WO2014061062A1 - Sel de sulfonium, générateur photoacide, composition polymérisable et composition de résine photosensible - Google Patents

Sel de sulfonium, générateur photoacide, composition polymérisable et composition de résine photosensible Download PDF

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Publication number
WO2014061062A1
WO2014061062A1 PCT/JP2012/006666 JP2012006666W WO2014061062A1 WO 2014061062 A1 WO2014061062 A1 WO 2014061062A1 JP 2012006666 W JP2012006666 W JP 2012006666W WO 2014061062 A1 WO2014061062 A1 WO 2014061062A1
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group
anion
photoacid generator
parts
resin
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PCT/JP2012/006666
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English (en)
Japanese (ja)
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卓也 池田
祐作 高嶋
鈴木　一生
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サンアプロ株式会社
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Priority to KR1020157012639A priority Critical patent/KR101959107B1/ko
Priority to PCT/JP2012/006666 priority patent/WO2014061062A1/fr
Priority to CN201280077742.3A priority patent/CN104918914A/zh
Publication of WO2014061062A1 publication Critical patent/WO2014061062A1/fr

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    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain

Definitions

  • the present invention relates firstly to a sulfonium salt, and secondly, when a cationically polymerizable compound is cured by applying an active energy ray such as light, electron beam or X-ray to a photoacid generator.
  • the present invention relates to a photoacid generator containing a suitable specific sulfonium salt.
  • the present invention relates to a curable composition containing the photoacid generator and a cured product obtained by curing the curable composition.
  • the present invention relates to a chemically amplified positive photoresist composition containing the photoacid generator and a method for producing a resist pattern using the same.
  • the present invention relates to a chemical amplification type chemically amplified negative photoresist composition containing the photoacid generator and a cured product obtained by curing the composition.
  • the photoacid generator is a general term for compounds that decompose to generate an acid upon irradiation with active energy rays such as light, electron beam, or X-ray, and an acid generated by irradiation with active energy rays is used as an active species. It is used for various reactions such as polymerization, crosslinking, and deprotection. Specific examples include polymerization of a cationic polymerizable compound, a crosslinking reaction in the presence of a phenol resin and a crosslinking agent, and an acid-catalyzed deprotection reaction of a polymer in which a protecting group is introduced into an alkali-soluble resin.
  • i-line is widely used. This is because an intermediate-pressure / high-pressure mercury lamp that is inexpensive and has good emission intensity can be used as an irradiation light source.
  • medium- and high-pressure mercury lamps are most commonly used in the fields of paint, adhesion, and coating other than photolithography.
  • LED lamps having an emission wavelength in the i-line region (360 nm to 390 nm) have become popular. It can also be mentioned. Therefore, the need for a photoacid generator exhibiting high sensitivity to i-line is expected to increase further in the future.
  • Patent Document 1 triarylsulfonium salts
  • Patent Document 2 phenacylsulfonium salts having a naphthalene skeleton
  • Patent Document 3 dialkylbenzylsulfonium salts
  • Patent Document 4 the sulfonium salt introduced with a thioxanthone skeleton
  • Patent Document 4 has a problem that the absorption rate is too large with respect to i-line, and therefore, light curing does not pass to the deep part at the time of thick film curing, resulting in a problem of poor curing.
  • the acid is generated from the photoacid generator by irradiation (exposure), and the diffusion of the acid and the acid catalyzed reaction are promoted by the heat treatment after the exposure, thereby improving the solubility of the base resin in the resin composition in the alkali.
  • the base resin that is insoluble in alkali before exposure is solubilized in alkali and is called a positive photoresist.
  • this resist composition contains oxime sulfonate, the storage stability is poor, and the storage temperature control of the resist composition is complicated, and there are practical problems.
  • a photosensitive resin composition using an alkali-soluble resin having a phenolic hydroxyl group and a triazine photoacid generator has been proposed for a surface protective film, an interlayer insulating film, etc. used in a semiconductor element of an electronic device (patent) References 6 and 7).
  • This triazine-based photoacid generator has a problem of contaminating equipment because the generated acid is hydrochloric acid or odorous acid and is likely to volatilize.
  • the first object of the present invention is to provide a new sulfonium salt having high photosensitivity to i-line.
  • the second object of the present invention is to store in a blend with a cationically polymerizable compound such as an epoxy compound having high photosensitivity to i-line and high compatibility with a cationically polymerizable compound such as an epoxy compound. It is to provide a new photoacid generator comprising a sulfonium salt having excellent stability.
  • the third object of the present invention is to provide an energy ray curable composition and a cured product using the photoacid generator.
  • a fourth object of the present invention is to provide a chemically amplified positive photoresist composition using the photoacid generator and a method for producing the same.
  • a fifth object of the present invention is to provide a chemically amplified positive photoresist composition using the photoacid generator and a cured product thereof.
  • the inventor has synthesized a sulfonium salt represented by the following formula (1) and found that it is suitable for each of the above purposes. That is, the present invention is a sulfonium salt represented by the following general formula (1).
  • R in the formula (1) represents an alkyl group or an aryl group
  • R 1 to R 3 are independently of each other an alkyl group, a hydroxyl group, an alkoxy group, an aryl group, an aryloxy group, a hydroxy (poly) alkyleneoxy group.
  • m 1 to m 3 each represent the number of R 1 to R 3
  • m 1 represents an integer of 0 to 4
  • m 2 and m 3 represent an integer of 0 to 5
  • X ⁇ represents a monovalent polyatomic anion.
  • the present invention also provides a photoacid generator containing the sulfonium salt.
  • the present invention also provides an energy beam curable composition comprising the photoacid generator and a cationically polymerizable compound.
  • the present invention is a cured product obtained by curing the energy beam curable composition.
  • the present invention provides a chemically amplified positive photoresist composition
  • a chemically amplified positive photoresist composition comprising the photoacid generator and a component (B) which is a resin whose solubility in alkali is increased by the action of an acid. is there.
  • the present invention provides a laminating step of laminating a photoresist layer having a film thickness of 5 to 150 ⁇ m made of the above-mentioned chemically amplified positive photoresist composition to obtain a photoresist laminate, and site-selectively selecting the photoresist laminate.
  • a method for producing a resist pattern comprising: an exposure step of irradiating light or radiation; and a development step of developing a photoresist laminate after the exposure step to obtain a resist pattern.
  • the present invention further includes a chemically amplified negative photo, comprising the photoacid generator, a component (F) which is an alkali-soluble resin having a phenolic hydroxyl group, and a crosslinking agent component (G). It is a resist composition.
  • the present invention is a cured product obtained by curing any one of the above chemically amplified negative photoresist compositions.
  • the sulfonium salt of the present invention has excellent photosensitivity to active energy rays such as visible light, ultraviolet rays, electron beams and X-rays, has high compatibility with cationically polymerizable compounds such as epoxy compounds, and cationic polymerization of epoxy compounds and the like. Storage stability is excellent in a blend with a functional compound.
  • the photoacid generator of the present invention has excellent curability due to the action of ultraviolet light, particularly i rays, when used for curing a cationically polymerizable compound, and cures a cationically polymerizable compound without using a sensitizer. Can be made.
  • the photoacid generator of the present invention is also excellent in thick film curability.
  • the energy beam curable composition of the present invention contains the above-mentioned photoacid generator, it can be cured with ultraviolet light. Moreover, since the energy beam curable composition of this invention has high storage stability and does not need to use a sensitizer, it is excellent in cost and workability
  • the sulfonium salt of the present invention is represented by the following general formula (1).
  • the alkyl group is a linear alkyl group having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and the like), a branched alkyl group having 1 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, Isohexyl and isooctadecyl), and cycloalkyl groups having 3 to 18 carbon atoms (such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl),
  • an aryl group in R includes an aryl group having 6 to 12 carbon atoms (phenyl, tolyl, dimethylphenyl, naphthyl, biphenylyl, etc.) and the like.
  • the alkyl group is a linear alkyl group having 1 to 18 carbon atoms (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, etc.), a branched alkyl group having 1 to 18 carbon atoms (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl and isooctadecyl), and cycloalkyl groups having 3 to 18 carbon atoms (such as cyclopropyl, cyclobutyl, cyclopentyl, cycl
  • the alkoxy group is a linear or branched alkoxy group having 1 to 18 carbon atoms (methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy Tert-butoxy, hexyloxy, decyloxy, dodecyloxy, octadecyloxy and the like.
  • examples of the aryl group include aryl groups having 6 to 10 carbon atoms (such as phenyl, tolyl, dimethylphenyl, naphthyl, and biphenylyl).
  • examples of the aryloxy group include aryloxy groups having 6 to 10 carbon atoms (such as phenoxy and naphthyloxy).
  • examples of the hydroxy (poly) alkyleneoxy group include a hydroxy (poly) alkyleneoxy group represented by formula (2).
  • HO (-AO) q- (2) [AO represents an ethyleneoxy group and / or propyleneoxy group, and q represents an integer of 1 to 5. ]
  • examples of the halogen atom group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • R 1 to R 3 are independent of each other, and therefore may be the same as or different from each other.
  • R is preferably an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably a methyl group, a butyl group, a phenyl group, a naphthyl group, or a biphenylyl group.
  • a methyl group and a phenyl group are particularly preferable.
  • R 1 to R 3 preferred are an alkyl group, an alkoxy group, an aryloxy group and a halogen atom, and particularly preferred are a methyl group, a methoxy group, a phenoxy group and a halogen atom.
  • m 1 to m 3 each represent the number of R 1 to R 3
  • m 1 is an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1, most preferably Is 0.
  • M 2 or m 3 is an integer of 0 to 5, preferably 0 to 2, more particularly preferably 0 or 1, and most preferably 0.
  • m 1 to m 3 are in these preferred ranges, the photosensitivity and solubility of the sulfonium salt will be good.
  • sulfoniums represented by the formula (1) those having the following structures are particularly preferred from the viewpoint of photosensitivity.
  • X ⁇ is an anion corresponding to an acid (HX) generated by irradiating a sulfonium salt with an active energy ray (visible light, ultraviolet ray, electron beam, X-ray, etc.).
  • X ⁇ is not limited except that it is a monovalent polyatomic anion, but MY a ⁇ , (Rf) b PF 6-b ⁇ , R 8 c BY 4-c ⁇ , R 8 c GaY 4 -c -, R 9 SO 3 - , (R 9 SO 2) 3 C - or (R 9 SO 2) 2 N - anion represented by are preferred.
  • M represents a phosphorus atom, a boron atom or an antimony atom.
  • Y represents a halogen atom (a fluorine atom is preferred).
  • Rf represents an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms) in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms.
  • alkyl group to be converted into Rf by fluorine substitution include linear alkyl groups (such as methyl, ethyl, propyl, butyl, pentyl and octyl), branched alkyl groups (such as isopropyl, isobutyl, sec-butyl and tert-butyl) and And cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and the like.
  • the ratio of hydrogen atoms of these alkyl groups substituted by fluorine atoms in Rf is preferably 80 mol% or more, more preferably 90, based on the number of moles of hydrogen atoms that the original alkyl group had. % Or more, particularly preferably 100%.
  • substitution ratio by fluorine atoms is within these preferable ranges, the photosensitivity of the sulfonium salt is further improved.
  • Rf As particularly preferred Rf, 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 Rf's are independent of each other, and therefore may be the same as or different from each other.
  • P represents a phosphorus atom
  • F represents a fluorine atom
  • R 8 represents a phenyl group in which a part of hydrogen atoms is substituted with at least one element or electron withdrawing group.
  • Examples of such one element include a halogen atom, and include a fluorine atom, a chlorine atom and a bromine atom.
  • Examples of the electron withdrawing group include a trifluoromethyl group, a nitro group, and a cyano group.
  • a phenyl group in which one hydrogen atom is substituted with a fluorine atom or a trifluoromethyl group is preferable.
  • c number of R 8 is independently from each other, therefore, it may be the same or different from each other.
  • B represents a boron atom
  • Ga represents a gallium atom
  • R 9 represents an alkyl group having 1 to 20 carbon atoms, a perfluoroalkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
  • the alkyl group and the perfluoroalkyl group are linear or branched. Alternatively, it may be cyclic, and the aryl group may be unsubstituted or may have a substituent.
  • S represents a sulfur atom
  • O represents an oxygen atom
  • C represents a carbon atom
  • N represents a nitrogen atom.
  • a represents an integer of 4 to 6.
  • b is preferably an integer of 1 to 5, more preferably 2 to 4, particularly preferably 2 or 3.
  • c is preferably an integer of 1 to 4, more preferably 4.
  • Examples of the anion 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.
  • Examples of the anion represented by R 8 c BY 4-c — include (C 6 F 5 ) 4 B ⁇ , ((CF 3 ) 2 C 6 H 3 ) 4 B ⁇ , and (CF 3 C 6 H 4 ) 4.
  • 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 ⁇ are exemplified. Of these, anions represented by (C 6 F 5 ) 4 B — and ((CF 3 ) 2 C 6 H 3 ) 4 B — are preferred.
  • Examples of the anion represented by R 8 c GaY 4-c — include (C 6 F 5 ) 4 Ga ⁇ , ((CF 3 ) 2 C 6 H 3 ) 4 Ga ⁇ , and (CF 3 C 6 H 4 ) 4.
  • 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 ⁇ are included.
  • anions represented by (C 6 F 5 ) 4 Ga ⁇ and ((CF 3 ) 2 C 6 H 3 ) 4 Ga ⁇ are preferable.
  • Examples of the anion represented by R 9 SO 3 — include trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nonafluorobutanesulfonic acid anion, pentafluorophenylsulfonic acid anion, p-toluene.
  • Examples include a sulfonate anion, a benzenesulfonate anion, a camphorsulfonate anion, a methanesulfonate anion, an ethanesulfonate anion, a propanesulfonate anion, and a butanesulfonate anion.
  • trifluoromethanesulfonate anion nonafluorobutanesulfonate anion, methanesulfonate anion, butanesulfonate anion, camphorsulfonate anion, benzenesulfonate anion and p-toluenesulfonate anion are preferred.
  • Examples of the anion represented by (R 9 SO 2 ) 3 C — include (CF 3 SO 2 ) 3 C ⁇ , (C 2 F 5 SO 2 ) 3 C ⁇ , and (C 3 F 7 SO 2 ) 3 C ⁇ . And an anion represented by (C 4 F 9 SO 2 ) 3 C — and the like.
  • Examples of the anion represented by (R 9 SO 2 ) 2 N ⁇ include (CF 3 SO 2 ) 2 N ⁇ , (C 2 F 5 SO 2 ) 2 N ⁇ , and (C 3 F 7 SO 2 ) 2 N ⁇ . And an anion represented by (C 4 F 9 SO 2 ) 2 N — and the like.
  • Monovalent polyatomic anions include MY a ⁇ , (Rf) b PF 6-b ⁇ , R 8 c BY 4-c ⁇ , R 8 c GaY 4-c ⁇ , R 9 SO 3 ⁇ , (R 9 In addition to anions represented by SO 2 ) 3 C — or (R 9 SO 2 ) 2 N — , perhalogenate ions (ClO 4 ⁇ , BrO 4 — etc.), halogenated sulfonate ions (FSO 3 ⁇ , ClSO 3 ⁇ etc.), sulfate ions (CH 3 SO 4 ⁇ , CF 3 SO 4 ⁇ , HSO 4 ⁇ etc.), carbonate ions (HCO 3 ⁇ , CH 3 CO 3 ⁇ etc.), aluminate ions (AlCl 4 ⁇ , AlF 4 -, etc.), hexafluoro bismuthate ions (BiF 6 -), carboxylate ion (CH 3
  • sulfonium salts represented by the formula (1) preferred examples include [4- (4-acetyl) phenylthio] phenyl diphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, [4- (4-acetyl) phenylthio ] Phenyl diphenylsulfonium tetrakis (pentafluorophenyl) borate, [4- (4-acetyl) phenylthio] phenyl diphenylsulfonium tris (trifluoromethanesulfonyl) methide, [4- (4-acetyl) phenylthio] phenyl diphenylsulfonium hexafluoroantimonate [4- (4-acetyl) phenylthio] phenyl diphenylsulfonium hexafluorophosphate, [4-
  • the sulfonium salt can be produced by the production method described below.
  • R, R 1 to R 3 , X ⁇ and m 1 to m 3 are the same as defined in the formula (1).
  • Al represents aluminum
  • Cl represents chlorine
  • X ′ represents a monovalent polyatomic anion.
  • Examples of X ′ include a methanesulfonate anion, a perfluoroalkylsulfonate anion, and a hydrogen sulfate anion.
  • the monovalent polyatomic anion (X ′ ⁇ ) can be exchanged for another anion (X ⁇ ) of the present invention by, for example, a metathesis reaction as described above.
  • MX represents an alkali metal (lithium, sodium, potassium, etc.) cation and another anion of the present invention (for example, MY a ⁇ , (Rf) b PF 6-b ⁇ , R 8 c BY 4-c ⁇ , R 8 c An anion represented by GaY 4-c ⁇ , R 9 SO 3 ⁇ , (R 9 SO 2 ) 3 C ⁇ , R 9 SO 2 ) 2 N ⁇ and the like.
  • the first-stage reaction may be carried out in the absence of a solvent, and if necessary, an organic solvent (general solvents used in Friedel-Crafts reaction such as chloroform, dichloromethane, chlorobenzene, nitromethane, etc.) You may go inside.
  • the reaction temperature is about ⁇ 20 to 150 ° C. depending on the boiling point of the solvent used.
  • the reaction time is about 1 to several tens of hours.
  • the second-stage reaction may be performed subsequent to the first-stage reaction, or may be performed after the precursor (2) is isolated (purified as necessary).
  • the precursor (2) and an aqueous solution of a salt (MX) of an alkali metal cation and a monovalent polyatomic anion were mixed and stirred to perform a metathesis reaction, and the precipitated solid was filtered or separated.
  • the sulfonium salt of the present invention is obtained as a solid or viscous liquid by extracting the oily substance with an organic solvent and removing the organic solvent.
  • the obtained solid or viscous liquid can be washed with a suitable organic solvent, if necessary, or purified by recrystallization or column chromatography.
  • the chemical structure of the sulfonium salt of the present invention can be determined by a general analytical method (for example, 1 H-, 11 B-, 13 C-, 19 F-, 31 P-nuclear magnetic resonance spectrum, infrared absorption spectrum and / or element). Analysis).
  • the photoacid generator of the present invention contains a sulfonium salt represented by the formula (1), but contains other conventionally known photoacid generators in addition to the photoacid generator represented by the formula (1). You may use it.
  • the content (mol%) of the other photoacid generator is 0 with respect to the total number of moles of the photoacid generator represented by the formula (1) of the present invention. 1 to 100 is preferable, and 0.5 to 50 is more preferable.
  • photoacid generators include conventionally known ones such as onium salts (sulfonium, iodonium, selenium, ammonium, phosphonium, etc.) and salts of transition metal complex ions with anions.
  • the photoacid generator represented by formula (1) does not hinder polymerization, crosslinking, deprotection reaction, etc. in advance in order to facilitate dissolution in a cationically polymerizable compound or a chemically amplified resist composition. It may be dissolved in a solvent.
  • Solvents include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate and diethyl carbonate; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone and 2-heptanone; ethylene glycol, ethylene glycol Polyhydric alcohols such as monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol and dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether And derivatives thereof; cyclic ethers such as dioxane Ethyl formate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoa
  • the proportion of the solvent used is preferably 15 to 1000 parts by weight, more preferably 30 to 500 parts by weight with respect to 100 parts by weight of the photoacid generator represented by the formula (1) of the present invention. It is.
  • the solvent to be used may be used independently or may use 2 or more types together.
  • the energy beam curable composition of the present invention comprises the photoacid generator and a cationically polymerizable compound.
  • Examples of the cationic polymerizable compound that is a constituent of the energy ray-curable composition include cyclic ethers (epoxides and oxetanes), ethylenically unsaturated compounds (vinyl ether and styrene, etc.), bicycloorthoesters, spiroorthocarbonates, and spiroorthoesters. ⁇ JP-A-11-060996, JP-A-09-302269, JP-A-2003-026993, etc. ⁇ .
  • epoxide known ones can be used, and aromatic epoxides, alicyclic epoxides and aliphatic epoxides are included.
  • aromatic epoxide examples include glycidyl ethers of monovalent or polyvalent phenols (phenol, bisphenol A, phenol novolac and compounds obtained by adducting these alkylene oxides) having at least one aromatic ring.
  • alicyclic epoxide a compound obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, etc.) Is mentioned.
  • Aliphatic epoxides include aliphatic polyhydric alcohols or polyglycidyl ethers of this alkylene oxide adduct (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc.), aliphatic polybasic acids Examples thereof include polyglycidyl esters (such as diglycidyl tetrahydrophthalate) and epoxidized products of long chain unsaturated compounds (such as epoxidized soybean oil and epoxidized polybutadiene).
  • oxetane known ones can be used. For example, 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3- Oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, oxetanylsilsesquioxetane, phenol novolac oxetane, etc. Is mentioned.
  • known cationically polymerizable monomers can be used, and examples thereof include aliphatic monovinyl ether, aromatic monovinyl ether, polyfunctional vinyl ether, styrene, and cationically polymerizable nitrogen-containing monomers.
  • Examples of the aliphatic monovinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.
  • aromatic monovinyl ether examples include 2-phenoxyethyl vinyl ether, phenyl vinyl ether and p-methoxyphenyl vinyl ether.
  • polyfunctional vinyl ethers examples include butanediol-1,4-divinyl ether and triethylene glycol divinyl ether.
  • styrene examples include styrene, ⁇ -methylstyrene, p-methoxystyrene and p-tert-butoxystyrene.
  • Examples of the cationic polymerizable nitrogen-containing monomer include N-vinylcarbazole and N-vinylpyrrolidone.
  • Bicycloorthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2.2.2] octane and 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo. -[2.2.2] octane and the like.
  • spiro orthocarbonates examples include 1,5,7,11-tetraoxaspiro [5.5] undecane and 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5.5] undecane. It is done.
  • Spiro orthoesters include 1,4,6-trioxaspiro [4.4] nonane, 2-methyl-1,4,6-trioxaspiro [4.4] nonane and 1,4,6-trioxas. Examples include pyro [4.5] decane.
  • polyorganosiloxane having at least one cationic polymerizable group in one molecule can be used (Japanese Patent Laid-Open No. 2001-348482, Journal of Polym.mSci., Part A, Polym.Chem., Vol. .28, 497 (1990)). These polyorganosiloxanes may be linear, branched or cyclic, or a mixture thereof.
  • cationically polymerizable compounds epoxide, oxetane and vinyl ether are preferable, epoxide and oxetane are more preferable, and alicyclic epoxide and oxetane are particularly preferable.
  • these cationically polymerizable compounds may be used alone or in combination of two or more.
  • the content of the photoacid generator represented by the formula (1) of the present invention in the energy ray curable composition is preferably 0.05 to 20 parts by weight, more preferably 100 parts by weight of the cationic polymerizable compound. Is 0.1 to 10 parts by weight. Within this range, the polymerization of the cationically polymerizable compound is further sufficient, and the physical properties of the cured product are further improved. This content is determined by considering various factors such as the nature of the cationically polymerizable compound, the type of energy beam and the irradiation amount, temperature, curing time, humidity, and coating thickness, and is limited to the above range. Not.
  • additives in the energy beam curable composition of the present invention, if necessary, known additives (sensitizers, pigments, fillers, antistatic agents, flame retardants, antifoaming agents, flow regulators, light stabilizers, An antioxidant, an adhesion-imparting agent, an ion scavenger, a coloring inhibitor, a solvent, a non-reactive resin, a radically polymerizable compound, and the like).
  • sensitizer known sensitizers (Japanese Patent Laid-Open Nos. 11-279212 and 09-183960, etc.) can be used.
  • Anthracene ⁇ anthracene, 9,10-dibutoxyanthracene, 9,10-dimethoxyanthracene , 9,10-diethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dipropoxyanthracene, etc. ⁇ ; pyrene; 1,2-benzanthracene; perylene; tetracene; coronene; thioxanthone ⁇ thioxanthone, 2 -Methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone and 2,4-diethylthioxanthone ⁇ ; phenothiazine ⁇ phenothiazin
  • the content of the sensitizer is preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, with respect to 100 parts of the photoacid generator.
  • pigments known pigments can be used, and examples include inorganic pigments (such as titanium oxide, iron oxide, and carbon black) and organic pigments (such as azo pigments, cyanine pigments, phthalocyanine pigments, and quinacridone pigments).
  • inorganic pigments such as titanium oxide, iron oxide, and carbon black
  • organic pigments such as azo pigments, cyanine pigments, phthalocyanine pigments, and quinacridone pigments.
  • the content of the pigment is preferably 0.5 to 400,000 parts by weight, more preferably 10 to 150,000 parts by weight with respect to 100 parts of the photoacid generator.
  • filler known fillers can be used, such as fused silica, crystalline silica, calcium carbonate, aluminum oxide, aluminum hydroxide, zirconium oxide, magnesium carbonate, mica, talc, calcium silicate and lithium aluminum silicate. Can be mentioned.
  • the content of the filler is preferably 50 to 600000 parts by weight, more preferably 300 to 200000 parts by weight with respect to 100 parts of the photoacid generator.
  • antistatic agent known antistatic agents can be used, and examples include nonionic antistatic agents, anionic antistatic agents, cationic antistatic agents, amphoteric antistatic agents, and polymeric antistatic agents. .
  • the content of the antistatic agent is preferably 0.1 to 20000 parts by weight, more preferably 0.6 to 5000 parts by weight with respect to 100 parts of the photoacid generator.
  • Inorganic flame retardant ⁇ antimony trioxide, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide , Magnesium hydroxide, calcium aluminate, etc. ⁇ ; bromine flame retardant ⁇ tetrabromophthalic anhydride, hexabromobenzene, decabromobiphenyl ether, etc. ⁇ ; and phosphate ester flame retardant ⁇ tris (tribromophenyl) phosphate, etc. ⁇ It is done.
  • the content of the flame retardant is preferably 0.5 to 40000 parts by weight, more preferably 5 to 10000 parts by weight with respect to 100 parts of the photoacid generator.
  • antifoaming agent known antifoaming agents can be used, such as alcohol defoaming agents, metal soap defoaming agents, phosphate ester defoaming agents, fatty acid ester defoaming agents, polyether defoaming agents, and silicone defoaming agents. And mineral oil defoaming agents.
  • known flow control agents can be used, and examples thereof include hydrogenated castor oil, polyethylene oxide, organic bentonite, colloidal silica, amide wax, metal soap, and acrylate polymer.
  • the light stabilizer known light stabilizers and the like can be used. Ultraviolet absorbing stabilizers ⁇ benzotriazole, benzophenone, salicylate, cyanoacrylate and derivatives thereof ⁇ ; radical scavenging stabilizers ⁇ hindered amines, etc. ⁇ ; and quenching And a type stabilizer ⁇ nickel complex etc. ⁇ .
  • antioxidants can be used, and examples include phenolic antioxidants (monophenolic, bisphenolic and polymeric phenolic), sulfur antioxidants and phosphorus antioxidants. It is done.
  • adhesion-imparting agent a known adhesion-imparting agent can be used, and examples thereof include a coupling agent, a silane coupling agent, and a titanium coupling agent.
  • ion scavenger known ion scavengers and the like can be used, and organic aluminum (alkoxyaluminum, phenoxyaluminum, etc.) and the like can be mentioned.
  • Known anti-coloring agents can be used as the anti-coloring agent. In general, antioxidants are effective.
  • Phenol type antioxidants (monophenol type, bisphenol type and high molecular phenol type, etc.), sulfur type oxidation Inhibitors and phosphorus-based antioxidants may be mentioned, but they are hardly effective in preventing coloring during a heat resistance test at high temperatures.
  • each content is based on 100 parts of the photoacid generator,
  • the amount is preferably 0.1 to 20000 parts by weight, more preferably 0.5 to 5000 parts by weight.
  • the solvent is not particularly limited as long as it can be used for dissolving the cationic polymerizable compound and adjusting the viscosity of the energy ray curable composition, and those mentioned as the solvent for the photoacid generator can be used.
  • the content of the solvent is preferably 50 to 2,000,000 parts by weight, more preferably 200 to 500,000 parts by weight with respect to 100 parts of the photoacid generator.
  • Non-reactive resins include polyester, polyvinyl acetate, polyvinyl chloride, polybutadiene, polycarbonate, polystyrene, polyvinyl ether, polyvinyl butyral, polybutene, hydrogenated styrene butadiene block copolymer, and (meth) acrylic ester co-polymer.
  • Examples include coalescence and polyurethane.
  • the number average molecular weight of these resins is preferably 1,000 to 500,000, more preferably 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 400000 parts by weight, more preferably 50 to 150,000 parts by weight with respect to 100 parts of the photoacid generator.
  • non-reactive resin When a non-reactive resin is contained, it is desirable to dissolve the non-reactive resin in a solvent in advance so that the non-reactive resin can be easily dissolved with the cationic polymerizable compound.
  • radically polymerizable compounds known ⁇ Photopolymer social gathering “Photopolymer Handbook” (1989, Industrial Research Committee), General Technology Center “UV / EB Curing Technology” (1982, General Technology Center), Radtech Research Can be used as radically polymerizable compounds such as “UV / EB Curing Materials” (1992, CMC), etc., monofunctional monomer, bifunctional monomer, polyfunctional monomer, epoxy (meth) acrylate, polyester (meth) Acrylate and urethane (meth) acrylate are included.
  • the content of the radical polymerizable compound is preferably 5 to 400000 parts by weight, more preferably 50 to 150,000 parts by weight with respect to 100 parts of the photoacid generator.
  • radical polymerization initiator that initiates polymerization by heat or light in order to increase the molecular weight thereof by radical polymerization.
  • radical polymerization initiator known radical polymerization initiators can be used, thermal radical polymerization initiators (organic peroxides, azo compounds, etc.) and photo radical polymerization initiators (acetophenone initiators, benzophenone initiators, Michler ketone-based initiator, benzoin-based initiator, thioxanthone-based initiator, acylphosphine-based initiator, etc.).
  • thermal radical polymerization initiators organic peroxides, azo compounds, etc.
  • photo radical polymerization initiators acetophenone initiators, benzophenone initiators, Michler ketone-based initiator, benzoin-based initiator, thioxanthone-based initiator, acylphosphine-based initiator, etc.
  • the content of the radical polymerization initiator is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts of the radical polymerizable compound. .
  • the energy ray-curable composition of the present invention comprises a cationically polymerizable compound, a photoacid generator, and optionally an additive, uniformly at room temperature (about 20 to 30 ° C.) or optionally heated (about 40 to 90 ° C.). Can be mixed and dissolved, or further kneaded with three rolls or the like.
  • the energy ray-curable composition of the present invention can be cured by irradiation with energy rays to obtain a cured product.
  • any energy ray may be used as long as it has energy that induces decomposition of the photoacid generator of the present invention, but a low pressure, medium pressure, high pressure or ultrahigh pressure mercury lamp, metal halide lamp, LED lamp, xenon lamp, carbon arc.
  • Energy rays in the ultraviolet to visible light region (wavelength: about 100 to about 800 nm) obtained from lamps, fluorescent lamps, solid-state semiconductor lasers, argon lasers, He—Cd lasers, KrF excimer lasers, ArF excimer lasers, F 2 lasers, etc. preferable.
  • the radiation which has high energy such as an electron beam or an X-ray, can also be used for an energy beam.
  • the irradiation time of the energy beam is affected by the intensity of the energy beam and the energy beam permeability to the energy beam curable composition, but about 0.1 to 10 seconds is sufficient at room temperature (about 20 to 30 ° C). It is. However, it may be preferable to spend more time when energy beam permeability is low or when the energy beam curable composition is thick.
  • Most energy ray-curable compositions are cured by cationic polymerization after 0.1 seconds to several minutes after irradiation with energy rays, but if necessary, after irradiation with energy rays, room temperature (about 20 to 30 ° C.) to 200 It is also possible to carry out after-curing by heating at a temperature of several seconds to several hours.
  • the energy ray curable composition of the present invention include paints, coating agents, various coating materials (hard coat, anti-stain coating, anti-fogging coating, touch-resistant coating, optical fiber, etc.), adhesive tape Back coating agent, Release coating material for adhesive labels (release paper, release plastic film, release metal foil, etc.), printing plate, dental material (dental compound, dental composite) ink, inkjet ink, positive Type resist (connecting terminals and wiring pattern formation for manufacturing electronic components such as circuit boards, CSPs, MEMS elements, etc.), resist films, liquid resists, negative resists (surface protective films for semiconductor elements, interlayer insulating films, planarization films) Permanent film materials, etc.), MEMS resists, positive photosensitive materials, negative photosensitive materials, various adhesives (temporary fixing agents for various electronic components) HDD adhesive, pickup lens adhesive, FPD functional film (deflection plate, antireflection film, etc.) adhesive, holographic resin, FPD material (color filter, black matrix, partition material, photo spacer, Ribs,
  • the photoacid generator of the present invention Since the photoacid generator of the present invention generates a strong acid upon irradiation with light, a chemical amplification type known in the art (JP 2003-267968 A, JP 2003-261529 A, JP 2002-193925 A, etc.) is used. It can also be used as a photoacid generator for resist materials. *
  • a two-component chemically amplified positive resist containing, as essential components, a resin that is soluble in an alkali developer by the action of an acid and a photoacid generator; (2) an alkali developer Soluble resin, a three-component chemical amplification type positive resist containing, as essential components, a dissolution inhibitor that becomes soluble in an alkali developer by the action of an acid and a photoacid generator, and (3) acceptable for an alkali developer.
  • a chemically amplified negative resist containing a cross-linking agent that crosslinks the resin by heat treatment in the presence of an acid and an acid and an insoluble in an alkaline developer and a photoacid generator as an essential component is included.
  • the chemically amplified positive photoresist composition of the present invention comprises a component (A) comprising a photoacid generator represented by the formula (1) of the present invention, which is a compound that generates an acid upon irradiation with light or radiation. It contains a resin component (B) whose solubility in alkali is increased by the action of an acid.
  • A comprising a photoacid generator represented by the formula (1) of the present invention, which is a compound that generates an acid upon irradiation with light or radiation. It contains a resin component (B) whose solubility in alkali is increased by the action of an acid.
  • 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, hydrazine sulfonate compounds, triazine compounds, and nitrobenzyl.
  • organic halides, disulfone and the like can be mentioned.
  • one or more of the group of onium compounds, sulfonimide compounds, diazomethane compounds and oxime sulfonate compounds are preferable.
  • the ratio of use may be arbitrary, but is usually 100 parts by weight of the total weight of the photoacid generator represented by the above formula (1).
  • the other photoacid generator is 10 to 900 parts by weight, preferably 25 to 400 parts by weight.
  • the content of the component (A) is preferably 0.05 to 5% by weight in the solid content of the chemically amplified positive photoresist composition.
  • Resin component (B) whose solubility in alkali is increased by the action of acid The aforementioned “resin (B) whose solubility in alkali is increased by the action of an acid” (hereinafter referred to as “component (B)”) used in the chemically amplified positive photoresist composition of the present invention.
  • component (B) used in the chemically amplified positive photoresist composition of the present invention.
  • Novolak resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3) or at least one resin selected from the group consisting of these resins, or a mixed resin or copolymer thereof.
  • Novolac resin (B1) As the novolac resin (B1), a resin represented by the following general formula (b1) can be used.
  • R 1b represents an acid dissociable, dissolution inhibiting group
  • R 2b and R 3b each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • n is in parentheses. Represents the number of repeating units in the structure.
  • examples of the acid dissociable, dissolution inhibiting group represented by R 1b include linear alkyl groups having 1 to 6 carbon atoms, branched alkyl groups having 3 to 6 carbon atoms, and cyclic groups having 3 to 6 carbon atoms. Are preferably an alkyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.
  • specific examples of the acid dissociable, dissolution inhibiting group represented by R 1b include methoxyethyl group, ethoxyethyl group, n-propoxyethyl group, isopropoxyethyl group, n-butoxyethyl group, isobutoxyethyl.
  • tert-butoxyethyl group cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group, tert-butoxycarbonyl group, tert-butoxy group
  • Examples 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 dissociable, dissolution inhibiting group
  • n represents the number of repeating units in the structure in parentheses.
  • the alkyl group having 1 to 6 carbon atoms is a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.
  • Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group. Etc.
  • the same acid dissociable, dissolution inhibiting groups as those exemplified for R 1b can be used.
  • the polyhydroxystyrene resin (B2) can contain other polymerizable compounds as constituent units for the purpose of appropriately controlling physical and chemical properties.
  • polymerizable compounds include known radical 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 an ester bond such as 2-methacryloyloxyethyl succinic acid; methyl (meth) acrylate, etc.
  • 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 each independently represent a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms.
  • Y b represents an optionally substituted aliphatic cyclic group or an alkyl group
  • n represents the number of repeating units of the structure in parentheses
  • p is an integer of 0 to 4
  • q is 0 or 1.
  • R 18b , R 20b, and R 21b each independently represent a hydrogen atom or a methyl group
  • R 19b is independently of each other a hydrogen atom, a hydroxyl group, a cyano group or a COOR 23b group (where R 23b is a hydrogen atom, a linear alkyl group having 1 to 4 carbon atoms or a branched group having 3 to 4 carbon atoms).
  • each R 22b is independently of each other a monovalent alicyclic group having 4 to 20 carbon atoms.
  • a linear alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a derivative thereof is represented.
  • the weight average molecular weight in terms of polystyrene 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. is there. By setting it as such a weight average molecular weight, the resin physical property of a resist becomes excellent.
  • the component (B) is preferably a resin having a dispersity of 1.05 or more.
  • the “dispersion degree” is a value obtained by dividing the weight average molecular weight by the number average molecular weight. By setting such a degree of dispersion, the resist plating resistance and resin physical properties are excellent.
  • the content of the component (B) is preferably 5 to 60% by weight in the solid text of the chemically amplified positive photoresist composition.
  • the chemically amplified positive photoresist composition of the present invention preferably further contains an alkali-soluble resin (hereinafter referred to as “component (C)”) in order to improve the resin physical properties of the resist.
  • component (C) is preferably at least one selected from the group consisting of novolak resins, polyhydroxystyrene resins, acrylic resins and polyvinyl resins.
  • the content of the component (C) is preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight with respect to 100 parts by weight of the component (B).
  • the amount is 5 parts by weight or more, the resin physical properties of the resist can be improved, and when the amount is 95 parts by weight or less, there is a tendency that film loss during development can be prevented.
  • the chemical amplification type positive photoresist composition of the present invention further comprises an acid diffusion control agent (D) (in the present specification, “component (D)”) in order to improve the resist pattern shape, the stability of holding and the like. It is preferable to contain.
  • component (D) a nitrogen-containing compound is preferable, and an organic carboxylic acid, an oxo acid of phosphorus, or a derivative thereof can be further contained as necessary.
  • the chemical amplification type positive photoresist composition of the present invention may further contain an adhesion assistant in order to improve the adhesion to the substrate.
  • an adhesion assistant used, a functional silane coupling agent is preferable.
  • the chemical amplification type positive photoresist composition of the present invention may further contain a surfactant in order to improve coating property, antifoaming 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 alkali developer.
  • the chemical amplification type positive photoresist composition of the present invention basically does not require a sensitizer, but can contain a sensitizer as necessary to complement the sensitivity.
  • a sensitizer conventionally known ones can be used, and specific examples thereof include those described above.
  • sensitizers are used in an amount of 5 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the total weight of the photoacid generator represented by the above formula (1).
  • an organic solvent can be appropriately blended in the chemically amplified positive photoresist composition of the present invention for viscosity adjustment.
  • Specific examples of the organic solvent include those described above.
  • the amount of these organic solvents used is such that the solid layer concentration is such that the film thickness of the photoresist layer obtained by using the chemically amplified positive photoresist composition of the present invention (for example, spin coating method) is 5 ⁇ m or more. Is preferably 30% by weight or more.
  • the chemical amplification type positive photoresist composition of the present invention can be prepared, for example, by mixing and stirring the above components by a usual method. If necessary, a disperser such as a dissolver, a homogenizer, or a three roll mill is used. They may be used for dispersion and mixing. Moreover, after mixing, you may further filter using a mesh, a membrane filter, etc.
  • a disperser such as a dissolver, a homogenizer, or a three roll mill is used. They may be used for dispersion and mixing. Moreover, after mixing, you may further filter using a mesh, a membrane filter, etc.
  • the chemically amplified positive photoresist composition of the present invention is suitable for forming a photoresist layer having a thickness of usually 5 to 150 ⁇ m, more preferably 10 to 120 ⁇ m, and 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 a conventionally known one can be used.
  • Examples thereof include a substrate for electronic parts and a substrate on which a predetermined wiring pattern is formed.
  • the substrate include a metal substrate such as silicon, silicon nitride, titanium, tantalum, palladium, titanium tungsten, copper, chromium, iron, and aluminum, a glass substrate, and the like.
  • the chemically amplified positive photoresist composition of the present invention can form a resist pattern satisfactorily even on a copper substrate.
  • As a material for the wiring pattern for example, copper, solder, chromium, aluminum, nickel, gold, or the like is used.
  • the photoresist laminate can be produced, for example, as follows. That is, a desired coating film is formed by applying a solution of a chemically amplified positive photoresist composition prepared as described above onto a support and removing the solvent by heating. As a coating method on the support, methods such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, and an applicator method can be employed.
  • the pre-baking conditions for the coating film of the composition of the present invention vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, etc., but are usually 70 to 150 ° C., preferably 80 to 140 ° C. What is necessary is just about 60 minutes.
  • the film thickness of the photoresist layer is usually 5 to 150 ⁇ m, preferably 10 to 120 ⁇ m, more preferably 10 to 100 ⁇ m.
  • light or radiation for example, having a wavelength of 300 to 500 nm is passed through the obtained photoresist layer through a mask having a predetermined pattern. Irradiation (exposure) with ultraviolet rays or visible rays may be performed selectively.
  • the “light” may be light that activates the photoacid generator to generate acid, and includes ultraviolet rays, visible rays, and far ultraviolet rays, and “radiation” means X-rays, electron beams, and the like. Means an ion beam or the like.
  • a light or radiation source a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an argon gas laser, an LED lamp, or the like can be used.
  • the radiation irradiation amount varies depending on the kind of each component in the composition, the blending amount, the film thickness of the coating film, and the like, but is, for example, 50 to 10,000 mJ / cm 2 when using an ultrahigh pressure mercury lamp.
  • the diffusion of the acid is promoted by heating using a known method to change the alkali solubility of the exposed photoresist layer.
  • a known method to change the alkali solubility of the exposed photoresist layer.
  • unnecessary portions are dissolved and removed to obtain a predetermined resist pattern.
  • the development time varies depending on the type of each component of the composition, the blending ratio, and the dry film thickness of the composition, but is usually 1 to 30 minutes.
  • the development method is a liquid piling method, dipping method, paddle method, spray development method. Any of these may be used. After development, washing with running water is performed for 30 to 90 seconds and dried using an air gun, oven, or the like.
  • connection terminals such as metal posts and bumps by embedding a conductor such as metal in the non-resist portion (the portion removed with the alkali developer) of the resist pattern thus obtained, for example, by plating.
  • the plating method is not particularly limited, and various conventionally known methods can be employed.
  • As the plating solution solder plating, copper plating, gold plating, or nickel plating solution is particularly preferably used.
  • the remaining resist pattern is finally removed using a stripping solution or the like according to a conventional method.
  • the chemically amplified positive photoresist composition of the present invention can also be used as a dry film.
  • This dry film has a protective film formed on both sides of a layer made of the chemically amplified positive photoresist composition of the present invention.
  • the thickness of the layer made of the chemically amplified positive photoresist composition is usually in the range of 10 to 150 ⁇ m, preferably 20 to 120 ⁇ m, more preferably 20 to 80 ⁇ m.
  • a protective film is not specifically limited,
  • the resin film conventionally used for the dry film can be used.
  • one may be a polyethylene terephthalate film and the other may be one selected from the group consisting of a polyethylene terephthalate film, a polypropylene film, and a polyethylene film.
  • the chemical amplification type positive dry film as described above can be manufactured, for example, as follows. That is, a solution of a chemically amplified positive photoresist composition prepared as described above is applied onto one protective film, and the solvent is removed by heating to form a desired coating film.
  • the drying conditions vary depending on the type of each component in the composition, the blending ratio, the coating film thickness, and the like, but are usually 60 to 100 ° C. and about 5 to 20 minutes.
  • one protective film of the chemically amplified positive dry film is peeled off and the exposed surface is directed to the support side described above. Then, after laminating on the support to obtain a photoresist layer, after prebaking to dry the resist, the other protective film may be peeled off.
  • a resist pattern can be formed in the same manner as described above with respect to the photoresist layer formed by coating directly on the support. .
  • the chemically amplified negative photoresist composition of the present invention comprises a component (E) comprising a photoacid generator represented by the general formula (1) of the present invention, which is a compound that generates an acid upon irradiation with light or radiation. And an alkali-soluble resin (F) having a phenolic hydroxyl group and a crosslinking agent (G).
  • Alkali-soluble resin (F) having phenolic hydroxyl group examples include, for example, novolak resin, polyhydroxystyrene, a copolymer of polyhydroxystyrene, hydroxystyrene and styrene. Copolymer, hydroxystyrene, styrene and (meth) acrylic acid derivative copolymer, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, phenol-dicyclopentadiene condensation resin, and the like.
  • novolak resins polyhydroxystyrene, copolymers of polyhydroxystyrene, copolymers of hydroxystyrene and styrene, copolymers of hydroxystyrene, styrene and (meth) acrylic acid derivatives, phenol-xylylene glycol Condensed resins are preferred.
  • these phenol resin (F) may be used individually by 1 type, and may mix and use 2 or more types.
  • the phenolic resin (F) may contain a phenolic low molecular compound as a part of the component.
  • a phenolic low molecular compound examples include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, and the like.
  • cross-linking agent (G) The “crosslinking agent” (hereinafter also referred to as “crosslinking agent (G)”) in the present invention is not particularly limited as long as it acts as a crosslinking component (curing component) that reacts with the phenol resin (F).
  • crosslinking agent (G) examples include a compound having at least two or more alkyl etherified amino groups in the molecule, a compound having at least two or more alkyl etherified benzenes in the molecule as a skeleton, An oxirane ring-containing compound, a thiirane ring-containing compound, an oxetanyl group-containing compound, an isocyanate group-containing compound (including a blocked one), and the like can be given.
  • crosslinking agents (G) compounds having at least two alkyl etherified amino groups in the molecule and oxirane ring-containing compounds are preferred. Furthermore, it is more preferable to use a compound having at least two alkyl etherified amino groups in the molecule and an oxirane ring-containing compound in combination.
  • the blending amount of the crosslinking agent (G) in the present invention is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the phenol resin (F).
  • the amount of the crosslinking agent (G) is 1 to 100 parts by weight, the curing reaction proceeds sufficiently, and the resulting cured product has a high resolution, good pattern shape, heat resistance, electrical insulation. It is preferable because of its excellent properties.
  • the content ratio of the oxirane ring-containing compound is the sum of the compound having an alkyl etherified amino group and the oxirane ring-containing compound being 100.
  • weight% it is preferably 50% by weight or less, more preferably 5 to 40% by weight, and particularly preferably 5 to 30% by weight. In this case, the obtained cured film is preferable because it is excellent in chemical resistance without impairing high resolution.
  • Cross-linked fine particles (H) The chemically amplified negative photoresist composition of the present invention further contains crosslinked fine particles (hereinafter also referred to as “crosslinked fine particles (H)”) in order to improve the durability and thermal shock resistance of the resulting cured product. Can be made.
  • the average particle size of the crosslinked fine particles (H) is usually 30 to 500 nm, preferably 40 to 200 nm, more preferably 50 to 120 nm.
  • the method for controlling the particle size of the crosslinked fine particles (H) is not particularly limited. For example, when the crosslinked fine particles are synthesized by emulsion polymerization, the number of micelles during emulsion polymerization is controlled by the amount of the emulsifier used, and the particle size is controlled. Can be controlled.
  • the average particle diameter of the crosslinked fine particles (H) is a value measured by diluting a dispersion of crosslinked fine particles according to a conventional method using a light scattering flow distribution measuring device or the like.
  • the amount of the crosslinked fine particles (H) is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the phenol resin (F).
  • the amount of the crosslinked fine particles (H) is 0.5 to 50 parts by weight, the compatibility or dispersibility with other components is excellent, and the thermal shock resistance and heat resistance of the resulting cured film are improved. be able to.
  • the chemically amplified negative photoresist composition of the present invention may contain an adhesion aid in order to improve the adhesion to the substrate.
  • the adhesion assistant include a functional silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group.
  • the blending amount of the adhesion assistant is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 8 parts by weight with respect to 100 parts by weight of the phenol resin (F).
  • a blending amount of the adhesion aid of 0.2 to 10 parts by weight is preferred because it is excellent in storage stability and good adhesion can be obtained.
  • the chemically amplified negative photoresist composition of the present invention may contain a solvent for improving the handleability of the resin composition and adjusting the viscosity and storage stability.
  • the solvent is not particularly limited, but specific examples include those described above.
  • the chemically amplified negative photoresist composition of the present invention can contain a sensitizer if necessary.
  • a sensitizer conventionally known ones can be used, and specific examples thereof include those described above.
  • sensitizers are used in an amount of 5 to 500 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the total weight of the photoacid generator represented by the general formula (1).
  • the chemically amplified negative photoresist composition of the present invention can contain other additives as necessary so as not to impair the characteristics of the present invention.
  • additives include inorganic fillers, quenchers, leveling agents and surfactants.
  • the method for preparing the chemically amplified negative photoresist composition of the present invention is not particularly limited, and can be prepared by a known method. It can also be prepared by stirring a sample bottle with each component in it and completely plugged on the wave rotor.
  • the cured product in the present invention is obtained by curing the chemically amplified negative photoresist composition.
  • the above-mentioned chemically amplified negative photoresist composition according to the present invention has a high residual film ratio and excellent resolution, and its cured product is excellent in electrical insulation, thermal shock, etc.
  • the cured product can be suitably used as a surface protective film, planarizing film, interlayer insulating film material, etc. for electronic components such as semiconductor elements and semiconductor packages.
  • the chemically amplified negative photoresist composition according to the present invention is used as a support (a silicon wafer with a resin-coated copper foil, a copper-clad laminate, a metal sputtered film, Coating onto an alumina substrate and the like, and drying to volatilize the solvent and the like to form a coating film. Then, it exposes through a desired mask pattern, heat processing (henceforth this heat processing is called "PEB”) is performed, and reaction with a phenol resin (F) and a crosslinking agent (G) is accelerated
  • PEB heat processing
  • a desired pattern can be obtained by melt
  • 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.
  • radiation used for exposure include ultraviolet rays such as low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, g-line steppers, h-line steppers, i-line steppers, gh-line steppers, and ghi-line steppers, electron beams, and laser beams. .
  • the exposure amount is appropriately selected depending on the light source used, the resin film thickness, and the like. For example, in the case of ultraviolet irradiation from a high-pressure mercury lamp, the resin film thickness is about 100 to 50000 J / m 2 when the resin film thickness is 1 to 50 ⁇ m.
  • the PEB treatment is performed to promote the curing reaction of the phenol resin (F) and the crosslinking agent (G) by the generated acid.
  • the PEB conditions vary depending on the blending amount of the resin composition and the film thickness used, but are usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes.
  • development is performed with an alkaline developer, and a desired pattern is formed by dissolving and removing unexposed portions. Examples of the developing method in this case include a shower developing method, a spray developing method, an immersion developing method, and a paddle developing method.
  • the development conditions are usually 20 to 40 ° C. and about 1 to 10 minutes.
  • the film in order to sufficiently develop the characteristics as an insulating film after development, can be sufficiently cured by heat treatment.
  • Such curing conditions are not particularly limited, but the composition can be cured by heating at a temperature of 50 to 250 ° C. for about 30 minutes to 10 hours depending on the use of the cured product.
  • it in order to sufficiently advance the curing or to prevent deformation of the obtained pattern shape, it can be heated in two stages. For example, in the first stage, the temperature is 50 to 120 ° C. for 5 minutes to 2 minutes. It can also be cured by heating for about an hour and further heating at a temperature of 80 to 250 ° C. for about 10 minutes to 10 hours. Under such curing conditions, a general oven, an infrared furnace, or the like can be used as a heating facility.
  • [4- (4-Acetyl) phenylthio] was prepared in the same manner as in Production Example 1 except that 32.7 parts of potassium tris (pentafluoroethyl) trifluorophosphate was changed to 46.3 parts of lithium tetrakis (pentafluorophenyl) borate. ] 60.4 parts of phenyl diphenylsulfonium tetrakis (pentafluorophenyl) borate were obtained (yield 90%). The product was identified by 1 H-NMR and infrared absorption spectroscopy (IR).
  • IR infrared absorption spectroscopy
  • [4- (4-Acetyl) phenylthio] was prepared in the same manner as in Production Example 1, except that 32.7 parts of potassium tris (pentafluoroethyl) trifluorophosphate was changed to 28.2 parts of tris (trifluoromethanesulfonyl) methide lithium. 45.6 parts of phenyl diphenylsulfonium tris (trifluoromethanesulfonyl) methide were obtained (90% yield). The product was identified by 1 H-NMR and infrared absorption spectroscopy (IR).
  • IR infrared absorption spectroscopy
  • [4- (4-Acetyl) phenylthio] phenyl diphenylsulfonium was prepared in the same manner as in Production Example 1 except that 32.7 parts of potassium tris (pentafluoroethyl) trifluorophosphate was changed to 18.6 parts of potassium hexafluoroantimonate. 35.9 parts of hexafluoroantimonate were obtained (90% yield).
  • the product was identified by 1 H-NMR and infrared absorption spectroscopy (IR).
  • [4- (4-Acetyl) phenylthio] phenyl diphenylsulfonium was prepared in the same manner as in Production Example 1 except that 32.7 parts of potassium tris (pentafluoroethyl) trifluorophosphate was changed to 12.4 parts of potassium hexafluorophosphate. 30.9 parts of hexafluorophosphate were obtained (90% yield). The product was identified by 1 H-NMR and infrared absorption spectroscopy (IR).
  • [4- (4-acetyl) phenylthio] phenyl diphenylsulfonium was prepared in the same manner as in Production Example 1 except that 32.7 parts of potassium tris (pentafluoroethyl) trifluorophosphate was changed to 12.7 parts of potassium trifluoromethanesulfonate. 31.1 parts of trifluoromethanesulfonate were obtained (yield 90%).
  • the product was identified by 1 H-NMR and infrared absorption spectroscopy (IR).
  • the solution was poured into 121 parts of an aqueous solution and stirred at room temperature (about 25 ° C.) for 1 hour to precipitate a yellow slightly viscous oil.
  • This oily substance was extracted with ethyl acetate, the organic layer was washed several times with water, the solvent was distilled off from the organic layer, and the resulting residue was dissolved by adding toluene.
  • the mixture was stirred well for 1 hour and allowed to stand. After 1 hour, since the solution was separated into two layers, the upper layer was removed by liquid separation. When hexane was added to the remaining lower layer and mixed well at room temperature (about 25 ° C.), pale yellow crystals were precipitated.
  • the sulfonium salt obtained in Production Example 5 and Comparative Example 5 is hexafluorophosphate, and the tris (pentafluoroethyl) trifluorophosphate of Production Examples 1 to 4, 7, 8 and Comparative Examples 1 to 4 is used.
  • Tetrakis (pentafluorophenyl) borate, tris (trifluoromethanesulfonyl) methideate and hexafluoroantimonate have lower acid strength and lower activity against cationic polymerization. A lot. Along with this, the amount of the solvent was increased.
  • the energy ray-curable composition obtained above was applied to a polyethylene terephthalate (PET) film with an applicator (25 ⁇ m).
  • PET film was irradiated with ultraviolet light having a wavelength limited by a filter using an ultraviolet irradiation device.
  • the filter used was an IRCF02 filter (manufactured by Eye Graphics Co., Ltd., a filter that cuts light of less than 340 nm).
  • the coating hardness after 40 minutes was measured with pencil hardness (JIS K5600-5-4: 1999) and evaluated according to the following criteria (the coating thickness after curing was about 25 ⁇ m). It is shown in Table 2.
  • Pencil hardness is 2H or more
  • Pencil hardness is H to B
  • Pencil hardness is 2B-4B
  • Ultraviolet light irradiation conditions ⁇ Ultraviolet irradiation device: Belt conveyor type UV irradiation device (manufactured by Eye Graphics Co., Ltd.) ⁇ Lamp: 1.5kW high pressure mercury lamp ⁇ Filter: IRCF02 filter (manufactured by Eye Graphics Co., Ltd.) Illuminance (measured with a 365 nm head illuminometer): 145 mW / cm 2
  • Condition-1 140 mJ / cm 2
  • Condition-2 170 mJ / cm 2
  • Condition-3 200 mJ / cm 2
  • ⁇ Storage stability> The energy ray-curable composition obtained above was heated at 80 ° C. under light shielding and stored for 1 month, and then the viscosity of the blended sample before and after heating was measured and evaluated according to the following criteria. The storage stability is better as the viscosity does not increase. (Evaluation criteria) X: Viscosity change after heating is 1.5 times or more. ⁇ : Viscosity change after heating is less than 1.5 times.
  • the sulfonium salt of the present invention was superior in curing performance (photosensitivity) of the cationically polymerizable compound under ultraviolet light of 365 nm or more as compared with the comparative sulfonium salt. .
  • ⁇ Sensitivity evaluation> The positive resist compositions prepared in Examples P1 to P6 and Comparative Examples P1 to P4 were spin-coated on a silicon wafer substrate, and then dried to obtain a photoresist layer having a thickness of about 20 ⁇ m. This resist layer was pre-baked at 130 ° C. for 6 minutes using a hot plate. After pre-baking, pattern exposure (i-line) was performed using TME-150RSC (Topcon), and post-exposure heating (PEB) was performed at 75 ° C. for 5 minutes using a hot plate.
  • i-line pattern exposure
  • TME-150RSC Topcon
  • PEB post-exposure heating
  • the chemically amplified positive photoresist compositions of Examples P1 to P6 are more sensitive than conventional photoacid generators as in Comparative Examples P1 to P4, and are stored in the same manner. It turns out that it is excellent in stability and pattern shape.
  • Examples N1 ⁇ N6 were prepared. Comparative examples were similarly carried out with the blending amounts shown in Table 5, and negative photoresist compositions (Comparative Examples N1 to N4) were prepared.
  • the chemically amplified negative photoresist compositions of Examples N1 to N6 are more sensitive than conventional photoacid generators as in Comparative Examples N1 to N4, and are stored in the same manner. It turns out that it is excellent in stability and pattern shape.
  • the sulfonium salt of the present invention comprises a coating material, a coating agent, various coating materials (hard coat, antifouling coating material, anti-fogging coating material, touch-proof coating material, optical fiber, etc.), a back treatment agent for adhesive tape, and a release sheet for an adhesive label.
  • Release coating material release paper, release plastic film, release metal foil, etc.
  • printing plate dental material (dental compound, dental composite) ink, inkjet ink, positive resist (circuit board, CSP, MEMS element) Connection terminal and wiring pattern formation, etc.
  • resist film for electronic component manufacturing, etc.
  • resist film liquid resist
  • negative resist permanent film materials such as surface protective films for semiconductor elements, interlayer insulation films, planarization films, etc.
  • MEMS Resist positive photosensitive material
  • negative photosensitive material various adhesives (temporary fixing agent for various electronic parts, HDD adhesive, pickup Adhesives, functional films for FPDs (deflection plates, antireflection films, etc.), holographic resins, FPD materials (color filters, black matrix, barrier rib materials, photo spacers, ribs, alignment films for liquid crystals , FPD sealant, etc.), optical members, molding materials (for building materials, optical components, lenses), casting materials, putty, glass fiber impregnating agents, sealing materials, sealing materials, sealing materials, optical semiconductors (LEDs) ) It is suitably used as a photoacid generator for use in encapsulants, optical waveguide materials, nanoimprint materials, photofabrication, and micro stereolithography materials.

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Abstract

La présente invention concerne un sel de sulfonium inédit hautement photosensible au rayonnement ultraviolet (i-line) ; et un générateur photoacide inédit contenant un sel de sulfonium, etc., qui se révèle hautement photosensible au rayonnement ultraviolet (i-line), qui présente une très bonne compatibilité avec les composés cationiquement polymérisables, tels que les composés époxy, et une remarquable stabilité en stockage sous la forme d'une composition. La présente invention concerne, donc, un sel de sulfonium représenté par la formule générale (1) et un générateur photoacide, etc., caractérisé en ce qu'il contient ledit sel de sulfonium (R représente un groupe alkyle ou aryle ; R1, R2 et R3 représentent indépendamment un groupe alkyle, hydroxyle, alcoxy, aryle, aryloxy, hydroxyl(poly)alkylèneoxy, cyano, nitro, ou un atome d'halogène ; m1, m² et m3 représentent chacun le nombre de groupes R1, R² et R3 ; m1 représente un nombre entier de 0 à 4 ; m2 et m3 représentent des nombres entiers de 0 à 5 ; et X- représente un anion polyatomique monovalent).
PCT/JP2012/006666 2012-10-18 2012-10-18 Sel de sulfonium, générateur photoacide, composition polymérisable et composition de résine photosensible WO2014061062A1 (fr)

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PCT/JP2012/006666 WO2014061062A1 (fr) 2012-10-18 2012-10-18 Sel de sulfonium, générateur photoacide, composition polymérisable et composition de résine photosensible
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018003470A1 (fr) * 2016-06-29 2018-01-04 サンアプロ株式会社 Sel de sulfonium, générateur de photoacide, composition photodurcissable et produit durci correspondan.
TWI697736B (zh) * 2015-12-29 2020-07-01 南韓商東友精細化工有限公司 黑色感光性樹脂組合物及含彼之柱狀間隔物
TWI699616B (zh) * 2015-09-30 2020-07-21 日商富士軟片股份有限公司 圖案形成方法及感光化射線性或感放射線性樹脂組成物
US11535590B2 (en) 2017-09-06 2022-12-27 Changzhou Tronly New Electronic Materials Co., Ltd. Sulfonium salt photoinitiator, preparation method therefor, photocurable composition comprising sulfonium salt photoinitiator, and use thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102384001B1 (ko) * 2016-03-24 2022-04-08 동우 화인켐 주식회사 착색 감광성 수지 조성물 및 이를 포함하는 컬러필터
US10416558B2 (en) * 2016-08-05 2019-09-17 Shin-Etsu Chemical Co., Ltd. Positive resist composition, resist pattern forming process, and photomask blank
JP6561937B2 (ja) * 2016-08-05 2019-08-21 信越化学工業株式会社 ネガ型レジスト組成物及びレジストパターン形成方法
JP7444791B2 (ja) * 2019-01-10 2024-03-06 サンアプロ株式会社 スルホニウム塩、光酸発生剤、硬化性組成物およびレジスト組成物
KR20220154085A (ko) * 2020-03-17 2022-11-21 산아프로 가부시키가이샤 술포늄염, 광산 발생제, 경화성 조성물 및 레지스트 조성물

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06286149A (ja) * 1993-02-03 1994-10-11 Canon Inc インクジェット記録ヘッドの製造方法
JP2000347403A (ja) * 1999-06-02 2000-12-15 Asahi Denka Kogyo Kk ビルドアップ用光硬化性組成物
WO2006006581A1 (fr) * 2004-07-14 2006-01-19 Jsr Corporation Composition de résine isolante photosensible, son produit durci et son utilisation
JP2007078889A (ja) * 2005-09-12 2007-03-29 Fujifilm Corp 感光性組成物、パターン形成材料、感光性積層体、並びにパターン形成装置及びパターン形成方法
WO2007034714A1 (fr) * 2005-09-22 2007-03-29 Konica Minolta Medical & Graphic, Inc. Encre pour impression par jet d'encre durcissable sous un rayonnement actif et procédé pour la formation d'une image utilisant celle-ci
JP2008026667A (ja) * 2006-07-21 2008-02-07 Nippon Kayaku Co Ltd 永久レジスト組成物、及びレジスト積層体
WO2009057600A1 (fr) * 2007-11-01 2009-05-07 Adeka Corporation Composé de type sel, initiateur de polymérisation cationique et composition cationiquement polymérisable
JP2010208023A (ja) * 2009-03-06 2010-09-24 Canon Inc インクジェットヘッドの製造方法及びインクジェットヘッド
JP2012137741A (ja) * 2010-12-07 2012-07-19 Tokyo Ohka Kogyo Co Ltd 厚膜用化学増幅型ポジ型ホトレジスト組成物及び厚膜レジストパターンの製造方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1516512A (en) 1974-05-02 1978-07-05 Gen Electric Chalcogenium salts
JP2742594B2 (ja) 1988-12-29 1998-04-22 広栄化学工業株式会社 光重合触媒およびそれを含有する硬化性組成物
JP3942202B2 (ja) 1994-12-15 2007-07-11 日本化薬株式会社 光重合開始剤、これを含有するエネルギー線硬化性組成物及びその硬化物
JPH09118663A (ja) 1995-08-22 1997-05-06 Nippon Soda Co Ltd 新規スルホニウム塩化合物、重合開始剤、該化合物を含有する硬化性組成物および硬化方法
DK199901098A (da) 1998-08-18 2000-02-19 Ciba Sc Holding Ag Sylfonyloximer til i-linie-fotoresists med høj følsomhed og høj resisttykkelse
JP2008077057A (ja) 2006-08-21 2008-04-03 Jsr Corp 感光性絶縁樹脂組成物及びその硬化物並びにそれを備える電子部品
WO2008117619A1 (fr) 2007-03-26 2008-10-02 Jsr Corporation Composition de résine isolante photosensible
JP5501679B2 (ja) * 2009-07-02 2014-05-28 株式会社Ａｄｅｋａ 硬化性樹脂組成物及びその硬化物
JP5387181B2 (ja) * 2009-07-08 2014-01-15 信越化学工業株式会社 スルホニウム塩、レジスト材料及びパターン形成方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06286149A (ja) * 1993-02-03 1994-10-11 Canon Inc インクジェット記録ヘッドの製造方法
JP2000347403A (ja) * 1999-06-02 2000-12-15 Asahi Denka Kogyo Kk ビルドアップ用光硬化性組成物
WO2006006581A1 (fr) * 2004-07-14 2006-01-19 Jsr Corporation Composition de résine isolante photosensible, son produit durci et son utilisation
JP2007078889A (ja) * 2005-09-12 2007-03-29 Fujifilm Corp 感光性組成物、パターン形成材料、感光性積層体、並びにパターン形成装置及びパターン形成方法
WO2007034714A1 (fr) * 2005-09-22 2007-03-29 Konica Minolta Medical & Graphic, Inc. Encre pour impression par jet d'encre durcissable sous un rayonnement actif et procédé pour la formation d'une image utilisant celle-ci
JP2008026667A (ja) * 2006-07-21 2008-02-07 Nippon Kayaku Co Ltd 永久レジスト組成物、及びレジスト積層体
WO2009057600A1 (fr) * 2007-11-01 2009-05-07 Adeka Corporation Composé de type sel, initiateur de polymérisation cationique et composition cationiquement polymérisable
JP2010208023A (ja) * 2009-03-06 2010-09-24 Canon Inc インクジェットヘッドの製造方法及びインクジェットヘッド
JP2012137741A (ja) * 2010-12-07 2012-07-19 Tokyo Ohka Kogyo Co Ltd 厚膜用化学増幅型ポジ型ホトレジスト組成物及び厚膜レジストパターンの製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI699616B (zh) * 2015-09-30 2020-07-21 日商富士軟片股份有限公司 圖案形成方法及感光化射線性或感放射線性樹脂組成物
TWI697736B (zh) * 2015-12-29 2020-07-01 南韓商東友精細化工有限公司 黑色感光性樹脂組合物及含彼之柱狀間隔物
WO2018003470A1 (fr) * 2016-06-29 2018-01-04 サンアプロ株式会社 Sel de sulfonium, générateur de photoacide, composition photodurcissable et produit durci correspondan.
US10683266B2 (en) 2016-06-29 2020-06-16 San Apro Ltd. Sulfonium salt, photoacid generator, photocurable composition, and cured product thereof
US11535590B2 (en) 2017-09-06 2022-12-27 Changzhou Tronly New Electronic Materials Co., Ltd. Sulfonium salt photoinitiator, preparation method therefor, photocurable composition comprising sulfonium salt photoinitiator, and use thereof

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