WO2018168714A1 - Oxime ester compound and photopolymerization initiator containing said compound - Google Patents

Oxime ester compound and photopolymerization initiator containing said compound Download PDF

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WO2018168714A1
WO2018168714A1 PCT/JP2018/009317 JP2018009317W WO2018168714A1 WO 2018168714 A1 WO2018168714 A1 WO 2018168714A1 JP 2018009317 W JP2018009317 W JP 2018009317W WO 2018168714 A1 WO2018168714 A1 WO 2018168714A1
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carbon atoms
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general formula
represented
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PCT/JP2018/009317
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良智 竹内
大樹 三原
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株式会社Adeka
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Priority to CN201880004717.XA priority Critical patent/CN110023307B/en
Priority to JP2019505981A priority patent/JP7482628B2/en
Priority to KR1020197014559A priority patent/KR102545326B1/en
Publication of WO2018168714A1 publication Critical patent/WO2018168714A1/en

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    • 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
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/80—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/56—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

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, and a photosensitizer containing the photopolymerization initiator and an ethylenically unsaturated compound.
  • the present invention relates to a sex composition.
  • the photosensitive composition is obtained by adding a photopolymerization initiator to an ethylenically unsaturated compound and can be polymerized and cured by irradiating energy rays (light). Therefore, a photocurable ink, a photosensitive printing plate It is used for various photoresists.
  • Patent Document 1 discloses a highly sensitive oxime ester photoinitiator having a heteroaromatic ring
  • Patent Document 2 discloses a photopolymerization initiator at 365 to 405 nm.
  • a high-sensitivity photopolymerization initiator having a large absorption capacity is disclosed
  • Patent Document 3 discloses a photopolymerization initiator that can achieve a photosensitive composition with high sensitivity and high resolution.
  • the sensitivity of the oxime ester compounds described in these patent documents is not always satisfactory, and further improvement in sensitivity is desired.
  • the colored alkali-developable photosensitive resin composition containing a colorant used for a color filter or the like is required to have particularly 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 photopolymerization initiator used has a high transmittance in the visible light region.
  • the transmittance in the visible light region is low, a problem such as a decrease in luminance occurs.
  • the photopolymerization initiator is used by being dissolved in an organic solvent when used in various applications, it is also required to have high solubility in the organic solvent.
  • the problem to be solved is that there has been no photopolymerization initiator having satisfactory sensitivity, high solubility in an organic solvent, and high transmittance in the visible light region.
  • an object of the present invention is a highly sensitive compound that can efficiently absorb and activate near ultraviolet light such as 365 nm, has high solubility in an organic solvent, and has high transmittance in the visible light region.
  • the object is to provide a novel compound useful as a polymerization initiator, a photopolymerization initiator using the compound, and a photosensitive composition.
  • the present invention achieves the above object by providing the following [1] to [11].
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a group represented by the following general formula (II), hydrogen atom, halogen atom, nitro group, cyano group , Hydroxyl group, carboxyl group, R 21 , OR 21 , SR 21 , NR 22 R 23 , COR 21 , SOR 21 , SO 2 R 21 or CONR 22 R 23 , At least one of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is a group represented by the following general formula (II), R 7 , R 8 , R 9 , R 10 and R 11 are each independently a group represented by the following general formula (III ⁇ ), a group represented by the following general formula (III ⁇ ), a hydrogen atom, a halogen atom, A nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 21 , OR 21 , SR 21 , NR 22 R 23
  • a mercapto group, an isocyanate group or a heterocycle-containing group, the hydrocarbon group having 2 to 20 carbon atoms or the methylene group in the heterocycle-containing group having 2 to 20 carbon atoms may be represented by —O— , —CO—, —COO—, —OCO—, —NR 24 —, —NR 24 CO—, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO
  • R 24 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • X 1 represents absence, direct bond, —CO—, —O— or —S—, R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 And R 11 , and R 11 and R 1 may combine to
  • R 31 and R 32 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms.
  • the hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms represented by R 31 and R 32 is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, It may be substituted with a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group, and the number of carbon atoms represented by R 31 and R 32 is 2 to
  • the methylene group in the hydrocarbon group having 20 or the heterocyclic group having 2 to 20 carbon atoms is —O—, —CO—, —COO—, —OCO—, —NR 33 —, —NR 33 CO—, May be substituted with —S—, —CS—, —SO 2 —, —SCO—, —COS
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 and R 50 are each independently a hydrogen atom, a halogen atom, a nitro group, or a cyano group.
  • R 51 , OR 51 , SR 51 , NR 52 R 53 , COR 51 , SOR 51 , SO 2 R 51 or CONR 52 R 53 , R 51 , R 52 and R 53 each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group containing 2 to 20 carbon atoms,
  • the hydrogen atoms in the groups represented by R 51 , R 52 and R 53 are halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups.
  • a mercapto group, an isocyanate group or a heterocycle-containing group, the hydrocarbon group having 2 to 20 carbon atoms or the methylene group in the heterocycle-containing group having 2 to 20 carbon atoms may be represented by —O— , —CO—, —COO—, —OCO—, —NR 54 —, —NR 54 CO—, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO May be replaced with- X 2 and X 3 represent —O—, —S— or —NR 54 —, R 54 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, * Represents a bond. )
  • R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 are each independently a group represented by the above general formula (II), a hydrogen atom, a halogen atom , A nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 121 , OR 121 , SR 121 , NR 122 R 123 , COR 121 , SOR 121 , SO 2 R 121 or CONR 122 R 123 , At least one of R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 is a group represented by the general formula (II), R 109 , R 110 , R 111 , R 112 and R 113 are each independently a group represented by the general formula (III ⁇ ), a group represented by the general formula (III ⁇ ), a hydrogen atom,
  • a mercapto group, an isocyanate group or a heterocycle-containing group, the hydrocarbon group having 2 to 20 carbon atoms or the methylene group in the heterocycle-containing group having 2 to 20 carbon atoms may be represented by —O— , —CO—, —COO—, —OCO—, —NR 124 —, —NR 124 CO—, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO May be replaced with- R 124 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, X 101 represents absence, direct bond, —CO—, —O— or —S—, R101 and R102 , R102 and R103 , R103 and R104 , R105 and R106 , R106 and R107 , R107 and R108 , R108 and R109 , R109 and R110 , R110 And R 111 , R 111
  • a photosensitive composition comprising the photopolymerization initiator (A) according to [5] and an ethylenically unsaturated compound (B).
  • a method for producing a cured product comprising the step of curing the composition using the photosensitive composition according to [6] or [7] or the alkali-developable photosensitive resin composition according to [8]. .
  • the oxime ester compound of the present invention is a novel compound represented by the above general formula (I ⁇ ) or (I ⁇ ).
  • the oxime ester compound has a geometric isomer due to an oxime double bond, but the present invention does not distinguish these. That is, in the present specification, the compound represented by the above general formula (I ⁇ ) or (I ⁇ ) and the exemplified compound thereof represent one or a mixture of two or more of these geometric isomers and have a structure. It is not limited to a specific isomer.
  • the hydrocarbon groups having 1 to 20 carbon atoms represented by R 21 to R 24 in the general formula (I ⁇ ) and R 121 to R 124 in the general formula (I ⁇ ) are not particularly limited.
  • an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, a carbon atom Represents an aryl group having 6 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms.
  • alkyl group having 1 to 20 carbon atoms examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl. 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like.
  • alkenyl group having 2 to 20 carbon atoms examples include vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, Examples include 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl and 4,8,12-tetradecatrienylallyl.
  • the above cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms.
  • Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo [1.1.1] pentanyl.
  • the cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with a cycloalkyl group.
  • aryl group having 6 to 20 carbon atoms examples include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl, biphenylyl, naphthyl, anthryl substituted with one or more of the above alkyl groups. It is done.
  • the arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with an aryl group.
  • Examples include benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and naphthylpropyl.
  • hydrocarbon groups having 1 to 20 carbon atoms because of their high sensitivity as a photopolymerization initiator, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 3 to 3 carbon atoms
  • a cycloalkyl group having 10 carbon atoms, a cycloalkylalkyl group having 4 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms and an arylalkyl group having 7 to 15 carbon atoms are particularly preferred.
  • heterocyclic group containing 2 to 20 carbon atoms represented by R 21 to R 23 in the general formula (I ⁇ ) and R 121 to R 123 in the general formula (I ⁇ ) include pyrrolyl, Pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl , Thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, urolidy
  • the heterocyclic group having 2 to 10 carbon atoms is particularly preferable because of its high sensitivity as a photopolymerization initiator.
  • the methylene group in the group represented by R 21 to R 23 in the general formula (I ⁇ ) is —O—, —CO—, —COO—, —OCO—, —NR 24 —, —NR 24 CO—.
  • —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO— may be substituted, and R 121 to R in the above general formula (I ⁇ ) methylene groups in the group represented by 123, -O -, - CO -, - COO -, - OCO -, - NR 124 -, - NR 124 CO -, - S -, - CS -, - SO 2 -, -SCO-, -COS-, -OCS- or CSO- may be substituted, and these substitutions are caused by one or more groups, and in the case of groups that can be substituted successively May be successively substituted by two
  • R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 R 11 , R 11 and R 1 , R 101 and R 102 , R 102 and R 103 , R 103 and R 104 , R 105 and R 106 , R 106 and R 107 , R 107 and R 108 , R 108 and R 109 , R 109 and R 110 , R 110 and R 111 , R 111 and R 112 , R 112 and R 113, and R 113 and R 101 may be combined to form, for example, cyclopentane, cyclohexane, cyclopentene, Benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, 5- to 7-membered rings such as lactone
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 31 to R 33 in the general formula (II) include R 21 to R 24 in the general formula (I ⁇ ) or the general formula (I ⁇ ). Examples thereof include the same hydrocarbon groups having 1 to 20 carbon atoms represented by R 121 to R 124 .
  • heterocyclic group having 2 to 20 carbon atoms represented by R 31 and R 32 in the general formula (II) examples include R 21 to R 23 in the general formula (I ⁇ ) and the general formula (I Examples thereof include those similar to the heterocyclic group having 2 to 20 carbon atoms represented by R 121 to R 123 in I ⁇ ).
  • the methylene group in the groups represented by R 31 and R 32 is —O—, —CO—, —COO—, —OCO—, —NR 33 —, —NR 33 CO May be substituted with —, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO—, this substitution being by one or more groups
  • the oxygen atom may be continuously substituted by two or more groups under the condition that they are not adjacent to each other.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 51 to R 54 in the general formulas (III ⁇ ) and (III ⁇ ) include R 21 to R 24 in the general formula (I ⁇ ) and the above general formulas Examples thereof include the same hydrocarbon groups having 1 to 20 carbon atoms represented by R 121 to R 124 in the formula (I ⁇ ).
  • Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R 51 to R 53 in the general formulas (III ⁇ ) and (III ⁇ ) include R 21 to R 23 in the general formula (I ⁇ ) and the above Examples thereof include those similar to the heterocyclic group having 2 to 20 carbon atoms represented by R 121 to R 123 in the general formula (I ⁇ ).
  • halogen atoms in the general formulas (I ⁇ ), (I ⁇ ), (II), (III ⁇ ) and (III ⁇ ) include fluorine, chlorine, bromine and iodine.
  • the oxime ester compound in which at least one of R 3 and R 5 in the general formula (I ⁇ ) is a group represented by the general formula (II) has a good yield at the time of synthesis. It is preferable because purification is easy.
  • an oxime ester compound in which at least one of R 103 and R 106 in the general formula (I ⁇ ) is a group represented by the general formula (II) has a yield during synthesis. It is preferable because it is well purified. From the same viewpoint, an oxime ester compound in which both R 103 and R 106 in the general formula (I ⁇ ) are groups represented by the general formula (II) is also preferable.
  • R 1 and R 101 are groups or atoms other than the group represented by the general formula (II)
  • R 1 and R 101 are hydrogen atoms or cyano groups
  • a hydrogen atom is preferable because it is easy to synthesize.
  • R 2 to R 5 and R 102 to R 107 is the same as R 1 . That is, when R 2 to R 5 and R 102 to R 106 are groups or atoms other than the group represented by formula (II), R 2 to R 5 and R 102 to R 106 are hydrogen atoms or cyano groups.
  • a hydrogen atom is preferable because synthesis is easy.
  • R 6 and R 108 are groups or atoms other than the group represented by the general formula (II), R 6 and R 108 are hydrogen atoms. Is preferable because it is easy to synthesize.
  • the oxime ester compound in which X 1 in the general formula (I ⁇ ) is absent and R 5 and R 6 are bonded to form a benzene ring is effective in the near ultraviolet light (especially 365 nm). It is preferable because it can be absorbed well.
  • X 1 is absent means that in the general formula (I ⁇ ), a bond represented by —X 1 — does not exist and a condensed ring skeleton containing an N atom and X 1 is formed. It means a state that is not done.
  • oxime ester compounds in which X 1 is to form a benzene ring bonded R 5 and R 6 in the absence described above, the triphenylamine skeleton rather than a condensed ring skeleton containing N atoms and X 1
  • Specific examples of the compound include compound Nos. Described later. 153 to 170.
  • “X 101 is absent” means that a bond represented by —X 101 — does not exist and a condensed ring skeleton containing an N atom and X 101 is not formed. means.
  • R 31 is an alkyl group having 1 to 12 carbon atoms are preferred because of their high solubility in organic solvents.
  • R 32 is an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group or a phenyl group. 4 is more preferable, and a methyl group is particularly preferable.
  • R 9 is preferably a group represented by the general formula (III ⁇ ).
  • R 9 is preferably a group represented by the general formula (III ⁇ ).
  • R 111 is preferably a group represented by the general formula (III ⁇ ).
  • R 111 is preferably a group represented by the general formula (III ⁇ ).
  • X 2 in the group represented by the general formula (III ⁇ ) is preferably an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom.
  • R 41 to R 45 in the group represented by the general formula (III ⁇ ) are preferably hydrogen atoms.
  • X 3 in the group represented by the general formula (III ⁇ ) is preferably an oxygen atom or a sulfur atom. This is because the oxime ester compound efficiently absorbs long-wavelength near-ultraviolet light and becomes highly sensitive as a photopolymerization initiator.
  • R 46 to R 50 in the group represented by the general formula (III ⁇ ) are preferably hydrogen atoms.
  • X 1 is preferably absent.
  • X 101 is preferably absent, and X 101 is preferably sulfur.
  • Preferred specific examples of the oxime ester compound of the present invention represented by the above general formula (I ⁇ ) or (I ⁇ ) include the following compound Nos. 1-No. 194. However, the present invention is not limited by the following compounds.
  • the oxime ester compound of the present invention represented by the above general formula (I ⁇ ) or (I ⁇ ) is not particularly limited, but can be synthesized, for example, by the method shown below.
  • an N-aryl compound that is an intermediate of the oxime ester compound of the present invention is obtained.
  • An example of a method for synthesizing this N-aryl compound is as follows. That is, a known and commercially available aldehyde compound and a known and commercially available fluorinated benzene compound are reacted with potassium carbonate to obtain a halogenated aryl compound, which is known as a halogenated aryl compound and is commercially available. By reacting the N-containing heterocyclic compound, an N-aryl compound is obtained.
  • the oxime compound of the present invention can be produced by the following method using the N-aryl compound according to the following reaction formula. That is, the ketone compound 1 is obtained by reacting the N-aryl compound with acid chloride, and the oxime compound 1 is obtained by reacting the ketone compound 1 with hydroxylamine hydrochloride. Subsequently, the oxime compound 1 is reacted with an acid anhydride or acid chloride to obtain the oxime ester compound 1 of the present invention represented by the above general formula (I ⁇ ) or (I ⁇ ).
  • the oxime compound 1 and the oxime ester compound 1 can also be produced by the method described in Japanese Patent No. 4223071.
  • the oxime compound of the present invention can be produced by the following method using the N-aryl compound according to the following reaction formula. That is, the ketone compound 2 is obtained by reacting the N-aryl compound with acid chloride, and the oxime compound 2 is obtained by reacting the ketone compound 2 with isobutyl nitrite. Subsequently, by reacting the oxime compound 2 with an acid anhydride or acid chloride, the oxime ester compound 2 of the present invention represented by the above general formula (I ⁇ ) or (I ⁇ ) is obtained.
  • the N-containing heterocyclic compound is previously reacted with an acid chloride to prepare a ketone body of the N-containing heterocyclic compound, and the ketone body is replaced with the N-containing heterocyclic compound.
  • the ketone compound 1 or 2 can also be obtained by reacting with the halogenated aryl compound.
  • novel oxime ester compound of the present invention described above is useful as a radical polymerization initiator, particularly a photopolymerization initiator or a thermal polymerization initiator. Moreover, the novel oxime ester compound of the present invention can also be suitably used as a sensitizer.
  • the photopolymerization initiator of the present invention contains at least one oxime ester compound of the present invention, and can further contain other photopolymerization initiators.
  • the content of the oxime ester compound of the present invention in the photopolymerization initiator is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.
  • the photopolymerization initiator of the present invention is useful as a photopolymerization initiator for ethylenically unsaturated compounds.
  • R 61 and R 62 are each independently a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom
  • R 63 and R 64 are each independently a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R 65 , OR 66 , SR 67 , NR 68 R 69 , COR 70 , SOR 71 , SO 2 R 72 or Represents CONR 73 R 74 , R 63 and R 64 may combine with each other to form a ring, R 63 and R 64 may be the same or different when there are a plurality of R 63 and R 64 respectively.
  • R 65 , R 66 , R 67 , R 68 , R 69 , R 70 , R 71 , R 72 , R 73 and R 74 are each independently an alkyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms.
  • X 4 represents a direct bond or CO
  • X 5 represents an oxygen atom, a sulfur atom, a selenium atom, CR 75 R 76 , CO, or PR 77 ;
  • R 75 , R 76 and R 77 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms,
  • a hydrogen atom in the alkyl group or arylalkyl group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic group,
  • the methylene group in the alkyl group or arylalkyl group may be substituted with —O—, a represents
  • the photosensitive composition of the present invention contains the photopolymerization initiator (A) of the present invention and an ethylenically unsaturated compound (B), and as optional components, a colorant (C), an alkali developable compound (D), It contains a combination of a solvent and any additive described below.
  • the content of the photopolymerization initiator (A) is not particularly limited, but is preferably 1 to 70 masses with respect to 100 mass parts of the ethylenically unsaturated compound (B). Parts, more preferably 1-50 parts by weight, most preferably 5-30 parts by weight.
  • the ethylenically unsaturated compound (B) is not particularly limited as long as it has an ethylenically unsaturated bond, and those conventionally used in photosensitive compositions can be used.
  • unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth) acrylic acid, ⁇ -chloroacrylic acid, itaconic acid, maleic acid, Citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2 -(Meth) acryloyloxyethyl], ⁇ -carboxypoly
  • A1-No. A4 methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxy
  • ethylenically unsaturated compound (B) examples include Kayrad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, and PET30 (Nippon Kayaku).
  • SPC-1000, SPC-3000 manufactured by Showa Denko), Aronix M-140, M-215, M-350 (manufactured by Toagosei), NK ester A-DPHA-TMPT, A-DCP, A-HD -N, A-9300, TMPT, DCP, NPG and HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • polyfunctional (meta) having a mono (meth) acrylate polymer having a carboxyl group and a hydroxyl group at both ends, one carboxyl group and two or more (meth) acryloyl groups is suitable for esters of acrylates, unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols.
  • the ethylenically unsaturated compounds can be used alone or in admixture of two or more, and when used in admixture of two or more, they are copolymerized in advance and used as a copolymer. You can also.
  • the photosensitive composition of the present invention may further contain a colorant (C) to form a colored photosensitive composition.
  • a colorant (C) examples include pigments, dyes, and natural pigments. These colorants 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; Compound; perylene compound; diketopyrrolopyrrole compound; thioindigo compound; dioxazine compound; triphenylmethane compound; quinophthalone compound; naphthalene tetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; furnace method, channel method or thermal 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 in a resin in a solvent and adsorbed with 20 to 200 mg / g of resin, an acid or alkaline surface treated carbon black, average Carbon black having a particle size of 8 nm or more and a DBP oil ab
  • 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 the like. These may be used alone or in combination.
  • the content of the colorant (C) is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts per 100 parts by mass of the ethylenically unsaturated compound (B). Part by mass.
  • the photosensitive composition of the present invention may further contain an alkali developable compound (D) to form an alkali developable photosensitive resin composition.
  • an alkali developable compound (D) to form an alkali developable photosensitive resin composition.
  • What contains a colorant (C) and an alkali developable compound (D) simultaneously is also called a colored alkali developable photosensitive resin composition.
  • the alkali-developable compound (D) is not particularly limited as long as it is a compound soluble in an alkaline aqueous solution, and examples thereof include resins described in JP-A No. 2004-264414.
  • alkali-developable compound (D) examples include acrylic acid ester copolymers, phenol and / or cresol novolac epoxy resins, polyphenylmethane type epoxy resins having polyfunctional epoxy groups, epoxy acrylate resins, A resin obtained by allowing an unsaturated monobasic acid to act on an epoxy group of an epoxy compound such as an epoxy compound represented by the formula (V) and further allowing a polybasic acid anhydride to act thereon can be used.
  • the epoxy acrylate resin here is one obtained by allowing (meth) acrylic acid to act on the above-mentioned epoxy compound. Examples thereof include Lipoxy SPC-2000, Dicklight UE-777 manufactured by DIC, and Nippon Iupika. Examples include Eupica 4015.
  • an epoxy acrylate resin and a resin obtained by allowing an unsaturated monobasic acid to act on an epoxy group of an epoxy compound represented by the following general formula (V) and further causing a polybasic acid anhydride to act Is preferred.
  • X 6 is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, —O—, —S—, —SO— 2 , —SS—, —SO—, —CO—, —OCO— or a group represented by the following [Chemical 35-1], [Chemical 35-2] or [Chemical 35-3], wherein the alkylidene group is a halogen atom.
  • Each of R 81 and R 82 independently represents 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 Represents a halogen atom, the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom, R 81 and R 82 may be the same or different when there are a plurality of R 81 and R 82 , c is an integer from 0 to 4, d is an integer from 0 to 4, m is an integer from 0 to 10, When m is not 0, an optical isomer exists, but any isomer may be used. )
  • Z 3 is a hydrogen atom, a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms
  • Y 1 is an alkyl group having 1 to 10 carbon atoms, 1 to 10 carbon atoms
  • An alkoxy 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
  • 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 carbon atoms which may be substituted with a halogen atom.
  • An arylalkenyl group having 6 to 20 carbon atoms that may be substituted, an arylalkyl group having 7 to 20 carbon atoms that may be substituted with a halogen atom, or a carbon that may be substituted with a halogen atom Represents a heterocyclic group having 2 to 20 atoms, or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl
  • Z 4 may form a ring with adjacent Z 4 , p represents an integer of 0 to 4, q represents an integer of 0 to 8, r Represents an integer from 0 to 4, s represents an integer from 0 to 4, and the total number of r and s is an integer from 2 to 4.
  • 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.
  • polybasic acid anhydride examples include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellit Acid anhydride, pyromellitic acid anhydride, 2,2'-3,3'-benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, nadic anhydride, methyl nadic 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 alkali developable compound may have an ethylenically unsaturated bond. That is, the ethylenically unsaturated compound (B) and the alkali developable compound (D) may be the same compound.
  • the compound having alkali developability and having an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalent of an unsaturated group.
  • this compound calculates content of the above-mentioned photoinitiator (A) and content of a coloring agent (C). Is included in the ethylenically unsaturated compound (B).
  • the content of the alkali-developable compound (D) that may have an ethylenically unsaturated bond is determined by the alkali-developable photosensitive composition of the present invention. 1 to 20 mass%, particularly 3 to 12 mass% is preferable in the conductive resin composition.
  • the alkali-developable compound (D) that may have an ethylenically unsaturated bond preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and is a monofunctional or polyfunctional epoxy compound.
  • the amount 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 is obtained. This is preferable.
  • the epoxy compound represented by the said general formula (V) can be used,
  • bisphenol-type epoxy compounds 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
  • the photosensitive composition of the present invention can further contain a solvent.
  • a solvent capable of dissolving or dispersing each of the above components (photopolymerization initiator (A), ethylenically unsaturated compound (B), etc.) as necessary, for example, methyl ethyl ketone, methyl amyl ketone, Ketones such as diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether, etc.
  • Ether solvents such as methyl acetate, ethyl acetate, acetate-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol, etc .; ethylene glycol monomethyl ether, ethylene glycol Cellosolve solvents such as methanol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene Ether ester solvents such as glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate;
  • solvents can be used as one or a mixture of two or more.
  • ketones, ether ester solvents, etc., particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. have good compatibility between the resist and the photopolymerization initiator (A) in the photosensitive composition. Therefore, it is preferable.
  • the content of the solvent is not particularly limited, but is preferably 30 to 95% by mass, more preferably 50 to 95% by mass in 100% by mass of the total amount of the photosensitive composition. It is.
  • the thickness of the cured product can be appropriately controlled when obtaining a cured product.
  • the photosensitive composition of the present invention may contain p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, an inorganic compound, a latent additive, an organic polymer, a chain transfer agent, and a sensitizer as necessary.
  • Surfactant silane coupling agent, melamine compound, thermal polymerization inhibitor; plasticizer; adhesion promoter; filler; antifoaming agent; leveling agent; surface conditioner; antioxidant;
  • Conventional additives such as a dispersion aid, an ink repellent agent, an aggregation inhibitor, a catalyst, a curing accelerator, a cross-linking agent, and a thickener can be added.
  • a colorant (C) and / or a dispersant for dispersing an inorganic compound can be added.
  • the dispersant is not limited as long as it can disperse and stabilize the colorant (C) or the inorganic compound, and a commercially available dispersant, for example, BYK series manufactured by BYK Chemie, Inc. can be used.
  • a polymer dispersant comprising a polyester, polyether, or polyurethane having a basic functional group, in particular, the basic functional group is an amine and / or a quaternary salt thereof, and the amine value is 1 to 100 mgKOH / g.
  • the basic functional group is an amine and / or a quaternary salt thereof, and the amine value is 1 to 100 mgKOH / g.
  • the latent additive is inactive at room temperature, in the light exposure step and in the pre-bake step, and is protected at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. Is activated by desorption. Examples of the effects obtained by activation include oxidation prevention, ultraviolet absorption, antifouling property, recoatability and adhesion.
  • the latent additive those described in International Publication No. 2014/021023 pamphlet can be preferably used.
  • Preferred examples of the latent additive include those represented by the following general formulas (A) to (C) in addition to the latent additive described in International Publication No. 2014/021023 pamphlet.
  • ring A 1 is a six-membered alicyclic ring, aromatic ring or heterocyclic ring;
  • R 81 , R 82 , R 83 , R 84 and R 85 each have 1 to 40 carbon atoms which may have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group or a substituent.
  • R 92 , R 93 , R 94 and R 95 are each a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, Represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and at least one of R 92 , R 93 , R 94 and R 95 One is not a hydrogen atom.
  • X 8 represents —CR 97 R 98 —, —NR 99 —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, and an aromatic group having 6 to 35 carbon atoms.
  • the methylene group in the aliphatic hydrocarbon group may be —O—, —S—, —CO—, —COO—, —OCO— or —NH—, or a combination of these without adjacent oxygen atoms.
  • R 97 and R 98 each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms
  • Z 5 and Z 6 are each independently a direct bond, —O—, —S—, —CO—, —CO—O—, —O—CO—, —SO 2 —, —SS—, —SO—.
  • Or -NR 100- R 99 and R 100 are each a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms that may have a substituent, or a 6 to 35 carbon atom that may have a substituent. Represents a heterocyclic group having 2 to 35 carbon atoms which may have an aromatic hydrocarbon group or a substituent, * Represents a bond. )
  • R 101 represents a hydrogen atom, a phenyl group which may have a substituent or a cycloalkyl group having 3 to 10 carbon atoms
  • R 102 represents an alkyl group having 1 to 10 carbon atoms
  • the alkyl group, alkoxy group and alkenyl group may have a substituent
  • f is 0 to (It is an integer of 5 and * represents a bond.)
  • R 103 and R 104 are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, or 6 carbon atoms which may have a substituent.
  • An arylalkenyl group having 6 to 20 carbon atoms that may have, an arylalkyl group having 7 to 20 carbon atoms that may have a substituent, and a carbon that may have a substituent Represents a heterocyclic group having 2 to 20 atoms or a halogen atom, and the methylene group in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, —O— or —S—, and R 103 is , Ring between adjacent R 103 B represents a number from 0 to 4, c represents a number from 0 to 8, g represents a number from 0 to 4, h represents a number from 0 to 4, g and (The total number of h is 2 to 4.)
  • R 111 , R 112 , R 113 and R 114 are a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an alkyl group having 1 to 40 carbon atoms which may have a substituent.
  • Y 11 represents a trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, or 6 to 35 carbon atoms.
  • Z 11 , Z 12 and Z 13 are each independently a direct bond, —O—, —S—, —CO—, —CO—O—, —O—CO—, —SO 2 —, —SS—, -SO -, - NR 121 -, - PR 121 -, which may have a substituent aliphatic hydrocarbon group having a carbon number of 1 to 35 carbon atoms which may have a substituent
  • R 121 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms,
  • Y 12 represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or 2 carbon atoms. Represents a heterocyclic group of ⁇ 35,
  • the methylene group in the aliphatic hydrocarbon group may be substituted with —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—
  • Z 11 to Z 14 are each independently a group within the same range as the group represented by Z 11 to Z 13 in the general formula (2).
  • Y 13 represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a complex having 2 to 30 carbon atoms. Represents a cyclic group, The aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—, Z 11 to Z 15 are each independently a group in the same range as the group represented by Z 11 to Z 13 in the general formula (2).
  • Y 14 represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a complex having 2 to 35 carbon atoms. Represents a cyclic group, The aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—, Z 11 to Z 16 are each independently a group in the same range as the group represented by Z 11 to Z 13 in the general formula (2).
  • cured material can also be improved by using the said organic polymer (except an ethylenically unsaturated compound (B) and an alkali developable compound (D)).
  • 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 ethylenically unsaturated compound (B).
  • 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-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; Cationic surfactants such as amine halides 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 interfaces Surfactants such as activators can be used, and these can be used alone or in combination.
  • fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates
  • anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulf
  • 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 or different from each other.
  • methylol groups that are not alkyletherified may be self-condensed within one molecule, and may be condensed between two molecules, resulting in the formation of an oligomer component.
  • hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used.
  • alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.
  • the leveling agent is not particularly limited as long as it has a leveling effect, and an existing leveling agent can be used. Among them, a silicone leveling agent and a fluorine leveling agent can be particularly preferably used. .
  • silicone leveling agent commercially available silicone leveling agents can be used.
  • fluorine leveling agent commercially available fluorine leveling agents can be used, such as OPTOOL DSX, OPTOOL DAC-HP (manufactured by Daikin Industries); Surflon S-242, Surflon S-243, Surflon S-420, Surflon S-611, Surflon S-651, Surflon S-386 (above, manufactured by AGC Seimi Chemical); BYK-340 (manufactured by Big Chemie Japan); AC110a, AC (100a (above, manufactured by Algin Chemie); Megafuck F-114, Megafuck F-410, Megafuck F-444, Megafuck EXPTP-2066, Megafuck F-430, Megafuck F-472SF, Megafuck F-477, Megafuck F-552, Megafuck F-553, Megafuck F- 54, Megafuck F-555, Megafuck R-94, Megafuck RS-72-K, Megafuck RS-75, Megafuck F-556, Mega
  • the photopolymerization initiator (A), the ethylenically unsaturated compound (B), the colorant (C), the alkali developable compound (D), any solvent, and an organic polymer are excluded.
  • the usage-amount of an additive is suitably selected according to the intended purpose and is not restrict
  • the photosensitive composition, the alkali-developable photosensitive resin composition, or the cured product of the present invention is used for display display devices, and more specifically for color display of display display devices (color televisions, PC monitors, portable information terminals, digital cameras, etc.). It is suitably used for a color filter in a liquid crystal display element.
  • Photocurable paint or varnish Photocurable adhesive; Printed circuit board; Color filter of CCD image sensor; Electrode material for plasma display panel; Powder coating; Printing ink; Printing plate; Adhesive; Photoresist for electronic engineering; Electroplating resist; Etching resist; Dry film; Solder resist; Resist to form various display device structures; Composition for encapsulating electrical and electronic parts; Solder resist Magnetic recording materials; micromechanical parts; waveguides; optical switches; plating masks; etching masks; color test systems; glass fiber cable coatings; screen printing stencils; materials for producing three-dimensional objects by stereolithography; Holographic recording material; Image recording 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,
  • the photosensitive composition or alkali-developable photosensitive resin composition of the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and for forming protrusions for vertical alignment type liquid crystal display elements.
  • it is useful as a photosensitive composition for simultaneously forming protrusions and spacers for a vertical alignment type liquid crystal display element.
  • the photosensitive composition or alkali-developable photosensitive resin composition of the present invention can be cured by irradiation with energy rays.
  • the photosensitive composition or alkali-developable photosensitive resin composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, etc. It can be applied on a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic.
  • support bases such as a film, it can also transfer on another support base
  • the energy ray used for curing the photosensitive composition alkali-developable photosensitive resin 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.
  • Electromagnetic energy rays having a wavelength of 2000 angstroms to 7000 angstroms obtained from light sources such as lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources,
  • High energy rays such as electron beams, X-rays and radiation can be used, but preferably an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, etc. that emits light having a wavelength of 300 to 450 nm.
  • the light source is used.
  • the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy.
  • the laser 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.
  • lasers that emit light in the visible to infrared region such as various semiconductor lasers and YAG lasers, are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.
  • the liquid crystal display panel spacer includes (1) a step of forming a coating film of the photosensitive composition of the present invention on a substrate, and (2) radiation through a mask having a predetermined pattern shape on the coating film. , (3) baking step after exposure, (4) step of developing the coating after exposure, and (5) step of heating the coating after development.
  • the photosensitive composition of the present invention contains an ink repellent
  • it is useful as a partition forming resin composition for an inkjet system, and the composition is used for a color filter, and particularly has a profile angle of 50 ° or more. It is preferably used for the partition for an inkjet color filter.
  • the ink repellent agent a composition comprising a fluorosurfactant and a fluorosurfactant is preferably used.
  • the partition formed from the photosensitive composition of the present invention is on the transfer target.
  • an optical element is manufactured by a method of forming an image region by applying droplets to the recessed portions on the partitioned transfer target member by an ink jet method.
  • the droplets contain a colorant and the image area is colored, whereby the pixel group composed of a plurality of colored areas is separated from the colored areas of the pixel group on the substrate.
  • An optical element having at least a partition is obtained.
  • Step 1 Preparation of intermediate 1A (halogenated aryl compound)
  • 2-chloro-4'-fluoroacetophenone (3.59 g)
  • salicylic aldehyde (5.08 g)
  • potassium carbonate (5.75 g)
  • acetone 15 g
  • ion-exchanged water 41.6 g was added, and the precipitate was collected by filtration and sufficiently dried to obtain Intermediate 1A (4.74 g: yield 95%) as a pale yellow solid.
  • Step 2 Production of Intermediate 1B (Ketone Compound)
  • Intermediate 1A 4.42 g
  • the following indole compound 1A 4.07 g
  • potassium carbonate 4.62 g
  • DMAc 23.25 g
  • Ion-exchanged water (15.5 g) and ethyl acetate (23.25 g) were added to separate the oil and water, and the organic layer was washed with water three times to remove the solvent.
  • Step 3 Production of Intermediate 1C (oxime compound)
  • Intermediate 1B (3.74 g) and DMF (12.93 g) were weighed into a 30 ml two-necked flask and stirred at 5 ° C with 35% hydrochloric acid 1.
  • 26 g and 0.87 g of isobutyl nitrite were added dropwise, and the mixture was stirred at room temperature for 30 hours.
  • Step 4 Compound No. 1 (Oxime ester compound of the present invention) Intermediate 1C (2.21 g) and THF (7.2 g) were weighed in a 30 ml two-necked eggplant flask, respectively, and acetyl chloride (2. 12 g) and triethylamine (2.72 g) were added dropwise, and the mixture was stirred at room temperature for 1 hour. Ion-exchanged water (7.2 g) and ethyl acetate (7.2 g) were added to separate the oil and water, and the organic layer was washed with water three times.
  • Step 2 Compound No. 189 (oxime ester compound of the present invention) Compound No. 1 was prepared in the same manner as in Step 4 of Example 1, except that Intermediate 1C was changed to Intermediate 2A. 189 was obtained.
  • Example 3 Compound no. Production of 190 (Step 1) Production of Intermediate 3B
  • the following Intermediate 3B was obtained in the same manner as in Step 2 of Example 1 except that the indole compound 1A was changed to the following carbazole compound 3A.
  • Step 2 Production of Intermediate 3C
  • Step 3 Preparation of Compound No. 190 was performed in the same manner as in Step 4 of Example 1, except that Intermediate 1C was changed to Intermediate 3C. 190 was obtained.
  • Example 4 Compound no. In the same manner as in Example 1 except that the intermediate 1A used in Step 2 of Example 1 was changed to the following intermediate 4A, the above compound No. 191 was prepared. 191 was obtained.
  • Example 5 Compound no. In the same manner as in Example 1 except that the intermediate 1A used in Step 2 of Example 1 was changed to the following Intermediate 5A, the above compound No. 192 was prepared. 192 was obtained.
  • Example 6 Compound no. Production of 193 (Step 1) Production of Intermediate 6B The following Intermediate 6B was obtained in the same manner as in Step 2 of Example 1, except that the indole compound 1A was changed to the following phenothiazine compound 6A.
  • Step 2 Production of Intermediate 6C
  • Intermediate 3B was changed to Intermediate 6B described above, and the same procedure as in Step 2 of Example 3 was conducted except that the equivalent amount of the reagent used was doubled.
  • Intermediate 6C was obtained.
  • Step 3 Production of Intermediate 6D
  • Intermediate 1B was changed to Intermediate 6C and the equivalent amount of the used reagent was doubled
  • the following intermediate 6D was obtained.
  • Step 4 Compound No.
  • Step 4 of Example 1 In the same manner as in Step 4 of Example 1, except that Intermediate 1C was changed to Intermediate 6D and the equivalent amount of the reagent used was doubled, the above-mentioned Compound No. 193 was obtained.
  • Example 7 Compound no. Production of 194 (Step 1) Production of Intermediate 7A Intermediate 7A shown below was obtained in the same manner as in Step 3 of Example 1 except that Intermediate 1B was changed to Intermediate 6C.
  • Step 2 Compound No. In the same manner as in Step 4 of Example 1, except that Intermediate 1C was changed to Intermediate 7A, Compound No. 194 was obtained.
  • the oxime ester compound of the present invention is useful because of its high solubility in a solvent represented by PGMEA.
  • A-4 Compound No. 191 (photopolymerization initiator of the present invention obtained in Example 4)
  • A-5 Compound No. 192 (photopolymerization initiator of the present invention obtained in Example 5)
  • A-6 Compound No. 193 (photopolymerization initiator of the present invention obtained in Example 6)
  • A-7 Compound No.
  • A-8 OXE 02 (photopolymerization initiator not belonging to the present invention; manufactured by BASF)
  • B-1 SPC-3000 (ethylenically unsaturated compound having an acid group; manufactured by Showa Denko; PGMEA solution having a solid content of 42.2% by mass)
  • B-2 Kayalad DPHA (ethylenically unsaturated compound; manufactured by Nippon Kayaku; solid content: 100% by mass)
  • C-1 Blue pigment dispersion No.
  • the photosensitive composition No. 1-No. 7 (Examples 8 to 14) and comparative photosensitive composition No. 8 (Comparative Example 1) was spin coated (at 500 rpm for 2 seconds, then at 900 rpm for 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then cooled at 23 ° C. for 40 seconds. Then, it exposed through the mask (mask opening 30 micrometers) using the high pressure mercury lamp (exposure amount 40mJ / cm ⁇ 2 >). After developing using a 2.5% by mass aqueous sodium carbonate solution as a developing solution, it was washed thoroughly with water and post-baked at 230 ° C. for 30 minutes using an oven to fix the pattern.
  • the obtained pattern was observed with an electron microscope, and the line width of the portion corresponding to the mask opening was measured.
  • a line width of 30 ⁇ m or more was designated as A, and a line width of less than 30 ⁇ m was designated as B.
  • the photosensitive composition No. 1-No. 7 (Examples 8 to 14) and comparative photosensitive composition No. 8 (Comparative Example 1) was spin coated (at 500 rpm for 2 seconds, then at 900 rpm for 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then cooled at 23 ° C. for 40 seconds. Then, it exposed at 100 mJ / cm ⁇ 2 > using the high pressure mercury lamp, and created the evaluation sample. From the transmittance of the obtained sample at 380 to 780 nm, the Y value was determined according to JIS Z8701. The higher the Y value, the higher the luminance and the higher the transmittance in the visible light region, which is useful.
  • the photosensitive composition using the oxime ester compound of the present invention is excellent in photolithography properties and the brightness of the resulting cured product
  • the oxime ester compound of the present invention is useful as a photopolymerization initiator. I understand that there is.
  • the oxime ester compound of the present invention provides a highly sensitive alkali-developable photosensitive resin composition that is capable of efficiently generating radicals with respect to bright lines such as 365 nm (i-line) and has excellent developability. In addition, it has high solubility in an organic solvent, and also has high transmittance in the visible light region, and is useful as a photopolymerization initiator used in a photosensitive composition.

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Abstract

Provided is an oxime ester compound represented by general formula (Iα) or (Iβ). (In the formulae: R1 to R6 and R101 to R108 each independently denote a group represented by general formula (II), a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or the like; one of R1 to R6 and R101 to R108 is a group represented by general formula (II); R7 to R11 and R109 to R113 each independently denote a group represented by general formula (IIIα) or (IIIβ), a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, or the like; at least one of R7 to R11 and R109 to R113 is a group represented by general formula (IIIα) or (IIIβ); and X1 and X101 are either not present or are each a direct bond, -CO-, -O- or -S-.)

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、並びに該光重合開始剤及びエチレン性不飽和化合物を含有する感光性組成物に関する。 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, and a photosensitizer containing the photopolymerization initiator and an ethylenically unsaturated compound. The present invention relates to a sex composition.
　感光性組成物は、エチレン性不飽和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 an ethylenically unsaturated compound and can be polymerized and cured by irradiating energy rays (light). Therefore, a photocurable ink, a photosensitive printing plate It is used for 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、下記特許文献１には、ヘテロ芳香族環を有する感受性の高いオキシムエステル光開始剤が開示され、下記特許文献２には、３６５～４０５ｎｍにおいて大きな吸収能を有する高感度な光重合開始剤が開示され、下記特許文献３には、高感度かつ高解像度な感光性組成物を達成できる光重合開始剤が開示されている。しかし、これらの特許文献に記載のオキシムエステル化合物の感度は、必ずしも満足できるものではなく、さらなる感度の向上が望まれている。 As a photopolymerization initiator used in the photosensitive composition, the following Patent Document 1 discloses a highly sensitive oxime ester photoinitiator having a heteroaromatic ring, and the following Patent Document 2 discloses a photopolymerization initiator at 365 to 405 nm. A high-sensitivity photopolymerization initiator having a large absorption capacity is disclosed, and the following Patent Document 3 discloses a photopolymerization initiator that can achieve a photosensitive composition with high sensitivity and high resolution. However, the sensitivity of the oxime ester compounds described in these patent documents is not always satisfactory, and further improvement in sensitivity is desired.
　カラーフィルタ等に用いられる、着色剤を含有する着色アルカリ現像性感光性樹脂組成物は、特に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る。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。 The colored alkali-developable photosensitive resin composition containing a colorant used for a color filter or the like is required to have particularly 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.
　また、カラーフィルタ等に用いられる、着色剤を含有する着色アルカリ現像性感光性樹脂組成物においては、使用する光重合開始剤が、可視光領域において高い透過率を有することも求められる。可視光領域における透過率が低いと、輝度の低下といった問題が発生する。
　更に、光重合開始剤は、各種用途に用いる際に有機溶剤に溶解して用いられるため、有機溶剤への溶解性が高いことも求められる。 Moreover, in the colored alkali-developable photosensitive resin composition containing a colorant used for a color filter or the like, it is also required that the photopolymerization initiator used has a high transmittance in the visible light region. When the transmittance in the visible light region is low, a problem such as a decrease in luminance occurs.
Furthermore, since the photopolymerization initiator is used by being dissolved in an organic solvent when used in various applications, it is also required to have high solubility in the organic solvent.
米国特許出願公開第２００６／２４１２５９号明細書US Patent Application Publication No. 2006/241259 特開２０１４－００９３２５号公報JP 2014-009325 A 特開２０１４－１５９３９０号公報JP 2014-159390 A
　解決しようとする問題点は、満足できる感度を有し、有機溶剤への溶解性が高く、且つ可視光領域の透過率が高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 been no photopolymerization initiator having satisfactory sensitivity, high solubility in an organic solvent, and high transmittance in the visible light region.
　従って、本発明の目的は、３６５ｎｍ等の近紫外光を効率よく吸収し活性化される高感度な化合物であり、有機溶剤への溶解性が高く、更に可視光領域の透過率も高い、光重合開始剤として有用な新規な化合物、及び該化合物を用いた光重合開始剤、並びに感光性組成物を提供することにある。 Therefore, an object of the present invention is a highly sensitive compound that can efficiently absorb and activate near ultraviolet light such as 365 nm, has high solubility in an organic solvent, and has high transmittance in the visible light region. The object is to provide a novel compound useful as a polymerization initiator, a photopolymerization initiator using the compound, and a photosensitive composition.
　本発明は、下記〔１〕～〔１１〕を提供することにより、上記目的を達成したものである。 The present invention achieves the above object by providing the following [1] to [11].
　〔１〕下記一般式（Iα）又は（Iβ）で表されるオキシムエステル化合物。 [1] An oxime ester compound represented by the following general formula (Iα) or (Iβ).
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は、それぞれ独立に、下記一般式（II）で表される基、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ２１、ＯＲ２１、ＳＲ２１、ＮＲ２２Ｒ２３、ＣＯＲ２１、ＳＯＲ２１、ＳＯ２Ｒ２１又はＣＯＮＲ２２Ｒ２３を表し、
　Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６のうち、少なくとも一つが下記一般式（II）で表される基であり、
　Ｒ７、Ｒ８、Ｒ９、Ｒ１０及びＲ１１は、それぞれ独立に、下記一般式（IIIα）で表される基、下記一般式（IIIβ）で表される基、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ２１、ＯＲ２１、ＳＲ２１、ＮＲ２２Ｒ２３、ＣＯＲ２１、ＳＯＲ２１、ＳＯ２Ｒ２１又はＣＯＮＲ２２Ｒ２３を表し、
　Ｒ７、Ｒ８、Ｒ９、Ｒ１０及びＲ１１のうち、少なくとも一つが下記一般式（IIIα）で表される基又は下記一般式（IIIβ）で表される基であり、
　Ｒ２１、Ｒ２２及びＲ２３は、それぞれ独立に、炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基を表し、
　Ｒ２１、Ｒ２２及びＲ２３で表される基中の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環含有基で置換される場合があり、炭素原子数２～２０の炭化水素基又は炭素原子数２～２０の複素環含有基中のメチレン基は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ２４－、－ＮＲ２４ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合があり、Ｒ２４は、水素原子又は炭素原子数１～２０の炭化水素基を表し、
　Ｘ１は、不存在、直接結合、－ＣＯ－、－Ｏ－又は－Ｓ－を表し、
　Ｒ１とＲ２、Ｒ２とＲ３、Ｒ３とＲ４、Ｒ５とＲ６、Ｒ６とＲ７、Ｒ７とＲ８、Ｒ８とＲ９、Ｒ９とＲ１０、Ｒ１０とＲ１１、及びＲ１１とＲ１は、結合して環を形成する場合がある。）
Figure JPOXMLDOC01-appb-C000005
 (Wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a group represented by the following general formula (II), hydrogen atom, halogen atom, nitro group, cyano group , Hydroxyl group, carboxyl group, R 21 , OR 21 , SR 21 , NR 22 R 23 , COR 21 , SOR 21 , SO 2 R 21 or CONR 22 R 23 ,
At least one of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is a group represented by the following general formula (II),
R 7 , R 8 , R 9 , R 10 and R 11 are each independently a group represented by the following general formula (IIIα), a group represented by the following general formula (IIIβ), a hydrogen atom, a halogen atom, A nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 21 , OR 21 , SR 21 , NR 22 R 23 , COR 21 , SOR 21 , SO 2 R 21 or CONR 22 R 23 ;
At least one of R 7 , R 8 , R 9 , R 10 and R 11 is a group represented by the following general formula (IIIα) or a group represented by the following general formula (IIIβ),
R 21 , R 22 and R 23 each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
The hydrogen atoms in the groups represented by R 21 , R 22 and R 23 are halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups. , A mercapto group, an isocyanate group or a heterocycle-containing group, the hydrocarbon group having 2 to 20 carbon atoms or the methylene group in the heterocycle-containing group having 2 to 20 carbon atoms may be represented by —O— , —CO—, —COO—, —OCO—, —NR 24 —, —NR 24 CO—, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO And R 24 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
X 1 represents absence, direct bond, —CO—, —O— or —S—,
R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 And R 11 , and R 11 and R 1 may combine to form a ring. )
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ３１及びＲ３２は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基を表し、
　Ｒ３１及びＲ３２で表される炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環含有基で置換される場合があり、Ｒ３１及びＲ３２で表される炭素原子数２～２０の炭化水素基又は炭素原子数２～２０の複素環含有基中のメチレン基は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ３３－、－ＮＲ３３ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合があり、Ｒ３３は、水素原子又は炭素原子数１～２０の炭化水素基を表し、
　ｎは０又は１を表し、＊は結合手を表す。）
Figure JPOXMLDOC01-appb-C000006
 (Wherein R 31 and R 32 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms. Represent,
The hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms represented by R 31 and R 32 is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, It may be substituted with a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group, and the number of carbon atoms represented by R 31 and R 32 is 2 to The methylene group in the hydrocarbon group having 20 or the heterocyclic group having 2 to 20 carbon atoms is —O—, —CO—, —COO—, —OCO—, —NR 33 —, —NR 33 CO—, May be substituted with —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO—, and R 33 represents a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. Table of hydrogen groups ,
n represents 0 or 1, and * represents a bond. )
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｒ４１、Ｒ４２、Ｒ４３、Ｒ４４、Ｒ４５、Ｒ４６、Ｒ４７、Ｒ４８、Ｒ４９及びＲ５０は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ５１、ＯＲ５１、ＳＲ５１、ＮＲ５２Ｒ５３、ＣＯＲ５１、ＳＯＲ５１、ＳＯ２Ｒ５１又はＣＯＮＲ５２Ｒ５３を表し、
　Ｒ５１、Ｒ５２及びＲ５３は、それぞれ独立に、炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基を表し、
　Ｒ５１、Ｒ５２及びＲ５３で表される基中の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環含有基で置換される場合があり、炭素原子数２～２０の炭化水素基又は炭素原子数２～２０の複素環含有基中のメチレン基は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ５４－、－ＮＲ５４ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合があり、
　Ｘ２及びＸ３は、－Ｏ－、－Ｓ－又は－ＮＲ５４－を表し、
　Ｒ５４は、水素原子又は炭素原子数１～２０の炭化水素基を表し、
　＊は結合手を表す。）
Figure JPOXMLDOC01-appb-C000007
 (In the formula, R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 and R 50 are each independently a hydrogen atom, a halogen atom, a nitro group, or a cyano group. , Hydroxyl group, carboxyl group, R 51 , OR 51 , SR 51 , NR 52 R 53 , COR 51 , SOR 51 , SO 2 R 51 or CONR 52 R 53 ,
R 51 , R 52 and R 53 each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group containing 2 to 20 carbon atoms,
The hydrogen atoms in the groups represented by R 51 , R 52 and R 53 are halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups. , A mercapto group, an isocyanate group or a heterocycle-containing group, the hydrocarbon group having 2 to 20 carbon atoms or the methylene group in the heterocycle-containing group having 2 to 20 carbon atoms may be represented by —O— , —CO—, —COO—, —OCO—, —NR 54 —, —NR 54 CO—, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO May be replaced with-
X 2 and X 3 represent —O—, —S— or —NR 54 —,
R 54 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
* Represents a bond. )
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７及びＲ１０８は、それぞれ独立に、上記一般式（II）で表される基、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ１２１、ＯＲ１２１、ＳＲ１２１、ＮＲ１２２Ｒ１２３、ＣＯＲ１２１、ＳＯＲ１２１、ＳＯ２Ｒ１２１又はＣＯＮＲ１２２Ｒ１２３を表し、
　Ｒ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７及びＲ１０８のうち、少なくとも一つが上記一般式（II）で表される基であり、
　Ｒ１０９、Ｒ１１０、Ｒ１１１、Ｒ１１２及びＲ１１３は、それぞれ独立に、上記一般式（IIIα）で表される基、上記一般式（IIIβ）で表される基、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ１２１、ＯＲ１２１、ＳＲ１２１、ＮＲ１２２Ｒ１２３、ＣＯＲ１２１、ＳＯＲ１２１、ＳＯ２Ｒ１２１又はＣＯＮＲ１２２Ｒ１２３を表し、
　Ｒ１０９、Ｒ１１０、Ｒ１１１、Ｒ１１２及びＲ１１３のうち、少なくとも一つが下記一般式（IIIα）で表される基又は下記一般式（IIIβ）で表される基であり、
　Ｒ１２１、Ｒ１２２及びＲ１２３は、それぞれ独立に、炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基を表し、
　Ｒ１２１、Ｒ１２２及びＲ１２３で表される基中の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環含有基で置換される場合があり、炭素原子数２～２０の炭化水素基又は炭素原子数２～２０の複素環含有基中のメチレン基は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ１２４－、－ＮＲ１２４ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合があり、
　Ｒ１２４は、水素原子又は炭素原子数１～２０の炭化水素基を表し、
　Ｘ１０１は、不存在、直接結合、－ＣＯ－、－Ｏ－又は－Ｓ－を表し、
　Ｒ１０１とＲ１０２、Ｒ１０２とＲ１０３、Ｒ１０３とＲ１０４、Ｒ１０５とＲ１０６、Ｒ１０６とＲ１０７、Ｒ１０７とＲ１０８、Ｒ１０８とＲ１０９、Ｒ１０９とＲ１１０、Ｒ１１０とＲ１１１、Ｒ１１１とＲ１１２、Ｒ１１２とＲ１１３及びＲ１１３とＲ１０１は、結合して環を形成する場合がある。）
Figure JPOXMLDOC01-appb-C000008
 Wherein R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 are each independently a group represented by the above general formula (II), a hydrogen atom, a halogen atom , A nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 121 , OR 121 , SR 121 , NR 122 R 123 , COR 121 , SOR 121 , SO 2 R 121 or CONR 122 R 123 ,
At least one of R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 is a group represented by the general formula (II),
R 109 , R 110 , R 111 , R 112 and R 113 are each independently a group represented by the general formula (IIIα), a group represented by the general formula (IIIβ), a hydrogen atom, a halogen atom, Nitro group, cyano group, hydroxyl group, carboxyl group, R 121 , OR 121 , SR 121 , NR 122 R 123 , COR 121 , SOR 121 , SO 2 R 121 or CONR 122 R 123
At least one of R 109 , R 110 , R 111 , R 112 and R 113 is a group represented by the following general formula (IIIα) or a group represented by the following general formula (IIIβ);
R 121 , R 122 and R 123 each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
The hydrogen atoms in the groups represented by R 121 , R 122 and R 123 are halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups. , A mercapto group, an isocyanate group or a heterocycle-containing group, the hydrocarbon group having 2 to 20 carbon atoms or the methylene group in the heterocycle-containing group having 2 to 20 carbon atoms may be represented by —O— , —CO—, —COO—, —OCO—, —NR 124 —, —NR 124 CO—, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO May be replaced with-
R 124 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
X 101 represents absence, direct bond, —CO—, —O— or —S—,
R101 and R102 , R102 and R103 , R103 and R104 , R105 and R106 , R106 and R107 , R107 and R108 , R108 and R109 , R109 and R110 , R110 And R 111 , R 111 and R 112 , R 112 and R 113, and R 113 and R 101 may combine to form a ring. )
〔２〕一般式（Iα）中のＲ３及びＲ５のうち少なくとも一つが、一般式（II）で表される基である〔１〕に記載のオキシムエステル化合物。 [2] The oxime ester compound according to [1], wherein at least one of R 3 and R 5 in the general formula (Iα) is a group represented by the general formula (II).
〔３〕一般式（Iβ）中のＲ１０３及びＲ１０６のうち少なくとも一つが、一般式（II）で表される基である〔１〕に記載のオキシムエステル化合物。 [3] The oxime ester compound according to [1], wherein at least one of R 103 and R 106 in the general formula (Iβ) is a group represented by the general formula (II).
〔４〕一般式（Iα）中のＸ１が不存在でＲ５とＲ６が結合してベンゼン環を形成する〔１〕又は〔２〕に記載のオキシムエステル化合物。 [4] The oxime ester compound according to [1] or [2], wherein X 1 in the general formula (Iα) is absent and R 5 and R 6 are bonded to form a benzene ring.
〔５〕〔１〕～〔４〕の何れか一項に記載のオキシムエステル化合物を含有する光重合開始剤。 [5] A photopolymerization initiator containing the oxime ester compound according to any one of [1] to [4].
〔６〕〔５〕に記載の光重合開始剤（Ａ）及びエチレン性不飽和化合物（Ｂ）を含有する感光性組成物。 [6] A photosensitive composition comprising the photopolymerization initiator (A) according to [5] and an ethylenically unsaturated compound (B).
〔７〕更に着色剤（Ｃ）を含有する〔６〕に記載の感光性組成物。 [7] The photosensitive composition according to [6], further containing a colorant (C).
〔８〕〔６〕又は〔７〕に記載の感光性組成物にアルカリ現像性化合物（Ｄ）を含有させてなるアルカリ現像性感光性樹脂組成物。 [8] An alkali-developable photosensitive resin composition obtained by adding the alkali-developable compound (D) to the photosensitive composition according to [6] or [7].
〔９〕〔６〕若しくは〔７〕に記載の感光性組成物又は〔８〕に記載のアルカリ現像性感光性樹脂組成物の硬化物。 [9] A cured product of the photosensitive composition according to [6] or [7] or the alkali-developable photosensitive resin composition according to [8].
〔１０〕〔９〕に記載の硬化物を含有するディスプレイ表示装置。 [10] A display device containing the cured product according to [9].
〔１１〕〔６〕若しくは〔７〕に記載の感光性組成物又は〔８〕に記載のアルカリ現像性感光性樹脂組成物を用い、該組成物を硬化させる工程を有する、硬化物の製造方法。 [11] A method for producing a cured product, comprising the step of curing the composition using the photosensitive composition according to [6] or [7] or the alkali-developable photosensitive resin composition according to [8]. .
　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本発明の光重合開始剤について、好ましい実施形態に基づき詳細に説明する。 Hereinafter, the oxime ester compound of the present invention and the photopolymerization initiator of the present invention containing the compound will be described in detail based on preferred embodiments.
　本発明のオキシムエステル化合物は、上記一般式（Iα）又は（Iβ）で表わされる新規な化合物である。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（Iα）又は（Iβ）で表わされる化合物及びその例示化合物は、これら幾何異性体の１種又は２種以上の混合物を表すものであり、構造を示した特定の異性体に限定されるものではない。 The oxime ester compound of the present invention is a novel compound represented by the above general formula (Iα) or (Iβ). The oxime ester compound has a geometric isomer due to an oxime double bond, but the present invention does not distinguish these.
That is, in the present specification, the compound represented by the above general formula (Iα) or (Iβ) and the exemplified compound thereof represent one or a mixture of two or more of these geometric isomers and have a structure. It is not limited to a specific isomer.
　上記一般式（Iα）中のＲ２１～Ｒ２４、及び上記一般式（Iβ）中のＲ１２１～Ｒ１２４で表される炭素原子数１～２０の炭化水素基は、特に限定されるものではないが、好ましくは炭素原子数１～２０のアルキル基、炭素原子数２～２０のアルケニル基、炭素原子数３～２０のシクロアルキル基、炭素原子数４～２０のシクロアルキルアルキル基、炭素原子数６～２０のアリール基及び炭素原子数７～２０のアリールアルキル基等を表す。 The hydrocarbon groups having 1 to 20 carbon atoms represented by R 21 to R 24 in the general formula (Iα) and R 121 to R 124 in the general formula (Iβ) are not particularly limited. Preferably, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, a carbon atom Represents an aryl group having 6 to 20 carbon atoms and an arylalkyl group having 7 to 20 carbon atoms.
　上記炭素原子数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、オクタデシル及びイコシル等が挙げられる。 Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl. 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like.
　炭素原子数２～２０のアルケニル基としては、例えば、ビニル、エチレン、２－プロペニル、３－ブテニル、２－ブテニル、４－ペンテニル、３－ペンテニル、２－ヘキセニル、３－ヘキセニル、５－ヘキセニル、２－ヘプテニル、３－ヘプテニル、４－ヘプテニル、３－オクテニル、３－ノネニル、４－デセニル、３－ウンデセニル、４－ドデセニル及び４，８，１２－テトラデカトリエニルアリル等が挙げられる。 Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, ethylene, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, Examples include 2-heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl and 4,8,12-tetradecatrienylallyl.
　上記炭素原子数３～２０のシクロアルキル基とは、３～２０個の炭素原子を有する、飽和単環式又は飽和多環式アルキル基を意味する。例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシル、アダマンチル、デカハイドロナフチル、オクタヒドロペンタレン及びビシクロ［１．１．１］ペンタニル等が挙げられる。 The above cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. Examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo [1.1.1] pentanyl.
　上記炭素原子数４～２０のシクロアルキルアルキル基とは、アルキル基の水素原子がシクロアルキル基で置換された、４～２０個の炭素原子を有する基を意味する。例えば、シクロプロピルメチル、２－シクロブチルエチル、３－シクロペンチルプロピル、４－シクロヘキシルブチル、シクロヘプチルメチル、シクロオクチルメチル、２－シクロノニルエチル、２－シクロデシルエチル、３－３－アダマンチルプロピル及びデカハイドロナフチルプロピル等が挙げられる。 The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with a cycloalkyl group. For example, cyclopropylmethyl, 2-cyclobutylethyl, 3-cyclopentylpropyl, 4-cyclohexylbutyl, cycloheptylmethyl, cyclooctylmethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-3-adamantylpropyl and deca And hydronaphthylpropyl.
　上記炭素原子数６～２０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。 Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl, biphenylyl, naphthyl, anthryl substituted with one or more of the above alkyl groups. It is done.
　上記炭素原子数７～２０のアリールアルキル基とは、アルキル基の水素原子がアリール基で置換された、７～２０の炭素原子を有する基を意味する。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、フェニルエチル及びナフチルプロピル等が挙げられる。 The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which a hydrogen atom of the alkyl group is substituted with an aryl group. Examples include benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl and naphthylpropyl.
　上記炭素原子数１～２０の炭化水素基の中でも、光重合開始剤として感度がよいことから、炭素原子数１～１２のアルキル基、炭素原子数２～１０のアルケニル基、炭素原子数３～１０のシクロアルキル基、炭素原子数４～１５のシクロアルキルアルキル基、炭素原子数６～１５のアリール基及び炭素原子数７～１５のアリールアルキル基が特に好ましい。 Among the above hydrocarbon groups having 1 to 20 carbon atoms, because of their high sensitivity as a photopolymerization initiator, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 3 to 3 carbon atoms A cycloalkyl group having 10 carbon atoms, a cycloalkylalkyl group having 4 to 15 carbon atoms, an aryl group having 6 to 15 carbon atoms and an arylalkyl group having 7 to 15 carbon atoms are particularly preferred.
　上記一般式（Iα）中のＲ２１～Ｒ２３、及び上記一般式（Iβ）中のＲ１２１～Ｒ１２３で表される炭素原子数２～２０の複素環含有基としては、例えば、ピロリル、ピリジル、ピリジルエチル、ピリミジル、ピリダジル、ピペラジル、ピペリジル、ピラニル、ピラニルエチル、ピラゾリル、トリアジル、トリアジルメチル、ピロリジル、キノリル、イソキノリル、イミダゾリル、ベンゾイミダゾリル、トリアゾリル、フリル、フラニル、ベンゾフラニル、チエニル、チオフェニル、ベンゾチオフェニル、チアジアゾリル、チアゾリル、ベンゾチアゾリル、オキサゾリル、ベンゾオキサゾリル、イソチアゾリル、イソオキサゾリル、インドリル、ユロリジル、モルフォリニル、チオモルフォリニル、２－ピロリジノン－１－イル、２－ピペリドン－１－イル、２，４－ジオキシイミダゾリジン－３－イル及び２，４－ジオキシオキサゾリジン－３－イル等が挙げられる。 Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R 21 to R 23 in the general formula (Iα) and R 121 to R 123 in the general formula (Iβ) include pyrrolyl, Pyridyl, pyridylethyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyranylethyl, pyrazolyl, triazyl, triazylmethyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl , Thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, urolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-pipe Examples include lidon-1-yl, 2,4-dioxyimidazolidin-3-yl and 2,4-dioxyoxazolidine-3-yl.
　上記炭素原子数２～２０の複素環含有基の中でも、光重合開始剤として感度がよいことから、炭素原子数２～１０の複素環含有基が特に好ましい。 Among the heterocyclic groups having 2 to 20 carbon atoms, the heterocyclic group having 2 to 10 carbon atoms is particularly preferable because of its high sensitivity as a photopolymerization initiator.
　上記一般式（Iα）中のＲ２１～Ｒ２３で表される基中のメチレン基は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ２４－、－ＮＲ２４ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合があり、また、上記一般式（Iβ）中のＲ１２１～Ｒ１２３で表される基中のメチレン基は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ１２４－、－ＮＲ１２４ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合があり、これらの置換は１種又は２種以上の基によるものであり、連続して置換し得る基の場合は、酸素原子が隣り合わない条件で２つ以上の基により連続して置換される場合がある。 The methylene group in the group represented by R 21 to R 23 in the general formula (Iα) is —O—, —CO—, —COO—, —OCO—, —NR 24 —, —NR 24 CO—. , —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO— may be substituted, and R 121 to R in the above general formula (Iβ) methylene groups in the group represented by 123, -O -, - CO -, - COO -, - OCO -, - NR 124 -, - NR 124 CO -, - S -, - CS -, - SO 2 -, -SCO-, -COS-, -OCS- or CSO- may be substituted, and these substitutions are caused by one or more groups, and in the case of groups that can be substituted successively May be successively substituted by two or more groups under conditions where the oxygen atoms are not adjacent.
　Ｒ１とＲ２、Ｒ２とＲ３、Ｒ３とＲ４、Ｒ５とＲ６、Ｒ６とＲ７、Ｒ７とＲ８、Ｒ８とＲ９、Ｒ９とＲ１０、Ｒ１０とＲ１１、Ｒ１１とＲ１、Ｒ１０１とＲ１０２、Ｒ１０２とＲ１０３、Ｒ１０３とＲ１０４、Ｒ１０５とＲ１０６、Ｒ１０６とＲ１０７、Ｒ１０７とＲ１０８、Ｒ１０８とＲ１０９、Ｒ１０９とＲ１１０、Ｒ１１０とＲ１１１、Ｒ１１１とＲ１１２、Ｒ１１２とＲ１１３及びＲ１１３とＲ１０１が結合して形成する環としては、例えば、シクロペンタン、シクロヘキサン、シクロペンテン、ベンゼン、ピロリジン、ピロール、ピペラジン、モルホリン、チオモルホリン、テトラヒドロピリジン、ラクトン環及びラクタム環等の５～７員環並びにナフタレン及びアントラセン等の縮合環等が挙げられる。 R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 R 11 , R 11 and R 1 , R 101 and R 102 , R 102 and R 103 , R 103 and R 104 , R 105 and R 106 , R 106 and R 107 , R 107 and R 108 , R 108 and R 109 , R 109 and R 110 , R 110 and R 111 , R 111 and R 112 , R 112 and R 113, and R 113 and R 101 may be combined to form, for example, cyclopentane, cyclohexane, cyclopentene, Benzene, pyrrolidine, pyrrole, piperazine, morpholine, thiomorpholine, tetrahydropyridine, 5- to 7-membered rings such as lactone ring and lactam ring, and condensed such as naphthalene and anthracene Examples include a fused ring.
　上記一般式（II）中のＲ３１～Ｒ３３で表される炭素原子数１～２０の炭化水素基としては、上記一般式（Iα）中のＲ２１～Ｒ２４又は上記一般式（Iβ）中のＲ１２１～Ｒ１２４で表される炭素原子数１～２０の炭化水素基と同様のものが挙げられる。 Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 31 to R 33 in the general formula (II) include R 21 to R 24 in the general formula (Iα) or the general formula (Iβ). Examples thereof include the same hydrocarbon groups having 1 to 20 carbon atoms represented by R 121 to R 124 .
　上記一般式（II）中の、Ｒ３１及びＲ３２で表される炭素原子数２～２０の複素環含有基としては、上記一般式（Iα）中のＲ２１～Ｒ２３及び上記一般式（Iβ）中のＲ１２１～Ｒ１２３で表される炭素原子数２～２０の複素環含有基と同様のものが挙げられる。 Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R 31 and R 32 in the general formula (II) include R 21 to R 23 in the general formula (Iα) and the general formula (I Examples thereof include those similar to the heterocyclic group having 2 to 20 carbon atoms represented by R 121 to R 123 in Iβ).
　上記一般式（II）中の、Ｒ３１及びＲ３２で表される基中のメチレン基は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ３３－、－ＮＲ３３ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合があり、この置換は１種又は２種以上の基によるものであり、連続して置換し得る基の場合は、酸素原子が隣り合わない条件で２つ以上の基により連続して置換される場合がある。 In the general formula (II), the methylene group in the groups represented by R 31 and R 32 is —O—, —CO—, —COO—, —OCO—, —NR 33 —, —NR 33 CO May be substituted with —, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO—, this substitution being by one or more groups In the case of a group that can be substituted continuously, the oxygen atom may be continuously substituted by two or more groups under the condition that they are not adjacent to each other.
　上記一般式（IIIα）及び（IIIβ）中のＲ５１～Ｒ５４で表される炭素原子数１～２０の炭化水素基としては、上記一般式（Iα）中のＲ２１～Ｒ２４及び上記一般式（Iβ）中のＲ１２１～Ｒ１２４で表される炭素原子数１～２０の炭化水素基と同様のものが挙げられる。 Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 51 to R 54 in the general formulas (IIIα) and (IIIβ) include R 21 to R 24 in the general formula (Iα) and the above general formulas Examples thereof include the same hydrocarbon groups having 1 to 20 carbon atoms represented by R 121 to R 124 in the formula (Iβ).
　上記一般式（IIIα）及び（IIIβ）中のＲ５１～Ｒ５３で表される炭素原子数２～２０の複素環含有基としては、上記一般式（Iα）中のＲ２１～Ｒ２３及び上記一般式（Iβ）中のＲ１２１～Ｒ１２３で表される炭素原子数２～２０の複素環含有基と同様のものが挙げられる。 Examples of the heterocyclic group containing 2 to 20 carbon atoms represented by R 51 to R 53 in the general formulas (IIIα) and (IIIβ) include R 21 to R 23 in the general formula (Iα) and the above Examples thereof include those similar to the heterocyclic group having 2 to 20 carbon atoms represented by R 121 to R 123 in the general formula (Iβ).
　上記一般式（Iα）、（Iβ）、（II）、（IIIα）及び（IIIβ）中の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。 The halogen atoms in the general formulas (Iα), (Iβ), (II), (IIIα) and (IIIβ) include fluorine, chlorine, bromine and iodine.
　本発明のオキシムエステル化合物の中でも、一般式（Iα）中のＲ３及びＲ５の少なくとも一つが、一般式（II）で表される基であるオキシムエステル化合物は、合成時に収率がよく、精製も容易なことから好ましい。
　また、本発明のオキシムエステル化合物の中でも、一般式（Iβ）中のＲ１０３及びＲ１０６の少なくとも一つが、一般式（II）で表される基であるオキシムエステル化合物は、合成時に収率がよく、精製も容易なことから好ましい。同様の観点から、一般式（Iβ）中のＲ１０３及びＲ１０６の両方が、一般式（II）で表される基であるオキシムエステル化合物も好ましい。 Among the oxime ester compounds of the present invention, the oxime ester compound in which at least one of R 3 and R 5 in the general formula (Iα) is a group represented by the general formula (II) has a good yield at the time of synthesis. It is preferable because purification is easy.
Among the oxime ester compounds of the present invention, an oxime ester compound in which at least one of R 103 and R 106 in the general formula (Iβ) is a group represented by the general formula (II) has a yield during synthesis. It is preferable because it is well purified. From the same viewpoint, an oxime ester compound in which both R 103 and R 106 in the general formula (Iβ) are groups represented by the general formula (II) is also preferable.
　上記一般式（Iα）及び（Iβ）において、Ｒ１及びＲ１０１が一般式（II）で表される基以外の基又は原子である場合、Ｒ１及びＲ１０１が水素原子又はシアノ基、特に水素原子であるものは、合成が容易なので好ましい。Ｒ２～Ｒ５及びＲ１０２～Ｒ１０７それぞれについても、Ｒ１と同様である。即ち、Ｒ２～Ｒ５及びＲ１０２～Ｒ１０６が一般式（II）で表される基以外の基又は原子である場合、Ｒ２～Ｒ５及びＲ１０２～Ｒ１０６が水素原子又はシアノ基、特に水素原子であると、合成が容易なので好ましい。
　また、上記一般式（Iα）及び（Iβ）において、Ｒ６及びＲ１０８が一般式（II）で表される基以外の基又は原子である場合、Ｒ６及びＲ１０８が水素原子であるものは、合成が容易なので好ましい。 In the above general formulas (Iα) and (Iβ), when R 1 and R 101 are groups or atoms other than the group represented by the general formula (II), R 1 and R 101 are hydrogen atoms or cyano groups, particularly A hydrogen atom is preferable because it is easy to synthesize. Each of R 2 to R 5 and R 102 to R 107 is the same as R 1 . That is, when R 2 to R 5 and R 102 to R 106 are groups or atoms other than the group represented by formula (II), R 2 to R 5 and R 102 to R 106 are hydrogen atoms or cyano groups. In particular, a hydrogen atom is preferable because synthesis is easy.
In the general formulas (Iα) and (Iβ), when R 6 and R 108 are groups or atoms other than the group represented by the general formula (II), R 6 and R 108 are hydrogen atoms. Is preferable because it is easy to synthesize.
　本発明のオキシムエステル化合物の中でも、一般式（Iα）中のＸ１が不存在でＲ５とＲ６が結合してベンゼン環を形成するオキシムエステル化合物は、近紫外光（特に３６５ｎｍ）を効率よく吸収できることから好ましい。
　尚、本明細書において、「Ｘ１が不存在」とは、一般式（Iα）において、－Ｘ１－で表される結合が存在せず、Ｎ原子及びＸ１を含む縮合環骨格が形成されていない状態を意味する。例えば、上述の「Ｘ１が不存在でＲ５とＲ６が結合してベンゼン環を形成するであるオキシムエステル化合物」は、Ｎ原子及びＸ１を含む縮合環骨格ではなくトリフェニルアミン骨格を有する化合物であり、該化合物の具体例としては後記の化合物Ｎｏ．１５３～１７０が挙げられる。
　また、一般式（Iβ）中の「Ｘ１０１が不存在」とは、－Ｘ１０１－で表される結合が存在せず、Ｎ原子及びＸ１０１を含む縮合環骨格が形成されていない状態を意味する。 Among the oxime ester compounds of the present invention, the oxime ester compound in which X 1 in the general formula (Iα) is absent and R 5 and R 6 are bonded to form a benzene ring is effective in the near ultraviolet light (especially 365 nm). It is preferable because it can be absorbed well.
In this specification, “X 1 is absent” means that in the general formula (Iα), a bond represented by —X 1 — does not exist and a condensed ring skeleton containing an N atom and X 1 is formed. It means a state that is not done. For example, "oxime ester compounds in which X 1 is to form a benzene ring bonded R 5 and R 6 in the absence" described above, the triphenylamine skeleton rather than a condensed ring skeleton containing N atoms and X 1 Specific examples of the compound include compound Nos. Described later. 153 to 170.
In the general formula (Iβ), “X 101 is absent” means that a bond represented by —X 101 — does not exist and a condensed ring skeleton containing an N atom and X 101 is not formed. means.
　上記一般式（II）において、Ｒ３１が炭素原子数１～１２のアルキル基であるものは、有機溶剤への溶解性が高いので好ましい。また、反応性が高くなるため、上記一般式（II）において、Ｒ３２がメチル基及びエチル基等の炭素原子数１～４のアルキル基又はフェニル基であるものが好ましく、炭素原子数１～４のアルキル基であるものがより好ましく、メチル基であるものが特に好ましい。 In the above general formula (II), those in which R 31 is an alkyl group having 1 to 12 carbon atoms are preferred because of their high solubility in organic solvents. In addition, since the reactivity is increased, in the general formula (II), it is preferable that R 32 is an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group or a phenyl group. 4 is more preferable, and a methyl group is particularly preferable.
　上記一般式（Iα）で表される本発明のオキシムエステル化合物においては、Ｒ９が上記一般式（IIIα）で表される基であることが好ましい。また、上記一般式（Iα）で表される本発明のオキシムエステル化合物においては、Ｒ９が上記一般式（IIIβ）で表される基であることが好ましい。
　上記一般式（Iβ）で表される本発明のオキシムエステル化合物においては、Ｒ１１１が上記一般式（IIIα）で表される基であることが好ましい。また、上記一般式（Iβ）で表される本発明のオキシムエステル化合物においては、Ｒ１１１が上記一般式（IIIβ）で表される基であることが好ましい。
　上記一般式（IIIα）で表される基中のＸ２は、酸素原子又は硫黄原子であることが好ましく、酸素原子であることが特に好ましい。オキシムエステル化合物が長波長の近紫外光を効率よく吸収するものとなり、光重合開始剤として高感度となるためである。上記一般式（IIIα）で表される基中のＲ４１～Ｒ４５は水素原子であることが好ましい。
　上記一般式（IIIβ）で表される基中のＸ３は、酸素原子又は硫黄原子であることが好ましい。オキシムエステル化合物が長波長の近紫外光を効率よく吸収するものとなり、光重合開始剤として高感度となるためである。上記一般式（IIIβ）で表される基中のＲ４６～Ｒ５０は水素原子であることが好ましい。 In the oxime ester compound of the present invention represented by the general formula (Iα), R 9 is preferably a group represented by the general formula (IIIα). In the oxime ester compound of the present invention represented by the general formula (Iα), R 9 is preferably a group represented by the general formula (IIIβ).
In the oxime ester compound of the present invention represented by the general formula (Iβ), R 111 is preferably a group represented by the general formula (IIIα). In the oxime ester compound of the present invention represented by the general formula (Iβ), R 111 is preferably a group represented by the general formula (IIIβ).
X 2 in the group represented by the general formula (IIIα) is preferably an oxygen atom or a sulfur atom, and particularly preferably an oxygen atom. This is because the oxime ester compound efficiently absorbs long-wavelength near-ultraviolet light and becomes highly sensitive as a photopolymerization initiator. R 41 to R 45 in the group represented by the general formula (IIIα) are preferably hydrogen atoms.
X 3 in the group represented by the general formula (IIIβ) is preferably an oxygen atom or a sulfur atom. This is because the oxime ester compound efficiently absorbs long-wavelength near-ultraviolet light and becomes highly sensitive as a photopolymerization initiator. R 46 to R 50 in the group represented by the general formula (IIIβ) are preferably hydrogen atoms.
　上記一般式（Iα）で表される本発明のオキシムエステル化合物においては、Ｘ１が不存在であることが好ましい。
　上記一般式（Iβ）で表される本発明のオキシムエステル化合物においては、Ｘ１０１が不存在であることが好ましく、Ｘ１０１が硫黄であることも好ましい。 In the oxime ester compound of the present invention represented by the general formula (Iα), X 1 is preferably absent.
In the oxime ester compound of the present invention represented by the above general formula (Iβ), X 101 is preferably absent, and X 101 is preferably sulfur.
　上記一般式（Iα）又は（Iβ）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．１９４が挙げられる。但し、本発明は以下の化合物により何ら制限を受けるものではない。 Preferred specific examples of the oxime ester compound of the present invention represented by the above general formula (Iα) or (Iβ) include the following compound Nos. 1-No. 194. However, the present invention is not limited by the following compounds.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
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
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　上記一般式（Iα）又は（Iβ）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、下記に示す方法で合成できる。 The oxime ester compound of the present invention represented by the above general formula (Iα) or (Iβ) is not particularly limited, but can be synthesized, for example, by the method shown below.
　まず、本発明のオキシムエステル化合物の中間体であるＮ－アリール化合物を得る。このＮ－アリール化合物の合成法の一例は、以下の通りである。
　即ち、公知であり市販されているアルデヒド化合物と公知であり市販されているフッ化ベンゼン化合物とを炭酸カリウムを用いて反応させることでハロゲン化アリール化合物を得、ハロゲン化アリール化合物と公知であり市販されているＮ含有複素環化合物を反応させることで、Ｎ－アリール化合物を得る。 First, an N-aryl compound that is an intermediate of the oxime ester compound of the present invention is obtained. An example of a method for synthesizing this N-aryl compound is as follows.
That is, a known and commercially available aldehyde compound and a known and commercially available fluorinated benzene compound are reacted with potassium carbonate to obtain a halogenated aryl compound, which is known as a halogenated aryl compound and is commercially available. By reacting the N-containing heterocyclic compound, an N-aryl compound is obtained.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　次いで、一般式（II）中のｎが０の場合、上記Ｎ－アリール化合物を用い、下記の反応式に従って以下の方法により、本発明のオキシム化合物を製造することができる。
　即ち、上記Ｎ－アリール化合物と酸クロリドと反応させることによりケトン化合物１を得、ケトン化合物１と塩酸ヒドロキシルアミンを反応させることにより、オキシム化合物１を得る。続いて、オキシム化合物１に、酸無水物又は酸クロリドを反応させることにより、上記一般式（Iα）又は（Iβ）で表される本発明のオキシムエステル化合物１を得る。
　尚、オキシム化合物１及びオキシムエステル化合物１は、特許第４２２３０７１号公報に記載の方法でも製造できる。 Next, when n in the general formula (II) is 0, the oxime compound of the present invention can be produced by the following method using the N-aryl compound according to the following reaction formula.
That is, the ketone compound 1 is obtained by reacting the N-aryl compound with acid chloride, and the oxime compound 1 is obtained by reacting the ketone compound 1 with hydroxylamine hydrochloride. Subsequently, the oxime compound 1 is reacted with an acid anhydride or acid chloride to obtain the oxime ester compound 1 of the present invention represented by the above general formula (Iα) or (Iβ).
The oxime compound 1 and the oxime ester compound 1 can also be produced by the method described in Japanese Patent No. 4223071.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　また、一般式（II）中のｎが１の場合、上記Ｎ－アリール化合物を用い、下記の反応式に従って以下の方法により、本発明のオキシム化合物を製造することができる。
　即ち、上記Ｎ－アリール化合物と酸クロリドと反応させることによりケトン化合物２を得、ケトン化合物２と亜硝酸イソブチルを反応させることにより、オキシム化合物２を得る。続いて、オキシム化合物２に、酸無水物又は酸クロリドを反応させることにより、上記一般式（Iα）又は（Iβ）で表される本発明のオキシムエステル化合物２を得る。 When n in the general formula (II) is 1, the oxime compound of the present invention can be produced by the following method using the N-aryl compound according to the following reaction formula.
That is, the ketone compound 2 is obtained by reacting the N-aryl compound with acid chloride, and the oxime compound 2 is obtained by reacting the ketone compound 2 with isobutyl nitrite. Subsequently, by reacting the oxime compound 2 with an acid anhydride or acid chloride, the oxime ester compound 2 of the present invention represented by the above general formula (Iα) or (Iβ) is obtained.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　尚、これらの反応式において、上記Ｎ含有複素環化合物に、予め酸クロリドを反応させてＮ含有複素環化合物のケトン体を作製しておき、上記Ｎ含有複素環化合物に代えて該ケトン体を上記ハロゲン化アリール化合物と反応させることによっても、ケトン化合物１又は２を得ることができる。 In these reaction formulas, the N-containing heterocyclic compound is previously reacted with an acid chloride to prepare a ketone body of the N-containing heterocyclic compound, and the ketone body is replaced with the N-containing heterocyclic compound. The ketone compound 1 or 2 can also be obtained by reacting with the halogenated aryl compound.
　以上説明した本発明の新規なオキシムエステル化合物は、ラジカル重合開始剤、特に光重合開始剤又は熱重合開始剤として有用である。また、本発明の新規なオキシムエステル化合物は、増感剤としても好適に用いることができる。 The novel oxime ester compound of the present invention described above is useful as a radical polymerization initiator, particularly a photopolymerization initiator or a thermal polymerization initiator. Moreover, the novel oxime ester compound of the present invention can also be suitably used as a sensitizer.
　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１種含有するものであり、更に他の光重合開始剤を含有することができる。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、エチレン性不飽和化合物の光重合開始剤として有用なものである。 The photopolymerization initiator of the present invention contains at least one oxime ester compound of the present invention, and can further contain other photopolymerization initiators. The content of the oxime ester compound of the present invention in the photopolymerization initiator is preferably 30 to 100% by mass, more preferably 50 to 100% by mass.
The photopolymerization initiator of the present invention is useful as a photopolymerization initiator for ethylenically unsaturated compounds.
　併用できる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、ＮＣＩ－８３１、ＮＣＩ－９３０（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（IV）で表される化合物等が挙げられる。尚、これらの光重合開始剤は、１種又は２種以上を組み合わせて用いることができる。 Conventionally known compounds can be used as other photopolymerization initiators that can be used in combination. 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-butyl Tylbenzoyltrichloromethane, 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, NCI-831, NCI-930 (manufactured by ADEKA), RGACURE369, IRGACURE907, IRGACURE OXE 01, IRGACURE
Examples include OXE 02 (manufactured by BASF), benzoyl peroxide, compounds represented by the following general formula (IV), and the like. In addition, these photoinitiators can be used 1 type or in combination of 2 or more types.
Figure JPOXMLDOC01-appb-C000035
 （式中、Ｒ６１及びＲ６２は、それぞれ独立に、シアノ基、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、
　Ｒ６３及びＲ６４は、それぞれ独立に、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ６５、ＯＲ６６、ＳＲ６７、ＮＲ６８Ｒ６９、ＣＯＲ７０、ＳＯＲ７１、ＳＯ２Ｒ７２又はＣＯＮＲ７３Ｒ７４を表し、
　Ｒ６３及びＲ６４は、互いに結合して環を形成する場合があり、
　Ｒ６３及びＲ６４は、それぞれ複数存在する場合、同一の場合も異なる場合があり、
　Ｒ６５、Ｒ６６、Ｒ６７、Ｒ６８、Ｒ６９、Ｒ７０、Ｒ７１、Ｒ７２、Ｒ７３及びＲ７４は、それぞれ独立に、炭素原子数１～２０のアルキル基、炭素原子数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、
　Ｘ４は、直接結合又はＣＯを表し、
　Ｘ５は、酸素原子、硫黄原子、セレン原子、ＣＲ７５Ｒ７６、ＣＯ、又はＰＲ７７を表し、
　Ｒ７５、Ｒ７６及びＲ７７は、それぞれ独立に、炭素原子数１～２０のアルキル基、炭素原子数６～３０のアリール基又は炭素原子数７～３０のアリールアルキル基を表し、
　該アルキル基又はアリールアルキル基中の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基又は複素環基で置換される場合があり、
　該アルキル基又はアリールアルキル基中のメチレン基は、－Ｏ－で置換される場合があり、
　ａは、０～４の整数を表し、
　ｂは、０～５の整数を表す。）
Figure JPOXMLDOC01-appb-C000035
 (Wherein R 61 and R 62 are each independently a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a carbon atom) Represents a heterocyclic group having 2 to 20 atoms,
R 63 and R 64 are each independently a halogen atom, nitro group, cyano group, hydroxyl group, carboxyl group, R 65 , OR 66 , SR 67 , NR 68 R 69 , COR 70 , SOR 71 , SO 2 R 72 or Represents CONR 73 R 74 ,
R 63 and R 64 may combine with each other to form a ring,
R 63 and R 64 may be the same or different when there are a plurality of R 63 and R 64 respectively.
R 65 , R 66 , R 67 , R 68 , R 69 , R 70 , R 71 , R 72 , R 73 and R 74 are each independently an alkyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. A 30 aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms;
X 4 represents a direct bond or CO,
X 5 represents an oxygen atom, a sulfur atom, a selenium atom, CR 75 R 76 , CO, or PR 77 ;
R 75 , R 76 and R 77 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms,
A hydrogen atom in the alkyl group or arylalkyl group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group or a heterocyclic group,
The methylene group in the alkyl group or arylalkyl group may be substituted with —O—,
a represents an integer of 0 to 4,
b represents an integer of 0 to 5. )
　次に、本発明の感光性組成物について説明する。
　本発明の感光性組成物は、本発明の光重合開始剤（Ａ）及びエチレン性不飽和化合物（Ｂ）を含有し、任意成分として、着色剤（Ｃ）、アルカリ現像性化合物（Ｄ）、溶剤や、後述の任意の添加物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.
The photosensitive composition of the present invention contains the photopolymerization initiator (A) of the present invention and an ethylenically unsaturated compound (B), and as optional components, a colorant (C), an alkali developable compound (D), It contains a combination of a solvent and any additive described below.
　本発明の感光性組成物において、光重合開始剤（Ａ）の含有量は特に限定されるものではないが、エチレン性不飽和化合物（Ｂ）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質量部である。 In the photosensitive composition of the present invention, the content of the photopolymerization initiator (A) is not particularly limited, but is preferably 1 to 70 masses with respect to 100 mass parts of the ethylenically unsaturated compound (B). Parts, more preferably 1-50 parts by weight, most preferably 5-30 parts by weight.
　上記エチレン性不飽和化合物（Ｂ）は、エチレン性の不飽和結合を有しているものであれば特に限定されず、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。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ル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 ethylenically unsaturated compound (B) is not particularly limited as long as it has an ethylenically unsaturated bond, and those conventionally used in photosensitive compositions can be used. For example, unsaturated aliphatic hydrocarbons such as ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, Citraconic acid, fumaric acid, hymic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic acid, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2 -(Meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc., polymer mono (meth) acrylate having a carboxyl group and a hydroxyl group at both ends; hydroxyethyl (meth) acrylate malate, hydroxy Propyl (meth) acrylate, Malay Unsaturated polybasic acids such as dicyclopentadiene malate or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups; (meth) acrylic acid-2-hydroxyethyl, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, the following compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Enoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyl toluene, vinyl benzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinyl benzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl 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 Macromonomers 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, divinyl succi Narate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomer and polyisocyanate compound vinyl urethane compound, hydroxyl group content The vinyl epoxy compound of a vinyl monomer and a polyepoxy compound is mentioned.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　上記エチレン性不飽和化合物（Ｂ）としては市販品を用いることもでき、市販品としては、例えば、カヤラッドＤＰＨＡ、ＤＰＥＡ－１２、ＰＥＧ４００ＤＡ、ＴＨＥ－３３０、ＲＰ－１０４０、ＮＰＧＤＡ、ＰＥＴ３０（日本化薬製）、ＳＰＣ－１０００、ＳＰＣ－３０００（昭和電工製）、アロニックスＭ－１４０、Ｍ－２１５、Ｍ－３５０（東亞合成社製）、ＮＫエステルＡ－ＤＰＨＡ－ＴＭＰＴ、Ａ－ＤＣＰ、Ａ－ＨＤ－Ｎ、Ａ－９３００、ＴＭＰＴ、ＤＣＰ、ＮＰＧ及びＨＤ－Ｎ（新中村化学工業社製）等が挙げられる。 Commercially available products may be used as the ethylenically unsaturated compound (B). Examples of commercially available products include Kayrad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, and PET30 (Nippon Kayaku). SPC-1000, SPC-3000 (manufactured by Showa Denko), Aronix M-140, M-215, M-350 (manufactured by Toagosei), NK ester A-DPHA-TMPT, A-DCP, A-HD -N, A-9300, TMPT, DCP, NPG and HD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.).
　これらのエチレン性不飽和化合物の中でも、両末端にカルボキシル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、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、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に、本発明のオキシムエステル化合物を含有する光重合開始剤は好適である。 Among these ethylenically unsaturated compounds, polyfunctional (meta) having a mono (meth) acrylate polymer having a carboxyl group and a hydroxyl group at both ends, one carboxyl group and two or more (meth) acryloyl groups. The photopolymerization initiator containing the oxime ester compound of the present invention is suitable for esters of acrylates, unsaturated monobasic acids and polyhydric alcohols or polyhydric phenols.
　エチレン性不飽和化合物は、単独で又は２種以上を混合して使用することができ、また２種以上を混合して使用する場合には、それらを予め共重合して共重合体として使用することもできる。 The ethylenically unsaturated compounds can be used alone or in admixture of two or more, and when used in admixture of two or more, they are copolymerized in advance and used as a copolymer. You can also.
　本発明の感光性組成物には、更に着色剤（Ｃ）を含有させて着色感光性組成物とすることができる。該着色剤（Ｃ）としては、顔料、染料、天然色素等が挙げられる。これらの着色剤は、単独で又は２種以上を混合して用いることができる。 The photosensitive composition of the present invention may further contain a colorant (C) to form a colored photosensitive composition. Examples of the colorant (C) include pigments, dyes, and natural pigments. These colorants 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剤中で樹脂に分散処理し、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; Compound; perylene compound; diketopyrrolopyrrole compound; thioindigo compound; dioxazine compound; triphenylmethane compound; quinophthalone compound; naphthalene tetracarboxylic acid; azo dye, metal complex compound of cyanine dye; lake pigment; furnace method, channel method or thermal 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 in a resin in a solvent and adsorbed with 20 to 200 mg / g of resin, an acid or alkaline surface treated carbon black, 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、単独で用いる場合があり、複数を混合して用いる場合がある。 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 the like. These may be used alone or in combination.
　本発明の感光性組成物において、上記着色剤（Ｃ）の含有量は、上記エチレン性不飽和化合物（Ｂ）１００質量部に対して、好ましくは５～１００質量部、より好ましくは１０～５０質量部である。 In the photosensitive composition of the present invention, the content of the colorant (C) is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts per 100 parts by mass of the ethylenically unsaturated compound (B). Part by mass.
　本発明の感光性組成物には、更にアルカリ現像性化合物（Ｄ）を含有させてアルカリ現像性感光性樹脂組成物とすることができる。着色剤（Ｃ）及びアルカリ現像性化合物（Ｄ）を同時に含むものは、着色アルカリ現像性感光性樹脂組成物ともいう。 The photosensitive composition of the present invention may further contain an alkali developable compound (D) to form an alkali developable photosensitive resin composition. What contains a colorant (C) and an alkali developable compound (D) simultaneously is also called a colored alkali developable photosensitive resin composition.
　上記アルカリ現像性化合物（Ｄ）としては、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、例えば、特開２００４－２６４４１４号公報に記載の樹脂等が挙げられる。 The alkali-developable compound (D) is not particularly limited as long as it is a compound soluble in an alkaline aqueous solution, and examples thereof include resins described in JP-A No. 2004-264414.
　また、上記アルカリ現像性化合物（Ｄ）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（Ｖ）で表されるエポキシ化合物等のエポキシ化合物のエポキシ基に、不飽和一塩基酸を作用させ、更に多塩基酸無水物を作用させて得られた樹脂を用いることができる。ここでいうエポキシアクリレート樹脂とは、上記エポキシ化合物に（メタ）アクリル酸を作用させたものであり、その例としては、Ｒｉｐｏｘｙ　ＳＰＣ－２０００、ＤＩＣ社製のディックライトＵＥ－７７７、日本ユピカ社製ユピカ４０１５等を挙げることができる。
　これらの中でも、エポキシアクリレート樹脂、及び、下記一般式（Ｖ）で表されるエポキシ化合物のエポキシ基に、不飽和一塩基酸を作用させ、更に多塩基酸無水物を作用させて得られた樹脂が好ましい。 Examples of the alkali-developable compound (D) include acrylic acid ester copolymers, phenol and / or cresol novolac epoxy resins, polyphenylmethane type epoxy resins having polyfunctional epoxy groups, epoxy acrylate resins, A resin obtained by allowing an unsaturated monobasic acid to act on an epoxy group of an epoxy compound such as an epoxy compound represented by the formula (V) and further allowing a polybasic acid anhydride to act thereon can be used. The epoxy acrylate resin here is one obtained by allowing (meth) acrylic acid to act on the above-mentioned epoxy compound. Examples thereof include Lipoxy SPC-2000, Dicklight UE-777 manufactured by DIC, and Nippon Iupika. Examples include Eupica 4015.
Among these, an epoxy acrylate resin and a resin obtained by allowing an unsaturated monobasic acid to act on an epoxy group of an epoxy compound represented by the following general formula (V) and further causing a polybasic acid anhydride to act Is preferred.
Figure JPOXMLDOC01-appb-C000040
 （式中、Ｘ６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－、－ＳＯ－2、－ＳＳ－、－ＳＯ－、－ＣＯ－、－ＯＣＯ－又は下記〔化３５－１〕、〔化３５－２〕若しくは〔化３５－３〕で表される基を表し、上記アルキリデン基はハロゲン原子で置換される場合があり、Ｒ８１及びＲ８２は、それぞれ独立に、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る場合があり、
　Ｒ８１及びＲ８２は、それぞれ複数存在する場合は、同一の場合も異なる場合があり、
　ｃは、０～４の整数であり、
　ｄは、０～４の整数であり、
　ｍは０～１０の整数であり、
　ｍが０でない場合には光学異性体が存在するが、いかなる異性体でもよい。）
Figure JPOXMLDOC01-appb-C000040
 (Wherein X 6 is a direct bond, a methylene group, an alkylidene group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, —O—, —S—, —SO— 2 , —SS—, —SO—, —CO—, —OCO— or a group represented by the following [Chemical 35-1], [Chemical 35-2] or [Chemical 35-3], wherein the alkylidene group is a halogen atom. Each of R 81 and R 82 independently represents 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 Represents a halogen atom, the alkyl group, alkoxy group and alkenyl group may be substituted with a halogen atom,
R 81 and R 82 may be the same or different when there are a plurality of R 81 and R 82 ,
c is an integer from 0 to 4,
d is an integer from 0 to 4,
m is an integer from 0 to 10,
When m is not 0, an optical isomer exists, but any isomer may be used. )
Figure JPOXMLDOC01-appb-C000041
 （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る場合があるフェニル基、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る場合がある炭素原子数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る場合があり、ｄは０～５の整数である。）
Figure JPOXMLDOC01-appb-C000041
 (Wherein Z 3 is a hydrogen atom, a phenyl group which may be substituted by an alkyl group having 1 to 10 carbon atoms or 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, 1 to 10 carbon atoms An alkoxy 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-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
 （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る場合がある炭素原子数１～１０のアルキル基、ハロゲン原子で置換されている場合がある炭素原子数６～２０のアリール基、ハロゲン原子で置換されている場合がある炭素原子数６～２０のアリールオキシ基、ハロゲン原子で置換されている場合がある炭素原子数６～２０のアリールチオ基、ハロゲン原子で置換されている場合がある炭素原子数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る場合がある炭素原子数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る場合がある炭素原子数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－で中断されている場合があり、Ｚ4は、隣接するＺ4同士で環を形成している場合があり、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-C000043
 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 carbon atoms which may be substituted with a halogen atom. An aryl group having 20 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms that may be substituted with a halogen atom, an arylthio group having 6 to 20 carbon atoms that may be substituted with a halogen atom, and a halogen atom An arylalkenyl group having 6 to 20 carbon atoms that may be substituted, an arylalkyl group having 7 to 20 carbon atoms that may be substituted with a halogen atom, or a carbon that may be substituted with a halogen atom Represents a heterocyclic group having 2 to 20 atoms, or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group is an unsaturated bond, —O— or —S—. Z 4 may form a ring with adjacent Z 4 , p represents an integer of 0 to 4, q represents an integer of 0 to 8, r Represents an integer from 0 to 4, s represents an integer from 0 to 4, and the total number of r and s is an integer from 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.
　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。 Examples of the polybasic acid anhydride that is acted after the unsaturated monobasic acid is allowed to act include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellit Acid anhydride, pyromellitic acid anhydride, 2,2'-3,3'-benzophenone tetracarboxylic acid anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride, methyl Tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1 , 2-Dicarboxylic anhydride, trialkyltetrahydro B 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及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.
　また、アルカリ現像性化合物は、エチレン性不飽和結合を有している場合がある。即ち、上記のエチレン性不飽和化合物（Ｂ）と、上記のアルカリ現像性化合物（Ｄ）とは同一の化合物である場合がある。この場合、アルカリ現像性を有し且つエチレン性不飽和結合を有する化合物は、不飽和基を０．２～１．０当量含有していることが好ましい。
　尚、アルカリ現像性を有し且つエチレン性不飽和結合を有する化合物を用いる場合、該化合物は、前述の光重合開始剤（Ａ）の含有量及び着色剤（Ｃ）の含有量を算出する際には、エチレン性不飽和化合物（Ｂ）に含めるものとする。 Moreover, the alkali developable compound may have an ethylenically unsaturated bond. That is, the ethylenically unsaturated compound (B) and the alkali developable compound (D) may be the same compound. In this case, the compound having alkali developability and having an ethylenically unsaturated bond preferably contains 0.2 to 1.0 equivalent of an unsaturated group.
In addition, when using the compound which has alkali developability and has an ethylenically unsaturated bond, when this compound calculates content of the above-mentioned photoinitiator (A) and content of a coloring agent (C). Is included in the ethylenically unsaturated compound (B).
　本発明の感光性組成物をアルカリ現像性感光性樹脂組成物とする場合、エチレン性不飽和結合を有する場合がある上記アルカリ現像性化合物（Ｄ）の含有量は、本発明のアルカリ現像性感光性樹脂組成物中、１～２０質量％、特に３～１２質量％が好ましい。 When the photosensitive composition of the present invention is an alkali-developable photosensitive resin composition, the content of the alkali-developable compound (D) that may have an ethylenically unsaturated bond is determined by the alkali-developable photosensitive composition of the present invention. 1 to 20 mass%, particularly 3 to 12 mass% is preferable in the conductive resin composition.
　酸価調整して本発明の（着色）アルカリ現像性感光性樹脂組成物の現像性を改良するため、エチレン性不飽和結合を有している場合がある上記アルカリ現像性化合物（Ｄ）と共に、更に単官能又は多官能エポキシ化合物を用いることができる。エチレン性不飽和結合を有している場合がある上記アルカリ現像性化合物（Ｄ）は、固形分の酸価が５～１２０ｍｇＫＯＨ／ｇの範囲であることが好ましく、単官能又は多官能エポキシ化合物の使用量は、上記酸価を満たすように選択するのが好ましい。 In order to improve the developability of the (colored) alkali-developable photosensitive resin composition of the present invention by adjusting the acid value, together with the alkali-developable compound (D) that may have an ethylenically unsaturated bond, Furthermore, a monofunctional or polyfunctional epoxy compound can be used. The alkali-developable compound (D) that may have an ethylenically unsaturated bond preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and is a monofunctional or polyfunctional epoxy compound. The amount 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、上記化合物Ｎｏ．Ａ２、Ｎｏ．Ａ３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 above compound N . A2, No. A3 etc. are mentioned.
　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１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（Ｖ）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 is obtained. This is preferable.
As said bisphenol-type epoxy compound, the epoxy compound represented by the said general formula (V) can be used, For example, bisphenol-type epoxy compounds, 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は、更に溶剤を含有させることができる。該溶剤としては、通常、必要に応じて上記の各成分（光重合開始剤（Ａ）及びエチレン性不飽和化合物（Ｂ）等）を溶解又は分散し得る溶剤、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剤；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剤；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剤；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剤；エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコール－１－モノメチルエーテル－２－アセテート（ＰＧＭＥＡ）、ジプロピレングリコールモノメチルエーテルアセテート、３－メトキシブチルエーテルアセテート、エトキシエチルエーテルプロピオネート等のエーテルエステル系溶剤；ベンゼン、トルエン、キシレン等のＢＴＸ系溶剤；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剤；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（コスモ松山石油社）、ソルベッソ＃１００（エクソン化学社）等のパラフィン系溶剤；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剤；クロロベンゼン等のハロゲン化芳香族炭化水素系溶剤；カルビトール系溶剤；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（ＤＭＡｃ）；Ｎ－メチルピロリドン；ジメチルスルホキシド；水等が挙げられ、これらの溶剤は１種又は２種以上の混合溶剤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剤等、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（Ａ）の相溶性がよいので好ましい。
　本発明の感光性組成物において、溶剤の含有量は、特に限定されるものではないが、感光性組成物全量１００質量％中で３０～９５質量％が好ましく、より好ましくは５０～９５質量％である。溶剤の含有量が上記範囲の場合、ハンドリング性（感光性組成物の粘度や濡れ性）、乾燥時のムラの低減、及び液安定性（組成物に含まれる成分の析出や沈降を伴わない）に優れる感光性組成物となり、硬化物を得る際に硬化物の厚さを適切にコントロールできることから好ましい。 The photosensitive composition of the present invention can further contain a solvent. As the solvent, usually, a solvent capable of dissolving or dispersing each of the above components (photopolymerization initiator (A), ethylenically unsaturated compound (B), etc.) as necessary, for example, methyl ethyl ketone, methyl amyl ketone, Ketones such as diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether, etc. Ether solvents such as methyl acetate, ethyl acetate, acetate-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol, etc .; ethylene glycol monomethyl ether, ethylene glycol Cellosolve solvents such as methanol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene Ether ester solvents such as glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate; BTX solvents such as benzene, toluene, xylene Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; Paraffinic solvents such as Luspirit, Swazol # 310 (Cosmo Matsuyama Oil), Solvesso # 100 (Exxon Chemical); Halogenated aliphatic carbonization such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane Hydrogenated solvents; Halogenated aromatic hydrocarbon solvents such as chlorobenzene; Carbitol solvents; Aniline; Triethylamine; Pyridine; Acetic acid; Acetonitrile; Carbon disulfide; N, N-dimethylformamide; ); N-methylpyrrolidone; dimethyl sulfoxide; water and the like. These solvents can be used as one or a mixture of two or more.
Among these, ketones, ether ester solvents, etc., particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone, etc. have good compatibility between the resist and the photopolymerization initiator (A) in the photosensitive composition. Therefore, it is preferable.
In the photosensitive composition of the present invention, the content of the solvent is not particularly limited, but is preferably 30 to 95% by mass, more preferably 50 to 95% by mass in 100% by mass of the total amount of the photosensitive composition. It is. When the solvent content is in the above range, handling properties (viscosity and wettability of the photosensitive composition), reduction of unevenness during drying, and liquid stability (no precipitation or sedimentation of components contained in the composition) It is preferable because the thickness of the cured product can be appropriately controlled when obtaining a cured product.
　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、無機化合物、潜在性添加剤、有機重合体、連鎖移動剤、増感剤、界面活性剤、シランカップリング剤、メラミン化合物、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；分散剤、分散助剤；撥インク剤；凝集防止剤；触媒；硬化促進剤；架橋剤；増粘剤等の慣用の任意の添加物を加えることができる。 The photosensitive composition of the present invention may contain p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, an inorganic compound, a latent additive, an organic polymer, a chain transfer agent, and a sensitizer as necessary. , Surfactant, silane coupling agent, melamine compound, thermal polymerization inhibitor; plasticizer; adhesion promoter; filler; antifoaming agent; leveling agent; surface conditioner; antioxidant; Conventional additives such as a dispersion aid, an ink repellent agent, an aggregation inhibitor, a catalyst, a curing accelerator, a cross-linking agent, and a thickener can be added.
　本発明の感光性組成物には、着色剤（Ｃ）及び／又は無機化合物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、着色剤（Ｃ）又は無機化合物を分散、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、とりわけ、該塩基性官能基がアミン及び／又はその四級塩であり、アミン価が１～１００ｍｇＫＯＨ／ｇのものが、好適に用いられる。 In the photosensitive composition of the present invention, a colorant (C) and / or a dispersant for dispersing an inorganic compound can be added. The dispersant is not limited as long as it can disperse and stabilize the colorant (C) or the inorganic compound, and a commercially available dispersant, for example, BYK series manufactured by BYK Chemie, Inc. can be used. In particular, a polymer dispersant comprising a polyester, polyether, or polyurethane having a basic functional group, in particular, the basic functional group is an amine and / or a quaternary salt thereof, and the amine value is 1 to 100 mgKOH / g. Are preferably used.
　上記潜在性添加剤とは、常温、光露光工程及びプリベーク工程では不活性であり、１００～２５０℃で加熱するか、又は酸／塩基触媒存在下で８０～２００℃で加熱することにより保護基が脱離して活性化するものである。活性化したことにより得られる効果としては、酸化防止、紫外線吸収、防汚性、リコート性及び密着性等が挙げられる。
　上記潜在性添加剤としては国際公開第２０１４／０２１０２３号パンフレットに記載されているものを好ましく使うことができる。 The latent additive is inactive at room temperature, in the light exposure step and in the pre-bake step, and is protected at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. Is activated by desorption. Examples of the effects obtained by activation include oxidation prevention, ultraviolet absorption, antifouling property, recoatability and adhesion.
As the latent additive, those described in International Publication No. 2014/021023 pamphlet can be preferably used.
　上記潜在性添加剤の好ましい例としては、国際公開第２０１４／０２１０２３号パンフレットに記載されている潜在性添加剤の他、下記一般式（Ａ）～（Ｃ）で表されるものが挙げられる。 Preferred examples of the latent additive include those represented by the following general formulas (A) to (C) in addition to the latent additive described in International Publication No. 2014/021023 pamphlet.
Figure JPOXMLDOC01-appb-C000044
 （式中、環Ａ１は、六員環の脂環、芳香環又は複素環であり、
　Ｒ８１、Ｒ８２、Ｒ８３、Ｒ８４及びＲ８５は、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有している場合がある炭素原子数１～４０のアルキル基、炭素原子数６～２０のアリール基、炭素原子数７～２０のアリールアルキル基若しくは炭素原子数２～２０の複素環含有基、又は－Ｏ－Ｒ８６を表し、Ｒ８１、Ｒ８２、Ｒ８３、Ｒ８４及びＲ８５のうち少なくとも１つは水素原子でなく、
　Ｒ８６は、炭素原子数１～２０のアルキル基、炭素原子数２～２０のアルケニル基、炭素原子数６～２０のアリール基、炭素原子数７～２０のアリールアルキル基、炭素原子数２～２０の複素環含有基又はトリアルキルシリル基を表す。）
Figure JPOXMLDOC01-appb-C000044
 (In the formula, ring A 1 is a six-membered alicyclic ring, aromatic ring or heterocyclic ring;
R 81 , R 82 , R 83 , R 84 and R 85 each have 1 to 40 carbon atoms which may have a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group or a substituent. Represents an alkyl group, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms, or —O—R 86 , R 81 , R 82 , R 83 , R 84 and R 85 are not hydrogen atoms,
R 86 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or 2 to 20 represents a heterocyclic group or a trialkylsilyl group. )
Figure JPOXMLDOC01-appb-C000045
 （式中、環Ａ１は上記一般式（Ａ）と同じであり、Ｒ９１は上記一般式（Ａ）におけるＲ８６と同じであり、
　Ｘ７は、下記一般式（１）で表される基であり、
　Ｒ９２、Ｒ９３、Ｒ９４及びＲ９５は、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、置換基を有している場合がある炭素原子数１～４０のアルキル基、炭素原子数６～２０のアリール基、炭素原子数７～２０のアリールアルキル基又は炭素原子数２～２０の複素環含有基を表し、Ｒ９２、Ｒ９３、Ｒ９４及びＲ９５のうち少なくとも１つは水素原子でない。）
Figure JPOXMLDOC01-appb-C000045
 (In the formula, ring A 1 is the same as the above general formula (A), R 91 is the same as R 86 in the above general formula (A),
X 7 is a group represented by the following general formula (1),
R 92 , R 93 , R 94 and R 95 are each a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkyl group having 1 to 40 carbon atoms which may have a substituent, Represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and at least one of R 92 , R 93 , R 94 and R 95 One is not a hydrogen atom. )
Figure JPOXMLDOC01-appb-C000046
 （上記一般式（１）中、Ｘ８は、－ＣＲ９７Ｒ９８－、－ＮＲ９９－、二価の炭素原子数１～３５の脂肪族炭化水素基、炭素原子数６～３５の芳香族炭化水素基若しくは炭素原子数２～３５の複素環基、又は、下記〔化３９〕〔化４０－１〕〔化４０－２〕に示す何れかの基を表し、
　該脂肪族炭化水素基中のメチレン基は、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－又は－ＮＨ－、或いは酸素原子が隣り合うことなしにこれらを組み合わせた結合基で置換される場合があり、
　Ｒ９７及びＲ９８は、水素原子、炭素原子数１～８のアルキル基、炭素原子数６～２０のアリール基又は炭素原子数７～２０のアリールアルキル基を表し、
　Ｚ５及びＺ６は、それぞれ独立に、直接結合、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－、－ＳＯ2－、－ＳＳ－、－ＳＯ－又は－ＮＲ１００－を表し、
　Ｒ９９及びＲ１００は、水素原子、置換基を有している場合がある炭素原子数１～３５の脂肪族炭化水素基、置換基を有している場合がある炭素原子数６～３５の芳香族炭化水素基又は置換基を有している場合がある炭素原子数２～３５の複素環基を表し、
　＊は結合手を表す。）
Figure JPOXMLDOC01-appb-C000046
 (In the general formula (1), X 8 represents —CR 97 R 98 —, —NR 99 —, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, and an aromatic group having 6 to 35 carbon atoms. A hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms, or any of the groups shown in the following [Chemical Formula 39] [Chemical Formula 40-1] [Chemical Formula 40-2],
The methylene group in the aliphatic hydrocarbon group may be —O—, —S—, —CO—, —COO—, —OCO— or —NH—, or a combination of these without adjacent oxygen atoms. May be substituted with a group,
R 97 and R 98 each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms,
Z 5 and Z 6 are each independently a direct bond, —O—, —S—, —CO—, —CO—O—, —O—CO—, —SO 2 —, —SS—, —SO—. Or -NR 100-
R 99 and R 100 are each a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms that may have a substituent, or a 6 to 35 carbon atom that may have a substituent. Represents a heterocyclic group having 2 to 35 carbon atoms which may have an aromatic hydrocarbon group or a substituent,
* Represents a bond. )
Figure JPOXMLDOC01-appb-C000047
 （上記式中、Ｒ１０１は水素原子、置換基を有している場合があるフェニル基又は炭素原子数３～１０のシクロアルキル基を表し、Ｒ１０２は炭素原子数１～１０のアルキル基、炭素原子数１～１０のアルコキシ基、炭素原子数２～１０のアルケニル基又はハロゲン原子を表し、上記アルキル基、アルコキシ基及びアルケニル基は置換基を有している場合があり、ｆは０～５の整数であり、＊は結合手を表す。）
Figure JPOXMLDOC01-appb-C000047
 (In the above formula, R 101 represents a hydrogen atom, a phenyl group which may have a substituent or a cycloalkyl group having 3 to 10 carbon atoms, R 102 represents an alkyl group having 1 to 10 carbon atoms, Represents an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a halogen atom, and the alkyl group, alkoxy group and alkenyl group may have a substituent, and f is 0 to (It is an integer of 5 and * represents a bond.)
Figure JPOXMLDOC01-appb-C000048
 （式中、＊は結合手を表す。）
Figure JPOXMLDOC01-appb-C000048
 (In the formula, * represents a bond.)
Figure JPOXMLDOC01-appb-C000049
 （上記式中、Ｒ１０３及びＲ１０４は、それぞれ独立に、置換基を有している場合がある炭素原子数１～１０のアルキル基、置換基を有している場合がある炭素原子数６～２０のアリール基、置換基を有している場合がある炭素原子数６～２０のアリールオキシ基、置換基を有している場合がある炭素原子数６～２０のアリールチオ基、置換基を有している場合がある炭素原子数６～２０のアリールアルケニル基、置換基を有している場合がある炭素原子数７～２０のアリールアルキル基、置換基を有している場合がある炭素原子数２～２０の複素環基又はハロゲン原子を表し、該アルキル基及びアリールアルキル基中のメチレン基は不飽和結合、－Ｏ－又は－Ｓ－で中断されている場合があり、Ｒ１０３は、隣接するＲ１０３同士で環を形成している場合があり、ｂは０～４の数を表し、ｃは０～８の数を表し、ｇは０～４の数を表し、ｈは０～４の数を表し、ｇとｈの数の合計は２～４である。）
Figure JPOXMLDOC01-appb-C000049
 (In the above formula, R 103 and R 104 are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent, or 6 carbon atoms which may have a substituent. An aryl group having 20 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms that may have a substituent, an arylthio group having 6 to 20 carbon atoms that may have a substituent, and a substituent. An arylalkenyl group having 6 to 20 carbon atoms that may have, an arylalkyl group having 7 to 20 carbon atoms that may have a substituent, and a carbon that may have a substituent Represents a heterocyclic group having 2 to 20 atoms or a halogen atom, and the methylene group in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, —O— or —S—, and R 103 is , Ring between adjacent R 103 B represents a number from 0 to 4, c represents a number from 0 to 8, g represents a number from 0 to 4, h represents a number from 0 to 4, g and (The total number of h is 2 to 4.)
Figure JPOXMLDOC01-appb-C000050
 （式中、ｋ＝２～６であり、Ｘ９は、ｋ＝２のとき上記一般式（１）で表される基であり、ｋ＝３のとき下記一般式（２）で表される基であり、ｋ＝４のとき下記一般式（３）で表される基であり、ｋ＝５のとき下記一般式（４）であり、ｋ＝６のとき下記一般式（５）であり、
　Ｒ１１１、Ｒ１１２、Ｒ１１３及びＲ１１４は、水素原子、ハロゲン原子、シアノ基、水酸基、ニトロ基、カルボキシル基、又は置換基を有している場合がある炭素原子数１～４０のアルキル基、炭素原子数６～２０のアリール基、炭素原子数７～２０のアリールアルキル基若しくは炭素原子数２～２０の複素環含有基を表し、Ｒ１１１、Ｒ１１２、Ｒ１１３及びＲ１１４のうち少なくとも１つは水素原子でなく、
　環Ａ１及びＲ８６は、上記一般式（Ａ）と同じである。）
Figure JPOXMLDOC01-appb-C000050
 (Wherein k = 2 to 6 and X 9 is a group represented by the general formula (1) when k = 2, and is represented by the following general formula (2) when k = 3. A group represented by the following general formula (3) when k = 4, a general formula (4) below when k = 5, and a general formula (5) below when k = 6 ,
R 111 , R 112 , R 113 and R 114 are a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, or an alkyl group having 1 to 40 carbon atoms which may have a substituent. Represents an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms, and includes at least one of R 111 , R 112 , R 113 and R 114 One is not a hydrogen atom,
Ring A 1 and R 86 are the same as those in the general formula (A). )
Figure JPOXMLDOC01-appb-C000051
 （上記一般式（２）中、Ｙ１１は、三価の炭素原子数１～３５の脂肪族炭化水素基、炭素原子数３～３５の脂環式炭化水素基、炭素原子数６～３５の芳香族炭化水素基又は炭素原子数２～３５の複素環基を表し、
　Ｚ１１、Ｚ１２及びＺ１３は、それぞれ独立に、直接結合、－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯ－Ｏ－、－Ｏ－ＣＯ－、－ＳＯ2－、－ＳＳ－、－ＳＯ－、－ＮＲ１２１－、－ＰＲ１２１－、置換基を有している場合がある炭素原子数１～３５の脂肪族炭化水素基、置換基を有している場合がある炭素原子数６～３５の芳香族炭化水素基、又は置換基を有している場合がある炭素原子数２～３５の複素環基を表し、
　Ｒ１２１は、水素原子、置換基を有している場合がある炭素原子数１～３５の脂肪族炭化水素基、置換基を有している場合がある炭素原子数６～３５の芳香族炭化水素基又は置換基を有している場合がある炭素原子数２～３５の複素環基を表し、該脂肪族炭化水素基中のメチレン基は、炭素－炭素二重結合、－Ｏ－、－ＣＯ－、－Ｏ－ＣＯ－、－ＣＯ－Ｏ－又は－ＳＯ２－で置換される場合がある。）
Figure JPOXMLDOC01-appb-C000051
 (In the above general formula (2), Y 11 represents a trivalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an alicyclic hydrocarbon group having 3 to 35 carbon atoms, or 6 to 35 carbon atoms. Represents an aromatic hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms,
Z 11 , Z 12 and Z 13 are each independently a direct bond, —O—, —S—, —CO—, —CO—O—, —O—CO—, —SO 2 —, —SS—, -SO -, - NR 121 -, - PR 121 -, which may have a substituent aliphatic hydrocarbon group having a carbon number of 1 to 35 carbon atoms which may have a substituent Represents a 6-35 aromatic hydrocarbon group or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent,
R 121 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms that may have a substituent, or an aromatic carbon group having 6 to 35 carbon atoms that may have a substituent. Represents a hydrogen group or a heterocyclic group having 2 to 35 carbon atoms which may have a substituent, and the methylene group in the aliphatic hydrocarbon group is a carbon-carbon double bond, —O—, — In some cases, CO—, —O—CO—, —CO—O— or —SO 2 — may be substituted. )
Figure JPOXMLDOC01-appb-C000052
 （上記一般式（３）中、Ｙ１２は、炭素原子、又は四価の炭素原子数１～３５の脂肪族炭化水素基、炭素原子数６～３５の芳香族炭化水素基若しくは炭素原子数２～３５の複素環基を表し、
　該脂肪族炭化水素基中のメチレン基は、－ＣＯＯ－、－Ｏ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＮＨ－又は－ＣＯＮＨ－で置換される場合があり、
　Ｚ11～Ｚ14は、それぞれ独立に、上記一般式（２）におけるＺ11～Ｚ13で表される基と同じ範囲の基である。）
Figure JPOXMLDOC01-appb-C000052
 (In the general formula (3), Y 12 represents a carbon atom, a tetravalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or 2 carbon atoms. Represents a heterocyclic group of ~ 35,
The methylene group in the aliphatic hydrocarbon group may be substituted with —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—,
Z 11 to Z 14 are each independently a group within the same range as the group represented by Z 11 to Z 13 in the general formula (2). )
Figure JPOXMLDOC01-appb-C000053
 （上記一般式（４）中、Ｙ１３は、五価の炭素原子数２～３５の脂肪族炭化水素基、炭素原子数６～３０の芳香族炭化水素基又は炭素原子数２～３０の複素環基を表し、
　該脂肪族炭化水素基は、－ＣＯＯ－、－Ｏ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＮＨ－又は－ＣＯＮＨ－で中断されている場合があり、
　Ｚ１１～Ｚ１５は、それぞれ独立に、上記一般式（２）におけるＺ１１～Ｚ１３で表される基と同じ範囲の基である。）
Figure JPOXMLDOC01-appb-C000053
 (In the general formula (4), Y 13 represents a pentavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a complex having 2 to 30 carbon atoms. Represents a cyclic group,
The aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—,
Z 11 to Z 15 are each independently a group in the same range as the group represented by Z 11 to Z 13 in the general formula (2). )
Figure JPOXMLDOC01-appb-C000054
 （上記一般式（５）中、Ｙ１４は、六価の炭素原子数２～３５の脂肪族炭化水素基、炭素原子数６～３５の芳香族炭化水素基又は炭素原子数２～３５の複素環基を表し、
　該脂肪族炭化水素基は、－ＣＯＯ－、－Ｏ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＮＨ－又は－ＣＯＮＨ－で中断されている場合があり、
　Ｚ11～Ｚ16は、それぞれ独立に、上記一般式（２）におけるＺ１１～Ｚ１３で表される基と同じ範囲の基である。）
Figure JPOXMLDOC01-appb-C000054
 (In the above general formula (5), Y 14 represents a hexavalent aliphatic hydrocarbon group having 2 to 35 carbon atoms, an aromatic hydrocarbon group having 6 to 35 carbon atoms, or a complex having 2 to 35 carbon atoms. Represents a cyclic group,
The aliphatic hydrocarbon group may be interrupted by —COO—, —O—, —OCO—, —NHCO—, —NH— or —CONH—,
Z 11 to Z 16 are each independently a group in the same range as the group represented by Z 11 to Z 13 in the general formula (2). )
　また、上記有機重合体（エチレン性不飽和化合物（Ｂ）及びアルカリ現像性化合物（Ｄ）を除く）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。
　有機重合体を使用する場合、その使用量は、エチレン性不飽和化合物（Ｂ）１００質量部に対して、好ましくは１０～５００質量部である。 Moreover, the characteristic of hardened | cured material can also be improved by using the said organic polymer (except an ethylenically unsaturated compound (B) and an alkali developable compound (D)). 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 an organic polymer is used, the amount used is preferably 10 to 500 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated compound (B).
　上記連鎖移動剤又は上記増感剤としては、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 the 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-C000055
Figure JPOXMLDOC01-appb-C000055
　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系界面活性剤；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、これらは単独で用いることも組み合わせて用いることもできる。 Examples of the surfactant include fluorine-based surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates; Cationic surfactants such as amine halides 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 interfaces Surfactants such as activators can be used, and these can be used alone or 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、互いに同一である場合があり、異なる場合がある。また、アルキルエーテル化されていないメチロール基は、一分子内で自己縮合している場合があり、二分子間で縮合して、その結果オリゴマー成分が形成されている場合がある。
　具体的には、ヘキサメトキシメチルメラミン、ヘキサブトキシメチルメラミン、テトラメトキシメチルグリコールウリル、テトラブトキシメチルグリコールウリル等を用いることができる。これらの中でも、ヘキサメトキシメチルメラミン、ヘキサブトキシメチルメラミン等のアルキルエーテル化されたメラミンが好ましい。 Examples of the melamine compound include all or part of active methylol groups (CH 2 OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. 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 or different from each other. In addition, methylol groups that are not alkyletherified may be self-condensed within one molecule, and may be condensed between two molecules, resulting in the formation of an oligomer component.
Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.
　上記レベリング剤としては、レベリング効果を有するものであれば特に限定されず、既存のレベリング剤を使用することができるが、その中でもシリコーン系レベリング剤及びフッ素系レベリング剤を特に好ましく使用することができる。 The leveling agent is not particularly limited as long as it has a leveling effect, and an existing leveling agent can be used. Among them, a silicone leveling agent and a fluorine leveling agent can be particularly preferably used. .
　上記シリコーン系レベリング剤としては、市販のシリコーン系レベリング剤を使用でき、例えば、ＢＹＫ－３００、ＢＹＫ－３０６、ＢＹＫ－３０７、ＢＹＫ－３１０、ＢＹＫ－３１５、ＢＹＫ－３１３、ＢＹＫ－３２０、ＢＹＫ－３２２、ＢＹＫ－３２３、ＢＹＫ－３２５、ＢＹＫ－３３０、ＢＹＫ－３３１、ＢＹＫ－３３３、ＢＹＫ－３３７、ＢＹＫ－３４１、ＢＹＫ－３４４、ＢＹＫ－３４７、ＢＹＫ－３４８、ＢＹＫ－３４９、ＢＹＫ－３７０、ＢＹＫ－３７５、ＢＹＫ－３７７、ＢＹＫ－３７８、ＢＹＫ－ＵＶ３５００、ＢＹＫ－ＵＶ３５１０、ＢＹＫ－ＵＶ３５７０、ＢＹＫ－３５５０、ＢＹＫ－ＳＩＬＣＬＥＡＮ３７００、ＢＹＫ－ＳＩＬＣＬＥＡＮ３７２０（以上、ビックケミー・ジャパン製）；ＡＣＦＳ １８０、ＡＣ ＦＳ ３６０、ＡＣ Ｓ２０（以上、Ａｌｇｉｎ Ｃｈｅｍｉｅ製）；ポリフローＫＬ－４００Ｘ、ポリフローＫＬ－４００ＨＦ、ポリフローＫＬ－４０１、ポリフローＫＬ－４０２、ポリフローＫＬ－４０３、ポリフローＫＬ－４０４（以上、共栄社化学製）；ＫＰ－３２３、ＫＰ－３２６、ＫＰ－３４１、ＫＰ－１０４、ＫＰ－１１０、ＫＰ－１１２（以上、信越化学工業製）；ＬＰ－７００１、ＬＰ－７００２、８０３２ＡＤＤＩＴＩＶＥ、５７ ＡＤＤＩＴＩＶＥ、Ｌ－７６０４、ＦＺ－２１１０、ＦＺ－２１０５、６７ＡＤＤＩＴＩＶＥ、８６１８ ＡＤＤＩＴＩＶＥ、３ＡＤＤＩＴＩＶＥ、５６ ＡＤＤＩＴＩＶＥ（以上、東レ・ダウコーニング製）等の市販品を使用することができる。 As the silicone leveling agent, commercially available silicone leveling agents can be used. For example, BYK-300, BYK-306, BYK-307, BYK-310, BYK-315, BYK-313, BYK-320, BYK- 322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-344, BYK-347, BYK-348, BYK-349, BYK-370, BYK-375, BYK-377, BYK-378, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-3550, BYK-SILCLEAN3700, BYK-SILCLEAN3720 (above, manufactured by BYK Chemie Japan); ACFS 180, AC FS 360, AC S20 (above, made by Algin Chemie); Polyflow KL-400X, Polyflow KL-400HF, Polyflow KL-401, Polyflow KL-402, Polyflow KL-403, Polyflow KL-404 (above, manufactured by Kyoeisha Chemical); KP-323, KP-326, KP-341, KP-104, KP-110, KP-112 (manufactured by Shin-Etsu Chemical Co., Ltd.); LP-7001, LP-7002, 8032ADDITIVE, 57 ADDITIVE, L-7604, FZ Commercial products such as -2110, FZ-2105, 67ADDITIVE, 8618８６ADDITIVE, 3ADDITIVE, 56 ADDITIVE (above, manufactured by Toray Dow Corning) can be used.
　上記フッ素系レベリング剤としては、市販のフッ素系レベリング剤を使用でき、例えば、オプツールＤＳＸ、オプツールＤＡＣ－ＨＰ（以上、ダイキン工業製）；サーフロンＳ－２４２、サーフロンＳ－２４３、サーフロンＳ－４２０、サーフロンＳ－６１１、サーフロンＳ－６５１、サーフロンＳ－３８６（以上、ＡＧＣセイミケミカル製）；ＢＹＫ－３４０（ビックケミー・ジャパン製）；ＡＣ１１０ａ、ＡＣ １００ａ（以上、ＡｌｇｉｎＣｈｅｍｉｅ製）；メガファックＦ－１１４、メガファックＦ－４１０、メガファックＦ－４４４、メガファックＥＸＰＴＰ－２０６６、メガファックＦ－４３０、メガファックＦ－４７２ＳＦ、メガファックＦ－４７７、メガファックＦ－５５２、メガファックＦ－５５３、メガファックＦ－５５４、メガファックＦ－５５５、メガファックＲ－９４、メガファックＲＳ－７２－Ｋ、メガファックＲＳ－７５、メガファックＦ－５５６、メガファックＥＸＰＴＦ－１３６７、メガファックＥＸＰ ＴＦ－１４３７、メガファックＦ－５５８、メガファックＥＸＰＴＦ－１５３７（以上、ＤＩＣ製）；ＦＣ－４４３０、ＦＣ－４４３２（以上、住友スリーエム製）；フタージェント１００、フタージェント １００Ｃ、フタージェント１１０、フタージェント １５０、フタージェント１５０ＣＨ、フタージェント Ａ－Ｋ、フタージェント５０１、フタージェント ２５０、フタージェント２５１、フタージェント ２２２Ｆ、フタージェント２０８Ｇ、フタージェント ３００、フタージェント３１０、フタージェント ４００ＳＷ（以上、ネオス製）；ＰＦ－１３６Ａ、ＰＦ－１５６Ａ、ＰＦ－１５１Ｎ、ＰＦ－６３６、ＰＦ－６３２０、ＰＦ－６５６、ＰＦ－６５２０」、ＰＦ－６５１、ＰＦ－６５２、ＰＦ－３３２０（以上、北村化学産業製）等の市販品を使用することができる。 As the fluorine leveling agent, commercially available fluorine leveling agents can be used, such as OPTOOL DSX, OPTOOL DAC-HP (manufactured by Daikin Industries); Surflon S-242, Surflon S-243, Surflon S-420, Surflon S-611, Surflon S-651, Surflon S-386 (above, manufactured by AGC Seimi Chemical); BYK-340 (manufactured by Big Chemie Japan); AC110a, AC （100a (above, manufactured by Algin Chemie); Megafuck F-114, Megafuck F-410, Megafuck F-444, Megafuck EXPTP-2066, Megafuck F-430, Megafuck F-472SF, Megafuck F-477, Megafuck F-552, Megafuck F-553, Megafuck F- 54, Megafuck F-555, Megafuck R-94, Megafuck RS-72-K, Megafuck RS-75, Megafuck F-556, Megafuck EXPTF-1367, Megafuck EXP TF-1437, Megafuck F -558, Megafuck EXPTF-1537 (above DIC); FC-4430, FC-4432 (above, Sumitomo 3M); Aftergent 100, Aftergent 100C, Aftergent 110, Aftergent 150, Aftergent 150CH, Aftergent AK, Aftergent 501, Aftergent 250, Aftergent 251, Aftergent フ 222F, Aftergent 208G, Aftergent 300, Aftergent 310, Aftergent 400SW PF-136A, PF-156A, PF-151N, PF-636, PF-6320, PF-656, PF-6520 ", PF-651, PF-652, PF-3320 (above, Kitamura Chemical) Commercial products such as those manufactured by Sangyo Co., Ltd. can be used.
　本発明の感光性組成物において、光重合開始剤（Ａ）、エチレン性不飽和化合物（Ｂ）、着色剤（Ｃ）、アルカリ現像性化合物（Ｄ）、溶剤及び有機重合体を除く、任意の添加物の使用量は、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、上記エチレン性不飽和化合物（Ｂ）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, the photopolymerization initiator (A), the ethylenically unsaturated compound (B), the colorant (C), the alkali developable compound (D), any solvent, and an organic polymer are excluded. Although the usage-amount of an additive is suitably selected according to the intended purpose and is not restrict | limited, Preferably it shall be 50 mass parts or less in total with respect to 100 mass parts of said ethylenically unsaturated compounds (B).
　本発明の感光性組成物、アルカリ現像性感光性樹脂組成物又は硬化物は、ディスプレイ表示装置、詳しくは、ディスプレイ表示装置（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に好適に用いられる。その他、光硬化性塗料又はワニス；光硬化性接着剤；プリント基板；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；種々のディスプレイ表示装置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, the alkali-developable photosensitive resin composition, or the cured product of the present invention is used for display display devices, and more specifically for color display of display display devices (color televisions, PC monitors, portable information terminals, digital cameras, etc.). It is suitably used for a color filter in a liquid crystal display element. Photocurable paint or varnish; Photocurable adhesive; Printed circuit board; Color filter of CCD image sensor; Electrode material for plasma display panel; Powder coating; Printing ink; Printing plate; Adhesive; Photoresist for electronic engineering; Electroplating resist; Etching resist; Dry film; Solder resist; Resist to form various display device structures; Composition for encapsulating electrical and electronic parts; Solder resist Magnetic recording materials; micromechanical parts; waveguides; optical switches; plating masks; etching masks; color test systems; glass fiber cable coatings; screen printing stencils; materials for producing three-dimensional objects by stereolithography; Holographic recording material; Image recording 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又はアルカリ現像性感光性樹脂組成物は、液晶表示パネル用の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 or alkali-developable photosensitive resin composition of the present invention can also be used for the purpose of forming spacers for liquid crystal display panels and for forming protrusions for vertical alignment type liquid crystal display elements. In particular, it is useful as a photosensitive composition for simultaneously forming protrusions and spacers for a vertical alignment type liquid crystal display element.
　本発明の感光性組成物又はアルカリ現像性感光性樹脂組成物を用いて硬化物を製造する方法について下記に詳細に説明する。 The method for producing a cured product using the photosensitive composition or alkali-developable photosensitive resin composition of the present invention will be described in detail below.
　本発明の感光性組成物又はアルカリ現像性感光性樹脂組成物は、エネルギー線を照射することにより硬化させることができる。
　本発明の感光性組成物又はアルカリ現像性感光性樹脂組成物は、硬化させるに先立って、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 or alkali-developable photosensitive resin composition of the present invention can be cured by irradiation with energy rays.
Prior to curing, the photosensitive composition or alkali-developable photosensitive resin composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, etc. It can be applied on a supporting substrate such as soda glass, quartz glass, semiconductor substrate, metal, paper, plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.
　また、本発明の感光性組成物アルカリ現像性感光性樹脂組成物を硬化させる際に用いられるエネルギー線としては、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光源等の光源から得られる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線や、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の光源が用いられる。 Further, the energy ray used for curing the photosensitive composition alkali-developable photosensitive resin 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. Electromagnetic energy rays having a wavelength of 2000 angstroms to 7000 angstroms obtained from light sources such as lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, High energy rays such as electron beams, X-rays and radiation can be used, but preferably an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, etc. that emits light having a wavelength of 300 to 450 nm. The light source is used.
　更に、露光光源にレーザー光を用いることにより、マスクを用いずに、コンピューター等のデジタル情報から直接画像を形成するレーザー直接描画法が、生産性のみならず、解像性や位置精度等の向上も図れることから有用であり、そのレーザー光としては、３４０～４３０ｎｍの波長の光が好適に使用されるが、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られる。これらのレーザーを使用する場合には、可視から赤外の当該領域を吸収する増感色素が加えられる。 Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser 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. In addition, lasers that emit light in the visible to infrared region, such as various semiconductor lasers and YAG lasers, are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.
　また、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放射線を照射する工程、（３）露光後のベーク工程、（４）露光後の該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、好ましく形成することができる。 The liquid crystal display panel spacer includes (1) a step of forming a coating film of the photosensitive composition of the present invention on a substrate, and (2) radiation through a mask having a predetermined pattern shape on the coating film. , (3) baking step after exposure, (4) step of developing the coating after exposure, and (5) step of heating the coating after development.
　また、本発明の感光性組成物は、撥インク剤を含有する場合、インクジェット方式用隔壁形成樹脂組成物として有用であり、該組成物はカラーフィルタ用として用いられ、特にプロファイル角が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からなる組成物が好適に用いられる。 Further, when the photosensitive composition of the present invention contains an ink repellent, it is useful as a partition forming resin composition for an inkjet system, and the composition is used for a color filter, and particularly has a profile angle of 50 ° or more. It is preferably used for the partition for an inkjet color filter. As the ink repellent agent, a composition comprising a fluorosurfactant and a fluorosurfactant is preferably used.
　本発明の感光性組成物を、撥インク剤を含有するものとし、上記インクジェット方式用隔壁形成樹脂組成物として用いる場合には、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のが好ましく、これにより、基板上に複数の着色領域からなる画素群と上記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光学素子が得られる。 When the photosensitive composition of the present invention contains an ink repellent and is used as the above-mentioned partition-forming resin composition for an inkjet system, the partition formed from the photosensitive composition of the present invention is on the transfer target. And an optical element is manufactured by a method of forming an image region by applying droplets to the recessed portions on the partitioned transfer target member by an ink jet method. At this time, it is preferable that the droplets contain a colorant and the image area is colored, whereby the pixel group composed of a plurality of colored areas is separated from the colored areas of the pixel group on the substrate. An optical element having at least a partition is obtained.
　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 Example 1 Compound No. 1 1 production
（工程１）中間体１Ａ（ハロゲン化アリール化合物）の製造
　１００ｍｌの４つ口フラスコに、２－クロロ－４’－フルオロアセトフェノン（３．５９ｇ）、サリチル酸アルデヒド（５．０８ｇ）、炭酸カリウム（５．７５ｇ）、アセトン（１５ｇ）をそれぞれ秤量した後、加熱還流を１時間行った。室温まで冷却後、イオン交換水（４１．６ｇ）を添加し、析出物をろ取し、十分に乾燥させ、淡黄色固体として中間体１Ａを（４．７４ｇ：収率９５％）得た。 (Step 1) Preparation of intermediate 1A (halogenated aryl compound) In a 100 ml four-necked flask, 2-chloro-4'-fluoroacetophenone (3.59 g), salicylic aldehyde (5.08 g), potassium carbonate (5 .75 g) and acetone (15 g) were weighed and then heated to reflux for 1 hour. After cooling to room temperature, ion-exchanged water (41.6 g) was added, and the precipitate was collected by filtration and sufficiently dried to obtain Intermediate 1A (4.74 g: yield 95%) as a pale yellow solid.
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
（工程２）中間体１Ｂ（ケトン化合物）の製造
　１００ｍｌの４つ口フラスコに、中間体１Ａ（４．４２ｇ）、下記インドール化合物１Ａ（４．０７ｇ）、炭酸カリウム（４．６２ｇ）及びＤＭＡｃ（２３．２５ｇ）をそれぞれ秤量した後、１１０℃で３時間反応させた。イオン交換水（１５．５ｇ）及び酢酸エチル（２３．２５ｇ）を加え、油水分離し、有機層を３回水洗し脱溶媒を行った。その後、得られた残渣に酢酸エチル（１５．５ｇ）及びヘキサン（２３．２５ｇ）を加え、加熱溶解後、冷却し再結晶を行った。５℃まで冷却後、析出物をろ取し、十分に乾燥させ、白色固体として中間体１Ｂを（６．８ｇ：収率８７％）得た。 (Step 2) Production of Intermediate 1B (Ketone Compound) In a 100 ml four-necked flask, Intermediate 1A (4.42 g), the following indole compound 1A (4.07 g), potassium carbonate (4.62 g) and DMAc ( 23.25 g) was weighed and then reacted at 110 ° C. for 3 hours. Ion-exchanged water (15.5 g) and ethyl acetate (23.25 g) were added to separate the oil and water, and the organic layer was washed with water three times to remove the solvent. Thereafter, ethyl acetate (15.5 g) and hexane (23.25 g) were added to the obtained residue, dissolved by heating, cooled and recrystallized. After cooling to 5 ° C., the precipitate was collected by filtration and sufficiently dried to obtain Intermediate 1B (6.8 g, yield 87%) as a white solid.
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
（工程３）中間体１Ｃ（オキシム化合物）の製造
　３０ｍｌの２つ口フラスコに中間体１Ｂ（３．７４ｇ）及びＤＭＦ（１２．９３ｇ）を秤量し、５℃で撹拌しながら３５％塩酸１．２６ｇ及び亜硝酸イソブチル０．８７ｇを滴下し、室温で３０時間撹拌した。イオン交換水（１１．９ｇ）及び酢酸エチル（１１．９ｇ）を加え、油水分離し、有機層を３回水洗した。有機層を脱溶媒後、シリカゲルカラム（酢酸エチル／ヘキサン＝1／９）により精製を行い淡黄色固体として中間体１Ｃ（３．０ｇ：収率７５％）を得た。 (Step 3) Production of Intermediate 1C (oxime compound) Intermediate 1B (3.74 g) and DMF (12.93 g) were weighed into a 30 ml two-necked flask and stirred at 5 ° C with 35% hydrochloric acid 1. 26 g and 0.87 g of isobutyl nitrite were added dropwise, and the mixture was stirred at room temperature for 30 hours. Ion-exchanged water (11.9 g) and ethyl acetate (11.9 g) were added to separate the oil and water, and the organic layer was washed with water three times. The organic layer was desolvated and then purified by a silica gel column (ethyl acetate / hexane = 1/9) to obtain Intermediate 1C (3.0 g: yield 75%) as a pale yellow solid.
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
（工程４）化合物Ｎｏ．１（本発明のオキシムエステル化合物）の製造
　３０ｍｌの２口ナスフラスコに中間体１Ｃ（２．２１ｇ）及びＴＨＦ（７．２ｇ）をそれぞれ秤量し、窒素気流、氷冷下において塩化アセチル（２．１２ｇ）、トリエチルアミン（２．７２ｇ）を滴下し、室温で１時間撹拌を行った。イオン交換水（７．２ｇ）及び酢酸エチル（７．２ｇ）を加え、油水分離し、有機層を３回水洗した。有機層を脱溶媒後、シリカゲルカラム（酢酸エチル／ヘキサン）により精製を行い、淡黄色固体として化合物Ｎｏ．１（１．５ｇ：収率６３％）を得た。
　得られた化合物Ｎｏ．１の分析結果を［表１］～［表３］に示す。尚、［表１］に併記したＯＸＥ　０２は、後述の比較例１で用いた市販の光重合開始剤である。 (Step 4) Compound No. 1 (Oxime ester compound of the present invention) Intermediate 1C (2.21 g) and THF (7.2 g) were weighed in a 30 ml two-necked eggplant flask, respectively, and acetyl chloride (2. 12 g) and triethylamine (2.72 g) were added dropwise, and the mixture was stirred at room temperature for 1 hour. Ion-exchanged water (7.2 g) and ethyl acetate (7.2 g) were added to separate the oil and water, and the organic layer was washed with water three times. The organic layer was desolvated and then purified by a silica gel column (ethyl acetate / hexane) to obtain compound No. 1 as a pale yellow solid. 1 (1.5 g: 63% yield) was obtained.
The obtained Compound No. The analysis results of 1 are shown in [Table 1] to [Table 3]. Note that OXE 02 listed in [Table 1] is a commercially available photopolymerization initiator used in Comparative Example 1 described later.
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
[実施例２]化合物Ｎｏ．１８９の製造
（工程１）中間体２Ａの製造
　上記中間体１Ｂを９．６ｇ、ジメチルホルムアセトアミドを３０．０ｇ、ヒドロキシアミン塩酸塩を２．２ｇ仕込んだ後、６０℃で水酸化ナトリウムを１．２ｇ仕込んだ。６０℃で２時間反応させた後、イオン交換水、クロロホルムを仕込み、加温しながら抽出した。有機層を３回水洗し、脱溶媒後、シリカゲルカラム（酢酸エチル／ヘキサン＝1／６）により精製を行い、下記中間体２Ａ（２．０ｇ：収率２５％）を得た。 Example 2 Compound No. Production of 189 (Step 1) Production of Intermediate 2A 9.6 g of the above Intermediate 1B, 30.0 g of dimethylformacetamide and 2.2 g of hydroxyamine hydrochloride were added, and then sodium hydroxide was added at 60 ° C. 2g was charged. After making it react at 60 degreeC for 2 hours, ion-exchange water and chloroform were prepared and it extracted, heating. The organic layer was washed three times with water, and after removing the solvent, purification was performed with a silica gel column (ethyl acetate / hexane = 1/6) to obtain the following intermediate 2A (2.0 g: yield 25%).
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
（工程２）化合物Ｎｏ．１８９（本発明のオキシムエステル化合物）の製造
　中間体１Ｃを上記中間体２Ａに変更した以外は実施例１の工程４と同様にして、化合物Ｎｏ．１８９を得た。 (Step 2) Compound No. 189 (oxime ester compound of the present invention) Compound No. 1 was prepared in the same manner as in Step 4 of Example 1, except that Intermediate 1C was changed to Intermediate 2A. 189 was obtained.
[実施例３]化合物Ｎｏ．１９０の製造
（工程１）中間体３Ｂの製造
　インドール化合物１Ａを下記カルバゾール化合物３Ａに変更した以外は実施例１の工程２と同様にして、下記中間体３Ｂを得た。 Example 3 Compound no. Production of 190 (Step 1) Production of Intermediate 3B The following Intermediate 3B was obtained in the same manner as in Step 2 of Example 1 except that the indole compound 1A was changed to the following carbazole compound 3A.
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
（工程２）中間体３Ｃの製造
　１００ｍｌの４つ口フラスコに塩化アルミニウムを２．７２ｇ、ジクロロエタンを３０．０ｇ仕込み、氷冷下、中間体３Ｂを７．５４ｇ添加し、次いでオクタノイルクロリドを３．３２ｇ添加した。室温で１時間反応させた後、反応液を氷水にあけ油水分離を行った。有機層を３回水洗後、脱溶媒を行い、シリカゲルカラム（酢酸エチル／ヘキサン＝1／１０）により下記中間体３Ｃ（１．１ｇ：収率１１％）を得た。 (Step 2) Production of Intermediate 3C A 100 ml four-necked flask was charged with 2.72 g of aluminum chloride and 30.0 g of dichloroethane, and 7.54 g of Intermediate 3B was added under ice cooling, followed by 3 octanoyl chloride. .32 g was added. After reacting at room temperature for 1 hour, the reaction solution was poured into ice water and oil-water separation was performed. The organic layer was washed with water three times, then the solvent was removed, and the following intermediate 3C (1.1 g: yield 11%) was obtained using a silica gel column (ethyl acetate / hexane = 1/10).
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
（工程３）Ｎｏ．１９０の製造
　中間体１Ｃを上記中間体３Ｃに変更した以外は実施例１の工程４と同様にして、上記化合物Ｎｏ．１９０を得た。 (Step 3) No. 190 Preparation of Compound No. 190 was performed in the same manner as in Step 4 of Example 1, except that Intermediate 1C was changed to Intermediate 3C. 190 was obtained.
[実施例４]化合物Ｎｏ．１９１の製造
　実施例１の工程２で使用した中間体１Ａを下記中間体４Ａに変更した以外は実施例１と同様にして、上記化合物Ｎｏ．１９１を得た。 Example 4 Compound no. In the same manner as in Example 1 except that the intermediate 1A used in Step 2 of Example 1 was changed to the following intermediate 4A, the above compound No. 191 was prepared. 191 was obtained.
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
[実施例５]化合物Ｎｏ．１９２の製造
　実施例１の工程２で使用した中間体１Ａを下記中間体５Ａに変更した以外は実施例１と同様にして、上記化合物Ｎｏ．１９２を得た。 Example 5 Compound no. In the same manner as in Example 1 except that the intermediate 1A used in Step 2 of Example 1 was changed to the following Intermediate 5A, the above compound No. 192 was prepared. 192 was obtained.
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
[実施例６]化合物Ｎｏ．１９３の製造
（工程１）中間体６Ｂの製造
　インドール化合物１Ａを下記フェノチアジン化合物６Ａに変更した以外は実施例１の工程２と同様にして、下記中間体６Ｂを得た。 Example 6 Compound no. Production of 193 (Step 1) Production of Intermediate 6B The following Intermediate 6B was obtained in the same manner as in Step 2 of Example 1, except that the indole compound 1A was changed to the following phenothiazine compound 6A.
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
（工程２）中間体６Ｃの製造
　中間体３Ｂを上記中間体６Ｂに変更し、用いた試薬の等量が２倍量になるように調製した以外は実施例３の工程２同様にして、下記中間体６Ｃを得た。 (Step 2) Production of Intermediate 6C Intermediate 3B was changed to Intermediate 6B described above, and the same procedure as in Step 2 of Example 3 was conducted except that the equivalent amount of the reagent used was doubled. Intermediate 6C was obtained.
Figure JPOXMLDOC01-appb-C000067
  
Figure JPOXMLDOC01-appb-C000067
  
（工程３）中間体６Ｄの製造
　中間体１Ｂを上記中間体６Ｃに変更し、用いた試薬の等量が２倍量になるように調製した以外は実施例１の工程３と同様にして、下記中間体６Ｄを得た。 (Step 3) Production of Intermediate 6D In the same manner as in Step 3 of Example 1, except that Intermediate 1B was changed to Intermediate 6C and the equivalent amount of the used reagent was doubled, The following intermediate 6D was obtained.
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
（工程４）化合物Ｎｏ．１９３の製造
　中間体１Ｃを上記中間体６Ｄに変更し、用いた試薬の等量が２倍量になるように調製した以外は実施例１の工程４と同様にして、上記化合物Ｎｏ．１９３を得た。 (Step 4) Compound No. In the same manner as in Step 4 of Example 1, except that Intermediate 1C was changed to Intermediate 6D and the equivalent amount of the reagent used was doubled, the above-mentioned Compound No. 193 was obtained.
[実施例７]化合物Ｎｏ．１９４の製造
（工程１）中間体７Ａの製造
　中間体１Ｂを上記中間体６Ｃに変更した以外は実施例１の工程３と同様にして、下記中間体７Ａを得た。 Example 7 Compound no. Production of 194 (Step 1) Production of Intermediate 7A Intermediate 7A shown below was obtained in the same manner as in Step 3 of Example 1 except that Intermediate 1B was changed to Intermediate 6C.
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000069
（工程２）]化合物Ｎｏ．１９４の製造
　中間体１Ｃを上記中間体７Ａに変更した以外は実施例１の工程４と同様にして、上記化合物Ｎｏ．１９４を得た。 (Step 2)] Compound No. In the same manner as in Step 4 of Example 1, except that Intermediate 1C was changed to Intermediate 7A, Compound No. 194 was obtained.
　得られた化合物Ｎｏ．１８９～１９４の分析結果を［表１］～［表３］に示す。 Compound No. obtained The analysis results of 189 to 194 are shown in [Table 1] to [Table 3].
Figure JPOXMLDOC01-appb-T000070
Figure JPOXMLDOC01-appb-T000070
Figure JPOXMLDOC01-appb-T000071
Figure JPOXMLDOC01-appb-T000071
Figure JPOXMLDOC01-appb-T000072
Figure JPOXMLDOC01-appb-T000072
　上記［表１］から明らかな通り、本発明のオキシムエステル化合物は、ＰＧＭＥＡに代表される溶剤への溶解度が高いため、有用である。 As apparent from the above [Table 1], the oxime ester compound of the present invention is useful because of its high solubility in a solvent represented by PGMEA.
［製造例１］ブルー顔料分散液Ｎｏ．１の製造
　分散剤としてＤＩＳＰＥＲＢＹＫ－１６１（１２．５質量部；ビックケミージャパン製）及び着色剤としてピグメントブルー１５：６（１５質量部）を、ＰＧＭＥＡ（７２．５質量部）にビーズミルを使用して分散させて、ブルー顔料分散液Ｎｏ．１を製造した。 [Production Example 1] Blue pigment dispersion No. 1 Using DISPERBYK-161 (12.5 parts by mass; manufactured by Big Chemie Japan) as a dispersant, Pigment Blue 15: 6 (15 parts by mass) as a colorant, and a bead mill for PGMEA (72.5 parts by mass) The blue pigment dispersion liquid No. 1 was produced.
［実施例８～１４及び比較例１］感光性組成物の調製
　下記［表４］の配合に従って各成分を混合し、感光性組成物Ｎｏ．１～Ｎｏ．７（実施例８～１４）及び比較用の感光性組成物Ｎｏ．８（比較例１）を得た。尚、表中の数字は質量部を表す。実施例８～１４及び比較例１においては、光重合開始剤をそれぞれ単独で使用した。
　また、表中の符号は、下記の成分を表す。
　Ａ－１：　化合物Ｎｏ．１（実施例１で得られた本発明の光重合開始剤）
　Ａ－２：　化合物Ｎｏ．１８９（実施例２で得られた本発明の光重合開始剤）
　Ａ－３：　化合物Ｎｏ．１９０（実施例３で得られた本発明の光重合開始剤）
　Ａ－４：　化合物Ｎｏ．１９１（実施例４で得られた本発明の光重合開始剤）
　Ａ－５：　化合物Ｎｏ．１９２（実施例５で得られた本発明の光重合開始剤）
　Ａ－６：　化合物Ｎｏ．１９３（実施例６で得られた本発明の光重合開始剤）
　Ａ－７：　化合物Ｎｏ．１９４（実施例７で得られた本発明の光重合開始剤）
　Ａ－８：　ＯＸＥ　０２（本発明に属さない光重合開始剤；ＢＡＳＦ社製）
　Ｂ－１：　ＳＰＣ－３０００（酸基を有するエチレン性不飽和化合物；昭和電工製；固形分４２．２質量％のＰＧＭＥＡ溶液）
　Ｂ－２：　カヤラッドＤＰＨＡ（エチレン性不飽和化合物；日本化薬製；固形分１００質量％）
　Ｃ－１：　ブルー顔料分散液Ｎｏ．１（製造例１で得られた分散液）
　Ｘ－１：　ＫＢＥ－４０３（シランカップリング剤；信越化学製）
　Ｘ－２：　Ｆ－５５４（フッ素系レベリング剤、含フッ素基・親油性基含有オリゴマー；ＤＩＣ製）
　Ｙ－１：　ＰＧＭＥＡ（溶剤）
　尚、ＳＰＣ－３０００（Ｂ－１）は、エチレン性不飽和結合を有し且つアルカリ現像性を有する化合物であり、カヤラッドＤＰＨＡ（Ｂ－２）は、エチレン性不飽和結合を有する化合物であるがアルカリ現像性は有しない。 [Examples 8 to 14 and Comparative Example 1] Preparation of photosensitive composition Each component was mixed according to the formulation shown in [Table 4] below. 1-No. 7 (Examples 8 to 14) and comparative photosensitive composition No. 8 (Comparative Example 1) was obtained. In addition, the number in a table | surface represents a mass part. In Examples 8 to 14 and Comparative Example 1, each photopolymerization initiator was used alone.
Moreover, the code | symbol in a table | surface represents the following component.
A-1: Compound No. 1 (photopolymerization initiator of the present invention obtained in Example 1)
A-2: Compound No. 189 (photopolymerization initiator of the present invention obtained in Example 2)
A-3: Compound No. 190 (photopolymerization initiator of the present invention obtained in Example 3)
A-4: Compound No. 191 (photopolymerization initiator of the present invention obtained in Example 4)
A-5: Compound No. 192 (photopolymerization initiator of the present invention obtained in Example 5)
A-6: Compound No. 193 (photopolymerization initiator of the present invention obtained in Example 6)
A-7: Compound No. 194 (photopolymerization initiator of the present invention obtained in Example 7)
A-8: OXE 02 (photopolymerization initiator not belonging to the present invention; manufactured by BASF)
B-1: SPC-3000 (ethylenically unsaturated compound having an acid group; manufactured by Showa Denko; PGMEA solution having a solid content of 42.2% by mass)
B-2: Kayalad DPHA (ethylenically unsaturated compound; manufactured by Nippon Kayaku; solid content: 100% by mass)
C-1: Blue pigment dispersion No. 1 (Dispersion obtained in Production Example 1)
X-1: KBE-403 (silane coupling agent; manufactured by Shin-Etsu Chemical)
X-2: F-554 (fluorine-based leveling agent, fluorine-containing / lipophilic group-containing oligomer; manufactured by DIC)
Y-1: PGMEA (solvent)
SPC-3000 (B-1) is a compound having an ethylenically unsaturated bond and having alkali developability, and Kayrad DPHA (B-2) is a compound having an ethylenically unsaturated bond. It does not have alkali developability.
＜感光性組成物及び硬化物の評価＞
　感光性組成物Ｎｏ．１～Ｎｏ．７及び比較用の感光性組成物Ｎｏ．８の感度並びにそれらから得られる硬化物の輝度の評価を下記の手順で行った。評価結果を［表４］に併記する。 <Evaluation of photosensitive composition and cured product>
Photosensitive composition No. 1-No. 7 and comparative photosensitive composition no. Evaluation of the sensitivity of 8 and the brightness | luminance of the hardened | cured material obtained from them was performed in the following procedure. The evaluation results are also shown in [Table 4].
（感度）
　ガラス基板上に感光性組成物Ｎｏ．１～Ｎｏ．７（実施例８～１４）及び比較用の感光性組成物Ｎｏ．８（比較例１）をスピンコート（５００ｒｐｍにて２秒間、次いで９００ｒｐｍにて５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後、２３℃で４０秒間冷却した。その後、高圧水銀ランプを用いてマスク（マスク開口３０μｍ）を介して露光した（露光量４０ｍＪ／ｃｍ２）。現像液として２．５質量％炭酸ナトリウム水溶液を用いて現像した後、よく水洗し、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。得られたパターンを電子顕微鏡で観察し、マスク開口に対応する部分の線幅を測定した。線幅が３０μｍ以上のものをＡ、３０μｍ未満のものをＢとした。線幅が大きいほど感度が良好であることを意味する。 (sensitivity)
On the glass substrate, the photosensitive composition No. 1-No. 7 (Examples 8 to 14) and comparative photosensitive composition No. 8 (Comparative Example 1) was spin coated (at 500 rpm for 2 seconds, then at 900 rpm for 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then cooled at 23 ° C. for 40 seconds. Then, it exposed through the mask (mask opening 30 micrometers) using the high pressure mercury lamp (exposure amount 40mJ / cm < 2 >). After developing using a 2.5% by mass aqueous sodium carbonate solution as a developing solution, it was washed thoroughly with water and post-baked at 230 ° C. for 30 minutes using an oven to fix the pattern. The obtained pattern was observed with an electron microscope, and the line width of the portion corresponding to the mask opening was measured. A line width of 30 μm or more was designated as A, and a line width of less than 30 μm was designated as B. The larger the line width, the better the sensitivity.
（輝度）
　ガラス基板上に感光性組成物Ｎｏ．１～Ｎｏ．７（実施例８～１４）及び比較用の感光性組成物Ｎｏ．８（比較例１）をスピンコート（５００ｒｐｍにて２秒間、次いで９００ｒｐｍにて５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後、２３℃で４０秒間冷却した。その後、高圧水銀ランプを用いて１００ｍＪ／ｃｍ２で露光し、評価サンプルを作成した。得られたサンプルの３８０～７８０ｎｍにおける透過率から、ＪＩＳ　Ｚ８７０１に準拠してＹ値を求めた。Ｙ値が高いほど輝度が高く可視光領域において高い透過率を有することを意味し、有用である。 (Luminance)
On the glass substrate, the photosensitive composition No. 1-No. 7 (Examples 8 to 14) and comparative photosensitive composition No. 8 (Comparative Example 1) was spin coated (at 500 rpm for 2 seconds, then at 900 rpm for 5 seconds), prebaked at 90 ° C. for 90 seconds using a hot plate, and then cooled at 23 ° C. for 40 seconds. Then, it exposed at 100 mJ / cm < 2 > using the high pressure mercury lamp, and created the evaluation sample. From the transmittance of the obtained sample at 380 to 780 nm, the Y value was determined according to JIS Z8701. The higher the Y value, the higher the luminance and the higher the transmittance in the visible light region, which is useful.
Figure JPOXMLDOC01-appb-T000073
Figure JPOXMLDOC01-appb-T000073
　上記〔表４〕より、本発明のオキシムエステル化合物は、比較例１で用いた化合物と比較して感度が高く、また本発明の硬化物は輝度が高いことが明らかである。 From the above [Table 4], it is clear that the oxime ester compound of the present invention has higher sensitivity than the compound used in Comparative Example 1, and the cured product of the present invention has high luminance.
　以上より、本発明のオキシムエステル化合物を用いた感光性組成物は、フォトリソグラフィー性に優れ、得られる硬化物の輝度に優れるため、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なものであることが分かる。 As mentioned above, since the photosensitive composition using the oxime ester compound of the present invention is excellent in photolithography properties and the brightness of the resulting cured product, the oxime ester compound of the present invention is useful as a photopolymerization initiator. I understand that there is.
　本発明のオキシムエステル化合物は、３６５ｎｍ（ｉ線）等の輝線に対して効率よくラジカルを発生させることができる高感度なものであり、現像性に優れたアルカリ現像性感光性樹脂組成物を提供することができ、また有機溶剤への溶解性も高く、更には可視光領域の透過率も高く、感光性組成物に用いられる光重合開始剤として有用なものである。 The oxime ester compound of the present invention provides a highly sensitive alkali-developable photosensitive resin composition that is capable of efficiently generating radicals with respect to bright lines such as 365 nm (i-line) and has excellent developability. In addition, it has high solubility in an organic solvent, and also has high transmittance in the visible light region, and is useful as a photopolymerization initiator used in a photosensitive composition.

Claims (11)

  1. 　下記一般式（Iα）又は（Iβ）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、Ｒ４、Ｒ５及びＲ６は、それぞれ独立に、下記一般式（II）で表される基、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ２１、ＯＲ２１、ＳＲ２１、ＮＲ２２Ｒ２３、ＣＯＲ２１、ＳＯＲ２１、ＳＯ２Ｒ２１又はＣＯＮＲ２２Ｒ２３を表し、
    　Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６のうち、少なくとも一つが下記一般式（II）で表される基であり、
    　Ｒ７、Ｒ８、Ｒ９、Ｒ１０及びＲ１１は、それぞれ独立に、下記一般式（IIIα）で表される基、下記一般式（IIIβ）で表される基、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ２１、ＯＲ２１、ＳＲ２１、ＮＲ２２Ｒ２３、ＣＯＲ２１、ＳＯＲ２１、ＳＯ２Ｒ２１又はＣＯＮＲ２２Ｒ２３を表し、
    　Ｒ７、Ｒ８、Ｒ９、Ｒ１０及びＲ１１のうち、少なくとも一つが下記一般式（IIIα）で表される基又は下記一般式（IIIβ）で表される基であり、
    　Ｒ２１、Ｒ２２及びＲ２３は、それぞれ独立に、炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基を表し、
    　Ｒ２１、Ｒ２２及びＲ２３で表される基中の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環含有基で置換される場合があり、炭素原子数２～２０の炭化水素基又は炭素原子数２～２０の複素環含有基中のメチレン基は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ２４－、－ＮＲ２４ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合があり、Ｒ２４は、水素原子又は炭素原子数１～２０の炭化水素基を表し、
    　Ｘ１は、不存在、直接結合、－ＣＯ－、－Ｏ－又は－Ｓ－を表し、
    　Ｒ１とＲ２、Ｒ２とＲ３、Ｒ３とＲ４、Ｒ５とＲ６、Ｒ６とＲ７、Ｒ７とＲ８、Ｒ８とＲ９、Ｒ９とＲ１０、Ｒ１０とＲ１１、及びＲ１１とＲ１は、結合して環を形成する場合がある。）
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ３１及びＲ３２は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基を表し、
    　Ｒ３１及びＲ３２で表される炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環含有基で置換される場合があり、Ｒ３１及びＲ３２で表される炭素原子数２～２０の炭化水素基又は炭素原子数２～２０の複素環含有基中のメチレン基は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ３３－、－ＮＲ３３ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合があり、Ｒ３３は、水素原子又は炭素原子数１～２０の炭化水素基を表し、
    　ｎは０又は１を表し、＊は結合手を表す。）
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ４１、Ｒ４２、Ｒ４３、Ｒ４４、Ｒ４５、Ｒ４６、Ｒ４７、Ｒ４８、Ｒ４９及びＲ５０は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ５１、ＯＲ５１、ＳＲ５１、ＮＲ５２Ｒ５３、ＣＯＲ５１、ＳＯＲ５１、ＳＯ２Ｒ５１又はＣＯＮＲ５２Ｒ５３を表し、
    　Ｒ５１、Ｒ５２及びＲ５３は、それぞれ独立に、炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基を表し、
    　Ｒ５１、Ｒ５２及びＲ５３で表される基中の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環含有基で置換される場合があり、炭素原子数２～２０の炭化水素基又は炭素原子数２～２０の複素環含有基中のメチレン基は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ５４－、－ＮＲ５４ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合があり、
    　Ｘ２及びＸ３は、－Ｏ－、－Ｓ－又は－ＮＲ５４－を表し、
    　Ｒ５４は、水素原子又は炭素原子数１～２０の炭化水素基を表し、
    　＊は結合手を表す。）
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７及びＲ１０８は、それぞれ独立に、上記一般式（II）で表される基、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ１２１、ＯＲ１２１、ＳＲ１２１、ＮＲ１２２Ｒ１２３、ＣＯＲ１２１、ＳＯＲ１２１、ＳＯ２Ｒ１２１又はＣＯＮＲ１２２Ｒ１２３を表し、
    　Ｒ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５、Ｒ１０６、Ｒ１０７及びＲ１０８のうち、少なくとも一つが上記一般式（II）で表される基であり、
    　Ｒ１０９、Ｒ１１０、Ｒ１１１、Ｒ１１２及びＲ１１３は、それぞれ独立に、上記一般式（IIIα）で表される基、上記一般式（IIIβ）で表される基、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ１２１、ＯＲ１２１、ＳＲ１２１、ＮＲ１２２Ｒ１２３、ＣＯＲ１２１、ＳＯＲ１２１、ＳＯ２Ｒ１２１又はＣＯＮＲ１２２Ｒ１２３を表し、
    　Ｒ１０９、Ｒ１１０、Ｒ１１１、Ｒ１１２及びＲ１１３のうち、少なくとも一つが下記一般式（IIIα）で表される基又は下記一般式（IIIβ）で表される基であり、
    　Ｒ１２１、Ｒ１２２及びＲ１２３は、それぞれ独立に、炭素原子数１～２０の炭化水素基又は炭素原子数２～２０の複素環含有基を表し、
    　Ｒ１２１、Ｒ１２２及びＲ１２３で表される基中の水素原子は、ハロゲン原子、ニトロ基、シアノ基、水酸基、アミノ基、カルボキシル基、メタクリロイル基、アクリロイル基、エポキシ基、ビニル基、ビニルエーテル基、メルカプト基、イソシアネート基又は複素環含有基で置換される場合があり、炭素原子数２～２０の炭化水素基又は炭素原子数２～２０の複素環含有基中のメチレン基は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ１２４－、－ＮＲ１２４ＣＯ－、－Ｓ－、－ＣＳ－、－ＳＯ２－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又はＣＳＯ－で置換される場合があり、
    　Ｒ１２４は、水素原子又は炭素原子数１～２０の炭化水素基を表し、
    　Ｘ１０１は、不存在、直接結合、－ＣＯ－、－Ｏ－又は－Ｓ－を表し、
    　Ｒ１０１とＲ１０２、Ｒ１０２とＲ１０３、Ｒ１０３とＲ１０４、Ｒ１０５とＲ１０６、Ｒ１０６とＲ１０７、Ｒ１０７とＲ１０８、Ｒ１０８とＲ１０９、Ｒ１０９とＲ１１０、Ｒ１１０とＲ１１１、Ｒ１１１とＲ１１２、Ｒ１１２とＲ１１３及びＲ１１３とＲ１０１は、結合して環を形成する場合がある。）     An oxime ester compound represented by the following general formula (Iα) or (Iβ).
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a group represented by the following general formula (II), hydrogen atom, halogen atom, nitro group, cyano group , Hydroxyl group, carboxyl group, R 21 , OR 21 , SR 21 , NR 22 R 23 , COR 21 , SOR 21 , SO 2 R 21 or CONR 22 R 23 ,
    At least one of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is a group represented by the following general formula (II),
    R 7 , R 8 , R 9 , R 10 and R 11 are each independently a group represented by the following general formula (IIIα), a group represented by the following general formula (IIIβ), a hydrogen atom, a halogen atom, A nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 21 , OR 21 , SR 21 , NR 22 R 23 , COR 21 , SOR 21 , SO 2 R 21 or CONR 22 R 23 ;
    At least one of R 7 , R 8 , R 9 , R 10 and R 11 is a group represented by the following general formula (IIIα) or a group represented by the following general formula (IIIβ),
    R 21 , R 22 and R 23 each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
    The hydrogen atoms in the groups represented by R 21 , R 22 and R 23 are halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups. , A mercapto group, an isocyanate group or a heterocycle-containing group, the hydrocarbon group having 2 to 20 carbon atoms or the methylene group in the heterocycle-containing group having 2 to 20 carbon atoms may be represented by —O— , —CO—, —COO—, —OCO—, —NR 24 —, —NR 24 CO—, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO And R 24 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
    X 1 represents absence, direct bond, —CO—, —O— or —S—,
    R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 And R 11 , and R 11 and R 1 may combine to form a ring. )
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 31 and R 32 each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocyclic-containing group having 2 to 20 carbon atoms. Represent,
    The hydrogen atom of the hydrocarbon group having 1 to 20 carbon atoms or the heterocyclic group having 2 to 20 carbon atoms represented by R 31 and R 32 is a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, It may be substituted with a carboxyl group, a methacryloyl group, an acryloyl group, an epoxy group, a vinyl group, a vinyl ether group, a mercapto group, an isocyanate group or a heterocyclic group, and the number of carbon atoms represented by R 31 and R 32 is 2 to The methylene group in the hydrocarbon group having 20 or the heterocyclic group having 2 to 20 carbon atoms is —O—, —CO—, —COO—, —OCO—, —NR 33 —, —NR 33 CO—, May be substituted with —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO—, and R 33 represents a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. Table of hydrogen groups ,
    n represents 0 or 1, and * represents a bond. )
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 , R 49 and R 50 are each independently a hydrogen atom, a halogen atom, a nitro group, or a cyano group. , Hydroxyl group, carboxyl group, R 51 , OR 51 , SR 51 , NR 52 R 53 , COR 51 , SOR 51 , SO 2 R 51 or CONR 52 R 53 ,
    R 51 , R 52 and R 53 each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group containing 2 to 20 carbon atoms,
    The hydrogen atoms in the groups represented by R 51 , R 52 and R 53 are halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups. , A mercapto group, an isocyanate group or a heterocycle-containing group, the hydrocarbon group having 2 to 20 carbon atoms or the methylene group in the heterocycle-containing group having 2 to 20 carbon atoms may be represented by —O— , —CO—, —COO—, —OCO—, —NR 54 —, —NR 54 CO—, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO May be replaced with-
    X 2 and X 3 represent —O—, —S— or —NR 54 —,
    R 54 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
    * Represents a bond. )
    Figure JPOXMLDOC01-appb-C000004
     Wherein R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 are each independently a group represented by the above general formula (II), a hydrogen atom, a halogen atom , A nitro group, a cyano group, a hydroxyl group, a carboxyl group, R 121 , OR 121 , SR 121 , NR 122 R 123 , COR 121 , SOR 121 , SO 2 R 121 or CONR 122 R 123 ,
    At least one of R 101 , R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 is a group represented by the general formula (II),
    R 109 , R 110 , R 111 , R 112 and R 113 are each independently a group represented by the general formula (IIIα), a group represented by the general formula (IIIβ), a hydrogen atom, a halogen atom, Nitro group, cyano group, hydroxyl group, carboxyl group, R 121 , OR 121 , SR 121 , NR 122 R 123 , COR 121 , SOR 121 , SO 2 R 121 or CONR 122 R 123
    At least one of R 109 , R 110 , R 111 , R 112 and R 113 is a group represented by the following general formula (IIIα) or a group represented by the following general formula (IIIβ);
    R 121 , R 122 and R 123 each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms,
    The hydrogen atoms in the groups represented by R 121 , R 122 and R 123 are halogen atoms, nitro groups, cyano groups, hydroxyl groups, amino groups, carboxyl groups, methacryloyl groups, acryloyl groups, epoxy groups, vinyl groups, vinyl ether groups. , A mercapto group, an isocyanate group or a heterocycle-containing group, the hydrocarbon group having 2 to 20 carbon atoms or the methylene group in the heterocycle-containing group having 2 to 20 carbon atoms may be represented by —O— , —CO—, —COO—, —OCO—, —NR 124 —, —NR 124 CO—, —S—, —CS—, —SO 2 —, —SCO—, —COS—, —OCS— or CSO May be replaced with-
    R 124 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms,
    X 101 represents absence, direct bond, —CO—, —O— or —S—,
    R101 and R102 , R102 and R103 , R103 and R104 , R105 and R106 , R106 and R107 , R107 and R108 , R108 and R109 , R109 and R110 , R110 And R 111 , R 111 and R 112 , R 112 and R 113, and R 113 and R 101 may combine to form a ring. )
  2. 　一般式（Ｉα）中のＲ３及びＲ５のうち少なくとも一つが、一般式（II）で表される基である請求項１に記載のオキシムエステル化合物。 The oxime ester compound according to claim 1, wherein at least one of R 3 and R 5 in the general formula (Iα) is a group represented by the general formula (II).
  3. 　一般式（Iβ）中のＲ１０３及びＲ１０６のうち少なくとも一つが、一般式（II）で表される基である請求項１に記載のオキシムエステル化合物。 The oxime ester compound according to claim 1, wherein at least one of R 103 and R 106 in the general formula (Iβ) is a group represented by the general formula (II).
  4. 　一般式（Ｉα）中のＸ１が不存在でＲ５とＲ６が結合してベンゼン環を形成する請求項１又は２に記載のオキシムエステル化合物。 The oxime ester compound according to claim 1 or 2, wherein X 1 in the general formula (Iα) is absent and R 5 and R 6 are bonded to form a benzene ring.
  5. 　請求項１～４の何れか一項に記載のオキシムエステル化合物を含有する光重合開始剤。 A photopolymerization initiator containing the oxime ester compound according to any one of claims 1 to 4.
  6. 　請求項５に記載の光重合開始剤（Ａ）及びエチレン性不飽和化合物（Ｂ）を含有する感光性組成物。 A photosensitive composition comprising the photopolymerization initiator (A) according to claim 5 and an ethylenically unsaturated compound (B).
  7. 　更に着色剤（Ｃ）を含有する請求項６に記載の感光性組成物。 The photosensitive composition according to claim 6, further comprising a colorant (C).
  8. 　請求項６又は７に記載の感光性組成物にアルカリ現像性化合物（Ｄ）を含有させてなるアルカリ現像性感光性樹脂組成物。 An alkali-developable photosensitive resin composition comprising the photosensitive composition according to claim 6 or 7 and an alkali-developable compound (D).
  9. 　請求項６若しくは７に記載の感光性組成物又は請求項８に記載のアルカリ現像性感光性樹脂組成物の硬化物。 A cured product of the photosensitive composition according to claim 6 or 7, or the alkali-developable photosensitive resin composition according to claim 8.
  10. 　請求項９に記載の硬化物を含有するディスプレイ表示装置。 A display device containing the cured product according to claim 9.
  11. 　請求項６若しくは７に記載の感光性組成物又は請求項８に記載のアルカリ現像性感光性樹脂組成物を用い、該組成物を硬化させる工程を有する、硬化物の製造方法。 The manufacturing method of hardened | cured material which has the process of hardening this composition using the photosensitive composition of Claim 6 or 7, or the alkali developable photosensitive resin composition of Claim 8.
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