WO2012132558A1 - Oxime ester compound and photoinitiator containing said compound - Google Patents

Oxime ester compound and photoinitiator containing said compound Download PDF

Info

Publication number
WO2012132558A1
WO2012132558A1 PCT/JP2012/052775 JP2012052775W WO2012132558A1 WO 2012132558 A1 WO2012132558 A1 WO 2012132558A1 JP 2012052775 W JP2012052775 W JP 2012052775W WO 2012132558 A1 WO2012132558 A1 WO 2012132558A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
compound
carbon atoms
acid
atom
Prior art date
Application number
PCT/JP2012/052775
Other languages
French (fr)
Japanese (ja)
Inventor
聖 村田
武雄 大石
孝一 君島
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 KR1020137016528A priority Critical patent/KR101930099B1/en
Priority to JP2013507233A priority patent/JP6000942B2/en
Priority to CN201280004665.9A priority patent/CN103298782B/en
Publication of WO2012132558A1 publication Critical patent/WO2012132558A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C391/00—Compounds containing selenium
    • C07C391/02—Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
    • C07C323/65—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/28—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • C07D303/23—Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/42—Singly bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a novel oxime ester compound useful as a photopolymerization initiator for use in a photosensitive composition, a photopolymerization initiator containing the compound, a polymerizable compound having an ethylenically unsaturated bond, and the photopolymerization initiator. And a cured product of the photosensitive composition.
  • the photosensitive composition is obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and can be polymerized and cured by irradiating energy rays (light). It is used for photosensitive printing plates and various photoresists.
  • Patent Documents 1 to 3 propose oxime ester compounds.
  • the oxime ester compound having satisfactory sensitivity has a problem of low transmittance in the visible light region and a desired color cannot be obtained with a color filter (particularly, protection).
  • a color filter particularly, protection
  • photosensitive compositions used for applications where transparency is required, such as films, and resists for color filters using blue pigments or dyes brightness and color purity decrease when compounds having absorption at 380 to 450 nm are mixed.
  • the oxime ester compound having a high visible light transmittance has a problem that the sensitivity is not sufficiently satisfactory, and a photopolymerization initiator having both characteristics has been demanded.
  • the colored alkali-developable photosensitive resin composition containing a color material used for a color filter or the like is required to have high sensitivity, and the photopolymerization initiator in the resist needs to have a high concentration.
  • a high concentration photopolymerization initiator has caused residues due to deterioration of developability, contamination of the photomask and heating furnace due to sublimation, and the like.
  • the problem to be solved is that there has never been a photopolymerization initiator having satisfactory sensitivity, high transmittance in the visible light region, and low sublimation.
  • the object of the present invention is high sensitivity that is excellent in stability, low sublimation, excellent developability, high transmittance in the visible light region, and efficiently absorbs near UV light such as 365 nm and is activated. It is in providing the photoinitiator of this.
  • the present inventors have made the compound used as a photopolymerization initiator react with a resin or the like when it is made into a resin composition, or react with a resin or the like when irradiated with energy rays (light). It has been found that the sublimation property is lower than that in the case where the compound exists as it is without reacting with.
  • the present invention has been made on the basis of the above findings, and provides an oxime ester compound represented by the following general formula (1) and a photopolymerization initiator containing the compound.
  • R 1 , R 2 , R 3 and R 4 each independently represents R 11 , OR 11 , COOR 11 , SR 11 , SO 2 R 11 , CONR 12 R 13 or CN;
  • R 11 , R 12 and R 13 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.
  • the hydrogen atom of the substituent represented by R 11 , R 12 and R 13 is further OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , —NR 22 —OR 23 , —NR 22 CO—.
  • R 21 , R 22 and R 23 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.
  • the hydrogen atom of the substituent represented by R 21 , R 22 and R 23 may be further substituted with CN, a halogen atom, a hydroxyl group or a carboxyl group,
  • the alkylene part of the substituent represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 is —O—, —S—, —COO—, —OCO—, —NR 24 —, — May be interrupted 1 to 5 times by NR 24 COO—, —OCONR 24 —, —SCO—, —COS—, —OCS— or —CSO—
  • R 24 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 group having 2 to 20 carbon
  • X represents an oxygen atom, a sulfur atom, a selenium atom, CR 31 R 32 , CO, NR 33 or PR 34
  • R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl having 7 to 30 carbon atoms.
  • R 31 , R 32 , R 33 and R 34 may have a branched side chain or may be a cyclic alkyl.
  • R 31 , R 32 , R 33 and R 34 The alkyl terminal of the substituent represented by the above formula may be an unsaturated bond, and R 31 , R 32 , R 33 and R 34 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 1 to 5
  • At least one of R 4 is —CR 21 ⁇ CR 22 R 23 , —CO—CR 21 ⁇ CR 22 R 23 , —O—CO—CR 21 ⁇ CR 22 R 23 , —N ⁇ C ⁇ O or an epoxy group It is group which has. )
  • the present invention also provides a photosensitive composition comprising the photopolymerization initiator and a polymerizable compound having an ethylenically unsaturated bond. Moreover, this invention provides the alkali developable photosensitive resin composition formed by making the said photosensitive composition contain the compound which provides alkali developability. The present invention also provides a colored alkali-developable photosensitive resin composition obtained by further adding a coloring material to the alkali-developable photosensitive resin composition.
  • the present invention also provides a cured product obtained by irradiating the photosensitive composition, the alkali-developable photosensitive resin composition, or the colored alkali-developable photosensitive resin composition with energy rays.
  • the oxime ester compound of the present invention has a high transmittance in the visible light region and efficiently generates radicals with respect to bright lines such as 365 nm (i-line) and is useful as a photopolymerization initiator.
  • the oxime ester compound of the present invention when used as a photopolymerization initiator in a resin composition, it reacts with a resin having a polymerizable group, so that there are few sublimates and further improves the heat resistance of the cured product. be able to.
  • the oxime ester compound of the present invention is a novel compound represented by the general formula (1).
  • the oxime ester compound has two geometric isomers due to an oxime double bond, but the present invention does not distinguish them. That is, in this specification, the general formula (1), the general formula (2) representing a preferred form of the compound represented by the general formula (1) described later, and the exemplified compound Nos. 1-No.
  • the chemical structural formula of 39 shows only one of the two geometric isomers, the oxime ester compound of the present invention is not limited to the geometric isomer represented by these formulas, and the other geometric isomer. Or a mixture of two geometric isomers.
  • alkyl group for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-butyl
  • alkyl group for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-butyl
  • Examples include octyl, nonyl, isononyl, decyl, isodecyl
  • aryl groups include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, and phenyl, biphenylyl, naphthyl, anthryl substituted with one or more of the above alkyl groups.
  • the optionally substituted heterocyclic group having 2 to 20 carbon atoms represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 in the general formula (1) Is, for example, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl Preferred examples thereof include 5- to 7-membered heterocycles such as
  • R 12 and R 13 , R 22 and R 23 can be formed together, and R 31 , R 32 , R 33 and R 34 are combined with the adjacent benzene ring.
  • Preferred examples of the ring that can be formed include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring.
  • examples of the halogen atom that may substitute R 11 , R 12 , R 13 , R 21 , R 22 , and R 23 include fluorine, chlorine, bromine, and iodine.
  • the alkylene moiety of the substituent represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 is —O—, —S—, —COO—, —OCO—, —NR 24 —. , —NR 24 COO—, —OCONR 24 —, —SCO—, —COS—, —OCS—, or —CSO— may be interrupted 1 to 5 times. Two or more groups may be used, and in the case of a group that can be interrupted continuously, two or more groups may be interrupted continuously.
  • the alkyl part of the substituent may have a branched side chain or may be a cyclic alkyl.
  • X is a sulfur atom or NR 33
  • R 33 may have a branched side chain, and may be a cyclic alkyl.
  • a compound having an alkyl group of ⁇ 20; a compound represented by the following general formula (2) is particularly preferred because of its high sensitivity and easy production.
  • R 5 is the same as R 4 in the above general formula (1), and at least R 5 represents at least a structure selected from —CR 21 ⁇ CR 22 R 23 , —CO—CR 21 ⁇ CR 22 R 23 , —O—CO—CR 21 ⁇ CR 22 R 23 , —N ⁇ C ⁇ O and an epoxy group.
  • c represents an integer of 0 to 4.
  • R 5 is —CR 21 ⁇ CR 22 R 23 , —CO—CR 21 ⁇ CR 22 R 23, or —O—CO—CR 21 ⁇ CR 22 R 23. Is more preferable because it has high reactivity and exhibits high heat resistance when combined with a resin composition having an unsaturated double bond, and R 5 has —N ⁇ C ⁇ O or an epoxy group. The compound is also more preferable because it exhibits high heat resistance when combined with a resin having active hydrogen such as alcohol, amine, amide and the like.
  • R 1 and R 2 in the above general formulas (1) and (2) may have 1 to 20 carbon atoms (especially 1 to 10 carbon atoms, especially carbon atoms). It is preferably an alkyl group having 1 to 4 atoms, a in the general formulas (1) and (2) is preferably 0 to 1, and b in the general formula (1) is 1 to 2 is preferable, and c in the general formula (2) is preferably 0 to 1.
  • R 3 is preferably a hydrogen atom.
  • X is preferably a sulfur atom.
  • —OCO—CR 21 ⁇ CR 22 R 23 is bonded to the carbon atom farthest from the oxygen atom of OR 11 when the hydrogen atom of R 11 of OR 11 is substituted.
  • the hydrogen atom of R 11 of COOR 11 is substituted, it is preferably bonded to the carbon atom located farthest from the COO group of COOR 11 .
  • b is 1, and R 4 is preferably bonded to the para position with respect to the carbon atom to which X is bonded.
  • the oxime ester compound of the present invention represented by the general formula (1) is not particularly limited, but can be produced, for example, according to the method described in JP-A No. 2000-80068. As one of the methods, it can be produced by the following method according to the following reaction formula 1. First, a (meth) acrylate body is obtained by reacting a ketone body with (meth) acrylic acid in the presence of a Lewis acid. Next, the oxime ester compound of the present invention represented by the above general formula (1) is obtained by reacting the (meth) acrylate body with a nitrite in the presence of hydrochloric acid, and subsequently reacting with an acid anhydride or acid chloride. Get.
  • reaction formula 1 describes the case where X is a sulfur atom, those in which X is an oxygen atom, a selenium atom, CR 31 R 32 , NR 33 or PR 34 are also produced according to the above method. be able to.
  • novel oxime ester compound of the present invention described above is useful as a photopolymerization initiator.
  • the photopolymerization initiator of the present invention contains at least one oxime ester compound of the present invention, and is particularly useful as a photopolymerization initiator for a polymerizable compound having an ethylenically unsaturated bond.
  • the content of the oxime ester compound of the present invention in the photopolymerization initiator of the present invention is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.
  • the photopolymerization initiator of the present invention may contain other photopolymerization initiator in addition to the oxime ester compound of the present invention. As other photopolymerization initiators, conventionally known compounds can be used.
  • R 1 , R 2 and R 33 are the same as those in the general formula (1), Y 3 represents a halogen atom or an alkyl group, and n is 0 to 5.
  • R 1 , R 2 and R 33 are the same as those in the general formula (1), Y 3 and n are the same as those in the general formula (4), and R ′ 1 and R ′ 2 are R 1 and R 2 are the same, R ′ 33 is the same as R 33 , Y ′ 3 is the same as Y 3 , R 8 is a diol residue or a dithiol residue, Z 5 is an oxygen atom Or represents a sulfur atom.
  • R 1 , R 2 and R 33 are the same as in the general formula (1), Y 3 and n are the same as in the general formula (4), and Z 6 is an oxygen atom or a sulfur atom. Or represents a selenium atom, A represents a heterocyclic group, t is an integer of 0 to 5, and u is 0 or 1.
  • the photosensitive composition of the present invention contains (A) a photopolymerization initiator of the present invention and (B) a polymerizable compound having an ethylenically unsaturated bond as essential components, and (C) an inorganic compound as an optional component. (D) It contains a combination of components such as a coloring material and a solvent.
  • the content of the photopolymerization initiator of the present invention is not particularly limited, but the content of the oxime ester compound of the present invention in the photosensitive composition of the present invention.
  • the amount is preferably 1 to 70 parts by weight, more preferably 1 to 50 parts by weight, and most preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymerizable compound (B) having an ethylenically unsaturated bond.
  • the polymerizable compound having an ethylenically unsaturated bond (B) is not particularly limited, and those conventionally used in photosensitive compositions can be used.
  • those conventionally used in photosensitive compositions can be used.
  • ethylene, propylene, butylene, isobutylene can be used.
  • Unsaturated polybasic acids such as polyfunctional (meth) acrylates; (meth) (-2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate; A1-No.
  • A4 methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (t-butyl) (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (
  • Examples of the polymerizable compound (B) having an ethylenically unsaturated bond include acrylic acid ester copolymers, phenol and / or cresol novolac epoxy resins, polyphenylmethane type epoxy resins having polyfunctional epoxy groups, and epoxy.
  • Resins obtained by allowing an unsaturated monobasic acid to act on an acrylate resin or an epoxy compound such as an epoxy compound represented by the following general formula (3), and further causing a polybasic acid anhydride to act on the epoxy compound can also be used.
  • a resin obtained by allowing an unsaturated monobasic acid to act on an epoxy compound such as an epoxy compound represented by the following general formula (3) and further causing a polybasic acid anhydride to act is preferable.
  • these compounds preferably contain 0.2 to 1.0 equivalent of unsaturated groups.
  • X 1 is a direct bond, methylene group, alkylidene group having 1 to 4 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, O, S, SO 2 , SS, SO, CO, OCO or a substituent represented by the following formula (I), (B) or (C), wherein the alkylidene group may be substituted with a halogen atom, and R 51 , R 52 , R 53 and R 54 are Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom, and the above alkyl group, alkoxy group and The alkenyl group may be substituted with a halogen atom, m is an integer of 0 to 10, and the optical isomer present when m is not 0 may be any isomer.)
  • Z 3 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group optionally substituted by an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, or A cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms
  • Y 1 is an alkyl group having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms Group, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, wherein the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and d is an integer of 0 to 5.
  • Y 2 and Z 4 are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 to 20 carbon atoms which may be substituted with a halogen atom.
  • Examples of the unsaturated monobasic acid that acts on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl Acrylate / malate, dicyclopentadiene / malate and the like can be mentioned.
  • the polybasic acid anhydride to be acted after the unsaturated monobasic acid is allowed to act is biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, Trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene -1,2-dicarboxylic an
  • the reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows. That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the hydroxyl group 1 of the epoxy adduct is It is preferable that the ratio of the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0. Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.
  • the amount used is preferably 50 to 99% by mass in the component (B).
  • the compound having an acid value can be used after adjusting the acid value by further reacting with a monofunctional or polyfunctional epoxy compound.
  • the alkali developability of the photosensitive resin can be improved by adjusting the acid value of the compound having an acid value.
  • the compound having an acid value (that is, a polymerizable compound having an ethylenically unsaturated bond imparting alkali developability) preferably has a solid acid value in the range of 5 to 120 mgKOH / g, and is monofunctional or polyfunctional.
  • the amount of the functional epoxy compound used is preferably selected so as to satisfy the acid value.
  • Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecy
  • the polyfunctional epoxy compound when one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers are used, a (colored) alkali-developable photosensitive resin composition having better characteristics can be obtained. Is preferable.
  • the bisphenol-type epoxy compound the epoxy compound represented by the general formula (3) can be used, and for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can also be used.
  • glycidyl ethers examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidy
  • novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocycl
  • Examples of the inorganic compound (C) that can be contained in the photosensitive composition of the present invention include nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, Metal oxides such as alumina; layered clay minerals, miloli blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides , Selenide, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper and the like.
  • glass frit, titanium oxide, silica, layered clay mineral, silver and the like are preferable.
  • the content of the inorganic compound (C) is preferably 0.1 to 1000 parts by mass with respect to 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond.
  • the amount is preferably 10 to 800 parts by mass.
  • inorganic compounds are used, for example, as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.
  • examples of the color material (D) that can be contained in the photosensitive composition of the present invention include pigments, dyes, and natural pigments. These color materials can be used alone or in admixture of two or more.
  • the pigment examples include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; Compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalene tetracarboxylic acids; azo dyes, metal complex compounds of cyanine dyes; Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black or lamp black; Prepared by coating or coating with an epoxy resin, carbon black previously dispersed with a resin in a solvent and adsorbed with 20 to 200 mg / g of resin, carbon black treated with an acidic or alkaline surface, average Carbon black having a particle size of 8 nm or more and a DBP oil absorption of 90 m
  • Graphitized carbon black activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene
  • aniline black pigment black 7, titanium black
  • chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese series Ferrus Organics such as fluoride, phosphate blue, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, synthetic iron black, amber, etc.
  • an inorganic pigment can be used. These pigments can be used alone or in combination.
  • pigments can also be used as the pigment, 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, 9 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148,
  • dyes As the above dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And dyes such as cyanine dyes, and a plurality of these may be used in combination.
  • the content thereof is preferably 50 to 350 parts by mass with respect to 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond. More preferably, it is 100 to 250 parts by mass.
  • the photosensitive composition of the present invention may contain a compound that does not have an ethylenically unsaturated bond and imparts alkali developability.
  • an alkaline aqueous solution can be obtained by having an acid value.
  • a typical example is an alkali-soluble novolak resin (hereinafter simply referred to as “novolak resin”).
  • the novolak resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.
  • phenols examples include phenol, o-cresol, m-cresol, p -cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, ⁇ -naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester, etc.
  • phenols are used.
  • phenol, o-cresol, m-cresol, p-cresol, 2,5-kis Silenol, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methylresorcinol and bisphenol A are preferred.
  • These phenols are used alone or in combination.
  • aldehydes examples include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, ⁇ -phenylpropylaldehyde, ⁇ -phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p N-butylbenzaldehyde is
  • the acid catalyst examples include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid.
  • the amount of these acid catalysts used is preferably 1 ⁇ 10 ⁇ 4 to 5 ⁇ 10 ⁇ 1 mol per mol of phenols.
  • water is usually used as a reaction medium.
  • the reaction medium is hydrophilic.
  • a solvent can also be used.
  • hydrophilic solvents examples include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane.
  • the amount of these reaction media used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material.
  • the reaction temperature of the condensation reaction can be appropriately adjusted according to the reactivity of the reaction raw materials, but is usually 10 to 200 ° C., preferably 70 to 150 ° C. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, the internal temperature is generally increased to 130 to 230 ° C., and the volatile component is distilled off under reduced pressure.
  • the melted novolac resin is collected on a steel belt or the like.
  • the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane or n-heptane to precipitate a novolak resin, and the precipitate is separated and dried by heating. It can also be recovered by doing so.
  • Examples other than the novolak resin include polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, and the like.
  • a solvent can be further added to the photosensitive composition of the present invention.
  • a solvent capable of dissolving or dispersing each of the above components ((A) the photopolymerization initiator of the present invention and (B) a polymerizable compound having an ethylenically unsaturated bond), for example, methyl ethyl ketone, Ketones such as methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, di Ether solvents such as propylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl
  • ketones, ether ester solvents, etc. particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. are preferable because the compatibility between the resist and the photopolymerization initiator is improved in the photosensitive composition.
  • the content of the solvent is not particularly limited, each component is uniformly dispersed or dissolved, and the photosensitive composition of the present invention exhibits a liquid or paste shape suitable for each application.
  • the solvent be contained so that the solid content (all components other than the solvent) in the photosensitive composition of the present invention is 10 to 50% by mass.
  • a dispersant for dispersing (C) an inorganic compound and / or (D) a coloring material can be added.
  • the dispersant is not limited as long as it can disperse and stabilize the (C) inorganic compound or (D) coloring material, and a commercially available dispersant, for example, BYK series manufactured by BYK Chemie, Inc. can be used.
  • a compound having an amine value of 1 to 100 m g KOH / g is preferably used.
  • cured material can also be improved by using another organic polymer with (B) the polymeric compound which has an ethylenically unsaturated bond.
  • 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 phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, etc.
  • polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferred. Arbitrariness.
  • the amount used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond.
  • a chain transfer agent a sensitizer, a surfactant, a silane coupling agent, a melamine compound, and the like can be further used in combination.
  • a sulfur atom-containing compound is generally used.
  • Alkyl compounds trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, diethylthioxanthone, diisopropyl
  • 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; 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, an isocyanate group, a methacryloyl group, or an epoxy group, such as KBE-9007, KBM-502, and KBE-403, can be used. A silane coupling 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.
  • nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea.
  • Examples include 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.
  • the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.
  • an oligomer component may be formed.
  • 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 of the present invention includes, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; a filler; Conventional additives such as a foaming agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid, a coagulation inhibitor, a catalyst, an effect accelerator, a cross-linking agent, and a thickener can be added.
  • the photopolymerization initiator of the present invention and (B) any component other than the polymerizable compound having an ethylenically unsaturated bond (however, (C) inorganic compound, (D) color
  • the amount of use is appropriately selected according to the purpose of use and is not particularly limited, but is preferably (B) in total based on 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. 50 parts by mass or less.
  • the photosensitive composition of the present invention can be cured by irradiating energy rays.
  • cured material is formed as a suitable shape according to a use.
  • the photosensitive composition of the present invention is prepared by using a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, dipping, etc.
  • the present invention can be applied to a supporting substrate such as glass, quartz glass, semiconductor substrate, metal, paper, and plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base
  • the light source of the energy ray used for curing the photosensitive composition of the present invention includes an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp, a carbon arc.
  • High energy rays such as electromagnetic energy, electron beam, X-ray, radiation, etc. having a wavelength of 2000 angstrom to 7000 angstrom obtained from lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source, etc.
  • 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 light light having a wavelength of 340 to 430 nm is preferably used, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser.
  • Various semiconductor lasers and YAG lasers that emit light in the visible to infrared region can also be used. When these laser beams are used, a sensitizing dye that absorbs the visible to infrared region is preferably added.
  • the photosensitive composition of the present invention comprises a photocurable paint or varnish; a photocurable adhesive; a printed circuit board; a color filter in a color display liquid crystal display element such as a color television, a PC monitor, a personal digital assistant, a digital camera; Color filter of image sensor; Electrode material for plasma display panel; Powder coating; Printing ink; Printing plate; Adhesive; Dental composition; Gel coat; Photoresist for electronics; Electroplating resist; Solder resists; resists for manufacturing color filters for various display applications or forming their structures in the manufacturing process of plasma display panels, electroluminescent display devices, and LCDs; for encapsulating electrical and electronic components Composition; solder resist; magnetic recording material; micromachine Article; waveguide; optical switch; plating mask; etching mask; color test system; glass fiber cable coating; stencil for screen printing; material for manufacturing three-dimensional objects by stereolithography; holographic recording material; Materials; fine electronic circuits; bleaching materials; bleaching materials for image recording materials; bleaching materials for image recording materials
  • the photosensitive composition of the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and for forming a protrusion for a vertical alignment type liquid crystal display element.
  • it is useful as a photosensitive composition for simultaneously forming protrusions and spacers for a vertical alignment type liquid crystal display element.
  • the spacer for a liquid crystal display panel includes (1) a step of forming a coating film of the photosensitive composition of the present invention on a substrate, and (2) an energy beam (through a mask having a predetermined pattern shape on the coating film). (3) baking step after exposure, (4) step of developing the film after exposure, and (5) step of heating the film after development.
  • the photosensitive composition of the present invention to which a coloring material is added is suitably used as a resist constituting each pixel such as RGB in a color filter and a black matrix resist forming a partition of each pixel. Furthermore, in the case of a black matrix resist to which an ink repellent agent is added, it is preferably used for a partition for an ink jet color filter having a profile angle of 50 ° or more.
  • the ink repellent agent a fluorosurfactant and a composition containing a fluorosurfactant are preferably used.
  • the partition formed from the photosensitive composition of the present invention partitions the transferred object, and droplets are applied to the recessed portions on the partitioned transferred object by the inkjet method.
  • an optical element is manufactured by a method of forming an image region.
  • the droplets contain a colorant and the image area is colored.
  • the optical element produced by the manufacturing method described above is formed from a plurality of colored areas on the substrate. And at least a partition that separates each colored region of the pixel group.
  • the photosensitive composition of the present invention can also be used as a protective film or insulating film composition.
  • an ultraviolet absorber, an alkylated modified melamine and / or an acrylic modified melamine, a mono- or bifunctional (meth) acrylate monomer containing an alcoholic hydroxyl group in the molecule, and / or a silica sol can be contained.
  • the photosensitive composition for the protective film and insulating film As the photosensitive composition for the protective film and insulating film, (A) the photopolymerization initiator of the present invention, (B) a polymerizable compound having an ethylenically unsaturated bond (preferably containing a carboxyl group-containing polymerizable compound having a weight average molecular weight of 2,000 to 40,000 and an acid value of 50 to 200 mgKOH / g), And (X) a resin composition mainly comprising an epoxy compound, With respect to 100 parts by weight of the component (B), the component (A) is 0.01 to 2.0 parts by weight in terms of the amount of the oxime ester compound of the present invention, and the component (X) is 10 to 40 parts by weight. Some are preferred.
  • the insulating film is used for the insulating resin layer in a laminate in which an insulating resin layer is provided on a peelable support substrate, and the laminate can be developed with an alkaline aqueous solution.
  • the film thickness is preferably 10 to 100 ⁇ m.
  • the photosensitive composition of the present invention can be used as a photosensitive paste composition by containing an inorganic compound (C).
  • the photosensitive paste composition can be used for forming a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.
  • Example 1 Compound No. 1 ⁇ Step 1> Methacrylateation 1- (4- (4- (2-hydroxyethoxy) phenylthio) phenyl) propan-1-one (hereinafter also referred to as ketone body a) 19.8 g (65 mmol), methacrylic acid A solution containing 56.2 g (653 mmol), p-toluenesulfonic acid monohydrate 5.0 g (26 mmol), BHT 1.2 g (5.6 mmol) and dichloroethane 121 g was stirred and refluxed for 10.5 hours. After cooling, ethyl acetate and water were added to separate the oil and water.
  • the organic layer was washed with water, an aqueous sodium bicarbonate solution, and water in this order.
  • the organic layer was dried over anhydrous magnesium sulfate and then the solvent was removed to obtain 26.3 g of the following methacrylate body a.
  • Step 2 Oximation A solution containing 26.0 g (70 mmol) of the methacrylate body a obtained in Step 1, 7.3 g (70 mmol) of concentrated hydrochloric acid and 70 g of dimethylformamide was cooled to 5 ° C., and isobutyl nitrite 10. 8 g (105 mmol) was added and stirred at room temperature for 3 hours. Ethyl acetate and water were added to separate the oil and water, and the organic layer was washed with water, an aqueous sodium hydrogen carbonate solution and water in this order. The organic layer was dried over anhydrous magnesium sulfate and then the solvent was removed to obtain 23.8 g of the following oxime body a.
  • Step 3 Oxime esterification A solution containing 23.8 g (60 mmol) of the oxime body a obtained in Step 2, 9.1 g (90 mmol) of acetic anhydride and 79 g of ethyl acetate was stirred at 70 ° C. for 4 hours. After cooling, water was added and the oil was separated. The organic layer was washed with water, an aqueous sodium bicarbonate solution, and water in this order. The organic layer was dried over anhydrous magnesium sulfate and then desolvated. 27.2 g of the obtained crude product was purified by a column chromatogram, and the compound no. 2.3 g of 1 was obtained. It was confirmed by analysis that the obtained compound was the target product. The analysis results are shown in [Table 1] to [Table 3].
  • Example 2 to 4 Compound No. 2, Compound No. 3, Compound No. 4 According to the method described in Example 1, except that the corresponding ketone body was used instead of ketone body a (and acrylic acid was used instead of methacrylic acid for compound No. 3), compound No. 3 was used. 2, Compound No. 3 and compound no. 4 were produced respectively.
  • the analysis results are shown in [Table 1] to [Table 3].
  • ⁇ Step 2> Alkali-developable photosensitive resin composition No. Preparation of Alkali Developable Resin No. 1 obtained in ⁇ Step 1> as component (B) imparting alkali developability 14.7 g of dipentaerythritol penta and hexaacrylate (Aronix M-402; manufactured by Toagosei Co., Ltd.) as a component (B), surfactant FZ-2122 (manufactured by Nippon Unicar Co., Ltd.) 1.8 g of a cyclohexanone 1% solution, 10.0 g of propylene glycol-1-monomethyl ether-2-acetate and 20.2 g of cyclohexanone were mixed, and the compound No. 1 obtained in Example 1 as component (A) was mixed. 0.3 g of No. 1 was added and stirred well, and the alkali-developable photosensitive resin composition No. 1 which is the photosensitive composition of the present invention. 1 was obtained.
  • component (B)
  • Example 6 Alkali-developable photosensitive resin composition No. Preparation of Compound No. 2 obtained in Example 1 1 to compound No. 1 obtained in Example 2. Except for changing to No. 2, in the same manner as in ⁇ Step 2> of Example 5, the alkali-developable photosensitive resin composition No. 1 as the photosensitive composition of the present invention was used. 2 was obtained.
  • Example 7 Alkali-developable photosensitive resin composition No. Preparation of Compound No. 3 obtained in Example 1 1 to compound No. 1 obtained in Example 3. 3 except that the alkaline developing photosensitive resin composition No. 1 which is the photosensitive composition of the present invention was prepared in the same manner as in ⁇ Step 2> of Example 5. 3 was obtained.
  • the permeability test of No. 5 was conducted as follows. That is, the alkali-developable photosensitive resin composition was spin-coated on a glass substrate (500 rpm for 2 seconds, 800 rpm for 6 seconds), and prebaked at 90 ° C. for 90 seconds using a hot plate. Next, after exposure to 150 mJ / cm 2 using a high-pressure mercury lamp as a light source, post-baking was performed at 230 ° C. for 30 minutes using an oven to obtain a cured film. About the obtained cured film, the transmittance
  • the photosensitive composition of the present invention using the oxime ester compound of the present invention as a photopolymerization initiator is more transparent than the photosensitive compositions of Comparative Examples 1 and 2 using a comparative compound. The rate is high.
  • Example 8 Conductive composition No. Production of Alkali Developable Resin No. 1 obtained in ⁇ Step 1> of Example 5 as component (B) for imparting alkali developability 14.1 g of 1, dipentaerythritol penta and hexaacrylate (Aronix M-402; manufactured by Toagosei Co., Ltd.) as component (B), surfactant BYK-323 (manufactured by Big Chemie Japan Co., Ltd.) 0.05 g, 11.3 g of texanol (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate), compound No.
  • Example 1 obtained in Example 1 as component (A) 0.7 g of 1 and 3.1 g of glass frit and 63.7 g of silver powder as component (C) were stirred and kneaded with a three-roll mill, and the conductive composition which is the photosensitive composition of the present invention. No. 1 was obtained.
  • Example 9 Colored alkali-developable photosensitive resin composition No. ⁇ Step 1> Production of Blue Dispersion 57.6 g of Blue Pigment Pigment Blue 15: 6, Dispersant Azisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) 20.0 g, Dispersing Agent Solsperse 5000 (Avicia Co., Ltd.) )) 2.4 g and propylene glycol-1-monomethyl ether-2-acetate 320.0 g are put into a 500 ml polyethylene container, and 350 g of zirconia beads having a particle diameter of 0.5 mm are used for 10 hours in a paint conditioner. After shaking, the zirconia beads were filtered off to obtain a blue dispersion.
  • ⁇ Step 2> Colored alkali-developable photosensitive resin composition No. Production of 1 (D) 10.63 g of the blue dispersion obtained in ⁇ Step 1> as component (B) Alkali developability obtained in ⁇ Step 1> of Example 5 as component (B) that imparts alkali developability Resin No.
  • the permeability test of No. 3 was conducted as follows. A colored alkali-developable photosensitive resin composition was spin-coated (500 rpm, 7 seconds) on a glass substrate, and prebaked at 90 ° C. for 90 seconds using a hot plate. Next, after exposure to 150 mJ / cm 2 using a high-pressure mercury lamp as a light source, post-baking was performed at 230 ° C. for 30 minutes using an oven to obtain a cured film. As a heat resistance test, the obtained cured film was further heated at 260 ° C. for 1 hour. The cured film after the heat resistance test was measured for transmittance at 420 nm using an absorptiometer. The results are shown in [Table 5].
  • the colored alkali-developable photosensitive resin composition of the present invention using the oxime ester compound of the present invention as a photopolymerization initiator is a colored alkali-developable feeling of Comparative Examples 3 and 4 using a comparative compound.
  • the transmittance is higher than that of the light-sensitive resin composition.
  • the weight reduction rate of the cured product was measured as follows. That is, the colored alkali-developable photosensitive resin composition was spin coated (500 rpm, 7 seconds) on a glass substrate, and prebaked at 90 ° C. for 90 seconds using a hot plate. Next, the film was exposed to 100 mJ / cm 2 using a high-pressure mercury lamp as a light source to obtain a cured film. About 3 mg of this cured film was scraped off, and the weight reduction rate when held at 230 ° C. for 30 minutes was measured with TG-DTA (manufactured by Seiko Instruments Inc.) using the scraped cured film as a sample. The results are shown in [Table 6].
  • the colored alkali-developable photosensitive resin composition which is the photosensitive composition of the present invention using the oxime ester compound of the present invention as a photopolymerization initiator, is colored in Comparative Examples 4 to 6 using the comparative compound. It is clear that it has excellent heat resistance and less outgas compared to the alkali-developable photosensitive resin composition. In addition, from this result, it is guessed that the oxime ester compound of this invention as a photoinitiator reacted with the resin component, and, thereby, the sublimation property of the oxime ester compound and / or resin component of this invention became low.
  • Example 10 Colored alkali-developable photosensitive resin composition No. 6.
  • Preparation (6) As component (D) 10.63 g of the blue dispersion obtained in ⁇ Step 1> of Example 9, and as component (B) imparting alkali developability, obtained in ⁇ Step 1> of Example 5 Alkali developable resin No.
  • sensitivity The sensitivity of the colored alkali-developable photosensitive resin composition was evaluated in the following four stages. That is, the exposure amount when the line width of the formed pattern exceeds the mask opening line width is 50 mJ / cm 2 , a is 100 mJ / cm 2 , b is 150 mJ / cm 2 The case where there was c and the case where a pattern was not formed even at 150 mJ / cm 2 was taken as d. (Adhesion) The adhesion of the colored alkali-developable photosensitive resin composition was evaluated in the following four stages.
  • Example 11 Colored alkali-developable photosensitive resin composition No. 11: (D) 7.06 g of a carbon black dispersion prepared by changing Pigment Blue 15: 6 in ⁇ Step 1> of Example 9 to carbon black as component (D), component (B) imparting alkali developability As the alkali developable resin No. obtained in ⁇ Step 1> of Example 5.
  • Example 12 Colored alkali-developable photosensitive resin composition No. No. 12 Compound No. obtained in Example 1 1 to compound No. 1 obtained in Example 2. A colored alkali-developable photosensitive resin composition No. 1 which is the photosensitive composition of the present invention was prepared in the same manner as in Example 11 except that it was changed to 2. 12 was obtained.
  • Example 13 Colored alkali-developable photosensitive resin composition No. Preparation of Compound No. 13 obtained in Example 1 1 to compound No. 1 obtained in Example 3. Except for the change to 3 in the same manner as in Example 11, the colored alkali-developable photosensitive resin composition No. 1 as the photosensitive composition of the present invention was used. 13 was obtained.
  • sensitivity The sensitivity of the colored alkali-developable photosensitive resin composition was evaluated in the following three stages. That is, when the line width of the formed pattern exceeds the mask opening line width, the exposure amount is 100 mJ / cm 2 , a is 120 mJ / cm 2 , b is 120 mJ / cm 2 The case where a pattern was not formed was defined as c.
  • Adhesion The adhesion of the colored alkali-developable photosensitive resin composition was evaluated in the following four stages.
  • the transparency and developability in the visible light region are excellent as compared with the compounds used in Comparative Examples 2, 3, 7, and 11.
  • the oxime ester compound of the present invention it is excellent in transparency, heat resistance, sensitivity, and adhesion in the visible light region as compared with the compounds used in Comparative Examples 4 and 8.
  • the oxime ester compound of this invention it is excellent in heat resistance, a sensitivity, and adhesiveness compared with the compound used in Comparative Examples 5, 9, and 12.
  • the oxime ester compound of the present invention it is excellent in transparency, heat resistance, sensitivity and adhesion in the visible light region as compared with the compounds used in Comparative Examples 1, 6 and 10.
  • the visible light region has high transparency, excellent heat resistance, and excellent photolithography properties.
  • the oxime ester compound of the present invention is useful as a photopolymerization initiator. is there.

Abstract

An oxime ester compound represented by general formula (1) [wherein R1 to R4 are each OR11, COOR11, or the like; R11 is a hydrogen atom, a C1-20 alkyl group, a C6-30 aryl group, a C7-30 arylalkyl group, or a C2-20 heterocyclic group, the hydrogen atoms of these groups being optionally replaced by -CR21=CR22R23, -CO-CR21=CR22R23, -O-CO-CR21=CR22R23, or the like (wherein R21 to R23 have the same meanings as defined above for R11); X is a sulfur atom, NR33 (wherein R33 is a hydrogen atom, a C1-20 alkyl group, or the like), or the like; a is an integer of 0 to 4; b is an integer of 1 to 5; and at least one of the R4 moieties is a group having -CR21=CR22R23, -CO-CR21=CR22R23, -O-CO-CR21=CR22R23 or the like].

Description

オキシムエステル化合物及び該化合物を含有する光重合開始剤Oxime ester compound and photopolymerization initiator containing the compound
　本発明は、感光性組成物に用いられる光重合開始剤として有用な新規なオキシムエステル化合物、該化合物を含有する光重合開始剤、エチレン性不飽和結合を有する重合性化合物に該光重合開始剤を含有させてなる感光性組成物、及び該感光性組成物の硬化物に関する。 The present invention relates to a novel oxime ester compound useful as a photopolymerization initiator for use in a photosensitive composition, a photopolymerization initiator containing the compound, a polymerizable compound having an ethylenically unsaturated bond, and the photopolymerization initiator. And a cured product of the photosensitive composition.
　感光性組成物は、エチレン性不飽和結合を有する重合性化合物に光重合開始剤を加えたものであり、エネルギー線（光）を照射することによって重合硬化させることができるため、光硬化性インキ、感光性印刷版、各種フォトレジスト等に用いられている。 The photosensitive composition is obtained by adding a photopolymerization initiator to a polymerizable compound having an ethylenically unsaturated bond, and can be polymerized and cured by irradiating energy rays (light). It is used for photosensitive printing plates and various photoresists.
　上記感光性組成物に用いられる光重合開始剤として、特許文献１～３には、オキシムエステル化合物が提案されている。
　しかし、特許文献１～３に記載のオキシムエステル化合物のうち、感度が満足できるオキシムエステル化合物は、可視光領域の透過率が低く、カラーフィルタで所望する色が得られないという問題（特に、保護膜のような透明性が求められる用途に使用する感光性組成物や、青色の顔料又は色素を用いたカラーフィルタ向けレジストでは、３８０～４５０ｎｍに吸収を持つ化合物が混在すると明度、色純度が低下する）があり、また、可視光領域の透過率が高いオキシムエステル化合物は、感度が十分満足できるものではないという問題があり、両特性を兼ね備える光重合開始剤が求められていた。
　また、カラーフィルタ等に用いられる色材を含有する着色アルカリ現像性感光性樹脂組成物は高感度であることが求められ、レジスト中における光重合開始剤を高濃度にする必要があった。しかし、高濃度の光重合開始剤は、現像性の悪化による残渣の発生や、昇華物によるフォトマスクや加熱炉の汚染等の原因となっていた。 As photopolymerization initiators used in the photosensitive composition, Patent Documents 1 to 3 propose oxime ester compounds.
However, among the oxime ester compounds described in Patent Documents 1 to 3, the oxime ester compound having satisfactory sensitivity has a problem of low transmittance in the visible light region and a desired color cannot be obtained with a color filter (particularly, protection). In photosensitive compositions used for applications where transparency is required, such as films, and resists for color filters using blue pigments or dyes, brightness and color purity decrease when compounds having absorption at 380 to 450 nm are mixed. The oxime ester compound having a high visible light transmittance has a problem that the sensitivity is not sufficiently satisfactory, and a photopolymerization initiator having both characteristics has been demanded.
In addition, the colored alkali-developable photosensitive resin composition containing a color material used for a color filter or the like is required to have high sensitivity, and the photopolymerization initiator in the resist needs to have a high concentration. However, a high concentration photopolymerization initiator has caused residues due to deterioration of developability, contamination of the photomask and heating furnace due to sublimation, and the like.
特開２０００－８００６８号公報Japanese Unexamined Patent Publication No. 2000-80068 特開２００１－２３３８４２号公報JP 2001-233842 A 特許第３８６０１７０号公報Japanese Patent No. 3860170
　解決しようとする問題点は、満足できる感度を有し、且つ可視光領域の透過率が高く、昇華性の低い光重合開始剤がこれまでなかったということである。 The problem to be solved is that there has never been a photopolymerization initiator having satisfactory sensitivity, high transmittance in the visible light region, and low sublimation.
　従って、本発明の目的は、安定性に優れ、低昇華性であり、現像性に優れ、可視光領域の透過率が高く、３６５ｎｍ等の近紫外光を効率よく吸収し活性化される高感度の光重合開始剤を提供することにある。 Therefore, the object of the present invention is high sensitivity that is excellent in stability, low sublimation, excellent developability, high transmittance in the visible light region, and efficiently absorbs near UV light such as 365 nm and is activated. It is in providing the photoinitiator of this.
　本発明者等は、鋭意検討した結果、光重合開始剤として用いる化合物を、樹脂組成物としたときに樹脂等と反応させるか、エネルギー線（光）照射時に樹脂等と反応させると、樹脂等と反応せずに化合物そのままの状態で存在する場合よりも低昇華性となることを知見した。 As a result of intensive studies, the present inventors have made the compound used as a photopolymerization initiator react with a resin or the like when it is made into a resin composition, or react with a resin or the like when irradiated with energy rays (light). It has been found that the sublimation property is lower than that in the case where the compound exists as it is without reacting with.
　本発明は、上記知見に基づきなされたもので、下記一般式（１）で表されるオキシムエステル化合物、及び該化合物を含有してなる光重合開始剤を提供するものである。 The present invention has been made on the basis of the above findings, and provides an oxime ester compound represented by the following general formula (1) and a photopolymerization initiator containing the compound.
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、それぞれ独立に、Ｒ11、ＯＲ11、ＣＯＯＲ11、ＳＲ11、ＳＯ2Ｒ11、ＣＯＮＲ12Ｒ13又はＣＮを表し、
　Ｒ11、Ｒ12及びＲ13は、それぞれ独立に、水素原子、又は炭素原子数１～２０のアルキル基、炭素原子数６～３０のアリール基、炭素原子数７～３０のアリールアルキル基若しくは炭素原子数２～２０の複素環基である置換基を表し、
　Ｒ11、Ｒ12及びＲ13で表わされる置換基の水素原子は、更にＯＲ21、ＣＯＲ21、ＳＲ21、ＮＲ22Ｒ23、ＣＯＮＲ22Ｒ23、－ＮＲ22－ＯＲ23、－ＮＲ22ＣＯ－ＯＣＯＲ23、－Ｃ（＝Ｎ－ＯＲ21）－Ｒ22、－Ｃ（＝Ｎ－ＯＣＯＲ21）－Ｒ22、ＣＮ、ハロゲン原子、－ＣＯＯＲ21、－ＣＲ21＝ＣＲ22Ｒ23、－ＣＯ－ＣＲ21＝ＣＲ22Ｒ23、－Ｏ－ＣＯ－ＣＲ21＝ＣＲ22Ｒ23、－Ｎ＝Ｃ＝Ｏ又はエポキシ基で置換されていてもよく、
　Ｒ21、Ｒ22及びＲ23は、それぞれ独立に、水素原子、又は炭素原子数１～２０のアルキル基、炭素原子数６～３０のアリール基、炭素原子数７～３０のアリールアルキル基若しくは炭素原子数２～２０の複素環基である置換基を表し、
　Ｒ21、Ｒ22及びＲ23で表される置換基の水素原子は、更に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てもよく、
　Ｒ11、Ｒ12、Ｒ13、Ｒ21、Ｒ22及びＲ23で表される置換基のアルキレン部分は、－Ｏ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ24－、－ＮＲ24ＣＯＯ－、－ＯＣＯＮＲ24－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又は－ＣＳＯ－により１～５回中断されていてもよく、
　Ｒ24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の複素環基を表し、
　Ｒ11、Ｒ12、Ｒ13、Ｒ21、Ｒ22及びＲ23で表される置換基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、また、Ｒ12とＲ13及びＲ22とＲ23はそれぞれ一緒になって環を形成していてもよく、
　Ｘは、酸素原子、硫黄原子、セレン原子、ＣＲ31Ｒ32、ＣＯ、ＮＲ33又はＰＲ34を表し、
　Ｒ31、Ｒ32、Ｒ33及びＲ34は、それぞれ独立に、水素原子、又は炭素原子数１～２０のアルキル基、炭素原子数６～３０のアリール基若しくは炭素原子数７～３０のアリールアルキル基である置換基を表し、
　Ｒ31、Ｒ32、Ｒ33及びＲ34で表される置換基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、Ｒ31、Ｒ32、Ｒ33及びＲ34で表される置換基のアルキル末端は不飽和結合であってもよく、Ｒ31、Ｒ32、Ｒ33及びＲ34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てもよく、
　ａは、０～４の整数を表し、
　ｂは、１～５の整数を表し、
　Ｒ4の少なくとも一つは、－ＣＲ21＝ＣＲ22Ｒ23、－ＣＯ－ＣＲ21＝ＣＲ22Ｒ23、－Ｏ－ＣＯ－ＣＲ21＝ＣＲ22Ｒ23、－Ｎ＝Ｃ＝Ｏ又はエポキシ基を有する基である。）
Figure JPOXMLDOC01-appb-C000002
 (Wherein R 1 , R 2 , R 3 and R 4 each independently represents R 11 , OR 11 , COOR 11 , SR 11 , SO 2 R 11 , CONR 12 R 13 or CN;
R 11 , R 12 and R 13 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 substituent which is a heterocyclic group having 2 to 20 atoms;
The hydrogen atom of the substituent represented by R 11 , R 12 and R 13 is further OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , —NR 22 —OR 23 , —NR 22 CO—. OCOR 23 , —C (═N—OR 21 ) —R 22 , —C (═N—OCOR 21 ) —R 22 , CN, halogen atom, —COOR 21 , —CR 21 ═CR 22 R 23 , —CO— CR 21 ═CR 22 R 23 , —O—CO—CR 21 ═CR 22 R 23 , —N═C═O or an epoxy group may be substituted,
R 21 , R 22 and R 23 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 substituent which is a heterocyclic group having 2 to 20 atoms;
The hydrogen atom of the substituent represented by R 21 , R 22 and R 23 may be further substituted with CN, a halogen atom, a hydroxyl group or a carboxyl group,
The alkylene part of the substituent represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 is —O—, —S—, —COO—, —OCO—, —NR 24 —, — May be interrupted 1 to 5 times by NR 24 COO—, —OCONR 24 —, —SCO—, —COS—, —OCS— or —CSO—,
R 24 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 group having 2 to 20 carbon atoms. ,
Alkyl moiety of the substituents represented by R 11, R 12, R 13 , R 21, R 22 and R 23, there may be branched side chain, may be a cyclic alkyl, and the R 12 R 13 and R 22 and R 23 may be combined to form a ring,
X represents an oxygen atom, a sulfur atom, a selenium atom, CR 31 R 32 , CO, NR 33 or PR 34 ;
R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl having 7 to 30 carbon atoms. Represents a substituent that is a group,
The alkyl part of the substituent represented by R 31 , R 32 , R 33 and R 34 may have a branched side chain or may be a cyclic alkyl. R 31 , R 32 , R 33 and R 34 The alkyl terminal of the substituent represented by the above formula may be an unsaturated bond, and R 31 , R 32 , R 33 and R 34 each independently form a ring together with one of the adjacent benzene rings. May be formed,
a represents an integer of 0 to 4,
b represents an integer of 1 to 5,
At least one of R 4 is —CR 21 ═CR 22 R 23 , —CO—CR 21 ═CR 22 R 23 , —O—CO—CR 21 ═CR 22 R 23 , —N═C═O or an epoxy group It is group which has. )
　また、本発明は、上記光重合開始剤、及びエチレン性不飽和結合を有する重合性化合物を含有してなる感光性組成物を提供するものである。
　また、本発明は、上記感光性組成物に、アルカリ現像性を付与する化合物を含有させてなるアルカリ現像性感光性樹脂組成物を提供するものである。
　また、本発明は、上記アルカリ現像性感光性樹脂組成物に、更に色材を含有させてなる着色アルカリ現像性感光性樹脂組成物を提供するものである。 The present invention also provides a photosensitive composition comprising the photopolymerization initiator and a polymerizable compound having an ethylenically unsaturated bond.
Moreover, this invention provides the alkali developable photosensitive resin composition formed by making the said photosensitive composition contain the compound which provides alkali developability.
The present invention also provides a colored alkali-developable photosensitive resin composition obtained by further adding a coloring material to the alkali-developable photosensitive resin composition.
　また、本発明は、上記感光性組成物、上記アルカリ現像性感光性樹脂組成物又は上記着色アルカリ現像性感光性樹脂組成物に、エネルギー線を照射してなる硬化物を提供するものである。 The present invention also provides a cured product obtained by irradiating the photosensitive composition, the alkali-developable photosensitive resin composition, or the colored alkali-developable photosensitive resin composition with energy rays.
　本発明のオキシムエステル化合物は、可視光領域の透過率が高く、３６５ｎｍ（ｉ線）等の輝線に対して効率よくラジカルを発生させ、光重合開始剤として有用なものである。また、本発明のオキシムエステル化合物は、光重合開始剤として樹脂組成物に配合して用いると、重合性基を有する樹脂と反応するため、昇華物が少なく、さらに硬化物の耐熱性を向上させることができる。 The oxime ester compound of the present invention has a high transmittance in the visible light region and efficiently generates radicals with respect to bright lines such as 365 nm (i-line) and is useful as a photopolymerization initiator. In addition, when the oxime ester compound of the present invention is used as a photopolymerization initiator in a resin composition, it reacts with a resin having a polymerizable group, so that there are few sublimates and further improves the heat resistance of the cured product. be able to.
　以下、本発明のオキシムエステル化合物及び該化合物を含有する光重合開始剤について詳細に説明する。 Hereinafter, the oxime ester compound of the present invention and the photopolymerization initiator containing the compound will be described in detail.
　本発明のオキシムエステル化合物は、上記一般式（１）で表される新規化合物である。該オキシムエステル化合物には、オキシムの二重結合による２つの幾何異性体が存在するが、本発明はこれらを区別するものではない。
　即ち、本明細書において、上記一般式（１）、並びに後述する上記一般式（１）で表される化合物の好ましい形態を表す一般式（２）、及び例示化合物Ｎｏ．１～Ｎｏ．３９の化学構造式は、２つの幾何異性体のうちの一方のみを示しているが、本発明のオキシムエステル化合物は、これらの式で示される幾何異性体に限定されず、もう一方の幾何異性体でもよいし、２つの幾何異性体の混合物であってもよい。 The oxime ester compound of the present invention is a novel compound represented by the general formula (1). The oxime ester compound has two geometric isomers due to an oxime double bond, but the present invention does not distinguish them.
That is, in this specification, the general formula (1), the general formula (2) representing a preferred form of the compound represented by the general formula (1) described later, and the exemplified compound Nos. 1-No. Although the chemical structural formula of 39 shows only one of the two geometric isomers, the oxime ester compound of the present invention is not limited to the geometric isomer represented by these formulas, and the other geometric isomer. Or a mixture of two geometric isomers.
　上記一般式（１）中の、Ｒ11、Ｒ12、Ｒ13、Ｒ21、Ｒ22、Ｒ23、Ｒ24、Ｒ31、Ｒ32、Ｒ33、Ｒ34で表される炭素数１～２０のアルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ－ブチル、ｔ－ブチル、アミル、イソアミル、ｔ－アミル、ヘキシル、ヘプチル、オクチル、イソオクチル、２－エチルヘキシル、ｔ－オクチル、ノニル、イソノニル、デシル、イソデシル、ウンデシル、ドデシル、テトラデシル、ヘキサデシル、オクタデシル、イコシル、シクロペンチル、シクロヘキシル、シクロヘキシルメチル等が挙げられる。 1 to 20 carbon atoms represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , R 31 , R 32 , R 33 , R 34 in the general formula (1). As the alkyl group, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-butyl Examples include octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl and the like.
　上記一般式（１）中の、Ｒ11、Ｒ12、Ｒ13、Ｒ21、Ｒ22、Ｒ23、Ｒ24、Ｒ31、Ｒ32、Ｒ33、Ｒ34で表される炭素原子数６～３０のアリール基としては、例えば、フェニル、トリル、キシリル、エチルフェニル、ナフチル、アンスリル、フェナンスレニル、上記アルキル基で１つ以上置換されたフェニル、ビフェニリル、ナフチル、アンスリル等が挙げられる。 6 to 6 carbon atoms represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , R 31 , R 32 , R 33 , R 34 in the general formula (1) Examples of 30 aryl groups include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, and phenyl, biphenylyl, naphthyl, anthryl substituted with one or more of the above alkyl groups.
　上記一般式（１）中の、Ｒ11、Ｒ12、Ｒ13、Ｒ21、Ｒ22、Ｒ23、Ｒ24、Ｒ31、Ｒ32、Ｒ33、Ｒ34で表される炭素原子数７～３０のアリールアルキル基としては、例えば、ベンジル、α－メチルベンジル、α、α－ジメチルベンジル、フェニルエチル等が挙げられる。 In the general formula (1), 7 to 7 carbon atoms represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , R 31 , R 32 , R 33 , R 34 Examples of the 30 arylalkyl group include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and the like.
　上記一般式（１）中の、Ｒ11、Ｒ12、Ｒ13、Ｒ21、Ｒ22、Ｒ23、Ｒ24で表される置換されていてもよい炭素原子数２～２０の複素環基としては、例えば、ピリジル、ピリミジル、フリル、チエニル、テトラヒドロフリル、ジオキソラニル、ベンゾオキサゾール－２－イル、テトラヒドロピラニル、ピロリジル、イミダゾリジル、ピラゾリジル、チアゾリジル、イソチアゾリジル、オキサゾリジル、イソオキサゾリジル、ピペリジル、ピペラジル、モルホリニル等の５～７員複素環が好ましく挙げられる。 As the optionally substituted heterocyclic group having 2 to 20 carbon atoms represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 in the general formula (1) Is, for example, pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl Preferred examples thereof include 5- to 7-membered heterocycles such as
　上記一般式（１）中、Ｒ12とＲ13、Ｒ22とＲ23が一緒になって形成しうる環及びＲ31、Ｒ32、Ｒ33及びＲ34が隣接するベンゼン環と一緒になって形成しうる環としては、例えば、シクロペンタン環、シクロヘキサン環、シクロペンテン環、ベンゼン環、ピペリジン環、モルホリン環、ラクトン環、ラクタム環等の５～７員環が好ましく挙げられる。 In the general formula (1), R 12 and R 13 , R 22 and R 23 can be formed together, and R 31 , R 32 , R 33 and R 34 are combined with the adjacent benzene ring. Preferred examples of the ring that can be formed include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring.
　また、上記一般式（１）中、Ｒ11、Ｒ12、Ｒ13、Ｒ21、Ｒ22、Ｒ23を置換してもよい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。 In the general formula (1), examples of the halogen atom that may substitute R 11 , R 12 , R 13 , R 21 , R 22 , and R 23 include fluorine, chlorine, bromine, and iodine.
　また、Ｒ11、Ｒ12、Ｒ13、Ｒ21、Ｒ22、Ｒ23で表される置換基のアルキレン部分は、－Ｏ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ24－、－ＮＲ24ＣＯＯ－、－ＯＣＯＮＲ24－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又は－ＣＳＯ－により１～５回中断されていてもよく、この時中断する結合基は１種又は２種以上の基でもよく、連続して中断しうる基の場合は２つ以上連続して中断してもよい。また、上記置換基のアルキル部分は分岐側鎖があってもよく、環状アルキルであってもよい。 The alkylene moiety of the substituent represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 is —O—, —S—, —COO—, —OCO—, —NR 24 —. , —NR 24 COO—, —OCONR 24 —, —SCO—, —COS—, —OCS—, or —CSO— may be interrupted 1 to 5 times. Two or more groups may be used, and in the case of a group that can be interrupted continuously, two or more groups may be interrupted continuously. The alkyl part of the substituent may have a branched side chain or may be a cyclic alkyl.
　本発明のオキシムエステル化合物の中でも、上記一般式（１）において、Ｘが硫黄原子又はＮＲ33であり、Ｒ33は分岐側鎖があってもよく、環状アルキルであってもよい炭素原子数１～２０のアルキル基である化合物；下記一般式（２）で表される化合物は、特に感度が高く、また製造が容易であるので好ましい。 Among the oxime ester compounds of the present invention, in the above general formula (1), X is a sulfur atom or NR 33 , R 33 may have a branched side chain, and may be a cyclic alkyl. A compound having an alkyl group of ˜20; a compound represented by the following general formula (2) is particularly preferred because of its high sensitivity and easy production.
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｘ及びａは上記一般式（１）と同じであり、Ｒ5は上記一般式（１）におけるＲ4と同じであり、少なくともＲ5は－ＣＲ21＝ＣＲ22Ｒ23、－ＣＯ－ＣＲ21＝ＣＲ22Ｒ23、－Ｏ－ＣＯ－ＣＲ21＝ＣＲ22Ｒ23、－Ｎ＝Ｃ＝Ｏ及びエポキシ基から選ばれる構造を少なくとも一つ有する基であり、ｃは０～４の整数を表す。）
Figure JPOXMLDOC01-appb-C000003
 (Wherein R 1 , R 2 , R 3 , R 4 , X and a are the same as in the above general formula (1), R 5 is the same as R 4 in the above general formula (1), and at least R 5 represents at least a structure selected from —CR 21 ═CR 22 R 23 , —CO—CR 21 ═CR 22 R 23 , —O—CO—CR 21 ═CR 22 R 23 , —N═C═O and an epoxy group. And c represents an integer of 0 to 4.)
　上記一般式（２）で表される化合物の中でも、Ｒ5が、－ＣＲ21＝ＣＲ22Ｒ23、－ＣＯ－ＣＲ21＝ＣＲ22Ｒ23又は－Ｏ－ＣＯ－ＣＲ21＝ＣＲ22Ｒ23を有する化合物は、反応性が高く、不飽和二重結合を有する樹脂組成物と組み合わせることで高い耐熱性を発現するため更に好ましく、また、Ｒ5が－Ｎ＝Ｃ＝Ｏ又はエポキシ基を有する化合物は、アルコール、アミン、アミドなどの活性水素を有する樹脂と組み合わせることで高い耐熱性を発現するため同様に更に好ましい。 Among the compounds represented by the general formula (2), R 5 is —CR 21 ═CR 22 R 23 , —CO—CR 21 ═CR 22 R 23, or —O—CO—CR 21 ═CR 22 R 23. Is more preferable because it has high reactivity and exhibits high heat resistance when combined with a resin composition having an unsaturated double bond, and R 5 has —N═C═O or an epoxy group. The compound is also more preferable because it exhibits high heat resistance when combined with a resin having active hydrogen such as alcohol, amine, amide and the like.
　また、本発明の効果をより高く奏させる上で、上記一般式（１）及び（２）中のＲ1及びＲ2は、炭素原子数１～２０（特に炭素原子数１～１０、とりわけ炭素原子数１～４）のアルキル基であることが好ましく、上記一般式（１）及び（２）中のａは０～１であることが好ましく、上記一般式（１）中のｂは１～２であることが好ましく、上記一般式（２）中のｃは０～１であることが好ましい。 In order to further enhance the effects of the present invention, R 1 and R 2 in the above general formulas (1) and (2) may have 1 to 20 carbon atoms (especially 1 to 10 carbon atoms, especially carbon atoms). It is preferably an alkyl group having 1 to 4 atoms, a in the general formulas (1) and (2) is preferably 0 to 1, and b in the general formula (1) is 1 to 2 is preferable, and c in the general formula (2) is preferably 0 to 1.
　本発明の効果を更に高く奏させる上で、上記Ｒ3は水素原子であることが好ましい。同様の理由で、上記Ｘは硫黄原子であることが好ましい。同様の理由で、上記Ｒ4は、ＯＲ11又はＣＯＯＲ11であり、且つ該Ｒ11が炭素原子数１～２０、特に炭素原子数１～１０、とりわけ炭素原子数１～６のアルキル基であり、該Ｒ11が有する水素原子のうちの少なくとも一つが－ＯＣＯ－ＣＲ21＝ＣＲ22Ｒ23に置換されており、該－ＯＣＯ－ＣＲ21＝ＣＲ22Ｒ23において、Ｒ21が水素原子又はメチル基であり、Ｒ22及びＲ23は水素原子であることが好ましい。この場合において、－ＯＣＯ－ＣＲ21＝ＣＲ22Ｒ23は、ＯＲ11のＲ11が有する水素原子を置換している場合には該ＯＲ11の酸素原子から最も遠い位置にある炭素原子に結合していることが好ましく、ＣＯＯＲ11のＲ11が有する水素原子を置換している場合には、該ＣＯＯＲ11のＣＯＯ基から最も遠い位置にある炭素原子に結合していることが好ましい。また、ｂが１であり、Ｒ4は、Ｘが結合している炭素原子に対してパラ位に結合していることが好ましい。 In order to further enhance the effects of the present invention, R 3 is preferably a hydrogen atom. For the same reason, X is preferably a sulfur atom. For the same reason, R 4 is OR 11 or COOR 11 , and R 11 is an alkyl group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, especially 1 to 6 carbon atoms. at least one of the hydrogen atoms to which the R 11 has has been substituted with a -OCO-CR 21 = CR 22 R 23, in the -OCO-CR 21 = CR 22 R 23, R 21 is a hydrogen atom or methyl And R 22 and R 23 are preferably hydrogen atoms. In this case, —OCO—CR 21 ═CR 22 R 23 is bonded to the carbon atom farthest from the oxygen atom of OR 11 when the hydrogen atom of R 11 of OR 11 is substituted. In the case where the hydrogen atom of R 11 of COOR 11 is substituted, it is preferably bonded to the carbon atom located farthest from the COO group of COOR 11 . Further, b is 1, and R 4 is preferably bonded to the para position with respect to the carbon atom to which X is bonded.
　上記一般式（１）で表される本発明のオキシムエステル化合物の好ましい具体例としては、以下の化合物Ｎｏ．１～Ｎｏ．３９の化合物が挙げられる。ただし、本発明は以下の化合物により何等制限を受けるものではない。 As preferred specific examples of the oxime ester compound of the present invention represented by the above general formula (1), the following compound No. 1-No. 39 compounds are mentioned. However, the present invention is not limited by the following compounds.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　上記一般式（１）で表される本発明のオキシムエステル化合物は、特に限定されないが、例えば、特開２０００－８００６８号公報に記載の方法に準じて製造できる。方法の一つとして、下記反応式１に従って、以下の方法により製造することができる。まず、ケトン体をルイス酸存在下で（メタ）アクリル酸と反応させることにより、（メタ）アクリレート体を得る。次に、該（メタ）アクリレート体と亜硝酸エステルを塩酸存在下で反応させ、続いて酸無水物又は酸クロリドと反応させて、上記一般式（１）で表される本発明のオキシムエステル化合物を得る。下記反応式１にはＸが硫黄原子の場合を記載しているが、Ｘが酸素原子、セレン原子、ＣＲ31Ｒ32、ＮＲ33又はＰＲ34であるものも、上記の方法に準じて製造することができる。 The oxime ester compound of the present invention represented by the general formula (1) is not particularly limited, but can be produced, for example, according to the method described in JP-A No. 2000-80068. As one of the methods, it can be produced by the following method according to the following reaction formula 1. First, a (meth) acrylate body is obtained by reacting a ketone body with (meth) acrylic acid in the presence of a Lewis acid. Next, the oxime ester compound of the present invention represented by the above general formula (1) is obtained by reacting the (meth) acrylate body with a nitrite in the presence of hydrochloric acid, and subsequently reacting with an acid anhydride or acid chloride. Get. Although the following reaction formula 1 describes the case where X is a sulfur atom, those in which X is an oxygen atom, a selenium atom, CR 31 R 32 , NR 33 or PR 34 are also produced according to the above method. be able to.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　以上説明した本発明の新規オキシムエステル化合物は、光重合開始剤として有用である。 The novel oxime ester compound of the present invention described above is useful as a photopolymerization initiator.
　本発明の光重合開始剤は、本発明のオキシムエステル化合物を少なくとも一種含有するものであり、特にエチレン性不飽和結合を有する重合性化合物の光重合開始剤として有用なものである。本発明の光重合開始剤中における本発明のオキシムエステル化合物の含有量は、好ましくは３０～１００質量％、より好ましくは５０～１００質量％である。本発明の光重合開始剤は、本発明のオキシムエステル化合物の他に、他の光重合開始剤を含有してもよい。他の光重合開始剤としては、従来既知の化合物を用いることが可能であり、例えば、ベンゾフェノン、フェニルビフェニルケトン、１－ヒドロキシ－１－ベンゾイルシクロヘキサン、ベンゾイン、ベンジルジメチルケタール、１－ベンジル－１－ジメチルアミノ－１－（４'－モルホリノベンゾイル）プロパン、２－モルホリル－２－（４'－メチルメルカプト）ベンゾイルプロパン、チオキサントン、１－クロル－４－プロポキシチオキサントン、イソプロピルチオキサントン、ジエチルチオキサントン、エチルアントラキノン、４－ベンゾイル－４'－メチルジフェニルスルフィド、ベンゾインブチルエーテル、２－ヒドロキシ－２－ベンゾイルプロパン、２－ヒドロキシ－２－（４'－イソプロ ピル）ベンゾイルプロパン、４－ブチルベンゾイルトリクロロメタン、４－フェノキシベンゾイルジクロロメタン、ベンゾイル蟻酸メチル、１，７－ビス（９'－アクリジニル）ヘプタン、９－ｎ－ブチル－３，６－ビス（２'－モルホリノイソブチロイル）カルバゾール、２－メチル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－フェニル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－ナフチル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２，２－ビス（２－クロロフェニル）－４，５，４’，５’－テトラフェニル－１－２’－ビイミダゾール、４、４－アゾビスイソブチロニトリル、トリフェニルホスフィン、カンファーキノン、Ｎ－１４１４、Ｎ－１７１７、Ｎ－１９１９、ＰＺ－４０８、ＮＣＩ－８３１、ＮＣＩ－９３０（（株）ＡＤＥＫＡ社製）、ＩＲＧＡＣＵＲＥ３６９、ＩＲＧＡＣＵＲＥ９０７、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０１、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０２（ＢＡＳＦ社製）、過酸化ベンゾイル、下記一般式（４）～（６）で表される化合物等が挙げられる。これらの本発明のオキシムエステル化合物以外の光重合開始剤を使用する場合、１種又は２種以上を組み合わせて用いることができる。 The photopolymerization initiator of the present invention contains at least one oxime ester compound of the present invention, and is particularly useful as a photopolymerization initiator for a polymerizable compound having an ethylenically unsaturated bond. The content of the oxime ester compound of the present invention in the photopolymerization initiator of the present invention is preferably 30 to 100% by mass, more preferably 50 to 100% by mass. The photopolymerization initiator of the present invention may contain other photopolymerization initiator in addition to the oxime ester compound of the present invention. As other photopolymerization initiators, conventionally known compounds can be used. For example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzoin, benzyldimethyl ketal, 1-benzyl-1- Dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4'-isopropyl) benzoylpropane, 4-butylben Yltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) -s -Triazine, 2,2-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1-2'-biimidazole, 4,4-azobisisobutyronitrile, triphenylphosphine, Camphorquinone, N-1414, N-1717, N-1919, PZ-408, NCI-831, NCI-930 (AD) EGA), IRGACURE 369, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02 (BASF), benzoyl peroxide, compounds represented by the following general formulas (4) to (6), and the like. When using photoinitiators other than these oxime ester compounds of this invention, it can be used 1 type or in combination of 2 or more types.
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ1、Ｒ2及びＲ33は、上記一般式（１）と同じであり、Ｙ3は、ハロゲン原子又はアルキル基を表し、ｎは０～５である。）
Figure JPOXMLDOC01-appb-C000010
 (In the formula, R 1 , R 2 and R 33 are the same as those in the general formula (1), Y 3 represents a halogen atom or an alkyl group, and n is 0 to 5.)
Figure JPOXMLDOC01-appb-C000011
 （式中、Ｒ1、Ｒ2及びＲ33は、上記一般式（１）と同じであり、Ｙ3及びｎは上記一般式 （４）と同じであり、Ｒ’1及びＲ’2は、Ｒ1及びＲ2と同じであり、Ｒ’33はＲ33と同じであり、Ｙ’3はＹ3と同じであり、Ｒ8はジオール残基又はジチオール残基を表し、Ｚ5は酸素原子又は硫黄原子を表す。）
Figure JPOXMLDOC01-appb-C000011
 (Wherein R 1 , R 2 and R 33 are the same as those in the general formula (1), Y 3 and n are the same as those in the general formula (4), and R ′ 1 and R ′ 2 are R 1 and R 2 are the same, R ′ 33 is the same as R 33 , Y ′ 3 is the same as Y 3 , R 8 is a diol residue or a dithiol residue, Z 5 is an oxygen atom Or represents a sulfur atom.)
Figure JPOXMLDOC01-appb-C000012
 （式中、Ｒ1、Ｒ2及びＲ33は、上記一般式（１）と同じであり、Ｙ3及びｎは、上記一般式（４）と同じであり、Ｚ6は酸素原子、硫黄原子又はセレン原子を表し、Ａは複素環基を表し、ｔは０～５の整数であり、ｕは０又は１である。）
Figure JPOXMLDOC01-appb-C000012
 (In the formula, R 1 , R 2 and R 33 are the same as in the general formula (1), Y 3 and n are the same as in the general formula (4), and Z 6 is an oxygen atom or a sulfur atom. Or represents a selenium atom, A represents a heterocyclic group, t is an integer of 0 to 5, and u is 0 or 1.)
　次に、本発明の感光性組成物について詳細に説明する。
　本発明の感光性組成物は、必須成分として、（Ａ）本発明の光重合開始剤及び（Ｂ）エチレン性不飽和結合を有する重合性化合物を含有し、任意成分として、（Ｃ）無機化合物、（Ｄ）色材、溶媒等の成分を組み合わせて含有するものである。 Next, the photosensitive composition of the present invention will be described in detail.
The photosensitive composition of the present invention contains (A) a photopolymerization initiator of the present invention and (B) a polymerizable compound having an ethylenically unsaturated bond as essential components, and (C) an inorganic compound as an optional component. (D) It contains a combination of components such as a coloring material and a solvent.
　本発明の感光性組成物において、（Ａ）本発明の光重合開始剤の含有量は特に限定されるものではないが、本発明の感光性組成物中における本発明のオキシムエステル化合物の含有量が、（Ｂ）エチレン性不飽和結合を有する重合性化合物１００質量部に対して、好ましくは１～７０質量部、より好ましくは１～５０質量部、最も好ましくは５～３０質量部となるようにする。 In the photosensitive composition of the present invention, (A) the content of the photopolymerization initiator of the present invention is not particularly limited, but the content of the oxime ester compound of the present invention in the photosensitive composition of the present invention. However, the amount is preferably 1 to 70 parts by weight, more preferably 1 to 50 parts by weight, and most preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymerizable compound (B) having an ethylenically unsaturated bond. To.
　上記（Ｂ）エチレン性不飽和結合を有する重合性化合物としては、特に限定されず、従来、感光性組成物に用いられているものを用いることができるが、例えば、エチレン、プロピレン、ブチレン、イソブチレン、塩化ビニル、塩化ビニリデン、フッ化ビニリデン、テトラフルオロエチレン等の不飽和脂肪族炭化水素；(メタ)アクリル酸、α―クロルアクリル酸、イタコン酸、マレイン酸、シトラコン酸、フマル酸、ハイミック酸、クロトン酸、イソクロトン酸、ビニル酢酸、アリル酢酸、桂皮酸、ソルビン酸、メサコン酸、コハク酸モノ［２－（メタ）アクリロイロキシエチル］、フタル酸モノ［２－（メタ）アクリロイロキシエチル］、ω－カルボキシポリカプロラクトンモノ（メタ）アクリレート等の両末端にカルボキシ基と水酸基とを有するポリマーのモノ（メタ）アクリレート；ヒドロキシエチル（メタ）アクリレート・マレート、ヒドロキシプロピル（メタ）アクリレート・マレート、ジシクロペンタジエン・マレート或いは1個のカルボキシル基と２個以上の(メタ)アクリロイル基とを有する多官能（メタ）アクリレート等の不飽和多塩基酸；(メタ) アクリル酸－２－ヒドロキシエチル、（メタ）アクリル酸－２－ヒドロキシプロピル、（メタ）アクリル酸グリシジル、下記化合物Ｎｏ．Ａ１～Ｎｏ．Ａ４、（メタ）アクリル酸メチル、 （メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸－ｔ－ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ｎ－オクチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸ジメチルアミノメチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸アミノプロピル、（メタ）アクリル酸ジメチルアミノプロピル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸ポリ（エトキシ）エチル、（メタ）アクリル酸ブトキシエトキシエチル、（メタ）アクリル酸エチルヘキシル、（メタ）アクリル酸フェノキシエチル、（メタ）アクリル酸テトラヒドロフリル、（メタ）アクリル酸ビニル、（メタ）アクリル酸アリル、（メタ）アクリル酸ベンジル、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリシクロデカンジメチロールジ（メタ）アクリレート、トリ［（メタ）アクリロイルエチル］イソシアヌレート、ポリエステル（メタ）アクリレートオリゴマー等の不飽和一塩基酸及び多価アルコール又は多価フェノールのエステル；（メタ）アクリル酸亜鉛、（メタ）アクリル酸マグネシウム等の不飽和多塩基酸の金属塩；マレイン酸無水物、イタコン酸無水物、シトラコン酸無水物、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸、５－（２，５－ジオキソテトラヒドロフリル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物、トリアルキルテトラヒドロ無水フタル酸－無水マレイン酸付加物、ドデセニル無水コハク酸、無水メチルハイミック酸等の不飽和多塩基酸の酸無水物；（メタ）アクリルアミド、メチレンビス－（メタ）アクリルアミド、ジエチレントリアミントリス（メタ）アクリルアミド、キシリレンビス（メタ）アクリルアミド、α－クロロアクリルアミド、Ｎ－２－ヒドロキシエチル（メタ）アクリルアミド等の不飽和一塩基酸及び多価アミンのアミド；アクロレイン等の不飽和アルデヒド；（メタ）アクリロニトリル、α－クロロアクリロニトリル、シアン化ビニリデン、シアン化アリル等の不飽和ニトリル；スチレン、４－メチルスチレン、４－エチルスチレン、４－メトキシスチレン、４－ヒドロキシスチレン、４－クロロスチレン、ジビニルベンゼン、ビニルトルエン、ビニル安息香酸、ビニルフェノール、ビニルスルホン酸、４－ビニルベンゼンスルホン酸、ビニルベンジルメチルエーテル、ビニルベンジルグリシジルエーテル等の不飽和芳香族化合物；メチルビニルケトン等の不飽和ケトン；ビニルアミン、アリルアミン、Ｎ－ビニルピロリドン、ビニルピペリジン等の不飽和アミン化合物；アリルアルコール、クロチルアルコール等のビニルアルコール；ビニルメチルエーテル、ビニルエチルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル、アリルグリシジルエーテル等のビニルエーテル；マレイミド、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等の不飽和イミド類；インデン、１－メチルインデン等のインデン類；１，３－ブタジエン、イソプレン、クロロプレン等の脂肪族共役ジエン類；ポリスチレン、ポリメチル（メタ）アクリレート、ポリ－ｎ－ブチル（メタ）アクリレート、ポリシロキサン等の重合体分子鎖の末端にモノ（メタ）アクリロイル基を有するマクロモノマー類；ビニルクロリド、ビニリデンクロリド、ジビニルスクシナート、ジアリルフタラート、トリアリルホスファート、トリアリルイソシアヌラート、ビニルチオエーテル、ビニルイミダゾール、ビニルオキサゾリン、ビニルカルバゾール、ビニルピロリドン、ビニルピリジン、水酸基含有ビニルモノマー及びポリイソシアネート化合物のビニルウレタン化合物、水酸基含有ビニルモノマー及びポリエポキシ化合物のビニルエポキシ化合物が挙げられる。 The polymerizable compound having an ethylenically unsaturated bond (B) is not particularly limited, and those conventionally used in photosensitive compositions can be used. For example, ethylene, propylene, butylene, isobutylene can be used. , Vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene, and other unsaturated aliphatic hydrocarbons; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, highmic acid, Crotonic acid, isocrotonic acid, vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] , Carboxy-carboxycaprolactone mono (meth) acrylate, etc. Mono (meth) acrylate of polymer having hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or one carboxyl group and two or more (meth) acryloyl groups Unsaturated polybasic acids such as polyfunctional (meth) acrylates; (meth) (-2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate; A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (t-butyl) (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenylmaleimide, N -Unsaturated imides such as cyclohexylmaleimide; Indenes such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromolecules having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc .; vinyl chloride, vinylidene chloride, divinyls Cuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and vinyl isocyanate compounds of polyisocyanate compounds, hydroxyl groups Examples thereof include vinyl monomers containing vinyl monomers and polyepoxy compounds.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　また、（Ｂ）エチレン性不飽和結合を有する重合性化合物としては、アクリル酸エステルの共重合体や、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、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、エポキシアクリレート樹脂、下記一般式（３）で表されるエポキシ化合物等のエポキシ化合物に、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を用いることもできる。これらの中でも、下記一般式（３）で表されるエポキシ化合物等のエポキシ化合物に、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が好ましい。また、これらの化合物は、不飽和基を０．２～１．０当量含有していることが好ましい。 Examples of the polymerizable compound (B) having an ethylenically unsaturated bond include acrylic acid ester copolymers, phenol and / or cresol novolac epoxy resins, polyphenylmethane type epoxy resins having polyfunctional epoxy groups, and epoxy. Resins obtained by allowing an unsaturated monobasic acid to act on an acrylate resin or an epoxy compound such as an epoxy compound represented by the following general formula (3), and further causing a polybasic acid anhydride to act on the epoxy compound can also be used. Among these, a resin obtained by allowing an unsaturated monobasic acid to act on an epoxy compound such as an epoxy compound represented by the following general formula (3) and further causing a polybasic acid anhydride to act is preferable. Further, these compounds preferably contain 0.2 to 1.0 equivalent of unsaturated groups.
Figure JPOXMLDOC01-appb-C000017
 （式中、Ｘ1は直接結合、メチレン基、炭素原子数１～４のアルキリデン基、炭素原子数３～２０の脂環式炭化水素基、Ｏ、Ｓ、ＳＯ2、ＳＳ、ＳＯ、ＣＯ、ＯＣＯ又は下記式（ イ）、（ロ）若しくは（ハ）で表される置換基を表し、上記アルキリデン基はハロゲン原子で置換されていてもよく、Ｒ51、Ｒ52、Ｒ53及びＲ54は、それぞれ独立に、水素原子、炭素原子数１～５のアルキル基、炭素原子数１～８のアルコキシ基、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、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｍは０～１０の整数であり、ｍが０で無いときに存在する光学異性体は、どの異性体でもよい。）
Figure JPOXMLDOC01-appb-C000017
 (Wherein X 1 is a direct bond, methylene group, alkylidene group having 1 to 4 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, O, S, SO 2 , SS, SO, CO, OCO or a substituent represented by the following formula (I), (B) or (C), wherein the alkylidene group may be substituted with a halogen atom, and R 51 , R 52 , R 53 and R 54 are Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom, and the above alkyl group, alkoxy group and The alkenyl group may be substituted with a halogen atom, m is an integer of 0 to 10, and the optical isomer present when m is not 0 may be any isomer.)
Figure JPOXMLDOC01-appb-C000018
 （式中、Ｚ3は水素原子、炭素原子数１～１０のアルキル基若しくは炭素原子数１～１０ のアルコキシ基により置換されていてもよいフェニル基、又は炭素原子数１～１０のアルキル基若しくは炭素原子数１～１０のアルコキシ基により置換されていてもよい炭素原子数３～１０のシクロアルキル基を示し、Ｙ1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示し、上記アルキル基、アルコキシ基及びアルケニル基はハロゲン原子で置換されていてもよく、ｄは０～５の整数である。）
Figure JPOXMLDOC01-appb-C000018
 (Wherein Z 3 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group optionally substituted by an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, or A cycloalkyl group having 3 to 10 carbon atoms which may be substituted by an alkoxy group having 1 to 10 carbon atoms, Y 1 is an alkyl group having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms Group, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, wherein the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, and d is an integer of 0 to 5.)
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
 （式中、Ｙ2及びＺ4は、それぞれ独立して、ハロゲン原子で置換されていてもよい炭素原子数１～１０のアルキル基、ハロゲン原子で置換されていてもよい炭素原子数６～２０のアリール基、ハロゲン原子で置換されていてもよい炭素原子数６～２０のアリールオキシ基、ハロゲン原子で置換されていてもよい炭素原子数６～２０のアリールチオ基、ハロゲン原子で置換されていてもよい炭素原子数６～２０のアリールアルケニル基、ハロゲン原子で置換されていてもよい炭素原子数７～２０のアリールアルキル基、ハロゲン原子で置換されていてもよい炭素原子数２～２０の複素環基、又はハロゲン原子を表し、上記アルキル基及びアリールアルキル基中のアルキレン部分は、不飽和結合、－Ｏ－又は－Ｓ－で中断されていてもよく、Ｚ4は、隣接するＺ4同士で環を形成していてもよく、ｐは０～４の整数を表し、ｑは０～８の整数を表し、ｒは０～４の整数を表し、ｓは０～４の整数を表し、ｒとｓの数の合計は２～４の整数である。）
Figure JPOXMLDOC01-appb-C000020
 Wherein Y 2 and Z 4 are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 to 20 carbon atoms which may be substituted with a halogen atom. An aryloxy group having 6 to 20 carbon atoms which may be substituted with a halogen atom, an arylthio group having 6 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom An arylalkenyl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms that may be substituted with a halogen atom, or a complex having 2 to 20 carbon atoms that may be substituted with a halogen atom ring group, or a halogen atom, the alkylene moiety in the alkyl group and arylalkyl group, an unsaturated bond, may be interrupted by -O- or -S-, Z 4 , May form a ring with the adjacent Z 4 each other, p represents an integer of 0 to 4, q represents an integer of 0 to 8, r represents an integer of 0 to 4, s is 0 ~ Represents an integer of 4, and the sum of r and s is an integer of 2 to 4.)
　上記エポキシ化合物に作用させる上記不飽和一塩基酸としては、アクリル酸、メタクリル酸、クロトン酸、桂皮酸、ソルビン酸、ヒドロキシエチルメタクリレート・マレート、ヒドロキシエチルアクリレート・マレート、ヒドロキシプロピルメタクリレート・マレート、ヒドロキシプロピルアクリレート・マレート、ジシクロペンタジエン・マレート等が挙げられる。 Examples of the unsaturated monobasic acid that acts on the epoxy compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl Acrylate / malate, dicyclopentadiene / malate and the like can be mentioned.
　また、上記不飽和一塩基酸を作用させた後に作用させる上記多塩基酸無水物としては、ビフェニルテトラカルボン酸二無水物、テトラヒドロ無水フタル酸、無水コハク酸、ビフタル酸無水物、無水マレイン酸、トリメリット酸無水物、ピロメリット酸無水物、２，２’－３，３’－ベンゾフェノンテトラカルボン酸無水物、エチレングリコールビスアンヒドロトリメリテート、グリセロールトリスアンヒドロトリメリテート、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、ナジック酸無水物、メチルナジック酸無水物、トリアルキルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、５－（２，５－ジオキソテトラヒドロフリル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物、トリアルキルテトラヒドロ無水フタル酸－無水マレイン酸付加物、ドデセニル無水コハク酸、無水メチルハイミック酸等が挙げられる。 In addition, the polybasic acid anhydride to be acted after the unsaturated monobasic acid is allowed to act is biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, Trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride , Methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene -1,2-dicarboxylic anhydride, trialkylte Rahidoro phthalic anhydride - maleic acid adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid.
　上記エポキシ化合物、上記不飽和一塩基酸及び上記多塩基酸無水物の反応モル比は、以下の通りとすることが好ましい。
　即ち、上記エポキシ化合物のエポキシ基1個に対し、上記不飽和一塩基酸のカルボキシル基が０．１～１．０個で付加させた構造を有するエポキシ付加物において、該エポキシ付加物の水酸基1個に対し、上記多塩基酸無水物の酸無水物構造が０．１～１．０個となる比率となるようにするのが好ましい。
　上記エポキシ化合物、上記不飽和一塩基酸および上記多塩基酸無水物の反応は、常法に従って行なうことができる。 The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows.
That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the hydroxyl group 1 of the epoxy adduct is It is preferable that the ratio of the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0.
Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.
　上記エチレン性不飽和結合を有する重合性化合物の中でも、酸価を有する化合物を用いた場合、本発明の感光性組成物にアルカリ現像性を付与することができる。上記酸価を有する化合物を用いる場合、その使用量は（Ｂ）成分中で５０～９９質量％となるようにすることが好ましい。
　また、上記酸価を有する化合物は、更に単官能又は多官能エポキシ化合物を反応させることにより酸価調整してから用いることもできる。上記酸価を有する化合物の酸価を調整することにより、感光性樹脂のアルカリ現像性を改良することができる。上記酸価を有する化合物（即ちアルカリ現像性を付与するエチレン性不飽和結合を有する重合性化合物）は、固形分の酸価が５～１２０ｍｇＫＯＨ／ｇの範囲であることが好ましく、単官能又は多官能エポキシ化合物の使用量は、上記酸価を満たすように選択するのが好ましい。 Among the polymerizable compounds having an ethylenically unsaturated bond, when a compound having an acid value is used, alkali developability can be imparted to the photosensitive composition of the present invention. When the compound having the acid value is used, the amount used is preferably 50 to 99% by mass in the component (B).
The compound having an acid value can be used after adjusting the acid value by further reacting with a monofunctional or polyfunctional epoxy compound. The alkali developability of the photosensitive resin can be improved by adjusting the acid value of the compound having an acid value. The compound having an acid value (that is, a polymerizable compound having an ethylenically unsaturated bond imparting alkali developability) preferably has a solid acid value in the range of 5 to 120 mgKOH / g, and is monofunctional or polyfunctional. The amount of the functional epoxy compound used is preferably selected so as to satisfy the acid value.
　上記単官能エポキシ化合物としては、グリシジルメタクリレート、メチルグリシジルエーテル、エチルグリシジルエーテル、プロピルグリシジルエーテル、イソプロピルグリシジルエーテル、ブチルグリシジルエーテル、イソブチルグリシジルエーテル、ｔ－ブチルグリシジルエーテル、ペンチルグリシジルエーテル、ヘキシルグリシジルエーテル、ヘプチルグリシジルエーテル、オクチルグリシジルエーテル、ノニルグリシジルエーテル、デシルグリシジルエーテル、ウンデシルグリシジルエーテル、ドデシルグリシジルエーテル、トリデシルグリシジルエーテル、テトラデシルグリシジルエーテル、ペンタデシルグリシジルエーテル、ヘキサデシルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、アリルグリシジルエーテル、プロパルギルグリシジルエーテル、p－メトキシエチルグリシジルエーテル、フェニルグリシジルエーテル、ｐ－メトキシグリシジルエーテル、ｐ－ブチルフェノールグリシジルエーテル、クレジルグリシジルエーテル、２－メチルクレジルグリシジルエーテル、４－ノニルフェニルグリシジルエーテル、ベンジルグリシジルエーテル、ｐ－クミルフェニルグリシジルエーテル、トリチルグリシジルエーテル、２，３－エポキシプロピルメタクリレート、エポキシ化大豆油、エポキシ化アマニ油、グリシジルブチレート、ビニルシクロヘキサンモノオキシド、１，２－エポキシ－４－ビニルシクロヘキサン、スチレンオキシド、ピネンオキシド、メチルスチレンオキシド、シクロヘキセンオキシド、プロピレンオキシド、下記化合物Ｎｏ．Ｅ１、Ｎｏ．Ｅ２等が挙げられる。 Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidyl A , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl Glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4- Vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, the following compound No.E1, No. E2 etc. are mentioned.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　上記多官能エポキシ化合物としては、ビスフェノール型エポキシ化合物及びグリシジルエーテル類からなる群から選択される一種以上の化合物を用いると、特性の一層良好な（着色）アルカリ現像性感光性樹脂組成物を得ることができるので好ましい。
　上記ビスフェノール型エポキシ化合物としては、上記一般式（３）で表されるエポキシ化合物を用いることができる他、例えば、水添ビスフェノール型エポキシ化合物等のビスフェノール型エポキシ化合物も用いることができる。
　また上記グリシジルエーテル類としては、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、１，８－オクタンジオールジグリシジルエーテル、１，１０－デカンジオールジグリシジルエーテル、２，２－ジメチル－１，３－プロパンジオールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリエチレングリコールジグリシジルエーテル、テトラエチレングリコールジグリシジルエーテル、ヘキサエチレングリコールジグリシジルエーテル、１，４－シクロヘキサンジメタノールジグリシジルエーテル、１，１，１－トリ（グリシジルオキシメチル）プロパン、１，１，１－トリ（グリシジルオキシメチル）エタン、１，１，１－トリ（グリシジルオキシメチル）メタン、１，１，１，１－テトラ（グリシジルオキシメチル）メタン等を用いることができる。
　その他、フェノールノボラック型エポキシ化合物、ビフェニルノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物、ビスフェノールＡノボラック型エポキシ化合物、ジシクロペンタジエンノボラック型エポキシ化合物等のノボラック型エポキシ化合物；３，４－エポキシ－６－メチルシクロヘキシルメチル－３，４－エポキシ－６－メチルシクロヘキサンカルボキシレート、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、１－エポキシエチル－３，４－エポキシシクロヘキサン等の脂環式エポキシ化合物；フタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、ダイマー酸グリシジルエステル等のグリシジルエステル類；テトラグリシジルジアミノジフェニルメタン、トリグリシジルＰ－アミノフェノール、Ｎ，Ｎ－ジグリシジルアニリン等のグリシジルアミン類；１，３－ジグリシジル－５，５－ジメチルヒダントイン、トリグリシジルイソシアヌレート等の複素環式エポキシ化合物；ジシクロペンタジエンジオキシド等のジオキシド化合物；ナフタレン型エポキシ化合物；トリフェニルメタン型エポキシ化合物；ジシクロペンタジエン型エポキシ化合物等を用いることもできる。 As the polyfunctional epoxy compound, when one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers are used, a (colored) alkali-developable photosensitive resin composition having better characteristics can be obtained. Is preferable.
As the bisphenol-type epoxy compound, the epoxy compound represented by the general formula (3) can be used, and for example, a bisphenol-type epoxy compound such as a hydrogenated bisphenol-type epoxy compound can also be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) can be used such as methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as pentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds can also be used.
　本発明の感光性組成物に含有させることができる上記（Ｃ）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（特にガラスフリット）、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。
　これらの中でも、ガラスフリット、酸化チタン、シリカ、層状粘土鉱物、銀等が好ましい。本発明の感光性組成物において、（Ｃ）無機化合物の含有量は、（Ｂ）エチレン性不飽和結合を有する重合性化合物１００質量部に対して、好ましくは０．１～１０００質量部、より好ましくは１０～８００質量部である。尚、これらの無機化合物は１種又は２種以上を使用することができる。 Examples of the inorganic compound (C) that can be contained in the photosensitive composition of the present invention include nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, Metal oxides such as alumina; layered clay minerals, miloli blue, calcium carbonate, magnesium carbonate, cobalt, manganese, glass powder (especially glass frit), mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides , Selenide, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper and the like.
Among these, glass frit, titanium oxide, silica, layered clay mineral, silver and the like are preferable. In the photosensitive composition of the present invention, the content of the inorganic compound (C) is preferably 0.1 to 1000 parts by mass with respect to 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond. The amount is preferably 10 to 800 parts by mass. These inorganic compounds can be used alone or in combination of two or more.
　これらの無機化合物は、例えば、充填剤、反射防止剤、導電剤、安定剤、難燃剤、機械的強度向上剤、特殊波長吸収剤、撥インク剤等として用いられる。 These inorganic compounds are used, for example, as fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.
　また、本発明の感光性組成物に含有させることができる上記（Ｄ）色材としては、顔料、染料、天然色素等が挙げられる。これらの色材は、単独で又は２種以上を混合して用いることができる。 In addition, examples of the color material (D) that can be contained in the photosensitive composition of the present invention include pigments, dyes, and natural pigments. These color materials can be used alone or in admixture of two or more.
　上記顔料としては、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、チャンネル法又はサーマル法によって得られるカーボンブラック、或いはアセチレンブラック、ケッチェンブラック又はランプブラック等のカーボンブラック；上記カーボンブラックをエポキシ樹脂で調整又は被覆したもの、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以下のカーボンブラック、９５０℃における揮発分中のＣＯ及びＣＯ2から算出した全酸素量が、表面積１００ｍ2当たり９ｍｇ以上であるカーボンブラック；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；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、アンバー等の有機又は無機顔料を用いることができる。これらの顔料は単独で、或いは複数を混合して用いることができる。 Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; Compounds; perylene compounds; diketopyrrolopyrrole compounds; thioindigo compounds; dioxazine compounds; triphenylmethane compounds; quinophthalone compounds; naphthalene tetracarboxylic acids; azo dyes, metal complex compounds of cyanine dyes; Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black or lamp black; Prepared by coating or coating with an epoxy resin, carbon black previously dispersed with a resin in a solvent and adsorbed with 20 to 200 mg / g of resin, carbon black treated with an acidic or alkaline surface, average Carbon black having a particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a carbon black having a total oxygen amount calculated from CO and CO 2 in a volatile content at 950 ° C. of 9 mg or more per 100 m 2 of surface area; Graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, pigment black 7, titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese series, Ferrus Organics such as fluoride, phosphate blue, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, synthetic iron black, amber, etc. Alternatively, an inorganic pigment can be used. These pigments can be used alone or in combination.
　上記顔料としては、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。 Commercially available pigments can also be used as the pigment, 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, 9 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.
　上記染料としては、アゾ染料、アントラキノン染料、インジゴイド染料、トリアリールメタン染料、キサンテン染料、アリザリン染料、アクリジン染料スチルベン染料、チアゾール染料、ナフトール染料、キノリン染料、ニトロ染料、インダミン染料、オキサジン染料、フタロシアニン染料、シアニン染料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。 As the above dyes, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes And dyes such as cyanine dyes, and a plurality of these may be used in combination.
　本発明の感光性組成物において（Ｄ）色材を含有させる場合、その含有量は、（Ｂ）エチレン性不飽和結合を有する重合性化合物１００質量部に対して、好ましくは５０～３５０質量部、より好ましくは１００～２５０質量部である。 When (D) the color material is contained in the photosensitive composition of the present invention, the content thereof is preferably 50 to 350 parts by mass with respect to 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond. More preferably, it is 100 to 250 parts by mass.
　また、本発明の感光性組成物は、エチレン性不飽和結合を有さず、アルカリ現像性を付与する化合物を含有してもよく、そのような化合物としては、酸価を有することでアルカリ水溶液に可溶な化合物であれば特に限定されないが、代表的なものとしてアルカリ可溶性ノボラック樹脂（以下、単に「ノボラック樹脂」という）が挙げられる。ノボラック樹脂は、フェノール類とアルデヒド類とを酸触媒の存在下に重縮合して得られる。 In addition, the photosensitive composition of the present invention may contain a compound that does not have an ethylenically unsaturated bond and imparts alkali developability. As such a compound, an alkaline aqueous solution can be obtained by having an acid value. Although it is not particularly limited as long as it is a compound soluble in water, a typical example is an alkali-soluble novolak resin (hereinafter simply referred to as “novolak resin”). The novolak resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.
　上記フェノール類としては、例えばフェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ －クレゾール、ｏ－エチルフェノール、ｍ－エチルフェノール、ｐ－エチルフェノール、ｏ－ブチルフェノール、ｍ－ブチルフェノール、ｐ－ブチルフェノール、２，３－キシレノール、２，４－キシレノール、２，５－キシレノール、３，４－キシレノール、３，５－キシレノール、２，３，５－トリメチルフェノール、ｐ－フェニルフェノール、ヒドロキノン、カテコール、レゾルシノール、２－メチルレゾルシノール、ピロガロール、α－ナフトール、ビスフェノールＡ、ジヒドロキシ安息香酸エステル、没食子酸エステル等が用いられ、これらのフェノール類のうちフェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、２，５－キシレノール、３，５－キシレノール、２，３，５－トリメチルフェノール、レゾルシノール、２－メチルレゾルシノールおよびビスフェノールＡが好ましい。これらのフェノール類は、単独でまたは２種以上混合して用いられる。 Examples of the phenols include phenol, o-cresol, m-cresol, p -cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester, etc. are used. Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-kis Silenol, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methylresorcinol and bisphenol A are preferred. These phenols are used alone or in combination.
　上記アルデヒド類としては、例えばホルムアルデヒド、パラホルムアルデヒド、アセトアルデヒド、プロピルアルデヒド、ベンズアルデヒド、フェニルアセトアルデヒド、α－フェニルプロピルアルデヒド、β－フェニルプロピルアルデヒド、ｏ－ヒドロキシベンズアルデヒド、ｍ－ヒドロキシベンズアルデヒド、ｐ－ヒドロキシベンズアルデヒド、ｏ－クロロベンズアルデヒド、ｍ－クロロベンズアルデヒド、ｐ－クロロベンズアルデヒド、ｏ－ニトロベンズアルデヒド、ｍ－ニトロベンズアルデヒド、ｐ－ニトロベンズアルデヒド、ｏ－メチルベンズアルデヒド、ｍ－メチルベンズアルデヒド、ｐ－メチルベンズアルデヒド、ｐ－エチルベンズアルデヒド、ｐ－ｎ－ブチルベンズアルデヒド等が用いられ、これらの化合物のうちホルムアルデヒド、アセトアルデヒドおよびベンズアルデヒドが好ましい。これらのアルデヒド類は、単独でまたは２種以上混合して用いられる。アルデヒド類はフェノール類１モル当たり、好ましくは０．７～３モル、特に好ましくは０．７～２モルの割合で使用される。 Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p N-butylbenzaldehyde is used, and among these compounds, formaldehyde Rudehydr, acetaldehyde and benzaldehyde are preferred. These aldehydes may be used alone or in combination of two or more. Aldehydes are preferably used in a proportion of 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of phenol.
　上記酸触媒としては、例えば塩酸、硝酸、硫酸等の無機酸、または蟻酸、蓚酸、酢酸等の有機酸が用いられる。これらの酸触媒の使用量は、フェノール類１モル当たり、１×１０-4～５×１０-1モルが好ましい。縮合反応においては、通常、反応媒質として水が用いられるが、縮合反応に用いられるフェノール類がアルデヒド類の水溶液に溶解せず、反応初期から不均一系になる場合には、反応媒質として親水性溶媒を使用することもできる。これらの親水性溶媒としては、例えばメタノール、エタノール、プロパノール、ブタノール等のアルコール類、またはテトラヒドロフラン、ジオキサン等の環状エーテル類が挙げられる。これらの反応媒質の使用量は、通常、反応原料１００質量部当たり、２０～１０００質量部である。縮合反応の反応温度は、反応原料の反応性に応じて適宜調整することができるが、通常、１０～２００℃、好ましくは７０～１５０℃である。縮合反応終了後、系内に存在する未反応原料、酸触媒および反応媒質を除去するため、一般的には内温を１３０～２３０℃に上昇させ、減圧下に揮撥分を留去し、次いで熔融したノボラック樹脂をスチール製ベルト等の上に流涎して回収する。
　また縮合反応終了後に、前記親水性溶媒に反応混合物を溶解し、水、ｎ－ヘキサン、ｎ－ヘプタン等の沈殿剤に添加することにより、ノボラック樹脂を析出させ、析出物を分離し、加熱乾燥することにより回収することもできる。 Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid. The amount of these acid catalysts used is preferably 1 × 10 −4 to 5 × 10 −1 mol per mol of phenols. In the condensation reaction, water is usually used as a reaction medium. However, if the phenols used in the condensation reaction do not dissolve in an aqueous solution of aldehydes and become heterogeneous from the beginning of the reaction, the reaction medium is hydrophilic. A solvent can also be used. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material. The reaction temperature of the condensation reaction can be appropriately adjusted according to the reactivity of the reaction raw materials, but is usually 10 to 200 ° C., preferably 70 to 150 ° C. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, the internal temperature is generally increased to 130 to 230 ° C., and the volatile component is distilled off under reduced pressure. Next, the melted novolac resin is collected on a steel belt or the like.
After completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane or n-heptane to precipitate a novolak resin, and the precipitate is separated and dried by heating. It can also be recovered by doing so.
　上記ノボラック樹脂以外の例としては、ポリヒドロキシスチレンまたはその誘導体、スチレン－無水マレイン酸共重合体、ポリビニルヒドロキシベンゾエート等が挙げられる。 Examples other than the novolak resin include polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, and the like.
　本発明の感光性組成物には、必要に応じて更に溶媒を加えることができる。該溶媒としては、通常、前記の各成分（（Ａ）本発明の光重合開始剤及び（Ｂ）エチレン性不飽和結合を有する重合性化合物等）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、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等のエーテルエステル系溶媒；ベンゼン、トルエン、キシレン等のＢＴＸ系溶媒；ヘキサン、ヘプタン、オクタン、シクロヘキサン等の脂肪族炭化水素系溶媒；テレピン油、Ｄ－リモネン、ピネン等のテルペン系炭化水素油；ミネラルスピリット、スワゾール＃３１０（コスモ松山石油（株））、ソルベッソ＃１００（エクソン化学（株））等のパラフィン系溶媒；四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン、１，２－ジクロロエタン等のハロゲン化脂肪族炭化水素系溶媒；クロロベンゼン等のハロゲン化芳香族炭化水素系溶媒；カルビトール系溶媒；アニリン；トリエチルアミン；ピリジン；酢酸；アセトニトリル；二硫化炭素；Ｎ，Ｎ－ジメチルホルムアミド；Ｎ，Ｎ－ジメチルアセトアミド；Ｎ－メチルピロリドン；ジメチルスルホキシド；水等を用いることができ、これらの溶媒は１種で又は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、レジストと光重合開始剤との相溶性がよくなるので好ましい。
　本発明の感光性組成物において、溶媒の含有量は、特に制限されず、各成分が均一に分散又は溶解され、また本発明の感光性組成物が各用途に適した液状ないしペースト状を呈する量であればよいが、通常、本発明の感光性組成物中の固形分（溶媒以外の全成分）の量が１０～５０質量％となる範囲で溶媒を含有させることが好ましい。 If necessary, a solvent can be further added to the photosensitive composition of the present invention. As the solvent, usually, a solvent capable of dissolving or dispersing each of the above components ((A) the photopolymerization initiator of the present invention and (B) a polymerizable compound having an ethylenically unsaturated bond), for example, methyl ethyl ketone, Ketones such as methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, di Ether solvents such as propylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; ethylene glycol monomethyl ether Cellosolv solvents such as ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene Ether ester solvents such as glycol-1-monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; BTX solvents such as benzene, toluene, xylene; hexane, heptane , Octane, cyclohexane, and other aliphatic hydrocarbon solvents; terpene hydrocarbon oils, such as turpentine oil, D-limonene, and pinene; mineral spirits, swazol # 31 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.) and other paraffinic solvents; carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane and other halogenated aliphatic hydrocarbons Solvent; Halogenated aromatic hydrocarbon solvent such as chlorobenzene; Carbitol solvent; Aniline; Triethylamine; Pyridine; Acetic acid; Acetonitrile; Carbon disulfide; N, N-dimethylformamide; Pyrrolidone; dimethyl sulfoxide; water and the like can be used, and these solvents can be used alone or as a mixed solvent of two or more.
Among these, ketones, ether ester solvents, etc., particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. are preferable because the compatibility between the resist and the photopolymerization initiator is improved in the photosensitive composition. .
In the photosensitive composition of the present invention, the content of the solvent is not particularly limited, each component is uniformly dispersed or dissolved, and the photosensitive composition of the present invention exhibits a liquid or paste shape suitable for each application. However, it is usually preferred that the solvent be contained so that the solid content (all components other than the solvent) in the photosensitive composition of the present invention is 10 to 50% by mass.
　本発明の感光性組成物には、（Ｃ）無機化合物及び／又は（Ｄ）色材を分散させる分散剤を加えることができる。該分散剤としては、（Ｃ）無機化合物又は（Ｄ）色材を分散、安定化できるものであれば制限されず、市販の分散剤、例えば、ビックケミー社製のＢＹＫシリーズ等を用いることができる。特に、塩基性官能基を有するポリエステル、ポリエーテル、又は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1～１００ｍ ｇＫＯＨ／ｇのものが好適に用いられる。 In the photosensitive composition of the present invention, a dispersant for dispersing (C) an inorganic compound and / or (D) a coloring material can be added. The dispersant is not limited as long as it can disperse and stabilize the (C) inorganic compound or (D) coloring material, and a commercially available dispersant, for example, BYK series manufactured by BYK Chemie, Inc. can be used. . In particular, a polymer dispersant made of polyester, polyether or polyurethane having a basic functional group, having a nitrogen atom as a basic functional group, and the functional group having a nitrogen atom being an amine and / or a quaternary salt thereof. A compound having an amine value of 1 to 100 m g KOH / g is preferably used.
　また、本発明の感光性組成物には、（Ｂ）エチレン性不飽和結合を有する重合性化合物と共に、他の有機重合体を用いることによって、硬化物の特性を改善することもできる。該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。
　他の有機重合体を使用する場合、その使用量は、（Ｂ）エチレン性不飽和結合を有する上記重合性化合物１００質量部に対して、好ましくは１０～５００質量部である。 Moreover, in the photosensitive composition of this invention, the characteristic of hardened | cured material can also be improved by using another organic polymer with (B) the polymeric compound which has an ethylenically unsaturated bond. 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 Examples thereof include polyester, phenol resin, phenoxy resin, polyamideimide resin, polyamic acid resin, epoxy resin, etc. Among these, polystyrene, (meth) acrylic acid-methyl methacrylate copolymer, and epoxy resin are preferred. Arbitrariness.
When another organic polymer is used, the amount used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the polymerizable compound (B) having an ethylenically unsaturated bond.
　本発明の感光性組成物には、更に、連鎖移動剤、増感剤、界面活性剤、シランカプリング剤、メラミン化合物等を併用することができる。 In the photosensitive composition of the present invention, a chain transfer agent, a sensitizer, a surfactant, a silane coupling agent, a melamine compound, and the like can be further used in combination.
　上記連鎖移動剤又は増感剤としては、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、ジエチルチオキサントン、ジイソプロピルチオキサントン、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 or 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, trishydroxyethyltristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, 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-C000023
Figure JPOXMLDOC01-appb-C000023
　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; 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等の、イソシアネート基、メタクリロイル基又は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, an isocyanate group, a methacryloyl group, or an epoxy group, such as KBE-9007, KBM-502, and KBE-403, can be used. A silane coupling 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等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、互いに同一であってもよいし、異なっていてもよい。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てもよく、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てもよい。
　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. Examples include 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. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed.
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.
　また、本発明の感光性組成物には、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；酸化防止剤；紫外線吸収剤；分散助剤；凝集防止剤；触媒；効果促進剤；架橋剤；増粘剤等の慣用の添加物を加えることができる。 In addition, the photosensitive composition of the present invention includes, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; a filler; Conventional additives such as a foaming agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid, a coagulation inhibitor, a catalyst, an effect accelerator, a cross-linking agent, and a thickener can be added.
　本発明の感光性組成物において、（Ａ）本発明の光重合開始剤及び（Ｂ）エチレン性不飽和結合を有する重合性化合物以外の任意成分（但し、（Ｃ）無機化合物、（Ｄ）色材、及び溶媒は除く）の使用量は、その使用目的に応じて適宜選択され特に制限されないが、好ましくは、（Ｂ）エチレン性不飽和結合を有する重合性化合物１００質量部に対して合計で５０質量部以下とする。 In the photosensitive composition of the present invention, (A) the photopolymerization initiator of the present invention and (B) any component other than the polymerizable compound having an ethylenically unsaturated bond (however, (C) inorganic compound, (D) color The amount of use (except for the material and the solvent) is appropriately selected according to the purpose of use and is not particularly limited, but is preferably (B) in total based on 100 parts by mass of the polymerizable compound having an ethylenically unsaturated bond. 50 parts by mass or less.
　本発明の感光性組成物は、エネルギー線を照射して硬化物とすることができる。該硬化物は、用途に応じた適宜な形状として形成される。例えば膜状の硬化物を形成する場合には、本発明の感光性組成物は、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 of the present invention can be cured by irradiating energy rays. This hardened | cured material is formed as a suitable shape according to a use. For example, in the case of forming a film-like cured product, the photosensitive composition of the present invention is prepared by using a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing, dipping, etc. The present invention can be applied to a supporting substrate such as glass, quartz glass, semiconductor substrate, metal, paper, and plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.
　本発明の感光性組成物を硬化させる際に用いられるエネルギー線の光源としては、超高圧水銀ランプ、高圧水銀ランプ、中圧水銀ランプ、低圧水銀ランプ、水銀蒸気アーク灯、キセノンアーク灯、カーボンアーク灯、メタルハライドランプ、蛍光灯、タングステンランプ、エキシマーランプ、殺菌灯、発光ダイオード、ＣＲＴ光源等から得られる２０００オングストロームから７０００オングストロームの波長を有する電磁波エネルギーや電子線、Ｘ線、放射線等の高エネルギー線を利用することができるが、好ましくは、波長３００～４５０ｎｍの光を発光する超高圧水銀ランプ、水銀蒸気アーク灯、カーボンアーク灯、キセノンアーク灯等が用いられる。 The light source of the energy ray used for curing the photosensitive composition of the present invention includes an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp, a carbon arc. High energy rays such as electromagnetic energy, electron beam, X-ray, radiation, etc. having a wavelength of 2000 angstrom to 7000 angstrom obtained from lamp, metal halide lamp, fluorescent lamp, tungsten lamp, excimer lamp, germicidal lamp, light emitting diode, CRT light source, etc. However, it is preferable to use an ultrahigh pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, or the like that emits light having a wavelength of 300 to 450 nm.
　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、エキシマーレーザー、窒素レーザー、アルゴンイオンレーザー、ヘリウムカドミウムレーザー、ヘリウムネオンレーザー、クリプトンイオンレーザー、各種半導体レーザー及びＹＡＧ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ることができる。これらのレーザー光を使用する場合には、好ましくは、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 light, light having a wavelength of 340 to 430 nm is preferably used, but excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser. Various semiconductor lasers and YAG lasers that emit light in the visible to infrared region can also be used. When these laser beams are used, a sensitizing dye that absorbs the visible to infrared region is preferably added.
　本発明の感光性組成物は、光硬化性塗料又はワニス；光硬化性接着剤；プリント基板；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素子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；プラズマ表示パネル用の電極材料；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；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；ドライフィルム；はんだレジスト；種々の表示用途用のカラーフィルタを製造するための或いはプラズマ表示パネル、電気発光表示装置、及びＬＣＤの製造工程においてそれらの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又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 of the present invention comprises a photocurable paint or varnish; a photocurable adhesive; a printed circuit board; a color filter in a color display liquid crystal display element such as a color television, a PC monitor, a personal digital assistant, a digital camera; Color filter of image sensor; Electrode material for plasma display panel; Powder coating; Printing ink; Printing plate; Adhesive; Dental composition; Gel coat; Photoresist for electronics; Electroplating resist; Solder resists; resists for manufacturing color filters for various display applications or forming their structures in the manufacturing process of plasma display panels, electroluminescent display devices, and LCDs; for encapsulating electrical and electronic components Composition; solder resist; magnetic recording material; micromachine Article; waveguide; optical switch; plating mask; etching mask; color test system; glass fiber cable coating; stencil for screen printing; material for manufacturing three-dimensional objects by stereolithography; holographic recording material; Materials; fine electronic circuits; bleaching materials; bleaching materials for image recording materials; bleaching materials for image recording materials using microcapsules; photoresist materials for printed wiring boards; photoresists for UV and visible laser direct imaging systems Material: It can be used for various applications such as a photoresist material or a protective film used for forming a dielectric layer in the sequential lamination of printed circuit boards, and the application is not particularly limited.
　本発明の感光性組成物は、液晶表示パネル用スペーサーを形成する目的及び垂直配向型液晶表示素子用突起を形成する目的で使用することもできる。特に垂直配向型液晶表示素子用の突起とスペーサーを同時に形成するための感光性組成物として有用である。 The photosensitive composition of the present invention can also be used for the purpose of forming a spacer for a liquid crystal display panel and for forming a protrusion for a vertical alignment type liquid crystal display element. In particular, it is useful as a photosensitive composition for simultaneously forming protrusions and spacers for a vertical alignment type liquid crystal display element.
　上記の液晶表示パネル用スペーサーは、（１）本発明の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エネルギー線（光）を照射する工程、（３）露光後のベーク工程、（４）露光後の被膜を現像する工程、（５）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。 The spacer for a liquid crystal display panel includes (1) a step of forming a coating film of the photosensitive composition of the present invention on a substrate, and (2) an energy beam (through a mask having a predetermined pattern shape on the coating film). (3) baking step after exposure, (4) step of developing the film after exposure, and (5) step of heating the film after development.
　（Ｄ）色材を添加した本発明の感光性組成物は、カラーフィルタにおけるＲＧＢ等の各画素を構成するレジストや、各画素の隔壁を形成するブラックマトリクス用レジストとして好適に用いられる。更に、撥インク剤を添加するブラックマトリクス用レジストの場合、プロファイル角が５０°以上であるインクジェット方式カラーフィルタ用隔壁に好ましく用いられる。該撥インク剤としては、フッ素系界面活性剤及びフッ素系界面活性剤を含有する組成物が好適に用いられる。 (D) The photosensitive composition of the present invention to which a coloring material is added is suitably used as a resist constituting each pixel such as RGB in a color filter and a black matrix resist forming a partition of each pixel. Furthermore, in the case of a black matrix resist to which an ink repellent agent is added, it is preferably used for a partition for an ink jet color filter having a profile angle of 50 ° or more. As the ink repellent agent, a fluorosurfactant and a composition containing a fluorosurfactant are preferably used.
　上記インクジェット方式カラーフィルタ用隔壁に用いた場合、本発明の感光性組成物から形成された隔壁が被転写体上を区画し、区画された被転写体上の凹部にインクジェット法により液滴を付与して画像領域を形成する方法により光学素子が製造される。この際、上記液滴が着色剤を含有し、上記画像領域が着色されていることが好ましく、その場合には、上記の製造方法により作製された光学素子は、基板上に複数の着色領域からなる画素群と該画素群の各着色領域を離隔する隔壁を少なくとも有するものとなる。 When used for the inkjet color filter partition, the partition formed from the photosensitive composition of the present invention partitions the transferred object, and droplets are applied to the recessed portions on the partitioned transferred object by the inkjet method. Thus, an optical element is manufactured by a method of forming an image region. At this time, it is preferable that the droplets contain a colorant and the image area is colored. In this case, the optical element produced by the manufacturing method described above is formed from a plurality of colored areas on the substrate. And at least a partition that separates each colored region of the pixel group.
　本発明の感光性組成物は、保護膜又は絶縁膜用組成物としても用いることができる。この場合、紫外線吸収剤、アルキル化変性メラミン及び／又はアクリル変性メラミン、分子中にアルコール性水酸基を含有する１又は２官能の（メタ）アクリレートモノマー及び／ 又はシリカゾルを含有することができる。 The photosensitive composition of the present invention can also be used as a protective film or insulating film composition. In this case, an ultraviolet absorber, an alkylated modified melamine and / or an acrylic modified melamine, a mono- or bifunctional (meth) acrylate monomer containing an alcoholic hydroxyl group in the molecule, and / or a silica sol can be contained.
　上記保護膜、絶縁膜用の感光性組成物としては、
　（Ａ）本発明の光重合開始剤、
　（Ｂ）エチレン性不飽和結合を有する重合性化合物（重量平均分子量が２，０００～４０，０００、酸価が５０～２００ｍｇＫＯＨ／ｇであるカルボキシル基含有の重合性化合物を含むことが好ましい）、及び
　（Ｘ）エポキシ化合物
を主成分とする樹脂組成物であって、
　（Ｂ）成分１００重量部に対して、（Ａ）成分が本発明のオキシムエステル化合物量に換算して０．０１～２．０重量部であり、（Ｘ）成分が１０～４０重量部であるものが好ましい。 As the photosensitive composition for the protective film and insulating film,
(A) the photopolymerization initiator of the present invention,
(B) a polymerizable compound having an ethylenically unsaturated bond (preferably containing a carboxyl group-containing polymerizable compound having a weight average molecular weight of 2,000 to 40,000 and an acid value of 50 to 200 mgKOH / g), And (X) a resin composition mainly comprising an epoxy compound,
With respect to 100 parts by weight of the component (B), the component (A) is 0.01 to 2.0 parts by weight in terms of the amount of the oxime ester compound of the present invention, and the component (X) is 10 to 40 parts by weight. Some are preferred.
　上記絶縁膜は、剥離可能な支持基材上に絶縁樹脂層が設けられた積層体における該絶縁樹脂層に用いられ、該積層体は、アルカリ水溶液による現像が可能なものであり、絶縁樹脂層の膜厚が１０～１００μｍであることが好ましい。 The insulating film is used for the insulating resin layer in a laminate in which an insulating resin layer is provided on a peelable support substrate, and the laminate can be developed with an alkaline aqueous solution. The film thickness is preferably 10 to 100 μm.
　本発明の感光性組成物は、（Ｃ）無機化合物を含有させることで、感光性ペースト組成物として用いることができる。該感光性ペースト組成物は、プラズマディスプレイパネルの隔壁パターン、誘電体パターン、電極パターン及びブラックマトリックスパターン等の焼成物パターンを形成するために用いることができる。 The photosensitive composition of the present invention can be used as a photosensitive paste composition by containing an inorganic compound (C). The photosensitive paste composition can be used for forming a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.
　以下、実施例及び比較例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 Comparative Examples, but the present invention is not limited to these Examples and the like.
〔実施例１〕化合物Ｎｏ．１の製造
＜ステップ１＞メタクリレート化
　１－（４－（４－（２－ヒドロキシエトキシ）フェニルチオ）フェニル）プロパン－１－オン（以下、ケトン体ａともいう）１９．８ｇ（６５ｍｍｏｌ）、メタクリル酸５６．２ｇ（６５３ｍｍｏｌ）、パラトルエンスルホン酸一水和物５．０ｇ（２６ｍｍｏｌ）、ＢＨＴ１．２ｇ（５．６ｍｍｏｌ）及びジクロロエタン１２１ｇを含む溶液を１０．５時間攪拌還流した。冷却後、酢酸エチルと水を加え油水分離した。有機層を水、炭酸水素ナトリウム水溶液、水の順序で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、脱溶媒し下記メタクリレート体ａを２６．３ｇ得た。 Example 1 Compound No. 1 <Step 1> Methacrylateation 1- (4- (4- (2-hydroxyethoxy) phenylthio) phenyl) propan-1-one (hereinafter also referred to as ketone body a) 19.8 g (65 mmol), methacrylic acid A solution containing 56.2 g (653 mmol), p-toluenesulfonic acid monohydrate 5.0 g (26 mmol), BHT 1.2 g (5.6 mmol) and dichloroethane 121 g was stirred and refluxed for 10.5 hours. After cooling, ethyl acetate and water were added to separate the oil and water. The organic layer was washed with water, an aqueous sodium bicarbonate solution, and water in this order. The organic layer was dried over anhydrous magnesium sulfate and then the solvent was removed to obtain 26.3 g of the following methacrylate body a.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
＜ステップ２＞オキシム化
　ステップ１で得られたメタクリレート体ａの２６．０ｇ（７０ｍｍｏｌ）、濃塩酸７．３ｇ（７０ｍｍｏｌ）及びジメチルホルムアミド７０ｇを含む溶液を５℃に冷却し、亜硝酸イソブチル１０．８ｇ（１０５ｍｍｏｌ）を加え室温で３時間攪拌した。酢酸エチルと水を加え油水分離し、有機層を水、炭酸水素ナトリウム水溶液、水の順序で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、脱溶媒し、下記オキシム体ａを２３．８ｇ得た。 <Step 2> Oximation A solution containing 26.0 g (70 mmol) of the methacrylate body a obtained in Step 1, 7.3 g (70 mmol) of concentrated hydrochloric acid and 70 g of dimethylformamide was cooled to 5 ° C., and isobutyl nitrite 10. 8 g (105 mmol) was added and stirred at room temperature for 3 hours. Ethyl acetate and water were added to separate the oil and water, and the organic layer was washed with water, an aqueous sodium hydrogen carbonate solution and water in this order. The organic layer was dried over anhydrous magnesium sulfate and then the solvent was removed to obtain 23.8 g of the following oxime body a.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
＜ステップ３＞オキシムエステル化
　ステップ２で得られたオキシム体ａの２３．８ｇ（６０ｍｍｏｌ）、無水酢酸９．１ｇ（９０ｍｍｏｌ）及び酢酸エチル７９ｇを含む溶液を７０℃で４時間攪拌した。冷却後、水を加え油水分離した。有機層を水、炭酸水素ナトリウム水溶液、水の順序で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、脱溶媒した。得られた粗生成物２７．２ｇをカラムクロマトグラムにより精製し化合物Ｎｏ．１を２．３ｇ得た。得られた化合物が目的物であることは、分析により確認した。分析結果を〔表１〕～〔表３〕に示す。 <Step 3> Oxime esterification A solution containing 23.8 g (60 mmol) of the oxime body a obtained in Step 2, 9.1 g (90 mmol) of acetic anhydride and 79 g of ethyl acetate was stirred at 70 ° C. for 4 hours. After cooling, water was added and the oil was separated. The organic layer was washed with water, an aqueous sodium bicarbonate solution, and water in this order. The organic layer was dried over anhydrous magnesium sulfate and then desolvated. 27.2 g of the obtained crude product was purified by a column chromatogram, and the compound no. 2.3 g of 1 was obtained. It was confirmed by analysis that the obtained compound was the target product. The analysis results are shown in [Table 1] to [Table 3].
〔実施例２～４〕化合物Ｎｏ．２、化合物Ｎｏ．３、化合物Ｎｏ．４の製造
　ケトン体ａに代えて対応するケトン体を用い（且つ化合物Ｎｏ．３については、メタクリル酸に代えてアクリル酸を用い）た以外は、実施例１に記載した方法に従って、化合物Ｎｏ．２、化合物Ｎｏ．３及び化合物Ｎｏ．４をそれぞれ製造した。分析結果を〔表１〕～〔表３〕に示す。 [Examples 2 to 4] Compound No. 2, Compound No. 3, Compound No. 4 According to the method described in Example 1, except that the corresponding ketone body was used instead of ketone body a (and acrylic acid was used instead of methacrylic acid for compound No. 3), compound No. 3 was used. 2, Compound No. 3 and compound no. 4 were produced respectively. The analysis results are shown in [Table 1] to [Table 3].
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
〔実施例５〕アルカリ現像性感光性樹脂組成物Ｎｏ．１の製造
＜ステップ１＞アルカリ現像性樹脂〔アルカリ現像性を付与する（Ｂ）成分〕の調製
　反応容器に、ビスフェノールフルオレン型エポキシ樹脂（エポキシ当量２３１、前記一般式（３）で表されるエポキシ化合物）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２３ｇを仕込み、１２０℃で１６時間攪拌した。反応液を室温まで冷却し、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３５ｇ、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時間攪拌した。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時間攪拌した後、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９０ｇを加えて、プロピレングリコール－１－モノメチルエーテル－２－アセテート溶液として目的物のアルカリ現像性樹脂Ｎｏ．１を得た（Ｍｗ＝５０００、Ｍｎ＝２１００、酸価（固形分）９２．７ｍｇＫＯＨ／ｇ）。 [Example 5] Alkali-developable photosensitive resin composition No. 1. Preparation of Step 1 <Preparation of Alkali Developable Resin [Component (B) that Gives Alkali Developability] In a reaction vessel, a bisphenolfluorene type epoxy resin (epoxy equivalent 231; an epoxy represented by the above general formula (3) Compound) 184 g, acrylic acid 58 g, 2,6-di-tert-butyl-p-cresol 0.26 g, tetra-n-butylammonium bromide 0.11 g and propylene glycol-1-monomethyl ether-2-acetate 23 g , And stirred at 120 ° C. for 16 hours. The reaction solution was cooled to room temperature, 35 g of propylene glycol-1-monomethyl ether-2-acetate, 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 stirred 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, and then propylene glycol-1-monomethyl ether Add 90 g of -2-acetate to obtain the target alkali developing resin No. 1 as a propylene glycol-1-monomethyl ether-2-acetate solution. 1 (Mw = 5000, Mn = 2100, acid value (solid content) 92.7 mgKOH / g) was obtained.
＜ステップ２＞アルカリ現像性感光性樹脂組成物Ｎｏ．１の調製
　アルカリ現像性を付与する（Ｂ）成分として＜ステップ１＞で得られたアルカリ現像性樹脂Ｎｏ．１の１４．７ｇ、（Ｂ）成分としてジペンタエリスリトールペンタ及びヘキサアクリレート（アロニックスＭ－４０２；東亜合成（株）製）３．０ｇ、界面活性剤ＦＺ－２１２２（日本ユニカー（株）製）のシクロヘキサノン１％溶液１．８ｇ、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１０．０ｇ、並びにシクロヘキサノン２０．２ｇを混合し、（Ａ）成分として実施例１で得られた化合物Ｎｏ．１の０．３ｇを添加してよく攪拌し、本発明の感光性組成物であるアルカリ現像性感光性樹脂組成物Ｎｏ．１を得た。 <Step 2> Alkali-developable photosensitive resin composition No. Preparation of Alkali Developable Resin No. 1 obtained in <Step 1> as component (B) imparting alkali developability 14.7 g of dipentaerythritol penta and hexaacrylate (Aronix M-402; manufactured by Toagosei Co., Ltd.) as a component (B), surfactant FZ-2122 (manufactured by Nippon Unicar Co., Ltd.) 1.8 g of a cyclohexanone 1% solution, 10.0 g of propylene glycol-1-monomethyl ether-2-acetate and 20.2 g of cyclohexanone were mixed, and the compound No. 1 obtained in Example 1 as component (A) was mixed. 0.3 g of No. 1 was added and stirred well, and the alkali-developable photosensitive resin composition No. 1 which is the photosensitive composition of the present invention. 1 was obtained.
〔実施例６〕アルカリ現像性感光性樹脂組成物Ｎｏ．２の製造
　実施例１で得られた化合物Ｎｏ．１を実施例２で得られた化合物Ｎｏ．２に替えた以外は、実施例５の＜ステップ２＞と同様の手法で、本発明の感光性組成物であるアルカリ現像性感光性樹脂組成物Ｎｏ．２を得た。 [Example 6] Alkali-developable photosensitive resin composition No. Preparation of Compound No. 2 obtained in Example 1 1 to compound No. 1 obtained in Example 2. Except for changing to No. 2, in the same manner as in <Step 2> of Example 5, the alkali-developable photosensitive resin composition No. 1 as the photosensitive composition of the present invention was used. 2 was obtained.
〔実施例７〕アルカリ現像性感光性樹脂組成物Ｎｏ．３の製造
　実施例１で得られた化合物Ｎｏ．１を実施例３で得られた化合物Ｎｏ．３に替えた以外は、実施例５の＜ステップ２＞と同様の手法で、本発明の感光性組成物であるアルカリ現像性感光性樹脂組成物Ｎｏ．３を得た。 [Example 7] Alkali-developable photosensitive resin composition No. Preparation of Compound No. 3 obtained in Example 1 1 to compound No. 1 obtained in Example 3. 3 except that the alkaline developing photosensitive resin composition No. 1 which is the photosensitive composition of the present invention was prepared in the same manner as in <Step 2> of Example 5. 3 was obtained.
〔比較例１〕アルカリ現像性感光性樹脂組成物Ｎｏ．４の製造
　実施例１で得られた化合物Ｎｏ．１を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）－１－ブタノンに替えた以外は、実施例５の＜ステップ２＞と同様の手法で、比較品であるアルカリ現像性感光性樹脂組成物Ｎｏ．４を得た。 [Comparative Example 1] Alkali-developable photosensitive resin composition No. Preparation of Compound No. 4 obtained in Example 1 Alkaline development as a comparative product was performed in the same manner as in <Step 2> of Example 5 except that 1 was replaced with 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone. Photosensitive resin composition No. 4 was obtained.
〔比較例２〕アルカリ現像性感光性樹脂組成物Ｎｏ．５の製造
　実施例１で得られた化合物Ｎｏ．１をエタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）に替えた以外は、実施例５の＜ステップ２＞と同様の手法で、比較品であるアルカリ現像性感光性樹脂組成物Ｎｏ．５を得た。 [Comparative Example 2] Alkali-developable photosensitive resin composition No. Production of Compound No. 5 obtained in Example 1 <Step of Example 5 except that 1 is replaced with ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) 2>, the comparative alkali-developable photosensitive resin composition No. 5 was obtained.
＜透過性＞
　得られたアルカリ現像性感光性樹脂組成物Ｎｏ．１～Ｎｏ．５の透過性試験を以下のようにして行った。
　即ち、ガラス基板上にアルカリ現像性感光性樹脂組成物をスピンコート（５００ｒｐｍで２秒間、８００ｒｐｍで６秒間）し、ホットプレートを用いて９０℃で９０秒間プリベークを行った。次いで、光源として高圧水銀ランプを用いて１５０ｍＪ／ｃｍ2露光した後、オーブンを用いて２３０℃で３０分間ポストベークを行って硬化膜を得た。得られた硬化膜について、吸光光度計を用いて３８０ｎｍにおける透過率を測定した。結果を〔表４〕に示す。 <Transparency>
The obtained alkali-developable photosensitive resin composition No. 1-No. The permeability test of No. 5 was conducted as follows.
That is, the alkali-developable photosensitive resin composition was spin-coated on a glass substrate (500 rpm for 2 seconds, 800 rpm for 6 seconds), and prebaked at 90 ° C. for 90 seconds using a hot plate. Next, after exposure to 150 mJ / cm 2 using a high-pressure mercury lamp as a light source, post-baking was performed at 230 ° C. for 30 minutes using an oven to obtain a cured film. About the obtained cured film, the transmittance | permeability in 380 nm was measured using the absorptiometer. The results are shown in [Table 4].
Figure JPOXMLDOC01-appb-T000029
Figure JPOXMLDOC01-appb-T000029
　表４に記載の通り、本発明のオキシムエステル化合物を光重合開始剤として用いた本発明の感光性組成物は、比較化合物を用いた比較例１及び２の感光性組成物に比べて、透過率が高い。 As shown in Table 4, the photosensitive composition of the present invention using the oxime ester compound of the present invention as a photopolymerization initiator is more transparent than the photosensitive compositions of Comparative Examples 1 and 2 using a comparative compound. The rate is high.
〔実施例８〕導電性組成物Ｎｏ．１の製造
　アルカリ現像性を付与する（Ｂ）成分として実施例５の＜ステップ１＞で得られたアルカリ現像性樹脂Ｎｏ．１の１４．１ｇ、（Ｂ）成分としてジペンタエリスリトールペンタ及びヘキサアクリレート（アロニックスＭ－４０２；東亜合成（株）製）７．１ｇ、界面活性剤ＢＹＫ－３２３（ビックケミー・ジャパン（株）製）０．０５ｇ、テキサノール（２，２，４－トリメチル－１，３－ペンタンジオールモノイソブチレート）１１．３ｇ、（Ａ）成分として実施例１で得られた化合物Ｎｏ．１の０．７ｇ、並びに（Ｃ）成分としてガラスフリット３．１ｇ及び銀粉６３．７ｇを混合して攪拌後、３本ロールミルにて混練し、本発明の感光性組成物である導電性組成物Ｎｏ．１を得た。 [Example 8] Conductive composition No. Production of Alkali Developable Resin No. 1 obtained in <Step 1> of Example 5 as component (B) for imparting alkali developability 14.1 g of 1, dipentaerythritol penta and hexaacrylate (Aronix M-402; manufactured by Toagosei Co., Ltd.) as component (B), surfactant BYK-323 (manufactured by Big Chemie Japan Co., Ltd.) 0.05 g, 11.3 g of texanol (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate), compound No. obtained in Example 1 as component (A) 0.7 g of 1 and 3.1 g of glass frit and 63.7 g of silver powder as component (C) were stirred and kneaded with a three-roll mill, and the conductive composition which is the photosensitive composition of the present invention. No. 1 was obtained.
〔実施例９〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．１の製造
＜ステップ１＞青色分散液の製造
　青色顔料ピグメントブルー１５：６の５７．６ｇ、分散剤アジスパーＰＢ８２１（味の素ファインテクノ（株）製）２０．０ｇ、分散助剤ソルスパース５０００（アビシア（株）製）２．４ｇ、及び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３２０．０ｇを、５００ｍｌポリエチレン製容器に入れ、粒子径０．５ｍｍのジルコニアビーズ３５０ｇを使用して、ペイントコンディショナーで１０時間振とう後、ジルコニアビーズをろ別して青色分散液を得た。 [Example 9] Colored alkali-developable photosensitive resin composition No. <Step 1> Production of Blue Dispersion 57.6 g of Blue Pigment Pigment Blue 15: 6, Dispersant Azisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) 20.0 g, Dispersing Agent Solsperse 5000 (Avicia Co., Ltd.) )) 2.4 g and propylene glycol-1-monomethyl ether-2-acetate 320.0 g are put into a 500 ml polyethylene container, and 350 g of zirconia beads having a particle diameter of 0.5 mm are used for 10 hours in a paint conditioner. After shaking, the zirconia beads were filtered off to obtain a blue dispersion.
＜ステップ２＞着色アルカリ現像性感光性樹脂組成物Ｎｏ．１の製造
　（Ｄ）成分として＜ステップ１＞で得られた青色分散液の１０．６３ｇ、アルカリ現像性を付与する（Ｂ）成分として実施例５の＜ステップ１＞で得られたアルカリ現像性樹脂Ｎｏ．１の２．９８ｇ、（Ｂ）成分としてジペンタエリスリトールペンタ及びヘキサアクリレート（アロニックスＭ－４０２；東亜合成（株）製）０．３１ｇ、（Ｂ）成分としてウレタンアクリレートＵＮ３３２０ＨＳ（根上工業（株）製）０．３１ｇ、界面活性剤ＢＹＫ－３２３（ビックケミー・ジャパン（株）製）のシクロヘキサノン１％溶液０．３０ｇ、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４．７０ｇ、並びにシクロヘキサノン１０．３６ｇを混合し、（Ａ）成分として実施例１で得られた化合物Ｎｏ．１の０．４１ｇを添加して攪拌し、本発明の感光性組成物である着色アルカリ現像性感光性樹脂組成物Ｎｏ．１を得た。 <Step 2> Colored alkali-developable photosensitive resin composition No. Production of 1 (D) 10.63 g of the blue dispersion obtained in <Step 1> as component (B) Alkali developability obtained in <Step 1> of Example 5 as component (B) that imparts alkali developability Resin No. 2.98 g of 1, dipentaerythritol penta and hexaacrylate (Aronix M-402; manufactured by Toagosei Co., Ltd.) as component (B), urethane acrylate UN3320HS (produced by Negami Kogyo Co., Ltd.) as component (B) 0.31 g, 0.30 g of a cyclohexanone 1% solution of the surfactant BYK-323 (manufactured by BYK Japan KK), 4.70 g of propylene glycol-1-monomethyl ether-2-acetate, and 10.36 g of cyclohexanone The compound No. obtained in Example 1 as component (A) was mixed. No. 1 of 0.41 g was added and stirred, and the colored alkali-developable photosensitive resin composition No. 1 which is the photosensitive composition of the present invention. 1 was obtained.
〔比較例３〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．２の製造
　実施例１で得られた化合物Ｎｏ．１をエタノン，１－［９－エチル－６－(２－メチル ベンゾイル)－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）に替えた以外は実施例９の＜ステップ２＞と同様の手法で、比較品である着色アルカリ現像性感光性樹脂組成物Ｎｏ．２を得た。 [Comparative Example 3] Colored alkali-developable photosensitive resin composition No. Preparation of Compound No. 2 obtained in Example 1 <Step 2 of Example 9 except that 1 is replaced with ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) > In the same manner as above, the colored alkali-developable photosensitive resin composition No. 2 was obtained.
〔比較例４〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．３の製造
　実施例１で得られた化合物Ｎｏ．１を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ン－１－オンに替えた以外は実施例９の＜ステップ２＞と同様の手法で、比較品である着色アルカリ現像性感光性樹脂組成物Ｎｏ．３を得た。 [Comparative Example 4] Colored alkali-developable photosensitive resin composition No. Preparation of Compound No. 3 obtained in Example 1 Colored alkali development as a comparative product in the same manner as in <Step 2> of Example 9 except that 1 was replaced with 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one Photosensitive resin composition No. 3 was obtained.
〔比較例５〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．４の製造
　実施例１で得られた化合物Ｎｏ．１を１，２－オクタンジオン，１－［４－（フェニルチオ）フェニル］－，２－（Ｏ－ベンゾイルオキシム）に替えた以外は実施例９の＜ステップ２＞と同様の手法で、比較品である着色アルカリ現像性感光性樹脂組成物Ｎｏ．４を得た。 [Comparative Example 5] Colored alkali-developable photosensitive resin composition No. Preparation of Compound No. 4 obtained in Example 1 A comparative product was prepared in the same manner as in <Step 2> of Example 9 except that 1 was replaced with 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime). Colored alkali-developable photosensitive resin composition No. 4 was obtained.
〔比較例６〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．５の製造
　実施例１で得られた化合物Ｎｏ．１を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）－１－ブタノンに替えた以外は実施例９の＜ステップ２＞と同様の手法で、比較品である着色アルカリ現像性感光性樹脂組成物Ｎｏ．５を得た。 [Comparative Example 6] Colored alkali-developable photosensitive resin composition No. Production of Compound No. 5 obtained in Example 1 Colored alkali development as a comparative product in the same manner as in <Step 2> of Example 9 except that 1 is replaced with 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone Photosensitive resin composition No. 5 was obtained.
＜透過性＞
　得られた着色アルカリ現像性感光性樹脂組成物Ｎｏ．１～Ｎｏ．３の透過性試験を以下のようにして行った。
　ガラス基板上に着色アルカリ現像性感光性樹脂組成物をスピンコート（５００ｒｐｍ、７秒間）し、ホットプレートを用いて９０℃で９０秒間プリベークを行った。次いで、光源として高圧水銀ランプを用いて１５０ｍＪ／ｃｍ2露光した後、オーブンを用いて２３０℃で３０分間ポストベークを行って硬化膜を得た。耐熱性試験として、得られた硬化膜を更に２６０℃で１時間加熱した。耐熱性試験後の硬化膜について、吸光光度計を用いて ４２０ｎｍにおける透過率を測定した。結果を〔表５〕に示す。 <Transparency>
The obtained colored alkali-developable photosensitive resin composition No. 1-No. The permeability test of No. 3 was conducted as follows.
A colored alkali-developable photosensitive resin composition was spin-coated (500 rpm, 7 seconds) on a glass substrate, and prebaked at 90 ° C. for 90 seconds using a hot plate. Next, after exposure to 150 mJ / cm 2 using a high-pressure mercury lamp as a light source, post-baking was performed at 230 ° C. for 30 minutes using an oven to obtain a cured film. As a heat resistance test, the obtained cured film was further heated at 260 ° C. for 1 hour. The cured film after the heat resistance test was measured for transmittance at 420 nm using an absorptiometer. The results are shown in [Table 5].
Figure JPOXMLDOC01-appb-T000030
Figure JPOXMLDOC01-appb-T000030
　表５に記載の通り、本発明のオキシムエステル化合物を光重合開始剤として用いた本発明の着色アルカリ現像性感光性樹脂組成物は、比較化合物を用いた比較例３及び４の着色アルカリ現像性感光性樹脂組成物に比べて、透過率が高い。 As shown in Table 5, the colored alkali-developable photosensitive resin composition of the present invention using the oxime ester compound of the present invention as a photopolymerization initiator is a colored alkali-developable feeling of Comparative Examples 3 and 4 using a comparative compound. The transmittance is higher than that of the light-sensitive resin composition.
＜アウトガス性＞
　得られた着色アルカリ現像性感光性樹脂組成物Ｎｏ．１、Ｎｏ．３～Ｎｏ．５のアウトガス性試験として、以下のようにして硬化物の重量減少率の測定を行った。
　即ち、ガラス基板上に着色アルカリ現像性感光性樹脂組成物をスピンコート（５００ｒｐｍ、７秒間）し、ホットプレートを用いて９０℃で９０秒間プリベークを行った。次いで、光源として高圧水銀ランプを用いて１００ｍＪ／ｃｍ2露光して硬化膜を得た。この硬化膜を約３ｍｇ削り取り、削り取った硬化膜を試料として用い、ＴＧ－ＤＴＡ（セイコーインスツル（株）製）により、２３０℃で３０分間保持した時の重量減少率を測定した。結果を〔表６〕に示す。 <Outgassing>
The obtained colored alkali-developable photosensitive resin composition No. 1, no. 3 to No. As an outgas test of No. 5, the weight reduction rate of the cured product was measured as follows.
That is, the colored alkali-developable photosensitive resin composition was spin coated (500 rpm, 7 seconds) on a glass substrate, and prebaked at 90 ° C. for 90 seconds using a hot plate. Next, the film was exposed to 100 mJ / cm 2 using a high-pressure mercury lamp as a light source to obtain a cured film. About 3 mg of this cured film was scraped off, and the weight reduction rate when held at 230 ° C. for 30 minutes was measured with TG-DTA (manufactured by Seiko Instruments Inc.) using the scraped cured film as a sample. The results are shown in [Table 6].
Figure JPOXMLDOC01-appb-T000031
Figure JPOXMLDOC01-appb-T000031
　表６から、本発明のオキシムエステル化合物を光重合開始剤として用いた本発明の感光性組成物である着色アルカリ現像性感光性樹脂組成物は、比較化合物を用いた比較例４～６の着色アルカリ現像性感光性樹脂組成物に比べて、耐熱性に優れ、アウトガスが少ないことが明らかである。尚、この結果から、光重合開始剤としての本発明のオキシムエステル化合物は樹脂成分と反応し、それによって、本発明のオキシムエステル化合物及び／又は樹脂成分の昇華性が低くなったと推察される。 From Table 6, the colored alkali-developable photosensitive resin composition, which is the photosensitive composition of the present invention using the oxime ester compound of the present invention as a photopolymerization initiator, is colored in Comparative Examples 4 to 6 using the comparative compound. It is clear that it has excellent heat resistance and less outgas compared to the alkali-developable photosensitive resin composition. In addition, from this result, it is guessed that the oxime ester compound of this invention as a photoinitiator reacted with the resin component, and, thereby, the sublimation property of the oxime ester compound and / or resin component of this invention became low.
〔実施例１０〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．６の製造
　（Ｄ）成分として実施例９の＜ステップ１＞で得られた青色分散液の１０．６３ｇ、アルカリ現像性を付与する（Ｂ）成分として実施例５の＜ステップ１＞で得られたアルカリ現像性樹脂Ｎｏ．１の２．９３ｇ、（Ｂ）成分としてジペンタエリスリトールペンタ及びヘキサアクリレート（アロニックスＭ－４０２；東亞合成（株）製）０．３０ｇ、（Ｂ）成分としてウレタンアクリレートＵＮ３３２０ＨＳ（根上工業（株）製）０．３０ｇ、増感剤ＤＥＴＸ－Ｓ（日本化薬（株）製）０．０５ｇ、界面活性剤ＢＹＫ－３２３（ビック ケミー・ジャパン（株）製）のシクロヘキサノン１％溶液０．３０ｇ、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４．７２ｇ、並びにシクロヘキサノン１０．３６ｇを混合し、（Ａ）成分として実施例１で得られた化合物Ｎｏ．１の０．４１ｇを添加してよく攪拌し、本発明の感光性組成物である着色アルカリ現像性感光性樹脂組成物Ｎｏ．６を得た。 [Example 10] Colored alkali-developable photosensitive resin composition No. 6. Preparation (6) As component (D) 10.63 g of the blue dispersion obtained in <Step 1> of Example 9, and as component (B) imparting alkali developability, obtained in <Step 1> of Example 5 Alkali developable resin No. 1.93 g of 1, dipentaerythritol penta and hexaacrylate (Aronix M-402; manufactured by Toagosei Co., Ltd.) as component (B), urethane acrylate UN3320HS (produced by Negami Kogyo Co., Ltd.) as component (B) 0.30 g, Sensitizer DETX-S (Nippon Kayaku Co., Ltd.) 0.05 g, Surfactant BYK-323 (Bic Chemie Japan Co., Ltd.) cyclohexanone 1% solution 0.30 g, Propylene Glycol-1-monomethyl ether-2-acetate (4.72 g) and cyclohexanone (10.36 g) were mixed, and the compound No. 1 obtained in Example 1 as component (A) was mixed. 0.41 g of No. 1 was added and stirred well, and the colored alkali-developable photosensitive resin composition No. 1 which is the photosensitive composition of the present invention. 6 was obtained.
〔比較例７〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．７の製造
　実施例１で得られた化合物Ｎｏ．１をエタノン，１－［９－エチル－６－(２－メチルベンゾイル)－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）に替えた以外は実施例１０と同様の手法で、比較品である着色アルカリ現像性感光性樹脂組成物Ｎｏ．７を得た。 [Comparative Example 7] Colored alkali-developable photosensitive resin composition No. Preparation of Compound No. 7 obtained in Example 1 The same procedure as in Example 10 except that 1 was replaced with ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) In comparison, the colored alkali-developable photosensitive resin composition No. 7 was obtained.
〔比較例８〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．８の製造
　実施例１で得られた化合物Ｎｏ．１を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ン－１－オンに替えた以外は実施例１０と同様の手法で、比較品である着色アルカリ現像性感光性樹脂組成物Ｎｏ．８を得た。 [Comparative Example 8] Colored alkali-developable photosensitive resin composition No. Preparation of Compound No. 8 obtained in Example 1 Colored alkali-developable photosensitive resin composition as a comparative product in the same manner as in Example 10 except that 1 was replaced with 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one Item No. 8 was obtained.
〔比較例９〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．９の製造
　実施例１で得られた化合物Ｎｏ．１を１，２－オクタンジオン，１－［４－（フェニルチオ）フェニル］－，２－（Ｏ－ベンゾイルオキシム）に替えた以外は実施例１０と同様の手法で、比較品である着色アルカリ現像性感光性樹脂組成物Ｎｏ．９を得た。 [Comparative Example 9] Colored alkali-developable photosensitive resin composition No. Preparation of Compound No. 9 obtained in Example 1 Colored alkali development as a comparative product in the same manner as in Example 10 except that 1 is replaced with 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) Photosensitive resin composition No. 9 was obtained.
〔比較例１０〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．１０の製造
　実施例１で得られた化合物Ｎｏ．１を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）－１－ブタノンに替えた以外は実施例１０と同様の手法で、比較品である着色アルカリ現像性感光性樹脂組成物Ｎｏ．１０を得た。 [Comparative Example 10] Colored alkali-developable photosensitive resin composition No. Preparation of Compound No. 10 obtained in Example 1 Colored alkali-developable photosensitive resin composition as a comparative product in the same manner as in Example 10 except that 1 was replaced with 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone Item No. 10 was obtained.
＜フォトリソグラフィー性＞
　得られた着色アルカリ現像性感光性樹脂組成物Ｎｏ．６～１０のフォトリソグラフィー性の評価として、以下の手順における感度、密着性及び残渣について、それぞれ以下の方法により評価を行った。結果を〔表７〕に示す。
　ガラス基板上に着色アルカリ現像性感光性樹脂組成物をスピンコート（５００ｒｐｍ、７秒間）し、ホットプレートを用いて９０℃で９０秒間プリベークを行った。次いで、光源として高圧水銀ランプを用いてマスクを介して所定量（５０、１００又は１５０ｍＪ／ｃｍ2）露光した。現像液として２．５質量％炭酸ナトリウム水溶液を用い、スピン現像機で４５秒間現像後、よく水洗し、次いでオーブンを用いて２３０℃で３０分ポストベークを行い、パターンを定着させた。 <Photolithography>
The obtained colored alkali-developable photosensitive resin composition No. As photolithography evaluations of 6 to 10, sensitivity, adhesion and residue in the following procedures were evaluated by the following methods, respectively. The results are shown in [Table 7].
A colored alkali-developable photosensitive resin composition was spin-coated (500 rpm, 7 seconds) on a glass substrate, and prebaked at 90 ° C. for 90 seconds using a hot plate. Next, a predetermined amount (50, 100 or 150 mJ / cm 2 ) of light was exposed through a mask using a high pressure mercury lamp as a light source. A 2.5 mass% sodium carbonate aqueous solution was used as a developing solution, developed with a spin developing machine for 45 seconds, washed thoroughly with water, and then post-baked at 230 ° C. for 30 minutes using an oven to fix the pattern.
（感度）
　着色アルカリ現像性感光性樹脂組成物の感度を、次の４段階で評価した。
　即ち、形成されたパターンの線幅が、マスク開口線幅を超えた時の露光量が５０ｍＪ／ｃｍ2であった場合をａ、１００ｍＪ／ｃｍ2であった場合をｂ、１５０ｍＪ／ｃｍ2であった場合をｃ、１５０ｍＪ／ｃｍ2でもパターンが形成されなかった場合をｄとした。
（密着性）
　着色アルカリ現像性感光性樹脂組成物の密着性を、次の４段階で評価した。
　即ち、１００ｍＪ／ｃｍ2で露光、現像した後に残ったパターンの最も細かいマスク線 幅が３μｍ以下であった場合をＡ、３μｍ超１０μｍ以下であった場合をＢ、１０μｍ超１５μｍ以下であった場合をＣ、１５μｍ超であった場合をＤとした。
（残渣）
　現像後、非露光部のガラス面に残渣が全く観察されなかった場合を○、一面に残渣が観察された場合を×とした。 (sensitivity)
The sensitivity of the colored alkali-developable photosensitive resin composition was evaluated in the following four stages.
That is, the exposure amount when the line width of the formed pattern exceeds the mask opening line width is 50 mJ / cm 2 , a is 100 mJ / cm 2 , b is 150 mJ / cm 2 The case where there was c and the case where a pattern was not formed even at 150 mJ / cm 2 was taken as d.
(Adhesion)
The adhesion of the colored alkali-developable photosensitive resin composition was evaluated in the following four stages.
That is, when the finest mask line width of the pattern remaining after exposure and development at 100 mJ / cm 2 is 3 μm or less, A is more than 3 μm and 10 μm or less, and B is more than 10 μm and 15 μm or less. Is C, and D is the case when it exceeds 15 μm.
(Residue)
After development, the case where no residue was observed on the glass surface of the non-exposed part was marked with ◯, and the case where the residue was observed on one side was marked with x.
Figure JPOXMLDOC01-appb-T000032
Figure JPOXMLDOC01-appb-T000032
　表７より、本発明のオキシムエステル化合物は、比較例７で用いた化合物と比較して、残渣が確認されないため現像性に優れることが分かる。また、本発明のオキシムエステル化合物を用いると、比較例８～１０で用いた化合物と比較して、感度・密着性に優れる。 From Table 7, it can be seen that the oxime ester compound of the present invention is superior in developability since no residue is confirmed as compared with the compound used in Comparative Example 7. Further, when the oxime ester compound of the present invention is used, the sensitivity and adhesion are excellent as compared with the compounds used in Comparative Examples 8 to 10.
〔実施例１１〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．１１の製造
　（Ｄ）成分として実施例９の＜ステップ１＞におけるピグメントブルー１５：６をカーボンブラックに変更して作製したカーボンブラック分散液の７．０６ｇ、アルカリ現像性を付与する（Ｂ）成分として実施例５の＜ステップ１＞で得られたアルカリ現像性樹脂Ｎｏ．１の３．０７ｇ、（Ｂ）成分としてジペンタエリスリトールペンタ及びヘキサアクリレート（アロニックスＭ－４０２；東亜合成（株）製）０．５３ｇ、界面活性剤ＢＹＫ－３２３（ビックケミー・ジャパン（株）製）のシクロヘキサノン１％溶液０．３０ｇ、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８．１６ｇ、並びにシクロヘキサノン１０．６９ｇを混合し、（Ａ）成分として実施例１で得られた化合物Ｎｏ．１の０．１９ｇを添加してよく攪拌し、本発明の感光性組成物である着色アルカリ現像性感光性樹脂組成物Ｎｏ．１１を得た。 Example 11 Colored alkali-developable photosensitive resin composition No. 11: (D) 7.06 g of a carbon black dispersion prepared by changing Pigment Blue 15: 6 in <Step 1> of Example 9 to carbon black as component (D), component (B) imparting alkali developability As the alkali developable resin No. obtained in <Step 1> of Example 5. 3.07 g of component 1, dipentaerythritol penta and hexaacrylate (Aronix M-402; manufactured by Toagosei Co., Ltd.) 0.53 g, surfactant BYK-323 (produced by Big Chemie Japan Co., Ltd.) A mixture of 0.30 g of a 1% solution of cyclohexanone, 8.16 g of propylene glycol-1-monomethyl ether-2-acetate, and 10.69 g of cyclohexanone was mixed and compound No. 1 obtained in Example 1 as component (A) was mixed. 0.19 g of No. 1 was added and stirred well, and the colored alkali-developable photosensitive resin composition No. 1 which is the photosensitive composition of the present invention. 11 was obtained.
〔実施例１２〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．１２の製造
　実施例１で得られた化合物Ｎｏ．１を実施例２で得られた化合物Ｎｏ．２に替えた以外は実施例１１と同様の手法で、本発明の感光性組成物である着色アルカリ現像性感光性樹脂組成物Ｎｏ．１２を得た。 [Example 12] Colored alkali-developable photosensitive resin composition No. No. 12 Compound No. obtained in Example 1 1 to compound No. 1 obtained in Example 2. A colored alkali-developable photosensitive resin composition No. 1 which is the photosensitive composition of the present invention was prepared in the same manner as in Example 11 except that it was changed to 2. 12 was obtained.
〔実施例１３〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．１３の製造
　実施例１で得られた化合物Ｎｏ．１を実施例３で得られた化合物Ｎｏ．３に替えた以外は実施例１１と同様の手法で、本発明の感光性組成物である着色アルカリ現像性感光性樹脂組成物Ｎｏ．１３を得た。 [Example 13] Colored alkali-developable photosensitive resin composition No. Preparation of Compound No. 13 obtained in Example 1 1 to compound No. 1 obtained in Example 3. Except for the change to 3 in the same manner as in Example 11, the colored alkali-developable photosensitive resin composition No. 1 as the photosensitive composition of the present invention was used. 13 was obtained.
〔比較例１１〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．１４の製造
　実施例１で得られた化合物Ｎｏ．１をエタノン，１－［９－エチル－６－(２－メチル ベンゾイル)－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）に替えた以外は実施例１１と同様の手法で、比較品である着色アルカリ現像性感光性樹脂組成物Ｎｏ．１４を得た。 [Comparative Example 11] Colored alkali-developable photosensitive resin composition No. Preparation of Compound No. 14 obtained in Example 1 The same procedure as in Example 11 except that 1 is replaced with ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) In comparison, the colored alkali-developable photosensitive resin composition No. 14 was obtained.
〔比較例１２〕着色アルカリ現像性感光性樹脂組成物Ｎｏ．１５の製造
　実施例１で得られた化合物Ｎｏ．１を１，２－オクタンジオン，１－［４－（フェニルチオ）フェニル］－，２－（Ｏ－ベンゾイルオキシム）に替えた以外は実施例１１と同様の手法で、比較品である着色アルカリ現像性感光性樹脂組成物Ｎｏ．１５を得た。 [Comparative Example 12] Colored alkali-developable photosensitive resin composition No. No. 15 Compound No. obtained in Example 1 Colored alkali development as a comparative product in the same manner as in Example 11 except that 1 was replaced with 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) Photosensitive resin composition No. 15 was obtained.
＜フォトリソグラフィー性＞
　得られた着色アルカリ現像性感光性樹脂組成物Ｎｏ．１１～１５のフォトリソグラフィー性の評価として、以下の手順における感度、密着性及び現像性について、それぞれ以下の方法により評価を行った。結果を〔表８〕に示す。
　ガラス基板上に着色アルカリ現像性感光性樹脂組成物をスピンコート（５００ｒｐｍ、７秒間）し、ホットプレートを用いて９０℃で９０秒間プリベークを行った。次いで、光源として高圧水銀ランプを用いてマスクを介して所定量（１００又は１２０ｍＪ／ｃｍ2）露光した。現像液として２．５質量％炭酸ナトリウム水溶液を用い、スピン現像機で４５秒間現像後、よく水洗し、次いでオーブンを用いて２３０℃で３０分ポストベークを行い、パターンを定着させた。 <Photolithography>
The obtained colored alkali-developable photosensitive resin composition No. As evaluations of photolithographic properties 11 to 15, the sensitivity, adhesion and developability in the following procedures were evaluated by the following methods, respectively. The results are shown in [Table 8].
A colored alkali-developable photosensitive resin composition was spin-coated (500 rpm, 7 seconds) on a glass substrate, and prebaked at 90 ° C. for 90 seconds using a hot plate. Next, a predetermined amount (100 or 120 mJ / cm 2 ) of light was exposed through a mask using a high-pressure mercury lamp as a light source. A 2.5 mass% sodium carbonate aqueous solution was used as a developing solution, developed with a spin developing machine for 45 seconds, washed thoroughly with water, and then post-baked at 230 ° C. for 30 minutes using an oven to fix the pattern.
（感度）
　着色アルカリ現像性感光性樹脂組成物の感度を、次の３段階で評価した。
　即ち、形成されたパターンの線幅が、マスク開口線幅を超えた時の露光量が１００ｍＪ／ｃｍ2であった場合をａ、１２０ｍＪ／ｃｍ2であった場合をｂ、１２０ｍＪ／ｃｍ2でもパターンが形成されなかった場合をｃとした。
（密着性）
　着色アルカリ現像性感光性樹脂組成物の密着性を、次の４段階で評価した。
　即ち、１００ｍＪ／ｃｍ2で露光、現像した後に残ったパターンの最も細かいマスク線幅が３μｍ以下であった場合をＡ、３μｍ超５μｍ以下であった場合をＢ、５μｍ超であった場合をＣとした。
（現像性）
　現像後、非露光部のガラス面に残渣が全く観察されなかった場合を○、一面に残渣が観察された場合を×とした。 (sensitivity)
The sensitivity of the colored alkali-developable photosensitive resin composition was evaluated in the following three stages.
That is, when the line width of the formed pattern exceeds the mask opening line width, the exposure amount is 100 mJ / cm 2 , a is 120 mJ / cm 2 , b is 120 mJ / cm 2 The case where a pattern was not formed was defined as c.
(Adhesion)
The adhesion of the colored alkali-developable photosensitive resin composition was evaluated in the following four stages.
That is, when the finest mask line width of the pattern remaining after exposure and development at 100 mJ / cm 2 is 3 μm or less, A is more than 3 μm and 5 μm or less, B is more than 5 μm, and C is more than 5 μm. It was.
(Developability)
After development, the case where no residue was observed on the glass surface of the non-exposed part was marked with ◯, and the case where the residue was observed on one side was marked with x.
Figure JPOXMLDOC01-appb-T000033
Figure JPOXMLDOC01-appb-T000033
　表８より、本発明のオキシムエステル化合物を用いると、比較例１２で用いた化合物と比較して、感度及び密着性が良好であることが分かる。また、感度及び密着性の良好な比較例１１と比べ、本発明のオキシムエステル化合物を用いると現像性に優れることが分かる。 From Table 8, it can be seen that when the oxime ester compound of the present invention is used, the sensitivity and adhesion are better than those of the compound used in Comparative Example 12. Moreover, it turns out that it is excellent in developability when the oxime ester compound of this invention is used compared with the comparative example 11 with favorable sensitivity and adhesiveness.
　以上の結果から、以下のことが分かる。
　本発明のオキシムエステル化合物を用いると、比較例２、３、７及び１１で用いた化合物と比較して、可視光領域の透過性及び現像性に優れる。
　また、本発明のオキシムエステル化合物を用いると、比較例４及び８で用いた化合物と比較して、可視光領域の透過性、耐熱性、感度及び密着性に優れる。
　また、本発明のオキシムエステル化合物を用いると、比較例５、９及び１２で用いた化合物と比較して、耐熱性、感度及び密着性に優れる。
　また、本発明のオキシムエステル化合物を用いると、比較例１、６及び１０で用いた化合物と比較して、可視光領域の透過性、耐熱性、感度及び密着性に優れる。 From the above results, the following can be understood.
When the oxime ester compound of the present invention is used, the transparency and developability in the visible light region are excellent as compared with the compounds used in Comparative Examples 2, 3, 7, and 11.
In addition, when the oxime ester compound of the present invention is used, it is excellent in transparency, heat resistance, sensitivity, and adhesion in the visible light region as compared with the compounds used in Comparative Examples 4 and 8.
Moreover, when the oxime ester compound of this invention is used, it is excellent in heat resistance, a sensitivity, and adhesiveness compared with the compound used in Comparative Examples 5, 9, and 12.
In addition, when the oxime ester compound of the present invention is used, it is excellent in transparency, heat resistance, sensitivity and adhesion in the visible light region as compared with the compounds used in Comparative Examples 1, 6 and 10.
　以上の通り、本発明のオキシムエステル化合物を用いると、可視光領域の透過性が高く、耐熱性に優れ、フォトリソグラフィー性に優れており、本発明のオキシムエステル化合物は光重合開始剤として有用である。 As described above, when the oxime ester compound of the present invention is used, the visible light region has high transparency, excellent heat resistance, and excellent photolithography properties. The oxime ester compound of the present invention is useful as a photopolymerization initiator. is there.

Claims (8)

  1. 　下記一般式（１）で表されるオキシムエステル化合物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1、Ｒ2、Ｒ3及びＲ4は、それぞれ独立に、Ｒ11、ＯＲ11、ＣＯＯＲ11、ＳＲ11、ＳＯ2Ｒ11、ＣＯＮＲ12Ｒ13又はＣＮを表し、
    　Ｒ11、Ｒ12及びＲ13は、それぞれ独立に、水素原子、又は炭素原子数１～２０のアルキル基、炭素原子数６～３０のアリール基、炭素原子数７～３０のアリールアルキル基若しくは炭素原子数２～２０の複素環基である置換基を表し、
    　Ｒ11、Ｒ12及びＲ13で表わされる置換基の水素原子は、更にＯＲ21、ＣＯＲ21、ＳＲ21、ＮＲ22Ｒ23、ＣＯＮＲ22Ｒ23、－ＮＲ22－ＯＲ23、－ＮＲ22ＣＯ－ＯＣＯＲ23、－Ｃ（＝Ｎ－ＯＲ21）－Ｒ22、－Ｃ（＝Ｎ－ＯＣＯＲ21）－Ｒ22、ＣＮ、ハロゲン原子、－ＣＯＯＲ21、－ＣＲ21＝ＣＲ22Ｒ23、－ＣＯ－ＣＲ21＝ＣＲ22Ｒ23、－Ｏ－ＣＯ－ＣＲ21＝ＣＲ22Ｒ23、－Ｎ＝Ｃ＝Ｏ又はエポキシ基で置換されていてもよく、
    　Ｒ21、Ｒ22及びＲ23は、それぞれ独立に、水素原子、又は炭素原子数１～２０のアルキル基、炭素原子数６～３０のアリール基、炭素原子数７～３０のアリールアルキル基若しくは炭素原子数２～２０の複素環基である置換基を表し、
    　Ｒ21、Ｒ22及びＲ23で表される置換基の水素原子は、更に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てもよく、
    　Ｒ11、Ｒ12、Ｒ13、Ｒ21、Ｒ22及びＲ23で表される置換基のアルキレン部分は、－Ｏ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ24－、－ＮＲ24ＣＯＯ－、－ＯＣＯＮＲ24－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又は－ＣＳＯ－により１～５回中断されていてもよく、
    　Ｒ24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の複素環基を表し、
    　Ｒ11、Ｒ12、Ｒ13、Ｒ21、Ｒ22及びＲ23で表される置換基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、また、Ｒ12とＲ13及びＲ22とＲ23はそれぞれ一緒になって環を形成していてもよく、
    　Ｘは、酸素原子、硫黄原子、セレン原子、ＣＲ31Ｒ32、ＣＯ、ＮＲ33又はＰＲ34を表し、
    　Ｒ31、Ｒ32、Ｒ33及びＲ34は、それぞれ独立に、水素原子、又は炭素原子数１～２０のアルキル基、炭素原子数６～３０のアリール基若しくは炭素原子数７～３０のアリールアルキル基である置換基を表し、
    　Ｒ31、Ｒ32、Ｒ33及びＲ34で表される置換基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、Ｒ31、Ｒ32、Ｒ33及びＲ34で表される置換基のアルキル末端は不飽和結合であってもよく、Ｒ31、Ｒ32、Ｒ33及びＲ34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てもよく、
    　ａは、０～４の整数を表し、
    　ｂは、１～５の整数を表し、
    　Ｒ4の少なくとも一つは、－ＣＲ21＝ＣＲ22Ｒ23、－ＣＯ－ＣＲ21＝ＣＲ22Ｒ23、－Ｏ－ＣＯ－ＣＲ21＝ＣＲ22Ｒ23、－Ｎ＝Ｃ＝Ｏ又はエポキシ基を有する基である。）     An oxime ester compound represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 , R 2 , R 3 and R 4 each independently represents R 11 , OR 11 , COOR 11 , SR 11 , SO 2 R 11 , CONR 12 R 13 or CN;
    R 11 , R 12 and R 13 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 substituent which is a heterocyclic group having 2 to 20 atoms;
    The hydrogen atom of the substituent represented by R 11 , R 12 and R 13 is further OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , —NR 22 —OR 23 , —NR 22 CO—. OCOR 23 , —C (═N—OR 21 ) —R 22 , —C (═N—OCOR 21 ) —R 22 , CN, halogen atom, —COOR 21 , —CR 21 ═CR 22 R 23 , —CO— CR 21 ═CR 22 R 23 , —O—CO—CR 21 ═CR 22 R 23 , —N═C═O or an epoxy group may be substituted,
    R 21 , R 22 and R 23 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 substituent which is a heterocyclic group having 2 to 20 atoms;
    The hydrogen atom of the substituent represented by R 21 , R 22 and R 23 may be further substituted with CN, a halogen atom, a hydroxyl group or a carboxyl group,
    The alkylene part of the substituent represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 is —O—, —S—, —COO—, —OCO—, —NR 24 —, — May be interrupted 1 to 5 times by NR 24 COO—, —OCONR 24 —, —SCO—, —COS—, —OCS— or —CSO—,
    R 24 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 group having 2 to 20 carbon atoms. ,
    Alkyl moiety of the substituents represented by R 11, R 12, R 13 , R 21, R 22 and R 23, there may be branched side chain, may be a cyclic alkyl, and the R 12 R 13 and R 22 and R 23 may be combined to form a ring,
    X represents an oxygen atom, a sulfur atom, a selenium atom, CR 31 R 32 , CO, NR 33 or PR 34 ;
    R 31 , R 32 , R 33 and R 34 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl having 7 to 30 carbon atoms. Represents a substituent that is a group,
    The alkyl part of the substituent represented by R 31 , R 32 , R 33 and R 34 may have a branched side chain or may be a cyclic alkyl. R 31 , R 32 , R 33 and R 34 The alkyl terminal of the substituent represented by the above formula may be an unsaturated bond, and R 31 , R 32 , R 33 and R 34 each independently form a ring together with one of the adjacent benzene rings. May be formed,
    a represents an integer of 0 to 4,
    b represents an integer of 1 to 5,
    At least one of R 4 is —CR 21 ═CR 22 R 23 , —CO—CR 21 ═CR 22 R 23 , —O—CO—CR 21 ═CR 22 R 23 , —N═C═O or an epoxy group It is group which has. )
  2. 　請求項１に記載のオキシムエステル化合物を含有してなる光重合開始剤。 A photopolymerization initiator comprising the oxime ester compound according to claim 1.
  3. 　（Ａ）請求項２に記載の光重合開始剤、及び（Ｂ）エチレン性不飽和結合を有する重合性化合物を含有してなる感光性組成物。 (A) A photosensitive composition comprising the photopolymerization initiator according to claim 2 and (B) a polymerizable compound having an ethylenically unsaturated bond.
  4. 　上記（Ｂ）エチレン性不飽和結合を有する重合性化合物の少なくとも一つが、アルカリ現像性を付与する化合物である請求項３に記載の感光性組成物。 The photosensitive composition according to claim 3, wherein at least one of the polymerizable compound (B) having an ethylenically unsaturated bond is a compound imparting alkali developability.
  5. 　更に（Ｃ）無機化合物を含有してなる請求項３又は４に記載の感光性組成物。 The photosensitive composition according to claim 3 or 4, further comprising (C) an inorganic compound.
  6. 　更に（Ｄ）色材を含有してなる請求項３～５の何れか一項に記載の感光性組成物。 The photosensitive composition according to any one of claims 3 to 5, further comprising (D) a coloring material.
  7. 　請求項３～６の何れか一項に記載の感光性組成物にエネルギー線を照射してなる硬化物。 A cured product obtained by irradiating the photosensitive composition according to any one of claims 3 to 6 with an energy ray.
  8. 　請求項７に記載の硬化物を用いたカラーフィルタ。 A color filter using the cured product according to claim 7.
PCT/JP2012/052775 2011-03-25 2012-02-07 Oxime ester compound and photoinitiator containing said compound WO2012132558A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020137016528A KR101930099B1 (en) 2011-03-25 2012-02-07 Oxime ester compound and photoinitiator containing said compound
JP2013507233A JP6000942B2 (en) 2011-03-25 2012-02-07 Oxime ester compound and photopolymerization initiator containing the compound
CN201280004665.9A CN103298782B (en) 2011-03-25 2012-02-07 Oxime ester compound and the Photoepolymerizationinitiater initiater containing this compound

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011067406 2011-03-25
JP2011-067406 2011-03-25

Publications (1)

Publication Number Publication Date
WO2012132558A1 true WO2012132558A1 (en) 2012-10-04

Family

ID=46930324

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/052775 WO2012132558A1 (en) 2011-03-25 2012-02-07 Oxime ester compound and photoinitiator containing said compound

Country Status (5)

Country Link
JP (1) JP6000942B2 (en)
KR (1) KR101930099B1 (en)
CN (1) CN103298782B (en)
TW (1) TWI541221B (en)
WO (1) WO2012132558A1 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5337293B1 (en) * 2012-11-13 2013-11-06 積水化学工業株式会社 Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element
CN104395824A (en) * 2012-11-01 2015-03-04 株式会社艾迪科 Alkali developable photosensitive composition
WO2015029846A1 (en) * 2013-08-29 2015-03-05 積水化学工業株式会社 Sealant for display element, and oxime ester initiator
JP2017078049A (en) * 2015-10-22 2017-04-27 株式会社Adeka Oxime ester compound and polymerization initiator comprising the compound
JP2017132863A (en) * 2016-01-26 2017-08-03 積水化学工業株式会社 Oxime ester initiator, curable resin composition, sealant for liquid crystal display elements, vertical conduction material, and liquid crystal display element
JP2019519518A (en) * 2016-05-19 2019-07-11 サムヤン コーポレイション Oxime ester derivative compound, photoinitiator containing the same, and photosensitive composition
WO2019168113A1 (en) * 2018-03-01 2019-09-06 日本化薬株式会社 Novel compound, photopolymerization initiator containing said compound, and photosensitive resin composition containing said photopolymerization initiator
US10921708B2 (en) 2015-12-08 2021-02-16 Fujifilm Corporation Radiation-sensitive resin composition, cured film, pattern forming method, solid-state imaging device, and image display device
WO2023085058A1 (en) 2021-11-09 2023-05-19 住友化学株式会社 Resin composition, resin film, and display device
WO2023085061A1 (en) 2021-11-09 2023-05-19 住友化学株式会社 Resin film and display device

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6788971B2 (en) * 2016-01-14 2020-11-25 東京応化工業株式会社 Photosensitive composition
WO2017169819A1 (en) * 2016-03-29 2017-10-05 株式会社Adeka Black photosensitive resin composition
WO2017200354A1 (en) * 2016-05-19 2017-11-23 주식회사 삼양사 Oxime ester derivative compound, photopolymerization initiator comprising same, and photosensitive composition
TWI774931B (en) * 2018-03-02 2022-08-21 日商日本化藥股份有限公司 Novel compound, photopolymerization initiator comprising the compound, and photosensitive resin composition containing the photopolymerization initiator
CN114127637A (en) * 2019-07-12 2022-03-01 株式会社三养社 Photosensitive resin composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007310317A (en) * 2006-05-22 2007-11-29 Fujifilm Corp Photopolymerization composition, color filter, and manufacturing method therefor
JP2009047871A (en) * 2007-08-20 2009-03-05 Fujifilm Corp Composition for holographic recording, holographic recording medium, information recording method and new compound
JP2009242469A (en) * 2008-03-28 2009-10-22 Fujifilm Corp Polymerizable composition, color filter, method for manufacturing color filter, and solid imaging element
JP2011099974A (en) * 2009-11-05 2011-05-19 Fujifilm Corp Colored photosensitive composition, color filter, and liquid crystal display device

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG77689A1 (en) * 1998-06-26 2001-01-16 Ciba Sc Holding Ag New o-acyloxime photoinitiators
JP5179379B2 (en) * 2006-12-27 2013-04-10 株式会社Ａｄｅｋａ Oxime ester compound and photopolymerization initiator containing the compound
JP4818458B2 (en) * 2009-11-27 2011-11-16 株式会社Ａｄｅｋａ Oxime ester compound and photopolymerization initiator containing the compound

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007310317A (en) * 2006-05-22 2007-11-29 Fujifilm Corp Photopolymerization composition, color filter, and manufacturing method therefor
JP2009047871A (en) * 2007-08-20 2009-03-05 Fujifilm Corp Composition for holographic recording, holographic recording medium, information recording method and new compound
JP2009242469A (en) * 2008-03-28 2009-10-22 Fujifilm Corp Polymerizable composition, color filter, method for manufacturing color filter, and solid imaging element
JP2011099974A (en) * 2009-11-05 2011-05-19 Fujifilm Corp Colored photosensitive composition, color filter, and liquid crystal display device

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104395824A (en) * 2012-11-01 2015-03-04 株式会社艾迪科 Alkali developable photosensitive composition
TWI619760B (en) * 2012-11-01 2018-04-01 Adeka Corp Alkali developed photosensitive composition
JP5337293B1 (en) * 2012-11-13 2013-11-06 積水化学工業株式会社 Sealant for liquid crystal display element, vertical conduction material, and liquid crystal display element
WO2015029846A1 (en) * 2013-08-29 2015-03-05 積水化学工業株式会社 Sealant for display element, and oxime ester initiator
JP2017078049A (en) * 2015-10-22 2017-04-27 株式会社Adeka Oxime ester compound and polymerization initiator comprising the compound
TWI731895B (en) * 2015-12-08 2021-07-01 日商富士軟片股份有限公司 Radiation-sensitive resin composition, cured film, pattern forming method, solid-state imaging device, and image display device
US10921708B2 (en) 2015-12-08 2021-02-16 Fujifilm Corporation Radiation-sensitive resin composition, cured film, pattern forming method, solid-state imaging device, and image display device
JP2017132863A (en) * 2016-01-26 2017-08-03 積水化学工業株式会社 Oxime ester initiator, curable resin composition, sealant for liquid crystal display elements, vertical conduction material, and liquid crystal display element
JP2021011486A (en) * 2016-05-19 2021-02-04 サムヤン コーポレイション Oxime ester derivative compounds, and photopolymerization initiator and photosensitive composition containing the same
JP2019519518A (en) * 2016-05-19 2019-07-11 サムヤン コーポレイション Oxime ester derivative compound, photoinitiator containing the same, and photosensitive composition
JP7002617B2 (en) 2016-05-19 2022-01-20 サムヤン コーポレイション Oxime ester derivative compound, photopolymerization initiator and photosensitive composition containing the same.
WO2019168113A1 (en) * 2018-03-01 2019-09-06 日本化薬株式会社 Novel compound, photopolymerization initiator containing said compound, and photosensitive resin composition containing said photopolymerization initiator
JPWO2019168113A1 (en) * 2018-03-01 2021-02-25 日本化薬株式会社 A novel compound, a photopolymerization initiator containing the compound, and a photosensitive resin composition containing the photopolymerization initiator.
JP7232241B2 (en) 2018-03-01 2023-03-02 日本化薬株式会社 Novel compound, photopolymerization initiator comprising said compound, and photosensitive resin composition containing said photopolymerization initiator
US11608316B2 (en) 2018-03-01 2023-03-21 Nippon Kayaku Kabushiki Kaisha Compound, photopolymerization initiator containing said compound, and photosensitive resin composition containing said photopolymerization initiator
WO2023085058A1 (en) 2021-11-09 2023-05-19 住友化学株式会社 Resin composition, resin film, and display device
WO2023085061A1 (en) 2021-11-09 2023-05-19 住友化学株式会社 Resin film and display device

Also Published As

Publication number Publication date
JP6000942B2 (en) 2016-10-05
CN103298782B (en) 2016-04-06
CN103298782A (en) 2013-09-11
KR101930099B1 (en) 2018-12-17
TWI541221B (en) 2016-07-11
KR20130140096A (en) 2013-12-23
JPWO2012132558A1 (en) 2014-07-24
TW201242931A (en) 2012-11-01

Similar Documents

Publication Publication Date Title
JP6000942B2 (en) Oxime ester compound and photopolymerization initiator containing the compound
JP4818458B2 (en) Oxime ester compound and photopolymerization initiator containing the compound
JP6595983B2 (en) Oxime ester compound and photopolymerization initiator containing the compound
JP6301249B2 (en) Photosensitive composition
KR102160115B1 (en) Photo-curable composition
JP2015007729A (en) Photocurable black composition
JP6572213B2 (en) Novel polymerization initiator and radically polymerizable composition containing the polymerization initiator
JP6457719B2 (en) Photocurable composition
JP2019168654A (en) Photosensitive composition
JP2015093842A (en) Oxime ester compound and photopolymerization initiator containing the compound
WO2020241529A1 (en) Carbamoyl oxime compound, and polymerization initiator and polymerizable composition containing said compound
JP6530902B2 (en) Novel polymerization initiator and radically polymerizable composition containing the polymerization initiator
KR102545326B1 (en) Oxime ester compound and photopolymerization initiator containing the compound
JP6539476B2 (en) Oxime ester compound and photopolymerization initiator containing the compound
JP2017179211A (en) Curable composition, alkali development curable composition, cured article and method for manufacturing cured article
JP2016079157A (en) New polymerization initiator and radical polymerizable composition containing polymerization initiator
JP6778108B2 (en) Photosensitive composition
JP2017124998A (en) Compound, composition and photopolymerization initiator

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201280004665.9

Country of ref document: CN

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

Ref document number: 12763061

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013507233

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20137016528

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12763061

Country of ref document: EP

Kind code of ref document: A1

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112013018908

Country of ref document: BR

REG Reference to national code

Ref country code: BR

Ref legal event code: B01E

Ref document number: 112013018908

Country of ref document: BR

ENPW Started to enter national phase and was withdrawn or failed for other reasons

Ref document number: 112013018908

Country of ref document: BR