WO2013141376A1 - Protecteur, procédé de fabrication d'un composé protégé par le protecteur, résine protégée par le protecteur, composition de résine photosensible contenant la résine protégée par le protecteur, matière de formation de motif, film photosensible, motif en relief durci, son procédé de fabrication et dispositif semi-conducteur - Google Patents

Protecteur, procédé de fabrication d'un composé protégé par le protecteur, résine protégée par le protecteur, composition de résine photosensible contenant la résine protégée par le protecteur, matière de formation de motif, film photosensible, motif en relief durci, son procédé de fabrication et dispositif semi-conducteur Download PDF

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Publication number
WO2013141376A1
WO2013141376A1 PCT/JP2013/058366 JP2013058366W WO2013141376A1 WO 2013141376 A1 WO2013141376 A1 WO 2013141376A1 JP 2013058366 W JP2013058366 W JP 2013058366W WO 2013141376 A1 WO2013141376 A1 WO 2013141376A1
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group
general formula
acid
aryl
alkyl
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PCT/JP2013/058366
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English (en)
Japanese (ja)
Inventor
恭平 荒山
雨宮　拓馬
稲崎　毅
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富士フイルム株式会社
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Priority to JP2014506302A priority Critical patent/JP5696254B2/ja
Publication of WO2013141376A1 publication Critical patent/WO2013141376A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B51/00—Introduction of protecting groups or activating groups, not provided for in the preceding groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/52—Preparation of compounds having groups by reactions producing groups by substitution of halogen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
    • C08F12/22—Oxygen
    • C08F12/24—Phenols or alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
    • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers

Definitions

  • the present invention relates to a protective agent for a carboxyl group or a hydroxyl group, a resin in which the carboxyl group or the hydroxyl group is protected by the protective agent, which is useful for use in the production of a chemically amplified resist composition, a pharmaceutical intermediate, and a paint.
  • a photosensitive resin composition containing the resin, a pattern forming material using the photosensitive resin composition, a photosensitive film, a cured film, and a method for producing a cured relief pattern using the photosensitive resin composition,
  • the present invention relates to a cured relief pattern obtained thereby and a semiconductor device provided with the cured relief pattern.
  • the hemiacetal ester compound or acetal compound is a chemically amplified resist composition as a compound or resin in which a carboxyl group or a hydroxyl group is protected because a group derived from an alkyl vinyl ether is easily eliminated by heat, an acid catalyst or the like. It is useful for the production of pharmaceutical intermediates and paints.
  • a hemiacetal ester compound or an acetal compound is usually produced by reacting with alkyl vinyl ether or alkyl vinyl ether added with hydrogen halide as a protective agent and reacting with a compound having a carboxyl group or hydroxyl group. Is done.
  • alkyl vinyl ethers and halogenated alkyl ethers are extremely unstable and easily polymerized.
  • 1-chloroethyl ethyl ether produced by the reaction of ethyl vinyl ether and hydrogen halide is reacted with a polymer having a carboxyl group or a hydroxyl group
  • a polymer derived from 1-chloroethyl ethyl ether is a subsidiary. There was a problem of being born.
  • R a , R b and R c are the same or different and each represents substituted or unsubstituted alkyl, substituted or unsubstituted aryl or substituted or unsubstituted aralkyl, or R a and R b are Together with adjacent carbon atoms form a cycloalkyl, X represents a halogen atom.
  • the object of the present invention is to protect the carboxyl group or hydroxyl group having excellent storage stability, the carboxyl group or hydroxyl group being protected by the protective agent, the resin having excellent storage stability, and the above-described protected product having excellent resolution and sensitivity.
  • Photosensitive resin composition containing the resin, pattern forming material using the photosensitive resin composition, photosensitive film, and cured film, and method for producing a cured relief pattern using the photosensitive resin composition, Another object of the present invention is to provide a cured relief pattern obtained by the above and a semiconductor device having the cured relief pattern.
  • a protective agent for a hydroxyl group or a carboxyl group which is a compound represented by the following general formula (I).
  • R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R 1 and R 2 is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
  • R 3 represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
  • R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
  • X represents a group capable of leaving by the action of the hydroxyl group or carboxyl group.
  • R 1 , R 2 and R 3 are respectively synonymous with R 1 , R 2 and R 3 in the general formula (I), and at least one of R 1 and R 2 is an aryl group.
  • R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R 1 and R 2 is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
  • R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
  • * Represents a binding site with a residue obtained by removing —OH from the hydroxyl group or carboxyl group of the resin.
  • All or part of the hydroxyl groups of the polyhydroxystyrene resin having a repeating unit represented by the following general formula (V) and having a weight average molecular weight of 1,000 to 100,000 are groups represented by the following general formula (III) Polyhydroxystyrene resin substituted with
  • R 4 represents a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group, an aryl group or an aralkyl group, and k represents an integer of 0 to 4)
  • R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R 1 and R 2 is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
  • R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
  • * Represents a binding site with a residue obtained by removing the hydroxyl group from the repeating unit represented by the general formula (V).
  • All or part of the hydroxyl groups of the novolak resin having a repeating unit represented by the following general formula (VI) and having a weight average molecular weight of 1,000 to 100,000 is substituted with a group represented by the following general formula (III) Novolac resin.
  • R 5 represents a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group, an aryl group or an aralkyl group
  • m represents an integer of 0 to 3
  • R 6 and R 7 each independently represents Represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
  • R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R 1 and R 2 is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
  • R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
  • * Represents a binding site with a residue obtained by removing the hydroxyl group from the repeating unit represented by the general formula (VI). ) [7] All or part of the carboxyl groups of the polymer having a repeating unit represented by the following general formula (VII) and having a weight average molecular weight of 1,000 to 100,000 are substituted with a group represented by the following general formula (IV) Polyacrylic acid resin or polymethacrylic acid resin.
  • R 8 represents a hydrogen atom or an alkyl group.
  • R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R 1 and R 2 is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
  • R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
  • * Represents a binding site with a residue obtained by removing the carboxyl group from the repeating unit represented by the general formula (VII).
  • R 9 represents a tetravalent organic group
  • R 10 represents a divalent organic group
  • R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R 1 and R 2 is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
  • R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
  • * Represents a binding site with a residue obtained by removing a carboxyl group from the repeating unit represented by the general formula (VIII).
  • R 11 represents a tetravalent organic group
  • R 12 represents a divalent organic group
  • R 1 and R 2 are each independently an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Represents a group or a halogen atom, and at least one of R 1 and R 2 is an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom.
  • R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
  • * Represents a binding site with a residue obtained by removing the hydroxyl group from the repeating unit represented by the general formula (IX).
  • [12] The pattern formation material which is the photosensitive resin composition as described in [10] or [11].
  • [13] [10] A photosensitive film formed by the photosensitive resin composition according to [11].
  • [14] A cured film obtained by heat-treating the photosensitive resin composition according to [10] or [11].
  • [15] (A) forming the photosensitive film according to [13] on a substrate; (A) a step of exposing the photosensitive film with actinic rays or radiation; (C) A process for developing the photosensitive film so as to remove the exposed portion with an aqueous alkaline developer, and (d) a method for producing a cured relief pattern comprising a step of heat-treating the obtained relief pattern.
  • [16] A cured relief pattern obtained by the production method according to [15].
  • [17] [16] A semiconductor device comprising the cured relief pattern according to [16].
  • a carboxyl group or hydroxyl group protecting agent having excellent storage stability having excellent storage stability
  • the carboxyl group or hydroxyl group being protected by the protecting agent
  • a resin having excellent storage stability and the above-described protected product having excellent resolution and sensitivity.
  • Photosensitive resin composition containing the resin, pattern forming material using the photosensitive resin composition, photosensitive film, and cured film, and method for producing a cured relief pattern using the photosensitive resin composition, The cured relief pattern obtained by the above and a semiconductor device comprising the cured relief pattern can be provided.
  • the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
  • exposure in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified.
  • the exposure with the particle beam is also included in the exposure.
  • hydroxyl group or carboxyl group which is a compound represented by formula (I)>
  • the hydroxyl group or carboxyl group protecting agent of the present invention (hereinafter also simply referred to as “protecting agent of the present invention”) is a compound represented by the following general formula (I).
  • R 1 and R 2 are each independently an alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, acyl group (alkanoyl group), alkoxycarbonyl group, aryloxycarbonyl Represents a group, a cyano group or a halogen atom, and at least one of R 1 and R 2 is an aryl group, an alkoxy group, an aryloxy group, an alkanoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.
  • R 3 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
  • R 1 and R 2 may be bonded to each other to form a ring, or R 1 or R 2 may be bonded to R 3 to form a ring.
  • X represents a group capable of leaving by the action of the hydroxyl group or carboxyl group.
  • the compound represented by the general formula (I) reacts with a hydroxyl group of a compound having a hydroxyl group or a carboxyl group of a compound having a carboxyl group without requiring a complicated operation, and is represented by the following general formula (III). A compound having a group can be produced.
  • R 1 , R 2 and R 3 are respectively synonymous with R 1 , R 2 and R 3 in the general formula (I), and at least one of R 1 and R 2 is an aryl group, alkoxy A group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group or a halogen atom.
  • * Represents a binding site with a residue obtained by removing —OH from the above group of a compound having a hydroxyl group or a carboxyl group.
  • the partial structure derived from the compound represented by the general formula (I) can be eliminated from the compound having the group represented by the general formula (III) without requiring a complicated operation, and a hydroxyl group or a carboxyl group. The group can be regenerated. Therefore, the compound represented by the general formula (I) functions as a hydroxyl group or carboxyl group protective agent.
  • the aryl group, alkoxy group, aryloxy group, alkanoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group or halogen atom for R 1 and R 2 is an electron withdrawing group.
  • At least one of 1 and R 2 is an aryl group, an alkoxy group, an aryloxy group, an alkanoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom, and is represented by the general formula (I)
  • the decomposition reaction of the compound can be suppressed, and the storage stability of the compound represented by the general formula (I) can be improved.
  • R 1 and R 2 are an aryl group, alkoxy group, aryloxy group, alkanoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group or halogen atom.
  • the compound having the group represented by the general formula (III) that is, a resin or compound in which a carboxyl group or a hydroxyl group is protected by the protective agent (hereinafter sometimes simply referred to as “protector”). Decomposition reaction can be suppressed and storage stability can be improved.
  • the alkyl group for R 1 , R 2 and R 3 may have a substituent and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and an oxygen atom in the alkyl chain, You may have a sulfur atom and a nitrogen atom.
  • the cycloalkyl group for R 1 , R 2 and R 3 may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, may be polycyclic, and has an oxygen atom in the ring. You may have. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.
  • the aryl group for R 1 , R 2 and R 3 may have a substituent and is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a naphthyl group and an anthryl group. Can be mentioned.
  • the aralkyl group for R 1 , R 2 and R 3 may have a substituent, preferably an aralkyl group having 7 to 20 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group. And naphthylethyl group.
  • the alkoxy group for R 1 and R 2 may have a substituent and is preferably an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group. , Pentyloxy group, hexyloxy group, heptyloxy group and the like.
  • the aryloxy group for R 1 and R 2 may have a substituent and is preferably an aryloxy group having 6 to 14 carbon atoms, such as a phenoxy group, a naphthoxy group, an anthryloxy group, etc. Is mentioned.
  • the acyl group (alkanoyl group) for R 1 and R 2 may have a substituent, and is preferably a linear or branched alkanoyl group having 2 to 7 carbon atoms, such as an acetyl group or propionyl group.
  • the aryloxycarbonyl group for R 1 and R 2 may have a substituent, and examples of the aryloxy moiety include those similar to those exemplified for the aryloxy group.
  • Examples of the halogen atom for R 1 and R 2 include fluorine, chlorine, bromine and iodine, preferably a chlorine atom.
  • the ring formed by combining R 1 and R 2 with each other may have a substituent, preferably has 3 to 8 carbon atoms, and may be saturated or unsaturated.
  • a cyclopropane ring examples include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclopentene ring, a 1,3-cyclopentadiene ring, a cyclohexene ring, and a cyclohexadiene ring.
  • the ring formed by combining R 1 or R 2 with R 3 may have a substituent, preferably has 5 to 8 carbon atoms, and specifically includes an oxolane ring, an oxane ring, an oxepane.
  • each of the above groups may have include a cyano group, a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkanoyl group, a carboxyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
  • the group capable of leaving by the action of the hydroxyl group or carboxyl group as X is, for example, a halogen atom such as chlorine atom, bromine atom, iodine atom, tosylate group, mesylate group, fluorosulfonate group, trifluoromethanesulfonate group, Examples thereof include a sulfonate group such as a nonafluorobutane sulfonate group, preferably a halogen atom, and more preferably a chlorine atom.
  • a halogen atom such as chlorine atom, bromine atom, iodine atom
  • tosylate group mesylate group, fluorosulfonate group, trifluoromethanesulfonate group
  • a sulfonate group such as a nonafluorobutane sulfonate group, preferably a halogen atom, and more preferably a chlorine atom.
  • R 1 and R 2 is an aryl group, and more preferably at least one of R 1 and R 2 is a phenyl group .
  • R 3 is preferably a group represented by the following general formula (X).
  • L 1 represents an alkylene group or a cycloalkylene group
  • L 2 represents a single bond or a divalent linking group
  • R 13 represents an alkyl group, an alicyclic group which may contain a hetero atom, or a hetero atom.
  • the alkylene group for L 1 is preferably an alkylene group having 1 to 8 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group.
  • the cycloalkylene group for L 1 is preferably a cycloalkylene group having 3 to 15 carbon atoms, and examples thereof include a cyclopentylene group and a cyclohexylene group.
  • the divalent linking group as L 2 is, for example, an alkylene group (preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group), a cycloalkylene A group (preferably a cycloalkylene group having 3 to 15 carbon atoms, such as a cyclopentylene group or a cyclohexylene group), —S—, —O—, —CO—, —CS—, —SO 2 —, —N ( R 0 ) —, or a combination of two or more thereof, and those having a total carbon number of 20 or less are preferred
  • R 0 is a hydrogen atom or an alkyl group (eg, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, Hexyl group and octyl group).
  • L 2 is preferably a single bond, an alkylene group, or a divalent linking group comprising a combination of an alkylene group and at least one of —O—, —CO—, —CS— and —N (R 0 ) —.
  • a divalent linking group comprising a bond, an alkylene group, or a combination of an alkylene group and —O— is more preferable.
  • R 0 has the same meaning as R 0 described above.
  • the alkyl group as R 13 is the same as the alkyl group described above, for example.
  • Examples of the alicyclic group and aromatic ring group as R 13 include the cycloalkyl group and aryl group described above.
  • the number of carbon atoms is preferably 3-18.
  • a group in which a plurality of aromatic rings are linked via a single bond is also included in the aromatic group as R 13 .
  • Examples of the alicyclic group containing a hetero atom and the aromatic ring group containing a hetero atom include, for example, thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole. And pyrrolidone.
  • the alicyclic group and aromatic ring group as R 13 may have a substituent, for example, an alkyl group, a cycloalkyl group, a cyano group, a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkanoyl group, Examples thereof include a carboxyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
  • the compound represented by the general formula (I) can be obtained by a known method [for example, “New Experimental Chemistry Course (Vol. 14) Synthesis and Reaction of Organic Compounds (I)” edited by The Chemical Society of Japan, pages 590-591, Maruzen Co., Ltd. Company (January 20, 1985) etc.] can be synthesized and obtained. Thereby, the compound represented by the general formula (I), which is difficult to produce by the production methods described in Patent Documents 1 and 2 described above, can be produced.
  • Examples of the alcohol include methanol, ethanol, propanol, isopropyl alcohol, n-butanol, isobutanol, sec-butyl alcohol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, benzyl alcohol and other monoalcohols, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6- Hexanediol, 1,8-octanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol , Do
  • Phenols include phenol, resorcinol, hydroquinone, pyrocatechol, bisphenol A, dihydroxydiphenylmethane (bisphenol F), bisphenol S, tetrabromobisphenol A, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,4'- Dihydroxy-3,3′-dimethyldiphenylmethane, 4,4′-dihydroxybenzophenone, tris (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, novolac phenol, novolac cresol, bis (3,5-dimethyl- 4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, low molecular phenol compounds such as hydroxystyrene, novolac resin, polyhydroxystyrene resin, hydroxy It has a hydroxyl group such as a copolymer obtained by copolymerizing styrene with another monomer copolyme
  • Examples thereof include resins and polymers.
  • the proportion of hydroxystyrene in the copolymer obtained by copolymerizing hydroxystyrene with another monomer copolymerizable therewith is not particularly limited, but is preferably 0.2 to 90 mol%, more preferably 0.8. 2 to 60 mol%.
  • Examples of the other monomer copolymerizable with hydroxystyrene include a polymerizable unsaturated monomer having a carboxyl group or another monomer copolymerizable therewith.
  • Examples of the polymerizable unsaturated monomer having a carboxyl group include unsaturated carboxylic acids such as (meth) acrylic acid, 2-hydroxymethyl-2-propenoic acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride. An acid or its acid anhydride is mentioned.
  • Examples of other monomers copolymerizable with a polymerizable unsaturated monomer having a carboxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Raw material is C1-C18 alcohol such as isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and (meth) acrylic acid Alkyl (meth) acrylates, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate and other (meth) acrylates, 2-hydroxyethyl (meth) acrylate , Hydroxyal
  • the polyhydroxystyrene resin or a copolymer obtained by copolymerizing hydroxystyrene with another monomer copolymerizable therewith may have a repeating unit represented by the following general formula (XI). preferable.
  • R 14 represents a hydrogen atom or a methyl group
  • Ar represents an arylene group.
  • R 14 is more preferably a hydrogen atom.
  • the arylene group represented by Ar may have a substituent.
  • These arylene groups are preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, more preferably a phenylene group or a naphthylene group which may have a substituent.
  • phenylene groups which may have Moreover, as a substituent which these may have, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group are mentioned, for example.
  • the polyhydroxystyrene resin is preferably a polyhydroxystyrene resin having a repeating unit represented by the following general formula (V) and having a weight average molecular weight of 1,000 to 100,000.
  • the polyhydroxystyrene resin in which is protected is preferably a polyhydroxystyrene resin in which all or part of the hydroxyl groups of the polyhydroxystyrene resin are substituted with groups represented by the following general formula (III): .
  • R 4 represents a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group, an aryl group or an aralkyl group, and k represents an integer of 0 to 4)
  • Specific examples and preferred examples of the halogen atom for R 4 include those similar to the specific examples and preferred examples described above as the halogen atoms for R 1 and R 2 in formula (I).
  • an alkoxy group, an alkyl group, an aryl group, and an aralkyl group for R 4 include an alkoxy group, an alkyl group, an aryl group for R 1 , R 2, and R 3 in the general formula (I), Examples of the aralkyl group are the same as the specific examples and preferred examples described above.
  • R 1 , R 2 and R 3 are respectively synonymous with R 1 , R 2 and R 3 in the general formula (I), and at least one of R 1 and R 2 is an aryl group.
  • novolak resins are available as commercial products.
  • an acidic catalyst for example, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid,
  • the above phenols and aldehydes can be used alone or in combination of two or more.
  • the novolak resin is preferably a novolak resin having a repeating unit represented by the following general formula (VI) and having a weight average molecular weight of 1,000 to 100,000, and the hydroxyl group is protected by the protective agent of the present invention.
  • the novolak resin is preferably a polyhydroxystyrene resin in which all or part of the hydroxyl groups of the novolak resin is substituted with a group represented by the following general formula (III).
  • R 5 represents a halogen atom, a hydroxyl group, an alkoxy group, an alkyl group, an aryl group or an aralkyl group
  • m represents an integer of 0 to 3
  • R 6 and R 7 each independently represents hydrogen Represents an atom, an alkyl group, an aryl group or an aralkyl group.
  • Specific examples and preferred examples of the halogen atom for R 5 include those similar to the specific examples and preferred examples described above as the halogen atoms for R 1 and R 2 in formula (I).
  • Specific examples and preferred examples of the alkoxy group for R 5 include those similar to the specific examples and preferred examples described above as the alkoxy groups for R 1 , R 2 and R 3 in the general formula (I).
  • alkyl group, aryl group and aralkyl group for R 5 , R 6 and R 7 include an alkoxy group, an alkyl group for R 1 , R 2 and R 3 in the general formula (I), Examples of the aryl group and aralkyl group are the same as the specific examples and preferred examples described above.
  • R 1 , R 2 and R 3 are respectively synonymous with R 1 , R 2 and R 3 in the general formula (I), and at least one of R 1 and R 2 is an aryl group.
  • Polyhydroxyamide functions and can be used as a polybenzoxazole precursor.
  • the polyhydroxyamide is preferably a polyhydroxyamide having a repeating unit represented by the following general formula (IX).
  • Examples of the polyhydroxyamide whose hydroxyl group is protected by the protecting agent of the present invention include all or part of the hydroxyl groups of the polyhydroxyamide having a repeating unit represented by the following general formula (IX).
  • R 11 represents a tetravalent organic group
  • R 12 represents a divalent organic group
  • R 1 , R 2 and R 3 are respectively synonymous with R 1 , R 2 and R 3 in the general formula (I), and at least one of R 1 and R 2 is an aryl group.
  • R 11 is preferably a tetravalent organic group containing an aromatic ring, and the two amino groups and the two hydroxyl groups are bonded directly to the aromatic ring, respectively. Is more preferably a phenolic hydroxyl group, specifically, a residue obtained by removing two hydroxyl groups and two amino groups of hydroxydiamine. Furthermore, in order to provide heat resistance, R 11 is preferably formed from bisaminophenol having one or more aromatic rings as a raw material.
  • bisaminophenol examples include 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′- Dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (4-amino-3-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) sulfone, Bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane 4,6-diaminoresorcinol, 4,5-diaminoresorcinol, etc., which may be used alone or It can be used in combination of more than seeds.
  • R 11 is particularly preferably a t
  • X 1 represents —O—, —S—, —C (CF 3 ) 2 —, —CH 2 —, —SO 2 —, —NHCO—.
  • * Represents a bonding position with —NH— or —OH bonded to R 11 in the general formula (IX).
  • R 12 is not particularly limited as long as it is a divalent organic group, but preferably contains one or more aromatic ring groups in order to impart heat resistance to polyoxazole.
  • the two bonding sites of R 12 are directly present on the aromatic ring.
  • the two bonding sites may be present on the same aromatic ring, but may be present on different aromatic rings when having a plurality of aromatic rings.
  • R 12 is a group containing a plurality of aromatic rings
  • the plurality of aromatic rings are a single bond, ether bond, methylene bond, ethylene bond, 2,2-propylene bond, 2,2-hexafluoropropylene.
  • the resin having the structural unit represented by the general formula (IX) is, for example, as shown in Polymer Science Society, New Polymer Experiments 3 Polymer Synthesis and Reaction (2) P177-P183 (1996).
  • it can be obtained by reacting dicarboxylic acid dihalide obtained by halogenating dicarboxylic acid and dihydroxydiamine.
  • dicarboxylic acid examples include isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) hexapropane, 4,4′-biphenyldicarboxylic acid, 4,4′-dicarboxyphenyl ether, bis (4- Carboxyphenyl) sulfone, 2,2-bis (4-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5-fluoroisophthalic acid, aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, 1,2 -Aliphatic dicarboxylic acids such as cyclobutanedicarboxylic acid, 1,4-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, oxalic acid, malonic acid, succinic acid, etc., and these may be used alone or in combination of two or more Can be used in combination.
  • the poly (meth) acrylate having a phenolic hydroxyl group preferably has a repeating unit represented by the following general formula (XII).
  • R 15 represents a hydrogen atom or a methyl group
  • L 2 represents a single bond or an alkylene group
  • Ar represents an arylene group.
  • R 15 is more preferably a methyl group.
  • the arylene group represented by Ar may have a substituent.
  • These arylene groups are preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, more preferably a phenylene group or a naphthylene group which may have a substituent.
  • phenylene groups which may have Moreover, as a substituent which these may have, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group are mentioned, for example.
  • substituents which may have, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group are mentioned, for example.
  • Specific examples of the repeating unit represented by the general formula (XII) are shown below, but the present invention is not limited thereto.
  • a commercially available resin can also be used as the hydroxyl group-containing resin or polymer.
  • the weight average molecular weight of the polymer having a hydroxyl group is preferably 1,000 to 200,000, more preferably 1,000 to 100,000, and 1,000 to 50,000. Further preferred.
  • the resin or polymer having a hydroxyl group can be purified and used as a solid. Moreover, when a solvent is used in the production, it can be used as a solution.
  • Compound having a carboxyl group that can be protected by reacting with the protective agent of the present invention, and a compound (resin) in which the carboxyl group is protected by the protective agent of the present invention examples include formic acid, acetic acid, propionic acid, propiolic acid, butyric acid, isobutyric acid, hexanoic acid, heptanoic acid, octylic acid, nonanoic acid, and isononanoic acid.
  • Monocarboxylic acids such as decanoic acid, dodecanoic acid, stearic acid, benzoic acid, cinnamic acid, 2-naphthoic acid, nicotinic acid, isonicotinic acid, amin oil fatty acid, tall oil fatty acid, soybean oil fatty acid, dehydrated castor oil fatty acid, Succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanediic acid, compound having decamethylene dicarboxyl group, phthalic acid, maleic acid, trimellitic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Polyvalent carboxylic acids such as methyl hexahydrophthalic acid, lactic acid, citric acid, hydroxy ⁇ , ⁇ -unsaturated monomers having a carboxyl group such as pivalic acid, hydroxycarboxylic acid such as 12-hydroxystea
  • Polymers polyesters having carboxyl groups, alkyd resins, urethane resins, epoxy resins, carboxyl group-modified epoxy resins, polymers containing carboxyl groups such as polyamic acids of polyimide precursors, etc., among others, containing carboxyl groups Polymerizable unsaturated monomer homopolymer, polymerizable unsaturated monomer containing carboxyl group, and Copolymers of copolymerizable other monomer, or polyamic acid used as a polyimide precursor preferable.
  • Examples of the polymerizable unsaturated monomer containing a carboxyl group and other monomers copolymerizable therewith include, for example, ⁇ a compound having a hydroxyl group that can be protected by reacting with the protective agent of the present invention, and the present invention. And the same as those described above in the section of compound (resin) in which the hydroxyl group is protected by the protecting agent. These monomers may be used alone or in combination of two or more. Polymerization of a polymerizable unsaturated monomer containing a carboxyl group and copolymerization of a polymerizable unsaturated monomer containing a carboxyl group and another monomer copolymerizable therewith are carried out by known methods. be able to.
  • a polyacrylic acid resin or polymethacrylic acid resin having a repeating unit represented by the following general formula (VII) is preferable.
  • the polyacrylic acid resin or polymethacrylic acid resin in which the carboxyl group is protected by the protective agent of the present invention has a repeating unit represented by the following general formula (VII) and has a weight average molecular weight of 1,000 to 100,000. It is preferable that all or part of the carboxyl group of the coalescence is a polyacrylic acid resin or a polymethacrylic acid resin substituted with a group represented by the following general formula (IV).
  • R 8 represents a hydrogen atom or an alkyl group.
  • R 1 , R 2 and R 3 are respectively synonymous with R 1 , R 2 and R 3 in the general formula (I), and at least one of R 1 and R 2 is an aryl group.
  • the alkyl group for R 8 may have a substituent and is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group and an ethyl group. Examples of the substituent that can be included include a hydroxyl group, a halogen atom (such as a fluorine atom and a chlorine atom), a cyano group, and the like, and a hydroxyl group
  • Polyamic acid can function and be used as a polyimide precursor. By using polyamic acid, it is possible to obtain a highly reliable cured relief pattern having excellent heat resistance and less outgassing after heat curing.
  • the polyamic acid containing the repeating unit represented by the following general formula (VIII) is preferable.
  • the polyamic acid in which the carboxyl group is protected by the protective agent of the present invention all or part of the carboxyl group of the polyamic acid having a repeating unit represented by the following general formula (VIII) is represented by the following general formula (IV).
  • a polyamic acid substituted with the group represented is preferable.
  • R 9 represents a tetravalent organic group
  • R 10 represents a divalent organic group
  • R 1, R 2 and R 3 are respectively synonymous with R 1, R 2 and R 3 in Formula (I)
  • at least one of R 1 and R 2 an aryl group, an alkoxy A group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, or a halogen atom
  • * represents a residue obtained by removing the carboxyl group from the repeating unit represented by the general formula (VIII).
  • the repeating unit represented by the general formula (VIII) includes a compound having four carboxyl groups with R 9 as a nucleus, a carboxylic acid anhydride thereof, or at least one of the four carboxyl groups represented by the general formula It composed of an acid component derived from a compound comprising substituted with a group represented by (IV), a diamine component derived from the R 10 in the compound having two amino groups as nucleus.
  • the tetravalent organic group R 9 preferably has 4 to 30 carbon atoms, and more preferably a tetravalent linking group having a monocyclic or condensed polycyclic aliphatic group or aromatic group. .
  • a plurality of R 9 present in the resin may be the same or different.
  • Examples of the monocyclic aromatic group in the tetravalent organic group R 9 include a benzene ring group and a pyridine ring group.
  • Examples of the condensed polycyclic aromatic group in the tetravalent organic group R 9 include a naphthalene ring group and a perylene ring group.
  • Examples of the monocyclic aliphatic group in the tetravalent organic group R 9 include a cyclobutane ring group, a cyclopentane ring group, and a cyclohexane ring group.
  • Examples of the condensed polycyclic aliphatic group in the tetravalent organic group R 9 include a bicyclo [2.2.1] heptane ring group, a bicyclo [2.2.2] octane ring group, and a bicyclo [2.2. 2] Oct-7-ene ring group and the like.
  • the tetravalent linking group having a monocyclic or condensed polycyclic aliphatic group or aromatic group for the tetravalent organic group R 9 the above-mentioned monocyclic or condensed polycyclic aliphatic group or The aromatic group itself may be used, but a plurality of monocyclic or condensed polycyclic aliphatic groups or aromatic groups are linked via a single bond or a divalent linking group, and 4 as R 9 A valent linking group may be formed.
  • the divalent linking group is preferably an alkylene group (an alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, or a propylene group), an oxygen atom, a sulfur atom, a divalent sulfone group, or an ester bond. , Ketone group, amide group and the like.
  • the acid component having a group derived from at least four carboxyl groups with R 9 as a nucleus include pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, 2, 3,3 ′, 4′-biphenyltetracarboxylic anhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 2 , 2 ′, 3,3′-benzophenonetetracarboxylic acid anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic acid anhydride, 1,2,5,6-naphthalenetetracarboxylic acid anhydride, 2, 3,6,7-naphthalenetetracarboxylic anhydride, 2,3,5,6-pyridinetetracarboxylic anhydride, 3,
  • Cyclobutanetetracarboxylic acid anhydride cyclopentanetetracarboxylic acid anhydride, cyclohexanetetracarboxylic acid anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane-2,3, 5,6-tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, or bicyclo [2.2.2] oct-7-ene-2,3,5 , 6-tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride, Examples include components derived from aliphatic tetracarboxylic anhydrides such as (1R, 2S, 4S, 5R) -
  • a component derived from pyromellitic acid anhydride a component derived from 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid anhydride
  • a component derived from pyromellitic anhydride a component derived from 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride
  • the content of the acid component derived from the compound having four carboxyl groups with R 9 as the nucleus in the resin is preferably 20 to 70 mol% with respect to all repeating units constituting the resin. More preferably, it is ⁇ 60 mol%.
  • the divalent organic group R 10 include a divalent group having an alicyclic group, a divalent group having an aromatic group, and a divalent group containing a silicon atom.
  • a plurality of R 10 present in the resin may be the same as or different from each other.
  • the alicyclic group that R 10 may have is preferably a divalent alicyclic group having 3 to 20 carbon atoms, such as a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or bicyclo [2.2. 1] Polycyclic cycloalkylene groups such as a heptylene group, norbornylene group, tetracyclodecanylene group, tetracyclododecanylene group, adamantylene group, and the like can be given.
  • the divalent group having an alicyclic group for R 10 may be the alicyclic group itself, but a plurality of alicyclic groups is preferably an alkylene group (an alkylene group having 1 to 6 carbon atoms, for example, Methylene group, ethylene group, propylene group, etc.) may be linked to form a divalent group having an alicyclic group as R 2 , and the amino group and alicyclic group in the diamine component are alkylene groups. You may connect with.
  • the alicyclic group and alkylene group that can form a divalent group having an alicyclic group may have a substituent, and an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) as such a substituent. ), Halogen atoms and the like.
  • Particularly preferred diamine components having an alicyclic group structure having R 10 as a nucleus include a 5-amino-1,3,3-trimethylcyclohexanemethylamine component, a cis-1,4-cyclohexanediamine component, and trans-1,4- Cyclohexanediamine component, 1,4-cyclohexanediamine component (cis, trans mixture), 4,4′-methylenebis (cyclohexylamine) component and its 3,3′-dimethyl-substituted product, bis (aminomethyl) bicyclo [2.2 .1] heptane component, 1,3-diaminoadamantane component, 3,3′-diamino-1,1′-biadamantyl component, 4,4′-hexafluoroisopropylidenebis (cyclohexylamine) component, Of which 3,3'-diamino-1,1'-biadamantyl component, trans-1,4-cycl From the viewpoint of he
  • the content of the alicyclic diamine component having two amino groups with R 10 as a nucleus in the resin is preferably 20 to 70 mol%, and preferably 30 to 60 mol based on all repeating units constituting the resin. % Is more preferable.
  • the aromatic group in the divalent group having an aromatic group for R 10 is preferably an aromatic group having 5 to 16 carbon atoms, and examples thereof include a phenylene group and a naphthylene group. Further, the aromatic group may contain a hetero atom such as a nitrogen atom or an oxygen atom, and examples thereof include a divalent benzoxazole group.
  • the divalent group having an aromatic group for R 10 may be the aromatic group itself, but a plurality of aromatic groups may be linked via a single bond or a divalent linking group to form R 2.
  • the divalent group which has an aromatic group as may be formed, and the amino group in the diamine component and the aromatic group may be linked via a divalent linking group.
  • the divalent linking group is preferably an alkylene group (an alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, or a propylene group), an oxygen atom, a sulfur atom, a divalent sulfone group, or an ester bond. , Ketone group, amide group and the like.
  • the aromatic group and alkylene group that can form a divalent group having an aromatic group may have a substituent, and an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) as such a substituent. ), An alkoxy group such as a halogen atom and a methoxy group, and an aryl group such as a cyano group and a phenyl group.
  • aromatic diamine component having R 10 as a core examples include, for example, an m-phenylenediamine component, a p-phenylenediamine component, a 2,4-tolylenediamine component, a 3,3′-diaminodiphenyl ether component, 3, 4'-diaminodiphenyl ether component, 4,4'-diaminodiphenyl ether component, 3,3'-diaminodiphenyl sulfone component, 4,4'-diaminodiphenyl sulfone component, 3,4'-diaminodiphenyl sulfone component, 3,3 ' -Diaminodiphenylmethane component, 4,4'-diaminodiphenylmethane component, 3,4'-diaminodiphenylmethane component, 4,4'-diaminodiphenyl sulfide component, 3,3'-diaminodip
  • aromatic diamine components include p-phenylenediamine component, 4,4′-diaminodiphenyl ether component, 3,3′-diaminodiphenylsulfone component, 4,4′-diaminodiphenylsulfone component, and 2,2′-bis.
  • (4-aminophenyl) hexafluoropropane component 1,4-bis (4-aminophenoxy) benzene component, imino-di-p-phenylenediamine component, 4,4'-diaminobiphenyl component, 4,4'-diamino Benzophenone component, 3,3′-dimethoxy-4,4′-diaminobiphenyl component, 3,3′-dimethyl-4,4′-diaminobiphenyl component, 2,2′-dimethyl 4,4′-diaminobiphenyl component, 2,2′-bis (trifluoromethyl) benzidine component, o-toluidine sulfone component, 2,2-bis (4-amino Nophenoxyphenyl) propane component, 9,9-bis (4-aminophenyl) fluorene component, 4,4′-di- (3-aminophenoxy) diphenylsulfone component, 4,4′-diaminobenz
  • the diamine component may be substituted with a hydroxyl group.
  • bisaminophenol components include 3,3′-dihydroxybenzidine component, 3,3′-diamino-4,4′-dihydroxybiphenyl component, and 4,4′-diamino-3,3′-dihydroxy.
  • Biphenyl component 3,3′-diamino-4,4′-dihydroxydiphenylsulfone component, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone component, bis- (3-amino-4-hydroxyphenyl) methane Component, 2,2-bis- (3-amino-4-hydroxyphenyl) propane component, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane component, 2,2-bis- (4 -Amino-3-hydroxyphenyl) hexafluoropropane component, bis- (4-amino-3-hydroxyphenyl) methane component, 2 2-bis- (4-amino-3-hydroxyphenyl) propane component, 4,4′-diamino-3,3′-dihydroxybenzophenone component, 3,3′-diamino-4,4′-dihydroxybenzophenone component, 4 , 4'-diamino-3,3'
  • a particularly preferred embodiment includes a case where R 10 in the general formula (VIII) is a divalent group having an aromatic group selected from the following.
  • X 1 represents —O—, —S—, —C (CF 3 ) 2 —, —CH 2 —, —SO 2 —, —NHCO—.
  • * Represents a bonding position with —NH— or —OH bonded to R 2 in the general formula (1).
  • —NH— and —OH bonded to R 2 are bonded to each other in the ortho position (adjacent position).
  • the content of the aromatic diamine component having two amino groups with R 10 as a nucleus in the resin is preferably 5 to 40 mol% with respect to all repeating units constituting the resin, and preferably 10 to 30 mol. % Is more preferable.
  • the R 10 to enhance the adhesion to the substrate can be a silicon diamine component as the diamine component to the nucleus.
  • examples include bis (4-aminophenyl) dimethylsilane component, bis (4-aminophenyl) tetramethylsiloxane component, bis (4-aminophenyl) tetramethyldisiloxane component, bis ( ⁇ -aminopropyl) tetramethyl.
  • Examples thereof include a disiloxane component, a 1,4-bis ( ⁇ -aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyldisiloxane component, and a bis ( ⁇ -aminopropyl) tetraphenyldisiloxane component.
  • a disiloxane component a 1,4-bis ( ⁇ -aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyldisiloxane component, and a bis ( ⁇ -aminopropyl) tetraphenyldisiloxane component.
  • a disiloxane component examples thereof include a disiloxane component, a 1,4-bis ( ⁇ -aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyld
  • R 16 represents a divalent organic group
  • R 17 represents a monovalent organic group.
  • a plurality of R 16 may be the being the same or different.
  • the plurality of R 17 may be the same as or different from each other.
  • Examples of the divalent organic group represented by R 16 include an optionally substituted linear or branched alkylene group having 1 to 20 carbon atoms, a phenylene group having 6 to 20 carbon atoms, and 3 to 3 carbon atoms.
  • 20 represents a divalent alicyclic group or a group formed by combining these.
  • the monovalent organic group represented by R 17 represents a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent. More specifically, the following can be mentioned.
  • the content of the silicon diamine component having at least two amino groups with R 10 as a nucleus in the resin is preferably 5 to 40 mol% with respect to all repeating units constituting the resin, and preferably 10 to 30 mol. % Is more preferable.
  • the polyamic acid containing the repeating unit represented by the general formula (VIII) is, for example, as shown in Polymer Science Society edited by New Polymer Experiments 3 Polymer Synthesis and Reaction (2) P155-P171 (1996). It can be obtained by reacting an acid component and a diamine in an organic solvent.
  • organic solvents examples include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, benzene, anisole, diphenyl ether, Aromatic solvents such as nitrobenzene, benzonitrile, pyridine, halogenated solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, ethers such as tetrahydrofuran, dioxane, diglyme Examples thereof include system solvents and dimethyl sulfoxide. Of these, amide solvents are preferred, and high molecular weight polyamic acid can be obtained.
  • amide solvents are preferred, and high molecular weight polyamic acid can be obtained.
  • terminal blocker react with the terminal of the polyamic acid containing the repeating unit represented by general formula (VIII).
  • the terminal capping agent monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used.
  • terminal blocker react it is preferable at the point which can control the repeating number of a structural unit, ie, molecular weight, in a preferable range.
  • acid deactivation due to neutralization of the terminal amine and the generated acid can be suppressed by the terminal blocking agent.
  • various organic groups such as a crosslinking reactive group having a carbon-carbon unsaturated bond can be introduced as a terminal group.
  • Monoamines used for end-capping agents are 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy- 6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2 -Hydroxynaphthalene, 1-carboxy-8-amino Phthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-
  • 5-amino-8-hydroxyquinoline 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2 -Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid 2-aminobenzenesulfonic acid, 3-aminobenzoic acid
  • Acid anhydrides, monocarboxylic acids, monoacid chloride compounds and active ester compounds used as end-capping agents are phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride Acid anhydrides such as 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1- Hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxyl Naphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxy
  • phthalic anhydride maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxy Naphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynyl benzoic acid Monocarboxylic acids, and monoacid chloride compounds
  • the introduction ratio of the monoamine used for the end-capping agent is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine component.
  • the introduction ratio of the compound selected from the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used as the end-capping agent is in the range of 0.1 to 100 mol% with respect to the diamine component.
  • the amount is particularly preferably 5 to 90 mol%.
  • a plurality of different end groups may be introduced by reacting a plurality of end capping agents.
  • the end-capping agent introduced into the polymer can be easily detected by the following method.
  • a polymer having an end-capping agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component that are constituent units of the polymer.
  • the end-capping agent can be easily detected by gas chromatography (GC) or NMR measurement.
  • GC gas chromatography
  • NMR nuclear magnetic resonance
  • PLC pyrolysis gas chromatography
  • infrared spectrum 13 CNMR spectrum.
  • a commercially available resin can also be used as the resin or polymer containing a carboxyl group.
  • the ratio of the carboxyl group in the resin or polymer containing a carboxyl group is not particularly limited, but the acid value is preferably 20 to 200, more preferably 40 to 160.
  • the acid value is the number of mg of potassium hydroxide necessary to neutralize the carboxyl group contained in 1 g of the polymer.
  • the weight average molecular weight of the resin or polymer containing a carboxyl group is preferably 1,000 to 200,000, more preferably 3,000 to 10,000, and still more preferably 3,000 to 50,000. 000.
  • the polymer containing a carboxyl group can be purified and used as a solid. Moreover, when a solvent is used in the production, it can be used as a solution.
  • a method for protecting a hydroxyl group or a carboxyl group of a compound having a hydroxyl group or a carboxyl group using the compound represented by the general formula (I) is a method for producing a compound having a group represented by the general formula (III). It is also a method. By reacting the compound represented by the general formula (I) with a compound having a hydroxyl group or a carboxyl group, the hydroxyl group or the carboxyl group can be protected and represented by the general formula (III). A compound having a group can be produced.
  • the use amount (molar ratio) of the compound represented by the general formula (I) with respect to the compound having a hydroxyl group or a carboxyl group is not particularly limited, but hydroxyl to be protected in a compound having a hydroxyl group or a carboxyl group
  • the amount is preferably 0.1 to 10 mol, more preferably 0.2 to 5 mol, and still more preferably 0.3 to 3 mol with respect to 1 mol of the group or carboxyl group.
  • the reaction temperature is preferably 0 to 100 ° C, more preferably 0 to 50 ° C, still more preferably 0 to 20 ° C.
  • the base is not particularly limited, and examples thereof include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as ethylamine, diethylamine, triethylamine, and diisopropylethylamine. Among them, triethylamine or diisopropylethylamine is preferable. .
  • the content of the base is not particularly limited, but is preferably 1 to 10 mol, and more preferably 1 to 3 mol, per 1 mol of the compound represented by the general formula (I). Moreover, you may use an organic solvent as needed.
  • organic solvent examples include hydrocarbon solvents such as hexane, toluene and xylene, ether solvents such as dioxane and tetrahydrofuran, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, N, N-dimethylacetamide, N , N-dimethylformamide, aprotic polar solvents such as dimethyl sulfoxide and the like, and one or more of them are used.
  • hydrocarbon solvents such as hexane, toluene and xylene
  • ether solvents such as dioxane and tetrahydrofuran
  • ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • N, N-dimethylacetamide, N , N-dimethylformamide aprotic polar solvents such as dimethyl sulfoxide and
  • the compound having a group represented by the general formula (III) is a compound having a polymerizable unsaturated double bond, if necessary, it may be used alone or in other polymerizable unsaturated units by a known method. It may be polymerized with a monomer.
  • Examples of the method for removing the protecting group include a method of treating a compound having a group represented by the general formula (III) with heat or an acid. When processing with heat, it is preferably performed at 150 to 250 ° C.
  • examples of the acid to be used include sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, camphorsulfonic acid and the like, and among them, p-toluenesulfonic acid is preferable.
  • the amount of the acid used is preferably 0.01 to 50 mol with respect to 1 mol of the structure derived from the compound represented by the general formula (I) to be eliminated.
  • the temperature during the treatment with an acid is preferably 20 to 150 ° C.
  • water may be added.
  • the amount of water used is preferably 0.1 to 100% by mass relative to the compound having a group represented by the general formula (III).
  • the temperature during the treatment with an acid is preferably 20 to 80 ° C.
  • an organic solvent may be used. Examples of the organic solvent include those described above, and the amount used is preferably 10 to 300% by mass, and 20 to 100% by mass with respect to the compound represented by the general formula (I). Is more preferable.
  • a compound having a group represented by the general formula (III) and a photoacid generator are allowed to coexist, and the photoacid generator is irradiated with radiation or the like to generate an acid, thereby deprotecting the hydroxyl group.
  • the carboxyl group can be regenerated.
  • the compound represented by the general formula (I) can be used for protecting and deprotecting a carboxyl group of a compound having a hydroxyl group or a compound having a carboxyl group. Therefore, the compound having a group represented by the general formula (III) can be used as a constituent component of a chemically amplified resist composition or the like.
  • the photosensitive resin composition of the present invention contains (a) a resin having a group represented by the general formula (III) or (IV), and (b) a compound that generates an acid upon irradiation with actinic rays or radiation. To do.
  • the resin having a group represented by the general formula (III) or (IV) (hereinafter sometimes simply referred to as “base polymer”) preferably has a repeating unit represented by the general formula (V).
  • the weight average molecular weight of the base polymer is preferably 1,000 to 200,000, more preferably 1,000 to 150,000, and still more preferably 1,000 to 100,000.
  • the resin (a) having a group represented by the general formula (III) or (IV) may be used alone or in combination of two or more. Moreover, you may contain resin other than resin (a) which has group represented by the said general formula (III) or (IV).
  • composition of the present invention is a compound that generates acid upon irradiation with actinic ray or radiation (also referred to as “photoacid generator” or “(b) component”). Containing. These may be used in combination of two or more. Moreover, a sensitizer etc. can also be used together for sensitivity adjustment.
  • the photoacid generator is used as a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, a photochromic agent, or a microresist.
  • Known compounds that generate an acid upon irradiation with active light or radiation and mixtures thereof can be appropriately selected and used.
  • Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.
  • a group that generates an acid upon irradiation with actinic rays or radiation or a compound in which a compound is introduced into the main chain or side chain of the polymer, such as US Pat. No. 3,849,137, German Patent No. 3914407, JP 63-26653, JP 55-164824, JP 62-69263, JP 63-146038, JP 63-163452, JP 62-153853, JP The compounds described in 63-146029 and the like can be used.
  • R 201 , R 202 and R 203 each independently represents an organic group.
  • X ⁇ represents a non-nucleophilic anion, preferably sulfonate anion, carboxylate anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide anion, BF 4 ⁇ , PF 6 ⁇ , SbF 6 — An organic anion having a carbon atom is preferable.
  • R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
  • X ⁇ represents a non-nucleophilic anion.
  • Preferred organic anions include organic anions represented by the following general formula.
  • Rc 1 represents an organic group.
  • the organic group in Rc 1 include those having 1 to 30 carbon atoms, and preferably an alkyl group, a cycloalkyl group, an aryl group, or a plurality of these which may be substituted is a single bond, —O—, — And groups linked by a linking group such as CO 2 —, —S—, —SO 3 —, —SO 2 N (Rd 1 ) —.
  • Rd 1 represents a hydrogen atom or an alkyl group.
  • Rc 3 , Rc 4 and Rc 5 each independently represents an organic group.
  • Examples of the organic group for Rc 3 , Rc 4 and Rc 5 include the same organic groups as those for Rc 1 , preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Rc 3 and Rc 4 may be bonded to form a ring. Examples of the group formed by combining Rc 3 and Rc 4 include an alkylene group, a cycloalkylene group, and an arylene group. A perfluoroalkylene group having 2 to 4 carbon atoms is preferred.
  • the organic group of Rc 1 and Rc 3 to Rc 5 is preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group.
  • a fluorine atom or a fluoroalkyl group By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased and the sensitivity is improved.
  • Rc 3 and Rc 4 are combined to form a ring, so that the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved, which is preferable.
  • the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Examples of the organic group for R 201 to R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
  • Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • Examples of the group formed by combining two of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
  • the aryl group of R 204 to R 207 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the aryl group of R 204 to R 207 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like.
  • the alkyl group and cycloalkyl group in R 204 to R 207 are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups having a number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent.
  • Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group represented by R 204 to R 207 may have include an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 to 15 carbon atoms). ), Aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups, and the like.
  • Triarylsulfonium salts are particularly preferable in terms of thermal stability and sensitivity, and it is preferable to use a sensitizer in combination. Two or more kinds of such compounds can be used in combination as required.
  • the triarylsulfonium salt it is preferable that at least one aryl group has an electron withdrawing group as a substituent, and the total Hammett value of the substituents bonded to the aryl skeleton is preferably larger than 0.18. .
  • the electron withdrawing group means a substituent having a Hammett value (Hammet substituent constant ⁇ ) larger than 0.
  • the sum total of the Hammett value is 0.18 or more substituents bonded to aryl skeletons in a particular photoacid generator, and more is greater than 0.46
  • it is more preferably larger than 0.60.
  • the Hammett value represents the degree of electron withdrawing property of a cation having a triarylsulfonium salt structure, and there is no particular upper limit from the viewpoint of increasing sensitivity, but from the viewpoint of reactivity and stability. Is preferably more than 0.46 and less than 4.0, more preferably more than 0.50 and less than 3.5, and particularly preferably more than 0.60 and less than 3.0.
  • the Hammett value in the present invention uses the numerical values described in Naoki Inamoto, Chemistry Seminar 10 Hammett's Law-Structure and Reactivity (published by Maruzen Co., Ltd. in 1983).
  • Examples of the electron withdrawing group introduced into the aryl skeleton include a trifluoromethyl group, a halogen atom, an ester group, a sulfoxide group, a cyano group, an amide group, a carboxyl group, and a carbonyl group.
  • the Hammett values of these substituents are shown below.
  • a trifluoromethyl group (—CF 3 , m: 0.43, p: 0.54), a halogen atom [eg, —F (m: 0.34, p: 0.06), —Cl (m: 0. 37, p: 0.23), -Br (m: 0.39, p: 0.23), -I (m: 0.35, p: 0.18)], an ester group (for example, -COCH 3 , O: 0.37, p: 0.45), sulfoxide group (for example, —SOCH 3 , m: 0.52, p: 0.45), cyano group (—CN, m: 0.56, p: 0.66), an amide group (for example, —NHCOCH 3 , m: 0.21, p: 0.00), a carboxy group (—COOH, m: 0.37, p: 0.45), a carbonyl group (— CHO, m: 0.36, p: (043)) and the
  • nonionic substituents such as a halogen atom and a halogenated alkyl group are preferable from the viewpoint of hydrophobicity.
  • —Cl is preferable from the viewpoint of reactivity, and imparts hydrophobicity.
  • —F, —CF 3 , —Cl, and —Br are preferable.
  • substituents may be introduced into any one of the three aryl skeletons of the triarylsulfonium salt structure, or may be introduced into two or more aryl skeletons. Moreover, the substituent introduced into each of the three aryl skeletons may be one or plural. In the present invention, the sum of Hammett values of substituents introduced into these aryl skeletons is preferably more than 0.18, more preferably more than 0.46.
  • the number of substituents to be introduced is arbitrary. For example, only one substituent having a particularly large Hammett value (for example, a Hammett value exceeding 0.46 alone) may be introduced into one position of an aryl skeleton having a triarylsulfonium salt structure. Moreover, for example, a plurality of substituents introduced and the sum of the Hammett values exceeding 0.46 may be introduced.
  • the Hammett value of the substituent varies depending on the position where it is introduced, the sum of Hammett values in the specific photoacid generator according to the present invention is determined by the type of substituent, the position of introduction, and the number of introductions. become.
  • the Hammett's rule is usually expressed in the m-position and p-position, but in the present invention, the substituent effect at the o-position is calculated as the same value as the p-position as an index of electron withdrawing property.
  • Preferred substitution positions are preferably m-position and p-position, and most preferably p-position from the viewpoint of synthesis.
  • Preferred in the present invention is a sulfonium salt that is tri- or more substituted with a halogen atom, and most preferred is a sulfonium salt that is tri-substituted with a chloro group, specifically, each of the three aryl skeletons. And preferably have a triarylsulfonium salt structure in which —Cl is introduced, and more preferably —Cl is substituted at the p-position.
  • Examples of the sulfonate anion possessed by the triarylsulfonium salt contained in the composition of the present invention include an aryl sulfonate anion, an alkane sulfonate anion, and the like, which are substituted with a fluorine atom or an organic group having a fluorine atom.
  • An anion is preferred.
  • Examples of the compound having a triarylsulfonium salt structure are J.P. Am. Chem. Soc. 112 (16), 1990; 6004-6015, J.A. Org. Chem. 1988; It can be easily synthesized by the methods described in 5571-5573, WO02 / 081439A1, European Patent (EP) 1113005, and the like.
  • triphenylsulfonium trifluoromethanesulfonate triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate or 4-phenylthiophenyl diphenylsulfonium trifluoroacetate and the like.
  • diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl, 4- (2'-hydroxy- 1'-tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecoxy) phenyliodonium hexafluoroantimonate, phenyl, 4- (2'-hydroxy-1'-tetra Decaoxy) phenyliodonium-p-toluenesulfonate, etc .; diazomethane derivatives such as bis (cyclohexylsulfonyl) diazomethane, bis (t-butyl) Sulfony
  • oxime compounds more preferably oxime sulfonate compounds, are the most preferable examples from the viewpoint of sensitivity, resolution, dielectric constant, dimensional stability, and the like. Can be mentioned.
  • Preferred examples of the oxime sulfonate compound that is, the compound having an oxime sulfonate residue include compounds containing an oxime sulfonate residue represented by the formula (b1).
  • R 5 represents an alkyl group or an aryl group. Any group may be substituted, and the alkyl group in R 5 may be linear, branched or cyclic. Acceptable substituents are described below.
  • the alkyl group for R 5 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the alkyl group represented by R 5 is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or the like). It may be substituted with a cyclic group, preferably a bicycloalkyl group or the like.
  • the aryl group for R 5 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group.
  • the aryl group for R 5 may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.
  • the compound containing the oxime sulfonate residue represented by the formula (b1) is an oxime sulfonate compound represented by the formula (OS-3), the formula (OS-4) or the formula (OS-5). Is particularly preferred.
  • R 1 represents an alkyl group, an aryl group or a heteroaryl group
  • each R 2 independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom
  • R 6 represents each independently a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
  • X represents O or S
  • n represents 1 or 2
  • m represents an integer of 0 to 6.
  • the alkyl group, aryl group or heteroaryl group in R 1 may have a substituent.
  • the alkyl group in R 1 is preferably a alkyl group having 1 atoms in total may be carbon 30 have a substituent.
  • the substituent that the alkyl group in R 1 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.
  • alkyl group in R 1 examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, benzyl group.
  • the aryl group for R 1 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
  • substituents that the aryl group in R 1 may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.
  • the aryl group in R 1, a phenyl group, p- methylphenyl group, p- chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o- methoxyphenyl groups include p- phenoxyphenyl group.
  • the heteroaryl group for R 1 is preferably a heteroaryl group having 4 to 30 carbon atoms which may have a substituent.
  • substituents that the heteroaryl group in R 1 may have include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl.
  • At least one of the heteroaryl groups in R 1 may be a heteroaromatic ring.
  • a heteroaromatic ring and a benzene ring are condensed. May be.
  • the heteroaryl group for R 1 is selected from the group consisting of optionally substituted thiophene ring, pyrrole ring, thiazole ring, imidazole ring, furan ring, benzothiophene ring, benzothiazole ring and benzimidazole ring. And a group obtained by removing one hydrogen atom from the ring.
  • R 2 is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
  • one or two of R 2 present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. More preferably an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the rest is a hydrogen atom.
  • the alkyl group or aryl group in R 2 may have a substituent. Examples of the substituent that the alkyl group or aryl group in R 2 may have include the same groups as the substituent that the alkyl group or aryl group in R 1 may have.
  • the alkyl group for R 2 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and is an alkyl group having 1 to 6 carbon atoms which may have a substituent. It is more preferable.
  • Examples of the alkyl group in R 2 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, and chloromethyl group.
  • a bromomethyl group, a methoxymethyl group, and a benzyl group are preferable, and a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and an n-hexyl group are preferable.
  • a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group are more preferable, and a methyl group is preferable.
  • the aryl group for R 2 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
  • the aryl group in R 2 is preferably a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, or a p-phenoxyphenyl group.
  • the halogen atom for R 2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable.
  • X represents O or S, and is preferably O.
  • the ring containing X as a ring member is a 5-membered ring or a 6-membered ring.
  • n represents 1 or 2, and when X is O, n is preferably 1, and when X is S, n is 2 is preferable.
  • the alkyl group and alkyloxy group in R 6 may have a substituent.
  • the alkyl group for R 6 is preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent.
  • the substituent that the alkyl group in R 6 may have include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. .
  • alkyl group for R 6 examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n -Octyl, n-decyl, n-dodecyl, trifluoromethyl, perfluoropropyl, perfluorohexyl and benzyl are preferred.
  • the alkyl group in R 6, is preferably an alkyl group having a total carbon number of 1 to 30 which may have a substituent.
  • substituents that the alkyl group optionally has at R 6, include a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an amino group It is done.
  • alkyloxy group in R 6 a methyloxy group, an ethyloxy group, a butyloxy group, a hexyloxy group, a phenoxyethyloxy group, a trichloromethyloxy group, or an ethoxyethyloxy group is preferable.
  • examples of the aminosulfonyl group for R 6 include a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, and an aminosulfonyl group. It is done.
  • examples of the alkoxysulfonyl group for R 6 include a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, and a butyloxysulfonyl group.
  • m represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. It is particularly preferred.
  • the compound containing an oxime sulfonate residue represented by the formula (b1) is particularly preferably an oxime sulfonate compound represented by any one of the following formulas (OS-6) to (OS-11). .
  • R 1 represents an alkyl group, an aryl group, or a heteroaryl group
  • R 7 represents a hydrogen atom or a bromine atom
  • R 8 represents a hydrogen atom
  • R 9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group
  • 10 represents a hydrogen atom or a methyl group.
  • R 1 in the formulas (OS-6) to (OS-11) has the same meaning as R 1 in the formulas (OS-3) to (OS-5), and preferred embodiments thereof are also the same.
  • R 7 in formula (OS-6) represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
  • R 8 in the formulas (OS-6) to (OS-11) is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl
  • R 9 in formula (OS-8) and formula (OS-9) represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
  • R 10 in the formulas (OS-8) to (OS-11) represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
  • the oxime steric structure (E, Z) may be either one or a mixture.
  • oxime sulfonate compounds represented by the above formulas (OS-3) to (OS-5) include the following exemplified compounds, but the present invention is not limited thereto.
  • the compound containing an oxime sulfonate residue represented by the formula (b1) is also preferably a compound represented by the formula (OS-1).
  • R 1 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or a heteroaryl. Represents a group.
  • R 2 represents an alkyl group or an aryl group.
  • R 21 to R 24 are each independently a hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxy group, amino group, alkoxycarbonyl group, alkylcarbonyl group, arylcarbonyl group, amide group, sulfo group, cyano group or Represents an aryl group. Two of R 21 to R 24 may be bonded to each other to form a ring.
  • R 21 to R 24 a hydrogen atom, a halogen atom and an alkyl group are preferable, and an embodiment in which at least two of R 21 to R 24 are bonded to each other to form an aryl group is also preferable. Among these, an embodiment in which R 21 to R 24 are all hydrogen atoms is preferable from the viewpoint of sensitivity. Any of the aforementioned functional groups may further have a substituent.
  • the compound represented by the formula (OS-1) is more preferably a compound represented by the following formula (OS-2).
  • R 1 , R 2 and R 21 to R 24 have the same meanings as in the formula (OS-1), and preferred examples thereof are also the same.
  • an embodiment in which R 1 in the formula (OS-1) and the formula (OS-2) is a cyano group or an aryl group is more preferable, represented by the formula (OS-2), in which R 1 is a cyano group, phenyl
  • the embodiment which is a group or a naphthyl group is most preferred.
  • the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
  • b-9, b-16, b-31, and b-33 are preferable from the viewpoint of achieving both sensitivity and stability.
  • the above compound containing an oxime sulfonate residue represented by the formula (b1) may be an oxime sulfonate compound represented by the following formula (b2).
  • R 5 represents an alkyl group or an aryl group
  • X represents an alkyl group, an alkoxy group, or a halogen atom
  • m represents an integer of 0 to 3
  • m is 2 or 3. In some cases, multiple Xs may be the same or different.
  • the alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • the halogen atom as X is preferably a chlorine atom or a fluorine atom.
  • m is preferably 0 or 1. In the formula (b2), m is 1, X is a methyl group, the substitution position of X is the ortho position, R 5 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl- A compound that is a 2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
  • the compound containing an oxime sulfonate residue represented by the formula (b1) may be an oxime sulfonate compound represented by the formula (b3).
  • R 5 has the same meaning as R 5 in the formula (b1), X 'is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and L represents an integer of 0 to 5.
  • R 5 in the formula (b3) is methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro
  • a fluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferred, and an n-octyl group is particularly preferred.
  • X ′ is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
  • L is preferably from 0 to 2, particularly preferably from 0 to 1.
  • Specific examples of the compound represented by the formula (b3) include ⁇ - (methylsulfonyloxyimino) benzyl cyanide, ⁇ - (ethylsulfonyloxyimino) benzyl cyanide, ⁇ - (n-propylsulfonyloxyimino) benzyl.
  • preferable oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used singly or in combination of two or more.
  • Compounds (i) to (viii) can be obtained as commercial products. It can also be used in combination with other types of (C) radiation-sensitive acid generators.
  • the content of the photoacid generator is preferably 1 to 30% by mass, more preferably 3 to 20% by mass based on the total solid content of the photosensitive resin composition.
  • the acid generator can be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more.
  • sensitizer may be added to the composition of the present invention in order to absorb actinic rays or radiation and promote the decomposition of the sulfonium salt.
  • the sensitizer absorbs actinic rays or radiation and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with sulfonium, and effects such as electron transfer, energy transfer, and heat generation occur.
  • the polymerization initiator undergoes a chemical change and decomposes to generate radicals, acids or bases.
  • preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in the 350 nm to 450 nm region.
  • Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene
  • xanthenes eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • cyanines eg, thiacarbocyanine, oxacarbocyanine
  • merocyanine Eg, merocyanine, carbomerocyanine
  • thiazines eg, thionine, methylene blue, toluidine blue
  • acridines eg, acridine orange, chloroflavin, acriflavine
  • anthraquinones eg, anthraquinone
  • squalium eg, , Squalium
  • coumarins eg, 7-diethylamino-4-methylcoumarin.
  • sensitizer include compounds represented by the following formulas (IX) to (XIV).
  • a 1 represents a sulfur atom or NR 50
  • R 50 represents an alkyl group or an aryl group
  • L 2 forms a basic nucleus of the dye together with adjacent A 1 and an adjacent carbon atom.
  • R 51 and R 52 each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R 51 and R 52 may be bonded to each other to form an acidic nucleus of the dye.
  • W represents an oxygen atom or a sulfur atom.
  • Ar 1 and Ar 2 each independently represent an aryl group and are linked via a bond with —L 3 —.
  • L 3 represents —O— or —S—.
  • W is synonymous with that shown in Formula (IX).
  • a 2 represents a sulfur atom or NR 59
  • L 4 represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent A 2 and a carbon atom
  • R 53 , R 54 , R 55 , R 56 , R 57 and R 58 each independently represent a monovalent nonmetallic atomic group
  • R 59 represents an alkyl group or an aryl group.
  • a 3 and A 4 each independently represent —S—, —NR 62 — or —NR 63 —, and R 62 and R 63 each independently represent a substituted or unsubstituted alkyl group, substituted or Represents an unsubstituted aryl group, and L 5 and L 6 each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A 3 , A 4, and adjacent carbon atoms, and R 60 , R 61 each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, or may be bonded to each other to form an aliphatic or aromatic ring.
  • R 66 represents an aromatic ring or a hetero ring which may have a substituent
  • a 5 represents an oxygen atom, a sulfur atom or ⁇ NR 67
  • R 64 , R 65 and R 67 each independently represent a hydrogen atom or a monovalent non-metallic atomic group
  • R 67 and R 64 , and R 65 and R 67 each represent an aliphatic or aromatic ring. Can be combined to form.
  • R 68 and R 69 each independently represent a hydrogen atom or a monovalent nonmetallic atomic group.
  • R 70 and R 71 each independently represent a monovalent nonmetallic atomic group, and n represents an integer of 0 to 4. When n is 2 or more, R 70 and R 71 can be bonded to each other to form an aliphatic or aromatic ring.
  • an anthracene derivative is particularly preferable.
  • the sensitizer as described above may be a commercially available one or may be synthesized by a known synthesis method.
  • the content of the sensitizer is preferably 1 to 30% by mass, more preferably 3 to 20% by mass based on the total solid content of the photosensitive resin composition.
  • composition according to the present invention preferably contains a basic compound in order to reduce a change in performance over time from exposure to heating.
  • Preferred examples of the basic compound include compounds having a structure represented by the following formulas (A) to (E).
  • R 200 , R 201 and R 202 may be the same or different and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number). 6-20), wherein R 201 and R 202 may combine with each other to form a ring.
  • R 203 , R 204 , R 205 and R 206 may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
  • the alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
  • Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
  • Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzimidazole and the like.
  • Examples of the compound having a diazabicyclo structure 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5,4,0 ] Undecar 7-ene and the like.
  • Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris ( t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like.
  • the compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate.
  • Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
  • aniline compounds include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
  • alkylamine derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine.
  • aniline derivatives having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline.
  • Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.
  • amine compound a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
  • the amine compound is more preferably a tertiary amine compound.
  • the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms).
  • 6 to 12 carbon atoms may be bonded to the nitrogen atom.
  • the amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
  • the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
  • an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
  • ammonium salt compound a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
  • the ammonium salt compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group, provided that at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.
  • the ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
  • the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
  • an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
  • Examples of the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable.
  • the halogen atom is particularly preferably chloride, bromide or iodide
  • the sulfonate is particularly preferably an organic sulfonate having 1 to 20 carbon atoms.
  • Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.
  • the alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups.
  • substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups.
  • Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.
  • Examples of the aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring and an anthracene ring.
  • the benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.
  • linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like.
  • substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.
  • An amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound.
  • the phenoxy group may have a substituent.
  • the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group.
  • the substitution position of the substituent may be any of the 2-6 positions.
  • the number of substituents may be any in the range of 1 to 5.
  • oxyalkylene group between the phenoxy group and the nitrogen atom.
  • the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
  • an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
  • the sulfonic acid ester group may be any of alkyl sulfonic acid ester, cycloalkyl group sulfonic acid ester, and aryl sulfonic acid ester.
  • the alkyl group has 1 to 20 carbon atoms
  • the cycloalkyl group has 3 to 20 carbon atoms
  • the aryl group has 6 carbon atoms.
  • Alkyl sulfonic acid ester, cycloalkyl sulfonic acid ester, and aryl sulfonic acid ester may have a substituent.
  • substituents include a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, and a sulfonic acid.
  • An ester group is preferred.
  • oxyalkylene group between the sulfonate group and the nitrogen atom.
  • the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
  • an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably oxy Ethylene group.
  • the following compounds are also preferable as the basic compound.
  • the composition according to the present invention may or may not contain a basic compound. However, when it is contained, the content of the basic compound is usually 0.001 to on the basis of the total solid content of the composition. It is 10% by mass, preferably 0.01-5% by mass.
  • the acid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.
  • the present invention may contain a thermal acid generator.
  • the thermal acid generator is a compound that generates an acid by heat, and is usually a compound having a thermal decomposition point in the range of 130 ° C. to 250 ° C., preferably 150 ° C. to 220 ° C., for example, sulfonic acid, It is a compound that generates a low nucleophilic acid such as carboxylic acid or disulfonylimide.
  • sulfonic acid, alkyl substituted with an electron withdrawing group or arylcarboxylic acid having a strong pKa of 2 or less, disulfonylimide substituted with an electron withdrawing group, and the like are preferable.
  • the electron withdrawing group examples include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.
  • the thermal acid generator is required not to be decomposed during storage time or in a pre-baking process after applying the composition, but to be quickly decomposed in a heat-curing process after patterning. Therefore, the thermal decomposition point is preferably 100 ° C to 300 ° C. More preferably, it is 120 ° C to 250 ° C, and further preferably 150 ° C to 200 ° C.
  • a photoacid generator that generates an acid by the above-described exposure can be applied.
  • Examples thereof include onium salts such as sulfonium salts and iodonium salts, N-hydroxyimide sulfonate compounds, oxime sulfonates, o-nitrobenzyl sulfonates and the like.
  • Preferred examples of the sulfonium salt include compounds represented by the following general formulas (TA-1) to (TA-3).
  • R T1 to R T5 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a halogen atom.
  • R T6 and R T7 each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.
  • R T8 and R T9 each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.
  • R T1 to R T5 , R T6 and R T7, and R T8 and R T9 may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom, a sulfur atom, a ketone A bond, an ester bond, or an amide bond may be included.
  • Examples of the group formed by combining any two or more of R T1 to R T5 , R T6 and R T7, and R T8 and R T9 include a butylene group and a pentylene group.
  • X ⁇ represents a non-nucleophilic anion, and has a strong pKa of 2 or less as described above, a sulfonic acid or an alkyl or aryl carboxylic acid substituted with an electron withdrawing group, or a disulfonylimide substituted with an electron withdrawing group.
  • Etc. are preferable.
  • the electron withdrawing group include a halogen atom such as an F atom, a haloalkyl group such as a trifluoromethyl group, a nitro group, and a cyano group.
  • R T10 and R T11 each independently represent an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.
  • R T10 and R T11 may be bonded to each other to form a ring structure, and this ring structure may contain an oxygen atom, a sulfur atom, a ketone bond, an ester bond, or an amide bond.
  • Examples of the group formed by combining R T10 and R T11 include a butylene group and a pentylene group.
  • R T12 to R T16 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a thioalkoxy group, or a hydroxyl group, and two or more of them are bonded to each other to form a naphthalene ring, an anthracene ring, etc.
  • a polycyclic aromatic ring may be formed.
  • X ⁇ represents a non-nucleophilic anion.
  • R T17 represents an alkyl group (straight chain or branched) or a cycloalkyl group, preferably a straight chain and branched alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms (for example, a methyl group, Ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group).
  • cycloalkyl group examples include not only a monocyclic cyclic alkyl group such as a cyclopentyl group and a cyclohexyl group, but also a cyclic alkyl group having a bridging site such as a norbornyl group, a tricyclodecanyl group, and an adamantyl group. it can.
  • R T18 and R T19 each independently represent a hydrogen atom, an alkyl group or a cycloalkyl group.
  • R T20 and R T21 each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.
  • R T18 and R T19 and R T20 and R T21 may be bonded to each other to form a ring structure, and this ring structure may contain an oxygen atom, a sulfur atom, a ketone bond, an ester bond, or an amide bond. Good.
  • Examples of the group formed by combining R T18 and R T19 and R T20 and R T21 include a butylene group and a pentylene group.
  • X ⁇ represents a non-nucleophilic anion.
  • the alkyl group as R T1 to R T17 may be linear or branched.
  • a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms for example, Methyl group, ethyl group, linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group).
  • the cycloalkyl group as R T1 to R T17 is meant to include a monocyclic alkyl group as well as a polycyclic and cyclic alkyl group having a bridging site, and the cycloalkyl group as R T12 to R T16 is preferably Is a cycloalkyl group having 3 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group).
  • the cycloalkyl group as R T17 has a cycloalkyl group having 3 to 8 carbon atoms (eg, cyclopentyl group, cyclohexyl group) and a cyclic group having a bridging site such as a norbornyl group, a tricyclodecanyl group, or an adamantyl group. Also preferred are alkyl groups.
  • the alkoxy group as R T1 to R T5 and R T12 to R T16 may be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 1 carbon atoms. 5 linear and branched alkoxy groups (for example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), cyclic alkoxy groups having 3 to 8 carbon atoms (for example, , Cyclopentyloxy group, cyclohexyloxy group).
  • the thioalkoxy group as R T12 to R T16 may be linear, branched or cyclic, for example, a thioalkoxy group having 1 to 10 carbon atoms, preferably a linear or branched group having 1 to 5 carbon atoms.
  • a thioalkoxy group for example, a thiomethoxy group, a thioethoxy group, a linear or branched thiopropoxy group, a linear or branched thiobutoxy group, a linear or branched thiopentoxy group
  • a cyclic thioalkoxy group having 3 to 8 carbon atoms for example, thiocyclopentyl) Oxy group, thiocyclohexyloxy group).
  • the non-nucleophilic anion as X ⁇ is preferably an organic anion, and particularly preferably an organic anion represented by the following general formula.
  • Rc 1 represents an organic group.
  • the organic group for Rc 1 include those having 1 to 30 carbon atoms, and preferably an alkyl group, a cycloalkyl group, an aryl group, or a plurality of these optionally having a substituent is a single bond, —O. -, - CO 2 -, - S -, - SO 3 -, - SO 2 N (Rd 1) - can be exemplified linked group a linking group such as.
  • Rd 1 represents a hydrogen atom or an alkyl group.
  • Rc 2 represents 1-position an alkyl group substituted with a fluorine atom or a fluoroalkyl group.
  • Rc 3 and Rc 4 each independently represents an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group. Preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. Rc 3 and Rc 4 may be bonded to each other to form a ring. Examples of the group formed by combining Rc 3 and Rc 4 include an alkylene group, a cycloalkylene group, and an arylene group. A perfluoroalkylene group having 2 to 4 carbon atoms is preferred.
  • Preferred examples of the iodonium salt include compounds represented by the following general formula (TA-4).
  • R 41 and R 42 each have a hydrogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or a substituent.
  • An alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, an acyloxy group which may have a substituent, a nitro group, a halogen atom, a hydroxyl group Represents a carboxyl group.
  • a represents 1 to 5
  • b represents 1 to 5.
  • R 41 and R 42 has an alkyl group having 5 or more carbon atoms, which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent.
  • X represents R—SO 3
  • R represents an aliphatic hydrocarbon group which may have a substituent and an aromatic hydrocarbon group which may have a substituent.
  • alkyl group for R 41 and R 42 an optionally substituted methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, Examples thereof include those having 1 to 25 carbon atoms such as hexyl group, heptyl group, octyl group, t-amyl group, decanyl group, dodecanyl group and hexadecanyl group.
  • the cycloalkyl group has 3 to 25 carbon atoms which may have a substituent, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecanyl group, cyclohexadecanyl group and the like. Things.
  • the alkoxy group may have a substituent, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group or a t-butoxy group, a pentyloxy group, t Examples thereof include those having 1 to 25 carbon atoms such as -amyloxy group, n-hexyloxy group, n-octyloxy group, n-dodecanoxy group and the like.
  • alkoxycarbonyl group a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group or t which may have a substituent may be used.
  • Those having 2 to 25 carbon atoms such as -butoxycarbonyl group, pentyloxycarbonyl group, t-amyloxycarbonyl group, n-hexyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecanoxycarbonyl group, etc. Can be mentioned.
  • the acyl group may have a substituent and has 1 carbon atom such as formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group, octanoyl group, t-butylcarbonyl group, t-amylcarbonyl group and the like. Up to 25 can be mentioned.
  • acyloxy group an acetoxy group, propionyloxy group, butyryloxy group, t-butyryloxy group, t-amylyloxy group, n-hexanecarbonyloxy group, n-octanecarbonyloxy group, which may have a substituent
  • substituent examples thereof include those having 2 to 25 carbon atoms such as n-dodecane carbonyloxy group, n-hexadecane carbonyloxy group, and the like.
  • halogen atom there can be mentioned a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • an alkoxy group having 1 to 4 carbon atoms a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, a carboxy group, An alkoxycarbonyl group, a nitro group, etc. can be mentioned.
  • R 1 and R 2 has 5 or more carbon atoms and may have a substituent, a cycloalkyl group that may have a substituent, An alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, an acyloxy group which may have a substituent .
  • substituent having 5 or more carbon atoms include those having 5 to 25 carbon atoms in the above specific examples.
  • examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and n-pentyl.
  • Group, t-amyl group, n-hexyl group, n-octyl group and decanyl group are preferable, and the cycloalkyl group is preferably a cyclohexyl group, cyclooctyl group or cyclododecanyl group which may have a substituent.
  • alkoxy group which may have a substituent
  • a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, a pentyloxy group, a t-amyloxy group, n -Hexyloxy group, n-octyloxy group and n-dodecanoxy group are preferable
  • the alkoxycarbonyl group may be a methoxy group which may have a substituent.
  • Carbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, t-amyloxycarbonyl group, n-hexyloxycarbonyl group, n -Octyloxycarbonyl group and n-dodecanoxycarbonyl group are preferred, and the acyl group may have a substituent, formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group, octanoyl group, t-butyl A carbonyl group and a t-amylcarbonyl group are preferable, and the acyloxy group may have an acetoxy group, a propionyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group
  • the alkyl group having 5 or more carbon atoms and optionally having a substituent is preferably an n-pentyl group, a t-amyl group, an n-hexyl group, an n-octyl group or a decanyl group.
  • the cycloalkyl group having 5 or more carbon atoms and optionally having a substituent is preferably a cyclohexyl group, a cyclooctyl group or a cyclododecanyl group.
  • the alkoxy group having 5 or more carbon atoms and optionally having a substituent is preferably a pentyloxy group, a t-amyloxy group, a hexyloxy group, an n-octyloxy group, or a dodecanoxy group.
  • Examples of the alkoxycarbonyl group having 5 or more carbon atoms which may have a substituent include a pentyloxycarbonyl group, a t-amyloxycarbonyl group, a hexyloxycarbonyl group, an n-octyloxycarbonyl group, and dodecaneoxycarbonyl. Groups are preferred.
  • the acyl group having 5 or more carbon atoms and optionally having a substituent is preferably a valeryl group, a hexanoyl group, an octanoyl group or a t-amylcarbonyl group.
  • Substituents for these groups include methoxy group, ethoxy group, t-butoxy group, chlorine atom, bromine atom, cyano group, hydroxyl group, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group Groups are preferred.
  • the iodonium compound represented by formula (TA-4) used in the present invention uses sulfonic acid having a specific structure as described above as its counter anion, X ⁇ .
  • X ⁇ its counter anion
  • examples of the aliphatic hydrocarbon group which may have an R substituent in the counter anion include a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic alkyl group.
  • R can mention the aromatic group which may have a substituent.
  • alkyl group for R examples include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, and 2-ethylhexyl, which may have a substituent. And those having 1 to 20 carbon atoms such as a group, a decyl group and a dodecyl group.
  • Examples of the cyclic alkyl group include an optionally substituted cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecyl group, adamantyl group, norbornyl group, camphor group, tricyclodecanyl group, menthyl group and the like. Can do.
  • Examples of the aromatic group include a phenyl group and a naphthyl group, which may have a substituent.
  • alkyl group which may have a substituent of R, a methyl group, a trifluoromethyl group, an ethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, n- Propyl group, n-butyl group, nonafluorobutyl group, n-pentyl group, n-hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, decyl group, dodecyl group, cyclic alkyl group A cyclopentyl group, a cyclohexyl group, and a camphor group can be mentioned.
  • substituents include a methoxyphenyl group, dodecylphenyl group, mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group, and 6-hydroxy-2-naphthyl group.
  • R 41 and R 42 are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, t- Amyl group, n-hexyl group, n-octyl group, cyclohexyl group, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, hexyloxy group, n -Octyloxy group, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, hexyloxycarbonyl group, n-octyloxycarbonyl group, formyl group, acetyl group,
  • more preferable groups having 5 or more carbon atoms include n-pentyl group, t-amyl group, n-hexyl group, n-octyl group, decanyl group, cyclohexyl group, pentyloxy group, t-amyloxy group, Hexyloxy group, n-octyloxy group, dodecaneoxy group, pentyloxycarbonyl group, t-amyloxycarbonyl group, hexyloxycarbonyl group, n-octyloxycarbonyl group, dodecanoxyoxycarbonyl group, valeryl group, hexanoyl group, octanoyl group A t-amylcarbonyl group, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octenecarbonyloxy group.
  • the more preferable sulfonic acid substituent R include methyl group, trifluoromethyl group, ethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, n-butyl group, nonafluorobutyl group, n-hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, camphor group, phenyl group, naphthyl group, pentafluorophenyl group, p-toluyl group, p-fluorophenyl group, p-chlorophenyl group P-methoxyphenyl group, dodecylphenyl group, mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group, 6-hydroxy-2-naphthyl group.
  • the total number of carbon atoms of the acid generated is preferably 1-30. More preferably, the number is 1 to 28, and still more preferably 1 to 25. If the total number of carbon atoms is less than 1, troubles such as poor resolution due to volatilization may occur, and if it exceeds 30, the development residue may be generated.
  • Specific examples of the compound represented by formula (TA-4) are shown below, but are not limited thereto. These compounds are used alone or in combination of two or more.
  • Examples of the imide sulfonate compound preferable as the thermal acid generator include compounds of the following general formula.
  • C 1 (carbon atom) and C 2 (carbon atom) are bonded by a single bond or a double bond
  • R 51 or R 52 may be the same or different
  • the following (1) to (4) (1) each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or (2) a monocyclic or polycyclic ring that may contain one or more heteroatoms together with C 1 and C 2
  • (3) represents a residue containing N-sulfonyloxyimide that forms a condensed aromatic ring containing C 1 and C 2 .
  • R 53 represents an alkyl group, a halogenated alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a camphor group.
  • the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a tert-butyl group.
  • the cycloalkyl group include those having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group and the like.
  • aryl group examples include those having 6 to 14 carbon atoms such as phenyl group, tolyl group, xylyl group, mesityl group, and naphthyl group.
  • R 51 and R 52 correspond to the case (2), for example, the following partial structure can be given.
  • R 51 and R 52 correspond to the case of (3), for example, the following partial structure can be given.
  • R 55 and R 56 each represents a hydrogen atom or a methyl group.
  • M represents an integer of 1 to 4.
  • Examples of the alkyl group for R 53 include linear or branched alkyl groups having 1 to 20 carbon atoms. Preferred is a linear or branched alkyl group having 1 to 16 carbon atoms, and more preferred is one having 1 to 12 carbon atoms. In the case of an alkyl group having 21 or more carbon atoms, sensitivity and resolving power decrease, which is not preferable.
  • Examples of the halogenated alkyl group include those in which one or two or more hydrogen atoms of the alkyl group are halogenated. Examples of the halogen atom to be substituted include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a fluorine atom a chlorine atom and a bromine atom
  • particularly preferred is a fluorine atom
  • the halogen atom to be substituted may be plural types per molecule.
  • the cyclic alkyl group include cycloalkyl groups having 3 to 12 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group, and polycyclic substituents such as norbornyl group, adamantyl group, and tricyclodecanyl group. I can give you.
  • the alkenyl group include linear or branched alkenyl groups having 2 to 20 carbon atoms.
  • a straight-chain or branched alkenyl group having 2 to 16 carbon atoms is preferable, and one having 2 to 12 carbon atoms is more preferable. In the case of an alkenyl group having 21 or more carbon atoms, sensitivity and resolving power decrease, which is not preferable.
  • Examples of the aryl group of R 53 include a phenyl group and a naphthyl group, and examples of the aralkyl group include a benzyl group.
  • Examples of the substituent of the aryl group and the aralkyl group include a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a tert-butyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a phenyl group, a toluyl group, Aryl groups such as xylyl and mesityl groups, methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, sec-butoxy groups, tert-butoxy groups and other lower alkoxy groups, vinyl groups, allyl groups, propenyl groups, butenyl groups, etc.
  • an acyl group such as alkenyl group, formyl group and acetyl group, and halogen atoms such as hydroxy group, carboxy group, cyano group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom.
  • a lower alkyl group such as a methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, cyclohexyl group, phenyl group, toluyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, sec-butoxy Group, lower alkoxy group such as tert-butoxy group, halogen atom such as cyano group, nitro group, fluorine atom, chlorine atom, bromine atom and iodine atom.
  • substituents on the aryl group and the aralkyl group may be used. Specific examples of these compounds are shown below, but are not limited thereto.
  • Preferred oxime sulfonate compounds as thermal acid generators include compounds of the following general formula.
  • R 61 and R 62 are an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, substituted group which may have a substituent having 1 to 16 carbon atoms.
  • R 61 and R 62 are an alkylene chain, alkenylene chain, alkynylline chain, which may have a substituent having 2 to 8 carbon atoms, or phenylene, freelen, thienylene, which may have a substituent, It may be bonded to R 61 or R 62 of the compound represented by another general formula (TA-6) through a linking chain containing —O—, —S—, —N—, and —CO—. . That is, the compound represented by the general formula (TA-6) includes those having two or three oxime sulfonate structures via a linking chain.
  • R 63 represents an alkyl group, a cycloalkyl group, or an aryl group which may have a substituent, which may have a substituent having 1 to 16 carbon atoms.
  • alkyl group having 1 to 16 carbon atoms in R 61 to R 63 examples include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a t-butyl group, a t-amyl group, alkyl groups such as n-hexyl group, n-octyl group, i-octyl group, n-decyl group, undecyl group, dodecyl group, hexadecyl group, trifluoromethyl group, perfluoropropyl group, perfluorobutyl group, perfluoro-t- Examples thereof include a butyl group, a perfluorooctyl group, a perfluoroundecyl group, and a 1,1-bistrifluoromethylethyl group.
  • alkenyl group for R 61 and R 62 examples include allyl group, methallyl group, vinyl group, methylallyl group, 1-butenyl group, 3-butenyl group, 2-butenyl group, 1,3-pentadienyl group, 5-hexenyl group, Examples include 2-oxo-3-pentenyl group, decapentaenyl group, 7-octenyl group and the like.
  • alkynyl group in R 61 and R 62 examples include ethynyl group, propargyl group, 2-butynyl group, 4-hexynyl group, 2-octynyl group, phenylethynyl group, cyclohexylethynyl group and the like.
  • Examples of the cycloalkyl group in R 61 to R 63 include those having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
  • Examples of the cycloalkenyl group for R 61 and R 62 include a cyclobutenyl group, a cyclohexenyl group, a cyclopentadienyl group, a bicyclo [4.2.4] dodeca-3,7-dien-5-yl group, and the like.
  • Examples of the aryl group in R 61 to R 63 include those having 6 to 14 carbon atoms, such as phenyl group, tolyl group, methoxyphenyl group, and naphthyl group, which may have a substituent.
  • the above substituents include alkyl groups, cycloalkyl groups, alkoxy groups, halogen atoms (fluorine atoms, chlorine atoms, iodine atoms), cyano groups, hydroxy groups, carboxy groups, nitro groups, aryloxy groups, alkylthio groups, aralkyls. And groups represented by the following general formula (1A).
  • the alkyl group and the cycloalkyl group have the same meanings as described above.
  • the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group.
  • the aralkyl group include a benzyl group, a naphthylmethyl group, a furyl group, and a thienyl group.
  • R 61 and R 62 have the same meanings as R 61 and R 62 in formula (TA-6).
  • Preferred examples of the oxime sulfonate-based acid generator as the thermal acid generator include compounds having at least one group represented by the following general formula (TA-7).
  • R 70a and R 70b each independently represents an organic group.
  • the organic group of R 70a and R 70b is a group containing a carbon atom, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.)) You may have.
  • As the organic group for R 70a a linear, branched, or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a fluorine atom and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.
  • “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent.
  • the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, and most preferably 1 to 4 carbon atoms.
  • a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable.
  • the partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated alkyl group means that all of the hydrogen atoms are halogen atoms.
  • the aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.
  • a partially or completely halogenated aryl group is particularly preferable.
  • the partially halogenated aryl group means an aryl group in which a part of hydrogen atoms is substituted with a halogen atom, and the fully halogenated aryl group means that all of the hydrogen atoms are halogen atoms.
  • R 70a is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.
  • R 70b a linear, branched, or cyclic alkyl group, aryl group, or cyano group is preferable.
  • the alkyl group and aryl group for R 70b the same alkyl groups and aryl groups as those described above for R 70a can be used.
  • R 70b is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.
  • a compound represented by the following general formula (TA-7a) or (TA-7b) is preferably used because of its high acid generation efficiency against electron beam irradiation.
  • m ′ is 0 or 1;
  • X is 1 or 2;
  • R 71 is a phenyl group, a heteroaryl group, or an alkyl group having 1 to 12 carbon atoms, or When m ′ is 0, an alkoxycarbonyl group having 2 to 6 carbon atoms, a phenoxycarbonyl group, CN (cyano group);
  • R 72 is synonymous with R 71 ;
  • R 73 ′ is 1 to 1 carbon atoms when X is 1;
  • R 74 and R 75 are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms;
  • A is —S— , -O-, -N (R 76 )-.
  • R76 represents an alkyl group, an aryl group or an aral
  • R 71 ′ is an alkylene group having 2 to 12 carbon atoms; R 72 , R 74 , R 75 and A are as defined above; R 73 is an alkyl group having 1 to 18 carbon atoms. . ]
  • the following thiolene-containing oxime sulfonate is particularly preferable.
  • Preferred examples of the general formula of nitrobenzyl sulfonate include compounds represented by the general formula (TA-9).
  • (Z in this formula is alkyl group, aryl group, alkylaryl group, halogen-substituted alkyl group, halogen-substituted aryl group, halogen-substituted alkylaryl group, nitro-substituted aryl group, nitro-substituted
  • Q m (NO ) is selected 2 from the groups having, R represents a hydrogen atom or a methyl group, R 'are selected from hydrogen atoms and methyl groups, and nitro substituted aryl groups, each Q is a hydrocarbon radical, Hidorokarubono Independently selected from a xyl group, NO 2 , a halogen atom and an organo
  • sulfonic acid esters can be used.
  • a sulfonic acid ester represented by the following general formula (TA-1) can be given.
  • R ′ and R ′′ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent or an optionally substituted carbon group having 6 carbon atoms.
  • Preferable specific examples of the sulfonic acid ester include the following.
  • TA-2 a compound represented by the following general formula (TA-2) is more preferable from the viewpoint of heat resistance.
  • the molecular weight of the sulfonate ester is generally 230 to 1000, preferably 230 to 800.
  • A represents an h-valent linking group.
  • R 0 represents an alkyl group, an aryl group, an aralkyl group, or a cyclic alkyl group.
  • R 0 ′ represents a hydrogen atom, an alkyl group, or an aralkyl group.
  • h represents an integer of 2 to 8.
  • the h-valent linking group as A includes, for example, an alkylene group (eg, methylene, ethylene, propylene, etc.), a cycloalkylene group (eg, cyclohexylene, cyclopentylene, etc.), an arylene group (1,2-phenylene, 1,3). -Phenylene, 1,4-phenylene, naphthylene, etc.), an ether group, a carbonyl group, an ester group, an amide group, and a group obtained by removing h-2 arbitrary hydrogen atoms from a divalent group combining these groups. Can be mentioned.
  • the carbon number of the h-valent linking group as A is generally 1 to 15, preferably 1 to 10, and more preferably 1 to 6.
  • the alkyl group for R 0 and R 0 ′ is generally an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. is there. Specific examples include methyl, ethyl, propyl, butyl, hexyl, octyl and the like.
  • the aralkyl group for R 0 and R 0 ′ is generally an aralkyl group having 7 to 25 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 15 carbon atoms. is there.
  • the cyclic alkyl group for R 0 is generally a cyclic alkyl group having 3 to 20 carbon atoms, preferably a cyclic alkyl group having 4 to 20 carbon atoms, more preferably a cyclic alkyl group having 5 to 15 carbon atoms. is there. Specific examples include cyclopentyl, cyclohexyl, norbornyl, camphor group and the like.
  • the linking group as A may further have a substituent.
  • the substituent is an alkyl group (an alkyl group having 1 to 10 carbon atoms, specifically, methyl, ethyl, propyl, butyl, hexyl). Octyl, etc.), aralkyl groups (aralkyl groups having 7 to 15 carbon atoms, specifically benzyl, toluylmethyl, mesitylmethyl, phenethyl, etc.), aryl groups (aryl groups having 6 to 10 carbon atoms, specifically Are phenyl, toluyl, xylyl, mesityl, naphthyl, etc.), an alkoxy group (the alkoxy group may be linear, branched or cyclic, and has 1 to 10 carbon atoms, specifically, Methoxy, ethoxy, linear or branched propoxy, linear or branched butoxy, linear or branched pentoxy, cyclopentyloxy, cyclohexy
  • R 0 is preferably an alkyl group or an aryl group.
  • R 0 ′ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a hydrogen atom.
  • Examples of the sulfonic acid ester in the present invention include the following specific compounds, but are not limited thereto.
  • sulfonic acid ester in the present invention a commercially available one may be used, or one synthesized by a known method may be used.
  • the sulfonic acid ester of the present invention can be synthesized, for example, by reacting sulfonyl chloride or sulfonic acid anhydride with a corresponding polyhydric alcohol under basic conditions.
  • the content of the thermal acid generator is preferably 1 to 20% by mass, more preferably 3 to 10% by mass based on the total solid content of the photosensitive resin composition.
  • composition of the present invention may contain a compound containing at least one of alkoxymethyl group and acyloxymethyl group. Even in the low-temperature curing process, it is possible to prevent melting and thermal shrinkage of the pattern during curing.
  • an alkoxymethyl group or an acyloxymethyl group a compound in which an alkoxymethyl group or an acyloxymethyl group is substituted directly on an aromatic group or a nitrogen atom of the following urea structure on a triazine
  • the alkoxymethyl group or acyloxymethyl group of the compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
  • the total number of alkoxymethyl groups and acyloxymethyl groups possessed by the compound is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 3 to 6.
  • the molecular weight of the compound is preferably 1500 or less, and preferably 180 to 1200.
  • R 100 represents an alkyl group or an acyl group.
  • R 101 and R 102 independently represent a monovalent organic group, and may be bonded to each other to form a ring.
  • Examples of the compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted with an aromatic group include compounds having the following general formula.
  • X represents a single bond or a divalent organic group
  • each R 104 independently represents an alkyl group or an acyl group
  • R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, Or a group that decomposes by the action of an acid to generate an alkali-soluble group (for example, a group that is eliminated by the action of an acid, a group represented by —C (R 4 ) 2 COOR 5 (R 4 is a hydrogen atom or a carbon number) Represents an alkyl group of 1 to 4, and R 5 represents a group capable of leaving by the action of an acid))).
  • R 105 each independently represents an alkyl group or an alkenyl group
  • a, b and c are each independently 1 to 3
  • d is 0 to 4
  • e is independently 0 to 3.
  • the group that decomposes by the action of an acid to generate an alkali-soluble group refers to a group that decomposes by the action of an acid to generate an alkali-soluble group such as a hydroxyl group or a carboxyl group (hereinafter also referred to as an acid-decomposable group).
  • a preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.
  • R 36 to R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • R 36 and R 37 may be bonded to each other to form a ring.
  • R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • Examples of the compound having an alkoxymethyl group include the following structures.
  • Examples of the compound having an acyloxymethyl group include compounds in which the alkoxymethyl group of the following compound is changed to an acyloxymethyl group.
  • Examples of the compound having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
  • the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available product or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, a compound in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring is preferable.
  • the addition amount of these compounds is preferably 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the total amount of the resin of the present invention.
  • composition of the present invention may contain a compound containing methacryloyl group or acryloyl group.
  • the compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of acrylic acid esters and methacrylic acid esters. Since these compounds are insoluble in an alkaline developer, they have a function of suppressing the alkali solubility of the composition, and are useful for good image formation in order to suppress film loss in unexposed areas.
  • the molecular weight of components constituting the composition partially increases due to the reaction of the acrylic group or methacrylic group with the compound in the composition at the stage of the cure reaction. As a result, film properties are improved. Therefore, it is preferable to use a compound having two or more acryloyl groups and methacryloyl groups in one molecule, more preferably four or more functional groups, because this compound can exhibit a function as a crosslinking compound.
  • EO ethylene oxide
  • PO propylene oxide
  • NK-10 series made by Shin-Nakamura Chemical Co., Ltd., monofunctional AMP-10G, AMP-20GY, AM30G, AM90G, AM230G, ACB-3, A-BH, A-IB, A-SA, A -OC-18E, 720A, S-1800A, ISA, AM-130G, LA, M-20G, M-90G, M230G, PHE-1G, SA, CB-1, CB-3, CB-23, TOPOLENE-M , S-1800M, IB, OC-18E, S, bifunctional A-200, A-400, A-600, A-1000, ABE-300, A-BPE-4, A-BPE-10, A- BPE-20, A-BPE-30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A-B1206PE, A-HD-N A-NOD-N, APG-100, APG-200
  • the addition amount of the compound containing a methacryloyl group or an acryloyl group in the molecule of the present invention is 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the resin having a repeating unit represented by the general formula (1). Is preferred. More preferably, they are 1 mass part or more and 20 mass parts or less, Most preferably, they are 2 mass parts or more and 15 mass parts or less.
  • an adhesion promoter such as an organosilicon compound, a silane coupling agent, and a leveling agent for imparting adhesion may be added as necessary.
  • an adhesion promoter such as an organosilicon compound, a silane coupling agent, and a leveling agent for imparting adhesion may be added as necessary. Examples of these are, for example, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl.
  • an adhesion promoter it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin of the present invention.
  • (G) Solvent The solvent is not particularly limited as long as it can dissolve the composition of the present invention. However, in order to prevent the solvent from evaporating more than necessary at the time of coating and precipitating the solid content of the composition at the time of coating, Solvents with the above boiling points are preferred. For example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound (preferably carbon And organic solvents such as alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, and amide solvents.
  • alkylene glycol monoalkyl ether carboxylate examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
  • alkylene glycol monoalkyl ether examples include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.
  • alkyl lactate examples include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
  • alkyl alkoxypropionate examples include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.
  • cyclic lactone examples include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -methyl- ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, and ⁇ -octano.
  • Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2 -Methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one 3-penten-2-one, cyclopentanone
  • alkylene carbonate examples include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
  • alkyl alkoxyacetate examples include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.
  • Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.
  • amide solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone and 1,3-dimethyl-2-imidazolidinone.
  • dimethyl sulfoxide and sulfolane are preferable.
  • N-methylpyrrolidone (NMP), ⁇ -butyrolactone (GBL), N, N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI) are more preferable solvents.
  • N, N-dimethylformamide (DMF) cyclopentanone, cyclohexanone, cycloheptanone and the like.
  • the total solid concentration in the photosensitive resin composition of the present invention is generally 10 to 40% by mass, more preferably 10 to 30% by mass, and still more preferably 15 to 30% by mass.
  • the photosensitive resin composition of the present invention the base polymer, a photoacid generator, and if necessary, photosensitizers, organic solvent, basic compound, surfactant, dissolution modifiers, ultraviolet absorbers, storage stability It can be prepared as a solution by mixing additives such as an agent and an antifoaming agent. The order and method of mixing are not particularly limited.
  • the photosensitive resin composition of the present invention may be a dry film.
  • the dry film can be prepared, for example, by applying the above solution onto a support such as metal or polyethylene terephthalate, drying, and then peeling off the support.
  • the support is a film of polyethylene terephthalate or the like, it can be used as it is as the photosensitive resin composition of the present invention.
  • a method for applying the photosensitive resin composition of the present invention on a support for example, spin coating, roll coating, flow coating, dip coating, spray coating, and a known method such as doctor coating.
  • the thickness of the applied film can be set according to the use, but is preferably 0.05 to 200 ⁇ m, more preferably 0.1 to 100 ⁇ m.
  • the film used as the support include polyethylene terephthalate, polypropylene, polyethylene, polyester, and polyvinyl alcohol.
  • the photosensitive resin composition of the present invention is a dry film
  • the photosensitive resin composition is coated with a protective film for the purpose of protecting the photosensitive resin composition from scratches, dust, chemicals, and the like. May be.
  • a protective film a polyethylene film, a polypropylene film, etc. are mentioned, for example, and the adhesive force with the photosensitive resin composition of this invention is smaller than a support body.
  • the dry film may be wound up into a roll.
  • the photosensitive resin composition of the present invention is a pattern forming material.
  • substrate For example, metal plates, such as aluminum, zinc, gold
  • the photosensitive resin composition of the present invention As a method for coating the photosensitive resin composition of the present invention on a substrate, when the photosensitive resin composition of the present invention is a solution, for example, spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating Known methods such as The thickness of the applied photosensitive film can be set according to the use, but is preferably 0.05 to 200 ⁇ m, more preferably 0.1 to 100 ⁇ m.
  • the photosensitive resin composition of the present invention is a dry film and there is a protective film, after the protective film is peeled off, the photosensitive resin composition layer is applied so as to directly touch the substrate, for example, a method of laminating Etc. By setting the temperature to 80 to 160 ° C.
  • the heat treatment in the next step can be omitted.
  • the substrate After applying the photosensitive resin composition of the present invention to a substrate, the substrate may be heated.
  • the heating method include known methods such as heating with a hot plate or an oven. By heating, it is possible to evaporate the organic solvent.
  • the heating temperature is preferably 80 ⁇ 160 ° C..
  • the photosensitive resin composition of the present invention is a dry film, this step can be omitted if heating is performed during lamination.
  • the photosensitive film can be irradiated with actinic rays or radiation using a photomask, a reduction projection exposure machine, a direct drawing machine or the like.
  • actinic rays or radiation examples include far-infrared rays, visible rays, g-rays, h-rays, i-rays and other near ultraviolet rays, KrF excimer lasers, ArF excimer lasers, DUV (far-ultraviolet rays), EUV (extreme ultraviolet rays), and electron beams. And X-rays. In a portion irradiated with radiation or the like, the photoacid generator is decomposed to generate an acid.
  • the substrate It is preferable to heat the substrate after irradiation.
  • the heating method include those used for heating after coating. By heating, the structure derived from the compound represented by the general formula (I) is eliminated from the compound having the group represented by the general formula (III), and the hydroxyl group or the carboxyl group is regenerated. The heating temperature is preferably 80 to 160 ° C. After heating, when the dry film is used, the support is removed, and when the dry film is not used, the development is performed with an alkaline developer to obtain a positive resist pattern. Examples of the developing method include known methods such as an immersion method, a paddle method, and a spray method.
  • alkaline developer examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.
  • a basic substance individually or in mixture of 2 or more types.
  • a suitable amount of a water-soluble organic solvent for example, an alcohol such as methanol or ethanol, or a surfactant can be added to the developer.
  • the substrate may be washed with water or heat-dried as necessary.
  • the pattern formed on the substrate may be a known pattern such as dry etching of the substrate with a chlorine-based gas, a fluorine-based gas (CF 4 / CH 2 F 2 mixed gas, etc.), an oxygen-based gas or the like using the pattern as a mask. It can be subjected to a process. Furthermore, this invention relates to the cured film obtained by heat-processing the said photosensitive resin composition.
  • a resin having a group represented by formula (III), all or part of the carboxyl groups of the polyimide precursor containing a repeating unit represented by the general formula (VIII) is formula (IV) All or part of the hydroxyl group of the polyimide precursor substituted with the group represented by the formula (II) or the polybenzoxazole precursor containing the repeating unit represented by the formula (IX) is represented by the formula (III)
  • a polyimide film or a polybenzoxazole film having excellent film characteristics can be formed by heat-treating the obtained pattern to form an imidized or oxazolated film.
  • the heating temperature is preferably 250 to 400 ° C.
  • the photosensitive resin composition of this invention is excellent in the stability in the heating process of the photosensitive film
  • the present invention also relates to a cured relief pattern and a method for producing the same.
  • the cured relief pattern of the present invention is (A) forming the photosensitive film on a substrate; (A) a step of exposing the photosensitive film with actinic rays or radiation; (C) It can be produced by a production method comprising a step of developing so as to remove an exposed portion of the photosensitive film with an aqueous alkaline developer, and (d) a step of heat-treating the obtained relief pattern. .
  • the photosensitive resin composition of the present invention is applied on a semiconductor element so that the thickness after heat curing becomes a predetermined thickness (for example, 0.1 to 30 ⁇ m), prebaked, exposed, developed, and heat cured.
  • a predetermined thickness for example, 0.1 to 30 ⁇ m
  • Synthesis Example 5 Synthesis of 2-acetyl-1-chloro-1-methoxypropane The same reaction as in Synthesis Example 1 except that 2-acetylpropionaldehyde was used instead of 2-phenylpropionaldehyde in Synthesis Example 1. And 2-acetyl-1-chloro-1-methoxypropane (a-5) was obtained as a transparent liquid.
  • Synthesis Example 6 Synthesis of 1-chloro-2- (ethoxycarbonyl) -1-methoxypropane Synthesis Example 1 except that 2- (ethoxycarbonyl) propionaldehyde was used instead of 2-phenylpropionaldehyde in Synthesis Example 1.
  • Synthesis Example 8 Synthesis of 1-chloro-2-cyano-1-methoxypropane The same reaction as in Synthesis Example 1 except that 2-cyanopropionaldehyde was used instead of 2-phenylpropionaldehyde in Synthesis Example 1. 1-Chloro-2-cyano-1-methoxypropane (a-8) was obtained as a transparent liquid.
  • Synthesis Example 9 Synthesis of 1,2-dichloro-1-methoxypropane A reaction was conducted in the same manner as in Synthesis Example 1 except that 2-chloropropionaldehyde was used instead of 2-phenylpropionaldehyde in Synthesis Example 1. 1,2-Dichloro-1-methoxypropane (a-9) was obtained as a transparent liquid.
  • Synthesis Example 10 Synthesis of 1-chloro-1- (cyclohexyloxy) -2-phenylpropane The same reaction as in Synthesis Example 2 was conducted except that cyclohexanol was used in place of 2-methoxyethanol in Synthesis Example 2. 1-chloro-1- (cyclohexyloxy) -2-phenylpropane (a-10) was obtained as a transparent liquid. (Synthesis Example 11) Synthesis of 1-chloro-1-phenoxy-2-phenylpropane A reaction was conducted in the same manner as in Synthesis Example 2 except that phenol was used instead of 2-methoxyethanol in Synthesis Example 2. -1-Phenoxy-2-phenylpropane (a-11) was obtained as a transparent liquid.
  • Example 1 to 13 and Comparative Examples 1 and 2 Storage Stability Test of Protective Agents 5 g of the protective agents obtained in Synthesis Examples 1 to 13 and Comparative Synthesis Examples 1 and 2 were each filled into a 10 ml glass vial, After sealing, it was aged for 15 days in a constant temperature layer at 50 ° C. The remaining amount of the protective agent was quantified from 1 H-NMR measurement (deuterated chloroform, internal standard: trimethoxybenzene) after the lapse of time, and the residual rate after aging was calculated based on the amount of the protective agent before the lapse of time. The results are shown in Table 1.
  • Comparative Examples 1 and 2 using a protective agent that does not satisfy the general formula (I) have a small residual rate after aging.
  • Examples 1 to 13 using the protective agent represented by the general formula (I) have a high residual ratio after aging and are extremely excellent in storage stability.
  • Example 17 Protection of hydroxyl group of m-cresol by 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane (a-2) 10.0 g of m-cresol was dissolved in 30 ml of tetrahydrofuran, After cooling to 0 ° C., 22.2 g of 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane was added, and 11.2 g of triethylamine was added dropwise over about 10 minutes with stirring. After completion of dropping, the mixture was stirred for about 2 hours.
  • a mixed solution of AIBN / propylene glycol monomethyl acetate 0.15 g / 0.3 g was added twice every 30 minutes and aged at 80 ° C. for 2 hours to complete the polymerization reaction.
  • the obtained resin solution was purified by reprecipitation with hexane to obtain 79 g of a white solid (d-1).
  • the weight average molecular weight of the solid was 7,500.
  • a mixed solution of AIBN / propylene glycol monomethyl acetate 0.15 g / 0.3 g was added twice every 30 minutes and aged at 80 ° C. for 2 hours to complete the polymerization reaction.
  • the obtained resin solution was purified by reprecipitation with hexane to obtain 83 g of a white solid (d-2).
  • the weight average molecular weight of the solid was 8,200.
  • Example 20 1-chloro-1-methoxy-2-phenylpropane according polyhydroxystyrene polyhydroxystyrene protected weight average molecular weight of 20,000 of the hydroxyl groups (manufactured by Aldrich) 2.7 g of N, N-dimethyl Dissolve in 17.5 ml of acetamide, add 2.04 g of 1-chloro-1-methoxy-2-phenylpropane to this solution, stir to dissolve completely, then add 2.23 g of triethylamine to about 30 with stirring. Added dropwise over a period of minutes. After completion of dropping, the mixture was stirred for about 3 hours.
  • Example 21 Protection of hydroxyl group of polyhydroxystyrene by 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane 2.7 g of polyhydroxystyrene (Aldrich) having a weight average molecular weight of 20,000 was used. After dissolving in 17.5 ml of N, N-dimethylacetamide and adding 2.52 g of 1-chloro-1- (2-methoxyethoxy) -2-phenylpropane to this solution and stirring to dissolve completely, While stirring, 2.23 g of triethylamine was added dropwise over about 30 minutes. After completion of dropping, the mixture was stirred for about 3 hours.
  • Example 22 Protection of carboxyl group of polyamic acid by 1-chloro-1-methoxy-2-phenylpropane
  • 250.0 g of the polyamic acid solution obtained in Synthesis Example 16 was equipped with a thermometer, a stirrer, and a nitrogen introduction tube. Then, 124.0 g of NMP was added and cooled, and 28.51 g of N, N-diisopropylethylamine was added at 0 ° C. or lower, followed by 37.60 g of 1-chloro-1-methoxy-2-phenylpropane.
  • the reaction solution was added to 1.5 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 29.96 g of a white solid (g-2).
  • the solid was dissolved in deuterated DMSO, and the 1 H-NMR spectrum was measured. From the peak integration ratio of the carboxylic acid ester to the carboxylic acid, 96% of the carboxyl groups were converted to 1- (2-methoxyethoxy) -2-phenylpropoxy groups. It was found that it was replaced.
  • the weight average molecular weight of the obtained resin was 24,400.
  • reaction solution was added to 1.5 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 22.95 g of a white solid (g-14).
  • the solid was dissolved in deuterated DMSO and 1 H-NMR spectrum was measured. From the peak integration ratio of the carboxylic acid ester and carboxylic acid, it was found that 77% of the carboxyl groups were substituted with 1-ethoxyethyl groups. The weight average molecular weight of the obtained resin was 20,900.
  • reaction solution was added to 1.5 L of isopropanol, and the precipitated solid was collected by filtration and dried to obtain 23.77 g of a white solid (g-15).
  • the solid was dissolved in heavy DMSO and 1 H-NMR spectrum was measured. From the peak integral ratio of carboxylic acid ester and carboxylic acid, 89% of the carboxyl groups were substituted with 1-methoxy-2-methylpropyl groups. I understood.
  • the weight average molecular weight of the obtained resin was 21,300.
  • the resulting polyhydroxyamide had a weight average molecular weight of 18,000.
  • Example 24 Protection of hydroxyl group of polyhydroxyamide by 1-chloro-1-methoxy-2-phenylpropane
  • 20 g of polyhydroxyamide obtained above and 200 g of ethyl acetate After stirring and dissolving, 99.4 g of 1-chloro-1-methoxy-2-phenylpropane was added, and then 20.5 g of triethylamine was stirred at room temperature for 1 hour. Thereafter, the reaction solution was transferred to a separating funnel and separated into an organic phase and an aqueous phase.
  • the precipitate is collected, washed with n-hexane and pure water, dried under reduced pressure, and 21.5 g of a white solid (h-14). Got. From the 1 H-NMR spectrum, it was found that 30 mol% of the hydroxyl groups were substituted with 1-ethoxyethyl groups. The weight average molecular weight of the target product was 19,300.
  • the precipitate is recovered, washed with n-hexane and pure water, dried under reduced pressure, and 22.0 g of a white solid (h-15). Got. From the 1 H-NMR spectrum, it was found that 38 mol% of the hydroxyl groups were substituted with 1-methoxy-2-methylpropyl groups. The weight average molecular weight of the target product was 19,800.
  • the protective agent described in Table 2 below and a compound (or resin) that can be protected by reacting therewith, the protective body described in Table 2 below was produced by the same synthesis method as described above.
  • the protection ratio (mol%) in the table is a value measured by 1 H-NMR spectrum.
  • PAI-101 ⁇ - (p-Tolylsulfonyloxyimino) -4-methoxyphenylacetonitrile (Midori Chemical Co., Ltd.)
  • NAI-105 N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide (manufactured by Midori Chemical Co., Ltd.)
  • TESPEC triethoxysilylpropyl ethyl carbamate
  • EOA amine of the following structure
  • PF6320 (made by OMNOVA, fluorine type)
  • PGMEA Propylene glycol monomethyl ether acetate
  • DMAc N, N-dimethylacetamide
  • a pattern was formed by the following method, and the pattern shape was evaluated.
  • ⁇ Pattern formation method> The prepared photosensitive resin composition was spin-coated on a 4 inch silicon wafer, subjected to pre-drying of 120 ° C. 3 minutes on a hot plate to give a film thickness of 5.0 ⁇ m film (photosensitive film).
  • pattern exposure was performed using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon, Inc.) using a 1-30 ⁇ m via hole repeating pattern mask.
  • ⁇ Sensitivity> The obtained pattern film was observed with a length measurement SEM (Hitachi, Ltd. S-8840), and the exposure amount obtained by resolving the via hole having the smallest dimension was defined as sensitivity.
  • a less than 100 mJ / cm 2 was A, 100 mJ / cm 2 or more.
  • 500 mJ / cm 2 less than the B, and 500 mJ / cm 2 or more was C.
  • a and B were set to pass.
  • Comparative Examples 29 to 38 are all inferior in resolution, and Comparative Examples 35 to 38 with respect to the cured relief pattern are also inferior in sensitivity.
  • the patterns obtained from the photosensitive resin compositions obtained in Examples 110 to 145 are excellent in both resolution and sensitivity.
  • Examples 146 to 169 of the cured relief pattern are both excellent in resolution and sensitivity.
  • a carboxyl group or hydroxyl group protecting agent having excellent storage stability having excellent storage stability
  • the carboxyl group or hydroxyl group being protected by the protecting agent
  • a resin having excellent storage stability and the above-described protected product having excellent resolution and sensitivity.
  • Photosensitive resin composition containing the resin, pattern forming material using the photosensitive resin composition, photosensitive film, and cured film, and method for producing a cured relief pattern using the photosensitive resin composition, The cured relief pattern obtained by the above and a semiconductor device comprising the cured relief pattern can be provided.

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Abstract

L'invention concerne : un protecteur de groupes carboxyle ou de groupes hydroxyle ayant une excellente stabilité de stockage ; une résine dans laquelle des groupes carboxyle ou des groupes hydroxyle sont protégés par le protecteur, la résine ayant une excellente stabilité au stockage ; une composition de résine photosensible contenant la résine protégée, la composition de résine photosensible ayant une excellente résolution et une excellente sensibilité ; une matière de formation de motif, un film photosensible et un film durci dans lequel la composition de résine photosensible est utilisée ; et un procédé de fabrication d'un motif en relief durci, le motif en relief durci étant obtenu par ce procédé et un dispositif semi-conducteur comportant le motif en relief durci, dans lequel la composition de résine photosensible est utilisée. L'invention concerne un protecteur de groupes hydroxyle ou de groupes carboxyle, lequel protecteur est un composé représenté par la formule générale (I). (Dans la formule générale, R1 et R2 représentent chacun indépendamment un groupe alkyle, un groupe cycloalkyle, un groupe aryle, un groupe aralkyle, un groupe alcoxy, un groupe aryloxy, un groupe acyle, un groupe alcoxycarbonyle, un groupe aryloxycarbonyle, un groupe cyano ou un atome d'halogène, R1 et/ou R2 représentant un groupe aryle, un groupe alcoxy, un groupe aryloxy, un groupe acyle, un groupe alcoxycarbonyle, un groupe aryloxycarbonyle, un groupe cyano ou un atome d'halogène. R3 représente un groupe alkyle, un groupe cycloalkyle, un groupe aryle ou un groupe aralkyle. R1 et R2 peuvent être reliés ensemble pour former un cycle, ou R1 ou R2 peut se lier à R3 pour former un cycle. X représente un groupe qui peut être désorbé par l'action des groupes hydroxyle ou des groupes carboxyle).
PCT/JP2013/058366 2012-03-23 2013-03-22 Protecteur, procédé de fabrication d'un composé protégé par le protecteur, résine protégée par le protecteur, composition de résine photosensible contenant la résine protégée par le protecteur, matière de formation de motif, film photosensible, motif en relief durci, son procédé de fabrication et dispositif semi-conducteur WO2013141376A1 (fr)

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JP2015068855A (ja) * 2013-09-26 2015-04-13 東京応化工業株式会社 レジスト組成物、レジストパターン形成方法
WO2016056448A1 (fr) * 2014-10-07 2016-04-14 国立大学法人九州大学 Agent introduisant un groupe protecteur destiné à un groupe hydroxy et/ou à un groupe mercapto
WO2016104455A1 (fr) * 2014-12-26 2016-06-30 富士フイルム株式会社 Composition de résine de polyamide et article moulé de résine de polyamide
JP2016212380A (ja) * 2015-04-28 2016-12-15 富士フイルム株式会社 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置、有機エレクトロルミネッセンス表示装置およびタッチパネル
WO2017115606A1 (fr) * 2015-12-28 2017-07-06 富士フイルム株式会社 Composition de résine photosensible, procédé de production de film durci, film durci, dispositif d'affichage à cristaux liquides, dispositif d'affichage électroluminescent organique, et panneau tactile
JP2017181895A (ja) * 2016-03-31 2017-10-05 東京応化工業株式会社 化学増幅型ポジ型感光性樹脂組成物
US20220002488A1 (en) * 2019-03-15 2022-01-06 Fujifilm Corporation Curable resin composition, cured film, laminate, method for manufacturing cured film, semiconductor device, and polymer precursor
WO2022044521A1 (fr) * 2020-08-27 2022-03-03 富士フイルム株式会社 Procédé de fabrication d'un produit durci, composition de résine, solution de développement, procédé de fabrication de corps stratifié, et procédé de fabrication de dispositif à semi-conducteur
CN116178145A (zh) * 2022-12-26 2023-05-30 徐州博康信息化学品有限公司 一种含氟光刻胶树脂单体及其中间体的制备方法

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WO2017115606A1 (fr) * 2015-12-28 2017-07-06 富士フイルム株式会社 Composition de résine photosensible, procédé de production de film durci, film durci, dispositif d'affichage à cristaux liquides, dispositif d'affichage électroluminescent organique, et panneau tactile
JPWO2017115606A1 (ja) * 2015-12-28 2018-08-02 富士フイルム株式会社 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置、有機エレクトロルミネッセンス表示装置およびタッチパネル
JP2017181895A (ja) * 2016-03-31 2017-10-05 東京応化工業株式会社 化学増幅型ポジ型感光性樹脂組成物
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CN116178145A (zh) * 2022-12-26 2023-05-30 徐州博康信息化学品有限公司 一种含氟光刻胶树脂单体及其中间体的制备方法

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