atom of the alkyl group substituted by a fluorine atom is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of fluorine atoms is less than 80%, the polymerization curability of the energy beam curable composition of the present invention is lowered.

Particularly preferred Rf is a linear or branched alkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%. Specific examples include CF ₃ , CF ₃ CF ₂ , (CF ₃ ) ₂ CF CF ₃ CF ₂ CF ₂ , CF ₃ CF ₂ CF ₂ CF ₂ , (CF ₃ ) ₂ CFCF ₂ , CF ₃ CF ₂ (CF ₃ ) CF, and (CF ₃ ) ₃ C.

In the formula (1), the number b of Rf is an integer of 1 to 5, preferably 2 to 4, particularly preferably 2 or 3. The b Rf's may be the same or different.

Specific examples of preferred fluorinated alkyl fluorophosphate anions include [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF). ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ and [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^-, and the like.

  Preferred specific examples of the fluorinated alkyl phosphate iodonium salt photoacid generator represented by the formula (1) include diphenyliodonium tris (pentafluoroethyl) trifluorophosphate, di-p-tolyliodonium tris (pentafluoroethyl). Trifluorophosphate, bis (4-dodecylphenyl) iodonium tris (pentafluoroethyl) trifluorophosphate, bis (4-methoxyphenyl) iodonium, (4-octyloxyphenyl) phenyliodonium tris (pentafluoroethyl) trifluorophosphate, Bis (4-decyloxy) phenyliodonium tris (pentafluoroethyl) trifluorophosphate, 4- (2-hydroxytetradecyloxy) phenylphenyliodonium tris (pentafluoroe Le) trifluoro phosphate, 4-isopropylphenyl (p- tolyl) iodonium tris (pentafluoroethyl) trifluoro phosphate and 4-isobutylphenyl (p- tolyl) iodonium tris (pentafluoroethyl) include trifluoromethyl phosphate.

  In addition to the photoacid generator represented by the formula (1) of the present invention, other conventionally known photoacid generators may be contained and used.

  When the other photoacid generator is contained, the content (mol%) of the other photoacid generator is 0 with respect to the total number of moles of the photoacid generator represented by the formula (1) of the present invention. .1 to 100 is preferable, and 0.5 to 50 is more preferable.

  Other photoacid generators include conventionally known compounds such as onium salts (sulfonium, iodonium, selenium, ammonium, phosphonium, etc.) and salts of transition metal complex ions with anions.

  The photoacid generator represented by the formula (1) of the present invention may be dissolved in advance in a solvent that does not inhibit cationic polymerization in order to facilitate dissolution in the cationic polymerizable compound.

  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 Polyacetates 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 Alcohols and derivatives thereof; cyclic ethers such as dioxane Class: ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate And esters such as 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 to 500 parts by weight with respect to 100 parts by weight of the photoacid generator represented by the formula (1) of the present invention. It is. The solvent to be used may be used independently or may use 2 or more types together.

  Examples of the cationic polymerizable compound that is a constituent of the energy ray-curable composition of the present invention include cyclic ethers (epoxides and oxetanes), ethylenically unsaturated compounds (vinyl ether and styrene, etc.), bicycloorthoesters, spiroorthocarbonates, and the like. Spiro orthoesters and the like (JP-A-11-060996, JP-A-09-302269, JP-A-2003-026993, JP-A-2002-206017, JP-A-11-349895, JP-A-10-212343, JP 2000-119306, JP 10-67812, JP 2000-186071, JP 08-85775, JP 08-134405, JP 2008-20838, JP 2008-20839, JP 2008. -20841, JP200 -26660, JP2008-26644, JP2007-277327, Photopolymer social gathering “Photopolymer Handbook” (1989, Industrial Research Committee), General Technology Center “UV / EB Curing Technology” (1982, General Technical Center), Radtech Study Group “UV / EB Curing Materials” (1992, CMC), Technical Information Association “UV Curing Failure / Inhibition Causes and Countermeasures” (2003, Technical Information Association), Color Material, 68, (5), 286-293 (1995), fine chemical, 29, (19), 5-14 (2000), etc.).

  Known epoxides can be used and include aromatic epoxides, alicyclic epoxides and aliphatic epoxides.

  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 cationically polymerizable monomers can be used, and examples thereof include aliphatic monovinyl ether, aromatic monovinyl ether, polyfunctional vinyl ether, styrene, and cationically polymerizable nitrogen-containing monomers.

  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. In addition, these cationically polymerizable compounds may be used alone or in combination of two or more.

  The content of the photoacid generator represented by the general formula (1) of the present invention in the energy ray curable composition is preferably 0.05 to 20 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound, and Preferably it is 0.1-10 weight part. Within this range, the cationically polymerizable compound is further sufficiently polymerized, 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 cationic polymerizable compound, the type and energy dose of the energy ray, temperature, curing time, humidity, and coating thickness, and is limited to the above range. Not.

  In the energy ray curable composition of the present invention, a known additive (sensitizer, pigment, filler, antistatic agent, flame retardant, antifoaming agent, flow control agent, light stabilizer, An antioxidant, an adhesion-imparting agent, an ion scavenger, a coloring inhibitor, a solvent, a non-reactive resin, a radical polymerizable compound, and the like).

  The energy beam curable composition of the present invention can contain a sensitizer if necessary. As such a sensitizer, known sensitizers (JP-A-11-279212 and JP-A-09-183960) can be used, and anthracene {anthracene, 9,10-dibutoxyanthracene, 9,10 -Dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc.}; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; thioxanthone { Thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone 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 and N-glycidylcarbazole and the like}; chrysene {1,4-dimethoxychrysene and 1,4-di-α-methylbenzyloxychrysene and the like}; Phenan Tren {9-hydroxyphenanthrene, 9-methoxyphenanthrene, 9-hydroxy-10-methoxyphenanthrene, 9-hydroxy-10-ethoxyphenanthrene, etc.} and the like.

  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 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 by weight, more preferably 10 to 150,000 parts by weight with respect to 100 parts of the photoacid generator.

  Known fillers can be used as fillers, 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 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 by weight, more preferably 0.6 to 5000 parts by weight, with respect 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 the flame retardant is contained, the content of the flame retardant is preferably 0.5 to 40,000 parts by weight, more preferably 5 to 10,000 parts by weight 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 amine, etc.}; and quenching And a type stabilizer {nickel complex etc.}.
As antioxidants, known antioxidants can be used, such as 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 an anti-coloring agent is contained, each content is based on 100 parts of the photoacid generator, The amount is preferably 0.1 to 20000 parts by weight, more preferably 0.5 to 5000 parts by weight.

  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 photoacid 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 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, 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, and more preferably 50 to 150,000 parts by weight with respect 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 so that the non-reactive resin can be easily dissolved with the cationic polymerizable compound.

  As radically polymerizable compounds, known {photopolymer social gathering edition “Photopolymer Handbook” (1989, Industrial Research Committee), General Technology Center “UV / EB Curing Technology” (1982, General Technology Center), Radtech Research The radical-polymerizable compounds in the “UV / EB Curing Materials” edition (1992, CMC) and the “Technical Information Association”, “Hardening Failure / Inhibition Causes in UV Curing and Countermeasures” (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 photoacid generator.

  When radically polymerizable compounds are contained, a radical polymerization initiator that initiates polymerization by heat or light is preferably used in order to increase the molecular weight 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, based on 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 optionally an additive, uniformly at room temperature (about 20 to 30 ° C.) or optionally heated (about 40 to 90 ° C.). Can be prepared by kneading with three rolls or the like.

The energy ray-curable composition of the present invention can be cured by irradiating 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 iodonium 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. From 0.1 seconds to several minutes after irradiation with energy rays, most energy ray curable compositions are cured by cationic polymerization. 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 ray-curable composition of the present invention include paints, coating agents, various coating materials (hard coat, anti-stain coating, anti-fogging coating, touch-resistant coating, optical fiber, etc.), adhesive tape Back surface treatment agent, Release coating material for adhesive label release sheet (release paper, release plastic film, release metal foil, etc.), printing plate, dental material (dental compound, dental composite) ink, inkjet ink, positive Type resist (formation of connection terminals and wiring patterns for manufacturing electronic components such as circuit boards, CSPs, MEMS elements, etc.), resist films, liquid resists, negative resists (surface protective films for semiconductor elements, interlayer insulation films, planarization films) Permanent film materials, etc.), MEMS resists, positive photosensitive materials, negative photosensitive materials, various adhesives (temporary fixing agents for various electronic components, DD adhesive, pickup lens adhesive, FPD functional film (deflector, antireflection film, etc.), holographic resin, FPD material (color filter, black matrix, partition material, photospacer, Ribs, alignment films for liquid crystals, sealants for FPDs, etc.), optical members, molding materials (for building materials, optical components, lenses), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, sealing Examples include materials, optical semiconductor (LED) sealing materials, optical waveguide materials, nanoimprint materials, photofabrication materials, and micro stereolithography materials.

  Since the iodonium salt of the present invention generates a strong acid when irradiated with light, a chemically amplified resist material known in the art (JP 2003-267968 A, JP 2003-261529 A, JP 2002-193925 A, etc.) is used. It can also be used as a photoacid generator for use.

  Chemically amplified resist materials include: (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; and (2) an alkali developer. Soluble resin, a three-component chemical amplification type positive resist containing, as essential components, a dissolution inhibitor and a photoacid generator that are soluble in an alkali developer by the action of an acid, and (3) suitable for an alkali developer. A chemically amplified negative resist containing a crosslinking agent that crosslinks the resin by heat treatment in the presence of a soluble resin and an acid and makes the resin 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 a component (A) comprising a photoacid generator represented by the general formula (1) of the present invention, which is a compound that generates an acid by irradiation with light or radiation. And a resin component (B) whose solubility in alkali is increased by the action of an acid.

  In the chemically amplified positive photoresist composition of the present invention, the component (A) may be used in combination with another conventionally known photoacid generator. Other acid generators include, for example, onium salt compounds, sulfone compounds, sulfonate ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, triazine compounds, 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 than the total weight of 100 parts by weight of the iodonium salt represented by the general formula (1). The photoacid generator is 10 to 900 parts 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 aforementioned “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 as “component (B)” in the present specification) .) 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 linear alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 3 to 6 carbon atoms, and cyclic groups 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-butoxy group Examples include carbonylmethyl 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 in 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 thereof 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 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, or 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 chain 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, 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 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 a carbon atom. 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 10,000-600,000, More preferably, it is 50,000-600,000, More preferably, it is 230,000-550,000. is there. 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 (referred to herein as “component (C)”) in order to improve the resin physical properties of the resist. . 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, 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)>
The chemical amplification type positive photoresist composition for thick film of the present invention further comprises an acid diffusion control agent (D) (in the present specification, “component ( D) ").) Is preferably included. As the component (D), a nitrogen-containing compound is preferable, and if necessary, an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be contained.

  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 aid 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.

  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.

  Further, the chemical amplification type positive 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 include those mentioned 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 iodonium salt represented by the general formula (1).

  The chemically amplified positive photoresist composition of the present invention can be appropriately mixed with an organic solvent for viscosity adjustment. Specific examples of the organic solvent include those described above.

  The amount of these organic solvents used is such that the concentration of the solid content is 5 μm or more so that the 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 thick film chemically amplified positive photoresist composition of the present invention can be prepared, for example, by mixing and stirring the above-mentioned components by a usual method. If necessary, a dissolver, a homogenizer, a three-roll mill, etc. You may disperse and mix using a disperser. Further, after mixing, it may be filtered using a mesh, a membrane filter or the like.

  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. This photoresist laminate is obtained by laminating a photoresist layer made of the chemically amplified positive photoresist composition of the present invention on a support.

  The support is not particularly limited, and a conventionally known one can be used. For example, a substrate for electronic parts or a substrate on which a predetermined wiring pattern is formed can be exemplified. Examples of the substrate include a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, and aluminum, and a glass substrate. 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 photoresist laminate can be produced, for example, as follows. That is, a desired coating film is formed by applying a solution of the 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 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 passed through the obtained photoresist layer through a mask having a predetermined pattern. Irradiation (exposure) with ultraviolet rays or visible rays may be performed selectively.

Here, “light” may be light that activates the acid generator to generate 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 ultra-high pressure mercury lamp, a metal halide lamp, an argon gas laser, an LED lamp, or the like can be used. Further, the radiation irradiation amount varies depending on the kind of each component in the composition, the blending amount, the film thickness of the coating film, etc., but is, for example, 50 to 10,000 mJ / cm ² when using an ultrahigh pressure mercury lamp.

  Then, after the exposure, the diffusion of the acid is promoted by heating using a known method to change the alkali solubility of the photoresist layer in the exposed portion. 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, and the development method is the liquid piling method, dipping method, paddle method, spray development method. 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, oven, or the like.

  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 alkaline developer) of the resist pattern thus obtained by, for example, 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 in the range of 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 manufactured, for example, as follows. That is, a solution of a chemically amplified positive photoresist composition prepared as described above is applied on 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, etc., 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 a photoacid generator represented by the general formula (1) of the present invention, which is a compound that generates an acid upon irradiation with light or radiation. And an alkali-soluble resin (F) having a phenolic hydroxyl group and a crosslinking agent (G).

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, 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 (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, 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.

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 In addition, the chemically amplified negative photoresist composition of the present invention may contain an adhesion aid in order to improve the adhesion to the substrate.
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 (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.

  In addition, 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 include those mentioned 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 photoacid generator represented by the general formula (1).

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 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 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.

<Preparation of energy ray-curable composition and its evaluation-1>
A photoacid generator (P-1 to 3) is added to an epoxide (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Dow Chemical Co., Ltd., UVR-6110) which is a cationic polymerizable compound. The energy ray-curable composition (Example C1 and Comparative Examples C1 and C2) was prepared by uniformly mixing in the blending amount shown in 1.

P-1: 4-isopropylphenyl (p-tolyl) iodonium tris (pentafluoroethyl) trifluorophosphate P-2: 4-isopropylphenyl (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate P-3: 4- Isopropylphenyl (p-tolyl) iodonium hexafluoroantimonate

<Sensitivity (cationic polymerization curability) evaluation>
The composition obtained above was applied to a polyethylene terephthalate (PET) film with a film thickness of 40 μm using an applicator. The PET film after the application was irradiated with ultraviolet rays using an ultraviolet irradiation device. Table 2 shows the results obtained by measuring the film hardness after 40 minutes after irradiation with pencil hardness (JIS K5600-5-4: 1999) and evaluating the film according to the following criteria. The higher the pencil hardness, the better the sensitivity (cationic polymerization curability) of the energy beam curable composition.

(Evaluation criteria)
◎: Pencil hardness is 2H or more ○: Pencil hardness is H to B
(Triangle | delta): Pencil hardness is 2B-4B
×: 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: 1.5 kW high-pressure mercury lamp Illuminance (measured with a 365 nm head illuminometer): 145 mW / cm ²

-Integrated light quantity (measured with 365nm head illuminometer):
Condition-1: 300 mJ / cm ²
Condition-2: 400 mJ / cm ²
Condition-3: 500 mJ / cm ²

<Preparation of energy ray-curable composition and its evaluation-2>
A photo-acid generator (P-1 to 3) is uniformly mixed in a blending amount shown in Table 3 to polyorganosiloxane (epoxy modified silicone resin, manufactured by Rhodia, Silicoly POLY200) which is a cationic polymerizable compound, and energy is obtained. A linear curable silicone composition (Example R1 and Comparative Examples R1, R2) was prepared.

<Sensitivity (cationic polymerization curability) evaluation>
The silicone composition obtained above was applied on a polyethylene terephthalate (PET) film at a film thickness of 4 μm with an applicator. The PET film after the application was irradiated with ultraviolet rays using an ultraviolet irradiation device. The degree of curing of the coating film after irradiation was judged by touch with the following evaluation criteria. These results are shown in Table 4. It shows that the sensitivity of the silicone composition is higher and the cationic polymerization curability is better as the integrated light amount is smaller and the degree of curing is higher.

(Evaluation criteria)
○: Completely cured (no tack or stickiness due to finger touch)
Δ: Surface hardening (no tack due to finger touch, but the inside of the coating is soft)
×: Uncured (with tack and stickiness due to finger touch)

(UV 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): 145 mW / cm ²
-Integrated light quantity (measured with 365nm head illuminometer):
Condition-1: 300 mJ / cm ²
Condition-2: 500 mJ / cm ²

<Measurement of peel force>
The silicone composition obtained above was applied to glassine paper with an RI tester at a coating amount of about 1.0 g / m ² , and then cured by irradiation with ultraviolet rays to prepare a release paper. An acrylic emulsion-type pressure-sensitive adhesive (manufactured by Toyo Ink Manufacturing Co., Ltd., trade name “Olivein BPW-5526”) was applied at 20 g / m ² on the surface of the cured film of the produced release paper and dried at 110 ° C. for 60 seconds. Then, a high quality paper was bonded to the treated surface and stored at 25 ° C. under a load of 20 g / cm ² for 15 hours. This is cut into a width of 50 mm, and a tensile tester is used to pull and peel the high-quality paper bonded at a peel rate of 0.3 m / min and 50 m / min at an angle of 180 ° C. (g / 50 mm) Was measured. The results are shown in Table 4.

From the results in Table 2, the energy ray curable composition of the present invention (Example C1) has high safety because it does not contain Sb, which is a toxic element, in the composition, which is higher than Comparative Examples C1 and C2. It can be seen that the sensitivity is high and the cationic polymerization curability is good.
Moreover, from the results of Table 4, the energy ray-curable silicone composition of the present invention (Example R1) also contains no Sb in the composition, and has better cationic polymerization curability than Comparative Examples R1 and R2. In addition, Example R1 has a peel strength equivalent to that of Comparative Examples R1 and R2, and is also useful as a release material for release sheets for adhesive labels (release paper, release plastic film, release metal foil, etc.). I understand that.

<Preparation of positive photoresist composition and its evaluation>
As shown in Table 5, 1 part by weight of the component (A) that is a photoacid generator, 40 parts by weight of the resin represented by the following chemical formula (Resin-1), and the resin component (C) as the resin component (B) 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, 0.25 parts by weight of isopropylthioxanthone as a sensitizer, and solvent-1 (propylene glycol monomethyl The resulting solution was uniformly dissolved in ether acetate) and filtered through a membrane filter having a pore diameter of 1 μm to prepare positive photoresist compositions (Example P1, Comparative Examples P1, P2) having a solid concentration of 40% by weight.

<Sensitivity evaluation>
A positive resist composition prepared in Example P1 and Comparative Examples P1 and P2 was spin coated on a silicon wafer substrate, and then dried to obtain a photoresist layer having a thickness of about 20 μm. After this resist layer was pre-baked, pattern exposure (i-line) was performed using TME-150RSC (manufactured by Topcon), and post-exposure heating (PEB) was performed at 130 ° C. for 5 minutes using a hot plate. Thereafter, development processing was performed for 5 minutes by an immersion method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, washed with running water, and blown with nitrogen to obtain a 10 μm line and space (L & S) pattern. Further, below that, the minimum exposure amount at which no residue of this pattern is recognized, that is, the minimum essential exposure amount (corresponding to the sensitivity) necessary for forming the resist pattern was measured. The results are shown in Table 6. The smaller the exposure amount, the higher the sensitivity.

<Preparation of negative photoresist composition and its evaluation>
As shown in Table 7, as a component (E) which is a photoacid generator, and a component (F) which is a phenol resin, a copolymer (p-hydroxystyrene / styrene = 80/20 (molar ratio)) ( 100 parts by weight of Mw = 10,000) and 20 parts by weight of hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., Ltd., trade name “Nicalak MW-390”) as a crosslinking agent (G) are crosslinked fine particles. As component (H), 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. ) As a component (I) which is an adhesion assistant, 5 parts by weight of γ-glycidoxypropyltrimethoxysilane (manufactured by Chisso Corporation, trade name “S510”) As a sensitizer, 0.25 parts by weight of isopropylthioxanthone is uniformly dissolved in 145 parts by weight of solvent-2 (ethyl lactate) to obtain a negative photoresist composition of the present invention (Example N1, Comparative Examples N1, N2). Was prepared.

<Sensitivity evaluation>
Each composition was spin-coated on a silicon wafer 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) 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, the film was developed for 2 minutes by an immersion method using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, washed with running water, and blown with nitrogen to obtain a 10 μm line and space pattern. Further, the minimum essential exposure amount (corresponding to the sensitivity) required to form a pattern having a remaining film ratio of 95% or more indicating the ratio of the remaining film before and after development was measured. The results are shown in Table 8. The smaller the exposure amount, the higher the sensitivity.

From the results of Tables 6 and 8, the positive resist composition (Example P1) and the negative resist composition (Example N1) of the present invention are safe because they do not contain Sb which is a toxic element in the composition. It can be seen that it is useful as a resist composition because it has high sensitivity and is more sensitive than Comparative Examples P1 and P2 of positive resist compositions and Comparative Examples N1 and N2 of negative resist compositions.

The composition of the present invention comprises paints, coating agents, various coating materials (hard coat, anti-stain coating, anti-fogging coating, anti-touch coating, optical fiber, etc.), back treatment agent for adhesive tape, release sheet for adhesive labels Release coating material (release paper, release plastic film, release metal foil, etc.), printing plate, dental material (dental compound, dental composite) ink, inkjet ink, positive resist (circuit board, CSP, MEMS element) Connection terminal and wiring pattern formation etc. of electronic parts manufacturing, etc.), resist film, liquid resist, negative resist (permanent film materials such as surface protection film for semiconductor elements, interlayer insulation film, planarization film, etc.), for MEMS Resist, positive photosensitive material, negative photosensitive material, various adhesives (various electronic component temporary fixing agents, HDD adhesives, pickup lens contacts) Agent, adhesive for FPD functional film (deflecting plate, antireflection film, etc.), holographic resin, FPD material (color filter, black matrix, partition material, photo spacer, rib, liquid crystal alignment film, for FPD Sealing agents, etc.), optical members, molding materials (for building materials, optical components, lenses), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, sealing materials, optical semiconductor (LED) sealing It is suitably used for materials, optical waveguide materials, nanoimprint materials, photofabrication, and micro stereolithography materials.

Claims (9)

An energy ray-curable composition comprising a fluorinated alkyl phosphate iodonium salt photoacid generator represented by the following general formula (1) and a cationically polymerizable compound.

[In Formula (1), R1 represents an organic group bonded to I (iodine), and Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms. b shows the number and is an integer of 1-5. The b Rf's may be the same or different. ]   A cured product obtained by curing the energy beam curable composition according to claim 1.   A chemically amplified positive photo composition comprising: a component (A) comprising the photoacid generator according to claim 1; 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 3 or 4, further comprising an alkali-soluble resin (C) and an acid diffusion controller (D).   A laminating step of laminating a 10 to 150 μm-thick photoresist layer comprising the chemically amplified positive photoresist composition according to any one of claims 3 to 5 on a support; A resist pattern comprising: an exposure step of selectively irradiating light or radiation to the photoresist laminate, and a development step of developing the photoresist laminate to obtain a resist pattern after the exposure step Method.   A chemical amplification comprising a component (E) comprising the photoacid generator according to claim 1, a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and a crosslinking agent component (G). Type negative photoresist composition.   The chemically amplified negative photoresist composition according to claim 7, further comprising a crosslinked fine particle component (H). A cured product obtained by curing the chemically amplified negative photoresist composition according to claim 7 or 8.