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WO2018168714A1 - Composé ester d'oxime et initiateur de photopolymérisation le contenant - Google Patents

Composé ester d'oxime et initiateur de photopolymérisation le contenant 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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represented
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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 KR1020197014559A priority Critical patent/KR102545326B1/ko
Priority to CN201880004717.XA priority patent/CN110023307B/zh
Priority to JP2019505981A priority patent/JP7482628B2/ja
Publication of WO2018168714A1 publication Critical patent/WO2018168714A1/fr

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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

L'invention concerne un composé ester d'oxime représenté par la formule générale (Iα) ou (Iβ). (Dans les formules : R1 à R6 et R101 à R108 représentent chacun indépendamment un groupe représenté par la formule générale (II), un atome d'hydrogène, un atome d'halogène, un groupe nitro, un groupe cyano, un groupe hydroxyle, un groupe carboxyle, ou similaire ; l'un de R1 à R6 et R101 à R108 est un groupe représenté par la formule générale (II) ; R7 à R11 et R109 à R113 représentent chacun indépendamment un groupe représenté par la formule générale (IIIα) ou (IIIβ), un atome d'hydrogène, un atome d'halogène, un groupe nitro, un groupe cyano, un groupe hydroxyle, un groupe carboxyle, ou similaire ; au moins l'un de R7 à R11 et R109 à R113 est un groupe représenté par la formule générale (IIIα) ou (IIIβ) ; et X1 et X101 sont absents ou sont chacun une liaison directe, -CO-, -O- ou -S-.)
PCT/JP2018/009317 2017-03-16 2018-03-09 Composé ester d'oxime et initiateur de photopolymérisation le contenant WO2018168714A1 (fr)

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JP2020086318A (ja) * 2018-11-29 2020-06-04 東京応化工業株式会社 感光性樹脂組成物、パターン化された硬化膜の製造方法、及びパターン化された硬化膜
WO2024004425A1 (fr) * 2022-06-27 2024-01-04 富士フイルム株式会社 Composition durcissable, procédé de production de produit durci, film, élément optique, capteur d'images, capteur d'images à l'état solide, dispositif d'affichage d'images, et initiateur de polymérisation radicalaire
WO2024143067A1 (fr) * 2022-12-26 2024-07-04 三菱ケミカル株式会社 Composition de résine photosensible, produit durci, paroi de séparation, élément électroluminescent organique, filtre coloré, appareil d'affichage d'image et procédé de formation de produit durci
WO2025041644A1 (fr) * 2023-08-24 2025-02-27 富士フイルム株式会社 Composition durcissable, procédé de production de pixel, film, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image, composé et photosensibilisateur
WO2025070233A1 (fr) * 2023-09-27 2025-04-03 東レ株式会社 Composition photosensible, produit durci, composant électronique et procédé de production de produit durci

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Publication number Priority date Publication date Assignee Title
JP2020086318A (ja) * 2018-11-29 2020-06-04 東京応化工業株式会社 感光性樹脂組成物、パターン化された硬化膜の製造方法、及びパターン化された硬化膜
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WO2024004425A1 (fr) * 2022-06-27 2024-01-04 富士フイルム株式会社 Composition durcissable, procédé de production de produit durci, film, élément optique, capteur d'images, capteur d'images à l'état solide, dispositif d'affichage d'images, et initiateur de polymérisation radicalaire
WO2024143067A1 (fr) * 2022-12-26 2024-07-04 三菱ケミカル株式会社 Composition de résine photosensible, produit durci, paroi de séparation, élément électroluminescent organique, filtre coloré, appareil d'affichage d'image et procédé de formation de produit durci
WO2025041644A1 (fr) * 2023-08-24 2025-02-27 富士フイルム株式会社 Composition durcissable, procédé de production de pixel, film, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image, composé et photosensibilisateur
WO2025070233A1 (fr) * 2023-09-27 2025-04-03 東レ株式会社 Composition photosensible, produit durci, composant électronique et procédé de production de produit durci

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