WO2022030139A1 - 光酸発生剤 - Google Patents

光酸発生剤 Download PDF

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Publication number
WO2022030139A1
WO2022030139A1 PCT/JP2021/024283 JP2021024283W WO2022030139A1 WO 2022030139 A1 WO2022030139 A1 WO 2022030139A1 JP 2021024283 W JP2021024283 W JP 2021024283W WO 2022030139 A1 WO2022030139 A1 WO 2022030139A1
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group
compound
production example
photoacid generator
nmr
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PCT/JP2021/024283
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English (en)
French (fr)
Japanese (ja)
Inventor
秀基 木村
篤志 白石
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サンアプロ株式会社
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Priority to KR1020227007502A priority Critical patent/KR102792755B1/ko
Priority to CN202180005348.8A priority patent/CN114402260A/zh
Priority to JP2022514259A priority patent/JPWO2022030139A1/ja
Publication of WO2022030139A1 publication Critical patent/WO2022030139A1/ja

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition

Definitions

  • the present invention relates to a photoacid generator useful as a photocurable composition and a chemically amplified negative photoresist composition, and is a photoacid generator useful for yellowing resistance of these compositions.
  • Onium salts such as sulfonium salts are used as photocationic polymerization initiators that cure cationically polymerizable compounds such as epoxy compounds by irradiation with active energy rays (hereinafter referred to as light) such as light and electron beams (Patent Documents 1 to 3).
  • light active energy rays
  • Patent Documents 4 to 6 it is known as a photoacid generator because it generates acid by light irradiation, and is widely used in photoresists, photosensitive materials, and the like.
  • the sulfonium salt produced by such a method produces a bissulfonium salt having two sulfonio groups in one molecule in addition to the monosulfonium salt having one sulfonio group in one molecule.
  • the bissulfonium salt has a higher photopolymerization initiation ability than the monosulfonium salt, but has low solubility in a cationically polymerizable monomer and a diluting solvent used as needed.
  • the problem that the bissulfonium salt precipitates and precipitates from the sulfonium salt solution over time may occur.
  • the cationically polymerizable compound containing a bissulfonium salt has a problem that it tends to thicken over time and cannot be stored for a long period of time. Therefore, the applicant discloses a production method for efficiently obtaining a high-purity monosulfonium salt in order to solve the above problems (Patent Document 7).
  • the change in hue of the cured product over time (a phenomenon in which the cured product is colored yellow to brown over time; hereinafter referred to as yellowing) is balanced with the curability. There was a request for further improvement in.
  • an object of the present invention is a useful photoacid generator for a photocurable composition or a chemically amplified negative photoresist composition, which is useful for yellowing resistance of these compositions. It is a provision of a photoacid generator.
  • the present invention contains a sulfonium salt (CA) represented by the following general formula (1) and a compound (S) represented by the general formula (2), and is the sum of the sulfonium salt (CA) and the compound (S).
  • CA sulfonium salt
  • S compound represented by the general formula (2)
  • the area ratio of the compound (S) is 0.02 or more and 3.0 or less. It is a photoacid generator characterized by being present.
  • R 1 to R 3 are organic groups bonded to the benzene ring, p, q, and r represent the number of R 1 to R 3 , respectively, and p is 0 to. It is an integer of 4, q and r are integers of 0 to 5, and when it is 0, hydrogen atoms are bonded, and when p, q and r are 2 or more, they are different even if they are the same. Also good, R 1 to R 3 are direct to each other or -O-, -S-, -SO-, -SO 2- , -NH-, -CO-, -COO-, -CONH-, alkylene group or phenylene.
  • a ring structure may be formed via a group
  • X is an atom (group) that can be a monovalent anion
  • Ar 1 to Ar 3 may have the same or different carbon atoms from each other.
  • a heteroaryl group having 4 to 18 carbon atoms and the aryl group or heteroaryl group of Ar 1 may be further substituted with a group represented by the formula (3), and R in the formula (3).
  • 2 , R 3 , r, q and X are the same as in equation (1), and n in equation (2) is an integer of 1 or 2.
  • the present invention is a photocurable composition
  • a photocurable composition comprising the photoresist generator and a cationically polymerizable compound; a curing characterized by being obtained by curing the photoresistable composition.
  • Body A chemically amplified negative photoresist composition comprising the above-mentioned photoacid generator, a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and a cross-linking agent component (G).
  • a cured product obtained by curing the chemically amplified negative photoresist composition.
  • the photoacid generator of the present invention has high activity against light, has cationic polymerization performance and cross-linking reaction performance, and is useful for yellowing resistance by using the photoacid generator of the present invention. Useful compositions can be obtained.
  • R 1 to R 3 in the formulas (1) to (3) represent an organic group bonded to a benzene ring, and may be the same or different.
  • Examples of the organic group of R 1 to R 3 include an aryl group having 6 to 30 carbon atoms, a heteroaryl 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 alkenyl group having 2 to 30 carbon atoms.
  • alkynyl group hydroxy group, 1 to 18 carbon number alkoxy group, 6 to 10 carbon number aryloxy group, 2 to 19 carbon number alkylcarbonyl group, 7 to 11 carbon number arylcarbonyl group, carbon An alkoxycarbonyl group having 2 to 19, an aryloxycarbonyl group having 7 to 11 carbon atoms, an arylthiocarbonyl group having 7 to 11 carbon atoms, an acyloxy group having 2 to 19 carbon atoms, an arylthio group having 6 to 20 carbon atoms, and carbon.
  • alkylthio group having 1 to 18 carbon atoms an alkylsulfinyl group having 1 to 18 carbon atoms, an arylsulfinyl group having 6 to 10 carbon atoms, an alkylsulfonyl group having 1 to 18 carbon atoms, an arylsulfonyl group having 6 to 10 carbon atoms, and an alkylene group.
  • alkylthio group having 1 to 18 carbon atoms an alkylsulfinyl group having 1 to 18 carbon atoms, an arylsulfinyl group having 6 to 10 carbon atoms, and an alkylene group.
  • alkylthio group having 1 to 18 carbon atoms an alkylsulfinyl group having 1 to 18 carbon atoms, an arylsulfinyl group having 6 to 10 carbon atoms, and an alkylene group.
  • alkylthio group having 1 to 18 carbon atoms an alkylsulfinyl group
  • the aryl group having 6 to 30 carbon atoms includes a monocyclic aryl group such as a phenyl group and a biphenylyl group, and naphthyl, anthrasenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthalsenyl, benzanthrasenyl, anthraquinolyl, fluorenyl, naphthoquinone and anthraquinone.
  • Examples thereof include fused polycyclic aryl groups such as.
  • heteroaryl group having 4 to 30 carbon atoms examples include cyclic compounds containing 1 to 3 complex atoms such as oxygen, nitrogen, and sulfur, which may be the same or different, and as a specific example.
  • monocyclic heteroaryl groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl.
  • Carbazolyl acridinyl, phenothiazinyl, phenazinyl, xanthenyl, thiantranyl, phenoxadinyl, phenoxatyynyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl, dibenzofuranyl and the like.
  • Alkyl groups having 1 to 30 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexadecyl and octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl and isohexyl. Examples thereof include branched alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • alkenyl group having 2 to 30 carbon atoms examples include vinyl, allyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl and the like.
  • alkynyl group having 2 to 30 carbon atoms examples include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-1-propynyl, 1-methyl-2-propynyl and the like. Can be mentioned.
  • alkoxy group having 1 to 18 carbon atoms examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, and dodecyloxy.
  • Examples of the aryloxy group having 6 to 10 carbon atoms include phenoxy and naphthyloxy.
  • alkylcarbonyl group having 2 to 19 carbon atoms examples include acetyl, trifluoroacetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyle, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl and the like.
  • arylcarbonyl group having 7 to 11 carbon atoms examples include benzoyl, 4-tert-butylbenzoyl, and naphthoyl.
  • alkoxycarbonyl group having 2 to 19 carbon atoms examples include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl and the like.
  • Examples of the aryloxycarbonyl group having 7 to 11 carbon atoms include phenoxycarbonyl and naphthoxycarbonyl.
  • arylthiocarbonyl group having 7 to 11 carbon atoms examples include phenylthiocarbonyl and naphthoxythiocarbonyl.
  • Examples of the asyloxy group having 2 to 19 carbon atoms include acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butylcarbonyloxy, tert-butylcarbonyloxy, octadecylcarbonyloxy and the like.
  • arylthio group having 6 to 20 carbon atoms examples include 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- Examples thereof include benzoyl-methylthiophenylthio, 4- (methylthiobenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio and the like.
  • alkylthio group having 1 to 18 carbon atoms examples include methylthio, ethylthio, propylthio, tert-butylthio, neopentylthio, dodecylthio and the like.
  • alkylsulfinyl group having 1 to 18 carbon atoms examples include methylsulfinyl, ethylsulfinyl, propylsulfinyl, tert-pentylsulfinyl, octylsulfinyl and the like.
  • arylsulfinyl group having 6 to 10 carbon atoms examples include phenylsulfinyl, trillsulfinyl, and naphthylsulfinyl.
  • alkylsulfonyl group having 1 to 18 carbon atoms examples include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, butylsulfonyl, and octylsulfonyl.
  • arylsulfonyl group having 6 to 10 carbon atoms examples include phenylsulfonyl, tolylsulfonyl, and naphthylsulfonyl.
  • halogen group examples include fluoro, chloro, bromo and iodine.
  • an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon atoms, and a carbon number of carbon atoms are preferable. It is an arylcarbonyl group having 7 to 11, an alkylthio group having 1 to 6 carbon atoms, an arylthio group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a chloro group and a fluorogroup, and more preferably 1 carbon group.
  • p, q, and r represent the number of R 1 to R 3 , respectively, p is an integer of 0 to 4, q, and r are integers of 0 to 5, and 0.
  • R 1 to R 3 may be directly or -O-, -S. -, -SO-, -SO 2- , -NH-, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group may form a ring structure.
  • R1s thereof are directly or -O-, -S-, -SO-, -SO 2- , -NH-, -CO-, -COO-, -CONH. -, Means to form a ring structure via an alkylene group or a phenylene group.
  • Ar 1 to Ar 3 are aryl groups having 6 to 18 carbon atoms or heteroaryl groups having 4 to 18 carbon atoms, which may be the same or different from each other, respectively.
  • the aryl group or heteroaryl group may be further substituted with the group represented by the formula (3).
  • Examples of the aryl group having 6 to 18 carbon atoms include the aryl group having 6 to 18 carbon atoms among the aryl groups having 6 to 30 carbon atoms in R1 to R3 in the above formula (1), and preferably. It is an aryl group having 6 to 14 carbon atoms.
  • heteroaryl group having 4 to 18 carbon atoms examples include heteroaryl groups having 4 to 18 carbon atoms among the heteroaryl groups having 4 to 30 carbon atoms in R1 to R3 in the above formula (1).
  • a heteroaryl group having 4 to 14 carbon atoms Preferably a heteroaryl group having 4 to 14 carbon atoms.
  • These aryl groups and heteroaryl groups may have a substituent, and the substituents include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms.
  • Examples thereof include an alkylcarbonyl group having 2 to 6 carbon atoms, an arylcarbonyl group having 7 to 11 carbon atoms, an arylthio group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a chloro group and a fluoro group.
  • n an integer of 1 or 2.
  • sulfonium salts (CA) represented by the formula (1) specific examples of the cation portion (C), which is more preferable from the viewpoint of sensitivity and solubility, are shown below.
  • X is an atom (group) that can be a monovalent anion, that is, X ⁇ irradiates a sulfonium salt with light (visible light, ultraviolet light, electron beam, X-ray, etc.). It is an anion corresponding to the acid (HX) generated by the above.
  • X - is not limited except that it is a monovalent polyatomic anion, but MY a- , (Rf) b PF 6-b- , R 8 c BY 4-c- , R 8 c GaY 4
  • Anions represented by -c- , R 9 SO 3- , (R 9 SO 2 ) 3 C- or (R 9 SO 2 ) 2 N- are preferred.
  • M represents a phosphorus atom, a boron atom or an antimony atom.
  • Y represents a halogen atom (preferably a fluorine atom).
  • Rf represents an alkyl group in which 80 mol% or more of a hydrogen atom is substituted with a fluorine atom (an alkyl group having 1 to 8 carbon atoms is preferable).
  • Alkyl groups to be Rf by fluorine substitution include linear alkyl groups (methyl, ethyl, propyl, butyl, pentyl, octyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, etc.) and Cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and the like can be mentioned.
  • the ratio of hydrogen atoms of these alkyl groups substituted with fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90, based on the number of moles of hydrogen atoms possessed by the original alkyl group. % Or more, particularly preferably 100%.
  • the substitution ratio by the fluorine atom is in these preferable ranges, the photosensitivity of the sulfonium salt is further improved.
  • Rf are 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-.
  • the b Rfs are independent of each other and therefore may be the same or different from each other.
  • P represents a phosphorus atom and F represents a fluorine atom.
  • R 8 represents a phenyl group in which a part of a hydrogen atom is substituted with at least one element or an electron-withdrawing group.
  • Examples of such one element include a halogen atom and include a fluorine atom, a chlorine atom, a bromine atom and the like.
  • Examples of the electron-withdrawing group include a trifluoromethyl group, a nitro group and a cyano group. Of these, a phenyl group in which one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable.
  • the c R8s are independent of each other and therefore may be the same or different from each other.
  • B represents a boron atom and Ga represents a gallium atom.
  • R 9 represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a fluorine atom, and the alkyl group and the perfluoroalkyl group are linear and fractionated. It may be branched or cyclic, and the aryl group may be unsubstituted or has a substituent.
  • S represents a sulfur atom
  • O represents an oxygen atom
  • C represents a carbon atom
  • N represents a nitrogen atom.
  • a represents an integer of 4 to 6.
  • b is preferably an integer of 1 to 5, more preferably 2 to 4, and particularly preferably 2 or 3.
  • c is preferably an integer of 1 to 4, and more preferably 4.
  • Examples of the anion represented by MY a ⁇ include anions represented by SbF 6 ⁇ , PF 6 ⁇ and BF 4 ⁇ .
  • the anions represented by (Rf) b PF 6-b- include (CF 3 CF 2 ) 2 PF 4- , (CF 3 CF 2 ) 3 PF 3- , ((CF 3 ) 2 CF) 2 PF 4 - , ((CF 3 ) 2 CF) 3 PF 3- , (CF 3 CF 2 CF 2 ) 2 PF 4- , (CF 3 CF 2 CF 2 ) 3 PF 3- , ((CF 3 ) 2 CFCF 2 ) 2 PF 4- , ((CF 3 ) 2 CFCF 2 ) 3 PF 3- , (CF 3 CF 2 CF 2 CF 2 ) 2 PF 4 - and (CF 3 CF 2 CF 2 CF 2 ) 3 PF 3- Examples thereof include anions to be formed.
  • the anions represented by R 8 c BY 4-c- are (C 6 F 5 ) 4 B- , ((CF 3 ) 2 C 6 H 3 ) 4 B- , (CF 3 C 6 H 4 ) 4 Examples thereof include anions represented by B- , (C 6 F 5 ) 2 BF 2- , C 6 F 5 BF 3- and (C 6 H 3 F 2 ) 4 B-. Of these, anions represented by (C 6 F 5 ) 4 B- and ((CF 3 ) 2 C 6 H 3 ) 4 B - are preferable.
  • the anions represented by R 8 c GaY 4-c- include (C 6 F 5 ) 4 Ga- , ((CF 3 ) 2 C 6 H 3 ) 4 Ga- , (CF 3 C 6 H 4 ) 4 Examples thereof include anions represented by Ga ⁇ , (C 6 F 5 ) 2 GaF 2 ⁇ , C 6 F 5 GaF 3 ⁇ and (C 6 H 3 F 2 ) 4 Ga ⁇ . Of these, anions represented by (C 6 F 5 ) 4 Ga ⁇ and ((CF 3 ) 2 C 6 H 3 ) 4 Ga ⁇ are preferred.
  • Examples of the anion represented by R 9 SO 3- include trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nonafluorobutane sulfonic acid anion, pentafluorophenylsulfonic acid anion, and fluorosulfonic acid.
  • Examples thereof include anion, p-toluene sulfonic acid anion, benzene sulfonic acid anion, camphor sulfonic acid anion, methane sulfonic acid anion, ethane sulfonic acid anion, propane sulfonic acid anion, butane sulfonic acid anion and octane sulfonic acid anion.
  • trifluoromethanesulfonic acid anion trifluoromethanesulfonic acid anion, nonafluorobutane sulfonic acid anion, methanesulfonic acid anion, butane sulfonic acid anion, camphor sulfonic acid anion, benzenesulfonic acid anion and p-toluene sulfonic acid anion are preferable.
  • the anions represented by (R 9 SO 2 ) 3 C- include (FSO 2 ) 3 C- , (CF 3 SO 2 ) 3 C- , (C 2 F 5 SO 2 ) 3 C- , and (C 3 ). Examples thereof include anions represented by F 7 SO 2 ) 3 C- and (C 4 F 9 SO 2 ) 3 C-.
  • the anions represented by (R 9 SO 2 ) 2 N- include (FSO 2 ) 2 N- , (CF 3 SO 2 ) 2 N- , (C 2 F 5 SO 2 ) 2 N- , and (C 3 ). Examples thereof include anions represented by F 7 SO 2 ) 2 N ⁇ and (C 4 F 9 SO 2 ) 2 N ⁇ .
  • the monovalent polyatomic anions include MY a- , (Rf) b PF 6-b- , R 8 c BY 4-c- , R 8 c GaY 4-c- , R 9 SO 3- , (R 9 ). SO 2 )
  • perhalochloride ion ClO 4- , BrO 4- , etc.
  • halogenated sulfonate ion FSO 3- , ClSO) 3 - etc.
  • Sulfate ion CH 3 SO 4- , CF 3 SO 4- , HSO 4- , etc.
  • Carbonate ion HCO 3- , CH 3 CO 3- , etc.
  • Aluminate ion AlCl 4- , AlF) 4- , Al (OC 4 F 9 ) 4- , etc.
  • Hexafluorobismuth acid ion BiF 6- )
  • Carboxylic acid ion CH
  • the sulfonium salt represented by the formula (1) can be produced by a known production method. For example, a method of reacting diaryl sulfide with chlorine, a method of reacting diaryl sulfide with aromatic hydrocarbons such as chlorine and benzene, a method of reacting diaryl sulfide with a copper-catalyzed diaryl iodonium salt, and a method of reacting diaryl sulfide and diaryl sulfoxide with a dehydrating agent. There is a way to react in the presence.
  • the dehydrating agent is not particularly limited as long as it is used as a dehydrating agent in an organic chemical reaction, and examples thereof include concentrated sulfuric acid, anhydrous phosphoric acid, methanesulfonic acid, trifluoromethanesulfonic acid or an anhydride thereof. Two or more of these may be mixed and used. Moreover, you may use a solvent as appropriate.
  • the molar ratio of sulfoxide: sulfide 10: 1 to 1: 1, more preferably 7: 1 to 2: 1, and most preferably 5: 1 to 2. It is 5: 1.
  • the reaction temperature is ⁇ 10 ° C. to 70 ° C., preferably 0 ° C. to 50 ° C., and most preferably 10 ° C. to 30 ° C.
  • a sulfonium salt can be efficiently produced by exchanging anions with an acid (HX) and a salt (AXn) having an anion represented by X in the formulas (1) and (3).
  • A is a counter cation of anion X ⁇
  • n represents the number of anions X with respect to the valence of cation A.
  • A represents an alkali metal such as Na, K, Li, an alkaline earth metal such as Mg, Ca, or an ammonium cation. Alkali metals are more preferable because of the availability of raw materials and the ease of purification of the sulfonium salt to be produced.
  • High performance liquid chromatography is used as a method for analyzing the content of a photoacid generator containing a sulfonium salt (CA) represented by the general formula (1) and a compound (S) represented by the general formula (2) of the present invention.
  • HPLC high performance liquid chromatography
  • the ratio of the peak area of the compound (S) when the peak areas of the sulfonium salt (CA) and the compound (S) obtained by the HPLC method are totaled and set to 100 may be obtained. The following are the measurement conditions for HPLC.
  • the contents of the sulfonium salt (CA) represented by the general formula (1) and the compound (S) represented by the general formula (2) are those of the sulfonium salt (CA) and the compound (S) according to the above-mentioned content measurement method.
  • the area ratio of the compound (S) when the total area is 100 is 0.02 or more and 3.0 or less.
  • Conjugate acid generated by containing a certain amount of the compound (S) represented by the general formula (2) with the sulfonium salt (CA) represented by the general formula (1) can be trapped, or oxygen in the system can be removed. It is considered that the trapping suppresses coloring due to protonation, oxidation, and the like.
  • the photoacid generator of the present invention may contain other conventionally known photoacid generators in addition to the sulfonium salts listed above, if necessary.
  • the photoacid generator of the present invention contains a sulfonium salt (CA) represented by the general formula (1) and a compound (S) represented by the general formula (2), and other photoacid generators are generated. It means that the agent is not included.
  • the content (mol%) of the other photoacid generator is based on the number of moles of the sulfonium salt (CA) represented by the general formula (1) of the present invention. It is preferably 0.1 to 100, more preferably 0.5 to 50.
  • photoacid generators include conventionally known salts such as onium salts (sulfonium, iodonium, selenium, ammonium and phosphonium, etc.) and salts of transition metal complex ions and anions.
  • the photoacid generator of the present invention may be previously dissolved in a solvent that does not inhibit polymerization, cross-linking, deprotection reaction, etc. in order to facilitate dissolution in a cationically polymerizable compound or a chemically amplified resist composition.
  • the solvent examples 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, methylisoamyl ketone and 2-heptanone; ethylene glycol and ethylene glycol.
  • Polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate.
  • cyclic ethers such as dioxane; ethyl acetate, 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
  • esters such as acetate and 3-methyl-3-methoxybutyl acetate; aromatic hydrocarbons such as toluene and xylene.
  • the ratio of the solvent used is preferably 15 to 1000 parts by weight, more preferably 30 to 500 parts by weight, based on 100 parts by weight of the photoacid generator of the present invention.
  • the solvent used may be used alone or in combination of two or more.
  • the photocurable composition of the present invention comprises the above photoacid generator and a cationically polymerizable compound.
  • Examples of the cationically polymerizable compound that is a constituent of the photocurable composition include cyclic ethers (epoxides and oxetane, etc.), ethylenically unsaturated compounds (vinyl ethers, styrene, etc.), bicycloorthoesters, spiroletocarbonates, spiroletoesters, and the like.
  • cyclic ethers epoxides and oxetane, etc.
  • ethylenically unsaturated compounds vinyl ethers, styrene, etc.
  • bicycloorthoesters ethylenically unsaturated compounds
  • spiroletocarbonates spiroletoesters
  • epoxide known epoxides and the like can be used, and aromatic epoxides, alicyclic epoxides and aliphatic epoxides are included.
  • aromatic epoxide examples include glycidyl ethers of monovalent or polyvalent phenols (phenols, bisphenol A, phenol novolacs and compounds obtained by adding alkylene oxides thereof) having at least one aromatic ring.
  • the alicyclic epoxide is 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.). Can be mentioned.
  • aliphatic epoxide examples include an aliphatic polyhydric alcohol or a polyglycidyl ether (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.) of this alkylene oxide adduct, and an aliphatic polybasic acid.
  • examples thereof include polyglycidyl esters (diglycidyl tetrahydrophthalate, etc.) and epoxidized long-chain unsaturated compounds (epoxidized soybean oil, epoxidized polybutadiene, etc.).
  • oxetane known ones and the like 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, oxetanyl sill sesquioxetane, phenol novolac oxetane, etc.
  • Oxetanylmethyl) ether 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, oxetanyl sill
  • known cationically polymerizable monomers and the like can be used, and include aliphatic monovinyl ethers, aromatic monovinyl ethers, polyfunctional vinyl ethers, styrene and cationically polymerizable nitrogen-containing monomers.
  • Examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether and the like.
  • aromatic monovinyl ether examples include 2-phenoxyethyl vinyl ether, phenyl vinyl ether and p-methoxyphenyl vinyl ether.
  • polyfunctional vinyl ether examples include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.
  • styrene examples include styrene, ⁇ -methylstyrene, p-methoxystyrene, p-tert-butoxystyrene and the like.
  • Examples of the cationically 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 can be mentioned.
  • spiro orthocarbonate examples include 1,5,7,11-tetraoxaspiro [5.5] undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5.5] undecane. Be done.
  • Spiro-ortho esters include 1,4,6-trioxaspiro [4.4] nonane, 2-methyl-1,4,6-trioxaspiro [4.4] nonane and 1,4,6-trioxas. Pyro [4.5] decane and the like can be mentioned.
  • polyorganosiloxane having at least one cationically polymerizable group in one molecule can be used (Japanese Patent Laid-Open Nos. 2001-348482, 2000-281965, 7-242828, JP. JP-A-2008-19593, Journal of Polymer. Sci., Part A, Polymer. Chem., Vol. 28,497 (1990), etc.). These polyorganosiloxanes may be linear, branched, or cyclic, or may be a mixture thereof.
  • cationically polymerizable compounds epoxides, oxetane and vinyl ethers are preferable, and epoxides and oxetanees are more preferable, and alicyclic epoxides and oxetanees are particularly preferable. Further, these cationically polymerizable compounds may be used alone or in combination of two or more.
  • the content of the photoacid generator of the present invention in the photocurable composition is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. be. Within this range, the polymerization of the cationically polymerizable compound becomes more sufficient, and the physical properties of the cured product become even better. This content is determined by considering various factors such as the properties of the cationically polymerizable compound, the type of light (light source, wavelength, etc.), irradiation amount, temperature, curing time, humidity, and coating thickness. , Not limited to the above range.
  • the photocurable composition of the present invention may contain known additives (sensitizers, pigments, fillers, antistatic agents, flame retardants, defoamers, flow modifiers, light stabilizers, oxidations, if necessary. It can contain an inhibitor, an adhesion-imparting agent, an ion-supplementing agent, an anti-coloring agent, a solvent, a non-reactive resin, a radically polymerizable compound, etc.).
  • sensitizer known sensitizers (Japanese Patent Laid-Open Nos. 11-279212 and Japanese Patent Laid-Open No. 09-183960, etc.) can be used, and anthracene ⁇ anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene, etc. can be used.
  • the content of the sensitizer is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, based on 100 parts by weight of the photoacid generator.
  • pigment known pigments and the like can be used, and examples thereof include inorganic pigments (titanium oxide, iron oxide, carbon black, etc.) and organic pigments (azo pigments, cyanine pigments, phthalocyanine pigments, quinacridone pigments, etc.).
  • inorganic pigments titanium oxide, iron oxide, carbon black, etc.
  • organic pigments azo pigments, cyanine pigments, phthalocyanine pigments, quinacridone pigments, etc.
  • the content of the pigment is preferably 0.5 to 400,000 parts by weight, more preferably 10 to 150,000 parts by weight, based on 100 parts by weight of the photoacid generator.
  • filler known fillers and the like can be used, and molten silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate, lithium aluminum silicate and the like can be used. Can be mentioned.
  • the content of the filler is preferably 50 to 600,000 parts by weight, more preferably 300 to 200,000 parts by weight, based on 100 parts by weight of the photoacid generator.
  • antistatic agent known antistatic agents and the like can be used, and examples thereof include non-ionic antistatic agents, anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents and polymer antistatic agents. ..
  • the content of the antistatic agent is preferably 0.1 to 20,000 parts by weight, more preferably 0.6 to 5,000 parts by weight, based on 100 parts by weight of the photoacid generator.
  • a known flame retardant or the like can be used, and an inorganic flame retardant ⁇ antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide , Magnesium hydroxide and calcium aluminate ⁇ ; brominated flame retardants ⁇ tetrabromophthalic anhydride, hexabromobenzene and decabromobiphenyl ethers, etc. ⁇ ; and phosphoric acid ester flame retardants ⁇ tris (tribromophenyl) phosphate, etc. ⁇ Be done.
  • 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, based on 100 parts by weight of the photoacid generator.
  • the defoaming agent a known defoaming agent or the like can be used, and an alcohol defoaming agent, a metal soap defoaming agent, a phosphoric acid ester defoaming agent, a fatty acid ester defoaming agent, a polyether defoaming agent, a silicone defoaming agent. And mineral oil defoaming agents and the like.
  • known fluidity adjusters and the like can be used, and examples thereof include hydrogenated castor oil, polyethylene oxide, organic bentonite, colloidal silica, amidowax, metal soap and acrylic acid ester polymers.
  • known light stabilizers and the like can be used, and ultraviolet absorption type stabilizers ⁇ benzotriazole, benzophenone, salicylate, cyanoacrylate and derivatives thereof, etc. ⁇ ; radical supplement type stabilizers ⁇ hindered amine, etc. ⁇ ; and quenching. Examples thereof include type stabilizers ⁇ nickel complexes, etc. ⁇ .
  • antioxidants and the like can be used, and examples thereof include phenol-based antioxidants (monophenol-based, bisphenol-based and high molecular weight phenol-based, etc.), sulfur-based antioxidants, phosphorus-based antioxidants, and the like. Be done.
  • adhesion-imparting agent a known adhesion-imparting agent or the like can be used, and examples thereof include a coupling agent, a silane coupling agent, and a titanium coupling agent.
  • ion catching agent known ion catching agents and the like can be used, and examples thereof include organoaluminum (alkoxyaluminum, phenoxyaluminum and the like).
  • an antioxidant is effective, and a phenol-based antioxidant (monophenol-based, bisphenol-based, polymer phenol-based, etc.), sulfur-based oxidation Examples thereof include antioxidants and phosphorus-based antioxidants, but they have little effect in preventing coloration during heat resistance tests at high temperatures.
  • the content of each is based on 100 parts of the photoacid generator. It 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 cationically polymerizable compound and adjusting the viscosity of the photocurable composition, and the solvent mentioned above as the solvent for the photoacid generator can be used.
  • the content of the solvent is preferably 50 to 2000000 parts by weight, more preferably 200 to 500,000 parts by weight, based on 100 parts by weight of the photoacid generator.
  • Non-reactive resins include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, styrene butadiene block copolymer hydrogenated materials, and (meth) acrylic acid esters.
  • Examples include coalescence and polyurethane.
  • the number average molecular weight of these resins is preferably 1000 to 500,000, more preferably 5000 to 100,000 (the number average molecular weight is a value measured by a general method such as GPC).
  • the content of the non-reactive resin is preferably 5 to 400,000 parts by weight, more preferably 50 to 150,000 parts by weight, based on 100 parts by weight of the photoacid generator.
  • non-reactive resin When a non-reactive resin is contained, it is desirable to dissolve the non-reactive resin in a solvent in advance in order to easily dissolve the non-reactive resin with a cationically polymerizable compound or the like.
  • Known radically polymerizable compounds include ⁇ Photopolymer Handbook edited by Photopolymer Council (1989, Industrial Research Council), UV / EB Curing Technology edited by Comprehensive Technology Center (1982, Comprehensive Technology Center), Radtech Research. "UV / EB Curing Materials” (1992, CMC) edited by the Society, “Causes of Curing Poorness / Inhibition in UV Curing and Countermeasures” (2003, Technical Information Association) ⁇ , etc. It can be used and includes monofunctional monomers, bifunctional monomers, polyfunctional monomers, epoxy (meth) acrylates, polyester (meth) acrylates and urethane (meth) acrylates.
  • the content of the radically polymerizable compound is preferably 5 to 400,000 parts by weight, more preferably 50 to 150,000 parts by weight, based on 100 parts by weight of the photoacid generator.
  • radical polymerization initiator that initiates polymerization by heat or light in order to increase the polymer by radical polymerization.
  • radical polymerization initiator a known radical polymerization initiator or the like can be used, and a thermal radical polymerization initiator (organic peroxide, azo compound, etc.) and a photoradical polymerization initiator (acetophenone-based initiator, benzophenone-based initiator, etc.) can be used. Michler ketone-based initiators, benzoin-based initiators, thioxanthone-based initiators, acylphosphine-based initiators, etc.) are included.
  • 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 by weight of the radically polymerizable compound. ..
  • the photocurable composition of the present invention uniformly comprises a cationically polymerizable compound, a photoacid generator and, if necessary, an additive at room temperature (about 20 to 30 ° C.) or, if necessary, heating (about 40 to 90 ° C.). It can be mixed and dissolved, or further kneaded with three rolls or the like to prepare.
  • the photocurable composition of the present invention can be cured by irradiating with light to obtain a cured product.
  • the light used here may be any light as long as it has the energy to induce the decomposition of the photoacid generator of the present invention, but low-pressure, medium-pressure, high-pressure or ultra-high-pressure mercury lamps, metal halide lamps, LED lamps, excimer lamps, etc.
  • Light in the ultraviolet to visible light region (wavelength: about 100 to about 800 nm) obtained from carbon arc lamp, fluorescent lamp, semiconductor solid-state laser, argon laser, He - Cd laser, KrF excimer laser, ArF excimer laser, F2 laser, etc. Is preferable.
  • As the light radiation having high energy such as electron beam or X-ray can also be used.
  • the irradiation time of light is affected by the intensity of the light source and the transparency of light to the photocurable composition, but at room temperature (about 20 to 30 ° C.), about 0.1 to 10 seconds is sufficient. However, when the light transmission is low or the film thickness of the photocurable composition is thick, it may be preferable to take a longer time. Most of the photocurable compositions are cured by cation polymerization 0.1 seconds to several minutes after light irradiation, but if necessary, after light irradiation, at room temperature (about 20 to 30 ° C.) to 200 ° C. for several seconds to It is also possible to heat for several hours and aftercure.
  • photocurable composition of the present invention include paints, coating agents, various coating materials (hard coats, stain-resistant coating materials, anti-fog coating materials, touch-resistant coating materials, optical fibers, etc.), and adhesive tapes.
  • Back treatment agent release coating material for adhesive label release sheet (release paper, release plastic film, release metal foil, etc.), printing board, dental material (dental compound, dental composite) ink, inkjet ink, resist film , Liquid resist, negative type resist (surface protective film for semiconductor elements, interlayer insulating film, permanent film material such as flattening film, etc.), resist for MEMS, negative type photosensitive material, various adhesives (temporary for various electronic parts)
  • the photoacid generator of the present invention Since the photoacid generator of the present invention generates a strong acid by light irradiation, it is a chemically amplified type known (Japanese Patent Laid-Open No. 2003-267768, JP-A-2003-261259, JP-A-2002-193925, etc.). It can also be used as a photoacid generator for resist materials.
  • the chemically amplified resist material includes (1) a two-component chemically amplified positive resist containing a resin that becomes soluble in an alkaline developer due to the action of an acid and a photoacid generator as essential components, and (2) an alkaline developer.
  • a two-component chemically amplified positive resist containing a resin that becomes soluble in an alkaline developer due to the action of an acid and a photoacid generator as essential components and (2) an alkaline developer.
  • 3-component chemically amplified positive resists containing a soluble resin, a dissolution inhibitor that becomes soluble in an alkaline developer due to the action of an acid, and a photoacid generator as essential components and (3) an alkaline developer.
  • the photoacid generator of the present invention is preferably used for a chemically amplified negative resist that is used as a protective film or the like even after pattern formation.
  • the chemically amplified negative photoresist composition of the present invention comprises a component (E) containing the photoacid generator of the present invention, which is a compound that generates an acid by light or irradiation, and an alkali-soluble having a phenolic hydroxyl group. It is characterized by containing a resin (F) and a cross-linking agent (G).
  • the component (E) may be used in combination with other conventionally known photoacid generators.
  • photoacid generators include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, disulfonyldiazomethane compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazinesulfonate compounds, triazine compounds, and nitrobenzyls.
  • organic halides, disulfones and the like can be mentioned.
  • photoacid generator preferably one or more selected from the group of onium compound, sulfoneimide compound, diazomethane compound and oxime sulfonate compound is preferable.
  • the proportion thereof may be arbitrary, but usually, the other photoacid generators are used with respect to 100 parts by weight of the total weight of the photoacid generators of the present invention. Is 10 to 900 parts by weight, preferably 25 to 400 parts by weight.
  • the content of the component (E) is preferably 0.01 to 10% by weight based on the solid content of the chemically amplified negative photoresist composition.
  • Alkali-soluble resin (F) having a phenolic hydroxyl group The "alkali-soluble resin having a phenolic hydroxyl group" (hereinafter referred to as "phenolic resin (F)") in the present invention includes, for example, novolak resin, polyhydroxystyrene, a copolymer of polyhydroxystyrene, hydroxystyrene and styrene. , Hydroxystyrene, styrene and (meth) acrylic acid derivative copolymers, phenol-xylylene glycol condensed resin, cresol-xylylene glycol condensed resin, phenol-dicyclopentadiene condensed resin and the like are used.
  • novolak resin polyhydroxystyrene, polyhydroxystyrene copolymer, hydroxystyrene and styrene copolymer, hydroxystyrene, styrene and (meth) acrylic acid derivative copolymer, phenol-xylylene glycol.
  • Condensed resin is preferred.
  • these phenol resins (F) may be used individually by 1 type, and may be used by mixing 2 or more types.
  • the phenol resin (F) may contain a phenolic small molecule compound as a part of the component.
  • phenolic small molecule compound examples include 4,4'-dihydroxydiphenylmethane and 4,4'-dihydroxydiphenyl ether.
  • crosslinking 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).
  • the cross-linking agent (G) include a compound having at least two or more alkyl etherified amino groups in the molecule, and a compound having at least two or more alkyl etherified benzenes in the molecule as a skeleton. Examples thereof include an oxylan ring-containing compound, a thiirane ring-containing compound, an oxetanyl group-containing compound, and an isocyanate group-containing compound (including blocked compounds).
  • cross-linking agents (G) a compound having at least two or more alkyl etherified amino groups in the molecule and an oxylan ring-containing compound are preferable. Furthermore, it is more preferable to use a compound having at least two or more alkyl etherified amino groups in the molecule and an oxylan ring-containing compound in combination.
  • the blending amount of the cross-linking agent (G) in the present invention is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the phenol resin (F).
  • the amount of the cross-linking agent (G) is 1 to 100 parts by weight, the curing reaction proceeds sufficiently, and the obtained cured product has a high resolution and a good pattern shape, and has heat resistance and electrical insulation. It is preferable because it has excellent properties.
  • the compound having an alkyl etherified amino group and the oxylan ring-containing compound are used in combination, the content ratio of the oxylan ring-containing compound is 100, which is the total of the compound having an alkyl etherified amino group and the oxylan ring-containing compound.
  • % by 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 has excellent chemical resistance without impairing high resolution.
  • Crosslinked 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 impact resistance of the obtained cured product. Can be made to.
  • the average particle size of the crosslinked fine particles (H) is usually 30 to 500 nm, preferably 40 to 200 nm, and 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 emulsifier used to control the particle size. You can control it.
  • the average particle size of the crosslinked fine particles (H) is a value measured by diluting the dispersion liquid of the crosslinked fine particles according to a conventional method using a light scattering flow distribution measuring device or the like.
  • the blending amount of the crosslinked fine particles (H) is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the phenol resin (F).
  • the blending 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 obtained cured film are improved. be able to.
  • the chemically amplified negative photoresist composition of the present invention may contain an adhesion aid in order to improve the adhesion to the substrate.
  • adhesion aid 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 blending amount of the adhesion aid is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the phenol resin (F).
  • the blending amount of this adhesion aid is 0.2 to 10 parts by weight, it is preferable because it is excellent in storage stability and good adhesion can be obtained.
  • the chemically amplified negative photoresist composition of the present invention can contain a solvent in order to improve the handleability of the resin composition and to adjust the viscosity and storage stability.
  • the solvent is not particularly limited, and specific examples thereof include those described above.
  • the chemically amplified negative photoresist composition of the present invention may contain, if necessary, other additives to the extent that the characteristics of the present invention are not impaired.
  • other additives include inorganic fillers, sensitizers, quenchers, leveling agents, surfactants and the like.
  • 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 inside and completely plugged on a wave rotor.
  • the cured product in the present invention is characterized in that the chemically amplified negative photoresist composition is cured.
  • the chemically amplified negative photoresist composition according to the present invention described above has a high residual film ratio and is excellent in resolution, and the cured product is excellent in electrical insulation, thermal shock resistance and the like.
  • the cured product can be suitably used as a surface protective film, a flattening film, an interlayer insulating film material, or the like for electronic components such as semiconductor devices and semiconductor packages.
  • the chemically amplified negative photoresist composition according to the present invention is used as a support (copper foil with resin, copper-clad laminate, silicon wafer with metal sputter film, or the like.
  • Alumina substrate, etc. is coated and dried to volatilize the solvent, etc. to form a coating film.
  • PEB heat treatment
  • the desired pattern can be obtained by developing with an alkaline developer to dissolve and remove the unexposed portion.
  • a cured film can be obtained by performing a heat treatment in order to exhibit the insulating film characteristics.
  • 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.
  • light is synonymous with active energy rays, and may be any light that activates a photoacid generator in order to generate an acid, and includes ultraviolet rays, visible rays, and far ultraviolet rays, and also “radiation”.
  • "" Means X-rays, electron beams, ion rays and the like.
  • Examples of the source of light or radiation include ultraviolet rays, electron beams, laser beams and the like of low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-ray steppers, h-ray steppers, i-line steppers, gh-line steppers, ghi-line steppers and the like. Be done.
  • 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 of 1 to 50 ⁇ m is about 100 to 50,000 J / m 2 .
  • the above PEB treatment is performed in order to accelerate the curing reaction between the phenol resin (F) and the cross-linking agent (G) by the generated acid.
  • the PEB conditions vary depending on the blending amount of the resin composition, the film thickness used, and the like, but are usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes.
  • it is developed with an alkaline developer to dissolve and remove the unexposed portion to form a desired pattern.
  • Examples of the developing method in this case include a shower developing method, a spray developing method, a dipping developing method, a paddle developing method, and the like.
  • the developing conditions are usually about 1 to 10 minutes at 20 to 40 ° C.
  • the composition in order to sufficiently exhibit the characteristics as an insulating film after development, it can be sufficiently cured by performing a heat treatment.
  • a heat treatment is 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 intended use of the cured product.
  • it can be heated in two steps in order to sufficiently proceed with curing and prevent deformation of the obtained pattern shape.
  • the temperature is 50 to 120 ° C. for 5 minutes to 2 minutes. It can be cured by heating for about an hour and then heating at a temperature of 80 to 250 ° C. for about 10 minutes to 10 hours.
  • a general oven, an infrared oven, or the like can be used as the heating equipment.
  • this pale yellow solid is a mixture of tetrakispentafluorophenyl gallate salt (CA-8) having a cationic structure of (C-2) and compound (S2-1). , The ratio was confirmed to be 99.11: 0.89.
  • this yellow solid is a tetrakispentafluorophenylborate salt (CA-10) having a cationic structure of (C-8), a compound (S8-1), and a compound (S8-). It was confirmed that it was a mixture of 2) and its ratio was 99.22: 0.75: 0.03.
  • this yellow solid is a tetrakispentafluorophenylborate salt (CA-13) having a cationic structure of (C-9), compound (S9-1), and compound (S9-). It was confirmed that it was a mixture of 2) and its ratio was 99.44: 0.54: 0.02.
  • this yellow solid is a tetrakispentafluorophenylborate salt (CA-16) having a cationic structure of (C-10), compound (S10-1), and compound (S10-). It was confirmed that it was a mixture of 2) and its ratio was 99.12: 0.85: 0.03.
  • the reaction solution was cooled to room temperature, poured into 100 mL of ion-exchanged water, extracted with 100 g 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 solid. This was washed with ethyl acetate and hexane, and the organic solvent was concentrated to obtain a methanesulfonate (intermediate-1) having a cationic structure of (C-3).
  • the structure was confirmed by 1 H-NMR.
  • this pale yellow solid is a hexafluorophosphate (CA-25) having a cationic structure of (C-5) and the compounds (S5-1) and (S5-2). ), And its ratio was confirmed to be 99.44: 0.55: 0.01.
  • this pale yellow solid is a hexafluorophosphate (CA-31) having a cationic structure of (C-7) and the compounds (S7-1) and (S7-2). ), And its ratio was confirmed to be 99.25: 0.52: 0.23.
  • this pale yellow solid is a trifluoromethanesulfonate (CA-32) having a cationic structure of (C-7) and compounds (S7-1) and (S7-2). ), And its ratio was confirmed to be 99.21: 0.56: 0.23.
  • this pale yellow solid is a tetrakispentafluorophenylborate salt (CA-33) having a cationic structure of (C-7) and the compounds (S7-1) and (S7-). It was confirmed that it was a mixture of 2) and its ratio was 99.33: 0.34: 0.33.
  • this pale yellow solid is a tohexafluorophosphate (CA-34) having a cationic structure of (C-11) and a compound (S11-1) and (S11-). It was confirmed that it was a mixture of 2) and its ratio was 99.62: 0.34: 0.04.
  • this pale yellow solid is a tetrakispentafluorophenylborate salt (CA-36) having a cationic structure of (C-11) and the compounds (S11-1) and (S11-). It was confirmed that it was a mixture of 2) and its ratio was 99.68: 0.25: 0.07.
  • this pale yellow solid is a tetrakispentafluorophenylborate salt (CA-41) having a cationic structure of (C-13) and the compounds (S13-1) and (S13-). It was confirmed that it was a mixture of 2) and its ratio was 98.98: 0.95: 0.07.
  • this pale yellow solid contains trifluoromethanesulfonate (CA-44) having a cationic structure of (C-14) and compounds (S14-1) to (S14-3). ), And its ratio was confirmed to be 99.03: 0.95: 0.01: 0.01.
  • this pale yellow solid contains trispentafluoroethyltrifluorophosphate (CA-45) having a cationic structure of (C-14) and compounds (S14-1) to (S14-1). It was confirmed that it was a mixture of S14-3) and its ratio was 99.11: 0.86: 0.02: 0.01.
  • this pale yellow solid contains hexafluorophosphate (CA-46) having a cationic structure of (C-15) and compounds (S15-1) to (S15-3). ), And its ratio was confirmed to be 99.29: 0.67: 0.02: 0.02.
  • this pale yellow solid is a tetrakispentafluorophenylborate salt (CA-47) having a cationic structure of (C-15) and compounds (S15-1) to (S15-). It was confirmed that it was a mixture of 3) and its ratio was 99.18: 0.76: 0.04: 0.02.
  • this pale yellow solid contains trispentafluoroethyltrifluorophosphate (CA-48) having a cationic structure of (C-15) and compounds (S15-1) to (S15-1). It was confirmed that it was a mixture of S15-3) and its ratio was 99.16: 0.80: 0.03: 0.01.
  • EP-1 2,2-bis (4-glycidyloxyphenyl) propane
  • EP-2 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate
  • EP-3 3-ethyl-3- ⁇ [(3-Ethyloxetane-3-yl) methoxy] Methyl ⁇ oxetane
  • the above composition was applied on a polyethylene terephthalate (PET) film with an applicator to a film thickness of 25 ⁇ m.
  • PET polyethylene terephthalate
  • the PET film after the coating was irradiated with light having a wavelength limited by a filter using an ultraviolet irradiation device.
  • an IRCF02 filter manufactured by Eye Graphics Co., Ltd., a filter that cuts light of less than 340 nm
  • the hardness of the coating film 40 minutes after the irradiation was measured by the pencil hardness (JIS K5600-5-4: 1999), and the evaluation results according to the following criteria are shown in Table 2. The higher the pencil hardness, the better the sensitivity (cationic polymerization curability) of the photocurable composition.
  • Pencil hardness is 2H or more
  • Pencil hardness is H to B
  • Pencil hardness is 2B-4B
  • Ultraviolet irradiation device Belt conveyor type UV irradiation device (manufactured by Eye Graphics)
  • Lamp 1.5kW high pressure mercury lamp
  • Filter IRCF02 filter (manufactured by Eye Graphics) -Illuminance (measured with a 365 nm head illuminance meter): 150 mW / cm 2 -Integrated light intensity (measured with a 365 nm head illuminance meter): 300 mJ / cm 2
  • ⁇ Yellow degeneration resistance evaluation-1> A Teflon (registered trademark) spacer having a length of 20 mm, a width of 20 mm, and a thickness of 0.1 mm was prepared and sandwiched with slide glass (trade name "S2111", manufactured by Matsunami Glass Co., Ltd.). The curable composition was cast into the gaps, irradiated with light in the same manner as described above, and left at room temperature for 60 minutes after light irradiation to obtain a cured product. The yellowness (YI) of the obtained cured product was measured using a spectrophotometer (“U-3900”, manufactured by Hitachi High-Tech). Let this be YI 0 . Further, the obtained cured product was heated at 180 ° C.
  • thermosetting product before heating obtained in the yellowing resistance evaluation-1 was irradiated with light under the conditions described below, and a light resistance test was carried out.
  • the light yellowing resistance was evaluated by measuring the yellowness YI 2 by the same method as described above. Based on the following formula, the degree of discoloration ⁇ YI value was obtained and compared. The results are shown in Table 2.
  • ⁇ YI (YI 2 )-(YI 0 ) (Light irradiation conditions)
  • Irradiation device "LC-8" (manufactured by Hamamatsu Photonics)
  • Illuminance (measured with a 365 nm head illuminance meter): 100 mW / cm 2
  • Integrated irradiation dose (measured with a 365 nm head illuminance meter): 10 J / cm 2
  • the photocurable composition containing the photoacid generator composition of the present invention is excellent in UV curability and yellowing resistance. Further, from Comparative Examples 1 to 8, it can be seen that the structure of the formula (1) alone has excellent UV curability, but the yellowing resistance is reduced. Further, as can be seen from Examples 27 to 34 and Comparative Examples 9 to 16, if the compound (S) represented by the formula (2) is contained in a certain ratio or more, the UV curability is deteriorated. It can be seen that the content needs to be 3.0 or less.
  • the UV curability and resistance of the photocurable composition containing the photoacid generator composition of the present invention are not limited to the anion structure and the type of epoxy resin. It can be seen that the yellowing is excellent.
  • the yellowness (YI) of the obtained cured product was measured using a spectrophotometer (“U-3900”, manufactured by Hitachi High-Tech). Let this be YI 0 . Further, the obtained cured product was heated at 180 ° C. for 30 minutes, and after heating, YI 3 of the cured product was measured. From these differences, the degree of discoloration ⁇ YI value was obtained and compared.
  • the sensitive energy ray-curable composition using the photoacid generator of the present invention is a paint, a coating agent, various coating materials (hard coat, stain-resistant coating material, anti-fog coating material, touch-resistant coating material, optical fiber, etc.).
  • Adhesive tape back treatment agent adhesive label release sheet (release paper, release plastic film, release metal foil, etc.) release coating material, printing board, dental material (dental compound, dental composite) ink, inkjet Ink, resist film, liquid resist, negative type resist (surface protective film for semiconductor elements, interlayer insulating film, permanent film material such as flattening film, etc.), MEMS resist, negative type photosensitive material, various adhesives (various types)
  • Temporary fixing agent for electronic parts adhesive for HDD, adhesive for pickup lens, adhesive for functional film for FPD (deflection plate, antireflection film, etc.), resin for holographic, FPD material (color filter, black matrix, etc.) , Bulkhead material, Photo spacer, Rib, Alignment film for liquid

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61212554A (ja) * 1985-03-15 1986-09-20 Asahi Denka Kogyo Kk 芳香族ジスルホニウム塩の製法
WO2005000801A1 (ja) * 2003-06-25 2005-01-06 San-Apro Limited モノスルホニウム塩の製造方法、カチオン重合開始剤、硬化性組成物および硬化物
JP2010254654A (ja) * 2009-04-28 2010-11-11 San Apro Kk スルホニウム塩，光酸発生剤，光硬化性組成物，及びその硬化体
WO2011016425A1 (ja) * 2009-08-03 2011-02-10 サンアプロ株式会社 光酸発生剤，光硬化性組成物，及びその硬化体

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4197174A (en) 1979-03-14 1980-04-08 American Can Company Method for producing bis-[4-(diphenylsulfonio) phenyl] sulfide bis-MX6
JPS61190524A (ja) 1985-01-25 1986-08-25 Asahi Denka Kogyo Kk エネルギ−線硬化性組成物
JP3567984B2 (ja) 1999-11-01 2004-09-22 日本電気株式会社 スルホニウム塩化合物、フォトレジスト組成物、およびそれを用いたパターン形成方法
JP4023086B2 (ja) 1999-12-27 2007-12-19 和光純薬工業株式会社 スルホニウム塩化合物
JP3351424B2 (ja) 1999-12-28 2002-11-25 日本電気株式会社 スルホニウム塩化合物及びレジスト組成物、並びにそれを用いたパターン形成方法
US20090163723A1 (en) * 2005-11-25 2009-06-25 Hideki Kimura Method for producing sulfonium fluorinated alkylfluorophosphate
JP2011039411A (ja) * 2009-08-17 2011-02-24 San Apro Kk 化学増幅型ポジ型フォトレジスト組成物及びレジストパターンの作製方法
JP5828679B2 (ja) * 2011-05-31 2015-12-09 サンアプロ株式会社 フッ素化アルキルリン酸オニウム塩系酸発生剤
KR101747769B1 (ko) * 2013-09-30 2017-06-15 후지필름 가부시키가이샤 감광성 수지 조성물, 경화막의 제조 방법, 경화막, 유기 el 표시 장치 및 액정 표시 장치
JP6708382B2 (ja) * 2015-09-03 2020-06-10 サンアプロ株式会社 硬化性組成物及びそれを用いた硬化体
JP2019086559A (ja) * 2017-11-02 2019-06-06 サンアプロ株式会社 ネガ型フォトレジスト用樹脂組成物及び硬化膜
JP2019212554A (ja) * 2018-06-07 2019-12-12 株式会社豊田自動織機 電池モジュール

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61212554A (ja) * 1985-03-15 1986-09-20 Asahi Denka Kogyo Kk 芳香族ジスルホニウム塩の製法
WO2005000801A1 (ja) * 2003-06-25 2005-01-06 San-Apro Limited モノスルホニウム塩の製造方法、カチオン重合開始剤、硬化性組成物および硬化物
JP2010254654A (ja) * 2009-04-28 2010-11-11 San Apro Kk スルホニウム塩，光酸発生剤，光硬化性組成物，及びその硬化体
WO2011016425A1 (ja) * 2009-08-03 2011-02-10 サンアプロ株式会社 光酸発生剤，光硬化性組成物，及びその硬化体

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