WO2022054554A1 - Générateur d'acide sensible aux rayons actiniques - Google Patents

Générateur d'acide sensible aux rayons actiniques Download PDF

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WO2022054554A1
WO2022054554A1 PCT/JP2021/030762 JP2021030762W WO2022054554A1 WO 2022054554 A1 WO2022054554 A1 WO 2022054554A1 JP 2021030762 W JP2021030762 W JP 2021030762W WO 2022054554 A1 WO2022054554 A1 WO 2022054554A1
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group
acid
carbon atoms
resin
chemically amplified
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PCT/JP2021/030762
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淳 舩山
篤志 白石
秀基 木村
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サンアプロ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/30—Sulfides having the sulfur atom of at least one thio group bound to two carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
    • C07D335/16—Oxygen atoms, e.g. thioxanthones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/08—Six-membered rings
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Definitions

  • the present invention first relates to an active energy linear acid generator, and more specifically to a sulfonium salt-based active energy linear acid generator. Secondly, the present invention relates to an active energy ray-curable composition, a chemically amplified positive photoresist composition and a chemically amplified negative photoresist composition containing the acid generator.
  • an onium salt such as a sulfonium salt is known as a cationic polymerization initiator that cures a cationically polymerizable compound by irradiation with an active energy ray such as light or an electron beam.
  • Photoacid generators that generate acid are known (Patent Documents 1 to 3). Further, these onium salts are also called acid generators because they generate an acid by irradiation with active energy rays, and are also used in resists and photosensitive materials (Patent Documents 4 to 6).
  • Patent Documents 1 and 3 known methods for producing active energy linear acid generators, particularly sulfonium salts, described in these specifications are used (Patent Documents 1 and 3).
  • the sulfonium salt produced by these methods has a problem in reactivity with active energy rays (that is, the amount of acid generated), and the bissulfonium salt produced as a by-product and decomposition over time make it an active energy ray-curable composition.
  • active energy rays that is, the amount of acid generated
  • the bissulfonium salt produced as a by-product and decomposition over time make it an active energy ray-curable composition.
  • the bissulfonium salt produced as a by-product and decomposition over time make it an active energy ray-curable composition.
  • improvements in the manufacturing method that suppresses the by-product of bissulfonium salt, which has been the cause of deterioration of storage stability have been reported, but even this does not mean that long-term storage stability is
  • the first object of the present invention is to have cation polymerization performance and cross-linking reaction performance by irradiation with active energy rays, and a curable composition using this is highly active with good storage stability. It is to provide a sensitive energy linear acid generator.
  • a second object of the present invention is to provide an active energy ray-curable composition, a chemically amplified positive photoresist composition, and a chemically amplified negative photoresist composition using the above acid generator.
  • the present inventor has found an active energy linear acid generator suitable for the above purpose. That is, the present invention contains a sulfonium salt (A) represented by the following general formula (1) and a sulfonium salt (B) represented by the following general formula (2), and the sulfonium salt (A) and the sulfonium salt (B). It is a sensitive energy linear acid generator (hereinafter referred to as a photoacid generator or an acid generator) in which the content of the sulfonium salt (B) is 0.01 to 2 mol% with respect to the total number of moles.
  • a sensitive energy linear acid generator hereinafter referred to as a photoacid generator or an acid generator
  • R 1 to R 4 are organic groups bonded to the benzene ring, the number of R 2 is 0 to 4, the number of R 1 , R 3 and R 4 is 0 to 5.
  • 0 means that hydrogen atoms are bonded, and when multiple R1 to R4 are bonded, they may be the same or different from each other, and R1 to R4 may be directly or -O-, respectively.
  • a ring structure may be formed via -S-, -SO-, -SO 2- , -NH-, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group, and X - is an element. It is a monovalent anion having a group 13 or group 15 element in the periodic table and having a halogen.
  • R 1 to R 4 are organic groups bonded to the benzene ring, and the number of R 2 is 0 to 4, the number of R 1 , R 3 and R 4 is 0 to 5.
  • 0 means that hydrogen atoms are bonded, and when multiple R1 to R4 are bonded, they may be the same or different from each other, and R1 to R4 may be directly or -O-, respectively.
  • a ring structure may be formed via -S-, -SO-, -SO 2- , -NH-, -CO-, -COO-, -CONH-, an alkylene group or a phenylene group, and Y - is a halogen. It is a monovalent anion selected from the group consisting of anions that do not have.]
  • the present invention is also characterized in that an active energy ray-curable composition containing the acid generator and a cationically polymerizable compound; obtained by curing the active energy ray-curable composition.
  • a chemically amplified negative photoresist composition comprising an agent, a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and a cross-linking agent component (G); the above-mentioned chemically amplified negative. It is a cured product characterized by being obtained by curing a type photoresist composition.
  • the acid generator of the present invention has high activity with respect to active energy rays, and also has cationic polymerization performance and cross-linking reaction performance, and a composition using this has good storage stability.
  • R 1 to R 4 in the formula (1) or (2) represent an organic group bonded to a benzene ring, and may be the same or different.
  • R 1 to R 4 include 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 alkenyl group having 2 to 30 carbon atoms.
  • examples of the aryl group having 6 to 30 carbon atoms include a monocyclic aryl group such as a phenyl group and a biphenylyl group, and naphthyl, anthrasenyl, phenanthrenyl, pyrenyl, chrysenyl, naphthalsenyl, benzanthrasenyl, anthracinyl, naphthoquinyl, fluorenyl and the like.
  • a fused polycyclic aryl group can be mentioned.
  • heterocyclic group having 4 to 30 carbon atoms examples include cyclic compounds containing 1 to 3 heterocyclic atoms such as oxygen, nitrogen, and sulfur, which may be the same or different, and are specific examples.
  • examples include monocyclic heterocyclic groups such as thienyl, furanyl, pyranyl, pyrrolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, pyrazinyl and indolyl, benzofuranyl, isobenzofuranyl, benzothienyl, isobenzothienyl, quinolyl, isoquinolyl, quinoxalinyl, etc.
  • Examples thereof include fused polycyclic heterocyclic groups such as quinazolinyl, carbazolyl, acridinyl, phenothiazine, phenazinyl, xanthenyl, thiantranyl, phenoxadinyl, phenoxatyynyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl and dibenzofuranyl.
  • fused polycyclic heterocyclic groups such as quinazolinyl, carbazolyl, acridinyl, phenothiazine, phenazinyl, xanthenyl, thiantranyl, phenoxadinyl, phenoxatyynyl, chromanyl, isochromanyl, dibenzothienyl, xanthonyl, thioxanthonyl and dibenzofur
  • 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.
  • Branched Alkyl Group, Cycloalkyl Group such as Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, etc.
  • alkenyl group having 2 to 30 carbon atoms examples include linear or branched alkenyl groups 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. Such as linear or branched ones can be mentioned.
  • the above-mentioned 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 is at least 1 It may have a substituent of the species, and examples of the substituent include a linear alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl and octadecyl; isopropyl, isobutyl, sec-butyl and tert-butyl.
  • Branched alkyl groups with 1 to 18 carbon atoms cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and other cycloalkyl groups with 3 to 18 carbon atoms; hydroxy groups; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, etc.
  • Linear or branched alkoxy group having 1 to 18 carbon atoms such as tert-butoxy and dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyle, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl and the like.
  • arylcarbonyl groups with 7-11 carbon atoms such as benzoyl, naphthoyl; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxy Linear or branched alkoxycarbonyl group with 2 to 19 carbon atoms such as carbonyl, tert-butoxycarbonyl; aryloxycarbonyl group with 7 to 11 carbon atoms such as phenoxycarbonyl and naphthoxycarbonyl; carbon such as phenylthiocarbonyl and naphthoxythiocarbonyl An arylthiocarbonyl group having a number of 7 to 11; a linear or linear group having 2 to 19 carbon atoms such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butyl
  • Branched asyloxy groups 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-methylthiophenylthio, 4- (methylthiobenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio, etc.
  • R1 to R4 When multiple R1 to R4 are bonded, they are directly or -O-, -S-, -SO-, -SO2- , -NH-, -CO-, -COO-, -CONH-, alkylene group.
  • a ring structure may be formed via a phenylene group.
  • R 1 when R 1 is 2 or more, two R 1s are directly or -O-, -S-, -SO-, -SO 2- , -NH-, -CO-, -COO-,-. It means forming a ring structure via a CONH-, an alkylene group or a phenylene group.
  • organic groups preferably 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 alkylthio group having 1 to 6 carbon atoms, and a carbon element number.
  • An arylthio group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a chlorine atom and a fluorine atom more preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms and 1 to 1 carbon atoms. It is an alkoxy group of 6.
  • the number of substituents R1 to R4 in the formula (1) or (2) is 0 to 5, and in the case of 0, a hydrogen atom is bonded.
  • the number of R 1 to R 4 is preferably 0 to 3, and more preferably 0 or 1. When the number of R 1 to R 4 is in these preferable ranges, the photosensitivity and solubility of the sulfonium salt become good.
  • X - is an acid generated by irradiating an atom (group) that can be a monovalent anion, that is, a sulfonium salt, with active energy rays (visible light, ultraviolet rays, electron beams, X-rays, etc.). It is an anion corresponding to (HX).
  • X - is not limited except that it is a monovalent polyatomic anion having Group 13 or Group 15 elements and having a halogen in the Periodic Table of the Elements, but MZ a- , (Rf) b PF.
  • Anions represented by 6 - b- , R 8 c BZ 4-c- , R 8 c GaZ 4-c - or (R 9 SO 2 ) 2 N- are preferable from the viewpoint of photosensitivity.
  • M represents a phosphorus atom, a boron atom or an antimony atom.
  • Z 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 a perfluoroalkyl group having 1 to 20 carbon atoms or a perfluoroaryl group having 6 to 20 carbon atoms, and the perfluoroalkyl group may be linear, branched or cyclic.
  • 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 MZ 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 BZ 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 preferred.
  • the anions represented by R 8 c GaZ 4-c- are (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.
  • Y - is a monovalent anion selected from the group consisting of halogen - free anions, and the atoms (groups) that can be monovalent anions are HSO 4- , HNO 3- , H 2 PO 4- , methanesulphonate anion, halogen-free carboxylic acid anion, and anion represented by the following general formula (3) are preferably selected from the group.
  • R 5 and R 6 are hydrogen atoms or organic groups, the number of R 5 and R 6 is 0 to 5, and in the case of 0, hydrogen atoms are bonded and R 5 and R 6 are bonded.
  • Carboxylic acids that do not have halogen include formic acid, glycolic acid, acetic acid, propionic acid, butyric acid, valeric acid, octyl acid, 2-ethylhexanoic acid, cyanoacetic acid, trimethylacetic acid, methoxyacetic acid, cyclopentanecarboxylic acid, and mercaptoacetic acid.
  • R 5 and R 6 of the formula (3) represent an organic group bonded to a benzene ring, and may be the same or different.
  • R 5 and R 6 include 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 alkenyl group having 2 to 30 carbon atoms.
  • the aryl group having 6 to 30 carbon atoms is the same as the specific example of the aryl group having 6 to 30 carbon atoms mentioned as R 1 to R 4 above.
  • the heterocyclic group having 4 to 30 carbon atoms is the same as the specific example of the heterocyclic group having 4 to 30 carbon atoms mentioned as R 1 to R 4 above.
  • the alkyl group having 1 to 30 carbon atoms is the same as the specific example of the alkyl group having 1 to 30 carbon atoms mentioned as R 1 to R 4 above.
  • the alkenyl group having 2 to 30 carbon atoms is the same as the specific example of the alkenyl group having 2 to 30 carbon atoms listed as R 1 to R 4 above.
  • the alkynyl group having 2 to 30 carbon atoms is the same as the specific example of the alkynyl group having 2 to 30 carbon atoms mentioned as R 1 to R 4 above.
  • the above-mentioned 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 is at least 1 It may have a substituent of the species, and examples of the substituent include a linear alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl and octadecyl; isopropyl, isobutyl, sec-butyl and tert-butyl.
  • Branched alkyl groups with 1 to 18 carbon atoms cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and other cycloalkyl groups with 3 to 18 carbon atoms; hydroxy groups; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, etc.
  • Linear or branched alkoxy group having 1 to 18 carbon atoms such as tert-butoxy and dodecyloxy; acetyl, propionyl, butanoyl, 2-methylpropionyl, heptanoyle, 2-methylbutanoyl, 3-methylbutanoyl, octanoyl and the like.
  • arylcarbonyl groups with 7-11 carbon atoms such as benzoyl, naphthoyl; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxy Linear or branched alkoxycarbonyl group with 2 to 19 carbon atoms such as carbonyl, tert-butoxycarbonyl; aryloxycarbonyl group with 7 to 11 carbon atoms such as phenoxycarbonyl and naphthoxycarbonyl; carbon such as phenylthiocarbonyl and naphthoxythiocarbonyl An arylthiocarbonyl group having a number of 7 to 11; a linear or linear group having 2 to 19 carbon atoms such as acetoxy, ethylcarbonyloxy, propylcarbonyloxy, isobutylcarbonyloxy, sec-butyl
  • Branched asyloxy groups 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-methylthiophenylthio, 4- (methylthiobenzoyl) phenylthio, 4- (p-tert-butylbenzoyl) phenylthio, etc.
  • R 5 and R 6 are directly with each other or via -O-, -S-, -SO-, -SO 2- , -NH-, -CO-, -COO-, -CONH-, alkylene group or phenylene group.
  • a ring structure may be formed.
  • an alkyl group having 1 to 6 carbon atoms preferably 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 alkylthio group having 1 to 6 carbon atoms, and a carbon element number. It is an arylthio group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, a chlorine atom and a fluorine atom, more preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms and 1 to 1 carbon atoms. It is an alkoxy group of 6.
  • an arylthio group and an arylsulfinyl group are preferable from the viewpoint of storage stability.
  • a more preferable structure as the formula (3) is the following structure.
  • the content of the sulfonium salt (B) is 0.01 to 2 mol with respect to the total number of moles of the sulfonium salt (A) represented by the general formula (1) and the sulfonium salt (B) represented by the general formula (2). %, If it is 0.01 mol% or more, the storage stability is good, and if it exceeds 2 mol%, the curability of cationic polymerization and the sensitivity of the resist are deteriorated. Further, from the viewpoint of storage stability, 0.1 to 2 mol% is preferable.
  • the sulfonium salt (A) represented by the general formula (1) and the sulfonium salt (B) represented by the general formula (2) can be produced by a known production method.
  • a method of reacting diaryl sulfide with chlorine a method of reacting diaryl sulfide with aromatic hydrocarbons such as chlorine and benzene, and a method of reacting diaryl sulfide with diaryl sulfoxide in the presence of a dehydrating agent.
  • 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, phosphoric acid anhydride, methanesulfonic acid, acetic acid anhydride, trifluoromethanesulfonic acid or an anhydride thereof. These may be mixed and used in two or more kinds. 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 50 ° C., preferably ⁇ 5 ° C. to 30 ° C., and most preferably 0 ° C. to 10 ° C.
  • the sulfonium salt can be efficiently produced by exchanging the anion with the acid (HX) and the salt (AXn) having the anion represented by X in the formula (1).
  • 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.
  • a sulfonium salt can be efficiently produced by exchanging anions with an acid (HY) and a salt (AYn) having an anion represented by Y in the general formula (2).
  • the acid generator of the present invention can be produced by mixing the sulfonium salts of the general formulas (1) and (2), and is represented by the sulfonium salt (A) represented by the general formula (1) and the general formula (2).
  • the content of the sulfonium salt (B) is 0.01 to 2 mol% with respect to the total number of moles of the sulfonium salt (B).
  • the acid generator of the present invention may contain other conventionally known acid generators in addition to the sulfonium salts listed above, if necessary.
  • the acid generator of the present invention comprises a sulfonium salt represented by the formulas (1) and (2), and does not contain other acid generators.
  • the content of the other acid generators is 0.1 to 100 with respect to the total number of moles of the sulfonium salt represented by the formulas (1) and (2) of the present invention. It is preferably mol, more preferably 0.5 to 50 mol.
  • acid 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.
  • onium salts sulfonium, iodonium, selenium, ammonium and phosphonium, etc.
  • salts of transition metal complex ions and anions sulfonium, iodonium, selenium, ammonium and phosphonium, etc.
  • the acid 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 acid generator of the present invention.
  • the solvent used may be used alone or in combination of two or more.
  • the active energy ray-curable composition of the present invention comprises the above acid generator and a cationically polymerizable compound.
  • the alkali metal content in the active energy ray-curable composition is preferably 1.5 ppm or less from the viewpoint of coloring the cured product.
  • Examples of the cationically polymerizable compound that is a component of the active energy ray-curable composition include cyclic ethers (epoxide and oxetane, etc.), ethylenically unsaturated compounds (vinyl ether, styrene, etc.), bicycloorthoesters, spirolotocarbonates, and spirololt. Examples thereof include: ⁇ Japanese Patent Laid-Open No. 11-060996, JP-A-09-302269, JP-A-2003-026993, JP-A-2002-206017, JP-A-11-349895, JP-A-10-212343, JP-A.
  • 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 novolak and compounds having alkylene oxide adducts 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.).
  • 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 and cyclohexyl vinyl ether.
  • 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.
  • a polyorganosiloxane having at least one cationically polymerizable group in one molecule can be used (Japanese Patent Laid-Open No. 2001-348482, JP-A-2000-281965, JP-A-7-242828, JP. JP-A-2008-19593, Journal of Polymer.Sci., Part A, Polymer. Chem., Vol. 28, 497 (1990), etc.
  • These polyorganosiloxanes are linear, branched chains. It may be in the form of a ring or a ring, and 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 acid generator of the present invention in the active energy ray-curable composition is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the cationically polymerizable compound. Is. 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 and irradiation amount of the active energy ray, the temperature, the curing time, the humidity, and the thickness of the coating film, and is within the above range. Not limited.
  • the active energy ray-curable composition of the present invention contains, if necessary, known additives (sensitizers, pigments, fillers, antistatic agents, flame retardants, defoamers, flow modifiers, light stabilizers). , Antioxidant, Adhesion-imparting agent, Ion-supplementing agent, Anticoloring agent, Solvent, Non-reactive resin, Radical polymerizable compound, etc.) can be contained.
  • 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 acid 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 acid 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 acid generator.
  • antistatic agent known antistatic agents and the like can be used, and examples thereof include nonionic 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 20000 parts by weight, more preferably 0.6 to 5000 parts by weight, based on 100 parts by weight of the acid 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, decabromobiphenyl ether, 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 acid 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, decabromobiphenyl ether, 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 acid 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).
  • antioxidants are effective, and phenol-based antioxidants (monophenol-based, bisphenol-based, high-molecular-weight 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 0 with respect to 100 parts of the acid generator. It is preferably 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 a cationically polymerizable compound or adjusting the viscosity of an active energy ray-curable composition, and the above-mentioned solvent for an acid 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 acid 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 acid 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 acid 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 active energy ray-curable composition of the present invention uniformly comprises a cationically polymerizable compound, an acid 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 prepared by mixing and dissolving in, or by kneading with three rolls or the like.
  • the active energy ray-curable composition of the present invention can be cured by irradiating it with active energy rays to obtain a cured product.
  • the active energy ray may be any as long as it has the energy to induce the decomposition of the acid generator of the present invention, but is low pressure, medium pressure, high pressure or ultra high pressure mercury lamp, metal halide lamp, LED lamp, xenon lamp, carbon arc.
  • Active energy rays in the ultraviolet to visible light region (wavelength: about 100 to about 800 nm) obtained from lamps, fluorescent lamps, semiconductor solid-state lasers, argon lasers, He-Cd lasers, KrF excima lasers, ArF excima lasers, F2 lasers, etc. preferable.
  • the active energy ray radiation having high energy such as an electron beam or an X-ray can also be used.
  • the irradiation time of the active energy ray is affected by the intensity of the active energy ray and the permeability of the active energy ray to the active energy ray curable composition, but at room temperature (about 20 to 30 ° C.), it is 0.1 second to 10 seconds. About seconds is enough. However, when the permeability of the active energy ray is low, or when the film thickness of the active energy ray-curable composition is thick, it may be preferable to take a longer time. Most of the active energy ray-curable compositions are cured by cationic polymerization 0.1 seconds to several minutes after irradiation with active energy rays, but if necessary, after irradiation with active energy rays, at room temperature (about 20 to 30 ° C.). ) -It is also possible to heat at 200 ° C. for several seconds to several hours for after-curing.
  • Specific applications of the active energy ray-curable composition of the present invention include paints, coating agents, various coating materials (hard coats, stain-resistant coating materials, anti-fog coating materials, anti-fog coating materials, anti-contact coating materials, optical fibers, etc.), adhesives, etc.
  • Tape 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, Positive resists (connection terminals for manufacturing electronic components such as circuit boards, CSPs, MEMS elements, wiring pattern formation, etc.), resist films, liquid resists, negative resists (surface protective films for semiconductor elements, interlayer insulating films, flattening, etc.) Permanent film materials such as films), resists for MEMS, positive photosensitive materials, negative photosensitive materials, various adhesives (temporary fixing agents for various electronic parts, adhesives for HDDs, adhesives for pickup lenses, adhesives for FPDs, etc.) Adhesives for functional films (deflectors, antireflection films, etc.), holographic resins, FPD materials (color filters, black matrices, partition materials, photospacers, ribs, alignment films for liquid crystals, sealants for FPDs, etc.) , Optical members, molding materials (for building
  • 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.
  • soluble resin a cross-linking agent that cross-links the resin by heat treatment in the presence of an acid to make it insoluble in an alkaline developer, and a chemically amplified negative resist containing a photoacid generator as an essential component.
  • the chemically amplified positive photoresist composition of the present invention has increased solubility in alkali due to the action of the component (A) containing the photoacid generator of the present invention, which is a compound that generates an acid by light irradiation, and the acid. It is characterized by containing the resin component (B).
  • the component (A) 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.
  • the other conventionally known photoacid generator preferably one or more of 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 (A) is preferably 0.05 to 5% by weight based on the solid content of the chemically amplified positive photoresist composition.
  • Resin component (B) whose solubility in alkali increases due to the action of acid>
  • component (B) used in the chemically amplified positive photoresist composition for a thick film of the present invention (referred to as "component (B)" in the present specification.
  • component (B) Is at least one resin selected from the group consisting of novolak resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3), or a mixed resin or copolymer thereof.
  • Novolak resin (B1) As the novolak resin (B1), a resin represented by the following general formula (b1) can be used.
  • R 1b represents an acid dissociative dissolution inhibitor
  • R 2b and R 3b each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • n is in parentheses. Represents the number of repeating units of the structure.
  • the acid dissociative dissolution inhibitor group represented by R 1b a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and a cyclic group having 3 to 6 carbon atoms are used.
  • Alkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, or trialkylsilyl group is preferable.
  • specific examples of the acid dissociative dissolution inhibitory group represented by R 1b are methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, and isobutoxyethyl.
  • 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
  • Examples thereof include a carbonylmethyl group, a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.
  • Polyhydroxystyrene resin (B2) As the polyhydroxystyrene resin (B2), a resin represented by the following general formula (b4) can be used.
  • R 8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 9b represents an acid dissociative dissolution inhibitory group
  • n represents the number of repeating units of the structure in parentheses. show.
  • the above-mentioned 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, a neopentyl group, and examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group. And so on.
  • the same acid dissociative dissolution inhibitory group as exemplified in R 1b can be used.
  • the polyhydroxystyrene resin (B2) can contain another polymerizable compound as a constituent unit for the purpose of appropriately controlling the physical and chemical properties.
  • a polymerizable compound include known radically polymerizable compounds and anionic polymerizable compounds.
  • 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 ester bond such as 2-methacryloyloxyethyl succinic acid; methyl (meth) acrylate and the like.
  • acrylic resin (B3) As the acrylic resin (B3), resins represented by the following general formulas (b5) to (b10) can be used.
  • R 10b to R 17b are independently hydrogen atoms, linear alkyl groups having 1 to 6 carbon atoms, and branched alkyl groups having 3 to 6 carbon atoms, respectively.
  • a hydrocarbon ring having 5 to 20 carbon atoms is formed, Y b represents an aliphatic cyclic group or an alkyl group which may have a substituent, and n represents the number of repeating units of the structure in parentheses.
  • p is an integer from 0 to 4, and q is 0 or 1.
  • R 18b , R 20b and R 21b represent hydrogen atoms or methyl groups independently of each other, and in the general formula (b8), respectively.
  • R 19b is a hydrogen atom, a hydroxyl group, a cyano group or a COOR 23b group (provided that R 23b is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a branch having 3 to 4 carbon atoms.
  • each R 22b is a monovalent alicyclic group having 4 to 20 carbon atoms independently of each other.
  • the remaining R 22b is a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. Or it represents a derivative thereof.
  • the polystyrene-equivalent weight average molecular weight of the component (B) is preferably 10,000 to 600,000, more preferably 50,000 to 600,000, and further preferably 230,000 to 550,000. be. By setting such a weight average molecular weight, the resin physical properties of the resist become excellent.
  • the component (B) is preferably a resin having a dispersity of 1.05 or more.
  • the "dispersity” is a value obtained by dividing the weight average molecular weight by the number average molecular weight. With such a degree of dispersion, the plating resistance of the resist and the physical characteristics of the resin 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.
  • the chemically amplified positive photoresist composition of the present invention further contains an alkali-soluble resin (referred to as "component (C)" in the present specification).
  • component (C) is preferably at least one selected from the group consisting of novolak resin, polyhydroxystyrene resin, acrylic resin and polyvinyl resin.
  • the content of the component (C) is preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, based on 100 parts by weight of the component (B).
  • 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, the film loss during development tends to be prevented.
  • the acid diffusion control agent (D) in the chemically amplified positive photoresist composition for thick films of the present invention, in order to improve the shape of the resist pattern, the retention stability, etc., the acid diffusion control agent (D) (in the present specification, the component ( D) ”) is preferably contained.
  • the component (D) a nitrogen-containing compound is preferable, and if necessary, an organic carboxylic acid or a phosphorus oxo acid or a derivative thereof can be contained.
  • the chemically amplified positive photoresist composition of the present invention may further contain an adhesive aid in order to improve the adhesiveness with the substrate.
  • an adhesive 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 coatability, defoaming property, leveling property 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 alkaline developer.
  • the chemically amplified positive photoresist composition of the present invention basically does not require a sensitizer, but may contain a sensitizer as necessary to supplement the sensitivity.
  • a sensitizer conventionally known ones can be used, and specific examples thereof include the above-mentioned ones.
  • 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 of the present invention.
  • an organic solvent can be appropriately added to the chemically amplified positive photoresist composition of the present invention in order to adjust the viscosity.
  • Specific examples of the organic solvent include those mentioned above.
  • the amount of these organic solvents used is such 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 ⁇ m or more. Is preferably in the range of 30% by weight or more.
  • the chemically amplified positive photoresist composition for thick films of the present invention for example, it is only necessary to mix and stir each of the above components by a usual method, and if necessary, a dissolver, a homogenizer, a three-roll mill, or the like. It may be dispersed and mixed using a disperser. Further, after mixing, the mixture may be further 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 film thickness of usually 5 to 150 ⁇ m, more preferably 10 to 120 ⁇ m, still more preferably 10 to 100 ⁇ m on a support. ing.
  • a photoresist layer made of the chemically amplified positive photoresist composition of the present invention is laminated on a support.
  • the support is not particularly limited, and conventionally known ones can be used, and examples thereof include a substrate for electronic components and a support on which a predetermined wiring pattern is formed.
  • this substrate include metal substrates such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, and aluminum, and glass substrates.
  • the chemically amplified positive photoresist composition of the present invention can satisfactorily form a resist pattern even on a copper substrate.
  • the material of the wiring pattern for example, copper, solder, chromium, aluminum, nickel, gold and the like are used.
  • the photoresist laminate can be manufactured, for example, as follows. That is, a solution of the chemically amplified positive photoresist composition prepared as described above is applied onto the support, and the solvent is removed by heating to form a desired coating film.
  • a coating method on the support a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, or the like can be adopted.
  • the prebaking conditions for the coating film of the composition of the present invention vary depending on the type of each component in the composition, the mixing ratio, the coating film thickness, etc., but are usually 70 to 150 ° C., preferably 80 to 140 ° C., 2 to It may be about 60 minutes.
  • the film thickness of the photoresist layer may be usually in the range of 5 to 150 ⁇ m, preferably 10 to 120 ⁇ m, and more preferably 10 to 100 ⁇ m.
  • light or radiation for example, a wavelength of 300 to 500 nm, is formed on the obtained photoresist layer through a mask of a predetermined pattern.
  • Ultraviolet rays or visible light may be irradiated (exposed) in a site-selective manner.
  • 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.
  • 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 as the radiation source of light or radiation.
  • the amount of radiation irradiation varies depending on the type of each component in the composition, the blending amount, the film thickness of the coating film, and the like, but is 50 to 10,000 mJ / cm 2 when, for example, an ultrahigh pressure mercury lamp is used.
  • the oxidation is promoted by heating using a known method to change the alkali solubility of the photoresist layer in the exposed portion.
  • a predetermined alkaline aqueous solution is used as a developing solution to dissolve and remove unnecessary portions to obtain a predetermined resist pattern.
  • the developing time varies depending on the type of each component of the composition, the mixing ratio, and the dry film thickness of the composition, but is usually 1 to 30 minutes, and the developing method is a liquid filling method, a dipping method, a paddle method, or a spray developing method. And so on.
  • After development wash with running water for 30 to 90 seconds, and dry using an air gun or an oven.
  • a connection terminal such as a metal post or a bump is formed.
  • the plating treatment method is not particularly limited, and various conventionally known methods can be adopted.
  • As the plating solution solder plating, copper plating, gold plating, and nickel plating solution are particularly preferably used.
  • the remaining resist pattern is 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.
  • protective films are formed on both sides of a layer made of the chemically amplified positive photoresist composition of the present invention.
  • the film thickness of the layer made of the chemically amplified positive photoresist composition may be usually in the range of 10 to 150 ⁇ m, preferably 20 to 120 ⁇ m, and more preferably 20 to 80 ⁇ m.
  • the protective film is not particularly limited, and a resin film conventionally used for a dry film can be used.
  • one can be a polyethylene terephthalate film, and the other can 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 the chemically amplified positive photoresist composition prepared as described above is applied onto one of the protective films, and the solvent is removed by heating to form a desired coating film.
  • the drying conditions vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, and the like, but are usually 60 to 100 ° C. for about 5 to 20 minutes.
  • one of the protective films of the chemically amplified positive dry film is peeled off and the exposed surface is directed toward the support side described above.
  • the photoresist layer may be obtained by laminating on the support with, and then prebaking is performed to dry the resist, and then the other protective film may be peeled off.
  • a resist pattern can be formed in the same manner as described above for the photoresist layer formed by directly applying the resist layer on the support. ..
  • 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 above 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 examples include 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 shock 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.
  • the radiation used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-ray steppers, h-ray 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.
  • 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.
  • Production Example 2 (Production of PAG-2) 96 g (yield 85%) of a white solid was obtained in the same manner as in Production Example 1 except that 43 g of potassium hexafluorophosphate was changed to 55 g of potassium hexafluoroantimonate.
  • Production Example 3 (Production of PAG-3) 121 g (yield 85%) of a white solid was obtained in the same manner as in Production Example 1 except that 43 g of potassium hexafluorophosphate was changed to 160 g of lithium tetrakispentafluorophenylborate.
  • the cation is (C-1) and the tetrakispentafluorophenylborate salt is 99.1%, and the cation is (C-1) and has the structure of (Y-1). It contained 0.9% of anionic salt.
  • Production Example 6 (Production of PAG-6) 130 g (yield 63%) of a white solid was obtained in the same manner as in Production Example 5, except that 43 g of potassium hexafluorophosphate was changed to 177 g of sodium tetrakispentafluorophenyl gallate.
  • the obtained product contained 99.8% of the tetrakispentafluorophenyl gallate salt having a cation of (C-1) and methanesulfone having a cation of (C-1). It contained 0.2% acid salt.
  • Production Example 7 (Production of PAG-7) 106 g (yield 70%) of a white solid was obtained in the same manner as in Production Example 5, except that 43 g of potassium hexafluorophosphate was changed to 101 g of potassium trispentafluoroethyltrifluorophosphate. As a result of the same analysis as in Production Example 1, the obtained product was 99.7% trispentafluoroethyltrifluorophosphate having a cation of (C-1) and having a cation of (C-1). It contained 0.3% methanesulfonate.
  • Production Example 8 (Production of PAG-8) 43 g of potassium hexafluorophosphate, 100 mL of acetonitrile, 55 g of 4-[(phenyl) sulfinyl] biphenyl, 60 g of acetic anhydride, and 20 g of methanesulfonic acid were charged and mixed uniformly. 51 g of 4- (phenylthio) biphenyl was added dropwise thereto so as not to exceed 40 ° C. After stirring at 40 ° C. for 1 hour, the mixture was cooled to room temperature, 200 mL of water was added, and the mixture was stirred for 10 minutes, and the oily substance was separated.
  • Production Example 10 (Production of PAG-10) 145 g (yield 76%) of a pale yellow solid was obtained in the same manner as in Production Example 9, except that 55 g of potassium hexafluoroantimonate was changed to 160 g of lithium tetrakispentafluorophenylborate.
  • the obtained product was 99.6% tetrakispentafluorophenylborate salt having a cation of (C-2) and (Y) having a cation of (C-2). It contained 0.4% of anion salt having the structure of -2).
  • Production Example 11 (Production of PAG-11) 152 g (yield 76%) of a pale yellow solid was obtained in the same manner as in Production Example 9, except that 55 g of potassium hexafluoroantimonate was changed to 177 g of lithium tetrakispentafluorophenyl gallate.
  • the obtained product was 99.5% tetrakispentafluorophenyl gallate salt having a cation of (C-2) and (Y) having a cation of (C-2). It contained 0.5% of anion salt having the structure of -2).
  • Production Example 12 (Production of PAG-12) 105 g (yield 69%) of a pale yellow solid was obtained in the same manner as in Production Example 9, except that 55 g of potassium hexafluoroantimonate was changed to 101 g of potassium trispentafluoroethyltrifluorophosphate.
  • the resulting product was 99.6% trispentafluoroethyltrifluorophosphate having a cation of (C-2) and a cation of (C-2). It contained 0.4% of the salt of the anion having the structure of (Y-2).
  • Production Example 14 (Production of PAG-14) 126 g (yield 78%) of a yellow solid was obtained in the same manner as in Production Example 13, except that 43 g of potassium hexafluorophosphate was changed to 55 g of potassium hexafluoroantimonate. As a result of the same analysis as in Production Example 1, the obtained product was 99.6% hexafluoroantimontate having a cation of (C-3) and (Y-) having a cation of (C-3). It contained 0.4% of anion salt having the structure of 3).
  • Production Example 15 (Production of PAG-15) 151 g of a pale yellow solid in the same manner as in Production Example 4 except that 40 g of diphenyl sulfoxide was changed to 47 g of 4,4'-difluorodiphenylsulfoxide and 43 g of potassium hexafluorophosphate was changed to 177 g of sodium tetrakispentafluorophenyl gallate in Production Example 4. Yield 71%) was obtained.
  • the obtained product contained 99.5% of the tetrakispentafluorophenyl gallate salt having a cation of (C-4) and a sulfate having a cation of (C-4). was contained at 0.5%.
  • Production Example 16 (Production of PAG-16) 87 g (yield 73%) of a pale yellow solid was obtained in the same manner as in Production Example 15 except that 177 g of sodium tetrakispentafluorophenyl gallate was changed to 55 g of potassium hexafluoroantimonate in Production Example 15. As a result of the same analysis as in Production Example 1, the obtained product was 99.5% hexafluoroantimontate having a cation of (C-4) and a sulfate having a cation of (C-4). It contained 0.5%.
  • Production Example 17 (Production of PAG-17) In Production Example 1, 101 g (70% yield) of a yellow solid was obtained in the same manner as in Production Example 1, except that 40 g of diphenyl sulfoxide was changed to 66 g of 2-phenylsulphenylanthraquinone and 36 g of diphenyl sulfide was changed to 61 g of 2-phenylthioanthraquinone. rice field. As a result of the same analysis as in Production Example 1, the obtained product was 98.8% hexafluorophosphate having a cation of (C-5) and (Y-) having a cation of (C-5). It contained 1.2% of anion salt having the structure of 5).
  • Production Example 18 (Production of PAG-18) 47 g of yellow solid (yield 32%) in the same manner as in Production Example 1 except that 40 g of diphenyl sulfoxide was changed to 67 g of 2-phenylsulphenylthiantorene and 36 g of diphenylsulfide was changed to 62 g of 2-phenylthiothiantolen.
  • the obtained product was 98.4% hexafluorophosphate having a cation of (C-6) and (Y-) having a cation of (C-6). It contained 1.6% of anion salt having the structure of 6).
  • Comparative Production Examples 7 to 15 (Production of PAG-H7 to H15) (Manufacturing of PAG-H7)
  • the crystallization filtrate obtained by the recrystallization operation in Comparative Production Example 1 was collected, concentrated, and the obtained oil was washed with methanol and hexane to obtain a pale yellow solid.
  • the same analysis as in Production Example 1 was performed, and the obtained solid contained 95.2% of cation hexafluorophosphate having the structure of (C-1), and the anion having the structure of (Y-1) thereof. It contained 4.8% salt.
  • Production Examples 19 to 27 (Production of PAG-19 to 27) PAG-1, 4, 5, 8, 9, 13, 16, 17, 18 were mixed with PAG-H7 to H15 obtained in Comparative Production Examples 7 to 15 in an appropriate amount, and a solid photoacid generator PAG-19 was mixed. -27 was obtained.
  • the composition of the obtained solid is as shown in Table 1.
  • 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
  • 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.
  • 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 coating film hardness 40 minutes after irradiation was measured by pencil hardness (JIS K5600-5-4: 1999), and the results evaluated according to the following criteria are shown in Tables 3 and 4. 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 Co., Ltd.) -Lamp: 1.5kW high-pressure mercury lamp-Filter: IRCF02 filter (manufactured by Eye Graphics Co., Ltd.) -Illuminance (measured with a 365 nm head illuminance meter): 150 mW / cm 2 -Integrated light intensity (measured with a 365 nm head illuminance meter): 200 mJ / cm 2
  • the composition containing the photoacid generator of the present invention has excellent UV curability and an excellent balance with storage stability.
  • Comparative Examples 1 to 6 it was found that a very high-purity photoacid generator has excellent UV curability but is inferior in storage stability, and a photoacid generator containing a small amount of anion Y is used as in the examples. It can be seen that this improves storage stability.
  • Comparative Examples 20 to 27 and Comparative Examples 7 to 15 it can be seen that if the molar ratio of anion Y is too large, the UV curability is affected, so that the molar ratio of anion Y is 2 mol% or less. ..
  • Examples 28 to 51 and Comparative Examples 16 to 27 it can be seen that the tendency does not depend on the type of the cationically polymerizable epoxy resin to be blended.
  • Comparative Examples were also carried out in the same manner as in the above Examples to prepare positive photoresist compositions (Comparative Examples 28 to 42). These compositions were stored at a predetermined temperature and for a period of time, and the positive photoresist composition was evaluated by the following method and compared with that immediately after compounding. The results are shown in Table 5.
  • ⁇ Sensitivity evaluation> The positive resist composition was spin-coated on a silicon wafer substrate and then dried to obtain a photoresist layer having a film thickness of about 20 ⁇ m. This resist layer was prebaked on a hot plate at 130 ° C. for 6 minutes. After pre-baking, pattern exposure (i-line) was performed using TME-150RSC (manufactured by Topcon), and post-exposure heating (PEB) was performed at 75 ° C. for 5 minutes using a hot plate.
  • i-line pattern exposure
  • TME-150RSC manufactured by Topcon
  • PEB post-exposure heating
  • the chemically amplified positive photoresist composition containing the photoacid generator of the present invention from Examples 52 to 78 and Comparative Examples 28 to 42 has excellent resist sensitivity and storage stability. Recognize. From Comparative Examples 28 to 33, it was found that the resist sensitivity is excellent in the very high-purity photoacid generator, but it affects the storage stability, and the photoacid generator containing a small amount of anion Y is used as in the examples. It can be seen that this improves storage stability. Further, comparing Examples 70 to 78 and Comparative Examples 34 to 42, if the molar ratio of anion Y is too large, the resist sensitivity and the pattern shape are affected. Therefore, the molar ratio of anion Y is preferably 2 mol% or less. I understand.
  • ⁇ Storage conditions Storage conditions: 20 ° C x 3 months ⁇ 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 film thickness of about 20 ⁇ m. Then, pattern exposure (i-line) was performed using TME-150RSC (manufactured by Topcon), and post-exposure heating (PEB) was performed at 110 ° C. for 3 minutes using a hot plate.
  • i-line pattern exposure
  • TME-150RSC manufactured by Topcon
  • PEB post-exposure heating
  • the chemically amplified negative photoresist composition containing the photoacid generator of the present invention is excellent in resist sensitivity and storage stability. Recognize. From Comparative Examples 43 to 48, it was found that the resist sensitivity was excellent in the very high-purity photoacid generator, but it affected the storage stability, and the photoacid generator containing a small amount of anion Y was used as in the examples. It can be seen that this improves storage stability. Further, comparing Examples 97 to 105 and Comparative Examples 49 to 57, if the molar ratio of anion Y is too large, the resist sensitivity and the pattern shape are affected. Therefore, the molar ratio of anion Y is preferably 2 mol% or less. I understand.
  • the active energy ray-curable composition using the active energy ray-curable acid 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.
  • 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.), resist for MEMS, negative type photosensitive material, various adhesives (Temporary fixing agents for various electronic parts, adhesives for HDDs, adhesives for pickup lenses, adhesives for functional films for FPDs (deflectors, antireflection films, etc.), etc.), resins for holographic, FPD materials (color filters, Black matrix, partition material, photo spacer, rib, liquid crystal alignment film, FPD sealant, etc.), optical member, molding material (building material, optical component, lens), casting material, putty, glass fiber impregnating agent, It is suitably used as a sealing material, a sealing material, a sealing material, an optical semiconductor (LED) sealing
  • LED optical

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Abstract

L'invention concerne un générateur d'acide sensible aux rayons actiniques hautement actif qui, lorsqu'il est irradié par des rayons actiniques, arrive à avoir une performance de polymérisation cationique ou une performance de réaction de réticulation et qui permet aux compositions durcissables contenant le générateur d'acide d'avoir une stabilité de stockage satisfaisante. Ce générateur d'acide sensible aux rayons actiniques comprend un sel de sulfonium (A), qui est représenté par la formule générale (1), et un sel de sulfonium (B), qui est représenté par la formule générale (2), et a une teneur en sel de sulfonium (B) de 0,01 à 2 % en moles par rapport au nombre total de moles du sel de sulfonium (A) et du sel de sulfonium (B).
PCT/JP2021/030762 2020-09-09 2021-08-23 Générateur d'acide sensible aux rayons actiniques WO2022054554A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016153044A1 (fr) * 2015-03-26 2016-09-29 東京応化工業株式会社 Composition photosensible négative et procédé de formation de motif
JP2019073470A (ja) * 2017-10-16 2019-05-16 サンアプロ株式会社 光酸発生剤、硬化性組成物及びレジスト組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016153044A1 (fr) * 2015-03-26 2016-09-29 東京応化工業株式会社 Composition photosensible négative et procédé de formation de motif
JP2019073470A (ja) * 2017-10-16 2019-05-16 サンアプロ株式会社 光酸発生剤、硬化性組成物及びレジスト組成物

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