WO2017170465A1 - Photosensitive composition - Google Patents

Photosensitive composition Download PDF

Info

Publication number
WO2017170465A1
WO2017170465A1 PCT/JP2017/012505 JP2017012505W WO2017170465A1 WO 2017170465 A1 WO2017170465 A1 WO 2017170465A1 JP 2017012505 W JP2017012505 W JP 2017012505W WO 2017170465 A1 WO2017170465 A1 WO 2017170465A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
represented
groups
general formula
Prior art date
Application number
PCT/JP2017/012505
Other languages
French (fr)
Japanese (ja)
Inventor
有希子 金原
友泰 川原
依純 松井
光裕 岡田
直美 佐藤
Original Assignee
株式会社Adeka
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社Adeka filed Critical 株式会社Adeka
Priority to KR1020187015981A priority Critical patent/KR102369445B1/en
Priority to CN201780005076.5A priority patent/CN108473611B/en
Priority to JP2018508022A priority patent/JP6849659B2/en
Publication of WO2017170465A1 publication Critical patent/WO2017170465A1/en

Links

Classifications

    • 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
    • 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
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • 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 has a latent additive, an ethylenically unsaturated bond, and a hydrophilic group that are inactive at normal temperature and activated by heating to a predetermined temperature to exhibit a function, and are constant.
  • the present invention relates to a photosensitive composition containing a polymer having a double bond equivalent of: Furthermore, the present invention relates to a colored photosensitive composition that can be polymerized by energy rays using the composition, and a color filter that uses the colored photosensitive composition.
  • Patent Document 1 In order to improve the weather resistance and heat resistance of a resin composition, a method of stabilizing by adding an ultraviolet absorber or an antioxidant is known (Patent Document 1).
  • Patent Document 6 Since phenolic antioxidants trap radicals that greatly affect the deterioration of the polymer, adding antioxidants to the polymerization system generally acts as a so-called polymerization inhibitor, causing inhibition of curing. Therefore, latent additives have been developed (Patent Document 6).
  • an object of the present invention is to have a latent additive, an ethylenically unsaturated bond and a hydrophilic group in one molecule which are inactive at room temperature and are activated by heating to a predetermined temperature to exhibit a function.
  • Another object of the present invention is to provide a photosensitive composition comprising a polymer having a certain double bond equivalent, an acrylic monomer, and a radical photopolymerization initiator.
  • the present invention has been made on the basis of the above findings, and is a latent additive (A) that is inactive at room temperature and is activated by heating to a predetermined temperature to express its function (hereinafter, the latent additive ( A)), a polymer (B) having an ethylenically unsaturated bond and a hydrophilic group in one molecule and having a double bond equivalent of 200 to 1000 (hereinafter also referred to as polymer (B))
  • the photosensitive composition containing an acrylic monomer (C) and a radical photopolymerization initiator (D) is provided.
  • the photosensitive composition of the present invention comprises a latent additive (A), a polymer (B) having an ethylenically unsaturated bond and a hydrophilic group in one molecule and a double bond equivalent of 200 to 1000, Contains an acrylic monomer (C) and a radical photopolymerization initiator (D).
  • a latent additive A
  • B a polymer having an ethylenically unsaturated bond and a hydrophilic group in one molecule and a double bond equivalent of 200 to 1000
  • C acrylic monomer
  • D radical photopolymerization initiator
  • the latent additive (A) used in the photosensitive composition of the present invention is inactive at room temperature or in the pre-baking step, and is heated at 100 to 250 ° C. or 80 to 200 ° C. in the presence of an acid / base catalyst. The protecting group is eliminated and becomes active by heating with.
  • the latent additive (A) is active, it means that it has reactivity with radicals, and when it is inactive, it means that it does not react with radicals or has extremely low reactivity.
  • the latent additive (A) has a skeleton represented by the following general formula (I) because synthesis is easy and heat resistance is high.
  • ring A 1 represents a 5-membered or 6-membered hydrocarbon ring, heterocyclic ring or condensed ring;
  • R 61 each independently has a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, a C 1-40 alkyl group that may have a substituent, or a substituent.
  • R 62 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, carbon Represents a heterocyclic group containing 2 to 20 atoms or a trialkylsilyl group
  • the methylene group in the alkyl group or arylalkyl group represented by R 61 and R 62 is a carbon-carbon double bond, —O—, —S—, —CO—, —O—CO—, —CO—O.
  • a group selected from —, —NH—CO—, —NH—CO—O—, —NR′—, —SS— or —SO 2 — is replaced with a group which is combined under the condition that oxygen atoms are not adjacent to each other.
  • R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • a plurality of R 61 may be bonded to each other to form a benzene ring or a naphthalene ring
  • d represents an integer of 0 to 4
  • k represents an integer of 1 to 5, but the sum of d and k is less than the number of substituents that ring A 1 can take;
  • * Means that it is bonded to an adjacent group at the * part. )
  • the heterocyclic group having 2 to 20 carbon atoms means a group containing at least one heterocyclic ring and having 2 to 20 carbon atoms in the whole group.
  • the heterocycle-containing group having 2 to 10 carbon atoms described later means a group containing at least one heterocycle and having 2 to 10 carbon atoms as a whole.
  • the heterocycle-containing group having 2 to 35 carbon atoms described later means a group containing at least one heterocycle and having 2 to 35 carbon atoms as a whole.
  • the number of carbon atoms of the whole group may exceed the upper limit of each group.
  • examples of the substituent include those exemplified as the substituent that may substitute a group represented by X 1 described later.
  • Examples of the five-membered hydrocarbon ring represented by A 1 in the general formula (I) include cyclopentadiene, and examples of the five-membered heterocyclic ring include furan, thiophene, pyrrole, pyrrolidine, pyrazolidine, and pyrazole.
  • Imidazole imidazolidine, oxazole, isoxazole, isoxazolidine, thiazole, isothiazole, isothiazolidine, etc., as the six-membered hydrocarbon ring, benzene and the like, and as the six-membered heterocyclic ring, Piperidine, piperazine, morpholine, thiomorpholine, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. are mentioned, and these rings may be condensed or substituted with other rings.
  • quinoline isoquinoline, indole, urolidine, ben
  • examples include zoxazole, benzotriazole, azulene, naphthalene, anthracene, fluorene, perylene, and pyrene.
  • halogen atom represented by R 61 in the general formula (I) examples include fluorine, chlorine, bromine and iodine. (In the description below, all the halogen atoms are the same as described above. ).
  • Examples of the alkyl group having 1 to 40 carbon atoms represented by R 61 in the general formula (I) 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,
  • Substituents for substituting the heterocyclic ring-containing groups include ethylenically unsaturated groups such as vinyl, allyl, acrylic and methacryl; halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl, 2-chloroacetyl, propionyl and octanoyl
  • Acyl groups such as acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-but
  • Examples of the aryl group having 6 to 20 carbon atoms represented by R 61 and R 62 in the general formula (I) 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-di
  • Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R 61 and R 62 in the general formula (I) include benzyl, 1-methyl-1-phenylethyl, 1-naphthylmethyl, 9-anthracenyl Examples include methyl, 9-fluorenyl, 3-phenylpropyl, methyl-2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, phenethyl, styryl, cinnamyl and the like.
  • Examples of the heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R 61 and R 62 in the general formula (I) include a pyridine ring, a pyrimidine ring, a pyridazine ring, a piperidine ring, a pyran ring, a pyrazoline ring, and a triazine ring.
  • Examples of the alkyl group having 1 to 20 carbon atoms represented by R 62 in the general formula (I) include those satisfying a predetermined number of carbon atoms among the alkyl groups represented by R 61 .
  • Examples of the alkenyl group having 2 to 20 carbon atoms represented by R 62 in the general formula (I) include vinyl, 1-methylethen-1-yl, propen-1-yl, propen-2-yl and propene-3. -Yl, buten-1-yl, buten-2-yl, 2-methylpropen-3-yl, 1,1-dimethylethen-2-yl, 1,1-dimethylpropen-3-yl, 3-butenyl, Examples include 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, tricoseni and the like.
  • Examples of the trialkylsilyl group represented by R 62 in the general formula (I) include alkyl groups having 1 to 6 carbon atoms such as trimethylsilane, triethylsilane, and ethyldimethylsilane (the three alkyl groups may be the same or different. Silyl group substituted with (good).
  • Examples of the alkyl group having 1 to 8 carbon atoms represented by R ′ in the general formula (I) include those satisfying a predetermined number of carbon atoms among the alkyl groups represented by R 61 .
  • R 61 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms because synthesis is easy.
  • R 62 is an alkyl group having 1 to 8 carbon atoms in which —CO—O— is bonded to the terminal on the oxygen atom side and functions effectively as a latent additive. Is preferable.
  • X 1 represents an m-valent organic group, specifically, a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, the following (Ia ) Or (Ib),>C ⁇ O,> NR 63 , —OR 63 , —SR 63 , —NR 63 R 64 , or the same number as m which may have a substituent.
  • the methylene group is a carbon-carbon double bond, —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO—O—, —O—CO—O.
  • X 1 is a nitrogen atom, a phosphorus atom or a group represented by the following (Ia) or (Ib), m is 3, X 1 is an oxygen atom or a sulfur atom, and> C ⁇ O , —NH—CO—, —CO—NH— or> NR 63 , m is 2, and when X 1 is —OR 63 , —SR 63 or —NR 63 R 64 , m is 1. X 1 may form a ring together with A 1 .
  • the latent additive represented by the general formula (IA) has a structure in which m specific groups are bonded to the m-valent specific atom or group represented by X 1 .
  • the m groups are the same as or different from each other.
  • the value of m is 1 to 10, and preferably 2 to 6 from the viewpoint of ease of synthesis.
  • m is monovalent, for example, methyl Ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, sec-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methyl Alkyl groups such as cyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl,
  • the aliphatic hydrocarbon group having 1 to 120 carbon atoms having the same valence as m represented by X 1 is methylene, ethylene where m is divalent.
  • Alkylene such as propylene, butylene, butyldiyl, etc .; in which the methylene chain of the alkylene is replaced by —O—, —S—, —CO—O—, —O—CO—; ethanediol, propanediol, butanediol, Residues of diols such as pentanediol and hexanediol; residues of dithiols such as ethanedithiol, propanedithiol, butanedithiol, pentanedithiol and hexanedithiol, and groups in which these groups are substituted by substituents described later, etc. .
  • Examples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same valence as m represented by X 1 in the general formula (IA) are those in which m is trivalent. Examples thereof include alkylidine such as pyridine and 1,1,3-butyridine, and groups in which these groups are substituted with a substituent described later.
  • M is monovalent, arylalkyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl and cinnamyl; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; phenylthio and naphthylthio And arylthio groups such as these, and groups in which these groups are substituted with a substituent described later.
  • m 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 and these groups Is a group substituted by a substituent described later.
  • m being trivalent include phenyl-1,3,5-trimethylene and groups in which these groups are substituted with a substituent described later.
  • m is As monovalent ones, pyridyl, pyrimidyl, pyrariayl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, 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
  • m is examples of the divalent group include 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 with a substituent described later. .
  • m is
  • the trivalent group 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 63 and R 64 include an aliphatic hydrocarbon group having 1 to 120 carbon atoms represented by the above X 1 Among the combinations of an aromatic hydrocarbon group or the aliphatic hydrocarbon group and a substituent described later, those satisfying a predetermined number of carbon atoms can be mentioned.
  • an aliphatic hydrocarbon group having 1 to 120 carbon atoms, 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 X 1 may be substituted.
  • substituents that may be substituted for the heterocyclic ring-containing groups include ethylenically unsaturated groups such as vinyl, allyl, acrylic, and methacryl; halogen atoms such as fluorine, chlorine, bromine, and iodine; acetyl, 2-chloroacetyl, propionyl , Octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearo Acyl groups such as acetyloxy, benzoyloxy, etc .; amino, ethylamino
  • Examples of the alkyl group having 1 to 8 carbon atoms represented by R ′ in the general formula (IA) include those having the predetermined number of carbon atoms among the alkyl groups represented by R 61 described above. Can be mentioned.
  • X 1 when m is 2, X 1 can also be represented by the following general formula (1).
  • Y 10 represents a single bond, —CR 65 R 66 —, —NR 67 —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, or 6 to 35 carbon atoms.
  • the terminal carbon atom of the aliphatic hydrocarbon group may be replaced with —O—, —S—, —CO—, —COO—, —OCO— or —NH—
  • the aliphatic hydrocarbon group may be substituted with a hydroxyl group, a halogen atom, a cyano group, a nitro group, a carboxyl group or an alkoxy group
  • Z 1 and Z 2 are each independently a direct bond, —O—, —S—,> CO, —CO—O—, —O—CO—, —SO 2 —, —SS—, —SO—,
  • Represents> NR 67 or> PR 67 , R 65 , R 66 and R 67 each independently have a hydrogen atom, a hydroxyl group or a substituent, or may have an aliphatic hydrocarbon group having 1 to 35 carbon atoms or a substituent.
  • R 71 represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms
  • R 72 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 may have a substituent
  • f is an integer of 0 to 5
  • * means that it is bonded to an adjacent group at the * portion.
  • R 73 and R 74 are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, or 6 carbon atoms 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 73 may form a ring with adjacent R 73 , p represents
  • X 1 can also be represented by the following general formula (2).
  • Y 11 represents a single bond, a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, a trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, 3 A valent aromatic hydrocarbon group having 6 to 35 carbon atoms or a trivalent heterocyclic 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—, — SO-,> NR 68 or> PR 68 , R 68 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 adjacent carbon atom of the aliphatic hydrocarbon group is interrupted by a carbon-carbon double bond, —O—, —CO—, —O—CO—, —CO—O— or —SO 2 —.
  • the terminal carbon atom of the aliphatic hydrocarbon group may be replaced with a carbon-carbon double bond, —O—, —CO—, —O—CO—, —CO—O— or —SO 2 —. is there. )
  • X 1 when m is 4, X 1 can also be represented by the following general formula (3).
  • Y 12 represents a single bond, a carbon atom, or a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms and a tetravalent aromatic carbon group having 6 to 35 carbon atoms.
  • the adjacent carbon atom of the aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—
  • the terminal carbon atom of the aliphatic hydrocarbon group may be replaced with —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—
  • 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).
  • Y 13 represents a single bond, a 5-valent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a 5-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a pentavalent group.
  • the adjacent carbon atom of the aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—
  • the terminal carbon atom of the aliphatic hydrocarbon group may be replaced with —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—
  • Z 1 to Z 5 are each independently a group within the same range as the group represented by Z 1 to Z 3 in the general formula (2).
  • Y 14 is a single bond, a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a hexavalent aromatic hydrocarbon group having 6 to 35 carbon atoms, or a hexavalent group.
  • the adjacent carbon atom of the aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—
  • the terminal carbon atom of the aliphatic hydrocarbon group may be replaced with —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—
  • 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).
  • the aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent represented by R 65 , R 66 and R 67 includes the general formula (I- A monovalent aliphatic hydrocarbon group having 1 to 120 carbon atoms exemplified as the m-valent organic group represented by X 1 in A) and these groups are represented by X 1 in the general formula (IA).
  • Examples include groups substituted by those exemplified as the substituent of the group representing the organic group, and these groups or 2 exemplified as the m-valent organic group represented by X 1 in the general formula (IA).
  • the heterocyclic group containing 2 to 35 carbon atoms which may have a substituent represented by R 65 , R 66 and R 67 is represented by X 1 in the above general formula (IA).
  • the monovalent heterocyclic group having 2 to 35 carbon atoms exemplified as the m-valent organic group and these groups represent the m-valent organic group represented by X 1 in the general formula (IA).
  • Examples of the divalent group in which the aromatic ring-containing hydrocarbon group having 2 to 35 is substituted with Z 1 and Z 2 include the divalent heterocyclic group having 2 to 35 carbon atoms represented by Y 10. .
  • examples of the cycloalkyl group having 3 to 10 carbon atoms represented by R 71 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and the like.
  • the alkyl group having 1 to 10 carbon atoms represented by R 72 is exemplified as the alkyl group having 1 to 40 carbon atoms represented by R 61 .
  • the groups satisfying a predetermined number of carbon atoms can be mentioned.
  • examples of the alkoxy group having 1 to 10 carbon atoms represented by R 72 include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, Tributyloxy, isobutyloxy, amyloxy, isoamyloxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyl Examples include oxy, nonyloxy, decyloxy and the like.
  • the substituent of the phenyl group, alkyl group, alkoxy group and alkenyl group is an m-valent organic compound represented by X 1 in the general formula (IA). The same as those exemplified as the substituent of the group representing the group.
  • the alkyl group having 1 to 10 carbon atoms which may have a substituent represented by R 73 and R 74 is represented by R 61.
  • R 61 groups satisfying a predetermined number of carbon atoms are exemplified.
  • the aryl group having 6 to 20 carbon atoms, which may have a substituent represented by R 73 and R 74 includes R 61 and R 62 Examples thereof include the groups exemplified as the aryl group having 6 to 20 carbon atoms.
  • the aryloxy group having 6 to 20 carbon atoms which may have a substituent represented by R 73 and R 74 includes 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, 3.5-dimethylphenyloxy, 2,4-di-tert-
  • the arylthio group having 6 to 20 carbon atoms which may have a substituent represented by R 73 and R 74 has the above substituent.
  • a group in which the oxygen atom of the aryloxy group having 6 to 20 carbon atoms is substituted with a sulfur atom is used.
  • the arylalkenyl group having 6 to 20 carbon atoms, which may have a substituent represented by R 73 and R 74 has the above substituent.
  • the oxygen atom of the aryloxy group having 6 to 20 carbon atoms may be vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl, etc. And a group substituted with an alkenyl group.
  • the arylalkyl group having 7 to 20 carbon atoms represented by R 73 and R 74 includes 7 to 20 carbon atoms represented by R 61 and R 62.
  • the groups exemplified as the arylalkyl group are examples of the arylalkyl group.
  • the heterocyclic group containing 2 to 20 carbon atoms which may have a substituent represented by R 73 and R 74 includes R 61 and R And the groups exemplified as the heterocyclic-containing group having 2 to 20 carbon atoms represented by 62 .
  • the trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 11 in the general formula (2) is an m-valent organic compound represented by X 1 in the general formula (IA).
  • Examples of the group substituted by 1 include those having a predetermined number of carbon atoms, such as trivalent groups substituted with Z 1 , Z 2 and Z 3 .
  • 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.
  • the trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 11 in the general formula (2) is an m-valent represented by X 1 in the general formula (IA).
  • Examples of monovalent to trivalent aromatic ring-containing hydrocarbon groups exemplified as the organic group and substituents of the groups in which these groups represent the m-valent organic group represented by X 1 in the general formula (IA) And a trivalent group in which a group substituted by the above is substituted with Z 1 , Z 2 and Z 3 .
  • Examples of the trivalent heterocyclic group having 2 to 35 carbon atoms represented by Y 11 in the general formula (2) include an m-valent organic group represented by X 1 in the general formula (IA).
  • the aromatic hydrocarbon group having 6 to 35 and the heterocyclic group having 2 to 35 carbon atoms which may have a substituent include R 65 and R 66 in the general formula (1), respectively.
  • Examples include the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, and heterocyclic ring-containing group exemplified in the description.
  • the tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 12 in the general formula (3) is an m-valent organic compound represented by X 1 in the general formula (IA).
  • Examples of the group substituted by 1 include those having a predetermined number of carbon atoms, such as tetravalent groups substituted with Z 1 , Z 2 , Z 3 and Z 4 .
  • the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 12 in the general formula (3) is an m-valent organic group represented by X 1 in the general formula (IA).
  • X 1 in the general formula (IA) By the exemplified monovalent to trivalent aromatic ring-containing hydrocarbon groups and those exemplified as substituents for the group representing the m-valent organic group represented by X 1 in the general formula (IA). Examples thereof include a tetravalent group in which a substituted group or the like is substituted with Z 1 , Z 2 , Z 3, or Z 4 .
  • the tetravalent heterocyclic containing group having a carbon number of 2 to 35 represented by Y 12 in general formula (3), m-valent organic group represented by X 1 in the above formula (I-A) The monovalent to trivalent heterocyclic-containing groups exemplified as above and these groups substituted by those exemplified as the substituents of the group representing the m-valent organic group represented by X 1 in the general formula (IA) And tetravalent groups in which the group and the like are substituted with Z 1 , Z 2 , Z 3 and Z 4 .
  • the pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 13 in the general formula (4) is an m-valent organic compound represented by X 1 in the general formula (IA).
  • Examples of monovalent to trivalent aliphatic hydrocarbon groups exemplified as the groups and substituents of the groups in which these groups represent the m-valent organic group represented by X 1 in the general formula (IA) Among the groups substituted by the above, there are pentavalent groups in which those satisfying the predetermined number of carbon atoms are substituted with Z 1 , Z 2 , Z 3 , Z 4 and Z 5 .
  • the pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 14 in the general formula (4) is an m-valent represented by X 1 in the general formula (IA).
  • Examples of monovalent to trivalent aromatic ring-containing hydrocarbon groups exemplified as organic groups and substituents of groups in which these groups represent an n-valent organic group represented by X 1 in the above general formula (IA)
  • a pentavalent group in which a group substituted by the above-described one is substituted with Z 1 , Z 2 , Z 3 , Z 4 and Z 5 .
  • the pentavalent C2-C35 heterocycle-containing group represented by Y 14 in the general formula (4) is X in the m valence represented by X 1 in the general formula (IA).
  • X 1 in the general formula (IA) Of the monovalent to trivalent heterocyclic group exemplified as the represented n-valent organic group and the group in which these groups represent the m-valent organic group represented by X 1 in the general formula (IA). Examples thereof include pentavalent groups in which groups substituted by those exemplified as the substituent are substituted with Z 1 , Z 2 , Z 3 , Z 4 and Z 5 .
  • the hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 14 in the general formula (5) is an m-valent organic compound represented by X 1 in the general formula (IA).
  • Examples of the group substituted by the above group include those having a predetermined number of carbon atoms and the like, and hexavalent groups substituted with Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 .
  • the hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 14 in the general formula (5) is an m-valent represented by X 1 in the general formula (IA).
  • Examples of monovalent to trivalent aromatic ring-containing hydrocarbon groups exemplified as the organic group and substituents of the groups in which these groups represent the m-valent organic group represented by X 1 in the general formula (IA)
  • a hexavalent group in which a group substituted by the above-described one is substituted with Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 .
  • the hexavalent heterocyclic group having 2 to 35 carbon atoms represented by Y 14 in the general formula (5) is an m-valent organic group represented by X 1 in the general formula (IA).
  • hexavalent to groups substituted by those exemplified as the substituents exemplified monovalent to trivalent heterocyclic containing groups is substituted with Z 1, Z 2, Z 3 , Z 4, Z 5 and Z 6 as And the like.
  • the sum of d and k is less than the number of substituents that can be taken by the ring A 1 .
  • the possible substituents of the ring A 1 are 6, and d + k ⁇ 5.
  • the possible substituents of the ring A 1 are 4, and d + k ⁇ 3.
  • ring A 2 is a six-membered alicyclic ring, aromatic ring or heterocyclic ring, and R 81 , R 82 , R 83 , R 84 and R 85 are a hydrogen atom, a halogen atom, a cyano group, or a hydroxyl group.
  • Nitro group carboxyl group, alkyl group having 1 to 40 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, carbon atom Represents a heterocyclic group containing 2 to 20 or —O—R 62 , wherein at least one of R 81 , R 82 , R 83 , R 84 and R 85 is not a hydrogen atom, and R 62 represents the above general formula Same as (I).)
  • X 2 is a group represented by the above general formula (1), and R 86 , R 87 , R 88 and R 89 are a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group.
  • R 86 , R 87 , R 88 and R 89 are a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group.
  • R 86 , R 87 , R 88 and R 89 is not a hydrogen atom
  • R 62 is the same as in the above general formula (I)
  • ring A 2 is (It is the same as general formula (II).)
  • R 91 , R 92 , R 93 and R 94 may have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group or a substituent.
  • Examples of the six-membered alicyclic, aromatic or heterocyclic ring represented by the ring A 2 in the general formula (II) include those exemplified in the description of A 1 in the general formula (I).
  • the halogen atom represented by R 81 , R 82 , R 83 , R 84 and R 85 in the general formula (II) an alkyl group having 1 to 40 carbon atoms which may have a substituent, a carbon atom
  • Examples of the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the heterocyclic ring-containing group having 2 to 20 carbon atoms are exemplified in the description of R 61 or R 62 in the general formula (I).
  • the halogen atom represented by R 86 , R 87 , R 88 and R 89 an alkyl group having 1 to 40 carbon atoms which may have a substituent, and 6 to 6 carbon atoms
  • Examples of the 20 aryl group, the arylalkyl group having 7 to 20 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms include those exemplified in the description of R 61 or R 62 in the general formula (I). It is done.
  • Examples of the 20 aryl group, the arylalkyl group having 7 to 20 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms include those exemplified in the description of R 61 or R 62 in the general formula (I). It is done.
  • Ring A 2 is preferably benzene or naphthalene
  • the groups other than hydrogen atoms include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 10 carbon atoms, and 7 to 7 carbon atoms. 12 arylalkyl groups and heterocycle-containing groups having 2 to 10 carbon atoms are preferred.
  • any one of R 81 to R 85 is an alkyl group having 1 to 4 carbon atoms or a heterocycle having 2 to 10 carbon atoms.
  • R 62 preferably has the following substituents via —CO—O—.
  • -Alkyl groups having 1 to 8 carbon atoms (particularly methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl) 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl) ⁇
  • Arylalkyl groups having 7 to 10 carbon atoms especially benzyl groups
  • Alkenyl groups having 2 to 6 carbon atoms (particularly propen-1-yl groups)
  • Ring A 2 is preferably benzene or naphthalene
  • groups other than hydrogen atoms include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aryls having 7 to 12 carbon atoms.
  • R 62 preferably has the following substituents via —CO—O—.
  • Y 10 is preferably a sulfur atom, an aromatic ring-containing hydrocarbon group having 6 to 25 carbon atoms, or a heterocyclic ring-containing group having 2 to 21 carbon atoms, Z 1 and Z 2 may be a direct bond, —CO—O—, —O—
  • groups other than hydrogen atoms include aryl groups having 6 to 10 carbon atoms, arylalkyl groups having 7 to 12 carbon atoms, and those having 2 to 10 carbon atoms.
  • Heterocycle-containing groups particularly those in which any one of R 91 to R 94 is an alkyl group having 1 to 4 carbon atoms or a heterocycle-containing group having 2 to 10 carbon atoms are preferred.
  • R 62 preferably has the following substituents via —CO—O—.
  • -Alkyl groups having 1 to 8 carbon atoms (particularly methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl) 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl).
  • Arylalkyl group having 7 to 10 carbon atoms (particularly benzyl group). 2 to 6 carbon atoms Alkenyl group (especially propen-1-yl group)
  • Y 10 is a sulfur atom, a divalent alkyl group having 1 to 20 carbon atoms.
  • Divalent aromatic ring-containing hydrocarbon group having 6 to 25 carbon atoms, divalent heterocyclic group containing 2 to 21 carbon atoms, 2,4,8,10-tetraoxaspiro [5,5] undecane In particular, a divalent alkyl group having 1 to 15 carbon atoms, a divalent aromatic ring-containing hydrocarbon group having 6 to 15 carbon atoms, 2,4,8,10-tetraoxaspiro [5,5] undecane
  • Z 1 and Z 2 may have a direct bond, —CO—O—, —O—CO— or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • Y 11 is a trivalent alkyl group having 1 to 20 carbon atoms, trivalent An aryl group having 6 to 10 carbon atoms, a trivalent arylalkyl group having 7 to 12 carbon atoms, a trivalent heterocyclic group having 2 to 10 carbon atoms, particularly a trivalent carbon atom having 1 to 8 carbon atoms.
  • An alkyl group, a trivalent aryl group having 6 to 9 carbon atoms, and a trivalent heterocyclic group having 1 to 6 carbon atoms, Z 1 , Z 2 and Z 3 are each a direct bond, —CO—O—, —O—CO— or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, particularly a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent is preferable.
  • Y 12 represents a tetravalent alkyl group having 1 to 20 carbon atoms, a tetravalent group.
  • An alkyl group, a tetravalent aryl group having 6 to 9 carbon atoms, and a tetravalent hetero ring-containing group having 1 to 6 carbon atoms, Z 1 to Z 4 are a direct bond, —CO—O—, —O—CO— or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • Y 13 is a pentavalent alkyl group having 1 to 20 carbon atoms, pentavalent An aryl group having 6 to 10 carbon atoms, an arylalkyl group having 5 to 7 carbon atoms, a 5-valent heterocyclic group having 2 to 10 carbon atoms, particularly a pentavalent carbon atom having 1 to 8 carbon atoms.
  • An alkyl group, a pentavalent aryl group having 6 to 9 carbon atoms, and a pentavalent hetero ring-containing group having 1 to 6 carbon atoms, Z 1 to Z 5 are each a direct bond, —CO—O—, —O—CO— or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • Y 14 is a hexavalent alkyl group having 1 to 20 carbon atoms, hexavalent Aryl groups having 6 to 10 carbon atoms, arylalkyl groups having 6 to 7 carbon atoms, heterocyclic groups having 6 to 6 carbon atoms, particularly hexavalent carbon atoms having 1 to 8 carbon atoms.
  • Z 1 to Z 6 are a direct bond, —CO—O—, —O—CO— or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • heterocyclic group having 2 to 10 carbon atoms described above examples include the heterocyclic group having 1 to 10 carbon atoms in the compounds exemplified as the heterocyclic group having 2 to 35 carbon atoms described above. It is done.
  • the content of the latent additive (A) is preferably 0.001 to 20% by mass, and more preferably 0.005 to 5% by mass.
  • the polymer (B) used in the photosensitive composition of the present invention is a polymer having an ethylenically unsaturated bond and a hydrophilic group in one molecule and having a double bond equivalent of 200 to 1,000.
  • the hydrophilic group possessed by the polymer (B) include a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, an amino group, an amide group, or a salt thereof. This is preferable because of its high solubility in water.
  • the preferred functional group equivalent of the hydrophilic group in the polymer (B) (the mass of the polymer containing 1 equivalent of hydrophilic group) is 50 to 10,000.
  • a preferred mass average molecular weight of the polymer (B) is 3000 to 50000.
  • Examples of the polymer (B) include (meth) acrylic acid, ⁇ -chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, and cinnamic acid. Sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ⁇ -carboxypolycaprolactone mono (meth) acrylate, etc.
  • Hydroxyl-containing polyfunctional amine Rate and succinic anhydride phthalic acid anhydride, a polyfunctional acrylate having an acid value which is a reaction product of a dibasic acid anhydride such as tetrahydrophthalic anhydride.
  • 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.
  • those having at least one selected from units represented by the following general formula (VI-4) are preferred because of their high developability and heat resistance.
  • Y 1 represents a hydrogen atom or a methyl group
  • X 4 represents a divalent linking group
  • R 1 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms
  • arylalkyl group having 7 to 30 carbon atoms
  • the hydrogen atom of the alkyl group, aryl group and arylalkyl group may be substituted with a halogen atom, a hydroxyl group, a nitro group or an epoxy group
  • methylene groups in arylalkyl groups may be replaced by linking groups of —O—, —S—, —CO—, —COO—, —OCO— or —NH—, or combinations thereof.
  • R 2 , R 3 and R 4 are each independently a hydrogen atom or a methyl group.
  • the divalent linking group represented by X 4 in the general formula (VI-2) is not particularly limited, but preferred examples include the structure represented by the general formula (1).
  • R 1 is preferably an alkyl group having 1 to 8 carbon atoms and an arylalkyl group having 7 to 30 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • X 4 is a structure in which a divalent linking group is represented by the following general formula (1), Y 10 is preferably an alkylene group having 1 to 15 carbon atoms, and has 7 carbon atoms having a cycloalkylene group. Those having a substituent having ⁇ 15 alkylene groups or carboxyl groups are more preferred.
  • the hydrogen atom in these alkylene groups may be substituted with a halogen atom, a hydroxyl group or a nitro atom, and the methylene group in the chain alkylene portion in the alkylene group is —O—, —S—, —CO. It may be replaced by a —, —COO—, —OCO— or —NH— group.
  • Z 1 and Z 2 are preferably direct bonds.
  • the polymer (B) has an acid value of preferably 10 to 200 mg / KOH, more preferably 30 to 150 mg / KOH. If the acid value is less than 10 mg / KOH, sufficient alkali developability may not be obtained, and if it is greater than 200 mg / KOH, the production of the polymer (B) may be difficult.
  • the acid value is based on JIS K 0050 and JIS K 0211.
  • the polymer (B) must have a double bond equivalent of 200 to 1000, preferably 300 to 500. If the double bond equivalent in the polymer (B) is less than 200, production is difficult, and if it is greater than 1000, sufficient durability cannot be obtained.
  • the content of the polymer (B) is preferably 1 to 20% by mass, particularly preferably 5 to 15% by mass in the photosensitive composition of the present invention.
  • the content of the polymer (B) is less than 1% by mass, resolution and durability may not be sufficiently obtained.
  • the content is more than 20% by mass, alkali developability and curability may not be sufficiently obtained. There is.
  • the acrylic monomer (C) used in the photosensitive composition of the present invention is not particularly limited and known ones can be used.
  • the content of the acrylic monomer (C) is preferably 1 to 20% by mass, particularly preferably 5 to 15% by mass in the photosensitive composition of the present invention.
  • the content of the acrylic monomer (C) is less than 1% by mass, sufficient curability and alkali developability may not be obtained.
  • the content is more than 20% by mass, sufficient resolution and durability may not be obtained. There is.
  • the radical photopolymerization initiator (D) used in the photosensitive composition of the present invention may be any compound that can initiate radical polymerization upon receiving light irradiation, such as an acetophenone compound or a benzyl compound.
  • Preferred examples include compounds, ketone compounds such as benzophenone compounds and thioxanthone 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 (VII) or (VIII) 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 be bonded to each other to form a ring, R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R RI
  • 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 5 represents an oxygen atom, a sulfur atom, a selenium atom, CR 75 R 76 , CO, NR 77 or PR 78
  • X 6 represents a single bond or CO
  • carbon atoms Represents a 6-30 aryl group or an arylalkyl group having 7-30 carbon atoms, and the methylene group in the alkyl group or arylalkyl group contains a halogen atom, a nitro
  • 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
  • photoradical polymerization initiators (D) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (py-1-yl) )] Titanium and the like.
  • photo radical polymerization initiators (D) can be used alone or in combination of two or more according to the desired performance.
  • the radical photopolymerization initiator (D) as described above is preferably 0.01 to 10% by mass, particularly preferably 0.1 to 1% by mass in the photosensitive composition of the present invention.
  • the content of the photo radical polymerization initiator is less than 0.01% by mass, curing by exposure may be insufficient.
  • the photo radical polymerization initiator is contained in the photosensitive composition. It may precipitate.
  • a coloring agent may be further added to the photosensitive composition to obtain a colored photosensitive composition.
  • 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, and more preferably 0.1 to 30% by mass. When the addition amount of the colorant is less than 0.01% by mass, the color is insufficient, and when it is greater than 50% by mass, the colorant may precipitate in the 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.
  • the water resistance and heat resistance can be improved by adding a crosslinking agent to the photosensitive composition of the present invention and reacting with the hydrophilic group of the polymer.
  • the crosslinking agent include polyoxazoline compounds, carbodiimide compounds, epoxy compounds, polyamines, polyols, dicyandiamide derivatives, hydrazine compounds, polyhydrazide compounds (dihydrazide, trihydrazide), aldehydes, methylol compounds, activated vinyl compounds, poly Isocyanate compounds, alkylene carbonate compounds of phenol compounds, polyvalent metal salts, silane coupling agents, organic titanium, etc.
  • polyoxazoline compounds and carbodiimide compounds react at a heat drying temperature of 100 to 120 ° C. preferable.
  • cross-linking agent Commercially available products may be used as the cross-linking agent.
  • Epocros WS-300, WS-500, WS-700 manufactured by Nippon Shokubai Co., Ltd.
  • Carbodilite V-02, V-02-L2, SV-02, And V-04, V-10, SW-12G, E-02, E-03A, E-05 manufactured by Nisshinbo.
  • a solvent can be added to the photosensitive composition and the colored photosensitive composition.
  • 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.
  • the above-mentioned colored photosensitive composition 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.
  • any colorant or inorganic compound can be used as long as it can disperse and stabilize, and commercially available dispersants such as BYK series manufactured by BYK Chemie can be used, and polyester having a basic functional group, Polymer dispersant made of 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 / g Those are preferably used.
  • the colored photosensitive composition includes, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; plasticizer; adhesion promoter; filler; Agents; leveling agents; surface conditioning agents; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants; UV absorbers; dispersion aids; aggregation inhibitors; catalysts; Conventional additives such as thickeners can be added.
  • thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine
  • plasticizer adhesion promoter
  • filler Agents; leveling agents; surface conditioning agents; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants; UV absorbers; dispersion aids; aggregation inhibitors; catalysts; Conventional additives such as
  • the properties of the cured product of the colored photosensitive composition of the present invention can be improved.
  • 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, melamine and the like can be used in combination with the colored photosensitive composition.
  • 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 as or different from each other.
  • methylol groups that are not alkyletherified may be self-condensed within one molecule, and 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 the colored photosensitive composition are prepared by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal. It can be applied on a supporting substrate such as paper or plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base
  • the active energy ray light source used for curing the photosensitive composition and the colored photosensitive composition those that emit 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 photosensitive composition and the colored photosensitive composition of the present invention can be temporarily cured by irradiating the active energy ray and further cured by heating.
  • the pattern can be formed by heating after irradiating the active energy ray, developing, and heating.
  • the photosensitive composition and the colored photosensitive composition are photocurable paints or varnishes, photocurable adhesives, printed boards, color televisions, PC monitors, portable information terminals, digital cameras, etc.
  • the photosensitive composition of the present invention can be used for a transparent conductive film, a reflective film, a polarizing plate, a protective film, etc., and is applied through a mask having a predetermined pattern shape by sequentially applying each of the above-described layers to a transparent substrate. It can be used as a transparent laminate obtained by irradiating light, developing the exposed film with a developer, and heating the developed film.
  • a transparent base material in which transparent thin film layers and metal thin film layers made of a composite oxide of indium oxide and cerium oxide are alternately arranged can be used.
  • a photosensitive composition containing the compound of the present invention as a latent additive may be used for each of the aforementioned layers, or the photosensitive composition may be used for any one or more layers.
  • the transparent laminate is suitably used for a display device.
  • the colored photosensitive composition 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.
  • the color filter for a display device includes (1) a step of forming a coating film of the colored photosensitive composition on a substrate, and (2) irradiating the coating film with active light through a mask having a predetermined pattern shape. It is preferably formed by a step, (3) a step of developing the film after exposure with a developer, and (4) a step of heating the film after development.
  • the colored photosensitive composition of the present invention is also useful as an inkjet colored photosensitive composition having no development step.
  • a multi-tone mask such as a halftone mask or a gray scale mask can be used.
  • reaction solution was cooled to room temperature, 160 g of PGMEA, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and after stirring at 120 ° C. for 4 hours, at 100 ° C. for 3 hours, at 80 ° C. for 4 hours, at 60 ° C. for 6 hours, and at 40 ° C.
  • Photosensitive composition No. 1-No. 11 and comparative photosensitive composition no. 1-No. Preparation of photosensitive composition No. 2 in accordance with the formulation of [Table 1] and [Table 2].
  • 1-No. 11 and comparative photosensitive composition no. 1-No. 2 was prepared. The numerical values in [Table 1] and [Table 2] are parts by mass.
  • A-1 to A-4 in [Table 1] and [Table 2] represent the following latent additives.
  • B-1 to B-4, B'-1, C-1 to C-2, D-1 to D-3, E-1 and F-1 in [Table 1] and [Table 2] are respectively The following compounds are represented.
  • B-1 SPC-1000 (Acrylic resin from Showa Denko; weight average molecular weight 31980, double bond equivalent 900)
  • B-2 SPC-3000 (Acrylic resin from Showa Denko; weight average molecular weight 7610, double bond equivalent 340)
  • B-3 Obtained in Production Example 1 (weight average molecular weight 22000, double bond equivalent 330)
  • B-4 Obtained in Production Example 2 (weight average molecular weight 5600, double bond equivalent 434)
  • B′-1 SPC-2000 Showa Denko acryl resin; weight average molecular weight 17500, double bond equivalent 0)
  • C-1 Aronix M450 (Toagosei Co., Ltd.
  • the photosensitive composition of the present invention is maintained with high transparency after firing, that is, it has high heat resistance and excellent solvent resistance.
  • the photosensitive composition which gives the hardened

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The purpose of the present invention is to provide a photosensitive composition that gives a cured product having a high heat resistance and a high solvent resistance. Provided is a photosensitive composition that contains a latent additive (A), a polymer (B) having an ethylenically unsaturated bond and a hydrophilic group in each molecule, with a double bond equivalent of 200 to 1,000, an acrylic monomer (C), and a photo-radical polymerization initiator (D). The content of the latent additive (A) in the photosensitive composition is preferably 0.001 to 20% by mass. This photosensitive composition is curable by actinic ray radiation.

Description

感光性組成物Photosensitive composition
　本発明は、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機能を発現する潜在性添加剤、エチレン性不飽和結合及び親水性基を一分子内に有し、且つ一定の二重結合当量を有する重合体、アクリルモノマー及び光ラジカル重合開始剤を含有する感光性組成物に関する。更には、該組成物を用いた、エネルギー線により重合可能な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 has a latent additive, an ethylenically unsaturated bond, and a hydrophilic group that are inactive at normal temperature and activated by heating to a predetermined temperature to exhibit a function, and are constant. The present invention relates to a photosensitive composition containing a polymer having a double bond equivalent of: Furthermore, the present invention relates to a colored photosensitive composition that can be polymerized by energy rays using the composition, and a color filter that uses the colored photosensitive composition.
　樹脂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）。 In order to improve the weather resistance and heat resistance of a resin composition, a method of stabilizing by adding an ultraviolet absorber or an antioxidant is known (Patent Document 1).
　また、感光性組成物において、樹脂の二重結合当量を一定範囲内に保つことにより、微細パターンを描いたり、硬化物のコントラストが向上することが知られている。しかしながら、樹脂の二重結合当量を一定の範囲内に保つことにより、耐溶剤性を向上させることは知られていない（特許文献２～５）。 In the photosensitive composition, it is known that a fine pattern is drawn and the contrast of the cured product is improved by keeping the double bond equivalent of the resin within a certain range. However, it is not known to improve the solvent resistance by keeping the double bond equivalent of the resin within a certain range (Patent Documents 2 to 5).
　フェノール系酸化防止剤は、ポリマ―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、酸化防止剤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６）。 Since phenolic antioxidants trap radicals that greatly affect the deterioration of the polymer, adding antioxidants to the polymerization system generally acts as a so-called polymerization inhibitor, causing inhibition of curing. Therefore, latent additives have been developed (Patent Document 6).
特開２００２－０９７２２４号公報JP 2002-097224 A 特開２００９－１３４０７８号公報JP 2009-134078 A 特開２０１３－０３７２７２号公報JP 2013-037272 A 米国特許出願公開第２０１５／２５４２１０号明細書US Patent Application Publication No. 2015/254210 特許第５４６０１７９号公報Japanese Patent No. 5460179 米国特許出願公開第２０１５／２９１７７２号明細書US Patent Application Publication No. 2015/291773
　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機能を発現する潜在性添加剤、エチレン性不飽和結合及び親水性基を一分子内に有し一定の二重結合当量を有する重合体、アクリルモノマー及び光ラジカル重合開始剤を含有する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 have a latent additive, an ethylenically unsaturated bond and a hydrophilic group in one molecule which are inactive at room temperature and are activated by heating to a predetermined temperature to exhibit a function. Another object of the present invention is to provide a photosensitive composition comprising a polymer having a certain double bond equivalent, an acrylic monomer, and a radical photopolymerization initiator.
　本発明者等は、鋭意検討を重ねた結果、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潜在性添加剤、エチレン性不飽和結合及び親水性基を一分子内に有し一定の二重結合当量を有する重合体、アクリルモノマー及び光ラジカル重合開始剤を含有する感光性組成物の硬化物が、耐熱性及び耐溶剤性が高く、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 inventors have found that a latent additive, an ethylenically unsaturated bond, and a hydrophilic group that are inactive at room temperature and are activated by heating to a predetermined temperature to exhibit functions. A cured product of a photosensitive composition containing a polymer having a certain double bond equivalent in one molecule, an acrylic monomer, and a photo radical polymerization initiator, has high heat resistance and solvent resistance, and is a liquid crystal display panel, etc. As a result, the present invention has been found.
　本発明は、上記知見に基づきなされたもので、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潜在性添加剤（Ａ）（以下、潜在性添加剤（Ａ）ともいう）、エチレン性不飽和結合及び親水性基を一分子内に有し、且つ二重結合当量が２００～１０００である重合体（Ｂ）（以下、重合体（Ｂ）ともいう）、アクリルモノマー（Ｃ）及び光ラジカル重合開始剤（Ｄ）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 on the basis of the above findings, and is a latent additive (A) that is inactive at room temperature and is activated by heating to a predetermined temperature to express its function (hereinafter, the latent additive ( A)), a polymer (B) having an ethylenically unsaturated bond and a hydrophilic group in one molecule and having a double bond equivalent of 200 to 1000 (hereinafter also referred to as polymer (B)) The photosensitive composition containing an acrylic monomer (C) and a radical photopolymerization initiator (D) is provided.
　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、潜在性添加剤（Ａ）、エチレン性不飽和結合及び親水性基を一分子内に有し、且つ二重結合当量２００～１０００である重合体（Ｂ）、アクリルモノマー（Ｃ）及び光ラジカル重合開始剤（Ｄ）を含有する。以下、各成分について順に説明する。 The photosensitive composition of the present invention comprises a latent additive (A), a polymer (B) having an ethylenically unsaturated bond and a hydrophilic group in one molecule and a double bond equivalent of 200 to 1000, Contains an acrylic monomer (C) and a radical photopolymerization initiator (D). Hereinafter, each component will be described in order.
＜潜在性添加剤（Ａ）＞
　本発明の感光性組成物に用いられる潜在性添加剤（Ａ）は、常温あるいは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。潜在性添加剤（Ａ）が活性であるとはラジカルに対し反応性を有することをいい、不活性であるとはラジカルと反応しないか又は反応性が極めて低いことをいう。本発明の感光性組成物において、潜在性添加剤（Ａ）は、下記一般式（Ｉ）で表される骨格を有するものが、合成が容易で耐熱性が高いので好ましい。 <Latent additive (A)>
The latent additive (A) used in the photosensitive composition of the present invention is inactive at room temperature or in the pre-baking step, and is heated at 100 to 250 ° C. or 80 to 200 ° C. in the presence of an acid / base catalyst. The protecting group is eliminated and becomes active by heating with. When the latent additive (A) is active, it means that it has reactivity with radicals, and when it is inactive, it means that it does not react with radicals or has extremely low reactivity. In the photosensitive composition of the present invention, it is preferable that the latent additive (A) has a skeleton represented by the following general formula (I) because synthesis is easy and heat resistance is high.
Figure JPOXMLDOC01-appb-C000001
（式中、環Ａ１は、五員環又は六員環の炭化水素環又は複素環あるいは縮合環を表し、
　Ｒ６１は、それぞれ独立に、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、
　Ｒ６２は、それぞれ独立に、炭素原子数１～２０のアルキル基、炭素原子数２～２０のアルケニル基、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の複素環含有基又はトリアルキルシリル基を表し、
　Ｒ６１及びＲ６２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、炭素－炭素二重結合、－Ｏ－、－Ｓ－、－ＣＯ－、－Ｏ－ＣＯ－、－ＣＯ－Ｏ－、－Ｏ－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られている場合があり、Ｒ’は、水素原子又は炭素原子数１～８のアルキル基を表し、
　複数のＲ６１同士は結合してベンゼン環又はナフタレン環を形成している場合もあり、
　ｄは、０～４の整数を表し、
　ｋは、１～５の整数を表すが、ｄとｋの合計は、環Ａ１が取り得る置換基の数より少なく、
　＊は、＊部分で、隣接する基と結合することを意味する。）
Figure JPOXMLDOC01-appb-C000001
(In the formula, ring A 1 represents a 5-membered or 6-membered hydrocarbon ring, heterocyclic ring or condensed ring;
R 61 each independently has a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, a C 1-40 alkyl group that may have a substituent, or a substituent. An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms that may have a substituent, or an aryl group having 2 to 20 carbon atoms that may have a substituent Represents a heterocyclic-containing group,
R 62 each independently represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, carbon Represents a heterocyclic group containing 2 to 20 atoms or a trialkylsilyl group,
The methylene group in the alkyl group or arylalkyl group represented by R 61 and R 62 is a carbon-carbon double bond, —O—, —S—, —CO—, —O—CO—, —CO—O. -, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH A group selected from —, —NH—CO—, —NH—CO—O—, —NR′—, —SS— or —SO 2 — is replaced with a group which is combined under the condition that oxygen atoms are not adjacent to each other. R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
A plurality of R 61 may be bonded to each other to form a benzene ring or a naphthalene ring,
d represents an integer of 0 to 4;
k represents an integer of 1 to 5, but the sum of d and k is less than the number of substituents that ring A 1 can take;
* Means that it is bonded to an adjacent group at the * part. )
　上記一般式（Ｉ）で表される骨格を有するものの中でも、下記一般式（Ｉ－Ａ）で表されるものが、特に耐熱性が高いので好ましい。 Among those having a skeleton represented by the above general formula (I), those represented by the following general formula (IA) are particularly preferable because of their high heat resistance.
Figure JPOXMLDOC01-appb-C000002
（式中、環Ａ１、Ｒ６１、Ｒ６２、ｄ及びｋは、上記一般式（Ｉ）と同じであり、
　ｍは、１～１０の整数を表し、
　Ｘ１は、ｍ価の有機基を表す。）
Figure JPOXMLDOC01-appb-C000002
(In the formula, the rings A 1 , R 61 , R 62 , d and k are the same as those in the general formula (I),
m represents an integer of 1 to 10,
X 1 represents an m-valent organic group. )
　本明細書において、炭素原子数２～２０の複素環含有基とは、複素環を少なくとも一つ含有し、基全体の炭素数が２～２０の基を意味する。同様に、後述する炭素原子数２～１０の複素環含有基とは、複素環を少なくとも一つ含有し、基全体の炭素数が２～１０の基を意味する。また、後述する炭素原子数２～３５の複素環含有基とは、複素環を少なくとも一つ含有し、基全体の炭素数が２～３５の基を意味する。これらの複素環を含有する基における該複素環が置換基を有する場合には、基全体の炭素原子数は、それぞれの基の上限値を超えている場合がある。複素環を含有する基における該複素環が置換基を有する場合、該置換基としては、例えば、後述するＸ１で表される基を置換する場合がある置換基として例示するものが挙げられる。 In the present specification, the heterocyclic group having 2 to 20 carbon atoms means a group containing at least one heterocyclic ring and having 2 to 20 carbon atoms in the whole group. Similarly, the heterocycle-containing group having 2 to 10 carbon atoms described later means a group containing at least one heterocycle and having 2 to 10 carbon atoms as a whole. Further, the heterocycle-containing group having 2 to 35 carbon atoms described later means a group containing at least one heterocycle and having 2 to 35 carbon atoms as a whole. When the heterocyclic ring in the group containing these heterocyclic rings has a substituent, the number of carbon atoms of the whole group may exceed the upper limit of each group. In the case where the heterocyclic ring in the group containing a heterocyclic ring has a substituent, examples of the substituent include those exemplified as the substituent that may substitute a group represented by X 1 described later.
　上記一般式（Ｉ）におけるＡ１で表される五員環の炭化水素環としては、シクロペンタジエン等が挙げられ、五員環の複素環としては、フラン、チオフェン、ピロール、ピロリジン、ピラゾリジン、ピラゾール、イミダゾール、イミダゾリジン、オキサゾール、イソキサゾール、イソオキサゾリジン、チアゾール、イソチアゾール、イソチアゾリジン等が挙げられ、六員環の炭化水素環としては、ベンゼン等が挙げられ、六員環の複素環としては、ピペリジン、ピペラジン、モルフォリン、チオモルフォリン、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン等が挙げられ、これらの環は、他の環と縮合されていたり置換されている場合があり、縮合環としては、例えば、キノリン、イソキノリン、インドール、ユロリジン、ベンゾオキサゾール、ベンゾトリアゾール、アズレン、ナフタレン、アントラセン、フルオレン、ペリレン、ピレン等が挙げられる。 Examples of the five-membered hydrocarbon ring represented by A 1 in the general formula (I) include cyclopentadiene, and examples of the five-membered heterocyclic ring include furan, thiophene, pyrrole, pyrrolidine, pyrazolidine, and pyrazole. , Imidazole, imidazolidine, oxazole, isoxazole, isoxazolidine, thiazole, isothiazole, isothiazolidine, etc., as the six-membered hydrocarbon ring, benzene and the like, and as the six-membered heterocyclic ring, Piperidine, piperazine, morpholine, thiomorpholine, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. are mentioned, and these rings may be condensed or substituted with other rings. For example, quinoline, isoquinoline, indole, urolidine, ben Examples include zoxazole, benzotriazole, azulene, naphthalene, anthracene, fluorene, perylene, and pyrene.
　上記一般式（Ｉ）におけるＲ６１で表されるハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる（尚、以下の明細書中の記載において、ハロゲン原子は全て、上記と同様である）。 Examples of the halogen atom represented by R 61 in the general formula (I) include fluorine, chlorine, bromine and iodine. (In the description below, all the halogen atoms are the same as described above. ).
　上記一般式（Ｉ）におけるＲ６１で表される炭素原子数１～４０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、 Examples of the alkyl group having 1 to 40 carbon atoms represented by R 61 in the general formula (I) 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,
　上記一般式（Ｉ）におけるＲ６１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。 In the general formula (I), 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 2 to 20 carbon atoms represented by R 61 Substituents for substituting the heterocyclic ring-containing groups include ethylenically unsaturated groups such as vinyl, allyl, acrylic and methacryl; halogen atoms such as fluorine, chlorine, bromine and iodine; acetyl, 2-chloroacetyl, propionyl and octanoyl Acyl groups such as acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl Acetyloxy Acyloxy groups such as benzoyloxy, 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-octade Substituted amino groups such as ruoxycarbonylamino, 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, Examples thereof include salts of phosphoric acid groups.
　上記一般式（Ｉ）におけるＲ６１及びＲ６２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る。 Examples of the aryl group having 6 to 20 carbon atoms represented by R 61 and R 62 in the general formula (I) 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-dimethyl Phenyl, 2,4-di-tert-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- Examples include trimethylphenyl and ferrocenyl.
　上記一般式（Ｉ）におけるＲ６１及びＲ６２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る。 Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R 61 and R 62 in the general formula (I) include benzyl, 1-methyl-1-phenylethyl, 1-naphthylmethyl, 9-anthracenyl Examples include methyl, 9-fluorenyl, 3-phenylpropyl, methyl-2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, phenethyl, styryl, cinnamyl and the like.
　上記一般式（Ｉ）におけるＲ６１及びＲ６２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る。 Examples of the heterocyclic ring-containing group having 2 to 20 carbon atoms represented by R 61 and R 62 in the general formula (I) include a pyridine ring, a pyrimidine ring, a pyridazine ring, a piperidine ring, a pyran ring, a pyrazoline ring, and a triazine ring. , Pyrroline ring, quinoline ring, isoquinoline ring, imidazoline ring, benzoimidazoline ring, triazoline ring, furan ring, benzofuran ring, thiadiazoline ring, thiazoline ring, benzothiazoline ring, thiophene ring, oxazoline ring, benzoxazoline ring, isothiazoline ring, iso Examples include groups in which a hetero ring such as an oxazoline ring, an indole ring, a pyrrolidine ring, a piperidone ring, or a dioxane ring and a methylene chain are combined.
　上記一般式（Ｉ）におけるＲ６２で表される炭素原子数１～２０のアルキル基としては、Ｒ６１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。 Examples of the alkyl group having 1 to 20 carbon atoms represented by R 62 in the general formula (I) include those satisfying a predetermined number of carbon atoms among the alkyl groups represented by R 61 .
　上記一般式（Ｉ）におけるＲ６２で表される炭素原子数２～２０のアルケニル基としては、ビニル、１－メチルエテン－１－イル、プロペン－１－イル、プロペン－２－イル、プロペン－３－イル、ブテン－１－イル、ブテン－２－イル、２－メチルプロペン－３－イル、１，１－ジメチルエテン－２－イル、１，１－ジメチルプロペン－３－イル、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、ぺンタデセニル、エイコセニル、トリコセニ等が挙げられる。　 Examples of the alkenyl group having 2 to 20 carbon atoms represented by R 62 in the general formula (I) include vinyl, 1-methylethen-1-yl, propen-1-yl, propen-2-yl and propene-3. -Yl, buten-1-yl, buten-2-yl, 2-methylpropen-3-yl, 1,1-dimethylethen-2-yl, 1,1-dimethylpropen-3-yl, 3-butenyl, Examples include 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, tricoseni and the like.
　上記一般式（Ｉ）におけるＲ６２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でも異なってよい）で置換されたシリル基が挙げられる。 Examples of the trialkylsilyl group represented by R 62 in the general formula (I) include alkyl groups having 1 to 6 carbon atoms such as trimethylsilane, triethylsilane, and ethyldimethylsilane (the three alkyl groups may be the same or different. Silyl group substituted with (good).
　上記一般式（Ｉ）におけるＲ’で表される炭素原子数１～８のアルキル基としては、Ｒ６１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。 Examples of the alkyl group having 1 to 8 carbon atoms represented by R ′ in the general formula (I) include those satisfying a predetermined number of carbon atoms among the alkyl groups represented by R 61 .
　一般式（Ｉ）においては、Ｒ６１が、水素原子、炭素原子数１～８のアルキル基、炭素原子数６～１２のアリール基であることが、合成が容易なため好ましい。
　一般式（Ｉ）においては、Ｒ６２が、炭素原子数１～８のアルキル基の酸素原子側の末端に－ＣＯ－Ｏ－が結合しているものが、潜在性添加剤として効率的に機能を発現するので好ましい。 In general formula (I), R 61 is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms because synthesis is easy.
In the general formula (I), R 62 is an alkyl group having 1 to 8 carbon atoms in which —CO—O— is bonded to the terminal on the oxygen atom side and functions effectively as a latent additive. Is preferable.
　上記一般式（Ｉ－Ａ）において、Ｘ１は、ｍ価の有機基を表し、具体的には、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、＞Ｃ＝Ｏ、＞ＮＲ６３、－ＯＲ６３、－ＳＲ６３、－ＮＲ６３Ｒ６４、又は置換基を有している場合もあるｍと同数の価数を有する炭素原子数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ｍと同数の価数を有する炭素原子数６～３５の芳香環含有炭化水素基、置換基を有している場合もあるｍと同数の価数を有する炭素原子数２～３５の複素環含有基を表し、Ｒ６３及びＲ６４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、該脂肪族炭化水素基、芳香環含有炭化水素基及び複素環含有基のメチレン基は、炭素一炭素二重結合、－Ｏ－、－Ｓ－、－ＣＯ－、－Ｏ－ＣＯ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－Ｏ－、－Ｏ－ＣＯ－Ｏ－、－Ｓ－ＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－Ｏ－、－Ｏ－ＣＯ－Ｓ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＮＨ－ＣＯ－Ｏ－、－ＮＨ－ＣＯ－Ｏ－、－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り、Ｒ’は、水素原子又は炭素原子数１～８のアルキル基を表す。
　但し、Ｘ１が窒素原子、リン原子又は下記（Ｉ－ａ）若しくは（Ｉ－ｂ）で表される基の場合、ｍは３であり、Ｘ１が酸素原子又は硫黄原子、＞Ｃ＝Ｏ、－ＮＨ－ＣＯ－、－ＣＯ－ＮＨ－又は＞ＮＲ６３の場合、ｍは２であり、Ｘ１が－ＯＲ６３、－ＳＲ６３又は－ＮＲ６３Ｒ６４の場合、ｍは１であり、Ｘ１は、Ａ１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 m-valent organic group, specifically, a direct bond, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, the following (Ia ) Or (Ib),>C═O,> NR 63 , —OR 63 , —SR 63 , —NR 63 R 64 , or the same number as m which may have a substituent. An aliphatic hydrocarbon group having 1 to 120 carbon atoms having a valence of 6 to 35, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms having the same valence as m that may have a substituent, A heterocyclic group containing 2 to 35 carbon atoms having the same valence as m, which may have a substituent, and R 63 and R 64 each having a hydrogen atom or a substituent There may also be an aliphatic hydrocarbon group having 1 to 35 carbon atoms, and may have a substituent. Represents an aromatic ring-containing hydrocarbon group or a heterocyclic ring-containing 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 The methylene group is a carbon-carbon double bond, —O—, —S—, —CO—, —O—CO—, —CO—O—, —O—CO—O—, —O—CO—O. -, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NH-, -NH-CO-, -NH-CO-O-, It may be replaced by a group selected from —NH—CO—O—, —NR′—, —S—S—, —SO 2 —, or a nitrogen atom, and R ′ is a hydrogen atom or 1 carbon atom. Represents an alkyl group of ˜8.
However, when X 1 is a nitrogen atom, a phosphorus atom or a group represented by the following (Ia) or (Ib), m is 3, X 1 is an oxygen atom or a sulfur atom, and> C═O , —NH—CO—, —CO—NH— or> NR 63 , m is 2, and when X 1 is —OR 63 , —SR 63 or —NR 63 R 64 , m is 1. X 1 may form a ring together with A 1 .
Figure JPOXMLDOC01-appb-C000003
（＊は、＊部分で、隣接する基と結合することを意味する。）
Figure JPOXMLDOC01-appb-C000003
(* Means that it is bonded to an adjacent group at the * portion.)
　上記一般式（Ｉ－Ａ）で表される潜在性添加剤は、Ｘ１で表されるｍ価の特定の原子又は基に、ｍ個の特定の基が結合した構造を有する。このｍ個の基は、互いに同じであるか又は異なる。ｍの値は１～１０であり、合成の容易さの点から、好ましくは２～６である。 The latent additive represented by the general formula (IA) has a structure in which m specific groups are bonded to the m-valent specific atom or group represented by X 1 . The m groups are the same as or different from each other. The value of m is 1 to 10, and preferably 2 to 6 from the viewpoint of ease of synthesis.
　上記一般式（Ｉ－Ａ）におけるＸ１で表される、ｍと同数の価数を有する炭素原子数１～１２０の脂肪族炭化水素基としては、ｍ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る。 As the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same valence as m represented by X 1 in the general formula (IA), m is monovalent, for example, methyl Ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, sec-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, bicyclohexyl, 1-methyl Alkyl groups such as cyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tertiary heptyl, n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, nonyl, isononyl, decyl; methyloxy, ethyloxy, propyloxy, Isopropyloxy, butyloxy, sec-butyloxy, tert-butyl Oxy, isobutyloxy, amyloxy, isoamyloxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyloxy , Alkoxy groups such as nonyloxy, decyloxy; methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, tert-butylthio, isobutylthio, amylthio, isoamylthio, tert-amylthio, hexylthio, cyclohexylthio, heptylthio, isoheptylthio, sec Alkylthio groups such as triheptylthio, 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, heptenyl, octenyl, decenyl, Examples include alkenyl groups such as pentadecenyl, eicosenyl, and tricosenyl, and groups in which these groups are substituted with a substituent described later.
　上記一般式（Ｉ－Ａ）における、Ｘ１で表されるｍと同数の価数を有する炭素原子数１～１２０の脂肪族炭化水素基としては、ｍ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る。 In the general formula (IA), the aliphatic hydrocarbon group having 1 to 120 carbon atoms having the same valence as m represented by X 1 is methylene, ethylene where m is divalent. Alkylene, such as propylene, butylene, butyldiyl, etc .; in which the methylene chain of the alkylene is replaced by —O—, —S—, —CO—O—, —O—CO—; ethanediol, propanediol, butanediol, Residues of diols such as pentanediol and hexanediol; residues of dithiols such as ethanedithiol, propanedithiol, butanedithiol, pentanedithiol and hexanedithiol, and groups in which these groups are substituted by substituents described later, etc. .
　上記一般式（Ｉ－Ａ）におけるＸ１で表される、ｍと同数の価数を有する炭素原子数１～１２０の脂肪族炭化水素基としては、ｍ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。 Examples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms and having the same valence as m represented by X 1 in the general formula (IA) are those in which m is trivalent. Examples thereof include alkylidine such as pyridine and 1,1,3-butyridine, and groups in which these groups are substituted with a substituent described later.
　上記一般式（Ｉ－Ａ）におけるＸ１で表される、ｍ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、ｍ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る。 Examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, which may have a substituent, having the same valence as m represented by X 1 in the general formula (IA). M is monovalent, arylalkyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl and cinnamyl; aryl groups such as phenyl and naphthyl; aryloxy groups such as phenoxy and naphthyloxy; phenylthio and naphthylthio And arylthio groups such as these, and groups in which these groups are substituted with a substituent described later.
　上記一般式（Ｉ－Ａ）におけるＸ１で表される、置換基を有している場合もあるｍと同数の価数を有する炭素原子数６～３５の芳香環含有炭化水素基としては、ｍ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る。 As the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same valence as m which may have a substituent, represented by X 1 in the general formula (IA), m 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 and these groups Is a group substituted by a substituent described later.
　上記一般式（Ｉ－Ａ）におけるＸ１で表される、置換基を有している場合もあるｍと同数の価数を有する炭素原子数６～３５の芳香環含有炭化水素基としては、ｍ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。 The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same valence as m, which may have a substituent, represented by X 1 in the general formula (IA), Examples of m being trivalent include phenyl-1,3,5-trimethylene and groups in which these groups are substituted with a substituent described later.
　上記一般式（Ｉ－Ａ）におけるＸ１で表される、置換基を有している場合もあるｍと同数の価数を有する炭素原子数２～３５の複素環含有基としては、ｍ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る。 As the heterocyclic group containing 2 to 35 carbon atoms and having the same valence as m which may have a substituent, represented by X 1 in the general formula (IA), m is As monovalent ones, pyridyl, pyrimidyl, pyridadyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, 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-dioxy Oxazolidin-3-yl, ben Examples thereof include zotriazoyl and the like and groups in which these groups are substituted with a substituent described later.
　上記一般式（Ｉ－Ａ）におけるＸ１で表される、置換基を有している場合もあるｍと同数の価数を有する炭素原子数２～３５の複素環含有基としては、ｍ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る。 As the heterocyclic group containing 2 to 35 carbon atoms having the same valence as m which may have a substituent, represented by X 1 in the general formula (IA), m is Examples of the divalent group include 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 with a substituent described later. .
　上記一般式（Ｉ－Ａ）におけるＸ１で表される、置換基を有している場合もあるｍと同数の価数を有する炭素原子数２～３５の複素環含有基としては、ｍ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。 As the heterocyclic group containing 2 to 35 carbon atoms and having the same valence as m which may have a substituent, represented by X 1 in the general formula (IA), m is Examples of the trivalent group 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.
　Ｒ６３及びＲ６４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で表される炭素原子数１～１２０の脂肪族炭化水素基、又は該脂肪族炭化水素基と後述する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る。 Examples of the aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent represented by R 63 and R 64 include an aliphatic hydrocarbon group having 1 to 120 carbon atoms represented by the above X 1 Among the combinations of an aromatic hydrocarbon group or the aliphatic hydrocarbon group and a substituent described later, those satisfying a predetermined number of carbon atoms can be mentioned.
　Ｒ６３及びＲ６４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若しくは炭素原子数２～３５の複素環含有基、又はこれらの基と後述する置換基とを組み合わせた基が挙げられる。 The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent represented by R 63 and R 64 or 2 to 35 carbon atoms which may have a substituent As the heterocyclic ring-containing group, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms or the heterocyclic ring-containing group having 2 to 35 carbon atoms represented by X 1 above, or a substituent described later with these groups And a combination of these.
　Ｘ１で表される、炭素原子数１～１２０の脂肪族炭化水素基、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の複素環含有基を置換する場合がある置換基、並びに、Ｒ６３及びＲ６で表される、炭素原子数１～３５の脂肪族炭化水素基、炭素原子数６～３５の芳香環含有炭化水素基及び炭素原子数２～３５の複素環含有基を置換する場合がある置換基としては、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。 In some cases, an aliphatic hydrocarbon group having 1 to 120 carbon atoms, 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 X 1 may be substituted. A certain substituent, and an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and 2 to 35 carbon atoms represented by R 63 and R 6 Examples of substituents that may be substituted for the heterocyclic ring-containing groups include ethylenically unsaturated groups such as vinyl, allyl, acrylic, and methacryl; halogen atoms such as fluorine, chlorine, bromine, and iodine; acetyl, 2-chloroacetyl, propionyl , Octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearo Acyl groups such as acetyloxy, benzoyloxy, etc .; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, acyl groups such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; 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-diethylamino Carbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N, N-dimethyl Substituted amino groups such as aminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group, mercapto group, imide group, carbamoyl group , Sulfonamide groups, phosphonic acid groups, phosphoric acid groups or carboxyl groups, sulfo groups, phosphonic acid groups, salts of phosphoric acid groups, and the like, 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）におけるＲ’で表される炭素原子数１～８のアルキル基としては、上述したＲ６１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。 Examples of the alkyl group having 1 to 8 carbon atoms represented by R ′ in the general formula (IA) include those having the predetermined number of carbon atoms among the alkyl groups represented by R 61 described above. Can be mentioned.
　上記一般式（Ｉ－Ａ）において、ｍが２であるとき、Ｘ１は、下記一般式（１）のように表すこともできる。 In the above general formula (IA), when m is 2, X 1 can also be represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000004
（上記一般式（１）中、Ｙ１０は、単結合、－ＣＲ６５Ｒ６６－、－ＮＲ６７－、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）で表される何れかの置換基を表し、
　該脂肪族炭化水素基の隣接する炭素原子は、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－又は－ＮＨ－、あるい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中断されている場合もあり、
　該脂肪族炭化水素基の末端の炭素原子は－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－又は－ＮＨ－で置き換えられている場合もあり、
　該脂肪族炭化水素基は、水酸基、ハロゲン原子、シアノ基、ニトロ基、カルボキシル基又はアルコキシ基で置換さ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－、＞ＮＲ６７又は＞ＰＲ６７を表し、
　Ｒ６５、Ｒ６６及びＲ６７は、それぞれ独立に、水素原子、水酸基、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-C000004
(In the general formula (1), Y 10 represents a single bond, —CR 65 R 66 —, —NR 67 —, 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 substituent represented by the following (1-1) to (1-3):
Adjacent carbon atoms of the aliphatic hydrocarbon group are —O—, —S—, —CO—, —COO—, —OCO— or —NH—, or a combination of these without adjacent oxygen atoms. Sometimes interrupted by a linking group,
The terminal carbon atom of the aliphatic hydrocarbon group may be replaced with —O—, —S—, —CO—, —COO—, —OCO— or —NH—,
The aliphatic hydrocarbon group may be substituted with a hydroxyl group, a halogen atom, a cyano group, a nitro group, a carboxyl group or an alkoxy group,
Z 1 and Z 2 are each independently a direct bond, —O—, —S—,> CO, —CO—O—, —O—CO—, —SO 2 —, —SS—, —SO—, Represents> NR 67 or> PR 67 ,
R 65 , R 66 and R 67 each independently have a hydrogen atom, a hydroxyl group or a substituent, or may have 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-C000005
（上記式中、Ｒ７１は水素原子、置換基を有している場合もあるフェニル基、又は炭素原子数３～１０のシクロアルキル基を表し、
　Ｒ７２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があり、
　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-C000005
(In the above formula, R 71 represents a hydrogen atom, a phenyl group which may have a substituent, or a cycloalkyl group having 3 to 10 carbon atoms,
R 72 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 may have a substituent,
f is an integer of 0 to 5, and * means that it is bonded to an adjacent group at the * portion. )
Figure JPOXMLDOC01-appb-C000006
（＊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
(* Means that it is bonded to an adjacent group at the * portion.)
Figure JPOXMLDOC01-appb-C000007
（上記式中、Ｒ７３及びＲ７４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があり、
　Ｒ７３は、隣接するＲ７３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-C000007
(In the above formula, R 73 and R 74 are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, or 6 carbon atoms 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 73 may form a ring with adjacent R 73 ,
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. )
　上記一般式（Ｉ－Ａ）において、ｍが３であるとき、Ｘ１は、下記一般式（２）のように表すこともできる。 In the above general formula (IA), when m is 3, X 1 can also be represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000008
（上記一般式（２）中、Ｙ１１は、単結合、３価の炭素原子数３～３５の脂肪族炭化水素基、３価の炭素原子数３～３５の脂環族炭化水素基、３価の炭素原子数６～３５の芳香族炭化水素基若しくは３価の炭素原子数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－、＞ＮＲ６８又は＞ＰＲ６８を表し、
　Ｒ６８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、
　該脂肪族炭化水素基の隣接する炭素原子は、炭素一炭素二重結合、－Ｏ－、－ＣＯ－、－Ｏ－ＣＯ－、－ＣＯ－Ｏ－又は－ＳＯ２－で中断されている場合もあり、
　該脂肪族炭化水素基の末端の炭素原子は炭素一炭素二重結合、－Ｏ－、－ＣＯ－、－Ｏ－ＣＯ－、－ＣＯ－Ｏ－又は－ＳＯ２－で置き換えられている場合がある。）
Figure JPOXMLDOC01-appb-C000008
(In the general formula (2), Y 11 represents a single bond, a trivalent aliphatic hydrocarbon group having 3 to 35 carbon atoms, a trivalent alicyclic hydrocarbon group having 3 to 35 carbon atoms, 3 A valent aromatic hydrocarbon group having 6 to 35 carbon atoms or a trivalent heterocyclic 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—, — SO-,> NR 68 or> PR 68 ,
R 68 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,
When the adjacent carbon atom of the aliphatic hydrocarbon group is interrupted by a carbon-carbon double bond, —O—, —CO—, —O—CO—, —CO—O— or —SO 2 —. There is also
The terminal carbon atom of the aliphatic hydrocarbon group may be replaced with a carbon-carbon double bond, —O—, —CO—, —O—CO—, —CO—O— or —SO 2 —. is there. )
　上記一般式（Ｉ－Ａ）において、ｍが４であるとき、Ｘ１は、下記一般式（３）のように表すこともできる。 In the above general formula (IA), when m is 4, X 1 can also be represented by the following general formula (3).
Figure JPOXMLDOC01-appb-C000009
（上記一般式（３）中、Ｙ１２は、単結合、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、４価の炭素原子数６～３５の芳香族炭化水素基若しくは４価の炭素原子数２～３５の複素環含有基を表し、
　該脂肪族炭化水素基の隣接する炭素原子は、－ＣＯＯ－、－Ｏ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＮＨ－又は－ＣＯＮＨ－で中断されている場合があり、
　該脂肪族炭化水素基の末端の炭素原子は、－ＣＯＯ－、－Ｏ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＮＨ－又は－ＣＯＮＨ－で置き換えらている場合があり、
　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る。）
Figure JPOXMLDOC01-appb-C000009
(In the general formula (3), Y 12 represents a single bond, a carbon atom, or a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms and a tetravalent aromatic carbon group having 6 to 35 carbon atoms. Represents a hydrogen group or a tetravalent heterocyclic group having 2 to 35 carbon atoms,
The adjacent carbon atom of the aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—,
The terminal carbon atom of the aliphatic hydrocarbon group may be replaced with —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—,
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). )
　上記一般式（Ｉ－Ａ）において、ｍが５であるとき、Ｘ１は、下記一般式（４）のように表すこともできる。 In the above general formula (IA), when m is 5, X 1 can also be represented by the following general formula (4).
Figure JPOXMLDOC01-appb-C000010
（上記一般式（４）中、Ｙ１３は、単結合、５価の炭素原子数２～３５の脂肪族炭化水素基、５価の炭素原子数６～２０の芳香族炭化水素基又は５価の炭素原子数２～２０の複素環含有基を表し、
　該脂肪族炭化水素基の隣接する炭素原子は、－ＣＯＯ－、－Ｏ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＮＨ－又は－ＣＯＮＨ－で中断されている場合があり、
　該脂肪族炭化水素基の末端の炭素原子は、－ＣＯＯ－、－Ｏ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＮＨ－又は－ＣＯＮＨ－で置き換えられている場合があり、
　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る。）
Figure JPOXMLDOC01-appb-C000010
(In the general formula (4), Y 13 represents a single bond, a 5-valent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a 5-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a pentavalent group. Represents a heterocyclic group having 2 to 20 carbon atoms,
The adjacent carbon atom of the aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—,
The terminal carbon atom of the aliphatic hydrocarbon group may be replaced with —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—,
Z 1 to Z 5 are each independently a group within the same range as the group represented by Z 1 to Z 3 in the general formula (2). )
　上記一般式（Ｉ－Ａ）において、ｍが６であるとき、Ｘ１は、下記一般式（５）のように表すこともできる。 In the above general formula (IA), when m is 6, X 1 can also be represented by the following general formula (5).
Figure JPOXMLDOC01-appb-C000011
（上記一般式（５）中、Ｙ１４は、単結合、６価の炭素原子数２～３５の脂肪族炭化水素基、６価の炭素原子数６～３５の芳香族炭化水素基又は６価の炭素原子数２～３５の複素環含有基を表し、
　該脂肪族炭化水素基の隣接する炭素原子は、－ＣＯＯ－、－Ｏ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＮＨ－又は－ＣＯＮＨ－で中断されている場合があり、
　該脂肪族炭化水素基の末端の炭素原子は、－ＣＯＯ－、－Ｏ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＮＨ－又は－ＣＯＮＨ－で置き換えられている場合があり、
　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る。）
Figure JPOXMLDOC01-appb-C000011
(In the above general formula (5), Y 14 is a single bond, a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, a hexavalent aromatic hydrocarbon group having 6 to 35 carbon atoms, or a hexavalent group. Represents a heterocyclic group having 2 to 35 carbon atoms,
The adjacent carbon atom of the aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—,
The terminal carbon atom of the aliphatic hydrocarbon group may be replaced with —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—,
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). )
　上記一般式（１）におけるＲ６５、Ｒ６６及びＲ６７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ｍ価の有機基として例示した１価の炭素原子数１～１２０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ｍ価の有機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、これらの基又は上記一般式（Ｉ－Ａ）におけるＸ１で表されるｍ価の有機基として例示した２価の脂肪族炭化水素基がＺ１及びＺ２で置換された２価の基が、Ｙ１０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挙げられる。
　Ｒ６５、Ｒ６６及びＲ６７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ｍ価の有機基として例示した１価の炭素原子数６～３５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ｍ価の有機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等が挙げられ、これらの基又は上記一般式（Ｉ－Ａ）におけるＸ１で表されるｍ価の有機基として例示した２価の炭素原子数６～３５の芳香環含有炭化水素基がＺ１及びＺ２で置換された２価の基が、Ｙ１０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 65 , R 66 and R 67 includes the general formula (I- A monovalent aliphatic hydrocarbon group having 1 to 120 carbon atoms exemplified as the m-valent organic group represented by X 1 in A) and these groups are represented by X 1 in the general formula (IA). And those satisfying a predetermined number of carbon atoms among the groups substituted by those exemplified as the substituent of the group substituted by those exemplified as the substituent of the group representing the m-valent organic group, Or a divalent group obtained by substituting the divalent aliphatic hydrocarbon group exemplified as the m-valent organic group represented by X 1 in the general formula (IA) with Z 1 and Z 2 , divalent aliphatic hydrocarbon group having a carbon number of 1 to 35 represented by Y 10 It is mentioned.
The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms which may have a substituent represented by R 65 , R 66 and R 67 is X 1 in the above general formula (IA). The monovalent aromatic group-containing hydrocarbon group having 6 to 35 carbon atoms exemplified as the m-valent organic group and the m-valent group represented by X 1 in the general formula (IA). Examples include groups substituted by those exemplified as the substituent of the group representing the organic group, and these groups or 2 exemplified as the m-valent organic group represented by X 1 in the general formula (IA). A divalent group in which a valent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms is substituted with Z 1 and Z 2 contains a divalent aromatic ring having 6 to 35 carbon atoms represented by Y 10 It is mentioned as a hydrocarbon group.
　Ｒ６５、Ｒ６６及びＲ６７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ｍ価の有機基として例示した１価の炭素原子数２～３５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ｍ価の有機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等が挙げられ、これらの基又は上記一般式（Ｉ－Ａ）におけるＸ１で表されるｍ価の有機基として例示した２価の炭素原子数２～３５の芳香環含有炭化水素基がＺ１及びＺ２で置換された２価の基が、Ｙ１０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挙げられる。 The heterocyclic group containing 2 to 35 carbon atoms which may have a substituent represented by R 65 , R 66 and R 67 is represented by X 1 in the above general formula (IA). The monovalent heterocyclic group having 2 to 35 carbon atoms exemplified as the m-valent organic group and these groups represent the m-valent organic group represented by X 1 in the general formula (IA). Groups substituted by those exemplified as the substituents of the groups, and the like, and these groups or the divalent carbon atoms exemplified as the m-valent organic group represented by X 1 in the general formula (IA). Examples of the divalent group in which the aromatic ring-containing hydrocarbon group having 2 to 35 is substituted with Z 1 and Z 2 include the divalent heterocyclic group having 2 to 35 carbon atoms represented by Y 10. .
　上記（１－１）で表される置換基において、Ｒ７１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る。
　上記（１－１）で表される置換基において、Ｒ７２で表される炭素原子数１～１０のアルキル基としては、Ｒ６１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る。
　上記（１－１）で表される置換基において、Ｒ７２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る。
　上記（１－１）で表される置換基において、上記フェニル基、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ｍ価の有機基を表す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 71 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. .
In the substituent represented by (1-1) above, the alkyl group having 1 to 10 carbon atoms represented by R 72 is exemplified as the alkyl group having 1 to 40 carbon atoms represented by R 61 . Among the groups, groups satisfying a predetermined number of carbon atoms can be mentioned.
In the substituent represented by (1-1) above, examples of the alkoxy group having 1 to 10 carbon atoms represented by R 72 include methyloxy, ethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, Tributyloxy, isobutyloxy, amyloxy, isoamyloxy, tertiary amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tertiary heptyloxy, n-octyloxy, isooctyloxy, tertiary octyloxy, 2-ethylhexyl Examples include oxy, nonyloxy, decyloxy and the like.
In the substituent represented by (1-1) above, the substituent of the phenyl group, alkyl group, alkoxy group and alkenyl group is an m-valent organic compound represented by X 1 in the general formula (IA). The same as those exemplified as the substituent of the group representing the group.
　上記（１－３）で表される基において、Ｒ７３及びＲ７４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、Ｒ６１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る。
　上記（１－３）で表される基において、Ｒ７３及びＲ７４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、Ｒ６１及びＲ６２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 73 and R 74 is represented by R 61. Of the groups exemplified as the alkyl group having 1 to 40 carbon atoms, groups satisfying a predetermined number of carbon atoms are exemplified.
In the group represented by (1-3) above, the aryl group having 6 to 20 carbon atoms, which may have a substituent represented by R 73 and R 74 , includes R 61 and R 62 Examples thereof include the groups exemplified as the aryl group having 6 to 20 carbon atoms.
　上記（１－３）で表される基において、Ｒ７３及びＲ７４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る。 In the group represented by (1-3) above, the aryloxy group having 6 to 20 carbon atoms which may have a substituent represented by R 73 and R 74 includes 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, 3.5-dimethylphenyloxy, 2,4-di-tert-butylphenyloxy, 2,5-di-tert-butylphenyloxy, 2,6-di-tert-butylphenyloxy, 2. Groups such as 4-di-tert-pentylphenyloxy, 2,5-tert-amylphenyloxy, 4-cyclohexylphenyloxy, 2,4,5-trimethylphenyloxy, ferrocenyloxy, etc. .
　上記（１－３）で表される基において、Ｒ７３及びＲ７４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る。
　上記（１－３）で表される基において、Ｒ７３及びＲ７４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る。
　上記（１－３）で表される基において、Ｒ７３及びＲ７４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、Ｒ６１及びＲ６２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る。
　上記（１－３）で表される基において、Ｒ７３及びＲ７４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、Ｒ６１及びＲ６２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 arylthio group having 6 to 20 carbon atoms which may have a substituent represented by R 73 and R 74 has the above substituent. In some cases, a group in which the oxygen atom of the aryloxy group having 6 to 20 carbon atoms is substituted with a sulfur atom is used.
In the group represented by (1-3) above, the arylalkenyl group having 6 to 20 carbon atoms, which may have a substituent represented by R 73 and R 74 , has the above substituent. The oxygen atom of the aryloxy group having 6 to 20 carbon atoms may be vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-octenyl, etc. And a group substituted with an alkenyl group.
In the group represented by (1-3) above, the arylalkyl group having 7 to 20 carbon atoms represented by R 73 and R 74 includes 7 to 20 carbon atoms represented by R 61 and R 62. And the groups exemplified as the arylalkyl group.
In the group represented by (1-3) above, the heterocyclic group containing 2 to 20 carbon atoms which may have a substituent represented by R 73 and R 74 includes R 61 and R And the groups exemplified as the heterocyclic-containing group having 2 to 20 carbon atoms represented by 62 .
　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ｍ価の有機基として例示した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ｍ価の有機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、Ｚ１、Ｚ２及びＺ３で置換された３価の基等が挙げられる。 The trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 11 in the general formula (2) is an m-valent organic compound represented by X 1 in the general formula (IA). Examples of monovalent to trivalent aliphatic hydrocarbon groups exemplified as the groups and substituents of the groups in which these groups represent the m-valent organic group represented by X 1 in the general formula (IA) Examples of the group substituted by 1 include those having a predetermined number of carbon atoms, such as trivalent groups substituted with Z 1 , Z 2 and Z 3 .
　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が、Ｚ１、Ｚ２及びＺ３で置換された３価の基等が挙げられる。 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] ] Groups such as octyl, spiro [4,4] nonanyl, spiro [4,5] decanyl, decalin, tricyclodecanyl, tetracyclododecanyl, cedrol, cyclododecanyl and the like are Z 1 , Z 2 and Z 3 Examples thereof include a substituted trivalent group.
　上記一般式（２）における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ｍ価の有機基として例示した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ｍ価の有機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等が、Ｚ１、Ｚ２及びＺ３で置換された３価の基等が挙げられる。 The trivalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 11 in the general formula (2) is an m-valent represented by X 1 in the general formula (IA). Examples of monovalent to trivalent aromatic ring-containing hydrocarbon groups exemplified as the organic group and substituents of the groups in which these groups represent the m-valent organic group represented by X 1 in the general formula (IA) And a trivalent group in which a group substituted by the above is substituted with Z 1 , Z 2 and Z 3 .
　上記一般式（２）における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ｍ価の有機基として例示した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ｍ価の有機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等が、Ｚ１、Ｚ２及びＺ３で置換された３価の基等が挙げられる。 Examples of the trivalent heterocyclic group having 2 to 35 carbon atoms represented by Y 11 in the general formula (2) include an m-valent organic group represented by X 1 in the general formula (IA). The monovalent to trivalent heterocyclic-containing groups exemplified as above and these groups substituted by those exemplified as the substituents of the group representing the m-valent organic group represented by X 1 in the general formula (IA) And a trivalent group substituted with Z 1 , Z 2 and Z 3 .
　また、上記一般式（２）におけるＲ６８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Ｒ６５及びＲ６６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。 In addition, the aliphatic hydrocarbon group having 1 to 35 carbon atoms which may have a substituent represented by R 68 in the general formula (2), and the carbon atom which may have a substituent. Examples of the aromatic hydrocarbon group having 6 to 35 and the heterocyclic group having 2 to 35 carbon atoms which may have a substituent include R 65 and R 66 in the general formula (1), respectively. Examples include the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, and heterocyclic ring-containing group exemplified in the description.
　上記一般式（３）における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ｍ価の有機基として例示した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ｍ価の有機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、Ｚ１、Ｚ２、Ｚ３及びＺ４で置換された４価の基等が挙げられる。
　上記一般式（３）におけるＹ１２で表される炭素原子数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ｍ価の有機基として例示した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ｍ価の有機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等がＺ１、Ｚ２、Ｚ３及びＺ４で置換された４価の基等が挙げられる。
　上記一般式（３）における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ｍ価の有機基として例示した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ｍ価の有機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等がＺ１、Ｚ２、Ｚ３及びＺ４で置換された４価の基等が挙げられる。 The tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms represented by Y 12 in the general formula (3) is an m-valent organic compound represented by X 1 in the general formula (IA). Examples of monovalent to trivalent aliphatic hydrocarbon groups exemplified as the groups and substituents of the groups in which these groups represent the m-valent organic group represented by X 1 in the general formula (IA) Examples of the group substituted by 1 include those having a predetermined number of carbon atoms, such as tetravalent groups substituted with Z 1 , Z 2 , Z 3 and Z 4 .
The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 12 in the general formula (3) is an m-valent organic group represented by X 1 in the general formula (IA). By the exemplified monovalent to trivalent aromatic ring-containing hydrocarbon groups and those exemplified as substituents for the group representing the m-valent organic group represented by X 1 in the general formula (IA). Examples thereof include a tetravalent group in which a substituted group or the like is substituted with Z 1 , Z 2 , Z 3, or Z 4 .
The tetravalent heterocyclic containing group having a carbon number of 2 to 35 represented by Y 12 in general formula (3), m-valent organic group represented by X 1 in the above formula (I-A) The monovalent to trivalent heterocyclic-containing groups exemplified as above and these groups substituted by those exemplified as the substituents of the group representing the m-valent organic group represented by X 1 in the general formula (IA) And tetravalent groups in which the group and the like are substituted with Z 1 , Z 2 , Z 3 and Z 4 .
　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ｍ価の有機基として例示した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ｍ価の有機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Ｚ１、Ｚ２、Ｚ３、Ｚ４及びＺ５で置換された５価の基等が挙げられる。
　上記一般式（４）における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ｍ価の有機基として例示した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価の有機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等がＺ１、Ｚ２、Ｚ３、Ｚ４及びＺ５で置換された５価の基等が挙げられる。
　上記一般式（４）における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ｍ価におけるＸで表されるｎ価の有機基として例示した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ｍ価の有機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等がＺ１、Ｚ２、Ｚ３、Ｚ４及びＺ５で置換された５価の基等が挙げられる。 The pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 13 in the general formula (4) is an m-valent organic compound represented by X 1 in the general formula (IA). Examples of monovalent to trivalent aliphatic hydrocarbon groups exemplified as the groups and substituents of the groups in which these groups represent the m-valent organic group represented by X 1 in the general formula (IA) Among the groups substituted by the above, there are pentavalent groups in which those satisfying the predetermined number of carbon atoms are substituted with Z 1 , Z 2 , Z 3 , Z 4 and Z 5 .
The pentavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 14 in the general formula (4) is an m-valent represented by X 1 in the general formula (IA). Examples of monovalent to trivalent aromatic ring-containing hydrocarbon groups exemplified as organic groups and substituents of groups in which these groups represent an n-valent organic group represented by X 1 in the above general formula (IA) And a pentavalent group in which a group substituted by the above-described one is substituted with Z 1 , Z 2 , Z 3 , Z 4 and Z 5 .
The pentavalent C2-C35 heterocycle-containing group represented by Y 14 in the general formula (4) is X in the m valence represented by X 1 in the general formula (IA). Of the monovalent to trivalent heterocyclic group exemplified as the represented n-valent organic group and the group in which these groups represent the m-valent organic group represented by X 1 in the general formula (IA). Examples thereof include pentavalent groups in which groups substituted by those exemplified as the substituent are substituted with Z 1 , Z 2 , Z 3 , Z 4 and Z 5 .
　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ｍ価の有機基として例示した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ｍ価の有機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Ｚ１、Ｚ２、Ｚ３、Ｚ４、Ｚ５及びＺ６で置換された６価の基等が挙げられる。
　上記一般式（５）における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ｍ価の有機基として例示した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ｍ価の有機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等がＺ１、Ｚ２、Ｚ３、Ｚ４、Ｚ５及びＺ６で置換された６価の基等が挙げられる。
　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ｍ価の有機基として例示した１価～３価の複素環含有基の置換基として例示したものにより置換された基等がＺ１、Ｚ２、Ｚ３、Ｚ４、Ｚ５及びＺ６で置換された６価の基等が挙げられる。 The hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms represented by Y 14 in the general formula (5) is an m-valent organic compound represented by X 1 in the general formula (IA). Examples of monovalent to trivalent aliphatic hydrocarbon groups exemplified as the groups and substituents of the groups in which these groups represent the m-valent organic group represented by X 1 in the general formula (IA) Examples of the group substituted by the above group include those having a predetermined number of carbon atoms and the like, and hexavalent groups substituted with Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 .
The hexavalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by Y 14 in the general formula (5) is an m-valent represented by X 1 in the general formula (IA). Examples of monovalent to trivalent aromatic ring-containing hydrocarbon groups exemplified as the organic group and substituents of the groups in which these groups represent the m-valent organic group represented by X 1 in the general formula (IA) And a hexavalent group in which a group substituted by the above-described one is substituted with Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 .
The hexavalent heterocyclic group having 2 to 35 carbon atoms represented by Y 14 in the general formula (5) is an m-valent organic group represented by X 1 in the general formula (IA). hexavalent to groups substituted by those exemplified as the substituents exemplified monovalent to trivalent heterocyclic containing groups is substituted with Z 1, Z 2, Z 3 , Z 4, Z 5 and Z 6 as And the like.
　上記一般式（Ｉ－Ａ）において、ｄとｋの合計は、環Ａ１の取り得る置換基の数より少ない。例えば、環Ａ１が六員環の芳香環であるとき、環Ａ１の取り得る置換基は６であり、ｄ＋ｋ≦５である。また、環Ａ１が五員環の複素環であるとき、環Ａ１の取り得る置換基は４であり、ｄ＋ｋ≦３である。 In the general formula (IA), the sum of d and k is less than the number of substituents that can be taken by the ring A 1 . For example, when the ring A 1 is a six-membered aromatic ring, the possible substituents of the ring A 1 are 6, and d + k ≦ 5. Further, when the ring A 1 is a 5-membered heterocyclic ring, the possible substituents of the ring A 1 are 4, and d + k ≦ 3.
　上記一般式（Ｉ－Ａ）で表される化合物としては、具体的には、例えば下記構造のものが挙げられる。 Specific examples of the compound represented by the general formula (IA) include those having the following structures.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　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）～（ＩＶ）で表されるものが、合成が容易で耐熱性が高くなるので好ましい。 Among the compounds represented by the general formula (IA), those represented by the following general formulas (II) to (IV) are preferable because they are easy to synthesize and have high heat resistance.
Figure JPOXMLDOC01-appb-C000013
（式中、環Ａ２は、六員環の脂環、芳香環又は複素環であり、Ｒ８１、Ｒ８２、Ｒ８３、Ｒ８４及びＲ８５は、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、炭素原子数２～２０の複素環含有基又は－Ｏ－Ｒ６２を表し、Ｒ８１、Ｒ８２、Ｒ８３、Ｒ８４及びＲ８５のうち少なくとも１つは水素原子でなく、Ｒ６２は、上記一般式（Ｉ）と同じである。）
Figure JPOXMLDOC01-appb-C000013
(In the formula, ring A 2 is a six-membered alicyclic ring, aromatic ring or heterocyclic ring, and R 81 , R 82 , R 83 , R 84 and R 85 are a hydrogen atom, a halogen atom, a cyano group, or a hydroxyl group. Nitro group, carboxyl group, alkyl group having 1 to 40 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, carbon atom Represents a heterocyclic group containing 2 to 20 or —O—R 62 , wherein at least one of R 81 , R 82 , R 83 , R 84 and R 85 is not a hydrogen atom, and R 62 represents the above general formula Same as (I).)
Figure JPOXMLDOC01-appb-C000014
（式中、Ｘ２は、上記一般式（１）で表される基であり、Ｒ８６、Ｒ８７、Ｒ８８及びＲ８９は、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、Ｒ８６、Ｒ８７、Ｒ８８及びＲ８９のうち少なくとも１つは水素原子でなく、Ｒ６２は、上記一般式（Ｉ）と同じであり、環Ａ２は、上記一般式（ＩＩ）と同じである。）
Figure JPOXMLDOC01-appb-C000014
(In the formula, X 2 is a group represented by the above general formula (1), and R 86 , R 87 , R 88 and R 89 are 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 an alkyl group having 2 to 20 carbon atoms. Represents a heterocyclic ring-containing group, at least one of R 86 , R 87 , R 88 and R 89 is not a hydrogen atom, R 62 is the same as in the above general formula (I), and ring A 2 is (It is the same as general formula (II).)
Figure JPOXMLDOC01-appb-C000015
（式中、ｒ＝２～６であり、Ｘ３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）で表される基であり、ｒ＝６のとき上記一般式（５）で表される基であり、Ｒ９１、Ｒ９２、Ｒ９３及びＲ９４は、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、Ｒ９１、Ｒ９２、Ｒ９３及びＲ９４のうち少なくとも１つは水素原子でなく、Ｒ６２は、上記一般式（Ｉ）と同じであり、環Ａ２は、上記一般式（ＩＩ）と同じである。）
Figure JPOXMLDOC01-appb-C000015
(Wherein r = 2 to 6 and X 3 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 group represented by the general formula (4) when r = 5, and the general formula when r = 6. In the case represented by (5), R 91 , R 92 , R 93 and R 94 may have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group or a substituent. Represents 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-containing group having 2 to 20 carbon atoms, R 91 , R 92, instead of at least one hydrogen atom of R 93 and R 94, R 62 is the same as in the general formula (I) Ri, ring A 2 are the same as in the general formula (II).)
　上記一般式（ＩＩ）における環Ａ2で表される六員環の脂環、芳香環又は複素環としては、上記一般式（Ｉ）におけるＡ１の説明で例示したものが挙げられる。
　上記一般式（ＩＩ）におけるＲ81、Ｒ82、Ｒ83、Ｒ84及びＲ85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Ｒ61又はＲ62の説明で例示したものが挙げられる。
　上記一般式（ＩＩＩ）におけるＲ86、Ｒ87、Ｒ88及びＲ89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Ｒ61又はＲ62の説明で例示したものが挙げられる。
　上記一般式（ＩＶ）におけるＲ91、Ｒ92、Ｒ93及びＲ94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Ｒ61又はＲ62の説明で例示したものが挙げられる。 Examples of the six-membered alicyclic, aromatic or heterocyclic ring represented by the ring A 2 in the general formula (II) include those exemplified in the description of A 1 in the general formula (I).
The halogen atom represented by R 81 , R 82 , R 83 , R 84 and R 85 in the general formula (II), an alkyl group having 1 to 40 carbon atoms which may have a substituent, a carbon atom Examples of the aryl group having 6 to 20 carbon atoms, the arylalkyl group having 7 to 20 carbon atoms, and the heterocyclic ring-containing group having 2 to 20 carbon atoms are exemplified in the description of R 61 or R 62 in the general formula (I). Things.
In the general formula (III), the halogen atom represented by R 86 , R 87 , R 88 and R 89 , an alkyl group having 1 to 40 carbon atoms which may have a substituent, and 6 to 6 carbon atoms Examples of the 20 aryl group, the arylalkyl group having 7 to 20 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms include those exemplified in the description of R 61 or R 62 in the general formula (I). It is done.
The halogen atom represented by R 91 , R 92 , R 93 and R 94 in the general formula (IV), an alkyl group having 1 to 40 carbon atoms which may have a substituent, and 6 to 6 carbon atoms Examples of the 20 aryl group, the arylalkyl group having 7 to 20 carbon atoms, and the heterocycle-containing group having 2 to 20 carbon atoms include those exemplified in the description of R 61 or R 62 in the general formula (I). It is done.
　上記一般式（ＩＩ）で表される化合物の中では、
　環Ａ2が、ベンゼン、ナフタレンであるものが好ましく、
　Ｒ81、Ｒ82、Ｒ83、Ｒ84及びＲ85のうち、水素原子以外の基としては、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２～１０の複素環含有基が好ましく、特にＲ81～Ｒ85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２～１０の複素環含有基であるものが好ましく、
　Ｒ62は、－ＣＯ－Ｏ－を介して、下記の置換基を有する者が好ましい。
　・炭素原子数１～８のアルキル基（特に、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、１－メチルブチル、２－メチルブチル、３－メチルブチル、１－エチルプロピル、１，１－ジメチルプロピル、１，２－ジメチルプロピル、２，２－ジメチルプロピル）
　・炭素原子数７～１０のアリールアルキル基（特にベンジル基）
　・炭素原子数２～６のアルケニル基（特にプロペン－１－イル基） Among the compounds represented by the general formula (II),
Ring A 2 is preferably benzene or naphthalene,
Among R 81 , R 82 , R 83 , R 84 and R 85 , the groups other than hydrogen atoms include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 10 carbon atoms, and 7 to 7 carbon atoms. 12 arylalkyl groups and heterocycle-containing groups having 2 to 10 carbon atoms are preferred. In particular, any one of R 81 to R 85 is an alkyl group having 1 to 4 carbon atoms or a heterocycle having 2 to 10 carbon atoms. Those containing groups are preferred,
R 62 preferably has the following substituents via —CO—O—.
-Alkyl groups having 1 to 8 carbon atoms (particularly methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl) 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl)
・ Arylalkyl groups having 7 to 10 carbon atoms (especially benzyl groups)
.Alkenyl groups having 2 to 6 carbon atoms (particularly propen-1-yl groups)
　上記一般式（ＩＩＩ）で表される化合物の中では、
　環Ａ2が、ベンゼン、ナフタレンであるものが好ましく、
　Ｒ86、Ｒ87、Ｒ88及びＲ89のうち、水素原子以外の基としては、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２～１０の複素環含有基、特に炭素原子数１～８のアルキル基、炭素原子数２～１０の複素環含有基であるものが好ましく、
　Ｒ62は、－ＣＯ－Ｏ－を介して、下記の置換基を有する者が好ましい。
　・炭素原子数１～８のアルキル基（特に、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、１－メチルブチル、２－メチルブチル、３－メチルブチル、１－エチルプロピル、１，１－ジメチルプロピル、１，２－ジメチルプロピル、２，２－ジメチルプロピル）
　・炭素原子数７～１０のアリールアルキル基（特にベンジル基）
　・炭素原子数２～６のアルケニル基（特にプロペン－１－イル基）
　Ｘ11を表す上記一般式（１）において、Ｙ10が、硫黄原子、炭素原子数６～２５の芳香環含有炭化水素基、炭素原子数２～２１の複素環含有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る場合がある炭素原子数１～２０の脂肪族炭化水素基、６～１０の芳香族炭化水素基、特に置換基を有している場合がある炭素原子数１～８の脂肪族炭化水素基であるものが好ましい。 Among the compounds represented by the general formula (III),
Ring A 2 is preferably benzene or naphthalene,
Among R 86 , R 87 , R 88 and R 89 , groups other than hydrogen atoms include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aryls having 7 to 12 carbon atoms. Preferred are alkyl groups, heterocycle-containing groups having 2 to 10 carbon atoms, particularly alkyl groups having 1 to 8 carbon atoms, and heterocycle-containing groups having 2 to 10 carbon atoms.
R 62 preferably has the following substituents via —CO—O—.
-Alkyl groups having 1 to 8 carbon atoms (particularly methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl) 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl)
・ Arylalkyl groups having 7 to 10 carbon atoms (especially benzyl groups)
.Alkenyl groups having 2 to 6 carbon atoms (particularly propen-1-yl groups)
In the general formula (1) representing X 11 , Y 10 is preferably a sulfur atom, an aromatic ring-containing hydrocarbon group having 6 to 25 carbon atoms, or a heterocyclic ring-containing group having 2 to 21 carbon atoms,
Z 1 and Z 2 may be a direct bond, —CO—O—, —O—CO—, or an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, 6 to 10 aromatics An aromatic hydrocarbon group, particularly an aliphatic hydrocarbon group having 1 to 8 carbon atoms, which may have a substituent, is preferred.
　上記一般式（ＩＶ）で表される化合物の中では、
　Ｒ91、Ｒ92、Ｒ93及びＲ94のうち、水素原子以外の基としては、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２～１０の複素環含有基、特にＲ91～Ｒ94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２～１０の複素環含有基であるものが好ましい。
　Ｒ62は、－ＣＯ－Ｏ－を介して、下記の置換基を有する者が好ましい。
　・炭素原子数１～８のアルキル基（特に、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、１－メチルブチル、２－メチルブチル、３－メチルブチル、１－エチルプロピル、１，１－ジメチルプロピル、１，２－ジメチルプロピル、２，２－ジメチルプロピル）・炭素原子数７～１０のアリールアルキル基（特にベンジル基）・炭素原子数２～６のアルケニル基（特にプロペン－１－イル基） Among the compounds represented by the general formula (IV),
Of the groups R 91 , R 92 , R 93 and R 94 , groups other than hydrogen atoms include aryl groups having 6 to 10 carbon atoms, arylalkyl groups having 7 to 12 carbon atoms, and those having 2 to 10 carbon atoms. Heterocycle-containing groups, particularly those in which any one of R 91 to R 94 is an alkyl group having 1 to 4 carbon atoms or a heterocycle-containing group having 2 to 10 carbon atoms are preferred.
R 62 preferably has the following substituents via —CO—O—.
-Alkyl groups having 1 to 8 carbon atoms (particularly methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl) 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl). Arylalkyl group having 7 to 10 carbon atoms (particularly benzyl group). 2 to 6 carbon atoms Alkenyl group (especially propen-1-yl group)
　上記一般式（ＩＶ）で表される化合物においてｒ＝２であり、Ｘ3が上記一般式（１）となる場合、Ｙ10が、硫黄原子、２価の炭素原子数１～２０のアルキル基、２価の炭素原子数６～２５の芳香環含有炭化水素基、２価の炭素原子数２～２１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、特に２価の炭素原子数１～１５のアルキル基、２価の炭素原子数６～１５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る場合がある２価の炭素原子数１～２０の脂肪族炭化水素基、２価の炭素原子数６～１０の芳香族炭化水素基、特に置換基を有している場合がある２価の炭素原子数１～８の脂肪族炭化水素基であるものが好ましい。 In the compound represented by the general formula (IV), when r = 2 and X 3 is the general formula (1), Y 10 is a sulfur atom, a divalent alkyl group having 1 to 20 carbon atoms. Divalent aromatic ring-containing hydrocarbon group having 6 to 25 carbon atoms, divalent heterocyclic group containing 2 to 21 carbon atoms, 2,4,8,10-tetraoxaspiro [5,5] undecane In particular, a divalent alkyl group having 1 to 15 carbon atoms, a divalent aromatic ring-containing hydrocarbon group having 6 to 15 carbon atoms, 2,4,8,10-tetraoxaspiro [5,5] undecane Some are preferred,
Z 1 and Z 2 may have a direct bond, —CO—O—, —O—CO— or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. An aromatic hydrocarbon group having 6 to 10 carbon atoms, particularly a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent is preferable.
　上記一般式（ＩＶ）で表される化合物においてｒ＝３であり、Ｘ3が上記一般式（２）となる場合、Ｙ11が、３価の炭素原子数１～２０のアルキル基、３価の炭素原子数６～１０のアリール基、３価の炭素原子数７～１２のアリールアルキル基、３価の炭素原子数２～１０の複素環含有基、特に３価の炭素原子数１～８のアルキル基、３価の炭素原子数６～９のアリール基、３価の炭素原子数１～６の複素環含有基であるものが好ましく、
　Ｚ1、Ｚ2及びＺ3は、直接結合、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－又は置換基を有している場合がある２価の炭素原子数１～２０の脂肪族炭化水素基、２価の炭素原子数６～１０の芳香族炭化水素基、特に置換基を有している場合がある２価の炭素原子数１～８の脂肪族炭化水素基であるものが好ましい。 In the compound represented by the general formula (IV), when r = 3 and X 3 is the general formula (2), Y 11 is a trivalent alkyl group having 1 to 20 carbon atoms, trivalent An aryl group having 6 to 10 carbon atoms, a trivalent arylalkyl group having 7 to 12 carbon atoms, a trivalent heterocyclic group having 2 to 10 carbon atoms, particularly a trivalent carbon atom having 1 to 8 carbon atoms. An alkyl group, a trivalent aryl group having 6 to 9 carbon atoms, and a trivalent heterocyclic group having 1 to 6 carbon atoms,
Z 1 , Z 2 and Z 3 are each a direct bond, —CO—O—, —O—CO— or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. A divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, particularly a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent is preferable.
　上記一般式（ＩＶ）で表される化合物においてｒ＝４であり、Ｘ3が上記一般式（３）となる場合、Ｙ12は、４価の炭素原子数１～２０のアルキル基、４価の炭素原子数６～１０のアリール基、４価の炭素原子数７～１２のアリールアルキル基、４価の炭素原子数２～１０の複素環含有基、特に４価の炭素原子数１～８のアルキル基、４価の炭素原子数６～９のアリール基、４価の炭素原子数１～６の複素環含有基であるものが好ましく、
　Ｚ1～Ｚ4は、直接結合、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－又は置換基を有している場合がある２価の炭素原子数１～２０の脂肪族炭化水素基、２価の炭素原子数６～１０の芳香族炭化水素基、特に置換基を有している場合がある２価の炭素原子数１～８の脂肪族炭化水素基であるものが好ましい。 In the compound represented by the general formula (IV), when r = 4 and X 3 is the general formula (3), Y 12 represents a tetravalent alkyl group having 1 to 20 carbon atoms, a tetravalent group. An aryl group having 6 to 10 carbon atoms, a tetraalkyl aryl group having 7 to 12 carbon atoms, a tetravalent heterocyclic group having 2 to 10 carbon atoms, particularly a tetravalent carbon atom having 1 to 8 carbon atoms. An alkyl group, a tetravalent aryl group having 6 to 9 carbon atoms, and a tetravalent hetero ring-containing group having 1 to 6 carbon atoms,
Z 1 to Z 4 are a direct bond, —CO—O—, —O—CO— or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. And an aromatic hydrocarbon group having 6 to 10 carbon atoms, particularly a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, is preferable.
　上記一般式（ＩＶ）で表される化合物においてｒ＝５であり、Ｘ3が上記一般式（４）となる場合、Ｙ13は、５価の炭素原子数１～２０のアルキル基、５価の炭素原子数６～１０のアリール基、５価の炭素原子数７～１２のアリールアルキル基、５価の炭素原子数２～１０の複素環含有基、特に５価の炭素原子数１～８のアルキル基、５価の炭素原子数６～９のアリール基、５価の炭素原子数１～６の複素環含有基であるものが好ましく、
　Ｚ1～Ｚ5は、直接結合、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－又は置換基を有している場合がある２価の炭素原子数１～２０の脂肪族炭化水素基、２価の炭素原子数６～１０の芳香族炭化水素基、特に置換基を有している場合がある２価の炭素原子数１～８の脂肪族炭化水素基であるものが好ましい。 In the compound represented by the general formula (IV), when r = 5 and X 3 is the general formula (4), Y 13 is a pentavalent alkyl group having 1 to 20 carbon atoms, pentavalent An aryl group having 6 to 10 carbon atoms, an arylalkyl group having 5 to 7 carbon atoms, a 5-valent heterocyclic group having 2 to 10 carbon atoms, particularly a pentavalent carbon atom having 1 to 8 carbon atoms. An alkyl group, a pentavalent aryl group having 6 to 9 carbon atoms, and a pentavalent hetero ring-containing group having 1 to 6 carbon atoms,
Z 1 to Z 5 are each a direct bond, —CO—O—, —O—CO— or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. And an aromatic hydrocarbon group having 6 to 10 carbon atoms, particularly a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, is preferable.
　上記一般式（ＩＶ）で表される化合物においてｒ＝６であり、Ｘ3が上記一般式（５）となる場合、Ｙ14は、６価の炭素原子数１～２０のアルキル基、６価の炭素原子数６～１０のアリール基、６価の炭素原子数７～１２のアリールアルキル基、６価の炭素原子数２～１０の複素環含有基、特に６価の炭素原子数１～８のアルキル基、６価の炭素原子数６～９のアリール基、６価の炭素原子数１～６の複素環含有基であるものが好ましく、
　Ｚ1～Ｚ6は、直接結合、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－又は置換基を有している場合がある２価の炭素原子数１～２０の脂肪族炭化水素基、２価の炭素原子数６～１０の芳香族炭化水素基、特に置換基を有している場合がある２価の炭素原子数１～８の脂肪族炭化水素基であるものが好ましい。 In the compound represented by the general formula (IV), when r = 6 and X 3 is the general formula (5), Y 14 is a hexavalent alkyl group having 1 to 20 carbon atoms, hexavalent Aryl groups having 6 to 10 carbon atoms, arylalkyl groups having 6 to 7 carbon atoms, heterocyclic groups having 6 to 6 carbon atoms, particularly hexavalent carbon atoms having 1 to 8 carbon atoms. Are preferably an alkyl group of the above, an aryl group having 6 to 9 carbon atoms and a heterocyclic group having 6 to 6 carbon atoms,
Z 1 to Z 6 are a direct bond, —CO—O—, —O—CO— or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. And an aromatic hydrocarbon group having 6 to 10 carbon atoms, particularly a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, is preferable.
　上述した、炭素原子数２～１０の複素環含有基としては、上述した炭素原子数２～３５の複素環含有基と例示した化合物において、炭素原子数が１～１０の複素環含有基が挙げられる。 Examples of the heterocyclic group having 2 to 10 carbon atoms described above include the heterocyclic group having 1 to 10 carbon atoms in the compounds exemplified as the heterocyclic group having 2 to 35 carbon atoms described above. It is done.
　本発明の感光性組成物において、上記潜在性添加剤（Ａ）の含有量は、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 latent additive (A) is preferably 0.001 to 20% by mass, and more preferably 0.005 to 5% by mass.
＜重合体（Ｂ）＞
　本発明の感光性組成物に用いられる重合体（Ｂ）は、エチレン性不飽和結合及び親水性基を一分子内に有し、且つ二重結合当量が２００～１０００である重合体である限り、特に限定されず従来用いられているものを用いることができる。
　重合体（Ｂ）が有する親水性基としては、水酸基、チオール基、カルボキシル基、スルホ基、アミノ基、アミド基又はその塩等が挙げられ、水酸基及びカルボキシル基が、重合体（Ｂ）のアルカリへの溶解性が高くなるため好ましい。
　重合体（Ｂ）における親水性基の好ましい官能基当量（親水性基１当量を含む重合体の質量）は、５０～１００００である。
　重合体（Ｂ）の好ましい質量平均分子量は、３０００～５００００である。 <Polymer (B)>
As long as the polymer (B) used in the photosensitive composition of the present invention is a polymer having an ethylenically unsaturated bond and a hydrophilic group in one molecule and having a double bond equivalent of 200 to 1,000. However, it is not particularly limited, and those conventionally used can be used.
Examples of the hydrophilic group possessed by the polymer (B) include a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, an amino group, an amide group, or a salt thereof. This is preferable because of its high solubility in water.
The preferred functional group equivalent of the hydrophilic group in the polymer (B) (the mass of the polymer containing 1 equivalent of hydrophilic group) is 50 to 10,000.
A preferred mass average molecular weight of the polymer (B) is 3000 to 50000.
　上記重合体（Ｂ）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・マレートあるいは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（Ｖ）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、下記一般式（Ｖ）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、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。 Examples of the polymer (B) include (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, and cinnamic acid. Sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. Mono (meth) acrylate, hydroxyethyl (meth) acrylate / malate, hydroxypropyl (meth) acrylate / malate, dicyclopentadiene / malate or one carboxyl group and two or more of polymers having a carboxyl group and a hydroxyl group at the terminal Multifunctional (meth) acrylic having (meth) acryloyl group Unsaturated polybasic acids such as carbonates; novolac epoxy compounds such as phenol and / or cresol novolac epoxy resins, novolak epoxy resins having a biphenyl skeleton and a naphthalene skeleton, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds A polyphenylmethane type epoxy resin having a polyfunctional epoxy group, a resin obtained by allowing an unsaturated monobasic acid to act on an epoxy group of an epoxy resin such as an epoxy compound represented by the following general formula (V), and the following general formula (V ) Resins obtained by allowing an unsaturated monobasic acid to act on an epoxy group of an epoxy resin such as an epoxy compound and a polybasic acid anhydride, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. Hydroxyl-containing polyfunctional amine Rate and succinic anhydride, 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-C000016
（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、
　ｎは０～１０の整数である。）
Figure JPOXMLDOC01-appb-C000016
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;
n is an integer of 0 to 10. )
　上記重合体（Ｂ）の中でも、下記一般式（ＶＩ－１）で表されるユニット、下記一般式（ＶＩ－２）で表されるユニット、下記一般式（ＶＩ－３）で表されるユニット及び下記一般式（ＶＩ－４）で表されるユニットから選択される何れか一つ以上を有するものが、現像性や耐熱性が高いので好ましい。 Among the polymers (B), a unit represented by the following general formula (VI-1), a unit represented by the following general formula (VI-2), and a unit represented by the following general formula (VI-3) And those having at least one selected from units represented by the following general formula (VI-4) are preferred because of their high developability and heat resistance.
Figure JPOXMLDOC01-appb-C000017
(式中、Ｙ１は水素原子又はメチル基を表し、Ｘ４は、２価の結合基であり、Ｒ１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、アリール基及びアリールアルキル基の水素原子は、ハロゲン原子、水酸基、ニトロ基又はエポキシ基で置換されている場合もあり、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、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－又は－ＮＨ－、あるいはこれらの組み合わせの結合基で置き換えられている場合もあり、Ｒ２、Ｒ３及びＲ４は、それぞれ独立に、水素原子又はメチル基である。）
Figure JPOXMLDOC01-appb-C000017
(Wherein Y 1 represents a hydrogen atom or a methyl group, X 4 represents a divalent linking group, R 1 represents 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 the hydrogen atom of the alkyl group, aryl group and arylalkyl group may be substituted with a halogen atom, a hydroxyl group, a nitro group or an epoxy group, And methylene groups in arylalkyl groups may be replaced by linking groups of —O—, —S—, —CO—, —COO—, —OCO— or —NH—, or combinations thereof. , R 2 , R 3 and R 4 are each independently a hydrogen atom or a methyl group.)
　上記一般式（ＶＩ－２）におけるＸ４で表される２価の結合基としては、特に限定されないが、上記一般式（１）で表される構造を好ましく挙げることができる。 The divalent linking group represented by X 4 in the general formula (VI-2) is not particularly limited, but preferred examples include the structure represented by the general formula (1).
　上記一般式（ＶＩ－１）～（ＶＩ－４）で表されるユニットの構成比は、（ＶＩ－１）：（ＶＩ－２）：（ＶＩ－３）：（ＶＩ－４）＝０～０．６５：０．１～１：０．００１～２：０～１であり、ランダム共重合、ブロック共重合、グラフト共重合など、何れの配列を取っていてもよい。 The composition ratio of the units represented by the general formulas (VI-1) to (VI-4) is (VI-1) :( VI-2) :( VI-3) :( VI-4) = 0 to It is 0.65: 0.1 to 1: 0.001 to 2: 0 to 1, and may have any arrangement such as random copolymerization, block copolymerization, and graft copolymerization.
　上記一般式（ＶＩ－１）、（ＶＩ－２）、（ＶＩ－３）及び（ＶＩ－４）で表されるユニットから選択される何れか一つ以上を有する重合体（Ｂ）の中では、以下のものが好ましい。
　Ｒ１は、炭素原子数１～８のアルキル基及び炭素原子数７～３０のアリールアルキル基が好ましく、炭素原子数１～４のアルキル基がより好ましい。
　Ｘ４は、２価の結合基が、下記一般式（１）で表される構造の場合、Ｙ１０は、炭素原子数１～１５のアルキレン基が好ましく、シクロアルキレン基を有する炭素原子数７～１５のアルキレン基あるいはカルボキシル基を有する置換基を有するものがより好ましい。これらのアルキレン基中の水素原子は、ハロゲン原子、水酸基又はニトロ原子で置換されている場合もあり、また、アルキレン基中の鎖状アルキレン部分におけるメチレン基は－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－又は－ＮＨ－基で置き換えられている場合もある。
　Ｚ１及びＺ２は、直接結合であるのが好ましい。 In the polymer (B) having any one or more selected from the units represented by the general formulas (VI-1), (VI-2), (VI-3) and (VI-4) The following are preferred.
R 1 is preferably an alkyl group having 1 to 8 carbon atoms and an arylalkyl group having 7 to 30 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
X 4 is a structure in which a divalent linking group is represented by the following general formula (1), Y 10 is preferably an alkylene group having 1 to 15 carbon atoms, and has 7 carbon atoms having a cycloalkylene group. Those having a substituent having ˜15 alkylene groups or carboxyl groups are more preferred. The hydrogen atom in these alkylene groups may be substituted with a halogen atom, a hydroxyl group or a nitro atom, and the methylene group in the chain alkylene portion in the alkylene group is —O—, —S—, —CO. It may be replaced by a —, —COO—, —OCO— or —NH— group.
Z 1 and Z 2 are preferably direct bonds.
　上記重合体（Ｂ）は、酸価が好ましくは１０～２００ｍｇ／ＫＯＨ、更に好ましくは３０～１５０ｍｇ／ＫＯＨである。酸価が１０ｍｇ／ＫＯＨ未満であると、アルカリ現像性が十分に得られない場合があり、２００ｍｇ／ＫＯＨより大きいと、重合体（Ｂ）の製造が困難である恐れがある。
　ここで、酸価とは、ＪＩＳ　Ｋ ００５０ 及び ＪＩＳ Ｋ　０２１１によるものである。 The polymer (B) has an acid value of preferably 10 to 200 mg / KOH, more preferably 30 to 150 mg / KOH. If the acid value is less than 10 mg / KOH, sufficient alkali developability may not be obtained, and if it is greater than 200 mg / KOH, the production of the polymer (B) may be difficult.
Here, the acid value is based on JIS K 0050 and JIS K 0211.
　上記重合体（Ｂ）は、二重結合当量が２００～１０００であることを必須とし、好ましくは、３００～５００である。上記重合体（Ｂ）における二重結合当量が２００より小さいと、製造が困難であり、１０００より大きいと、耐久性が十分に得られない。
　二重結合当量は、重合体（Ｂ）における二重結合１個当りの重量平均分子量のことであり、下記の式により算出することができる。二重結合当量＝（重合体（Ｂ）の総質量）／｛（重合体（Ｂ）のモル数）×（重合体（Ｂ）中のエチレン性不飽和基の数）｝ The polymer (B) must have a double bond equivalent of 200 to 1000, preferably 300 to 500. If the double bond equivalent in the polymer (B) is less than 200, production is difficult, and if it is greater than 1000, sufficient durability cannot be obtained.
The double bond equivalent is a weight average molecular weight per double bond in the polymer (B), and can be calculated by the following formula. Double bond equivalent = (total mass of polymer (B)) / {(number of moles of polymer (B)) × (number of ethylenically unsaturated groups in polymer (B))}
　本発明の感光性組成物において、上記重合体（Ｂ）の含有量は、本発明の感光性組成物中、１～２０質量％、特に５～１５質量％が好ましい。上記重合体（Ｂ）の含有量が１質量％より小さいと、解像度及び耐久性が十分に得られない場合があり、２０質量％より大きいとアルカリ現像性及び硬化性が十分に得られない場合がある。 In the photosensitive composition of the present invention, the content of the polymer (B) is preferably 1 to 20% by mass, particularly preferably 5 to 15% by mass in the photosensitive composition of the present invention. When the content of the polymer (B) is less than 1% by mass, resolution and durability may not be sufficiently obtained. When the content is more than 20% by mass, alkali developability and curability may not be sufficiently obtained. There is.
＜アクリルモノマー（Ｃ）＞
　本発明の感光性組成物に用いられるアクリルモノマー（Ｃ）としては、特に制限されず公知のものを用いることができるが、例えば、アクリル酸－２－ヒドロキシエチル、アクリル酸－２－ヒドロキシプロピル、アクリル酸イソブチル、アクリル酸ｎ－オクチル、アクリル酸イソオクチル、アクリル酸イソノニル、アクリル酸ステアリル、アクリル酸メトキシエチル、アクリル酸ジメチルアミノエチル、アクリル酸亜鉛、１，６－ヘキサンジオールジアクリレート、トリメチロールプロパントリアクリレート、メタクリル酸－２－ヒドロキシエチル、メタクリル酸－２－ヒドロキシプロピル、メタクリル酸ブチル、メタクリル酸ターシャリーブチル、メタクリル酸シクロヘキシル、トリメチロールプロパントリメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールトリアクリレート、ビスフェノールＡジグリシジルエーテル（メタ）アクリレート、ビスフェノールＦジグリシジルエーテル（メタ）アクリレート、ビスフェノールＺジグリシジルエーテル（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート等が挙げられる。
　上記の中でも、不飽和結合を複数有するモノマーが、耐熱性を向上させることができるため好ましい。　 <Acrylic monomer (C)>
The acrylic monomer (C) used in the photosensitive composition of the present invention is not particularly limited and known ones can be used. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, Isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, methoxyethyl acrylate, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane tri Acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaeri Ritolol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, bisphenol A diglycidyl ether (meth) acrylate, bisphenol F diglycidyl ether (meth) acrylate, bisphenol Z diglycidyl ether (meth) acrylate And tripropylene glycol di (meth) acrylate.
Among these, a monomer having a plurality of unsaturated bonds is preferable because it can improve heat resistance.
　本発明の感光性組成物において、上記アクリルモノマー（Ｃ）の含有量は、本発明の感光性組成物中、１～２０質量％、特に５～１５質量％が好ましい。上記アクリルモノマー（Ｃ）の含有量が１質量％より小さいと、硬化性及びアルカリ現像性が十分に得られない場合があり、２０質量％より大きいと解像度及び耐久性が十分に得られない場合がある。 In the photosensitive composition of the present invention, the content of the acrylic monomer (C) is preferably 1 to 20% by mass, particularly preferably 5 to 15% by mass in the photosensitive composition of the present invention. When the content of the acrylic monomer (C) is less than 1% by mass, sufficient curability and alkali developability may not be obtained. When the content is more than 20% by mass, sufficient resolution and durability may not be obtained. There is.
＜光ラジカル重合開始剤（Ｄ）＞
　本発明の感光性組成物に用いられる光ラジカル重合開始剤（Ｄ）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。 <Photoradical polymerization initiator (D)>
The radical photopolymerization initiator (D) used in the photosensitive composition of the present invention may be any compound that can initiate radical polymerization upon receiving light irradiation, such as an acetophenone compound or a benzyl compound. Preferred examples include compounds, ketone compounds such as benzophenone compounds and thioxanthone 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（ＶＩＩ）又は（ＶＩＩＩ）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 (VII) or (VIII) is particularly preferable from the viewpoint of sensitivity and heat resistance.
Figure JPOXMLDOC01-appb-C000018
（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があり、
　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、
　Ｘ５は、酸素原子、硫黄原子、セレン原子、ＣＲ７５Ｒ７６、ＣＯ、ＮＲ７７又はＰＲ７８を表し、
　Ｘ６は、単結合又はＣＯを表し、
　Ｒ５１、Ｒ５２、Ｒ５５、Ｒ５６、Ｒ５７、Ｒ５８、Ｒ５９、Ｒ６０、Ｒ６５、Ｒ６６、Ｒ６７及びＲ６８中の炭素原子数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換されている場合があり、－Ｏ－で置き換えられている場合があり、
　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があり、
　ａは、０～４の整数を表し、
　ｂは、０～５の整数を表す。）
Figure JPOXMLDOC01-appb-C000018
(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 be bonded to 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 5 represents an oxygen atom, a sulfur atom, a selenium atom, CR 75 R 76 , CO, NR 77 or PR 78 ,
X 6 represents a single bond or CO,
R 51 , R 52 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 65 , R 66 , R 67 and R 68 alkyl group having 1 to 20 carbon atoms, carbon atoms Represents a 6-30 aryl group or an arylalkyl group having 7-30 carbon atoms, and the methylene group in the alkyl group or arylalkyl group contains a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic ring May be substituted with a group, may be substituted with —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-C000019
（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、ハロゲン原子、又はＣＯＯＲ121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-C000019
(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, halogen atom, or COOR 121 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 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R 108 represents 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 , a hydroxyl group, CN or a halogen atom,
w represents 0 or 1. )
　その他の光ラジカル重合開始剤（Ｄ）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）］チタニウムなどが挙げられる。 Other photoradical polymerization initiators (D) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (py-1-yl) )] Titanium and the like.
　これらの光ラジカル重合開始剤（Ｄ）は１種あるいは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 (D) 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（Ｄ）は、本発明の感光性組成物中、０．０１～１０質量％、特に０．１～１質量％が好ましい。上記光ラジカル重合開始剤の含有量が０．０１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、１０質量％より大きいと、感光性組成物中に光ラジカル重合開始剤が析出する場合がある。 The radical photopolymerization initiator (D) as described above is preferably 0.01 to 10% by mass, particularly preferably 0.1 to 1% by mass in the photosensitive composition of the present invention. When the content of the photo radical polymerization initiator is less than 0.01% by mass, curing by exposure may be insufficient. When the content is more than 10% by mass, the photo radical polymerization initiator is contained in the photosensitive composition. It may precipitate.
　上記感光性組成物に、更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。
　上記着色感光性組成物において、着色剤の添加量は、０．０１～５０質量％が好ましく、０．１～３０質量％がより好ましい。上記着色剤の添加量は０．０１質量％より小さいと、色味が不十分であり、５０質量％より大きいと、感光性組成物中に着色剤が析出する場合がある。 A coloring agent may be further added to the photosensitive composition to obtain a colored photosensitive composition. The cured product of the colored photosensitive composition is suitably used as a color filter.
In the colored photosensitive composition, the addition amount of the colorant is preferably 0.01 to 50% by mass, and more preferably 0.1 to 30% by mass. When the addition amount of the colorant is less than 0.01% by mass, the color is insufficient, and when it is greater than 50% by mass, the colorant may precipitate in the 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、ある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、ある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, or acetylene black, ketjen black or lamp black Carbon black prepared and coated with an epoxy resin, carbon black previously dispersed with a resin in a solvent and adsorbed with 20 to 200 mg / g of resin, the carbon black is acidic or Alkaline surface treatment, average particle size of 8 nm or more, DBP oil absorption of 90 ml / 100 g or less, CO in volatile matter at 950 ° C., total oxygen amount calculated from CO 2 is 9 mg per 100 m 2 of carbon black surface area Above, 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, Miroli Blue, Koba Ruto green, cobalt blue, manganese-based, ferrocyanide, phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridiane, emerald green, lead sulfate, yellow lead, zinc yellow, red rose (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に、更に架橋剤を加え、上記重合体の親水性基と反応させることにより、耐水性及び耐熱性を向上させることもできる。該架橋剤としては、ポリオキサゾリン化合物、カルボジイミド化合物、エポキシ化合物、ポリアミン類、ポリオール類、ジシアンジアミド誘導体、ヒドラジン化合物、ポリヒドラジド化合物（ジヒドラジド、トリヒドラジド）、アルデヒド類、メチロール化合物、活性化ビニル化合物、ポリイソシアネート系化合物、フェノール系化合物のアルキレンカーボネート化合物、多価金属塩、シランカップリング剤、有機チタン等が挙げられ、中でもポリオキサゾリン化合物及びカルボジイミド化合物が、１００～１２０℃の熱乾燥温度で反応するので好ましい。 The water resistance and heat resistance can be improved by adding a crosslinking agent to the photosensitive composition of the present invention and reacting with the hydrophilic group of the polymer. Examples of the crosslinking agent include polyoxazoline compounds, carbodiimide compounds, epoxy compounds, polyamines, polyols, dicyandiamide derivatives, hydrazine compounds, polyhydrazide compounds (dihydrazide, trihydrazide), aldehydes, methylol compounds, activated vinyl compounds, poly Isocyanate compounds, alkylene carbonate compounds of phenol compounds, polyvalent metal salts, silane coupling agents, organic titanium, etc. Among them, polyoxazoline compounds and carbodiimide compounds react at a heat drying temperature of 100 to 120 ° C. preferable.
　上記架橋剤としては、市販品を用いることもでき、例えば、エポクロスＷＳ－３００、ＷＳ－５００、ＷＳ－７００（日本触媒社製）；カルボジライトＶ－０２、Ｖ－０２－Ｌ２、ＳＶ－０２、Ｖ－０４、Ｖ－１０、ＳＷ－１２Ｇ、Ｅ－０２、Ｅ－０３Ａ、Ｅ－０５（日清紡社製）等が挙げられる。 Commercially available products may be used as the cross-linking agent. For example, Epocros WS-300, WS-500, WS-700 (manufactured by Nippon Shokubai Co., Ltd.); Carbodilite V-02, V-02-L2, SV-02, And V-04, V-10, SW-12G, E-02, E-03A, E-05 (manufactured by Nisshinbo).
　上記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、Ｎ－エチルピロリドン、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。 Further, a solvent can be added to the photosensitive composition and the colored photosensitive composition. 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, N-ethylpyrrolidone, dimethyl sulfoxide, water and the like, and these solvents can be used as one kind or a mixture of two or more kinds. 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.
　上記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 above-mentioned colored photosensitive composition 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.
　上記着色感光性組成物において、顔料及び／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。該分散剤としては色材、無機化合物を分散、安定化できるものであれば何でも良く、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 above colored photosensitive composition, when a pigment and / or an inorganic compound is used, a dispersant can be added. As the dispersant, any colorant or inorganic compound can be used as long as it can disperse and stabilize, and commercially available dispersants such as BYK series manufactured by BYK Chemie can be used, and polyester having a basic functional group, Polymer dispersant made of 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 / g Those are preferably used.
　また、上記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；増粘剤等の慣用の添加物を加えることができる。 In addition, the colored photosensitive composition includes, if necessary, thermal polymerization inhibitors such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; plasticizer; adhesion promoter; filler; Agents; leveling agents; surface conditioning agents; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants; UV absorbers; dispersion aids; aggregation inhibitors; catalysts; Conventional additives such as thickeners 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体とともに、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。 Further, by using another organic polymer in addition to the polymer having an ethylenically unsaturated bond having the acid value, the properties of the cured product of the colored photosensitive composition of the present invention can be improved. 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.
　上記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、メラミン等を併用することができる。 Further, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, melamine and the like can be used in combination with the colored photosensitive composition.
　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-C000020
Figure JPOXMLDOC01-appb-C000020
　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、互いに同一であるか、又は異なる場合がある。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があり、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がある。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。これらの中でも、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 as or different from each other. In addition, methylol groups that are not alkyletherified may be self-condensed within one molecule, and 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.
　上記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 the colored photosensitive composition are prepared by known means such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal. It can be applied on a supporting substrate such as paper or 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、上記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エネルギー線の光源としては、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。 As the active energy ray light source used for curing the photosensitive composition and the colored photosensitive composition, those that emit 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及び着色感光性組成物は、上記活性エネルギー線を照射することにより一時硬化させ、更に加熱することにより硬化させることができる。また、上記活性エネルギー線を照射することにより硬化させ、現像した後、加熱することによりパターンを形成することもできる。 The photosensitive composition and the colored photosensitive composition of the present invention can be temporarily cured by irradiating the active energy ray and further cured by heating. Alternatively, the pattern can be formed by heating after irradiating the active energy ray, developing, and heating.
　上記感光性組成物及び着色感光性組成物（又はその硬化物）は、光硬化性塗料あるいはワニス、光硬化性接着剤、プリント基板、あるいはカラーテレビ、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、接着剤、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ある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ある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 a cured product thereof) are photocurable paints or varnishes, photocurable adhesives, printed boards, color televisions, PC monitors, portable information terminals, digital cameras, etc. Color filters for liquid crystal display panels for color displays, 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 plates, adhesives, dentistry For manufacturing compositions, stereolithography resins, gel coats, photoresists for electronics, electroplating resists, etching resists, both liquid and dry films, solder resists, color filters for various display applications or plasmas Display panel, electroluminescent display device, and L Resist for forming structure in manufacturing process of D, composition for encapsulating electrical and electronic components, solder resist, magnetic recording material, micro mechanical component, waveguide, optical switch, plating mask, etching mask, color Test system, glass fiber cable coating, stencil for screen printing, material for producing 3D objects by stereolithography, holographic recording material, image recording material, fine electronic circuit, decoloring material, decolorization for image recording material Materials, bleaching materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, photoresist materials for UV and visible laser direct imaging systems, used for dielectric layer formation in sequential lamination of printed circuit boards Photoresist material or 3D mounting photoresist material Can be used for various applications such as protective film, there is no particular limitation on the application.
　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、透明基板に前述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。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、本発明の化合物を潜在性添加剤として含有する感光性組成物を用いてもよいし、何れか一以上の層に該感光性組成物を用いてもよい。また、更に、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, etc., and is applied through a mask having a predetermined pattern shape by sequentially applying each of the above-described layers to a transparent substrate. It can be used as a transparent laminate obtained by irradiating light, developing the exposed film with a developer, and heating the developed film. For example, a transparent base material in which transparent thin film layers and metal thin film layers made of a composite oxide of indium oxide and cerium oxide are alternately arranged can be used. A photosensitive composition containing the compound of the present invention as a latent additive may be used for each of the aforementioned layers, or the photosensitive composition may be used for any one or more layers. Furthermore, the transparent laminate is suitably used for a display device.
　上記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 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.
　上記表示デバイス用カラーフィルタは、（１）上記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、現像工程のな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 on a substrate, and (2) irradiating the coating film with active light through a mask having a predetermined pattern shape. It is preferably formed by a step, (3) a step of developing the film after exposure with a developer, and (4) a step of heating the film after development. The colored photosensitive composition of the present invention is also useful as an inkjet colored photosensitive composition having no development step.
As the mask, a multi-tone mask such as a halftone mask or a gray scale mask can be used.
　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.
[製造例１]重合体Ｂ－３の調製
　反応容器に、グリシジルメタクリレート１４２ｇ、スチレン８．３ｇ、ベンジルメタクリレート３．５ｇ、アゾビスイソブチロニトリル１．０ｇ及びＰＧＭＥＡ３８．５ｇを仕込み、９０℃で９時間攪拌した。その後、反応液を室温まで冷却し、ＰＧＭＥＡ１５０ｇ、アクリル酸７２ｇ、及びテトラ－ｎ－ブチルアンモニウムブロミド０．２４ｇを加えて、１２０℃で４時間攪拌した。更に、テトラヒドロ無水フタル酸９９．６ｇを加え、１００℃で４時間、６０℃で６時間、撹拌した後、ＰＧＭＥＡ１３６．５ｇを加えて、ＰＧＭＥＡ溶液として目的物の重合体Ｂ－３を得た（Ｍｗ＝２２０００、Ｍｎ＝６０００、酸価（固形分）１０１ｍｇＫＯＨ／ｇ）。 [Production Example 1] Preparation of polymer B-3 A reaction vessel was charged with 142 g of glycidyl methacrylate, 8.3 g of styrene, 3.5 g of benzyl methacrylate, 1.0 g of azobisisobutyronitrile and 38.5 g of PGMEA at 90 ° C. Stir for 9 hours. Thereafter, the reaction solution was cooled to room temperature, 150 g of PGMEA, 72 g of acrylic acid, and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. Further, 99.6 g of tetrahydrophthalic anhydride was added and stirred at 100 ° C. for 4 hours and at 60 ° C. for 6 hours, and then 136.5 g of PGMEA was added to obtain a target polymer B-3 as a PGMEA solution ( Mw = 22000, Mn = 6000, acid value (solid content) 101 mgKOH / g).
　[製造例２]重合体Ｂ－４の調製
　反応容器に、１，１－ビス〔４－（２，３－エポキシプロピルオキシ）フェニル〕インダン１８４ｇ、アクリル酸５８ｇ、２，６－ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール０．２６ｇ、テトラ－ｎ－ブチルアンモニウムブロミド０．１１ｇ及びＰＧＭＥＡ１０５ｇを仕込み、１２０℃で１６時間撹拌した。その後、反応液を室温まで冷却し、ＰＧＭＥＡ１６０ｇ、ビフタル酸無水物５９ｇ及びテトラ－ｎ－ブチルアンモニウムブロミド０．２４ｇを加えて、１２０℃で４時間撹拌した。更に、テトラヒドロ無水フタル酸２０ｇを加え、１２０℃で４時間、１００℃で３時間、８０℃で４時間、６０℃で６時間、４０℃で１１時間撹拌した後、ＰＧＭＥＡ１２８ｇを加えて、ＰＧＭＥＡ溶液として重合体Ｂ－４を得た（Ｍｗ＝５０００、Ｍｎ＝２１００、酸価（固形分）９２．７ｍｇＫＯＨ／ｇ）。 [Production Example 2] Preparation of polymer B-4 In a reaction vessel, 184 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 58 g of acrylic acid, 2,6-di-tert- 0.26 g of butyl-p-cresol, 0.11 g of tetra-n-butylammonium bromide and 105 g of PGMEA were charged and stirred at 120 ° C. for 16 hours. Thereafter, the reaction solution was cooled to room temperature, 160 g of PGMEA, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and after stirring at 120 ° C. for 4 hours, at 100 ° C. for 3 hours, at 80 ° C. for 4 hours, at 60 ° C. for 6 hours, and at 40 ° C. for 11 hours, PGMEA 128 g was added to obtain a PGMEA solution As a result, a polymer B-4 was obtained (Mw = 5000, Mn = 2100, acid value (solid content) 92.7 mgKOH / g).
　［実施例１～１１及び比較例１～２］感光性組成物Ｎｏ．１～Ｎｏ．１１及び比較感光性組成物Ｎｏ．１～Ｎｏ．２の調製
　[表１]及び[表２]の配合に従い、感光性組成物Ｎｏ．１～Ｎｏ．１１及び比較感光性組成物Ｎｏ．１～Ｎｏ．２を調製した。尚、[表１]及び[表２]中の数値は質量部である。 [Examples 1 to 11 and Comparative Examples 1 and 2] Photosensitive composition No. 1-No. 11 and comparative photosensitive composition no. 1-No. Preparation of photosensitive composition No. 2 in accordance with the formulation of [Table 1] and [Table 2]. 1-No. 11 and comparative photosensitive composition no. 1-No. 2 was prepared. The numerical values in [Table 1] and [Table 2] are parts by mass.
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
　[表１]及び[表２]中のＡ－１～Ａ－４は下記の潜在性添加剤を表す。 A-1 to A-4 in [Table 1] and [Table 2] represent the following latent additives.
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
　[表１]及び[表２]中の符号Ｂ－１～Ｂ－４、Ｂ’－１、Ｃ－１～Ｃ－２、Ｄ－１～Ｄ－３、Ｅ－１及びＦ－１はそれぞれ下記の化合物を表す。Ｂ－１　　ＳＰＣ－１０００（昭和電工社製アクリル樹脂；重量平均分子量３１９８０，二重結合当量９００）Ｂ－２　　ＳＰＣ－３０００（昭和電工社製アクリル樹脂；重量平均分子量７６１０，二重結合当量３４０）Ｂ－３　　製造例１で得られたもの（重量平均分子量２２０００，二重結合当量３３０）Ｂ－４　　製造例２で得られたもの（重量平均分子量５６００，二重結合当量４３４）Ｂ’－１　ＳＰＣ－２０００（昭和電工社製アクリル樹脂；重量平均分子量１７５００，二重結合当量０）Ｃ－１　　アロニックスＭ４５０（東亞合成社製アクリル系モノマー）Ｃ－２ 　カヤラッドＤＰＨＡ（多官能アクリレート；日本化薬社製）Ｄ－１　　ＮＣＩ－９３０（ＡＤＥＫＡ社製）Ｄ－２　　ＩＲＧＡＣＵＲＥ－ＯＸＥ０１（ＢＡＳＦ社製）Ｄ－３　　ＴＲ－ＰＢＧ－３０４（Ｔｒｏｎｌｙ社製）Ｅ－１　　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Ｆ－１　　ブルー顔料分散液（着色剤としてＣ．Ｉ．ピグメントブルー１５：６を１５質量部、分散剤としてＢＹＫ1６1（ビックケミー（ＢＹＫ）社製）１２．５質量部（固形分濃度４０質量％）、溶媒としてプロピレングリコールモノメチルエーテルアセテート７２．５質量部を用いて、ビーズミルにより処理することにより調製した。） The symbols B-1 to B-4, B'-1, C-1 to C-2, D-1 to D-3, E-1 and F-1 in [Table 1] and [Table 2] are respectively The following compounds are represented. B-1 SPC-1000 (Acrylic resin from Showa Denko; weight average molecular weight 31980, double bond equivalent 900) B-2 SPC-3000 (Acrylic resin from Showa Denko; weight average molecular weight 7610, double bond equivalent 340) B-3 Obtained in Production Example 1 (weight average molecular weight 22000, double bond equivalent 330) B-4 Obtained in Production Example 2 (weight average molecular weight 5600, double bond equivalent 434) B′-1 SPC-2000 (Showa Denko acryl resin; weight average molecular weight 17500, double bond equivalent 0) C-1 Aronix M450 (Toagosei Co., Ltd. acrylic monomer) C-2 kayarad DPHA (polyfunctional acrylate; Nippon Kayaku Co., Ltd.) D-1 NCI-930 (ADEKA) D-2 IRGACURE-OXE01 (BA) F-3) D-3 TR-PBG-304 (manufactured by Tolly) E-1 Propylene glycol-1-monomethyl ether-2-acetate F-1 Blue pigment dispersion (CI Pigment Blue 15 as colorant: By using a bead mill, 15 parts by mass of 6 and 12.5 parts by mass of BYK16 1 (produced by BYK) as a dispersant (solid content concentration 40% by mass) and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent Prepared by processing.)
　［評価例１－１～１－１１及び比較評価例１－１～１－２］焼成による耐熱性評価
　実施例１～１１で調製した感光性組成物Ｎｏ．１～Ｎｏ．１１並びに比較例１～２で調製した比較感光性組成物Ｎｏ．１～Ｎｏ．２を、それぞれガラス基板に４１０ｒｐｍ×７ｓｅｃの条件で塗工し、ホットプレートで乾燥（９０℃、９０ｓｅｃ）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℃×９０分の条件で焼成し、焼成後の塗膜の４００ｎｍにおける透過率を測定した。結果を［表３］に示す。 [Evaluation Examples 1-1 to 1-11 and Comparative Evaluation Examples 1-1 to 1-2] Evaluation of heat resistance by firing Photosensitive composition Nos. 1 to 11 prepared in Examples 1 to 11 were used. 1-No. 11 and Comparative Photosensitive Composition No. 1 prepared in Comparative Examples 1-2. 1-No. 2 were each applied to a glass substrate under conditions of 410 rpm × 7 sec and dried on a hot plate (90 ° C., 90 sec). The obtained coating film was exposed (40 mJ / cm 2 ) with an ultrahigh pressure mercury lamp. The exposed coating film was baked under the conditions of 230 ° C. × 90 minutes, and the transmittance of the baked coating film at 400 nm was measured. The results are shown in [Table 3].
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
［評価例２－１～２－１１及び比較評価例２－１～２－２］耐溶剤性評価
　実施例１～１０で得られた感光性組成物Ｎｏ．１～Ｎｏ．１１及び比較例１～２で得られた比較感光性組成物Ｎｏ．１～Ｎｏ．２をガラス基板に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）した後、シクロヘキサノン、ＰＧＭＥＡ、Ｎ－メチルピロリドン、Ｎ－エチルピロリドンにそれぞれ３０分浸漬した。その後、イオン交換水で洗浄乾燥し、各溶剤に対する浸漬試験前後の膜厚を調べた。膨潤率（％）＝（試験後の膜厚－試験前の膜厚）／試験前の膜厚×１００とし、膨潤率が０～２％未満の場合はＡ、２～８％未満の場合はＢ、８％以上の場合はＣ、試験前より試験後の膜厚が減った場合をＤとした。結果を［表４］に示す。 [Evaluation Examples 2-1 to 2-11 and Comparative Evaluation Examples 2-1 to 2-2] Solvent Resistance Evaluation The photosensitive composition Nos. Obtained in Examples 1 to 10 were used. 1-No. No. 11 and Comparative Photosensitive Composition Nos. 1-No. 2 was 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, and then immersed in cyclohexanone, PGMEA, N-methylpyrrolidone, and N-ethylpyrrolidone for 30 minutes. Then, it washed and dried with ion-exchange water, and investigated the film thickness before and behind the immersion test with respect to each solvent. Swelling rate (%) = (film thickness after test−film thickness before test) / film thickness before test × 100. A when the swelling rate is less than 0 to 2%, A when 2 to less than 8% B, C when 8% or more, and D when the film thickness after the test decreased from before the test. The results are shown in [Table 4].
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
　以上の結果より、本発明の感光性組成物は、焼成後の透明性が高いまま維持されている、すなわち耐熱性が高く、かつ耐溶剤性に優れる。 From the above results, the photosensitive composition of the present invention is maintained with high transparency after firing, that is, it has high heat resistance and excellent solvent resistance.
　本発明によれば、耐熱性及び耐溶剤性の高い硬化物を与える感光性組成物を提供することができる。
  According to this invention, the photosensitive composition which gives the hardened | cured material with high heat resistance and solvent resistance can be provided.

Claims (3)

  1. 　潜在性添加剤（Ａ）、エチレン性不飽和結合及び親水性基を一分子内に有し、且つ二重結合当量が２００～１０００である重合体（Ｂ）、アクリルモノマー（Ｃ）及び光ラジカル重合開始剤（Ｄ）を含有する感光性組成物。 A latent additive (A), a polymer (B) having an ethylenically unsaturated bond and a hydrophilic group in one molecule and a double bond equivalent of 200 to 1000, an acrylic monomer (C), and a photoradical A photosensitive composition containing a polymerization initiator (D).
  2. 　請求項１に記載の感光性組成物を、活性エネルギー線を照射することにより硬化させる方法。 A method of curing the photosensitive composition according to claim 1 by irradiating active energy rays.
  3. 　請求項１に記載の感光性組成物の硬化物。 A cured product of the photosensitive composition according to claim 1.
PCT/JP2017/012505 2016-03-29 2017-03-28 Photosensitive composition WO2017170465A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020187015981A KR102369445B1 (en) 2016-03-29 2017-03-28 photosensitive composition
CN201780005076.5A CN108473611B (en) 2016-03-29 2017-03-28 Photosensitive composition
JP2018508022A JP6849659B2 (en) 2016-03-29 2017-03-28 Photosensitive composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016066634 2016-03-29
JP2016-066634 2016-03-29

Publications (1)

Publication Number Publication Date
WO2017170465A1 true WO2017170465A1 (en) 2017-10-05

Family

ID=59965739

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/012505 WO2017170465A1 (en) 2016-03-29 2017-03-28 Photosensitive composition

Country Status (5)

Country Link
JP (1) JP6849659B2 (en)
KR (1) KR102369445B1 (en)
CN (1) CN108473611B (en)
TW (1) TWI729100B (en)
WO (1) WO2017170465A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020209105A1 (en) * 2019-04-11 2020-10-15 キヤノン株式会社 Photocurable resin composition for three-dimensional modeling and method for producing article
WO2020230732A1 (en) * 2019-05-15 2020-11-19 株式会社Adeka Composition, cured product, cured product production method, and additive

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019151256A1 (en) * 2018-01-30 2019-08-08 ナミックス株式会社 Resin composition and cured material of same, adhesive, semiconductor device, and electronic component
CN109852202B (en) * 2019-01-09 2021-05-14 山西大学 Use of thioesters containing a benzo-heterocycle skeleton as UV absorbers

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014021023A1 (en) * 2012-07-31 2014-02-06 株式会社Adeka Latent additive and composition containing latent additive
JP2015132791A (en) * 2013-12-13 2015-07-23 株式会社Adeka Colored photosensitive composition
JP2015131937A (en) * 2013-12-11 2015-07-23 株式会社Adeka Coloring compositions
JP2015163671A (en) * 2013-12-13 2015-09-10 株式会社Adeka Radical-polymerizable composition
JP2016038569A (en) * 2014-08-05 2016-03-22 株式会社Adeka Photosensitive composition
JP2016056290A (en) * 2014-09-10 2016-04-21 株式会社Adeka Latent additive and photosensitive composition
JP2016183305A (en) * 2015-03-26 2016-10-20 Jsr株式会社 Composition for forming cured film, cured film for display element, method for forming cured film for display element, display element, and method for manufacturing display element
JP2017008219A (en) * 2015-06-23 2017-01-12 株式会社Adeka Composition
WO2017030005A1 (en) * 2015-08-17 2017-02-23 株式会社Adeka Composition
WO2017033880A1 (en) * 2015-08-24 2017-03-02 株式会社Adeka Oxime ester compound and polymerization initiator containing compound
WO2017043353A1 (en) * 2015-09-11 2017-03-16 株式会社Adeka Novel compound, latent additive, and composition containing said additive
WO2017051680A1 (en) * 2015-09-25 2017-03-30 株式会社Adeka Oxime ester compound and polymerization initiator containing said compound

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3956597B2 (en) 2000-09-26 2007-08-08 三菱化学株式会社 Photocurable composition and cured product thereof
JP2009134078A (en) 2007-11-30 2009-06-18 Sumitomo Chemical Co Ltd Photosensitive resin composition
JP5460179B2 (en) 2009-08-25 2014-04-02 株式会社Ｄｎｐファインケミカル Photosensitive red composition for color filter and color filter using the same
JP2013037272A (en) 2011-08-10 2013-02-21 Mitsubishi Paper Mills Ltd Photosensitive resin composition and photosensitive film
JP2013182174A (en) * 2012-03-02 2013-09-12 Toyo Ink Sc Holdings Co Ltd Photosensitive resin composition
JP6318710B2 (en) 2014-03-06 2018-05-09 富士ゼロックス株式会社 Information processing apparatus, document processing system, information processing system, and information processing program

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014021023A1 (en) * 2012-07-31 2014-02-06 株式会社Adeka Latent additive and composition containing latent additive
JP2015131937A (en) * 2013-12-11 2015-07-23 株式会社Adeka Coloring compositions
JP2015132791A (en) * 2013-12-13 2015-07-23 株式会社Adeka Colored photosensitive composition
JP2015163671A (en) * 2013-12-13 2015-09-10 株式会社Adeka Radical-polymerizable composition
JP2016038569A (en) * 2014-08-05 2016-03-22 株式会社Adeka Photosensitive composition
JP2016056290A (en) * 2014-09-10 2016-04-21 株式会社Adeka Latent additive and photosensitive composition
JP2016183305A (en) * 2015-03-26 2016-10-20 Jsr株式会社 Composition for forming cured film, cured film for display element, method for forming cured film for display element, display element, and method for manufacturing display element
JP2017008219A (en) * 2015-06-23 2017-01-12 株式会社Adeka Composition
WO2017030005A1 (en) * 2015-08-17 2017-02-23 株式会社Adeka Composition
WO2017033880A1 (en) * 2015-08-24 2017-03-02 株式会社Adeka Oxime ester compound and polymerization initiator containing compound
WO2017043353A1 (en) * 2015-09-11 2017-03-16 株式会社Adeka Novel compound, latent additive, and composition containing said additive
WO2017051680A1 (en) * 2015-09-25 2017-03-30 株式会社Adeka Oxime ester compound and polymerization initiator containing said compound

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020209105A1 (en) * 2019-04-11 2020-10-15 キヤノン株式会社 Photocurable resin composition for three-dimensional modeling and method for producing article
JP2020172103A (en) * 2019-04-11 2020-10-22 キヤノン株式会社 Photocurable resin composition for three-dimensional modeling and method for producing article
JP7566547B2 (en) 2019-04-11 2024-10-15 キヤノン株式会社 Photocurable resin composition for three-dimensional modeling and method for manufacturing article
WO2020230732A1 (en) * 2019-05-15 2020-11-19 株式会社Adeka Composition, cured product, cured product production method, and additive

Also Published As

Publication number Publication date
KR102369445B1 (en) 2022-03-03
CN108473611A (en) 2018-08-31
JPWO2017170465A1 (en) 2019-02-07
KR20180123003A (en) 2018-11-14
TWI729100B (en) 2021-06-01
CN108473611B (en) 2024-05-14
JP6849659B2 (en) 2021-03-24
TW201736967A (en) 2017-10-16

Similar Documents

Publication Publication Date Title
JP6741711B2 (en) Latent additive and composition containing said additive
JP6730287B2 (en) Composition
JP6889151B2 (en) Photosensitive compositions and novel compounds
JP2017008219A (en) Composition
JP6518195B2 (en) Novel compound and composition containing the compound
JP6875376B2 (en) Compositions and latent additives
JP6849659B2 (en) Photosensitive composition
JP2015132791A (en) Colored photosensitive composition
JP6748083B2 (en) Novel compound, latent additive and composition containing said additive
WO2020032131A1 (en) Compound,thiol generator, composition, cured product, and cured product production method
KR102723373B1 (en) Novel compounds, potential additives and compositions containing the additives

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2018508022

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20187015981

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 201780005076.5

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17775002

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 17775002

Country of ref document: EP

Kind code of ref document: A1