WO2017170182A1 - Photosensitive composition and novel compound - Google Patents

Photosensitive composition and novel compound Download PDF

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Publication number
WO2017170182A1
WO2017170182A1 PCT/JP2017/011885 JP2017011885W WO2017170182A1 WO 2017170182 A1 WO2017170182 A1 WO 2017170182A1 JP 2017011885 W JP2017011885 W JP 2017011885W WO 2017170182 A1 WO2017170182 A1 WO 2017170182A1
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group
carbon atoms
photosensitive composition
substituent
represented
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PCT/JP2017/011885
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French (fr)
Japanese (ja)
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依純 松井
光裕 岡田
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株式会社Adeka
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Priority to CN201780005927.6A priority Critical patent/CN108473609B/en
Priority to KR1020187015982A priority patent/KR102316645B1/en
Priority to JP2018509214A priority patent/JP6889151B2/en
Publication of WO2017170182A1 publication Critical patent/WO2017170182A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms
    • C07D251/34—Cyanuric or isocyanuric esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/20—Spiro-condensed systems
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators

Definitions

  • the present invention relates to a photosensitive composition containing a compound having a specific structure, which is inactive at room temperature and is activated by heating to a predetermined temperature to exhibit a function, and a novel compound. Furthermore, the present invention relates to a colored photosensitive composition obtained by adding a colorant to the photosensitive composition, and a color filter using the colored photosensitive composition.
  • Patent Documents 1 to 4 In order to improve the weather resistance and heat resistance of the photosensitive composition, a method of stabilizing by adding an ultraviolet absorber or an antioxidant is known (Patent Documents 1 to 4).
  • Phenolic antioxidants and UV absorbers have the effect of trapping radicals that greatly affect the deterioration of the polymer, so adding them into the polymerization system generally acts as a so-called polymerization inhibitor and inhibits curing. Therefore, latent additives have been developed (Patent Document 5).
  • a composition using a conventional latent additive has a large amount of outgas, so that there is a problem that the heating device is contaminated or the physical properties of the composition are lowered. There are problems of contamination of equipment and reduction of physical properties.
  • the composition using the conventional latent additive has a problem that the cured product has low solvent resistance, and thus the cured product is eluted, and the luminance of the color filter is lowered, for example.
  • Patent Document 6 discloses a triallylphenol compound useful as a curing agent, but does not suggest a photosensitive composition containing the triallylphenol compound.
  • JP 2011-048382 A US Patent Application Publication No. 2016/016919 JP2015-108649A JP2015-132791A International Publication No. 2014/021023 Japanese Patent Laid-Open No. 3-232732
  • an object of the present invention is to use a compound that is inactive at normal temperature and activated by heating to a predetermined temperature and that exhibits a function as an antioxidant or an ultraviolet absorber, and has a low outgas.
  • the object is to provide a photosensitive composition having high solvent resistance.
  • Another object of the present invention is to provide a colored photosensitive composition obtained by adding a colorant to the photosensitive composition, particularly a colored photosensitive composition suitable for a color filter.
  • a photosensitive composition using a compound having a specific protecting group has less outgas, and the cured product has high solvent resistance. It was found that a colored photosensitive composition obtained by adding a colorant to a photosensitive composition is suitable for a color filter for an image display device such as a liquid crystal display panel without reducing the luminance of an optical filter (particularly a color filter).
  • the present invention has been reached.
  • the present invention has been made based on the above findings, and provides a photosensitive composition containing a compound having a substituent represented by the following general formula (1).
  • R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an alkyl having 1 to 40 carbon atoms which may have a substituent
  • An aryl group having 6 to 20 carbon atoms which may have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, or a substituent In some cases represents a C2-C20 heterocyclic-containing group or a trialkylsilyl group
  • the methylene group in the alkyl group or arylalkyl group represented by R 1 and R 2 is —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO—.
  • R' is a hydrogen atom or a carbon atom Represents an alkyl group of 1 to 8, j represents a number from 1 to 3, * Means that it is bonded to an adjacent group at the * part. )
  • the photosensitive composition of the present invention contains a compound having a substituent represented by the above general formula (I).
  • n represents an integer of 1 to 10
  • X 1 represents an n-valent linking group
  • R 1 , R 2 and j are the same as in the general formula (I).
  • Examples of the halogen atom represented by R 1 and R 2 include fluorine, chlorine, bromine and iodine.
  • Examples of the alkyl group having 1 to 20 carbon atoms represented by R 1 and R 2 include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl Tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, adamantyl and the like,
  • Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R 1 and R 2 include benzyl, 1-methyl-1-phenylethyl, 1-naphthylmethyl, 9-anthracenylmethyl, 9-fluorenyl, 3 -Phenylpropyl, methyl-2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, phenethyl, styryl, cinnamyl and the like,
  • Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R 1 and R 2 include a pyridine ring, a pyrimidine ring, a pyridazine ring, a piperidine ring, a pyran ring, a pyrazoline ring, a triazine ring, a pyrroline ring, a quinoline ring, Isoquinoline ring, imidazoline ring, benzimi
  • alkyl group having 1 to 8 carbon atoms represented by R ′ examples include those satisfying a predetermined number of carbon atoms among the above alkyl groups represented by R 1 . Containing an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic ring having 2 to 20 carbon atoms represented by R 1 and R 2 Substituents for substituting groups include ethylenically unsaturated groups such as vinyl, allyl, acryl and methacryl; halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl and methacryloyl Acyl groups such as phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoro
  • R 1 and R 2 a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms are preferable because of less outgassing. It is more preferable that R 1 and R 2 are either a hydrogen atom or a branched alkyl group having 1 to 8 carbon atoms, particularly a t-butyl group, because outgas is small.
  • X 1 represents an n-valent linking group. Specifically, for example, a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, the following (I -a) or (I-b), a group represented by, -CO -, - NH-CO -, - CO-NH -, - NR 3 -, - oR 3, -SR 3, -NR 3 R 4, Or an aliphatic hydrocarbon group having 1 to 120 carbon atoms which may have a substituent having the same valence as n, and 6 to 35 carbon atoms which may have a substituent.
  • R 3 and R 4 have a hydrogen atom or a substituent.
  • n is 3
  • X 1 is an oxygen atom or a sulfur atom, —CO— , —NH—CO—, —CO—NH— or —NR 3 —
  • n is 2
  • X 1 is a hydrogen atom, —OR 3 , —SR 3 or —NR 3 R 4 , n is 1 and X 1 may form a ring together with the benzene ring.
  • the n groups are the same or different from each other.
  • the value of n is 1 to 10, and preferably 2 to 6 from the viewpoint of low outgas.
  • the aliphatic hydrocarbon group having 1 to 120 carbon atoms which may have a substituent represented by X 1 in the general formula (IA) and having the same valence as n is n are monovalent, for example, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3- Alkyl such as hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl
  • Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, which may have a substituent having the same valence as n are those in which n is monovalent, such as benzyl, phenethyl, diphenylmethyl, Arylalkyl groups such as triphenylmethyl, styryl and cinnamyl; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; arylthio groups such as phenylthio and naphthylthio; and these groups are substituted by substituents described later Group, etc.
  • n is divalent, arylene groups such as phenylene and naphthylene; residues of bifunctional phenols such as catechol and bisphenol; 2,4,8,10-tetraoxaspiro [5,5] undecane and the like; A group in which the group is substituted by a substituent described later,
  • Examples of the trivalent n include phenyl-1,3,5-trimethylene and groups in which these groups are substituted with a substituent described later.
  • the heterocycle-containing group having 2 to 35 carbon atoms that may have a substituent having the same number of valences as n includes those in which n is monovalent, pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl , Pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyo
  • Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent represented by R 3 and R 4 include the aliphatic hydrocarbon group represented by X 1 and the aliphatic hydrocarbon group.
  • Examples of the heterocyclic ring-containing group include an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and a heterocyclic ring-containing group having 2 to 35 carbon atoms represented by the above X 1 and these groups and substituents described later.
  • substituents include ethylenically unsaturated groups such as vinyl, allyl, acryl and methacryl; halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl and phenylcarbonyl ( Benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl, etc .; acetyloxy, benzoyloxy, etc.
  • X 1 when n is 2 to 6, X 1 can also be represented by the following general formulas (1) to (5), respectively.
  • Y 1 represents a single bond, —CR 5 R 6 —, —NR 7 —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, or 6 to 35 carbon atoms.
  • the aliphatic hydrocarbon group has —O—, —S—, —CO—, —COO—, —OCO—, —NH—, —SO 2 —, —CONH— or —NHCO—, or an oxygen atom.
  • Z 1 and Z 2 are each independently a direct bond, —O—, —S—,> CO, —CO—O—, —O—CO—, —SO 2 —, —SS—, —SO—,
  • R 5 , R 6 and R 7 may each independently have a hydrogen atom, a substituent, or an aliphatic hydrocarbon group having 1 to 35 carbon atoms or a substituent.
  • R 8 represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms
  • R 9 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom
  • the alkyl group, alkoxy group and alkenyl group are substituents.
  • May have f is an integer from 0 to 5, * Means that it is bonded to an adjacent group at the * part.
  • R 10 and R 11 are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a carbon atom having 6 substituents which may have a substituent.
  • the methylene group in the alkyl group and arylalkyl group may be replaced with an unsaturated bond, —O— or —S—, R 10 may form a ring with adjacent R 10 , p
  • Y 11 represents a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, or 6 to 35 carbon atoms.
  • Z 1 , Z 2 and Z 3 are each independently a direct bond, —O—, —S—, —CO—, —CO—O—, —O—CO—, —SO 2 —, —SS—
  • R 12 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, or an aromatic carbon group having 6 to 35 carbon atoms which may have a substituent.
  • the aliphatic hydrocarbon group includes a carbon-carbon double bond, —O—, —S—, —CO—, —COO—, —OCO—, —NH—, —SO 2 —, —CONH— or —NHCO—.
  • the oxygen atom may be replaced by a linking group combining these without being adjacent to each other, * Means that it is bonded to an adjacent group at the * part.
  • Y 12 represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or 2 carbon atoms. Represents ⁇ 35 heterocycle-containing groups,
  • the aliphatic hydrocarbon group is a carbon-carbon double bond, —O—, —S—, —CO—, —COO—, —OCO—, —NH—, —SO 2 —, —CONH— or —NHCO.
  • Z 1 to Z 4 are each independently a group in the same range as the group represented by Z 1 to Z 3 in the general formula (2), * Means that it is bonded to an adjacent group at the * part. )
  • Y 13 represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a complex having 2 to 20 carbon atoms. Represents a ring-containing group, The aliphatic hydrocarbon group is a carbon-carbon double bond, —O—, —S—, —CO—, —COO—, —OCO—, —NH—, —SO 2 —, —CONH— or —NHCO.
  • Z 1 to Z 5 are each independently a group in the same range as the group represented by Z 1 to Z 3 in the general formula (2), * Means that it is bonded to an adjacent group at the * part. )
  • Y 14 represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a complex having 2 to 35 carbon atoms. Represents a ring-containing group, The aliphatic hydrocarbon group is a carbon-carbon double bond, —O—, —S—, —CO—, —COO—, —OCO—, —NH—, —SO 2 —, —CONH— or —NHCO.
  • Z 1 to Z 6 are each independently a group in the same range as the group represented by Z 1 to Z 3 in the general formula (2), * Means that it is bonded to an adjacent group at the * part. )
  • the aliphatic hydrocarbon group having 1 to 35 carbon atoms, which may have a substituent, represented by R 5 , R 6 and R 7 includes the above general formula ( The monovalent aliphatic hydrocarbon group exemplified as the n-valent linking group represented by X 1 in IA), and the n valence represented by X 1 in the general formula (IA).
  • Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent represented by R 5 , R 6 and R 7 include X 1 in the above general formula (IA).
  • groups substituted by those exemplified as the substituents in the above those satisfying a predetermined number of carbon atoms, etc.
  • the heterocyclic group having 2 to 35 carbon atoms which may have a substituent represented by R 5 , R 6 and R 7 is represented by X 1 in the above general formula (IA).
  • monovalent heterocycle-containing groups exemplified as the n-valent linking group, and these groups are exemplified as substituents of the group representing the n-valent bond represented by X 1 in the general formula (IA).
  • those substituted by the above those satisfying a predetermined number of carbon atoms can be mentioned.
  • the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 1 in the general formula (1) is an n represented by X 1 in the general formula (IA).
  • Examples of the divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 1 include the divalent groups exemplified as the n-valent linking group represented by X 1 in the general formula (IA).
  • Examples of the divalent heterocyclic group having 2 to 35 carbon atoms represented by Y 1 include the divalent aromatic compounds exemplified as the n-valent linking group represented by X 1 in the general formula (IA). Of the ring-containing hydrocarbon groups and groups substituted by those exemplified as the substituents of the group representing the n-valent linking group represented by X 1 in the general formula (IA) And the like satisfying the number of carbon atoms.
  • examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R 8 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and the like.
  • the alkyl group having 1 to 10 carbon atoms represented by R 9 satisfies the predetermined number of carbon atoms among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R 1 and R 2. Groups, etc.
  • Examples of the alkoxy group having 1 to 10 carbon atoms represented by R 9 include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy Hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, etc.
  • the substituents of the phenyl group, cycloalkyl group, alkyl group, alkoxy group and alkenyl group are the same as those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA). is there.
  • the alkyl group having 1 to 10 carbon atoms, which may have a substituent, represented by R 10 and R 11 includes R 1 and R 2 Among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by the following: Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent represented by R 10 and R 11 include an aryl group having 6 to 20 carbon atoms represented by R 1 and R 2 And the groups exemplified as Examples of the aryloxy group having 6 to 20 carbon atoms which may have a substituent represented by R 10 and R 11 include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy 4-methylphenyloxy, 4-vinylphenyldioxy, 3-iso-propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hex
  • arylthio group having 6 to 20 carbon atoms which may have a substituent represented by R 10 and R 11 is an arylthio group having 6 to 20 carbon atoms which may have the above-mentioned substituent.
  • the arylalkenyl group having 8 to 20 carbon atoms which may have a substituent, represented by R 10 and R 11 , may have 6 to 20 carbon atoms which may have the above-mentioned substituent.
  • Examples of the trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 11 in the general formula (2) include an n-valent bond represented by X 1 in the general formula (IA).
  • those satisfying the predetermined number of carbon atoms include trivalent groups substituted with Z 1 , Z 2 and Z 3 , etc.
  • Examples of the trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms represented by Y 11 in the general formula (2) include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecanyl, 1-adamantyl, 2- Adamantyl, noradamantyl, 2-methyladamantyl, norbornyl, isonorbornyl, perhydronaphthyl, perhydroanthracenyl, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1.
  • Examples of the trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 11 include the trivalent groups exemplified as the n-valent linking group represented by X 1 in the general formula (IA). Of the aromatic ring-containing hydrocarbon group and a group in which these groups are substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA). And those that satisfy the number of atoms.
  • Examples of the trivalent heterocyclic group having 2 to 35 carbon atoms represented by Y 11 include the trivalent complex exemplified as the n-valent linking group represented by X 1 in the general formula (IA).
  • the tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 12 in the general formula (3) is an n-valent aliphatic hydrocarbon group represented by X 1 in the general formula (IA).
  • X 1 n-valent aliphatic hydrocarbon group represented by X 1 in the general formula (IA).
  • Examples of the tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 12 include the monovalent groups exemplified as the n-valent linking group represented by X 1 in the general formula (IA). To a trivalent aromatic ring-containing hydrocarbon group and a group in which these groups are substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA).
  • Examples of the tetravalent heterocyclic group having 2 to 35 carbon atoms represented by Y 12 include monovalent to 3 exemplified as the n-valent linking group represented by X 1 in the general formula (IA).
  • a valent heterocyclic ring-containing group and a tetravalent group derived from these groups substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA).
  • those satisfying a predetermined number of carbon atoms can be mentioned.
  • the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 13 in the general formula (4) is an n-valent bond represented by X 1 in the general formula (IA).
  • the monovalent to trivalent aliphatic hydrocarbon groups exemplified as the groups and these groups are substituted by those exemplified as the substituents of the n-valent linking group represented by X 1 in the general formula (IA).
  • the pentavalent groups derived from these groups those satisfying a predetermined number of carbon atoms, etc.
  • the pentavalent aromatic group-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 14 is a monovalent group exemplified as the n-valent linking group represented by X 1 in the general formula (IA).
  • Examples of the pentavalent heterocyclic group having 2 to 35 carbon atoms represented by Y 14 include monovalent to 3 exemplified as the n-valent linking group represented by X 1 in the general formula (IA).
  • a valent heterocyclic ring-containing group and a pentavalent group derived from these groups substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA).
  • the groups those satisfying a predetermined number of carbon atoms can be mentioned.
  • the hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 14 in the general formula (5) is an n-valent bond represented by X 1 in the general formula (IA).
  • the monovalent to trivalent aliphatic hydrocarbon groups exemplified as the groups and these groups are substituted by those exemplified as the substituents of the n-valent linking group represented by X 1 in the general formula (IA).
  • the hexavalent groups derived from these groups those satisfying a predetermined number of carbon atoms, etc.
  • the hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 14 is a monovalent group exemplified as the n-valent linking group represented by X 1 in the general formula (IA).
  • X 1 n-valent linking group represented by X 1 in the general formula (IA)
  • Examples of the hexavalent heterocyclic group having 2 to 35 carbon atoms represented by Y 14 include monovalent to 3 exemplified as the n-valent linking group represented by X 1 in the general formula (IA).
  • the groups those satisfying a predetermined number of carbon atoms can be mentioned.
  • each of R 82 , R 83 and R 84 independently has a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or a substituent, which may have 1 carbon atom.
  • R 92 and R 93 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an alkyl group having 1 to 40 carbon atoms, which may have a substituent, Represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms, wherein R 1 and R 2 are the same as those in the above general formula (I) .)
  • R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group,
  • Y 1 , Z 1 and Z 2 are the same as those in the general formula (1).
  • the aryl group the arylalkyl group having 7 to 20 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms, those exemplified in the description of R 1 and R 2 in the general formula (I) can be given. .
  • Examples of the arylalkyl group having 7 to 20 carbon atoms and the heterocyclic ring-containing group having 2 to 20 carbon atoms include those exemplified in the description of R 1 and R 2 in the general formula (I).
  • Examples of the alkyl group having 1 to 40 atoms, the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the heterocyclic-containing group having 2 to 20 carbon atoms include those represented by the general formula (I).
  • the thing illustrated by description of R ⁇ 1 > and R ⁇ 2 > in can be mentioned.
  • R 1 is a branched alkyl group having 1 to 8 carbon atoms, particularly a t-butyl group, and R 2 is a hydrogen atom;
  • R 82 , R 83 and R 84 are each independently a hydrogen atom,
  • An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, a heterocyclic-containing group having 1 to 10 carbon atoms, particularly R 82 , R 83 and R 84 are preferably an alkyl group having 1 to 4 carbon atoms or a heterocyclic ring-containing group having 1 to 10 carbon atoms.
  • R 1 is a branched alkyl group having 1 to 8 carbon atoms, particularly a t-butyl group, and R 2 is a hydrogen atom;
  • R 92 and R 93 are each independently a hydrogen atom or carbon atom number
  • An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, a heterocyclic-containing group having 1 to 10 carbon atoms, particularly R 92 or R 93 Is preferably an alkyl group having 1 to 4 carbon atoms or a heterocyclic-containing group having 1 to 10 carbon atoms.
  • Y 10 is a sulfur atom, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring-containing hydrocarbon group having 6 to 25 carbon atoms, the number of carbon atoms 2 to 21 divalent heterocyclic ring-containing groups, divalent groups derived from 2,4,8,10-tetraoxaspiro [5,5] undecane, particularly alkylene groups having 1 to 15 carbon atoms, A divalent aromatic ring-containing hydrocarbon group having 6 to 15 carbon atoms and a divalent group derived from 2,4,8,10-tetraoxaspiro [5,5] undecane are preferred, Z 1 and Z 2 are a direct bond, —CO—O—, —O—CO—, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or 6 to 10 carbon atoms.
  • an aromatic hydrocarbon group particularly an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent
  • Y 11 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or a carbon atom
  • Z 1 , Z 2 and Z 3 are preferably the same as Z 1 and Z 2
  • Y 12 is preferably a tetravalent group corresponding to the group listed above as preferred Y 11 , Z 1 to Z 4 are preferably
  • the production method of the compound having a substituent represented by the above general formula (I) is not particularly limited.
  • JP-A-57-111375, JP-A-3-173843, JP-A-6-128195, JP-A-6-128195 It can be obtained by reacting a phenolic compound produced by the methods described in JP-A-7-206871, JP-A-7-252191 and JP-T-2004-501128 with an allyl halide compound.
  • the compound having a substituent represented by the general formula (I) can be used as a latent additive in the photosensitive composition of the present invention.
  • the latent additive is inactive in a pre-bake process at room temperature or 150 ° C. or less, for example 150 ° C. or less, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. By heating, the protecting group is eliminated and becomes active.
  • the content of the compound having a substituent represented by the general formula (I) as a latent additive is 0.001 to 20 in the solid content of the composition of the present invention. % By mass is preferable, and 0.005 to 5% by mass is more preferable.
  • the photosensitive composition of the present invention is a composition whose properties are changed by light irradiation.
  • a positive resist is one that is soluble in a chemical reaction
  • a negative resist is one that is insoluble in a chemical reaction.
  • the photosensitive composition of the present invention contains a compound having a substituent represented by the above general formula (I) as a latent antioxidant, a polymerizable compound having an ethylenically unsaturated bond having an acid value, and light.
  • a radical polymerization initiator is contained as an essential component.
  • Examples of the polymerizable compound having an ethylenically unsaturated bond having an acid value include (meth) acrylic acid, ⁇ -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, and isocrotonic acid.
  • X 41 is a direct bond, an alkylene group having 1 to 4 carbon atoms which may have a substituent, or an alicyclic group having 3 to 20 carbon atoms which may have a substituent.
  • Hydrocarbon group, —O—, —S—, —SO 2 —, —SS—, —SO—, —CO—, —OCO— or a substitution represented by the above (1-1) to (1-3) Represents a group, R 41 , R 42 , R 43 and R 44 each independently have a hydrogen atom, a substituent or a C 1-5 alkyl group or a substituent.
  • polymerizable compounds having an ethylenically unsaturated bond having an acid value can be used alone or in admixture of two or more, and are polymerizable having an ethylenically unsaturated bond having no acid value. It can be used in combination with a compound. When two or more kinds are mixed and used, they may be copolymerized in advance and used as a copolymer.
  • the content of the polymerizable compound having an ethylenically unsaturated bond having an acid value is preferably 20 to 80% by mass in the solid content of the composition of the present invention. More preferred is 30 to 70% by mass.
  • Examples of the polymerizable compound having an ethylenically unsaturated bond having no acid value include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, The following compound No. A1-No.
  • A4 methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (
  • a monofunctional or polyfunctional epoxy compound can be used together with the polymerizable compound having an ethylenically unsaturated bond having the acid value.
  • the polymerizable compound having an ethylenically unsaturated bond having an acid value preferably has a solid content acid value of 5 to 120 mgKOH / g, and the amount of the monofunctional or polyfunctional epoxy compound used is It is preferable to select so as to satisfy the value.
  • Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecy
  • the polyfunctional epoxy compound it is preferable to use one or more selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a photosensitive composition with better characteristics can be obtained.
  • the bisphenol type epoxy compound an epoxy compound represented by the above general formula (III) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
  • glycidyl ethers examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1 , 10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (g Glycidyl oxymethyl) ethane, 1,1,1-tri (g
  • novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl-p-aminophenol and N, N-diglycidylaniline; hetero
  • the photo radical polymerization initiator may be any compound that can initiate radical polymerization upon receiving light irradiation.
  • ketones such as acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, etc.
  • preferred compounds include oxime compounds and oxime compounds.
  • acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl-2.
  • benzylic compound examples include benzyl and anisyl.
  • benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like.
  • thioxanthone compound examples include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.
  • oxime compound a compound represented by the following general formula (IV) or (V) is particularly preferable from the viewpoint of sensitivity and heat resistance.
  • R 51 and R 52 each independently have a hydrogen atom, a cyano group, a substituent, or an alkyl group having 1 to 20 carbon atoms or a substituent.
  • a certain aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent or a complex having 2 to 20 carbon atoms which may have a substituent Represents a ring-containing group
  • R 53 and R 54 are each independently a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R 55 , OR 56 , SR 57 , NR 58 R 59 , COR 60 , SOR 61 , SO 2 R 62 or CONR 63 R 64 , R 53 and R 54 may combine with each other to form a ring, R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62
  • alkyl groups aryl groups having 6 to 30 carbon atoms which may have substituents
  • arylalkyl groups having 7 to 30 carbon atoms which may have substituents or substituents
  • X 3 represents an oxygen atom, a sulfur atom, a selenium atom, CR 75 R 76 , CO, NR 77 or PR 78
  • X 4 represents a single bond or CO
  • R 75 to R 78 represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and methylene in the alkyl group or arylalkyl group
  • the group may be replaced by a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic group, or may be replaced
  • R 101 and R 102 each independently represent R 111 , OR 111 , COR 111 , SR 111 , CONR 112 R 113 or CN;
  • R 111 , R 112 and R 113 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom.
  • R 111 , R 112 and R 113 Represents a heterocyclic-containing group of formula 2 to 20,
  • the hydrogen atoms of the groups represented by R 111 , R 112 and R 113 are further R 121 , OR 121 , COR 121 , SR 121 , NR 122 R 123 , CONR 122 R 123 , —NR 122 —OR 123 , —NCOR 122.
  • R 121 , R 122 and R 123 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom Represents a heterocyclic-containing group of formula 2 to 20,
  • the hydrogen atom of the group represented by R 121 , R 122 and R 123 may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, a hydroxyl group or a carboxyl group,
  • the alkyl part of the group represented by R 111 , R 112 , R 113 , R 121 , R 122 , R 123 and R 124 may have a branched side chain or a cyclic alkyl.
  • R 103 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms.
  • the alkyl part of the group represented by R 103 may have a branched side chain or may be a cyclic alkyl, and R 103 and R 107 , R 103 and R 108 , R 104 and R 105 , R 105 and R 106 and R 106 and R 107 may be combined to form a ring, Hydrogen atoms in the group represented by R 103 may further R 121, OR 121, COR 121 , SR 121, NR 122 R 123, CONR 122 R 123, -NR 122 -OR 123, -NCOR 122 -OCOR 123, NR 122 COR 121 , OCOR 121 , COOR 121 , SCOR 121 , OCSR 121 , COSR 121 , CSOR 121 , hydroxyl group, nitro group, CN, halogen atom, or COOR 121 may be substituted, R 104 , R 105 , R 106 and R
  • radical photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyr-1-yl)] titanium Etc.
  • photo radical polymerization initiators can be used alone or in combination of two or more according to the desired performance.
  • the content of the radical photopolymerization initiator as described above is preferably 0.1 to 30% by mass, particularly preferably 0.5 to 10% by mass, based on the solid content of the photosensitive composition of the present invention.
  • the content of the photo radical polymerization initiator is less than 0.1% by mass, curing by exposure may be insufficient, and when it is greater than 30% by mass, the initiator is precipitated in the photosensitive composition. There is.
  • the photosensitive composition of the present invention can be made into a colored photosensitive composition by further adding a colorant.
  • the cured product of the colored photosensitive composition is suitably used as a color filter.
  • the addition amount of the colorant is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass in the solid content of the colored photosensitive composition of the present invention. .
  • the content of the colorant is less than 0.01% by mass, desired chromaticity may not be obtained.
  • the colorant may be precipitated in the colored photosensitive composition. .
  • the colorant examples include dyes and pigments.
  • the dye is not particularly limited as long as it is a compound having absorption at 380 to 1200 nm.
  • inorganic pigments or organic pigments can be used.
  • inorganic pigment or organic pigment commercially available pigments can also be used.
  • a solvent can be further added to the photosensitive composition and the colored photosensitive composition of the present invention.
  • the solvent is usually a solvent that can dissolve or disperse each of the above components as necessary, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc.
  • Ketones such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate Ester solvents such as n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; cellosolv solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol Alcohol solvents such as ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, diacetone alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-a
  • ketones, ether ester solvents, etc. particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable because the compatibility of the resist and the radical photopolymerization initiator is good in the photosensitive composition.
  • a solvent it is preferable from the viewpoint of handling and the like that the solid content of the photosensitive composition or colored photosensitive composition of the present invention is 25 to 35% by mass.
  • the photosensitive composition and the colored photosensitive composition of the present invention can further contain an inorganic compound.
  • the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper Etc.
  • a dispersant can be added.
  • the dispersant is not particularly limited as long as it can disperse and stabilize colorants and inorganic compounds, and commercially available dispersants such as BYK series manufactured by BYK Chemie can be used and have a basic functional group.
  • Polymer dispersing agent comprising polyester, polyether, polyurethane, having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH / Those having g are preferably used.
  • the photosensitive composition and the colored photosensitive composition of the present invention include, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine; plasticizers; Agents; fillers; antifoaming agents; leveling agents; surface conditioning agents; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants; UV absorbers; dispersion aids; Conventional additives such as an agent, a catalyst, an effect promoter, a cross-linking agent, and a thickener can be added.
  • thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine
  • plasticizers Agents
  • Fillers such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants
  • UV absorbers such as phenolic antioxidants, phos
  • the characteristics of the cured product of the photosensitive composition of the present invention and the colored photosensitive composition are improved by using another organic polymer together with the polymerizable compound having an ethylenically unsaturated bond having the acid value.
  • the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate.
  • Copolymer ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenolic resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, and the like.
  • polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are included. Masui.
  • a chain transfer agent a sensitizer, a surfactant, a silane coupling agent, a melamine compound, and the like can be further used in combination.
  • a sulfur atom-containing compound is generally used.
  • Alkyl compounds trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. C1, aliphatic polyfunctional thiol
  • the surfactant examples include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.
  • fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates
  • anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates,
  • silane coupling agent for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403 and the like, silane cups having an isocyanate group, a methacryloyl group, and an epoxy group. A ring agent is preferably used.
  • Examples of the melamine compound include all or part of active methylol groups (CH 2 OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified.
  • examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same or different.
  • methylol groups that are not alkyl etherified may be self-condensed within one molecule or may be condensed between two molecules, resulting in the formation of an oligomer component.
  • hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used.
  • alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.
  • the photosensitive composition and colored photosensitive composition of the present invention are prepared by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, and semiconductor substrate. It can be applied on a supporting substrate such as metal, paper, and plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base
  • the active light source used for curing the photosensitive composition and the colored photosensitive composition of the present invention those capable of emitting light having a wavelength of 300 to 450 nm can be used.
  • Mercury vapor arc, carbon arc, xenon arc, etc. can be used.
  • the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy.
  • the laser beam light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.
  • the photosensitive composition and the colored photosensitive composition of the present invention can also be patterned through a double patterning process in which patterning is performed twice using two photosensitive compositions or colored photosensitive compositions.
  • the method of curing the photosensitive composition or colored photosensitive composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, It includes a step of forming a coating film on a supporting substrate such as quartz glass, semiconductor substrate, metal, paper, plastic, and the like, and a step of exposing the coating film to exposure and curing the active light.
  • the photosensitive composition and the colored photosensitive composition (or cured product thereof) of the present invention are a photocurable paint or varnish, an adhesive such as a photocurable adhesive, a printed circuit board, a color television, a PC monitor, or portable information.
  • Color filters for color display liquid crystal display panels such as terminals and digital cameras, color filters for CCD image sensors, photo spacers, black column spacers, electrode materials for plasma display panels, touch panels, touch sensors, powder coatings, printing inks, printing To produce plates, dental compositions, stereolithography resins, gel coats, photoresists for electronics, electroplating resists, etching resists, both liquid and dry films, solder resists, and color filters for various display applications Or plasma display panel, electroluminescent display, and LC Resist for forming structures in the manufacturing process, composition for encapsulating electrical and electronic components, solder resist, magnetic recording materials, micromechanical components, waveguide, optical switch, plating mask, etching mask, color test Systems, glass fiber cable coatings, stencils
  • the photosensitive composition of the present invention can be used as a transparent structure by curing.
  • transparent structures include columnars called photo spacers (PS) and column spacers (CS); fine patterns of (nano) imprints; production of large advertising signs, color filters for liquid crystal displays, and alignment films
  • PS photo spacers
  • CS column spacers
  • fine patterns of (nano) imprints production of large advertising signs, color filters for liquid crystal displays, and alignment films
  • Examples thereof include an ink jet receiving layer used for manufacturing electronic devices such as printing.
  • the transparent structure of the present invention is suitably used for display devices.
  • the photosensitive composition of the present invention can be used for a transparent conductive film, a reflective film, a polarizing plate, a protective film, and the like, and each desired layer is sequentially applied to a transparent substrate and activated through a mask having a predetermined pattern shape. It can be used as a transparent laminate obtained by irradiating light, developing the exposed film with a developer, and heating the developed film. As a transparent laminated body, the thing etc. with which the transparent thin film layer and metal thin film layer which consist of a complex oxide of an indium oxide and a cerium oxide are alternated on the transparent base material are mentioned, for example.
  • the photosensitive composition of the present invention containing a compound having a substituent represented by the general formula (I) as a latent additive may be used for each of the above-described layers, and the photosensitive composition may be used for any of the layers.
  • a composition may be used.
  • the transparent laminate is suitably used for a display device.
  • the colored photosensitive composition of the present invention is used for the purpose of forming pixels of a color filter, and is particularly useful as a photosensitive composition for forming a color filter for a display device for an image display device such as a liquid crystal display panel. is there.
  • the color filter for a display device includes (1) a step of forming a coating film of the colored photosensitive composition of the present invention on a substrate, and (2) active light through a mask having a predetermined pattern shape on the coating film.
  • the step of irradiating, (3) the step of developing the film after exposure with a developer, and (4) the step of heating the film after development are preferably formed.
  • the colored photosensitive composition of the present invention is also useful as an inkjet-type colored photosensitive composition without a development step.
  • a multi-tone mask such as a halftone mask or a gray scale mask can be used.
  • novel compound of the present invention is represented by any of the following structures.
  • the production method of the novel compound of the present invention is not particularly limited.
  • a phenolic compound produced by the method described in each publication of JP-A-2004-501128 and an allyl halide compound can be obtained.
  • novel compound of the present invention can be used as a latent antioxidant, a latent ultraviolet absorber, a dissolution regulator and the like.
  • Example 1-1 Compound No. 1 Synthesis of Compound 1 Potassium carbonate (2 equivalents with respect to one phenol group) was added to a dimethylacetamide solution of 1 equivalent of 1 ′ phenol compound (3 times the theoretical yield), and the mixture was stirred at room temperature for 30 minutes. Allyl bromide (1.5 equivalent to one phenol group) was added, and the mixture was stirred at 60 ° C. for 5 hours. After adding ethyl acetate and washing with 1% hydrochloric acid solution, oil-water separation was performed, and after drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off and crystallization was performed. The obtained solid was dried under reduced pressure at 60 ° C. for 3 hours to obtain the desired product. It was confirmed by 1 H-NMR and IR that the obtained solid was the desired product. The results are shown in [Table 1] to [Table 2].
  • Example 1-1 Compound No. Synthesis of 2 to 6
  • the following compound No. instead of the phenol compound of 1 ′, the following compound No.
  • the target compound No. 2 was prepared in the same manner as in Example 1-1, except that 2 ′ to 6 ′ phenolic compounds were used. 2-6 were synthesized. It was confirmed by 1 H-NMR and IR that the obtained solid was the desired product. The results are shown in [Table 1] to [Table 2].
  • Example 2-1 and Comparative Evaluation Examples 2-1 and 2-2 Solvent Resistance Evaluation
  • the photosensitive composition No. obtained in Example 2-1 was used.
  • Comparative photosensitive composition Nos. 1 and 2 obtained in Comparative Examples 2-1 and 2-3. 1 and no. 3 were each coated on a glass substrate under conditions of 410 rpm ⁇ 7 seconds and dried on a hot plate (90 ° C. ⁇ 90 seconds).
  • the obtained coating film was exposed (40 mJ / cm 2 ) with an ultrahigh pressure mercury lamp.
  • the exposed coating film was baked under conditions of 230 ° C. ⁇ 30 minutes.
  • the film thickness of the obtained coating film After measuring the film thickness of the obtained coating film, it was immersed in PGMEA, cyclohexanone, N-methylpyrrolidone, and N-ethylpyrrolidone at room temperature for 30 minutes, and the film thickness after immersion was measured. It was evaluated that the solvent resistance was higher as the film thickness ratio before and after immersion (film thickness after immersion ⁇ 100 / film thickness before immersion) was closer to 100%.
  • comparative photosensitive composition No. containing no antioxidant was used.
  • a comparative photosensitive composition No. 1 containing a conventional phenolic antioxidant was used.
  • the photosensitive composition No. 1 using the compound according to the present application as a latent additive was used. It is clear that No. 1 maintains the same solvent resistance as when no antioxidant is contained.
  • the photosensitive composition using the compound of the present invention as a latent additive has less outgas and the cured product is excellent in solvent resistance.

Abstract

A photosensitive composition containing a compound having a substituent indicated by general formula (1). (In the formula, R1 and R2 each independently indicate a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, a C1-40 alkyl group that may have a substituent group, a C6-20 aryl group, a C7-20 arylalkyl group, a C2-20 heterocyclic ring-containing group, or a trialkylsilyl group. j indicates 1-3 and * indicates bonding with an adjacent group, at the * section.)

Description

感光性組成物及び新規化合物Photosensitive composition and novel compound
　本発明は、特定の構造を有し、常温では不活性であり所定の温度に加熱することにより活性化されて機能を発現する化合物を含有する感光性組成物、及び新規化合物に関する。更には、本発明は、該感光性組成物に着色剤を加えた着色感光性組成物及び該着色感光性組成物を用いたカラーフィルタに関する。 The present invention relates to a photosensitive composition containing a compound having a specific structure, which is inactive at room temperature and is activated by heating to a predetermined temperature to exhibit a function, and a novel compound. Furthermore, the present invention relates to a colored photosensitive composition obtained by adding a colorant to the photosensitive composition, and a color filter using the colored photosensitive composition.
　感光性組成物の耐候性や耐熱性を向上させるために、紫外線吸収剤や酸化防止剤を添加して安定化させる方法が知られている（特許文献１～４）。 In order to improve the weather resistance and heat resistance of the photosensitive composition, a method of stabilizing by adding an ultraviolet absorber or an antioxidant is known (Patent Documents 1 to 4).
　フェノール系酸化防止剤及び紫外線吸収剤は、ポリマーの劣化に大きく影響するラジカルをトラップする作用があるため、これらを重合系内に添加すると、一般に、いわゆる重合禁止剤として作用し、硬化阻害を起こすことが問題となっていることから、潜在性添加剤が開発されてきた（特許文献５）。 Phenolic antioxidants and UV absorbers have the effect of trapping radicals that greatly affect the deterioration of the polymer, so adding them into the polymerization system generally acts as a so-called polymerization inhibitor and inhibits curing. Therefore, latent additives have been developed (Patent Document 5).
　しかし、従来の潜在性添加剤を用いた組成物はアウトガスが多く、そのため、加熱装置が汚染されたり、組成物の物性が低下するという問題がある。装置の汚染や物性の低減化という問題がある。また、従来の潜在性添加剤を用いた組成物は、その硬化物の耐溶剤性が低く、そのため硬化物の溶出が起こり、例えばカラーフィルタの輝度を低下させるという問題もある。 However, a composition using a conventional latent additive has a large amount of outgas, so that there is a problem that the heating device is contaminated or the physical properties of the composition are lowered. There are problems of contamination of equipment and reduction of physical properties. Moreover, the composition using the conventional latent additive has a problem that the cured product has low solvent resistance, and thus the cured product is eluted, and the luminance of the color filter is lowered, for example.
　また、特許文献６には、硬化剤として有用なトリアリルフェノール化合物が開示されているが、該トリアリルフェノール化合物を含有する感光性組成物は示唆されていない。 Also, Patent Document 6 discloses a triallylphenol compound useful as a curing agent, but does not suggest a photosensitive composition containing the triallylphenol compound.
特開２０１１－０４８３８２号公報JP 2011-048382 A 米国特許出願公開第２０１６／０１６９１９号明細書US Patent Application Publication No. 2016/016919 特開２０１５－１０８６４９号公報JP2015-108649A 特開２０１５－１３２７９１号公報JP2015-132791A 国際公開第２０１４／０２１０２３号International Publication No. 2014/021023 特開平３－２３２８３２号公報Japanese Patent Laid-Open No. 3-232732
　従って、本発明の目的は、常温では不活性であり所定の温度に加熱することにより活性化されて酸化防止剤や紫外線吸収剤としての機能を発現する化合物を用いた、アウトガスが少なく硬化物の耐溶剤性が高い感光性組成物を提供することにある。また、本発明の別の目的は、上記感光性組成物に着色剤を加えた着色感光性組成物、特にカラーフィルタに好適な着色感光性組成物を提供することにある。 Accordingly, an object of the present invention is to use a compound that is inactive at normal temperature and activated by heating to a predetermined temperature and that exhibits a function as an antioxidant or an ultraviolet absorber, and has a low outgas. The object is to provide a photosensitive composition having high solvent resistance. Another object of the present invention is to provide a colored photosensitive composition obtained by adding a colorant to the photosensitive composition, particularly a colored photosensitive composition suitable for a color filter.
　本発明者等は、鋭意検討を重ねた結果、特定の保護基を有する化合物を用いた感光性組成物は、アウトガスが少なく、その硬化物の耐溶剤性が高いことを知見し、また、上記感光性組成物に着色剤を加えた着色感光性組成物が、光学フィルタ（特にカラーフィルタ）の輝度を低下させず、液晶表示パネル等の画像表示装置用カラーフィルタに好適であることを知見し、本発明に到達した。 As a result of intensive studies, the present inventors have found that a photosensitive composition using a compound having a specific protecting group has less outgas, and the cured product has high solvent resistance. It was found that a colored photosensitive composition obtained by adding a colorant to a photosensitive composition is suitable for a color filter for an image display device such as a liquid crystal display panel without reducing the luminance of an optical filter (particularly a color filter). The present invention has been reached.
　本発明は、上記知見に基づきなされたもので、下記一般式（１）で表される置換基を有する化合物を含有する感光性組成物を提供するものである。 The present invention has been made based on the above findings, and provides a photosensitive composition containing a compound having a substituent represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ１及びＲ２は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有している場合もある炭素原子数１～４０のアルキル基、置換基を有している場合もある炭素原子数６～２０のアリール基、置換基を有している場合もある炭素原子数７～２０のアリールアルキル基、置換基を有している場合もある炭素原子数２～２０の複素環含有基又はトリアルキルシリル基を表し、
　Ｒ１及びＲ２で表されるアルキル基又はアリールアルキル基中のメチレン基は、－Ｏ－、－Ｓ－、－ＣＯ－、－Ｏ－ＣＯ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－Ｏ－、－Ｓ－ＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－Ｏ－、－Ｏ－ＣＯ－Ｓ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＮＨ－ＣＯ－Ｏ－、－ＮＲ’－、－Ｓ－Ｓ－又は－ＳＯ２－から選ばれた基を酸素原子が隣り合わない条件で組み合わせた基で置き換えている場合もあり、Ｒ’は、水素原子又は炭素原子数１～８のアルキル基を表し、
　ｊは、１～３の数を表し、
　＊は、＊部分で、隣接する基と結合することを意味する。）
Figure JPOXMLDOC01-appb-C000006
 (Wherein R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an alkyl having 1 to 40 carbon atoms which may have a substituent) An aryl group having 6 to 20 carbon atoms which may have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, or a substituent In some cases represents a C2-C20 heterocyclic-containing group or a trialkylsilyl group,
The methylene group in the alkyl group or arylalkyl group represented by R 1 and R 2 is —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO—. O—, —S—CO—, —CO—S—, —S—CO—O—, —O—CO—S—, —CO—NH—, —NH—CO—, —NH—CO—O—. , -NR '-, - S- S- or -SO 2 - from selected based on some cases where the oxygen atoms are replaced by a group composed of a combination under conditions which are not adjacent, R' is a hydrogen atom or a carbon atom Represents an alkyl group of 1 to 8,
j represents a number from 1 to 3,
* Means that it is bonded to an adjacent group at the * part. )
　以下、本発明について、好ましい実施形態に基づき詳細に説明する。 Hereinafter, the present invention will be described in detail based on preferred embodiments.
　本発明の感光性組成物は、上記一般式（Ｉ）で表される置換基を有する化合物を含有する。 The photosensitive composition of the present invention contains a compound having a substituent represented by the above general formula (I).
　上記一般式（Ｉ）で表される置換基を有する化合物の中でも、下記一般式（Ｉ－Ａ）で表されるものが、特に耐熱性が高くアウトガスが少ないので好ましい。 Among the compounds having a substituent represented by the above general formula (I), those represented by the following general formula (IA) are particularly preferable because of their high heat resistance and low outgassing.
Figure JPOXMLDOC01-appb-C000007
 （式中、ｎは、１～１０の整数を表し、
　Ｘ１は、ｎ価の結合基を表し、
　Ｒ１、Ｒ２及びｊは、上記一般式（Ｉ）と同じである。）
Figure JPOXMLDOC01-appb-C000007
 (In the formula, n represents an integer of 1 to 10,
X 1 represents an n-valent linking group,
R 1 , R 2 and j are the same as in the general formula (I). )
　Ｒ１及びＲ２で表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられ、
　Ｒ１及びＲ２で表される炭素原子数１～２０のアルキル基としては、メチル、エチル、プロピル、ｉｓｏ－プロピル、ブチル、ｓｅｃ－ブチル、ｔｅｒｔ－ブチル、ｉｓｏ－ブチル、アミル、ｉｓｏ－アミル、ｔｅｒｔ－アミル、シクロペンチル、ヘキシル、２－ヘキシル、３－ヘキシル、シクロヘキシル、４－メチルシクロヘキシル、ヘプチル、２－ヘプチル、３－ヘプチル、ｉｓｏ－ヘプチル、ｔｅｒｔ－ヘプチル、１－オクチル、ｉｓｏ－オクチル、ｔｅｒｔ－オクチル、アダマンチル等が挙げられ、
　Ｒ１及びＲ２で表される炭素原子数６～２０のアリール基としては、フェニル、ナフチル、アントラセニル、フェナントリル、フルオレニル、インデニル、２－メチルフェニル、３－メチルフェニル、４－メチルフェニル、４－ビニルフェニル、３－ｉｓｏ－プロピルフェニル、４－ｉｓｏ－プロピルフェニル、４－ブチルフェニル、４－ｉｓｏ－ブチルフェニル、４－ｔｅｒｔ－ブチルフェニル、４－ヘキシルフェニル、４－シクロヘキシルフェニル、４－オクチルフェニル、４－（２－エチルヘキシル）フェニル、４－ステアリルフェニル、２，３－ジメチルフェニル、２，４－ジメチルフェニル、２，５－ジメチルフェニル、２，６－ジメチルフェニル、３，４－ジメチルフェニル、３，５－ジメチルフェニル、２，４－ジ－ｔｅｒｔ－ブチルフェニル、２，５－ジ－ｔｅｒｔ－ブチルフェニル、２，６－ジ－ｔｅｒｔ－ブチルフェニル、２，４－ジ－ｔｅｒｔ－ペンチルフェニル、２，５－ジ－ｔｅｒｔ－アミルフェニル、２，５－ジ－ｔｅｒｔ－オクチルフェニル、２，４－ジクミルフェニル、４－シクロヘキシルフェニル、（１，１’－ビフェニル）－４－イル、２，４，５－トリメチルフェニル、フェロセニル等が挙げられ、
　Ｒ１及びＲ２で表される炭素原子数７～２０のアリールアルキル基としては、ベンジル、１－メチル－１－フェニルエチル、１－ナフチルメチル、９－アントラセニルメチル、９－フルオレニル、３－フェニルプロピル、メチル－２－フェニルプロパン－２－イル、ジフェニルメチル、トリフェニルメチル、フェネチル、スチリル、シンナミル等が挙げられ、
　Ｒ１及びＲ２で表される炭素原子数２～２０の複素環含有基としては、ピリジン環、ピリミジン環、ピリダジン環、ピペリジン環、ピラン環、ピラゾリン環、トリアジン環、ピロリン環、キノリン環、イソキノリン環、イミダゾリン環、ベンゾイミダゾリン環、トリアゾリン環、フラン環、ベンゾフラン環、チアジアゾリン環、チアゾリン環、ベンゾチアゾリン環、チオフェン環、オキサゾリン環、ベンゾオキサゾリン環、イソチアゾリン環、イソオキサゾリン環、インドール環、ピロリジン環、ピペリドン環、ジオキサン環等の複素環とメチレン鎖を組み合わせた基が挙げられ、
　Ｒ１及びＲ２で表されるトリアルキルシリル基としては、トリメチルシラン、トリエチルシラン、エチルジメチルシラン等の炭素原子数１～６のアルキル基（３つのアルキル基は同一かあるいは異なる）で置換されたシリル基が挙げられる。
　Ｒ’で表される炭素原子数１～８のアルキル基としては、Ｒ１で表される上記アルキル基のうち、所定の炭素原子数を満たすものが挙げられる。
　Ｒ１及びＲ２で表される炭素原子数１～４０のアルキル基、炭素原子数６～２０のアリール基、炭素原子数７～２０のアリールアルキル基又は炭素原子数２～２０の複素環含有基を置換する置換基としては、ビニル、アリル、アクリル、メタクリル等のエチレン性不飽和基；フッ素、塩素、臭素、ヨウ素等のハロゲン原子；アセチル、２－クロロアセチル、プロピオニル、オクタノイル、アクリロイル、メタクリロイル、フェニルカルボニル（ベンゾイル）、フタロイル、４－トリフルオロメチルベンゾイル、ピバロイル、サリチロイル、オキザロイル、ステアロイル、メトキシカルボニル、エトキシカルボニル、ｔ－ブトキシカルボニル、ｎ－オクタデシルオキシカルボニル、カルバモイル等のアシル基；アセチルオキシ、ベンゾイルオキシ等のアシルオキシ基；アミノ、エチルアミノ、ジメチルアミノ、ジエチルアミノ、ブチルアミノ、シクロペンチルアミノ、２－エチルヘキシルアミノ、ドデシルアミノ、アニリノ、クロロフェニルアミノ、トルイジノ、アニシジノ、Ｎ－メチル－アニリノ、ジフェニルアミノ，ナフチルアミノ、２－ピリジルアミノ、メトキシカルボニルアミノ、フェノキシカルボニルアミノ、アセチルアミノ、ベンゾイルアミノ、ホルミルアミノ、ピバロイルアミノ、ラウロイルアミノ、カルバモイルアミノ、Ｎ，Ｎ－ジメチルアミノカルボニルアミノ、Ｎ，Ｎ－ジエチルアミノカルボニルアミノ、モルホリノカルボニルアミノ、メトキシカルボニルアミノ、エトキシカルボニルアミノ、ｔ－ブトキシカルボニルアミノ、ｎ－オクタデシルオキシカルボニルアミノ、Ｎ－メチル－メトキシカルボニルアミノ、フェノキシカルボニルアミノ、スルファモイルアミノ、Ｎ，Ｎ－ジメチルアミノスルホニルアミノ、メチルスルホニルアミノ、ブチルスルホニルアミノ、フェニルスルホニルアミノ等の置換アミノ基；スルホンアミド基、スルホニル基、カルボキシル基、シアノ基、スルホ基、水酸基、ニトロ基、メルカプト基、イミド基、カルバモイル基、スルホンアミド基、ホスホン酸基、リン酸基又はカルボキシル基、スルホ基、ホスホン酸基、リン酸基の塩等が挙げられる。
　Ｒ１及びＲ２としては、水素原子、炭素原子数１～８のアルキル基、炭素原子数６～１２のアリール基が、アウトガスが少ないため好ましい。Ｒ１及びＲ２が水素原子又は分岐を有する炭素原子数１～８のアルキル基、特にｔ－ブチル基の何れかであるものが、アウトガスが少ないためさらに好ましい。 Examples of the halogen atom represented by R 1 and R 2 include fluorine, chlorine, bromine and iodine.
Examples of the alkyl group having 1 to 20 carbon atoms represented by R 1 and R 2 include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl Tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso-octyl, tert-octyl, adamantyl and the like,
Examples of the aryl group having 6 to 20 carbon atoms represented by R 1 and R 2 include phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4- Vinylphenyl, 3-iso-propylphenyl, 4-iso-propylphenyl, 4-butylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl 4- (2-ethylhexyl) phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-ter -Butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5-di-tert-amylphenyl, 2, 5-di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1′-biphenyl) -4-yl, 2,4,5-trimethylphenyl, ferrocenyl, etc.
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R 1 and R 2 include benzyl, 1-methyl-1-phenylethyl, 1-naphthylmethyl, 9-anthracenylmethyl, 9-fluorenyl, 3 -Phenylpropyl, methyl-2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, phenethyl, styryl, cinnamyl and the like,
Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R 1 and R 2 include a pyridine ring, a pyrimidine ring, a pyridazine ring, a piperidine ring, a pyran ring, a pyrazoline ring, a triazine ring, a pyrroline ring, a quinoline ring, Isoquinoline ring, imidazoline ring, benzimidazoline ring, triazoline ring, furan ring, benzofuran ring, thiadiazoline ring, thiazoline ring, benzothiazoline ring, thiophene ring, oxazoline ring, benzoxazoline ring, isothiazoline ring, isoxazoline ring, indole ring, pyrrolidine Examples include groups combining heterocycles such as rings, piperidone rings, dioxane rings and methylene chains,
The trialkylsilyl group represented by R 1 and R 2 is substituted with an alkyl group having 1 to 6 carbon atoms (three alkyl groups are the same or different) such as trimethylsilane, triethylsilane, and ethyldimethylsilane. And silyl group.
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ′ include those satisfying a predetermined number of carbon atoms among the above alkyl groups represented by R 1 .
Containing an alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic ring having 2 to 20 carbon atoms represented by R 1 and R 2 Substituents for substituting groups include ethylenically unsaturated groups such as vinyl, allyl, acryl and methacryl; halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl and methacryloyl Acyl groups such as phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; Benzoylo Acyloxy group such as amino; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino , Methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarboni Substituted amino groups such as ruamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl Group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group, sulfonamide group, phosphonic acid group, phosphoric acid group or carboxyl group, sulfo group, phosphonic acid group, phosphoric acid group And the like.
As R 1 and R 2 , a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms are preferable because of less outgassing. It is more preferable that R 1 and R 2 are either a hydrogen atom or a branched alkyl group having 1 to 8 carbon atoms, particularly a t-butyl group, because outgas is small.
　上記一般式（Ｉ－Ａ）において、Ｘ１は、ｎ価の結合基を表し、具体的には、例えば、直接結合、水素原子、窒素原子、酸素原子、硫黄原子、リン原子、下記（Ｉ－ａ）若しくは（Ｉ－ｂ）で表される基、－ＣＯ－、－ＮＨ－ＣＯ－、－ＣＯ－ＮＨ－、－ＮＲ３－、－ＯＲ３、－ＳＲ３、－ＮＲ3Ｒ４、又は、ｎと同数の価数を有する、置換基を有している場合もある炭素原子数１～１２０の脂肪族炭化水素基、置換基を有している場合もある炭素原子数６～３５の芳香環含有炭化水素基、若しくは置換基を有している場合もある炭素原子数２～３５の複素環含有基を表し、Ｒ３及びＲ４は、水素原子、置換基を有している場合もある炭素原子数１～３５の脂肪族炭化水素基、置換基を有している場合もある炭素原子数６～３５の芳香環含有炭化水素基又は置換基を有している場合もある炭素原子数２～３５の複素環含有基を表し、脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基は、炭素－炭素二重結合、－Ｏ－、－Ｓ－、－ＣＯ－、－Ｏ－ＣＯ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－Ｏ－、－Ｓ－ＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－Ｏ－、－Ｏ－ＣＯ－Ｓ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＮＨ－ＣＯ－Ｏ－、－Ｏ－ＣＯ－ＮＨ－、－ＮＲ’－、－Ｓ－Ｓ－、－ＳＯ２－又は窒素原子から選ばれた基で置き換わっている場合もある。
　但し、Ｘ１が窒素原子、リン原子又は下記（Ｉ－ａ）若しくは（Ｉ－ｂ）で表される結合基の場合、ｎは３であり、Ｘ１が酸素原子又は硫黄原子、－ＣＯ－、－ＮＨ－ＣＯ－、－ＣＯ－ＮＨ－又は－ＮＲ３－の場合、ｎは２であり、Ｘ１が水素原子、－ＯＲ３、－ＳＲ３又は－ＮＲ３Ｒ４の場合、ｎは１であり、Ｘ１は、ベンゼン環と一緒になって環を形成している場合もある。 In the general formula (IA), X 1 represents an n-valent linking group. Specifically, for example, a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, the following (I -a) or (I-b), a group represented by, -CO -, - NH-CO -, - CO-NH -, - NR 3 -, - oR 3, -SR 3, -NR 3 R 4, Or an aliphatic hydrocarbon group having 1 to 120 carbon atoms which may have a substituent having the same valence as n, and 6 to 35 carbon atoms which may have a substituent. Represents an aromatic ring-containing hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms, which may have a substituent, and R 3 and R 4 have a hydrogen atom or a substituent. In some cases, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, or an aromatic hydrocarbon group having 6 to 35 carbon atoms that may have a substituent. Represents a ring-containing hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms, which may have a substituent, and the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocyclic ring-containing group are carbon -Carbon double bond, -O-, -S-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -S-CO-, -CO-S-, —S—CO—O—, —O—CO—S—, —CO—NH—, —NH—CO—, —NH—CO—O—, —O—CO—NH—, —NR′—, — In some cases, the group is replaced with a group selected from S—S—, —SO 2 — or a nitrogen atom.
However, when X 1 is a nitrogen atom, a phosphorus atom, or a linking group represented by the following (Ia) or (Ib), n is 3, X 1 is an oxygen atom or a sulfur atom, —CO— , —NH—CO—, —CO—NH— or —NR 3 —, n is 2, and when X 1 is a hydrogen atom, —OR 3 , —SR 3 or —NR 3 R 4 , n is 1 and X 1 may form a ring together with the benzene ring.
Figure JPOXMLDOC01-appb-C000008
 （＊は、＊部分で、隣接する基と結合することを意味する。）
Figure JPOXMLDOC01-appb-C000008
 (* Means that it is bonded to an adjacent group at the * portion.)
　上記一般式（I－Ａ）で表される化合物は、Ｘ１で表されるｎ価の結合基に、ｎ個の特定の基が結合した構造を有する。このｎ個の基は、互いに同じであるか又は異なる。ｎの値は１～１０であり、低アウトガスの観点から、好ましくは２～６である。 The formula (I-A) compound represented by the n-valent linking group represented by X 1, having a structure in which n-number of a particular group is bonded. The n groups are the same or different from each other. The value of n is 1 to 10, and preferably 2 to 6 from the viewpoint of low outgas.
　上記一般式（I－Ａ）におけるＸ１で表され、ｎと同数の価数を有する、置換基を有している場合もある炭素原子数１～１２０の脂肪族炭化水素基としては、ｎが１価のものとして、例えば、メチル、エチル、プロピル、イソプロピル、シクロプロピル、ブチル、第二ブチル、第三ブチル、イソブチル、アミル、イソアミル、第三アミル、シクロペンチル、ヘキシル、２－ヘキシル、３－ヘキシル、シクロヘキシル、ビシクロヘキシル、１－メチルシクロヘキシル、ヘプチル、２－ヘプチル、３－ヘプチル、イソヘプチル、第三ヘプチル、ｎ－オクチル、イソオクチル、第三オクチル、２－エチルヘキシル、ノニル、イソノニル、デシル等のアルキル基；メチルオキシ、エチルオキシ、プロピルオキシ、イソプロピルオキシ、ブチルオキシ、第二ブチルオキシ、第三ブチルオキシ、イソブチルオキシ、アミルオキシ、イソアミルオキシ、第三アミルオキシ、ヘキシルオキシ、シクロヘキシルオキシ、ヘプチルオキシ、イソヘプチルオキシ、第三ヘプチルオキシ、ｎ－オクチルオキシ、イソオクチルオキシ、第三オクチルオキシ、２－エチルヘキシルオキシ、ノニルオキシ、デシルオキシ等のアルコキシ基；メチルチオ、エチルチオ、プロピルチオ、イソプロピルチオ、ブチルチオ、第二ブチルチオ、第三ブチルチオ、イソブチルチオ、アミルチオ、イソアミルチオ、第三アミルチオ、ヘキシルチオ、シクロヘキシルチオ、ヘプチルチオ、イソヘプチルチオ、第三ヘプチルチオ、ｎ－オクチルチオ、イソオクチルチオ、第三オクチルチオ、２－エチルヘキシルチオ等のアルキルチオ基；ビニル、１－メチルエテニル、２－メチルエテニル、２－プロペニル、１－メチル－３－プロペニル、３－ブテニル、１－メチル－３－ブテニル、イソブテニル、３－ペンテニル、４－ヘキセニル、シクロヘキセニル、ビシクロヘキセニル、ヘプテニル、オクテニル、デセニル、ペンタデセニル、エイコセニル、トリコセニル等のアルケニル基；及びこれらの基が後述する置換基により置換された基等が挙げられ、
　ｎが２価のものとして、メチレン、エチレン、プロピレン、ブチレン、ブチルジイル等のアルキレン；前記アルキレンのメチレン鎖が－Ｏ－、－Ｓ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－で置き換えられたもの；エタンジオール、プロパンジオール、ブタンジオール、ペンタンジオール、ヘキサンジオール等のジオールの残基；エタンジチオール、プロパンジチオール、ブタンジチオール、ペンタンジチオール、ヘキサンジチオール等のジチオールの残基；及びこれらの基が後述する置換基により置換された基等が挙げられ、
　ｎが３価のものとして、例えば、プロピリジン、１，１，３－ブチリジン等のアルキリジン；及びこれらの基が後述する置換基により置換された基が挙げられる。
　ｎと同数の価数を有する、置換基を有している場合もある炭素原子数６～３５の芳香環含有炭化水素基としては、ｎが１価のものとして、ベンジル、フェネチル、ジフェニルメチル、トリフェニルメチル、スチリル、シンナミル等のアリールアルキル基；フェニル、ナフチル等のアリール基；フェノキシ、ナフチルオキシ等のアリールオキシ基；フェニルチオ、ナフチルチオ等のアリールチオ基；及びこれらの基が後述する置換基により置換された基等が挙げられ、
　ｎが２価のものとして、フェニレン、ナフチレン等のアリーレン基；カテコール、ビスフェノール等の二官能フェノールの残基；２，４，８，１０－テトラオキサスピロ[５，５]ウンデカン等；及びこれらの基が後述する置換基により置換された基が挙げられ、
　ｎが３価のものとして、フェニル－１，３，５－トリメチレン及びこれらの基が後述する置換基により置換された基が挙げられる。
　ｎと同数の価数を有する、置換基を有している場合もある炭素原子数２～３５の複素環含有基としては、ｎが１価のものとして、ピリジル、ピリミジル、ピリダジル、ピペリジル、ピラニル、ピラゾリル、トリアジル、ピロリル、キノリル、イソキノリル、イミダゾリル、ベンゾイミダゾリル、トリアゾリル、フリル、フラニル、ベンゾフラニル、チエニル、チオフェニル、ベンゾチオフェニル、チアジアゾリル、チアゾリル、ベンゾチアゾリル、オキサゾリル、ベンゾオキサゾリル、イソチアゾリル、イソオキサゾリル、インドリル、２－ピロリジノン－１－イル、２－ピペリドン－１－イル、２，４－ジオキシイミダゾリジン－３－イル、２，４－ジオキシオキサゾリジン－３－イル、ベンゾトリアゾイル等；及びこれらの基が後述する置換基により置換された基等が挙げられ、
　ｎが２価のものとして、ピリジン環、ピリミジン環、ピペリジン環、ピペラジン環、トリアジン環、フラン環、チオフェン環、インドール環等を有する基；及びこれらの基が後述する置換基により置換された基が挙げられ、
　ｎが３価のものとしては、イソシアヌル環を有する基、トリアジン環を有する基；及びこれらの基が後述する置換基により置換された基が挙げられる。
　Ｒ３及びＲ４で表される、置換基を有している場合もある炭素原子数１～３５の脂肪族炭化水素基としては、上記Ｘ１で表される脂肪族炭化水素基及び該脂肪族炭化水素基と上記置換基との組み合わせのうち、所定の炭素原子数を満たすものが挙げられ、
　Ｒ３及びＲ４で表される、置換基を有している場合もある炭素原子数６～３５の芳香環含有炭化水素基及び置換基を有している場合もある炭素原子数２～３５の複素環含有基としては、上記Ｘ１で表される炭素原子数６～３５の芳香環含有炭化水素基及び炭素原子数２～３５の複素環含有基並びにこれらの基と後述する置換基とを組み合わせた基のうち、所定の炭素原子数を満たすものが挙げられる。
　置換基としては、ビニル、アリル、アクリル、メタクリル等のエチレン性不飽和基；フッ素、塩素、臭素、ヨウ素等のハロゲン原子；アセチル、２－クロロアセチル、プロピオニル、オクタノイル、アクリロイル、メタクリロイル、フェニルカルボニル（ベンゾイル）、フタロイル、４－トリフルオロメチルベンゾイル、ピバロイル、サリチロイル、オキザロイル、ステアロイル、メトキシカルボニル、エトキシカルボニル、ｔ－ブトキシカルボニル、ｎ－オクタデシルオキシカルボニル、カルバモイル等のアシル基；アセチルオキシ、ベンゾイルオキシ等のアシルオキシ基；アミノ、エチルアミノ、ジメチルアミノ、ジエチルアミノ、ブチルアミノ、シクロペンチルアミノ、２－エチルヘキシルアミノ、ドデシルアミノ、アニリノ、クロロフェニルアミノ、トルイジノ、アニシジノ、Ｎ－メチル－アニリノ、ジフェニルアミノ、ナフチルアミノ、２－ピリジルアミノ、メトキシカルボニルアミノ、フェノキシカルボニルアミノ、アセチルアミノ、ベンゾイルアミノ、ホルミルアミノ、ピバロイルアミノ、ラウロイルアミノ、カルバモイルアミノ、Ｎ，Ｎ－ジメチルアミノカルボニルアミノ、Ｎ，Ｎ－ジエチルアミノカルボニルアミノ、モルホリノカルボニルアミノ、メトキシカルボニルアミノ、エトキシカルボニルアミノ、ｔ－ブトキシカルボニルアミノ、ｎ－オクタデシルオキシカルボニルアミノ、Ｎ－メチル－メトキシカルボニルアミノ、フェノキシカルボニルアミノ、スルファモイルアミノ、Ｎ，Ｎ－ジメチルアミノスルホニルアミノ、メチルスルホニルアミノ、ブチルスルホニルアミノ、フェニルスルホニルアミノ等の置換アミノ基；スルホンアミド基、スルホニル基、カルボキシル基、シアノ基、スルホ基、水酸基、ニトロ基、メルカプト基、イミド基、カルバモイル基、スルホンアミド基、ホスホン酸基、リン酸基又はカルボキシル基、スルホ基、ホスホン酸基、リン酸基の塩等が挙げられ、これらの基は更に置換されている場合もある。また、カルボキシル基及びスルホ基は塩を形成している場合もある。 The aliphatic hydrocarbon group having 1 to 120 carbon atoms which may have a substituent represented by X 1 in the general formula (IA) and having the same valence as n is n Are monovalent, for example, methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3- Alkyl such as hexyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl Groups: methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, 2-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy Alkoxy groups such as 2-ethylhexyloxy, nonyloxy, decyloxy; methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tert-amylthio, hexylthio, cyclohexylthio, Alkylthio groups such as heptylthio, isoheptylthio, tertiary heptylthio, n-octylthio, isooctylthio, tertiary octylthio, 2-ethylhexylthio; Vinyl, 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, Alkenyl groups such as heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, tricosenyl; and groups in which these groups are substituted with substituents described later, and the like,
n is divalent, alkylene such as methylene, ethylene, propylene, butylene, butyldiyl; the methylene chain of the alkylene is replaced by —O—, —S—, —CO—O—, —O—CO— Residues of diols such as ethanediol, propanediol, butanediol, pentanediol, hexanediol; residues of dithiols such as ethanedithiol, propanedithiol, butanedithiol, pentanedithiol, hexanedithiol; and these groups are described later Groups substituted by substituents to
Examples of those in which n is trivalent include alkylidines such as propyridine and 1,1,3-butyridine; and groups in which these groups are substituted with substituents described later.
Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, which may have a substituent having the same valence as n, are those in which n is monovalent, such as benzyl, phenethyl, diphenylmethyl, Arylalkyl groups such as triphenylmethyl, styryl and cinnamyl; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; arylthio groups such as phenylthio and naphthylthio; and these groups are substituted by substituents described later Group, etc.
n is divalent, arylene groups such as phenylene and naphthylene; residues of bifunctional phenols such as catechol and bisphenol; 2,4,8,10-tetraoxaspiro [5,5] undecane and the like; A group in which the group is substituted by a substituent described later,
Examples of the trivalent n include phenyl-1,3,5-trimethylene and groups in which these groups are substituted with a substituent described later.
The heterocycle-containing group having 2 to 35 carbon atoms that may have a substituent having the same number of valences as n includes those in which n is monovalent, pyridyl, pyrimidyl, pyridazyl, piperidyl, pyranyl , Pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl, benzotriazoyl, etc .; and these groups Will be described later Groups substituted by substituent can be mentioned,
a group having a pyridine ring, a pyrimidine ring, a piperidine ring, a piperazine ring, a triazine ring, a furan ring, a thiophene ring, an indole ring or the like, and a group in which these groups are substituted by a substituent described later, Are mentioned,
Examples of the group in which n is trivalent include a group having an isocyanuric ring, a group having a triazine ring; and a group in which these groups are substituted with a substituent described later.
Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent represented by R 3 and R 4 include the aliphatic hydrocarbon group represented by X 1 and the aliphatic hydrocarbon group. Among the combinations of group hydrocarbon groups and the above substituents, those satisfying a predetermined number of carbon atoms can be mentioned,
The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent represented by R 3 and R 4 and 2 to 35 carbon atoms which may have a substituent Examples of the heterocyclic ring-containing group include an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and a heterocyclic ring-containing group having 2 to 35 carbon atoms represented by the above X 1 and these groups and substituents described later. Among the groups in which are combined, those satisfying a predetermined number of carbon atoms can be mentioned.
Examples of the substituent include ethylenically unsaturated groups such as vinyl, allyl, acryl and methacryl; halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl and phenylcarbonyl ( Benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl, etc .; acetyloxy, benzoyloxy, etc. Acyloxy group; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chloro Enylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N, N -Dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino Sulfamoylamino, N, N-dimethylaminosulfonylamino, methylsulfonylamino, butyls Substituted amino groups such as phonylamino, phenylsulfonylamino, etc .; sulfonamide groups, sulfonyl groups, carboxyl groups, cyano groups, sulfo groups, hydroxyl groups, nitro groups, mercapto groups, imide groups, carbamoyl groups, sulfonamide groups, phosphonic acid groups, phosphorus Examples thereof include salts of acid groups or carboxyl groups, sulfo groups, phosphonic acid groups, and phosphoric acid groups, and these groups may be further substituted. In addition, the carboxyl group and the sulfo group may form a salt.
　上記一般式（I－Ａ）において、ｎが２～６であるとき、Ｘ１は、それぞれ下記一般式
（１）～（５）のように表すこともできる。 In the above general formula (IA), when n is 2 to 6, X 1 can also be represented by the following general formulas (1) to (5), respectively.
Figure JPOXMLDOC01-appb-C000009
 （上記一般式（１）中、Ｙ１は、単結合、－ＣＲ５Ｒ６－、－ＮＲ７－、２価の炭素原子数１～３５の脂肪族炭化水素基、炭素原子数６～３５の芳香族炭化水素基若しくは炭素原子数２～３５の複素環含有基、又は、下記（１－１）～（１－３）で表されるいずれかの置換基を表し、
　該脂肪族炭化水素基は、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－ＳＯ2－、－ＣＯＮＨ－若しくは－ＮＨＣＯ－、又は酸素原子が隣り合うことなしにこれらを組み合わせた結合基で置き換えられている場合もあり、
　Ｚ1及びＺ２は、それぞれ独立に、直接結合、－Ｏ－、－Ｓ－、＞ＣＯ、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－、－ＳＯ2－、－ＳＳ－、－ＳＯ－、－ＮＲ７－又は－ＰＲ７－を表し、
　Ｒ５、Ｒ６及びＲ７は、それぞれ独立に、水素原子、置換基を有している場合もある炭素原子数１～３５の脂肪族炭化水素基、置換基を有している場合もある炭素原子数６～３５の芳香族炭化水素基又は置換基を有している場合もある炭素原子数２～３５の複素環含有基を表し、
　＊は、＊部分で、隣接する基と結合することを意味する。）
Figure JPOXMLDOC01-appb-C000009
 (In the general formula (1), Y 1 represents a single bond, —CR 5 R 6 —, —NR 7 —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, or 6 to 35 carbon atoms. An aromatic hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms, or any of the substituents represented by the following (1-1) to (1-3):
The aliphatic hydrocarbon group has —O—, —S—, —CO—, —COO—, —OCO—, —NH—, —SO 2 —, —CONH— or —NHCO—, or an oxygen atom. In some cases, it is replaced with a combination of these without combining,
Z 1 and Z 2 are each independently a direct bond, —O—, —S—,> CO, —CO—O—, —O—CO—, —SO 2 —, —SS—, —SO—, Represents —NR 7 — or —PR 7 —,
R 5 , R 6 and R 7 may each independently have a hydrogen atom, a substituent, or an aliphatic hydrocarbon group having 1 to 35 carbon atoms or a substituent. Represents an aromatic hydrocarbon group having 6 to 35 carbon atoms or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent,
* Means that it is bonded to an adjacent group at the * part. )
Figure JPOXMLDOC01-appb-C000010
 （上記式中、Ｒ８は水素原子、又は置換基を有している場合もあるフェニル基若しくは炭素原子数３～１０のシクロアルキル基を表し、
　Ｒ９は炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数２～１０のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基は置換基を有している場合もあり、
　ｆは０～５の整数であり、
　＊は、＊部分で、隣接する基と結合することを意味する。）
Figure JPOXMLDOC01-appb-C000010
 (In the above formula, R 8 represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms,
R 9 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, alkoxy group and alkenyl group are substituents. May have
f is an integer from 0 to 5,
* Means that it is bonded to an adjacent group at the * part. )
Figure JPOXMLDOC01-appb-C000011
 （＊は、＊部分で、隣接する基と結合することを意味する。）
Figure JPOXMLDOC01-appb-C000011
 (* Means that it is bonded to an adjacent group at the * portion.)
Figure JPOXMLDOC01-appb-C000012
 （上記式中、Ｒ10及びＲ11は、それぞれ独立に、置換基を有している場合もある炭素原子数１～１０のアルキル基、置換基を有している場合もある炭素原子数６～２０のアリール基、置換基を有している場合もある炭素原子数６～２０のアリールオキシ基、置換基を有している場合もある炭素原子数６～２０のアリールチオ基、置換基を有している場合もある炭素原子数６～２０のアリールアルケニル基、置換基を有している場合もある炭素原子数７～２０のアリールアルキル基、置換基を有している場合もある炭素原子数２～２０の複素環含有基又はハロゲン原子を表し、
　該アルキル基及びアリールアルキル基中のメチレン基は、不飽和結合、－Ｏ－又は－Ｓ－で置き換えられている場合もあり、
　Ｒ10は、隣接するＲ10同士で環を形成している場合もあり、
　ｐは０～４の数を表し、
　ｑは０～８の数を表し、
　ｇは０～４の数を表し、
　ｈは０～４の数を表し、
　ｇとｈの数の合計は２～４であり、
　＊は、＊部分で、隣接する基と結合することを意味する。）
Figure JPOXMLDOC01-appb-C000012
 (In the above formula, R 10 and R 11 are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a carbon atom having 6 substituents which may have a substituent. An aryl group having 20 to 20 atoms, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, an arylthio group having 6 to 20 carbon atoms which may have a substituent, and a substituent; An arylalkenyl group having 6 to 20 carbon atoms which may have, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, and a carbon which may have a substituent Represents a heterocycle-containing group having 2 to 20 atoms or a halogen atom,
The methylene group in the alkyl group and arylalkyl group may be replaced with an unsaturated bond, —O— or —S—,
R 10 may form a ring with adjacent R 10 ,
p represents a number from 0 to 4,
q represents a number from 0 to 8,
g represents a number from 0 to 4,
h represents a number from 0 to 4,
The total number of g and h is 2-4,
* Means that it is bonded to an adjacent group at the * part. )
Figure JPOXMLDOC01-appb-C000013
 （上記一般式（２）中、Ｙ１１は、３価の炭素原子数３～３５の脂肪族炭化水素基、炭素原子数３～３５の脂環族炭化水素基、炭素原子数６～３５の芳香族炭化水素基若しくは炭素原子数２～３５の複素環含有基を表し、
　Ｚ1、Ｚ２及びＺ３は、それぞれ独立に、直接結合、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－、－ＳＯ2－、－ＳＳ－、－ＳＯ－、－ＮＲ12－又は－ＰＲ12－を表し、
　Ｒ12は、水素原子、置換基を有している場合もある炭素原子数１～３５の脂肪族炭化水素基、置換基を有している場合もある炭素原子数６～３５の芳香族炭化水素基又は置換基を有している場合もある炭素原子数２～３５の複素環含有基を表し、
　脂肪族炭化水素基は、炭素－炭素二重結合、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－ＳＯ2－、－ＣＯＮＨ－若しくは－ＮＨＣＯ－、又は酸素原子が隣り合うことなしにこれらを組み合わせた結合基で置き換えられている場合もあり、
　＊は、＊部分で、隣接する基と結合することを意味する。）
Figure JPOXMLDOC01-appb-C000013
 (In the above general formula (2), Y 11 represents a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, or 6 to 35 carbon atoms. Represents an aromatic hydrocarbon group or a heterocyclic-containing group having 2 to 35 carbon atoms,
Z 1 , Z 2 and Z 3 are each independently a direct bond, —O—, —S—, —CO—, —CO—O—, —O—CO—, —SO 2 —, —SS—, Represents —SO—, —NR 12 — or —PR 12 —,
R 12 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, or an aromatic carbon group having 6 to 35 carbon atoms which may have a substituent. Represents a hydrogen-containing group or a substituent containing 2 to 35 carbon atoms which may have a substituent,
The aliphatic hydrocarbon group includes a carbon-carbon double bond, —O—, —S—, —CO—, —COO—, —OCO—, —NH—, —SO 2 —, —CONH— or —NHCO—. Or the oxygen atom may be replaced by a linking group combining these without being adjacent to each other,
* Means that it is bonded to an adjacent group at the * part. )
Figure JPOXMLDOC01-appb-C000014
 （上記一般式（３）中、Ｙ１２は、炭素原子、又は４価の炭素原子数１～３５の脂肪族炭化水素基、炭素原子数６～３５の芳香族炭化水素基若しくは炭素原子数２～３５の複素環含有基を表し、
　該脂肪族炭化水素基は、炭素－炭素二重結合、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－ＳＯ2－、－ＣＯＮＨ－若しくは－ＮＨＣＯ－、又は酸素原子が隣り合うことなしにこれらを組み合わせた結合基で置き換えられている場合もあり、
　Ｚ1～Ｚ4は、それぞれ独立に、上記一般式（２）におけるＺ1～Ｚ３で表される基と同じ範囲の基であり、
　＊は、＊部分で、隣接する基と結合することを意味する。）
Figure JPOXMLDOC01-appb-C000014
 (In the general formula (3), Y 12 represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or 2 carbon atoms. Represents ~ 35 heterocycle-containing groups,
The aliphatic hydrocarbon group is a carbon-carbon double bond, —O—, —S—, —CO—, —COO—, —OCO—, —NH—, —SO 2 —, —CONH— or —NHCO. -, Or in some cases, oxygen atoms are replaced by linking groups combining them without being adjacent,
Z 1 to Z 4 are each independently a group in the same range as the group represented by Z 1 to Z 3 in the general formula (2),
* Means that it is bonded to an adjacent group at the * part. )
Figure JPOXMLDOC01-appb-C000015
 （上記一般式（４）中、Ｙ１３は、５価の炭素原子数２～３５の脂肪族炭化水素基、炭素原子数６～２０の芳香族炭化水素基又は炭素原子数２～２０の複素環含有基を表し、
　該脂肪族炭化水素基は、炭素－炭素二重結合、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－ＳＯ2－、－ＣＯＮＨ－若しくは－ＮＨＣＯ－、又は酸素原子が隣り合うことなしにこれらを組み合わせた結合基で置き換えられている場合もあり、
　Ｚ1～Ｚ5は、それぞれ独立に、上記一般式（２）におけるＺ1～Ｚ３で表される基と同じ範囲の基であり、
　＊は、＊部分で、隣接する基と結合することを意味する。）
Figure JPOXMLDOC01-appb-C000015
 (In the above general formula (4), Y 13 represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a complex having 2 to 20 carbon atoms. Represents a ring-containing group,
The aliphatic hydrocarbon group is a carbon-carbon double bond, —O—, —S—, —CO—, —COO—, —OCO—, —NH—, —SO 2 —, —CONH— or —NHCO. -, Or in some cases, oxygen atoms are replaced by linking groups combining them without being adjacent,
Z 1 to Z 5 are each independently a group in the same range as the group represented by Z 1 to Z 3 in the general formula (2),
* Means that it is bonded to an adjacent group at the * part. )
Figure JPOXMLDOC01-appb-C000016
 （上記一般式（５）中、Ｙ１４は、６価の炭素原子数２～３５の脂肪族炭化水素基、炭素原子数６～３５の芳香族炭化水素基又は炭素原子数２～３５の複素環含有基を表し、
　該脂肪族炭化水素基は、炭素－炭素二重結合、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－ＳＯ2－、－ＣＯＮＨ－若しくは－ＮＨＣＯ－、又は酸素原子が隣り合うことなしにこれらを組み合わせた結合基で置き換えられている場合もあり、
　Ｚ1～Ｚ6は、それぞれ独立に、上記一般式（２）におけるＺ1～Ｚ３で表される基と同じ範囲の基であり、
　＊は、＊部分で、隣接する基と結合することを意味する。）
Figure JPOXMLDOC01-appb-C000016
 (In the above general formula (5), Y 14 represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a complex having 2 to 35 carbon atoms. Represents a ring-containing group,
The aliphatic hydrocarbon group is a carbon-carbon double bond, —O—, —S—, —CO—, —COO—, —OCO—, —NH—, —SO 2 —, —CONH— or —NHCO. -, Or in some cases, oxygen atoms are replaced by linking groups combining them without being adjacent,
Z 1 to Z 6 are each independently a group in the same range as the group represented by Z 1 to Z 3 in the general formula (2),
* Means that it is bonded to an adjacent group at the * part. )
　上記一般式（１）において、Ｒ５、Ｒ６及びＲ７で表される、置換基を有している場合もある炭素原子数１～３５の脂肪族炭化水素基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した１価の脂肪族炭化水素基、及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基を表す基の置換基として例示したものにより置換された基のうち、所定の炭素原子数を満たすもの等が挙げられ、
　Ｒ５、Ｒ６及びＲ７で表される、置換基を有している場合もある炭素原子数６～３５の芳香環含有炭化水素基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した１価の芳香環含有炭化水素基、及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基を表す基の置換基として例示したものにより置換された基のうち、所定の炭素原子数を満たすもの等が挙げられ、
　Ｒ５、Ｒ６及びＲ７で表される、置換基を有している場合もある炭素原子数２～３５の複素環含有基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した１価の複素環含有基、及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合を表す基の置換基として例示したものにより置換された基のうち、所定の炭素原子数を満たすもの等が挙げられる。
　また、上記一般式（１）においてＹ1で表される、２価の炭素原子数１～３５の脂肪族炭化水素基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した２価の脂肪族炭化水素基、及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基を表す基の置換基として例示したものにより置換された基のうち、所定の炭素原子数を満たすもの等が挙げられ、
　Ｙ1で表される２価の炭素原子数６～３５の芳香環含有炭化水素基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した２価の芳香環含有炭化水素基、及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基を表す基の置換基として例示したものにより置換された基のうち、所定の炭素原子数を満たすもの等が挙げられ、
　Ｙ1で表される２価の炭素原子数２～３５の複素環含有基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した２価の芳香環含有炭化水素基、及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基を表す基の置換基として例示したものにより置換された基のうち、所定の炭素原子数を満たすもの等が挙げられる。 In the general formula (1), the aliphatic hydrocarbon group having 1 to 35 carbon atoms, which may have a substituent, represented by R 5 , R 6 and R 7 includes the above general formula ( The monovalent aliphatic hydrocarbon group exemplified as the n-valent linking group represented by X 1 in IA), and the n valence represented by X 1 in the general formula (IA). Among the groups substituted by those exemplified as the substituent of the group representing the bonding group, those satisfying the predetermined number of carbon atoms, and the like can be mentioned,
Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent represented by R 5 , R 6 and R 7 include X 1 in the above general formula (IA). A monovalent aromatic ring-containing hydrocarbon group exemplified as an n-valent linking group represented by formula (I), and a group in which these groups represent an n-valent linking group represented by X 1 in formula (IA). Among the groups substituted by those exemplified as the substituents in the above, those satisfying a predetermined number of carbon atoms, etc.
The heterocyclic group having 2 to 35 carbon atoms which may have a substituent represented by R 5 , R 6 and R 7 is represented by X 1 in the above general formula (IA). And monovalent heterocycle-containing groups exemplified as the n-valent linking group, and these groups are exemplified as substituents of the group representing the n-valent bond represented by X 1 in the general formula (IA). Among those substituted by the above, those satisfying a predetermined number of carbon atoms can be mentioned.
In addition, the divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 1 in the general formula (1) is an n represented by X 1 in the general formula (IA). Examples of the divalent aliphatic hydrocarbon group exemplified as the valent linking group, and substituents of the group representing the n-valent linking group represented by X 1 in the general formula (IA). Among the groups substituted by ones, those satisfying a predetermined number of carbon atoms, etc. are mentioned,
Examples of the divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 1 include the divalent groups exemplified as the n-valent linking group represented by X 1 in the general formula (IA). Of these aromatic ring-containing hydrocarbon groups and groups substituted by those exemplified as the substituents of the group representing the n-valent linking group represented by X 1 in the general formula (IA). And those satisfying a predetermined number of carbon atoms.
Examples of the divalent heterocyclic group having 2 to 35 carbon atoms represented by Y 1 include the divalent aromatic compounds exemplified as the n-valent linking group represented by X 1 in the general formula (IA). Of the ring-containing hydrocarbon groups and groups substituted by those exemplified as the substituents of the group representing the n-valent linking group represented by X 1 in the general formula (IA) And the like satisfying the number of carbon atoms.
　上記（１－１）で表される置換基において、Ｒ８で表される炭素原子数３～１０のシクロアルキル基としては、シクロプロピル、シクロブチル、シクロペンチル、シクロへブチル、シクロオクチル等が挙げられ、
　Ｒ９で表される炭素原子数１～１０のアルキル基としては、Ｒ１及びＲ２で表される炭素原子数１～４０のアルキル基として例示した基のうち、所定の炭素原子数を満たす基等が挙げられ、
　Ｒ９で表される炭素原子数１～１０のアルコキシ基としては、メチルオキシ、エチルオキシ、プロピルオキシ、イソプロピルオキシ、ブチルオキシ、第二ブチルオキシ、第三ブチルオキシ、イソブチルオキシ、アミルオキシ、イソアミルオキシ、第三アミルオキシ、ヘキシルオキシ、シクロヘキシルオキシ、ヘプチルオキシ、イソヘプチルオキシ、第三ヘプチルオキシ、ｎ－オクチルオキシ、イソオクチルオキシ、第三オクチルオキシ、２－エチルヘキシルオキシ、ノニルオキシ、デシルオキシ等が挙げられ、
　フェニル基、シクロアルキル基、アルキル基、アルコキシ基及びアルケニル基の置換基は、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものと同様である。 In the substituent represented by (1-1) above, examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R 8 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. ,
The alkyl group having 1 to 10 carbon atoms represented by R 9 satisfies the predetermined number of carbon atoms among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by R 1 and R 2. Groups, etc.
Examples of the alkoxy group having 1 to 10 carbon atoms represented by R 9 include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, tert-butyloxy, isobutyloxy, amyloxy, isoamyloxy, tert-amyloxy Hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, etc.
The substituents of the phenyl group, cycloalkyl group, alkyl group, alkoxy group and alkenyl group are the same as those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA). is there.
　上記（１－３）で表される基において、Ｒ10及びＲ11で表される、置換基を有している場合もある炭素原子数１～１０のアルキル基としては、Ｒ１及びＲ２で表される炭素原子数１～４０のアルキル基として例示した基のうち、所定の炭素原子数を満たす基等が挙げられ、
　Ｒ10及びＲ11で表される、置換基を有している場合もある炭素原子数６～２０のアリール基としては、Ｒ１及びＲ２で表される炭素原子数６～２０のアリール基として例示した基等が挙げられ、
　Ｒ10及びＲ11で表される、置換基を有している場合もある炭素原子数６～２０のアリールオキシ基としては、フェニルオキシ、ナフチルオキシ、２－メチルフェニルオキシ、３－メチルフェニルオキシ、４－メチルフェニルオキシ、４－ビニルフェニル二オキシ、３－ｉｓｏ－プロピルフェニルオキシ、４－ｉｓｏ－プロピルフェニルオキシ、４－ブチルフェニルオキシ、４－ｔｅｒｔ－ブチルフェニルオキシ、４－へキシルフェニルオキシ、４－シクロヘキシルフェニルオキシ、４－オクチルフェニルオキシ、４－（２－エチルヘキシル）フェニルオキシ、２，３－ジメチルフェニルオキシ、２，４－ジメチルフェニルオキシ、２，５－ジメチルフェニルオキシ、２．６－ジメチルフェニルオキシ、３．４－ジメチルフェニルオキシ、３．５－ジメチルフェニルオキシ、２，４－ジーｔｅｒｔ－ブチルフェニルオキシ、２，５－ジーｔｅｒｔ－ブチルフェニルオキシ、２，６－ジーｔｅｒｔ－ブチルフェニルオキシ、２．４－ジーｔｅｒｔ－ペンチルフェニルオキシ、２，５－ｔｅｒｔ－アミルフェニルオキシ、４－シクロへキシルフェニルオキシ、２，４，５－トリメチルフェニルオキシ、フェロセニルオキシ等の基が奉げられ、
　Ｒ10及びＲ11で表される、置換基を有している場合もある炭素原子数６～２０のアリールチオ基としては、上記置換基を有している場合もある炭素原子数６～２０のアリールオキシ基の酸素原子を硫黄原子に置換した基等が奉げられ、
　Ｒ10及びＲ11で表される、置換基を有している場合もある炭素原子数８～２０のアリールアルケニル基としては、上記置換基を有している場合もある炭素原子数６～２０のアリールオキシ基の酸素原子をビニル、アリル、１－プロペニル、イソプロペニル、２－ブテニル、１，３－ブタジエニル、２－ペンテニル、２－オクテニル等のアルケニル基で置換した基等が挙げられ、
　Ｒ10及びＲ11で表される、置換基を有している場合もある炭素原子数７～２０のアリールアルキル基としては、Ｒ１及びＲ２で表される炭素原子数７～２０のアリールアルキル基として例示した基等が挙げられ、
　Ｒ10及びＲ11で表される、置換基を有している場合もある炭素原子数２～２０の複素環含有基としては、Ｒ１及びＲ２で表される炭素原子数２～２０の複素環含有基として例示した基等が挙げられる。 In the group represented by (1-3) above, the alkyl group having 1 to 10 carbon atoms, which may have a substituent, represented by R 10 and R 11 includes R 1 and R 2 Among the groups exemplified as the alkyl group having 1 to 40 carbon atoms represented by the following:
Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent represented by R 10 and R 11 include an aryl group having 6 to 20 carbon atoms represented by R 1 and R 2 And the groups exemplified as
Examples of the aryloxy group having 6 to 20 carbon atoms which may have a substituent represented by R 10 and R 11 include phenyloxy, naphthyloxy, 2-methylphenyloxy, 3-methylphenyloxy 4-methylphenyloxy, 4-vinylphenyldioxy, 3-iso-propylphenyloxy, 4-iso-propylphenyloxy, 4-butylphenyloxy, 4-tert-butylphenyloxy, 4-hexylphenyloxy 4-cyclohexylphenyloxy, 4-octylphenyloxy, 4- (2-ethylhexyl) phenyloxy, 2,3-dimethylphenyloxy, 2,4-dimethylphenyloxy, 2,5-dimethylphenyloxy, 2.6 -Dimethylphenyloxy, 3.4-dimethylphenyloxy, 3. -Dimethylphenyloxy, 2,4-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, 2,6-di-tert-butylphenyloxy, 2.4-di-tert-pentylphenyloxy, 2 , 5-tert-amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, ferrocenyloxy, etc.
The arylthio group having 6 to 20 carbon atoms which may have a substituent represented by R 10 and R 11 is an arylthio group having 6 to 20 carbon atoms which may have the above-mentioned substituent. A group in which the oxygen atom of the aryloxy group is replaced with a sulfur atom, etc.
The arylalkenyl group having 8 to 20 carbon atoms which may have a substituent, represented by R 10 and R 11 , may have 6 to 20 carbon atoms which may have the above-mentioned substituent. Groups in which the oxygen atom of the aryloxy group is substituted with an alkenyl group such as vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl, and the like,
Examples of the arylalkyl group having 7 to 20 carbon atoms which may have a substituent represented by R 10 and R 11 include aryl having 7 to 20 carbon atoms represented by R 1 and R 2 Examples include the groups exemplified as the alkyl group,
Examples of the heterocyclic group having 2 to 20 carbon atoms which may have a substituent represented by R 10 and R 11 include those having 2 to 20 carbon atoms represented by R 1 and R 2 . The group etc. which were illustrated as a heterocyclic containing group are mentioned.
　上記一般式（２）におけるＹ11で表される３価の炭素原子数１～３５の脂肪族炭化水素基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した３価の脂肪族炭化水素基及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものにより置換された基のうち、所定の炭素原子数を満たすもの等が、Ｚ1、Ｚ2及びＺ3で置換された３価の基等が挙げられ、
　上記一般式（２）におけるＹ11で表される３価の炭素原子数３～３５の脂環族炭化水素基としては、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロデカニル、１－アダマンチル、２－アダマンチル、ノルアダマンチル、２－メチルアダマンチル、ノルボルニル、イソノルボルニル、パーヒドロナフチル、パーヒドロアントラセニル、ビシクロ［１．１．０］ブチル、ビシクロ［１．１．１］ペンチル、ビシクロ［２．１．０］ペンチル、ビシクロ［３．１．０］ヘキシル、ビシクロ［２．１．１］ヘキシル、ビシクロ［２．２．０］ヘキシル、ビシクロ［４．１．０］ヘプチル、ビシクロ［３．２．０］ヘプチル、ビシクロ［３．１．１］ヘプチル、ビシクロ［２．２．１］ヘプチル、ビシクロ［５．１．０］オクチル、ビシクロ［４．２．０］オクチル、ビシクロ［４．１．１］オクチル、ビシクロ［３．３．０］オクチル、ビシクロ［３．２．１］オクチル、ビシクロ［２．２．２］オクチル、スピロ〔４，４〕ノナニル、スピロ〔４，５〕デカニル、デカリン、トリシクロデカニル、テトラシクロドデカニル、セドロール、シクロドデカニル等の基から誘導される３価の基等が挙げられ、
　Ｙ11で表される３価の炭素原子数６～３５の芳香環含有炭化水素基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した３価の芳香環含有炭化水素基及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものにより置換された基のうち、所定の炭素原子数を満たすもの等が挙げられ、
　Ｙ11で表される３価の炭素原子数２～３５の複素環含有基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した３価の複素環含有基及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものにより置換された基のうち、所定の炭素原子数を満たすもの等が挙げられる。
　また、Ｒ１２で表される、置換基を有している場合もある炭素原子数１～３５の脂肪族炭化水素基、置換基を有している場合もある炭素原子数６～３５の芳香族炭化水素基及び置換基を有している場合もある炭素原子数２～３５の複素環含有基としては、それぞれ、上記一般式（１）におけるＲ５、Ｒ６及びＲ７の説明で例示した脂肪族炭化水素基、芳香環含有炭化水素基、複素環含有基が挙げられる。 Examples of the trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 11 in the general formula (2) include an n-valent bond represented by X 1 in the general formula (IA). Of the trivalent aliphatic hydrocarbon group exemplified as the group and groups substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA). Among them, those satisfying the predetermined number of carbon atoms include trivalent groups substituted with Z 1 , Z 2 and Z 3 , etc.
Examples of the trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms represented by Y 11 in the general formula (2) include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecanyl, 1-adamantyl, 2- Adamantyl, noradamantyl, 2-methyladamantyl, norbornyl, isonorbornyl, perhydronaphthyl, perhydroanthracenyl, bicyclo [1.1.0] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.1. 0] pentyl, bicyclo [3.1.0] hexyl, bicyclo [2.1.1] hexyl, bicyclo [2.2.0] hexyl, bicyclo [4.1.0] heptyl, bicyclo [3.2. 0] heptyl, bicyclo [3.1.1] heptyl, bicyclo [2.2.1] heptyl, bicyclo [5.1.0] Octyl, bicyclo [4.2.0] octyl, bicyclo [4.1.1] octyl, bicyclo [3.3.0] octyl, bicyclo [3.2.1] octyl, bicyclo [2.2.2] And trivalent groups derived from groups such as octyl, spiro [4,4] nonanyl, spiro [4,5] decanyl, decalin, tricyclodecanyl, tetracyclododecanyl, cedrol, cyclododecanyl, etc. ,
Examples of the trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 11 include the trivalent groups exemplified as the n-valent linking group represented by X 1 in the general formula (IA). Of the aromatic ring-containing hydrocarbon group and a group in which these groups are substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA). And those that satisfy the number of atoms.
Examples of the trivalent heterocyclic group having 2 to 35 carbon atoms represented by Y 11 include the trivalent complex exemplified as the n-valent linking group represented by X 1 in the general formula (IA). Among the ring-containing groups and groups substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the above general formula (IA), the predetermined number of carbon atoms is satisfied. And the like.
In addition, an aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent represented by R 12 , and an aromatic group having 6 to 35 carbon atoms which may have a substituent. Examples of the heterocyclic group having 2 to 35 carbon atoms which may have a hydrocarbon group and a substituent may be exemplified in the description of R 5 , R 6 and R 7 in the general formula (1). And aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, and heterocyclic ring-containing groups.
　上記一般式（３）においてＹ12で表される、４価の炭素原子数１～３５の脂肪族炭化水素基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した１価～３価の脂肪族炭化水素基及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものにより置換された基から誘導される４価の基のうち、所定の炭素原子数を満たすもの等が挙げられ、
　Ｙ12で表される４価の炭素原子数６～３５の芳香環含有炭化水素基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した１価～３価の芳香環含有炭化水素基及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものにより置換された基から誘導される４価の基のうち、所定の炭素原子数を満たすもの等が挙げられ、
　Ｙ12で表される４価の炭素原子数２～３５の複素環含有基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した１価～３価の複素環含有基及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものにより置換された基から誘導される４価の基のうち、所定の炭素原子数を満たすもの等が挙げられる。 The tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 12 in the general formula (3) is an n-valent aliphatic hydrocarbon group represented by X 1 in the general formula (IA). Monovalent to trivalent aliphatic hydrocarbon groups exemplified as the linking group and these groups substituted by those exemplified as the substituents of the n-valent linking group represented by X 1 in the general formula (IA). Among the tetravalent groups derived from the generated groups, those satisfying a predetermined number of carbon atoms, and the like can be mentioned,
Examples of the tetravalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 12 include the monovalent groups exemplified as the n-valent linking group represented by X 1 in the general formula (IA). To a trivalent aromatic ring-containing hydrocarbon group and a group in which these groups are substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA). Among the tetravalent groups that satisfy the predetermined number of carbon atoms, and the like,
Examples of the tetravalent heterocyclic group having 2 to 35 carbon atoms represented by Y 12 include monovalent to 3 exemplified as the n-valent linking group represented by X 1 in the general formula (IA). A valent heterocyclic ring-containing group and a tetravalent group derived from these groups substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA). Among the groups, those satisfying a predetermined number of carbon atoms can be mentioned.
　上記一般式（４）におけるＹ13で表される５価の炭素原子数２～３５の脂肪族炭化水素基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した１価～３価の脂肪族炭化水素基及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものにより置換された基から誘導される５価の基のうち、所定の炭素原子数を満たすもの等が挙げられ、
　Ｙ14で表される５価の炭素原子数６～３５の芳香環含有炭化水素基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した１価～３価の芳香環含有炭化水素基及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものにより置換された基から誘導される５価の基のうち、所定の炭素原子数を満たすもの等が挙げられ、
　Ｙ14で表される５価の炭素原子数２～３５の複素環含有基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した１価～３価の複素環含有基及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものにより置換された基から誘導される５価の基のうち、所定の炭素原子数を満たすもの等が挙げられる。 The pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 13 in the general formula (4) is an n-valent bond represented by X 1 in the general formula (IA). The monovalent to trivalent aliphatic hydrocarbon groups exemplified as the groups and these groups are substituted by those exemplified as the substituents of the n-valent linking group represented by X 1 in the general formula (IA). Among the pentavalent groups derived from these groups, those satisfying a predetermined number of carbon atoms, etc.
The pentavalent aromatic group-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 14 is a monovalent group exemplified as the n-valent linking group represented by X 1 in the general formula (IA). To a trivalent aromatic ring-containing hydrocarbon group and a group in which these groups are substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA). Among the pentavalent groups that satisfy the predetermined number of carbon atoms, and the like,
Examples of the pentavalent heterocyclic group having 2 to 35 carbon atoms represented by Y 14 include monovalent to 3 exemplified as the n-valent linking group represented by X 1 in the general formula (IA). A valent heterocyclic ring-containing group and a pentavalent group derived from these groups substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA). Among the groups, those satisfying a predetermined number of carbon atoms can be mentioned.
　上記一般式（５）におけるＹ14で表される６価の炭素原子数２～３５の脂肪族炭化水素基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した１価～３価の脂肪族炭化水素基及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものにより置換された基から誘導される６価の基のうち、所定の炭素原子数を満たすもの等が挙げられ、
　Ｙ14で表される６価の炭素原子数６～３５の芳香環含有炭化水素基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した１価～３価の芳香環含有炭化水素基及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものにより置換された基から誘導される６価の基のうち、所定の炭素原子数を満たすもの等が挙げられ、
　Ｙ14で表される６価の炭素原子数２～３５の複素環含有基としては、上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基として例示した１価～３価の複素環含有基及びこれらの基が上記一般式（Ｉ－Ａ）におけるＸ１で表されるｎ価の結合基の置換基として例示したものにより置換された基から誘導される６価の基のうち、所定の炭素原子数を満たすもの等が挙げられる。 The hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 14 in the general formula (5) is an n-valent bond represented by X 1 in the general formula (IA). The monovalent to trivalent aliphatic hydrocarbon groups exemplified as the groups and these groups are substituted by those exemplified as the substituents of the n-valent linking group represented by X 1 in the general formula (IA). Among the hexavalent groups derived from these groups, those satisfying a predetermined number of carbon atoms, etc.
The hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 14 is a monovalent group exemplified as the n-valent linking group represented by X 1 in the general formula (IA). To a trivalent aromatic ring-containing hydrocarbon group and a group in which these groups are substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA). Among the hexavalent groups that satisfy the predetermined number of carbon atoms, and the like,
Examples of the hexavalent heterocyclic group having 2 to 35 carbon atoms represented by Y 14 include monovalent to 3 exemplified as the n-valent linking group represented by X 1 in the general formula (IA). A hexavalent divalent ring-containing group and a hexavalent group derived from the group substituted by those exemplified as the substituent of the n-valent linking group represented by X 1 in the general formula (IA). Among the groups, those satisfying a predetermined number of carbon atoms can be mentioned.
　上記一般式（Ｉ－Ａ）で表される化合物の中でも、下記一般式（ＩＩ－１）～（ＩＩ－３）で表されるものが、耐熱性が高くなるので好ましい。 Among the compounds represented by the above general formula (IA), those represented by the following general formulas (II-1) to (II-3) are preferable because of high heat resistance.
Figure JPOXMLDOC01-appb-C000017
 （式中、Ｒ８２、Ｒ８３及びＲ８４は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、又は置換基を有している場合もある炭素原子数１～４０のアルキル基、炭素原子数６～２０のアリール基、炭素原子数７～２０のアリールアルキル基若しくは炭素原子数２～２０の複素環含有基を表し、Ｒ１及びＲ２は、上記一般式（Ｉ）と同じである。）
Figure JPOXMLDOC01-appb-C000017
 (In the formula, each of R 82 , R 83 and R 84 independently has a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or a substituent, which may have 1 carbon atom. Represents an alkyl group having ˜40, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, wherein R 1 and R 2 are Same as formula (I).)
Figure JPOXMLDOC01-appb-C000018
 （式中、ｒ＝２～６であり、Ｘ２は、ｒ＝２のとき上記一般式（１）で表される基であり、ｒ＝３のとき上記一般式（２）で表される基であり、ｒ＝４のとき上記一般式（３）で表される基であり、ｒ＝５のとき上記一般式（４）であり、ｒ＝６のとき上記一般式（５）であり、Ｒ９２及びＲ９３は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、又は置換基を有している場合もある炭素原子数１～４０のアルキル基、炭素原子数６～２０のアリール基、炭素原子数７～２０のアリールアルキル基若しくは炭素原子数２～２０の複素環含有基を表し、Ｒ１及びＲ２は、上記一般式（Ｉ）と同じである。）
Figure JPOXMLDOC01-appb-C000018
 (Wherein r = 2 to 6 and X 2 is a group represented by the general formula (1) when r = 2, and represented by the general formula (2) when r = 3. A group represented by the general formula (3) when r = 4, a general formula (4) when r = 5, and a general formula (5) when r = 6. , R 92 and R 93 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an alkyl group having 1 to 40 carbon atoms, which may have a substituent, Represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms or a heterocyclic ring-containing group having 2 to 20 carbon atoms, wherein R 1 and R 2 are the same as those in the above general formula (I) .)
Figure JPOXMLDOC01-appb-C000019
 　（式中、Ｒ２０１、Ｒ２０２、Ｒ２０３、Ｒ２０４、Ｒ２０５、Ｒ２０６、Ｒ２０７、Ｒ２０８は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有している場合もある炭素原子数１～４０のアルキル基、炭素原子数６～２０のアリール基、炭素原子数７～２０のアリールアルキル基又は炭素原子数２～２０の複素環含有基を表し、Ｙ１、Ｚ１及びＺ２は、上記一般式（１）と同じである。）
Figure JPOXMLDOC01-appb-C000019
 (Wherein R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, An alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic ring having 2 to 20 carbon atoms, which may have a substituent Represents a containing group, and Y 1 , Z 1 and Z 2 are the same as those in the general formula (1).
　上記一般式（ＩＩ－１）におけるＲ82、Ｒ83及びＲ84で表されるハロゲン原子、置換基を有している場合もある炭素原子数１～４０のアルキル基、炭素原子数６～２０のアリール基、炭素原子数７～２０のアリールアルキル基、炭素原子数２～２０の複素環含有基としては、上記一般式（Ｉ）におけるＲ１及びＲ２の説明で例示したものが挙げられる。
　上記一般式（ＩＩ－２）におけるＲ92及びＲ93で表されるハロゲン原子、置換基を有している場合もある炭素原子数１～４０のアルキル基、炭素原子数６～２０のアリール基、炭素原子数７～２０のアリールアルキル基、炭素原子数２～２０の複素環含有基としては、上記一般式（Ｉ）におけるＲ１及びＲ２の説明で例示したものが挙げられる。
　上記一般式（ＩＩ－３）におけるＲ２０１、Ｒ２０２、Ｒ２０３、Ｒ２０４、Ｒ２０５、Ｒ２０６、Ｒ２０７、Ｒ２０８で表されるハロゲン原子、置換基を有している場合もある炭素原子数１～４０のアルキル基、炭素原子数６～２０のアリール基、炭素原子数７～２０のアリールアルキル基、炭素原子数２～２０の複素環含有基としては、上記一般式（Ｉ）におけるＲ１及びＲ２の説明で例示したものが挙げられる。 The halogen atom represented by R 82 , R 83 and R 84 in the general formula (II-1), an alkyl group having 1 to 40 carbon atoms which may have a substituent, and 6 to 20 carbon atoms As the aryl group, the arylalkyl group having 7 to 20 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms, those exemplified in the description of R 1 and R 2 in the general formula (I) can be given. .
The halogen atom represented by R 92 and R 93 in the general formula (II-2), an alkyl group having 1 to 40 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms Examples of the arylalkyl group having 7 to 20 carbon atoms and the heterocyclic ring-containing group having 2 to 20 carbon atoms include those exemplified in the description of R 1 and R 2 in the general formula (I).
Carbons that may have a halogen atom or a substituent represented by R 201 , R 202 , R 203 , R 204 , R 205 , R 206 , R 207 , R 208 in the general formula (II-3) Examples of the alkyl group having 1 to 40 atoms, the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the heterocyclic-containing group having 2 to 20 carbon atoms include those represented by the general formula (I). The thing illustrated by description of R < 1 > and R < 2 > in can be mentioned.
　上記一般式（ＩＩ－１）で表される化合物の中では、
　Ｒ１が分岐を有する炭素原子数１～８のアルキル基、特にｔ－ブチル基であり、Ｒ２が水素原子であるもの；Ｒ82、Ｒ83及びＲ84が、それぞれ独立に、水素原子、炭素原子数１～２０のアルキル基、炭素原子数６～１０のアリール基、炭素原子数７～１２のアリールアルキル基、炭素原子数１～１０の複素環含有基であるもの、特に、Ｒ82、Ｒ83及びＲ84の何れか１つが炭素原子数１～４のアルキル基又は炭素原子数１～１０の複素環含有基であるものが好ましい。 Among the compounds represented by the general formula (II-1),
R 1 is a branched alkyl group having 1 to 8 carbon atoms, particularly a t-butyl group, and R 2 is a hydrogen atom; R 82 , R 83 and R 84 are each independently a hydrogen atom, An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, a heterocyclic-containing group having 1 to 10 carbon atoms, particularly R 82 , R 83 and R 84 are preferably an alkyl group having 1 to 4 carbon atoms or a heterocyclic ring-containing group having 1 to 10 carbon atoms.
　上記一般式（ＩＩ－２）で表される化合物の中では、
　Ｒ１が分岐を有する炭素原子数１～８のアルキル基、特にｔ－ブチル基であり、Ｒ２が水素原子であるもの；Ｒ92及びＲ93が、それぞれ独立に、水素原子、炭素原子数１～２０のアルキル基、炭素原子数６～１０のアリール基、炭素原子数７～１２のアリールアルキル基、炭素原子数１～１０の複素環含有基であるもの、特に、Ｒ92又はＲ93が炭素原子数１～４のアルキル基又は炭素原子数１～１０の複素環含有基であるものが好ましい。
　Ｘ２が上記一般式（１）となる場合、Ｙ10が、硫黄原子、炭素原子数１～２０のアルキレン基、炭素原子数６～２５の２価の芳香環含有炭化水素基、炭素原子数２～２１の２価の複素環含有基、２，４，８，１０－テトラオキサスピロ［５，５］ウンデカンから誘導される２価の基、特に、炭素原子数１～１５のアルキレン基、炭素原子数６～１５の２価の芳香環含有炭化水素基、２，４，８，１０－テトラオキサスピロ［５，５］ウンデカンから誘導される２価の基であるものが好ましく、
　Ｚ1及びＺ2が直接結合、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－、又は置換基を有していても良い炭素原子数１～２０の脂肪族炭化水素基、炭素原子数６～１０の芳香族炭化水素基、特に置換基を有していても良い炭素原子数１～８の脂肪族炭化水素基であるものが好ましい。
　Ｘ２が上記一般式（２）となる場合、Ｙ11が、炭素原子数１～２０のアルキル基、炭素原子数６～１０のアリール基、炭素原子数７～１２のアリールアルキル基又は炭素原子数１～１０の複素環含有基から誘導される３価の基、特に、炭素原子数１～８のアルキル基、炭素原子数６～９のアリール基又は炭素原子数１～６の複素環含有基から誘導される３価の基であるものが好ましく、
　Ｚ1、Ｚ2及びＺ3は、Ｚ1及びＺ2と同様のものが好ましく、
　Ｘ２が上記一般式（３）となる場合、Ｙ12は、好ましいＹ11として上に挙げた基に対応する４価の基が好ましく、
　Ｚ1～Ｚ4は、Ｚ1及びＺ2と同様であるものが好ましく、
　Ｘ２が上記一般式（４）となる場合、Ｙ13は、好ましいＹ11として上に挙げた基に対応する５価の基が好ましく、
　Ｚ1～Ｚ5はＺ1及びＺ2と同様であるものが好ましく、
　Ｘ２が上記一般式（５）となる場合、Ｙ14は、好ましいＹ11として上に挙げた基に対応する６価の基が好ましく、
　Ｚ1～Ｚ6は、Ｚ1及びＺ2と同様であるものが好ましい。 Among the compounds represented by the general formula (II-2),
R 1 is a branched alkyl group having 1 to 8 carbon atoms, particularly a t-butyl group, and R 2 is a hydrogen atom; R 92 and R 93 are each independently a hydrogen atom or carbon atom number An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, a heterocyclic-containing group having 1 to 10 carbon atoms, particularly R 92 or R 93 Is preferably an alkyl group having 1 to 4 carbon atoms or a heterocyclic-containing group having 1 to 10 carbon atoms.
When X 2 is the above general formula (1), Y 10 is a sulfur atom, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring-containing hydrocarbon group having 6 to 25 carbon atoms, the number of carbon atoms 2 to 21 divalent heterocyclic ring-containing groups, divalent groups derived from 2,4,8,10-tetraoxaspiro [5,5] undecane, particularly alkylene groups having 1 to 15 carbon atoms, A divalent aromatic ring-containing hydrocarbon group having 6 to 15 carbon atoms and a divalent group derived from 2,4,8,10-tetraoxaspiro [5,5] undecane are preferred,
Z 1 and Z 2 are a direct bond, —CO—O—, —O—CO—, an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, or 6 to 10 carbon atoms. Of these, an aromatic hydrocarbon group, particularly an aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, is preferred.
When X 2 is the above general formula (2), Y 11 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or a carbon atom A trivalent group derived from a heterocyclic group having 1 to 10 carbon atoms, particularly an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 9 carbon atoms, or a heterocyclic ring having 1 to 6 carbon atoms Those which are trivalent groups derived from a group are preferred,
Z 1 , Z 2 and Z 3 are preferably the same as Z 1 and Z 2 ,
When X 2 is the above general formula (3), Y 12 is preferably a tetravalent group corresponding to the group listed above as preferred Y 11 ,
Z 1 to Z 4 are preferably the same as Z 1 and Z 2 ,
When X 2 is the above general formula (4), Y 13 is preferably a pentavalent group corresponding to the group listed above as preferred Y 11 ,
Z 1 to Z 5 are preferably the same as Z 1 and Z 2 ,
When X 2 is represented by the general formula (5), Y 14 is preferably a hexavalent group corresponding to the group listed above as preferred Y 11 ,
Z 1 to Z 6 are preferably the same as Z 1 and Z 2 .
　上記一般式（Ｉ）で表される化合物うち、好ましいものとしては、下記[化１４]～[化１５]に示す化合物が挙げられるが、本発明はこれらの化合物に制限されない。 Among the compounds represented by the above general formula (I), preferred are the compounds shown in the following [Chemical 14] to [Chemical 15], but the present invention is not limited to these compounds.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　上記一般式（Ｉ）で表される置換基を有する化合物の製造方法は特に限定されないが、例えば、特開昭５７－１１１３７５号、特開平３－１７３８４３号、特開平６－１２８１９５号、特開平７－２０６７７１号、特開平７－２５２１９１号、特表２００４－５０１１２８の各公報に記載された方法により製造されたフェノール系化合物と、ハロゲン化アリル化合物等を反応させて得ることができる。 The production method of the compound having a substituent represented by the above general formula (I) is not particularly limited. For example, JP-A-57-111375, JP-A-3-173843, JP-A-6-128195, JP-A-6-128195 It can be obtained by reacting a phenolic compound produced by the methods described in JP-A-7-206871, JP-A-7-252191 and JP-T-2004-501128 with an allyl halide compound.
　上記一般式（Ｉ）で表される置換基を有する化合物は、本発明の感光性組成物において、潜在性添加剤として用いることができる。
　上記潜在性添加剤とは、常温、あるいは１５０℃以下、例えば１５０℃以下のプリベーク工程では不活性であり、１００～２５０℃で加熱するか、あるいは酸／塩基触媒存在下で８０～２００℃で加熱することにより、保護基が脱離して活性となるものである。 The compound having a substituent represented by the general formula (I) can be used as a latent additive in the photosensitive composition of the present invention.
The latent additive is inactive in a pre-bake process at room temperature or 150 ° C. or less, for example 150 ° C. or less, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. By heating, the protecting group is eliminated and becomes active.
　本発明の感光性組成物において、潜在性添加剤としての上記一般式（Ｉ）で表される置換基を有する化合物の含有量は、本発明の組成物の固形分中、０．００１～２０質量％が好ましく、０．００５～５質量％がより好ましい。 In the photosensitive composition of the present invention, the content of the compound having a substituent represented by the general formula (I) as a latent additive is 0.001 to 20 in the solid content of the composition of the present invention. % By mass is preferable, and 0.005 to 5% by mass is more preferable.
　本発明の感光性組成物は、光照射により性質が変わる組成物であり、化学反応に対して可溶となるものにポジ型レジスト、化学反応に対して不溶となるものにネガ型レジストがある。本発明の感光性組成物は、上記一般式（Ｉ）で表される置換基を有する化合物を潜在性酸化防止剤として含む他、酸価を有するエチレン性不飽和結合を有する重合性化合物及び光ラジカル重合開始剤を必須成分として含む。
　該酸価を有するエチレン性不飽和結合を有する重合性化合物としては、(メタ)アクリル酸、α－クロルアクリル酸、イタコン酸、マレイン酸、シトラコン酸、フマル酸、ハイミック酸、クロトン酸、イソクロトン酸、ビニル酢酸、アリル酢酸、桂皮酸、ソルビン酸、メサコン酸、コハク酸モノ［２－（メタ）アクリロイロキシエチル］、フタル酸モノ［２－（メタ）アクリロイロキシエチル］、ω－カルボキシポリカプロラクトンモノ（メタ）アクリレート等の両末端にカルボキシ基と水酸基とを有するポリマーのモノ（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート・マレート、ヒドロキシプロピル（メタ）アクリレート・マレート、ジシクロペンタジエン・マレート或いは1個のカルボキシル基と２個以上の(メタ)アクリロイル基とを有する多官能（メタ）アクリレート等の不飽和多塩基酸；フェノール及び／又はクレゾールノボラックエポキシ樹脂、ビフェニル骨格、ナフタレン骨格を有するノボラックエポキシ樹脂、ビスフェノールＡノボラック型エポキシ化合物、ジシクロペンタジエンノボラック型エポキシ化合物等のノボラック型エポキシ化合物、多官能エポキシ基を有するポリフェニルメタン型エポキシ樹脂、下記一般式（III）で表されるエポキシ化合物等のエポキシ樹脂のエポキシ基に不飽和一塩基酸を作用させた樹脂、エポキシ樹脂のエポキシ基に不飽和一塩基酸を作用させ、更に多塩基酸無水物を作用させて得られた樹脂、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート等の水酸基含有多官能アクリレートと無水コハク酸、無水フタル酸、テトラヒドロ無水フタル酸等の二塩基酸無水物の反応物である酸価を有する多官能アクリレート等が挙げられる。 The photosensitive composition of the present invention is a composition whose properties are changed by light irradiation. A positive resist is one that is soluble in a chemical reaction, and a negative resist is one that is insoluble in a chemical reaction. . The photosensitive composition of the present invention contains a compound having a substituent represented by the above general formula (I) as a latent antioxidant, a polymerizable compound having an ethylenically unsaturated bond having an acid value, and light. A radical polymerization initiator is contained as an essential component.
Examples of the polymerizable compound having an ethylenically unsaturated bond having an acid value include (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, and isocrotonic acid. Vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypoly Mono (meth) acrylate, hydroxyethyl (meth) acrylate / malate, hydroxypropyl (meth) acrylate / malate, dicyclopentadiene / malate, which has a carboxy group and a hydroxyl group at both ends, such as caprolactone mono (meth) acrylate 1 carboxyl group and 2 or more (meth) acryloyl Unsaturated polybasic acids such as polyfunctional (meth) acrylates having a group; phenol and / or cresol novolac epoxy resin, biphenyl skeleton, novolac epoxy resin having naphthalene skeleton, bisphenol A novolac epoxy compound, dicyclopentadiene novolac type An unsaturated monobasic acid is allowed to act on the epoxy group of an epoxy resin such as an epoxy compound such as an epoxy compound, a polyphenylmethane type epoxy resin having a polyfunctional epoxy group, and an epoxy compound represented by the following general formula (III) Resin obtained by allowing unsaturated monobasic acid to act on the epoxy group of epoxy resin, epoxy resin, and polybasic acid anhydride, polyfunctional acrylate containing hydroxyl group such as pentaerythritol triacrylate, dipentaerythritol pentaacrylate When Water succinic acid, phthalic acid anhydride, a polyfunctional acrylate having an acid value which is a reaction product of a dibasic acid anhydride such as tetrahydrophthalic anhydride.
Figure JPOXMLDOC01-appb-C000022
 （式中、Ｘ41は直接結合、置換基を有している場合もある炭素原子数１～４のアルキレン基、置換基を有している場合もある炭素原子数３～２０の脂環式炭化水素基、－Ｏ－、－Ｓ－、－ＳＯ2－、－ＳＳ－、－ＳＯ－、－ＣＯ－、－ＯＣＯ－又は上記（１－１）～（１－３）で表される置換基を表し、
　Ｒ41、Ｒ42、Ｒ43及びＲ44は、それぞれ独立に、水素原子、置換基を有している場合もある炭素原子数１～５のアルキル基、置換基を有している場合もある炭素原子数１～８のアルコキシ基、置換基を有している場合もある炭素原子数２～５のアルケニル基又はハロゲン原子を表し、
　ｍは０～１０の整数である。）
Figure JPOXMLDOC01-appb-C000022
 Wherein X 41 is a direct bond, an alkylene group having 1 to 4 carbon atoms which may have a substituent, or an alicyclic group having 3 to 20 carbon atoms which may have a substituent. Hydrocarbon group, —O—, —S—, —SO 2 —, —SS—, —SO—, —CO—, —OCO— or a substitution represented by the above (1-1) to (1-3) Represents a group,
R 41 , R 42 , R 43 and R 44 each independently have a hydrogen atom, a substituent or a C 1-5 alkyl group or a substituent. An alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms which may have a substituent, or a halogen atom;
m is an integer of 0 to 10. )
　これらの酸価を有するエチレン性不飽和結合を有する重合性化合物は、単独で又は２種以上を混合して使用することができ、また、酸価を有しないエチレン性不飽和結合を有する重合性化合物と組み合わせて使用することができる。２種以上を混合して使用する場合には、それらを予め共重合して共重合体として使用してもよい。
　本発明の感光性組成物において、酸価を有するエチレン性不飽和結合を有する重合性化合物の含有量は、本発明の組成物の固形分中、２０～８０質量％が好ましく、固形分中の３０～７０質量％がさらに好ましい。 These polymerizable compounds having an ethylenically unsaturated bond having an acid value can be used alone or in admixture of two or more, and are polymerizable having an ethylenically unsaturated bond having no acid value. It can be used in combination with a compound. When two or more kinds are mixed and used, they may be copolymerized in advance and used as a copolymer.
In the photosensitive composition of the present invention, the content of the polymerizable compound having an ethylenically unsaturated bond having an acid value is preferably 20 to 80% by mass in the solid content of the composition of the present invention. More preferred is 30 to 70% by mass.
　上記酸価を有しないエチレン性不飽和結合を有する重合性化合物としては、例えば、(メタ)アクリル酸－２－ヒドロキシエチル、（メタ）アクリル酸－２－ヒドロキシプロピル、（メタ）アクリル酸グリシジル、下記化合物Ｎｏ．Ａ１～Ｎｏ．Ａ４、（メタ）アクリル酸メチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸－ｔ－ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸ジメチルアミノメチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸アミノプロピル、（メタ）アクリル酸ジメチルアミノプロピル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸ポリ（エトキシ）エチル、（メタ）アクリル酸ブトキシエトキシエチル、（メタ）アクリル酸エチルヘキシル、（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸テトラヒドロフリル、（メタ）アクリル酸ビニル、（メタ）アクリル酸アリル、（メタ）アクリル酸ベンジル、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリシクロデカンジメチロールジ（メタ）アクリレート、トリ［（メタ）アクリロイルエチル］イソシアヌレート、ポリエステル（メタ）アクリレートオリゴマー等の不飽和一塩基酸及び多価アルコール又は多価フェノールのエステル；（メタ）アクリル酸亜鉛、（メタ）アクリル酸マグネシウム等の不飽和多塩基酸の金属塩；マレイン酸無水物、イタコン酸無水物、シトラコン酸無水物、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸、５－（２，５－ジオキソテトラヒドロフリル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物、トリアルキルテトラヒドロ無水フタル酸－無水マレイン酸付加物、ドデセニル無水コハク酸、無水メチルハイミック酸等の不飽和多塩基酸の酸無水物；（メタ）アクリルアミド、メチレンビス－（メタ）アクリルアミド、ジエチレントリアミントリス（メタ）アクリルアミド、キシリレンビス（メタ）アクリルアミド、α－クロロアクリルアミド、Ｎ－２－ヒドロキシエチル（メタ）アクリルアミド等の不飽和一塩基酸及び多価アミンのアミド；アクロレイン等の不飽和アルデヒド；（メタ）アクリロニトリル、α－クロロアクリロニトリル、シアン化ビニリデン、シアン化アリル等の不飽和ニトリル；スチレン、４－メチルスチレン、４－エチルスチレン、４－メトキシスチレン、４－ヒドロキシスチレン、４－クロロスチレン、ジビニルベンゼン、ビニルトルエン、ビニル安息香酸、ビニルフェノール、ビニルスルホン酸、４－ビニルベンゼンスルホン酸、ビニルベンジルメチルエーテル、ビニルベンジルグリシジルエーテル等の不飽和芳香族化合物；メチルビニルケトン等の不飽和ケトン；ビニルアミン、アリルアミン、Ｎ－ビニルピロリドン、ビニルピペリジン等の不飽和アミン化合物；ビニルメチルエーテル、ビニルエチルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル、アリルグリシジルエーテル等のビニルエーテル；マレイミド、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等の不飽和イミド類；インデン、１－メチルインデン等のインデン類；１，３－ブタジエン、イソプレン、クロロプレン等の脂肪族共役ジエン類；ポリスチレン、ポリメチル（メタ）アクリレート、ポリ－ｎ－ブチル（メタ）アクリレート、ポリシロキサン等の重合体分子鎖の末端にモノ（メタ）アクリロイル基を有するマクロモノマー類；（メタ）アクリロニトリル、エチレン、プロピレン、ブチレン、塩化ビニル、酢酸ビニル等のその他のビニル化合物、及びポリメチルメタクリレートマクロモノマー、ポリスチレンマクロモノマー等のマクロモノマー類、トリシクロデカン骨格のモノメタクリレート、Ｎ－フェニルマレイミド、メタクリロイルオキシメチル－３－エチルオキセタン等と、（メタ）アクリル酸との共重合体及びこれらに昭和電工（株）社製カレンズＭＯＩ、ＡＯＩのような不飽和結合を有するイソシアネート化合物を反応させた（メタ）アクリル酸の共重合体や、ビニルクロリド、ビニリデンクロリド、ジビニルスクシナート、ジアリルフタラート、トリアリルホスファート、トリアリルイソシアヌラート、ビニルチオエーテル、ビニルイミダゾール、ビニルオキサゾリン、ビニルカルバゾール、ビニルピロリドン、ビニルピリジン、水酸基含有ビニルモノマー及びポリイソシアネート化合物のビニルウレタン化合物、水酸基含有ビニルモノマー及びポリエポキシ化合物のビニルエポキシ化合物、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート等の水酸基含有多官能アクリレートとトリレンジイソシアネート、ヘキサメチレンジイソシアネート等の多官能イソシアネートの反応物等が挙げられる。 Examples of the polymerizable compound having an ethylenically unsaturated bond having no acid value include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, The following compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Enoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyl toluene, vinyl benzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide; indene Indene such as 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; polystyrene, polymethyl (meth) acrylate, poly-n- Macromonomers having a mono (meth) acryloyl group at the end of the polymer molecular chain such as til (meth) acrylate and polysiloxane; (meth) acrylonitrile, ethylene, propylene, butylene, vinyl chloride, vinyl acetate and other vinyls (Meth) acrylic acid, a compound, macromonomers such as polymethyl methacrylate macromonomer and polystyrene macromonomer, tricyclodecane skeleton monomethacrylate, N-phenylmaleimide, methacryloyloxymethyl-3-ethyloxetane, etc. Polymers and copolymers of (meth) acrylic acid in which an isocyanate compound having an unsaturated bond such as Karenz MOI and AOI manufactured by Showa Denko Co., Ltd. is reacted, vinyl chloride, vinylidene chloride, divinyl succin Naruto, Allyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and polyisocyanate vinyl urethane compounds, hydroxyl group-containing vinyl monomers And a reaction product of a polyfunctional isocyanate such as tolylene diisocyanate and hexamethylene diisocyanate with a hydroxyl group-containing polyfunctional acrylate such as a vinyl epoxy compound of a polyepoxy compound, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　酸価調整して本発明の感光性組成物の現像性を改良するため、上記酸価を有するエチレン性不飽和結合を有する重合性化合物と共に、更に単官能又は多官能エポキシ化合物を用いることができる。上記酸価を有するエチレン性不飽和結合を有する重合性化合物は、固形分の酸価が５～１２０ｍｇＫＯＨ／ｇの範囲であることが好ましく、単官能又は多官能エポキシ化合物の使用量は、上記酸価を満たすように選択するのが好ましい。 In order to improve the developability of the photosensitive composition of the present invention by adjusting the acid value, a monofunctional or polyfunctional epoxy compound can be used together with the polymerizable compound having an ethylenically unsaturated bond having the acid value. . The polymerizable compound having an ethylenically unsaturated bond having an acid value preferably has a solid content acid value of 5 to 120 mgKOH / g, and the amount of the monofunctional or polyfunctional epoxy compound used is It is preferable to select so as to satisfy the value.
　上記単官能エポキシ化合物としては、グリシジルメタクリレート、メチルグリシジルエーテル、エチルグリシジルエーテル、プロピルグリシジルエーテル、イソプロピルグリシジルエーテル、ブチルグリシジルエーテル、イソブチルグリシジルエーテル、ｔ－ブチルグリシジルエーテル、ペンチルグリシジルエーテル、ヘキシルグリシジルエーテル、ヘプチルグリシジルエーテル、オクチルグリシジルエーテル、ノニルグリシジルエーテル、デシルグリシジルエーテル、ウンデシルグリシジルエーテル、ドデシルグリシジルエーテル、トリデシルグリシジルエーテル、テトラデシルグリシジルエーテル、ペンタデシルグリシジルエーテル、ヘキサデシルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、アリルグリシジルエーテル、プロパルギルグリシジルエーテル、p－メトキシエチルグリシジルエーテル、フェニルグリシジルエーテル、ｐ－メトキシグリシジルエーテル、ｐ－ブチルフェノールグリシジルエーテル、クレジルグリシジルエーテル、２－メチルクレジルグリシジルエーテル、４－ノニルフェニルグリシジルエーテル、ベンジルグリシジルエーテル、ｐ－クミルフェニルグリシジルエーテル、トリチルグリシジルエーテル、２，３－エポキシプロピルメタクリレート、エポキシ化大豆油、エポキシ化アマニ油、グリシジルブチレート、ビニルシクロヘキサンモノオキシド、１，２－エポキシ－４－ビニルシクロヘキサン、スチレンオキシド、ピネンオキシド、メチルスチレンオキシド、シクロヘキセンオキシド、プロピレンオキシド等が挙げられる。 Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidyl A , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl Glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4- Examples include vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, and propylene oxide.
　上記多官能エポキシ化合物としては、ビスフェノール型エポキシ化合物及びグリシジルエーテル類からなる群から選択される一種以上を用いると、特性の一層良好な感光性組成物を得ることができるので好ましい。該ビスフェノール型エポキシ化合物としては、上記一般式（III）で表されるエポキシ化合物を用いることができる他、例えば、水添ビスフェノール型エポキシ化合物等のビスフェノール型エポキシ化合物も用いることができる。該グリシジルエーテル類としては、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、１，８－オクタンジオールジグリシジルエーテル、１，１０－デカンジオールジグリシジルエーテル、２，２－ジメチル－１，３－プロパンジオールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリエチレングリコールジグリシジルエーテル、テトラエチレングリコールジグリシジルエーテル、ヘキサエチレングリコールジグリシジルエーテル、１，４－シクロヘキサンジメタノールジグリシジルエーテル、１，１，１－トリ（グリシジルオキシメチル）プロパン、１，１，１－トリ（グリシジルオキシメチル）エタン、１，１，１－トリ（グリシジルオキシメチル）メタン、１，１，１，１－テトラ（グリシジルオキシメチル）メタンが挙げられる。
　その他、フェノールノボラック型エポキシ化合物、ビフェニルノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ビスフェノールＡノボラック型エポキシ化合物、ジシクロペンタジエンノボラック型エポキシ化合物等のノボラック型エポキシ化合物；３，４－エポキシ－６－メチルシクロヘキシルメチル－３，４－エポキシ－６－メチルシクロヘキサンカルボキシレート、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、１－エポキシエチル－３，４－エポキシシクロヘキサン等の脂環式エポキシ化合物；フタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、ダイマー酸グリシジルエステル等のグリシジルエステル類；テトラグリシジルジアミノジフェニルメタン、トリグリシジル－ｐ－アミノフェノール、Ｎ，Ｎ－ジグリシジルアニリン等のグリシジルアミン類；１，３－ジグリシジル－５，５－ジメチルヒダントイン、トリグリシジルイソシアヌレート等の複素環式エポキシ化合物；ジシクロペンタジエンジオキシド等のジオキシド化合物；ナフタレン型エポキシ化合物、トリフェニルメタン型エポキシ化合物、ジシクロペンタジエン型エポキシ化合物等を用いることもできる。 As the polyfunctional epoxy compound, it is preferable to use one or more selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a photosensitive composition with better characteristics can be obtained. As the bisphenol type epoxy compound, an epoxy compound represented by the above general formula (III) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used. Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1 , 10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (g Glycidyl oxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) include methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl-p-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as cyclopentadiene dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds and the like can also be used.
　上記光ラジカル重合開始剤は、光照射を受けることによってラジカル重合を開始させることが可能となる化合物であればよく、例えば、アセトフェノン系化合物、ベンジル系化合物、ベンゾフェノン系化合物、チオキサントン系化合物等のケトン系化合物、オキシム系化合物などを好ましいものとして例示することができる。 The photo radical polymerization initiator may be any compound that can initiate radical polymerization upon receiving light irradiation. For example, ketones such as acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone compounds, etc. Examples of preferred compounds include oxime compounds and oxime compounds.
　アセトフェノン系化合物としては例えば、ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、４’－イソプロピル－２－ヒドロキシ－２－メチルプロピオフェノン、２－ヒドロキシメチル－２－メチルプロピオフェノン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、ｐ－ジメチルアミノアセトフェノン、ｐ－ターシャリブチルジクロロアセトフェノン、ｐ－ターシャリブチルトリクロロアセトフェノン、ｐ－アジドベンザルアセトフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパノン－１、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン－ｎ－ブチルエーテル、ベンゾインイソブチルエーテル、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン等が挙げられる。 Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl-2. -Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidobenzal Acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, benzo Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane -1-one and the like.
　ベンジル系化合物としては、ベンジル、アニシル等が挙げられる。 Examples of the benzylic compound include benzyl and anisyl.
　ベンゾフェノン系化合物としては、例えば、ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、ミヒラーケトン、４，４’－ビスジエチルアミノベンゾフェノン、４，４’－ジクロロベンゾフェノン、４－ベンゾイル－４’－メチルジフェニルスルフィドなどが挙げられる。 Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like. .
　チオキサントン系化合物としては、チオキサントン、２－メチルチオキサントン、２－エチルチオキサントン、２－クロロチオキサントン、２－イソプロピルチオキサントン、２，４－ジエチルチオキサントン等が挙げられる。 Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.
　オキシム系化合物としては、特に、下記一般式（IV）又は（Ｖ）で表される化合物が、感度及び耐熱性の点から好ましい。 As the oxime compound, a compound represented by the following general formula (IV) or (V) is particularly preferable from the viewpoint of sensitivity and heat resistance.
Figure JPOXMLDOC01-appb-C000027
 （式中、Ｒ５１及びＲ５２は、それぞれ独立に、水素原子、シアノ基、置換基を有している場合もある炭素原子数１～２０のアルキル基、置換基を有している場合もある炭素原子数６～３０のアリール基、置換基を有している場合もある炭素原子数７～３０のアリールアルキル基又は置換基を有している場合もある炭素原子数２～２０の複素環含有基を表し、
　Ｒ５３及びＲ５４は、それぞれ独立に、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ５５、ＯＲ５６、ＳＲ５７、ＮＲ５８Ｒ５９、ＣＯＲ６０、ＳＯＲ６１、ＳＯ２Ｒ６２又はＣＯＮＲ６３Ｒ６４を表し、Ｒ５３及びＲ５４は、互いに結合して環を形成している場合もあり、
　Ｒ５５、Ｒ５６、Ｒ５７、Ｒ５８、Ｒ５９、Ｒ６０、Ｒ６１、Ｒ６２、Ｒ６３及びＲ６４は、それぞれ独立に、置換基を有している場合もある炭素原子数１～２０のアルキル基、置換基を有している場合もある炭素原子数６～３０のアリール基、置換基を有している場合もある炭素原子数７～３０のアリールアルキル基又は置換基を有している場合もある炭素原子数２～２０の複素環含有基を表し、
　Ｘ３は、酸素原子、硫黄原子、セレン原子、ＣＲ７５Ｒ７６、ＣＯ、ＮＲ７７又はＰＲ７８を表し、
　Ｘ４は、単結合又はＣＯを表し、
　Ｒ７５～Ｒ７８は、炭素原子数１～２０のアルキル基、炭素原子数６～３０のアリール基又は炭素原子数７～３０のアリールアルキル基を表し、該アルキル基又はアリールアルキル基中のメチレン基は、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基又は複素環含有基で置き換えられている場合もあり、－Ｏ－で置き換えられている場合もあり、
　Ｒ５３及びＲ５４は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成している場合もあり、
　ａは、０～４の整数を表し、
　ｂは、０～５の整数を表す。）
Figure JPOXMLDOC01-appb-C000027
 (In the formula, R 51 and R 52 each independently have a hydrogen atom, a cyano group, a substituent, or an alkyl group having 1 to 20 carbon atoms or a substituent. A certain aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent or a complex having 2 to 20 carbon atoms which may have a substituent Represents a ring-containing group,
R 53 and R 54 are each independently a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R 55 , OR 56 , SR 57 , NR 58 R 59 , COR 60 , SOR 61 , SO 2 R 62 or CONR 63 R 64 , R 53 and R 54 may combine with each other to form a ring,
R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 and R 64 each independently have 1 to 1 carbon atoms which may have a substituent. 20 alkyl groups, aryl groups having 6 to 30 carbon atoms which may have substituents, arylalkyl groups having 7 to 30 carbon atoms which may have substituents or substituents Represents a heterocyclic group containing 2 to 20 carbon atoms, which may be
X 3 represents an oxygen atom, a sulfur atom, a selenium atom, CR 75 R 76 , CO, NR 77 or PR 78 ,
X 4 represents a single bond or CO,
R 75 to R 78 represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms, and methylene in the alkyl group or arylalkyl group The group may be replaced by a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic group, or may be replaced by -O-
R 53 and R 54 may each independently form a ring together with one of the adjacent benzene rings,
a represents an integer of 0 to 4,
b represents an integer of 0 to 5. )
Figure JPOXMLDOC01-appb-C000028
 （式中、Ｒ101及びＲ102は、それぞれ独立に、Ｒ111、ＯＲ111、ＣＯＲ111、ＳＲ111、ＣＯＮＲ112Ｒ113又はＣＮを表し、
　Ｒ111、Ｒ112及びＲ113は、それぞれ独立に、水素原子、炭素原子数１～２０のアルキル基、炭素原子数６～３０のアリール基、炭素原子数７～３０のアリールアルキル基又は炭素原子数２～２０の複素環含有基を表し、
　Ｒ111、Ｒ112及びＲ113で表わされる基の水素原子は、更にＲ121、ＯＲ121、ＣＯＲ121、ＳＲ121、ＮＲ122Ｒ123、ＣＯＮＲ122Ｒ123、－ＮＲ122－ＯＲ123、－ＮＣＯＲ122－ＯＣＯＲ123、ＮＲ122ＣＯＲ121、ＯＣＯＲ121、ＣＯＯＲ121、ＳＣＯＲ121、ＯＣＳＲ121、ＣＯＳＲ121、ＣＳＯＲ121、水酸基、ニトロ基、ＣＮ又はハロゲン原子で置き換えられている場合もあり、
　Ｒ121、Ｒ122及びＲ123は、それぞれ独立に、水素原子、炭素原子数１～２０のアルキル基、炭素原子数６～３０のアリール基、炭素原子数７～３０のアリールアルキル基又は炭素原子数２～２０の複素環含有基を表し、
　Ｒ121、Ｒ122及びＲ123で表される基の水素原子は、更に水酸基、ニトロ基、ＣＮ、ハロゲン原子、水酸基又はカルボキシル基で置換されている場合もあり、
　Ｒ111、Ｒ112、Ｒ113、Ｒ121、Ｒ122及びＲ123で表される基のアルキレン部分は、－Ｏ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ124－、－ＮＲ124ＣＯＯ－、－ＯＣＯＮＲ124－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又は－ＣＳＯ－により酸素原子が隣り合わない条件で１～５回置き換えられている場合もあり、
　Ｒ124は、水素原子、炭素原子数１～２０のアルキル基、炭素原子数６～３０のアリール基、炭素原子数７～３０のアリールアルキル基又は炭素原子数２～２０の複素環含有基を表し、
　Ｒ111、Ｒ112、Ｒ113、Ｒ121、Ｒ122、Ｒ123及びＲ124で表される基のアルキル部分は、分岐側鎖がある場合もあり、環状アルキルである場合もあり、
　Ｒ103は、水素原子、炭素原子数１～２０のアルキル基、炭素原子数６～３０のアリール基、炭素原子数７～３０のアリールアルキル基又は炭素原子数２～２０の複素環含有基を表し、Ｒ103で表される基のアルキル部分は、分岐側鎖がある場合もあり、環状アルキルである場合もあり、また、Ｒ103とＲ107、Ｒ103とＲ108、Ｒ104とＲ105、Ｒ105とＲ106及びＲ106とＲ107はそれぞれ一緒になって環を形成している場合もあり、
　Ｒ103で表わされる基の水素原子は、更にＲ121、ＯＲ121、ＣＯＲ121、ＳＲ121、ＮＲ122Ｒ123、ＣＯＮＲ122Ｒ123、－ＮＲ122－ＯＲ123、－ＮＣＯＲ122－ＯＣＯＲ123、ＮＲ122ＣＯＲ121、ＯＣＯＲ121、ＣＯＯＲ121、ＳＣＯＲ121、ＯＣＳＲ121、ＣＯＳＲ121、ＣＳＯＲ121、水酸基、ニトロ基、ＣＮ、ハロゲン原子、又はＣＯＯＲ121で置換されている場合もあり、
　Ｒ104、Ｒ105、Ｒ106及びＲ107は、それぞれ独立に、Ｒ111、ＯＲ111、ＳＲ111、ＣＯＲ114、ＣＯＮＲ151Ｒ116、ＮＲ112ＣＯＲ111、ＯＣＯＲ111、ＣＯＯＲ114、ＳＣＯＲ111、ＯＣＳＲ111、ＣＯＳＲ114、ＣＳＯＲ111、水酸基、ＣＮ又はハロゲン原子を表し、Ｒ104とＲ105、Ｒ105とＲ106及びＲ106とＲ107はそれぞれ一緒になって環を形成している場合もあり、
　Ｒ114、Ｒ115及びＲ116は、水素原子又は炭素原子数１～２０のアルキル基を表し、
　Ｒ108は、Ｒ111、ＯＲ111、ＳＲ111、ＣＯＲ111、ＣＯＮＲ112Ｒ113、ＮＲ112ＣＯＲ111、ＯＣＯＲ111、ＣＯＯＲ111、ＳＣＯＲ111、ＯＣＳＲ111、ＣＯＳＲ111、ＣＳＯＲ111、水酸基、ＣＮ又はハロゲン原子を表し、
　ｗは、０又は１を表す。）
Figure JPOXMLDOC01-appb-C000028
 (Wherein R 101 and R 102 each independently represent R 111 , OR 111 , COR 111 , SR 111 , CONR 112 R 113 or CN;
R 111 , R 112 and R 113 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. Represents a heterocyclic-containing group of formula 2 to 20,
The hydrogen atoms of the groups represented by R 111 , R 112 and R 113 are further R 121 , OR 121 , COR 121 , SR 121 , NR 122 R 123 , CONR 122 R 123 , —NR 122 —OR 123 , —NCOR 122. -OCOR 123 , NR 122 COR 121 , OCOR 121 , COOR 121 , SCOR 121 , OCSR 121 , COSR 121 , CSOR 121 , hydroxyl group, nitro group, CN or halogen atom may be substituted,
R 121 , R 122 and R 123 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom Represents a heterocyclic-containing group of formula 2 to 20,
The hydrogen atom of the group represented by R 121 , R 122 and R 123 may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, a hydroxyl group or a carboxyl group,
The alkylene part of the group represented by R 111 , R 112 , R 113 , R 121 , R 122 and R 123 is —O—, —S—, —COO—, —OCO—, —NR 124 —, —NR 124 COO—, —OCONR 124 —, —SCO—, —COS—, —OCS— or —CSO— may be substituted 1 to 5 times under the condition that the oxygen atoms are not adjacent to each other,
R 124 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms. Represent,
The alkyl part of the group represented by R 111 , R 112 , R 113 , R 121 , R 122 , R 123 and R 124 may have a branched side chain or a cyclic alkyl.
R 103 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic ring-containing group having 2 to 20 carbon atoms. The alkyl part of the group represented by R 103 may have a branched side chain or may be a cyclic alkyl, and R 103 and R 107 , R 103 and R 108 , R 104 and R 105 , R 105 and R 106 and R 106 and R 107 may be combined to form a ring,
Hydrogen atoms in the group represented by R 103 may further R 121, OR 121, COR 121 , SR 121, NR 122 R 123, CONR 122 R 123, -NR 122 -OR 123, -NCOR 122 -OCOR 123, NR 122 COR 121 , OCOR 121 , COOR 121 , SCOR 121 , OCSR 121 , COSR 121 , CSOR 121 , hydroxyl group, nitro group, CN, halogen atom, or COOR 121 may be substituted,
R 104 , R 105 , R 106 and R 107 are each independently R 111 , OR 111 , SR 111 , COR 114 , CONR 151 R 116 , NR 112 COR 111 , OCOR 111 , COOR 114 , SCOR 111 , OCSR 111 , COSR 114 , CSOR 111 , a hydroxyl group, CN or a halogen atom, R 104 and R 105 , R 105 and R 106, and R 106 and R 107 may be combined to form a ring,
R 114 , R 115 and R 116 each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms;
R 108 is R 111 , OR 111 , SR 111 , COR 111 , CONR 112 R 113 , NR 112 COR 111 , OCOR 111 , COOR 111 , SCOR 111 , OCSR 111 , COSR 111 , CSOR 111 , hydroxyl group, CN or halogen atom Represents
w represents 0 or 1. )
　その他の光ラジカル重合開始剤としては、２，４，６－トリメチルベンゾイルジフェニルフォスフェインオキサイド、ビス（シクロペンタジエニル）－ビス［２，６－ジフルオロ－３－（ピル－１－イル）］チタニウム等が挙げられる。 Other radical photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyr-1-yl)] titanium Etc.
　これらの光ラジカル重合開始剤は、１種であるいは２種以上のものを所望の性能に応じて配合して、使用することができる。 These photo radical polymerization initiators can be used alone or in combination of two or more according to the desired performance.
　以上のような光ラジカル重合開始剤の含有量は、本発明の感光性組成物の固形分中、０．１～３０質量％、特に０．５～１０質量％が好ましい。上記光ラジカル重合開始剤の含有量が０．１質量％より小さいと、露光による硬化が不十分になる場合があり、３０質量％より大きいと、感光性組成物中に開始剤が析出する場合がある。 The content of the radical photopolymerization initiator as described above is preferably 0.1 to 30% by mass, particularly preferably 0.5 to 10% by mass, based on the solid content of the photosensitive composition of the present invention. When the content of the photo radical polymerization initiator is less than 0.1% by mass, curing by exposure may be insufficient, and when it is greater than 30% by mass, the initiator is precipitated in the photosensitive composition. There is.
　本発明の感光性組成物は、さらに着色剤を加えて着色感光性組成物とすることもできる。該着色感光性組成物の硬化物は、カラーフィルタとして好適に用いられる。
　本発明の着色感光性組成物において、着色剤の添加量は、本発明の着色感光性組成物の固形分中、０．０１～５０質量％が好ましく、０．１～３０質量％がより好ましい。上記着色剤の含有量が０．０１質量％より小さいと、所望の色度が得られない場合があり、５０質量％より大きいと、着色感光性組成物中に着色剤が析出する場合がある。 The photosensitive composition of the present invention can be made into a colored photosensitive composition by further adding a colorant. The cured product of the colored photosensitive composition is suitably used as a color filter.
In the colored photosensitive composition of the present invention, the addition amount of the colorant is preferably 0.01 to 50% by mass, more preferably 0.1 to 30% by mass in the solid content of the colored photosensitive composition of the present invention. . When the content of the colorant is less than 0.01% by mass, desired chromaticity may not be obtained. When the content is greater than 50% by mass, the colorant may be precipitated in the colored photosensitive composition. .
　上記着色剤としては、染料あるいは顔料が挙げられる。
　染料としては、３８０～１２００ｎｍに吸収を有する化合物であれば特に限定されないが、例えば、アゾ化合物、アントラキノン化合物、インジゴイド化合物、トリアリールメタン化合物、キサンテン化合物、アリザリン化合物、アクリジン化合物、スチルベン化合物、チアゾール化合物、ナフトール化合物、キノリン化合物、ニトロ化合物、インダミン化合物、オキサジン化合物、フタロシアニン化合物、シアニン化合物、ジインモニウム化合物、シアノエテニル化合物、ジシアノスチレン化合物、ローダミン化合物、ペリレン化合物、ポリエンナフトラクタム化合物、クマリン化合物、スクアリリウム化合物、クロコニウム化合物、スピロピラン化合物、スピロオキサジン化合物、メロシアニン化合物、オキソノール化合物、スチリル化合物、ピリリウム化合物、ローダニン化合物、オキサゾロン化合物、フタルイミド化合物、シンノリン化合物、ナフトキノン化合物、アザアントラキノン化合物、ポルフィリン化合物、アザポルフィリン化合物、ピロメテン化合物、キナクリドン化合物、ジケトピロロピロール化合物、インジゴ化合物、アクリジン化合物、アジン化合物、アゾメチン化合物、アニリン化合物、キナクリドン化合物、キノフタロン化合物、キノンイミン化合物、イリジウム錯体化合物、ユーロピウム錯体化合物等の染料等が挙げられ、これらは複数を混合して用いてもよい。 Examples of the colorant include dyes and pigments.
The dye is not particularly limited as long as it is a compound having absorption at 380 to 1200 nm. For example, azo compound, anthraquinone compound, indigoid compound, triarylmethane compound, xanthene compound, alizarin compound, acridine compound, stilbene compound, thiazole compound , Naphthol compound, quinoline compound, nitro compound, indamine compound, oxazine compound, phthalocyanine compound, cyanine compound, diimmonium compound, cyanoethenyl compound, dicyanostyrene compound, rhodamine compound, perylene compound, polyenenaphtholactam compound, coumarin compound, squarylium compound, croconium Compound, spiropyran compound, spirooxazine compound, merocyanine compound, oxonol compound, styrylation Product, pyrylium compound, rhodanine compound, oxazolone compound, phthalimide compound, cinnoline compound, naphthoquinone compound, azaanthraquinone compound, porphyrin compound, azaporphyrin compound, pyromethene compound, quinacridone compound, diketopyrrolopyrrole compound, indigo compound, acridine compound, azine Examples thereof include dyes such as compounds, azomethine compounds, aniline compounds, quinacridone compounds, quinophthalone compounds, quinoneimine compounds, iridium complex compounds, and europium complex compounds, and these may be used in combination.
　顔料としては、無機顔料あるいは有機顔料を用いることができ、例えば、ニトロソ化合物、ニトロ化合物、アゾ化合物、ジアゾ化合物、キサンテン化合物、キノリン化合物、アントラキノン化合物、クマリン化合物、フタロシアニン化合物、イソインドリノン化合物、イソインドリン化合物、キナクリドン化合物、アンタンスロン化合物、ペリノン化合物、ペリレン化合物、ジケトピロロピロール化合物、チオインジゴ化合物、ジオキサジン化合物、トリフェニルメタン化合物、キノフタロン化合物、ナフタレンテトラカルボン酸；アゾ染料、シアニン染料の金属錯体化合物；レーキ顔料；ファーネス法、チャンネル法、サーマル法によって得られるカーボンブラック、或いはアセチレンブラック、ケッチェンブラック又はランプブラック等のカーボンブラック；上記カーボンブラックをエポキシ樹脂で調整、被覆したもの、上記カーボンブラックを予め溶媒中で樹脂で分散処理し、２０～２００ｍｇ／ｇの樹脂を吸着させたもの、上記カーボンブラックを酸性又はアルカリ性表面処理したもの、平均粒径が８ｎｍ以上でＤＢＰ吸油量が９０ｍｌ／１００ｇ以下のもの、９５０℃における揮発分中のＣＯ、ＣＯ2から算出した全酸素量が、カーボンブラックの表面積１００ｍ２当たり９ｍｇ以上であるもの；黒鉛、黒鉛化カーボンブラック、活性炭、炭素繊維、カーボンナノチューブ、カーボンマイクロコイル、カーボンナノホーン、カーボンエアロゲル、フラーレン；アニリンブラック、ピグメントブラック７、チタンブラック；疎水性樹脂、酸化クロム緑、ミロリブルー、コバルト緑、コバルト青、マンガン系、フェロシアン化物、リン酸塩群青、紺青、ウルトラマリン、セルリアンブルー、ピリジアン、エメラルドグリーン、硫酸鉛、黄色鉛、亜鉛黄、べんがら（赤色酸化鉄(III)）、カドミウム赤、合成鉄黒、アンバー等の無機含量又は有機顔料を用いることができる。これらの顔料は単独で、或いは複数を混合して用いることができる。 As the pigment, inorganic pigments or organic pigments can be used. For example, nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, Indoline compounds, quinacridone compounds, anthanthrone compounds, perinone compounds, perylene compounds, diketopyrrolopyrrole compounds, thioindigo compounds, dioxazine compounds, triphenylmethane compounds, quinophthalone compounds, naphthalene tetracarboxylic acids; azo dyes, metal complex compounds of cyanine dyes; Lake pigment: Carbon black obtained by furnace method, channel method, thermal method, acetylene black, ketjen black or lamp black Carbon black prepared by coating and coating the above-described carbon black with an epoxy resin, dispersed in a solvent in advance with the above-described carbon black and adsorbed with 20 to 200 mg / g of resin, and the above-described carbon black being acidic or alkaline Surface treatment, average particle diameter of 8 nm or more, DBP oil absorption of 90 ml / 100 g or less, total oxygen amount calculated from CO and CO 2 in volatile matter at 950 ° C. is 9 mg or more per 100 m 2 of carbon black surface area Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; hydrophobic resin, chromium oxide green, miloli blue , Koval Green, cobalt blue, manganese-based, ferrocyanide, phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), An inorganic content or organic pigment such as cadmium red, synthetic iron black, or amber can be used. These pigments can be used alone or in combination.
　上記無機顔料又は有機顔料としては、市販の顔料を用いることもでき、例えば、ピグメントレッド１、２、３、９、１０、１４、１７、２２、２３、３１、３８、４１、４８、４９、８８、９０、９７、１１２、１１９、１２２、１２３、１４４、１４９、１６６、１６８、１６９、１７０、１７１、１７７、１７９、１８０、１８４、１８５、１９２、２００、２０２、２０９、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２４０、２５４；ピグメントオレンジ１３、３１、３４、３６、３８、４３、４６、４８、４９、５１、５２、５５、５９、６０、６１、６２、６４、６５、７１；ピグメントイエロー１、３、１２、１３、１４、１６、１７、２０、２４、５５、６０、７３、８１、８３、８６、９３、９５、９７、９８、１００、１０９、１１０、１１３、１１４、１１７、１２０、１２５、１２６、１２７、１２９、１３７、１３８、１３９、１４７、１４８、１５０、１５１、１５２、１５３、１５４、１６６、１６８、１７５、１８０、１８５；ピグメントグリ－ン７、１０、３６；ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：５、１５：６、２２、２４、５６、６０、６１、６２、６４；ピグメントバイオレット１、１９、２３、２７、２９、３０、３２、３７、４０、５０等が挙げられる。 As the inorganic pigment or organic pigment, commercially available pigments can also be used. For example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, and the like.
　本発明の感光性組成物及び着色感光性組成物には、更に溶媒を加えることができる。該溶媒としては、通常、必要に応じて上記の各成分を溶解又は分散しえる溶媒、例えば、メチルエチルケトン、メチルアミルケトン、ジエチルケトン、アセトン、メチルイソプロピルケトン、メチルイソブチルケトン、シクロヘキサノン、２－ヘプタノン等のケトン類；エチルエーテル、ジオキサン、テトラヒドロフラン、１，２－ジメトキシエタン、１，２－ジエトキシエタン、ジプロピレングリコールジメチルエーテル等のエーテル系溶媒；酢酸メチル、酢酸エチル、酢酸－ｎ－プロピル、酢酸イソプロピル、酢酸ｎ－ブチル、酢酸シクロヘキシル、乳酸エチル、コハク酸ジメチル、テキサノール等のエステル系溶媒；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル等のセロソルブ系溶媒；メタノール、エタノール、イソ－又はｎ－プロパノール、イソ－又はｎ－ブタノール、アミルアルコール、ジアセトンアルコール等のアルコール系溶媒；エチレングリコールモノメチルアセテート、エチレングリコールモノエチルアセテート、プロピレングリコール－１－モノメチルエーテル－２－アセテート（ＰＧＭＥＡ）、ジプロピレングリコールモノメチルエーテルアセテート、３－メトキシブチルアセテート、エトキシエチルプロピオネート、１－ｔ－ブトキシ－２－プロパノール、３－メトキシブチルアセテート、シクロヘキサノールアセテート等のエーテルエステル系溶媒；ベンゼン、トルエン、キシレン等のＢＴＸ系溶媒；ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素系溶媒；テレピン油、Ｄ－リモネン、ピネン等のテルペン系炭化水素油；ミネラルスピリット、スワゾール＃３１０（コスモ松山石油（株））、ソルベッソ＃１００（エクソン化学（株））等のパラフィン系溶媒；四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン、１，２－ジクロロエタン等のハロゲン化脂肪族炭化水素系溶媒；クロロベンゼン等のハロゲン化芳香族炭化水素系溶媒；カルビトール系溶媒、アニリン、トリエチルアミン、ピリジン、酢酸、アセトニトリル、二硫化炭素、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、ジメチルスルホキシド、水等が挙げられ、これらの溶媒は１種又は２種以上の混合溶媒として使用することができる。これらの中でもケトン類、エーテルエステル系溶媒等、特にプロピレングリコール－１－モノメチルエーテル－２－アセテート、シクロヘキサノン等が、感光性組成物においてレジストと光ラジカル重合開始剤の相溶性がよいので好ましい。溶媒を使用する場合、本発明の感光性組成物又は着色感光性組成物の固形分が２５～３５質量％となる量で使用することが、ハンドリング等の観点から好ましい。 A solvent can be further added to the photosensitive composition and the colored photosensitive composition of the present invention. The solvent is usually a solvent that can dissolve or disperse each of the above components as necessary, for example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, etc. Ketones; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate Ester solvents such as n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; cellosolv solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methanol Alcohol solvents such as ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, diacetone alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate Ether ester solvents such as (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate, 1-t-butoxy-2-propanol, 3-methoxybutyl acetate, cyclohexanol acetate; benzene BTX solvents such as toluene, xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; turpentine oil, D-limonene, pinene Terpene hydrocarbon oils; paraffinic solvents such as mineral spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1 Halogenated aliphatic hydrocarbon solvents such as 1,2-dichloroethane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N- Examples thereof include dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water and the like, and these solvents can be used as one or a mixture of two or more. Among these, ketones, ether ester solvents, etc., particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, and the like are preferable because the compatibility of the resist and the radical photopolymerization initiator is good in the photosensitive composition. When a solvent is used, it is preferable from the viewpoint of handling and the like that the solid content of the photosensitive composition or colored photosensitive composition of the present invention is 25 to 35% by mass.
　本発明の感光性組成物及び着色感光性組成物には、更に無機化合物を含有させることができる。該無機化合物としては、例えば、酸化ニッケル、酸化鉄、酸化イリジウム、酸化チタン、酸化亜鉛、酸化マグネシウム、酸化カルシウム、酸化カリウム、シリカ、アルミナ等の金属酸化物；層状粘土鉱物、ミロリブルー、炭酸カルシウム、炭酸マグネシウム、コバルト系、マンガン系、ガラス粉末、マイカ、タルク、カオリン、フェロシアン化物、各種金属硫酸塩、硫化物、セレン化物、アルミニウムシリケート、カルシウムシリケート、水酸化アルミニウム、白金、金、銀、銅等が挙げられる。 The photosensitive composition and the colored photosensitive composition of the present invention can further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper Etc.
　本発明の感光性組成物及び着色感光性組成物において、顔料等の着色剤及び／又は無機化合物を用いる場合、分散剤を加えることができる。該分散剤としては着色剤、無機化合物を分散、安定化できるものであれば特に制限はなく、市販の分散剤、例えばビックケミー社製、ＢＹＫシリーズ等を用いることができ、塩基性官能基を有するポリエステル、ポリエーテル、ポリウレタンからなる高分子分散剤、塩基性官能基として窒素原子を有し、窒素原子を有する官能基がアミン、及び／又はその四級塩であり、アミン価が1～１００ｍｇＫＯＨ/ｇのものが好適に用いられる。 In the photosensitive composition and colored photosensitive composition of the present invention, when a colorant such as a pigment and / or an inorganic compound is used, a dispersant can be added. The dispersant is not particularly limited as long as it can disperse and stabilize colorants and inorganic compounds, and commercially available dispersants such as BYK series manufactured by BYK Chemie can be used and have a basic functional group. Polymer dispersing agent comprising polyester, polyether, polyurethane, having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH / Those having g are preferably used.
　また、本発明の感光性組成物及び着色感光性組成物には、必要に応じて、ｐ－アニソール、ハイドロキノン、ピロカテコール、ｔ－ブチルカテコール、フェノチアジン等の熱重合抑制剤；可塑剤；接着促進剤；充填剤；消泡剤；レベリング剤；表面調整剤；フェノール系酸化防止剤、ホスファイト系酸化防止剤、チオエーテル系酸化防止剤等の酸化防止剤；紫外線吸収剤；分散助剤；凝集防止剤；触媒；効果促進剤；架橋剤；増粘剤等の慣用の添加物を加えることができる。 In addition, the photosensitive composition and the colored photosensitive composition of the present invention include, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, and phenothiazine; plasticizers; Agents; fillers; antifoaming agents; leveling agents; surface conditioning agents; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants; UV absorbers; dispersion aids; Conventional additives such as an agent, a catalyst, an effect promoter, a cross-linking agent, and a thickener can be added.
　また、上記酸価を有するエチレン性不飽和結合を有する重合性化合物とともに、他の有機重合体を用いることによって、本発明の感光性組成物及び着色感光性組成物の硬化物の特性を改善することもできる。上記有機重合体としては、例えば、ポリスチレン、ポリメチルメタクリレート、メチルメタクリレート－エチルアクリレート共重合体、ポリ（メタ）アクリル酸、スチレン－（メタ）アクリル酸共重合体、（メタ）アクリル酸－メチルメタクリレート共重合体、エチレン－塩化ビニル共重合体、エチレン－ビニル共重合体、ポリ塩化ビニル樹脂、ＡＢＳ樹脂、ナイロン６、ナイロン６６、ナイロン１２、ウレタン樹脂、ポリカーボネートポリビニルブチラール、セルロースエステル、ポリアクリルアミド、飽和ポリエステル、フェノール樹脂、フェノキシ樹脂、ポリアミドイミド樹脂、ポリアミック酸樹脂、エポキシ樹脂等が挙げられ、これらの中でも、ポリスチレン、（メタ）アクリル酸－メチルメタクリレート共重合体、エポキシ樹脂が好ましい。 Moreover, the characteristics of the cured product of the photosensitive composition of the present invention and the colored photosensitive composition are improved by using another organic polymer together with the polymerizable compound having an ethylenically unsaturated bond having the acid value. You can also Examples of the organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid-methyl methacrylate. Copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl copolymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated Polyester, phenolic resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, and the like. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are included. Masui.
　本発明の感光性組成物及び着色感光性組成物には、更に、連鎖移動剤、増感剤、界面活性剤、シランカップリング剤、メラミン化合物等を併用することができる。 In the photosensitive composition and colored photosensitive composition of the present invention, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, and the like can be further used in combination.
　上記連鎖移動剤、増感剤としては、一般的に硫黄原子含有化合物が用いられる。例えばチオグリコール酸、チオリンゴ酸、チオサリチル酸、２－メルカプトプロピオン酸、３－メルカプトプロピオン酸、３－メルカプト酪酸、Ｎ－（２－メルカプトプロピオニル）グリシン、２－メルカプトニコチン酸、３－［Ｎ－（２－メルカプトエチル）カルバモイル］プロピオン酸、３－［Ｎ－（２－メルカプトエチル）アミノ］プロピオン酸、Ｎ－（３－メルカプトプロピオニル）アラニン、２－メルカプトエタンスルホン酸、３－メルカプトプロパンスルホン酸、４－メルカプトブタンスルホン酸、ドデシル（４－メチルチオ）フェニルエーテル、２－メルカプトエタノール、３－メルカプト－１，２－プロパンジオール、１－メルカプト－２－プロパノール、３－メルカプト－２－ブタノール、メルカプトフェノール、２－メルカプトエチルアミン、２－メルカプトイミダゾール、２－メルカプトベンゾイミダゾール、２－メルカプト－３－ピリジノール、２－メルカプトベンゾチアゾール、メルカプト酢酸、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）等のメルカプト化合物、該メルカプト化合物を酸化して得られるジスルフィド化合物、ヨード酢酸、ヨードプロピオン酸、２－ヨードエタノール、２－ヨードエタンスルホン酸、３－ヨードプロパンスルホン酸等のヨード化アルキル化合物、トリメチロールプロパントリス（３－メルカプトイソブチレート）、ブタンジオールビス（３－メルカプトイソブチレート）、ヘキサンジチオール、デカンジチオール、１，４－ジメチルメルカプトベンゼン、ブタンジオールビスチオプロピオネート、ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、トリメチロールプロパントリスチオグリコレート、ブタンジオールビスチオプロピオネート、トリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、下記化合物Ｎｏ．Ｃ１、トリメルカプトプロピオン酸トリス（２－ヒドロキシエチル）イソシアヌレート等の脂肪族多官能チオール化合物、昭和電工社製カレンズＭＴ　ＢＤ１、ＰＥ１、ＮＲ１等が挙げられる。 As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compound, iodoacetates such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compounds, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. C1, aliphatic polyfunctional thiol compounds such as trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, Karenz MT BD1, PE1, NR1, etc. manufactured by Showa Denko K.K.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　上記界面活性剤としては、パーフルオロアルキルリン酸エステル、パーフルオロアルキルカルボン酸塩等のフッ素界面活性剤、高級脂肪酸アルカリ塩、アルキルスルホン酸塩、アルキル硫酸塩等のアニオン系界面活性剤、高級アミンハロゲン酸塩、第四級アンモニウム塩等のカチオン系界面活性剤、ポリエチレングリコールアルキルエーテル、ポリエチレングリコール脂肪酸エステル、ソルビタン脂肪酸エステル、脂肪酸モノグリセリド等の非イオン界面活性剤、両性界面活性剤、シリコーン系界面活性剤等の界面活性剤を用いることができ、これらは組み合わせて用いてもよい。 Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.
　上記シランカップリング剤としては、例えば信越化学社製シランカップリング剤を用いることができ、その中でもＫＢＥ－９００７、ＫＢＭ－５０２、ＫＢＥ－４０３等、イソシアネート基、メタクリロイル基、エポキシ基を有するシランカップリング剤が好適に用いられる。 As the silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Among them, KBE-9007, KBM-502, KBE-403 and the like, silane cups having an isocyanate group, a methacryloyl group, and an epoxy group. A ring agent is preferably used.
　上記メラミン化合物としては、（ポリ）メチロールメラミン、（ポリ）メチロールグリコールウリル、（ポリ）メチロールベンゾグアナミン、（ポリ）メチロールウレア等の窒素化合物中の活性メチロール基（ＣＨ2ＯＨ基）の全部又は一部（少なくとも２つ）がアルキルエーテル化された化合物を挙げることができる。ここで、アルキルエーテルを構成するアルキル基としては、メチル基、エチル基又はブチル基が挙げられ、互いに同一である場合もあるし、異なる場合もある。また、アルキルエーテル化されていないメチロール基は、一分子内で自己縮合している場合もあり、二分子間で縮合して、その結果オリゴマー成分が形成されている場合もある。具体的には、ヘキサメトキシメチルメラミン、ヘキサブトキシメチルメラミン、テトラメトキシメチルグリコールウリル、テトラブトキシメチルグリコールウリル等を用いることができる。これらのなかでも、ヘキサメトキシメチルメラミン、ヘキサブトキシメチルメラミン等のアルキルエーテル化されたメラミンが好ましい。 Examples of the melamine compound include all or part of active methylol groups (CH 2 OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same or different. In addition, methylol groups that are not alkyl etherified may be self-condensed within one molecule or may be condensed between two molecules, resulting in the formation of an oligomer component. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.
　本発明の感光性組成物及び着色感光性組成物は、スピンコーター、ロールコーター、バーコーター、ダイコーター、カーテンコーター、各種の印刷、浸漬等の公知の手段で、ソーダガラス、石英ガラス、半導体基板、金属、紙、プラスチック等の支持基体上に適用することができる。また、一旦フィルム等の支持基体上に施した後、他の支持基体上に転写することもでき、その適用方法に制限はない。 The photosensitive composition and colored photosensitive composition of the present invention are prepared by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, and semiconductor substrate. It can be applied on a supporting substrate such as metal, paper, and plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.
　また、本発明の感光性組成物及び着色感光性組成物を硬化させる際に用いられる活性光の光源としては、波長３００～４５０ｎｍの光を発光するものを用いることができ、例えば、超高圧水銀、水銀蒸気アーク、カーボンアーク、キセノンアーク等を用いることができる。 In addition, as the active light source used for curing the photosensitive composition and the colored photosensitive composition of the present invention, those capable of emitting light having a wavelength of 300 to 450 nm can be used. Mercury vapor arc, carbon arc, xenon arc, etc. can be used.
　更に、露光光源にレーザー光を用いることにより、マスクを用いずに、コンピューター等のデジタル情報から直接画像を形成するレーザー直接描画法が、生産性のみならず、解像性や位置精度等の向上も図れることから有用であり、そのレーザー光としては、３４０～４３０ｎｍの波長の光が好適に使用されるが、アルゴンイオンレーザー、ヘリウムネオンレーザー、ＹＡＧレーザー、及び半導体レーザー等の可視から赤外領域の光を発するものも用いられる。これらのレーザーを使用する場合には、可視から赤外の当該領域を吸収する増感色素が加えられる。 Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser beam, light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.
　本発明の感光性組成物及び着色感光性組成物は、二つの感光性組成物又は着色感光性組成物を用いて二回に分けてパターニングを行うダブルパターニングプロセスを経てパターニングを行うこともできる。 The photosensitive composition and the colored photosensitive composition of the present invention can also be patterned through a double patterning process in which patterning is performed twice using two photosensitive compositions or colored photosensitive compositions.
　本発明の感光性組成物又は着色感光性組成物を硬化させる方法は、上記スピンコーター、ロールコーター、バーコーター、ダイコーター、カーテンコーター、各種の印刷、浸漬等の公知の手段で、ソーダガラス、石英ガラス、半導体基板、金属、紙、プラスチック等の支持基体上に塗布して塗膜を形成する工程、及び該塗膜に上記活性光を露光して硬化させる工程を含む。 The method of curing the photosensitive composition or colored photosensitive composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, It includes a step of forming a coating film on a supporting substrate such as quartz glass, semiconductor substrate, metal, paper, plastic, and the like, and a step of exposing the coating film to exposure and curing the active light.
　本発明の感光性組成物及び着色感光性組成物（又はその硬化物）は、光硬化性塗料又はワニス、光硬化性接着剤等の接着剤、プリント基板、或いはカラーテレビ、ＰＣモニタ、携帯情報端末、デジタルカメラ等のカラー表示の液晶表示パネルにおけるカラーフィルタ、ＣＣＤイメージセンサのカラーフィルタ、フォトスペーサ、ブラックカラムスペーサ、プラズマ表示パネル用の電極材料、タッチパネル、タッチセンサー、粉末コーティング、印刷インク、印刷版、歯科用組成物、光造形用樹脂、ゲルコート、電子工学用のフォトレジスト、電気メッキレジスト、エッチングレジスト、液状及び乾燥膜の双方、はんだレジスト、種々の表示用途用のカラーフィルタを製造するための或いはプラズマ表示パネル、電気発光表示装置、及びＬＣＤの製造工程において構造を形成するためのレジスト、電気及び電子部品を封入するための組成物、ソルダーレジスト、磁気記録材料、微小機械部品、導波路、光スイッチ、めっき用マスク、エッチングマスク、カラー試験系、ガラス繊維ケーブルコーティング、スクリーン印刷用ステンシル、ステレオリトグラフィによって三次元物体を製造するための材料、ホログラフィ記録用材料、画像記録材料、微細電子回路、脱色材料、画像記録材料のための脱色材料、マイクロカプセルを使用する画像記録材料用の脱色材料、印刷配線板用フォトレジスト材料、ＵＶ及び可視レーザー直接画像系用のフォトレジスト材料、プリント回路基板の逐次積層における誘電体層形成に使用するフォトレジスト材料、３Ｄ実装用フォトレジスト材料或いは保護膜等の各種の用途に使用することができ、その用途に特に制限はない。 The photosensitive composition and the colored photosensitive composition (or cured product thereof) of the present invention are a photocurable paint or varnish, an adhesive such as a photocurable adhesive, a printed circuit board, a color television, a PC monitor, or portable information. Color filters for color display liquid crystal display panels such as terminals and digital cameras, color filters for CCD image sensors, photo spacers, black column spacers, electrode materials for plasma display panels, touch panels, touch sensors, powder coatings, printing inks, printing To produce plates, dental compositions, stereolithography resins, gel coats, photoresists for electronics, electroplating resists, etching resists, both liquid and dry films, solder resists, and color filters for various display applications Or plasma display panel, electroluminescent display, and LC Resist for forming structures in the manufacturing process, composition for encapsulating electrical and electronic components, solder resist, magnetic recording materials, micromechanical components, waveguide, optical switch, plating mask, etching mask, color test Systems, glass fiber cable coatings, stencils for screen printing, materials for producing three-dimensional objects by stereolithography, holographic recording materials, image recording materials, fine electronic circuits, decoloring materials, decoloring materials for image recording materials Decolorizing materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct image systems, photo for dielectric layer formation in sequential lamination of printed circuit boards Resist material, 3D mounting photoresist material or protective material Can be used in various applications of film or the like, there is no particular limitation on the application.
　本発明の感光性組成物は、硬化させることにより、透明構造体として用いることができる。透明構造体としては、例えば、フォトスペーサー（ＰＳ）、カラムスペーサー（ＣＳ）と呼ばれる柱形物；（ナノ）インプリントの微細パターン；大型広告看板等の製造や液晶ディスプレイ用カラーフィルターや配向膜の印刷など電子デバイス製造に用いるインクジェット受容層等が挙げられる。本発明の透明構造体は、表示デバイスに好適に用いられる。 The photosensitive composition of the present invention can be used as a transparent structure by curing. Examples of transparent structures include columnars called photo spacers (PS) and column spacers (CS); fine patterns of (nano) imprints; production of large advertising signs, color filters for liquid crystal displays, and alignment films Examples thereof include an ink jet receiving layer used for manufacturing electronic devices such as printing. The transparent structure of the present invention is suitably used for display devices.
　本発明の感光性組成物は、透明導電膜、反射膜、偏光板、保護膜等に用いることができ、透明基板に所望の各層を順次塗布し、所定のパターン形状を有するマスクを介して活性光を照射し、露光後の被膜を現像液にて現像し、現像後の被膜を加熱することにより積層した透明積層体として用いることができる。透明積層体としては、例えば、透明基材に、酸化インジウムと酸化セリウムの複合酸化物からなる透明薄膜層と金属薄膜層とが交互にされているもの等が挙げられる。前述の各層それぞれに、一般式（Ｉ）で表される置換基を有する化合物を潜在性添加剤として含有する本発明の感光性組成物を用いてもよいし、いずれかの層に該感光性組成物を用いてもよい。また、さらに、該透明積層体は、表示装置に好適に用いられる。 The photosensitive composition of the present invention can be used for a transparent conductive film, a reflective film, a polarizing plate, a protective film, and the like, and each desired layer is sequentially applied to a transparent substrate and activated through a mask having a predetermined pattern shape. It can be used as a transparent laminate obtained by irradiating light, developing the exposed film with a developer, and heating the developed film. As a transparent laminated body, the thing etc. with which the transparent thin film layer and metal thin film layer which consist of a complex oxide of an indium oxide and a cerium oxide are alternated on the transparent base material are mentioned, for example. The photosensitive composition of the present invention containing a compound having a substituent represented by the general formula (I) as a latent additive may be used for each of the above-described layers, and the photosensitive composition may be used for any of the layers. A composition may be used. Furthermore, the transparent laminate is suitably used for a display device.
　本発明の着色感光性組成物は、カラーフィルタの画素を形成する目的で使用され、特に液晶表示パネル等の画像表示装置用の表示デバイス用カラーフィルタを形成するための感光性組成物として有用である。 The colored photosensitive composition of the present invention is used for the purpose of forming pixels of a color filter, and is particularly useful as a photosensitive composition for forming a color filter for a display device for an image display device such as a liquid crystal display panel. is there.
　上記表示デバイス用カラーフィルタは、（１）本発明の着色感光性組成物の塗膜を基板上に形成する工程、（２）該塗膜に所定のパターン形状を有するマスクを介して活性光を照射する工程、（３）露光後の被膜を現像液にて現像する工程、（４）現像後の該被膜を加熱する工程により好ましく形成される。また、本発明の着色感光性組成物は、現像工程の無いインクジェット方式の着色感光性組成物としても有用である。
　上記マスクとしては、ハーフトーンマスク又はグレースケールマスク等の多階調マスクを用いることもできる。 The color filter for a display device includes (1) a step of forming a coating film of the colored photosensitive composition of the present invention on a substrate, and (2) active light through a mask having a predetermined pattern shape on the coating film. Preferably, the step of irradiating, (3) the step of developing the film after exposure with a developer, and (4) the step of heating the film after development are preferably formed. In addition, the colored photosensitive composition of the present invention is also useful as an inkjet-type colored photosensitive composition without a development step.
As the mask, a multi-tone mask such as a halftone mask or a gray scale mask can be used.
　次に、本発明の新規化合物について説明する。本発明の新規化合物は、下記構造のいずれかで表される。 Next, the novel compound of the present invention will be described. The novel compound of the present invention is represented by any of the following structures.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　本発明の新規化合物の製造方法は特に限定されないが、例えば、特開昭５７－１１１３７５号、特開平３－１７３８４３号、特開平６－１２８１９５号、特開平７－２０６７７１号、特開平７－２５２１９１号、特表２００４－５０１１２８号の各公報に記載された方法により製造されたフェノール系化合物と、ハロゲン化アリル化合物等を反応させて得ることができる。 The production method of the novel compound of the present invention is not particularly limited. For example, JP-A-57-111375, JP-A-3-173843, JP-A-6-128195, JP-A-7-207771, JP-A-7-252191. And a phenolic compound produced by the method described in each publication of JP-A-2004-501128 and an allyl halide compound can be obtained.
　本発明の新規化合物は、潜在性酸化防止剤、潜在性紫外線吸収剤、溶解調整剤等に用いることができる。 The novel compound of the present invention can be used as a latent antioxidant, a latent ultraviolet absorber, a dissolution regulator and the like.
　以下、実施例等を挙げて本発明を更に詳細に説明するが、本発明はこれらの実施例等に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to these examples and the like.
　［実施例１－１］化合物Ｎｏ．１の合成
　下記化合物Ｎｏ．１’のフェノール化合物１当量のジメチルアセトアミド溶液（理論収量の３倍量）に炭酸カリウム（１つのフェノール基に対して２当量）を加え、室温で３０分撹拌した。アリルブロマイド（１つのフェノール基に対して１．５当量）を加え、６０℃で５時間撹拌した。酢酸エチルを加えて１％塩酸溶液で洗浄した後油水分離を行い、有機層を無水硫酸ナトリウムで乾燥後、溶媒を留去し、晶析を行った。得られた固体を６０℃で３時間減圧乾燥させ、目的物を得た。得られた固体が目的物であることは１Ｈ－ＮＭＲ、ＩＲにて確認した。結果を［表１］～［表２］に示す。 [Example 1-1] Compound No. 1 Synthesis of Compound 1 Potassium carbonate (2 equivalents with respect to one phenol group) was added to a dimethylacetamide solution of 1 equivalent of 1 ′ phenol compound (3 times the theoretical yield), and the mixture was stirred at room temperature for 30 minutes. Allyl bromide (1.5 equivalent to one phenol group) was added, and the mixture was stirred at 60 ° C. for 5 hours. After adding ethyl acetate and washing with 1% hydrochloric acid solution, oil-water separation was performed, and after drying the organic layer with anhydrous sodium sulfate, the solvent was distilled off and crystallization was performed. The obtained solid was dried under reduced pressure at 60 ° C. for 3 hours to obtain the desired product. It was confirmed by 1 H-NMR and IR that the obtained solid was the desired product. The results are shown in [Table 1] to [Table 2].
　［実施例１－２～１－６］化合物Ｎｏ．２～６の合成
　実施例１－１において、下記化合物Ｎｏ．１’のフェノール化合物に代えて、下記化合物Ｎｏ．２’～６’のフェノール化合物を用いた以外は実施例１－１と同様にして、目的物である化合物Ｎｏ．２～６を合成した。得られた固体が目的物であることは１Ｈ－ＮＭＲ、ＩＲにて確認した。結果を［表１］～［表２］に示す。 [Examples 1-2 to 1-6] Compound No. Synthesis of 2 to 6 In Example 1-1, the following compound No. Instead of the phenol compound of 1 ′, the following compound No. The target compound No. 2 was prepared in the same manner as in Example 1-1, except that 2 ′ to 6 ′ phenolic compounds were used. 2-6 were synthesized. It was confirmed by 1 H-NMR and IR that the obtained solid was the desired product. The results are shown in [Table 1] to [Table 2].
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000035
Figure JPOXMLDOC01-appb-T000036
Figure JPOXMLDOC01-appb-T000036
　［実施例２－１～２－２及び比較例２－１～２－３］感光性組成物Ｎｏ．１～Ｎｏ．２及び比較感光性組成物Ｎｏ．１～Ｎｏ．３の調製
　ＳＰＣ－１０００（昭和電工社製、固形分２９％のＰＧＭＥＡ溶液）５０．０ｇ、アロニックスＭ－４５０（東亜合成社製）１１．６ｇ、ＮＣＩ－９３０（ＡＤＥＫＡ社製）０．３ｇ、ＰＧＭＥＡ３４．７ｇ、ＦＺ２１２２（東レ・ダウコーニング社製、固形分１％のＰＧＭＥＡ溶液）２．９ｇ及び[表３]記載の化合物０．８１ｇを混合し、不溶物が無くなるまで撹拌し、感光性組成物Ｎｏ．１～Ｎｏ．２及び比較感光性組成物Ｎｏ．１～Ｎｏ．３を得た。 [Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-3] Photosensitive composition Nos. 1-No. 2 and comparative photosensitive composition no. 1-No. Preparation of 3 SPC-1000 (manufactured by Showa Denko KK, PGMEA solution with a solid content of 29%) 50.0 g, Aronix M-450 (manufactured by Toagosei), 11.6 g, NCI-930 (manufactured by ADEKA) 0.3 g, 34.7 g of PGMEA, 2.9 g of FZ2122 (manufactured by Toray Dow Corning Co., Ltd., PGMEA solution with a solid content of 1%) and 0.81 g of the compound described in [Table 3] are mixed, and stirred until insoluble matter is eliminated, and photosensitive composition Item No. 1-No. 2 and comparative photosensitive composition no. 1-No. 3 was obtained.
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　［評価例１－１及び比較評価例１－１］アウトガス評価
　化合物Ｎｏ．１、化合物Ｎｏ．２並びに比較化合物Ｎｏ．２をそれぞれ５ｍｇ測り取り、熱質量測定装置にて室温から２３０℃まで昇温（２０℃／ｍｉｎ．）した後、２３０℃で３０分間保持した時点での重量減少率を測定して、感光性組成物Ｎｏ．１～Ｎｏ．２及び比較感光性組成物Ｎｏ．２のアウトガス評価とした。重量減少が小さいほど、アウトガスが少ないことを示す。結果を［表４］に示す。 [Evaluation Example 1-1 and Comparative Evaluation Example 1-1] Outgas Evaluation 1, compound no. 2 and comparative compound no. 5 mg of each 2 was measured, and the temperature was increased from room temperature to 230 ° C. (20 ° C./min.) With a thermal mass measuring device, and then the weight reduction rate at the time of holding at 230 ° C. for 30 minutes was measured. Composition No. 1-No. 2 and comparative photosensitive composition no. An outgas rating of 2 was assigned. A smaller weight loss indicates less outgas. The results are shown in [Table 4].
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000041
　上記結果より、本発明に係る化合物はアウトガスが少なく、本発明に係る化合物を含有する本発明の感光性組成物はアウトガスが少なくなることが明らかである。 From the above results, it is clear that the compound according to the present invention has less outgas, and the photosensitive composition of the present invention containing the compound according to the present invention has less outgas.
　［評価例２－１及び比較評価例２－１～２－２］耐溶剤性評価
　上記実施例２－１で得られた感光性組成物Ｎｏ．１及び比較例２－１及び２－３で得られた比較感光性組成物Ｎｏ．１及びＮｏ．３を、それぞれガラス基板に４１０ｒｐｍ×７秒の条件で塗工し、ホットプレートで乾燥（９０℃×９０秒）させた。得られた塗膜に超高圧水銀ランプで露光（４０ｍＪ／ｃｍ２）した。露光後の塗膜を、２３０℃×３０分の条件で焼成した。得られた塗膜の膜厚を測定した後、室温で３０分間、ＰＧＭＥＡ、シクロヘキサノン、Ｎ－メチルピロリドン、Ｎ－エチルピロリドンに浸漬させ、浸漬後の膜厚を測定した。浸漬前後での膜厚比（浸漬後の膜厚×１００／浸漬前の膜厚）が１００％に近いほど、耐溶剤性は高いと評価した。 [Evaluation Example 2-1 and Comparative Evaluation Examples 2-1 and 2-2] Solvent Resistance Evaluation The photosensitive composition No. obtained in Example 2-1 was used. Comparative photosensitive composition Nos. 1 and 2 obtained in Comparative Examples 2-1 and 2-3. 1 and no. 3 were each coated on a glass substrate under conditions of 410 rpm × 7 seconds and dried on a hot plate (90 ° C. × 90 seconds). The obtained coating film was exposed (40 mJ / cm 2 ) with an ultrahigh pressure mercury lamp. The exposed coating film was baked under conditions of 230 ° C. × 30 minutes. After measuring the film thickness of the obtained coating film, it was immersed in PGMEA, cyclohexanone, N-methylpyrrolidone, and N-ethylpyrrolidone at room temperature for 30 minutes, and the film thickness after immersion was measured. It was evaluated that the solvent resistance was higher as the film thickness ratio before and after immersion (film thickness after immersion × 100 / film thickness before immersion) was closer to 100%.
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000042
　[表５]より、酸化防止剤を含有しない比較感光性組成物Ｎｏ．３の硬化物に比べて、従来のフェノール系酸化防止剤を含有する比較感光性組成物Ｎｏ．１の硬化物は耐溶剤性が低下するが、本願に係る化合物を潜在性添加剤として用いた感光性組成物Ｎｏ．１は、酸化防止剤を含有しない場合と同じ耐溶剤性を維持していることが明らかである。 From [Table 5], comparative photosensitive composition No. containing no antioxidant was used. As compared with the cured product of No. 3, a comparative photosensitive composition No. 1 containing a conventional phenolic antioxidant was used. Although the cured product of No. 1 has low solvent resistance, the photosensitive composition No. 1 using the compound according to the present application as a latent additive was used. It is clear that No. 1 maintains the same solvent resistance as when no antioxidant is contained.
　以上の結果より、本発明の化合物を潜在性添加剤として用いた感光性組成物はアウトガスが少なく、その硬化物が耐溶剤性に優れることは明白である。 From the above results, it is clear that the photosensitive composition using the compound of the present invention as a latent additive has less outgas and the cured product is excellent in solvent resistance.
　本発明によれば、常温では不活性であり所定の温度に加熱することにより活性化されて酸化防止剤や紫外線吸収剤としての機能を発現する化合物を用いた、アウトガスが少なく硬化物の耐溶剤性が高い感光性組成物を提供することが出来る。
  According to the present invention, there is little outgassing and a solvent resistance of a cured product using a compound that is inactive at room temperature and activated by heating to a predetermined temperature and exhibits a function as an antioxidant or an ultraviolet absorber. Highly sensitive photosensitive composition can be provided.

Claims (9)

  1. 下記一般式（Ｉ）で表される置換基を有する化合物を含有する感光性組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１及びＲ２は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有している場合もある炭素原子数１～４０のアルキル基、置換基を有している場合もある炭素原子数６～２０のアリール基、置換基を有している場合もある炭素原子数７～２０のアリールアルキル基、置換基を有している場合もある炭素原子数２～２０の複素環含有基又はトリアルキルシリル基を表し、
    　Ｒ１及びＲ２で表されるアルキル基又はアリールアルキル基中のメチレン基は、－Ｏ－、－Ｓ－、－ＣＯ－、－Ｏ－ＣＯ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－Ｏ－、－Ｓ－ＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－Ｏ－、－Ｏ－ＣＯ－Ｓ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＮＨ－ＣＯ－Ｏ－、－ＮＲ’－、－Ｓ－Ｓ－又は－ＳＯ２－から選ばれた基を酸素原子が隣り合わない条件で組み合わせた基で置き換えている場合もあり、Ｒ’は、水素原子又は炭素原子数１～８のアルキル基を表し、
    　ｊは、１～３の数を表し、
    　＊は、＊部分で、隣接する基と結合することを意味する。）     The photosensitive composition containing the compound which has a substituent represented with the following general formula (I).
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an alkyl having 1 to 40 carbon atoms which may have a substituent) An aryl group having 6 to 20 carbon atoms which may have a substituent, an arylalkyl group having 7 to 20 carbon atoms which may have a substituent, or a substituent In some cases represents a C2-C20 heterocyclic-containing group or a trialkylsilyl group,
    The methylene group in the alkyl group or arylalkyl group represented by R 1 and R 2 is —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO—. O—, —S—CO—, —CO—S—, —S—CO—O—, —O—CO—S—, —CO—NH—, —NH—CO—, —NH—CO—O—. , -NR '-, - S- S- or -SO 2 - from selected based on some cases where the oxygen atoms are replaced by a group composed of a combination under conditions which are not adjacent, R' is a hydrogen atom or a carbon atom Represents an alkyl group of 1 to 8,
    j represents a number from 1 to 3,
    * Means that it is bonded to an adjacent group at the * part. )
  2. 　上記一般式（Ｉ）で表される置換基を有する化合物が、下記一般式（Ｉ－Ａ）で表される化合物である請求項１に記載の感光性組成物。
    Figure JPOXMLDOC01-appb-C000002
     （式中、ｎは、１～１０の整数を表し、
    　Ｘ１は、ｎ価の結合基を表し、
    　Ｒ１、Ｒ２及びｊは、上記一般式（Ｉ）と同じである。）     The photosensitive composition according to claim 1, wherein the compound having a substituent represented by the general formula (I) is a compound represented by the following general formula (IA).
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, n represents an integer of 1 to 10,
    X 1 represents an n-valent linking group,
    R 1 , R 2 and j are the same as in the general formula (I). )
  3. 　請求項１又は２に記載の感光性組成物の硬化物。 Hardened | cured material of the photosensitive composition of Claim 1 or 2.
  4. 　請求項３に記載の硬化物を用いて形成される透明積層体又は透明構造体を少なくとも一部に具備してなる表示デバイス。 A display device comprising at least a part of a transparent laminate or a transparent structure formed using the cured product according to claim 3.
  5. 　請求項１又は２に記載の感光性組成物にさらに着色剤を含有させてなる着色感光性組成物。 A colored photosensitive composition obtained by further adding a colorant to the photosensitive composition according to claim 1.
  6. 　請求項５に記載の着色感光性組成物の硬化物。 A cured product of the colored photosensitive composition according to claim 5.
  7. 　請求項６に記載の硬化物を用いて形成されるカラーフィルタ。 A color filter formed using the cured product according to claim 6.
  8. 　請求項１若しくは２に記載の感光性組成物又は請求項５に記載の着色感光性組成物を支持基体上に塗布して塗膜を形成する工程、及び該塗膜に活性光を露光して硬化させる工程を含む、請求項１若しくは２に記載の感光性組成物又は請求項５に記載の着色感光性組成物を硬化させる方法。 A step of coating the photosensitive composition according to claim 1 or 2 or the colored photosensitive composition according to claim 5 on a supporting substrate to form a coating film, and exposing the coating film to active light The method to harden the photosensitive composition of Claim 1 or 2 or the colored photosensitive composition of Claim 5 including the process to harden | cure.
  9. 　下記構造（Ａ）ないし（Ｏ）のいずれかで表される新規化合物。
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
           A novel compound represented by any of the following structures (A) to (O).
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
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