WO2008035671A1 - Composition de coloration photosensible et filtre de couleur - Google Patents

Composition de coloration photosensible et filtre de couleur Download PDF

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Publication number
WO2008035671A1
WO2008035671A1 PCT/JP2007/068082 JP2007068082W WO2008035671A1 WO 2008035671 A1 WO2008035671 A1 WO 2008035671A1 JP 2007068082 W JP2007068082 W JP 2007068082W WO 2008035671 A1 WO2008035671 A1 WO 2008035671A1
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WIPO (PCT)
Prior art keywords
group
coloring composition
substituent
photosensitive coloring
general formula
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PCT/JP2007/068082
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English (en)
Japanese (ja)
Inventor
Yukino Miyagawa
Kenro Sunahara
Masaki Kanno
Nozomi Yokozawa
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Toyo Ink Mfg. Co., Ltd.
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Publication of WO2008035671A1 publication Critical patent/WO2008035671A1/fr

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    • 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
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof

Definitions

  • the present invention relates to a photosensitive coloring composition, and in particular for color filters used in liquid crystal display devices and solid-state imaging devices, each color filter segment such as red, green, blue, yellow, orange, cyan, magenta, and black matrix. It is related with the highly sensitive photosensitive coloring composition useful for formation of the above.
  • the present invention also relates to a color filter formed using the photosensitive coloring composition.
  • a color filter includes two or more kinds of fine stripe-shaped filter segments of different colors formed on the surface of a transparent substrate such as glass. These filter segments are arranged parallel to or crossing each other, or arranged in a constant vertical and horizontal arrangement. The filter segments have a fine width of several microns to several hundred microns, and are arranged in a predetermined arrangement for each hue.
  • a transparent electrode for driving a liquid crystal is formed on the color filter by vapor deposition or sputtering, and the liquid crystal is aligned in a certain direction on the transparent electrode.
  • An alignment film is formed.
  • their formation must generally be performed at a high temperature of 200 ° C or higher, preferably 230 ° C or higher.
  • a photosensitive coloring composition in which a pigment is dispersed in a photosensitive transparent resin solution is applied to a transparent substrate such as glass, and the solvent is removed by drying.
  • a photosensitive coloring composition pigment resist
  • a photosensitive transparent resin solution in which a pigment is dispersed in a photosensitive transparent resin solution is applied to a transparent substrate such as glass, and the solvent is removed by drying.
  • remove the unexposed areas in the development process to form the first color pattern apply heat treatment if necessary, and then repeat the same operation for the remaining filter colors.
  • a color filter can be manufactured.
  • color liquid crystal display devices have been used for liquid crystal color televisions, car navigation systems, and A large market has been formed for notebook personal computers with integrated liquid crystal display devices, and it has begun to spread as monitors and televisions for desktop computers that take advantage of energy and space saving features.
  • Color liquid crystal display devices are attracting attention as an alternative to conventional CRTs, but at present, the color reproduction characteristics of liquid crystal display devices are inferior to those of CRTs!
  • a black matrix is generally arranged between filter segments of each color of the color filter.
  • a resin black matrix in which a light-shielding colorant is dispersed in a resin has attracted attention instead of a metal chromium black matrix.
  • the resin black matrix has a problem of low light shielding (optical density) compared to black matrix made of chromium metal.
  • the content of the colorant in the photosensitive coloring composition is increased, or the photosensitive coloring composition It is necessary to increase the coating film thickness.
  • the content of the colorant is increased, the sensitivity is lowered, and problems such as deterioration in developability and resolution occur. If the film thickness is increased, the exposure light does not reach the bottom of the film, causing problems such as poor pattern shape.
  • JP 2001-233842 A discloses a photoinitiator made of a specific oxime ester compound
  • JP 2001-264530 A discloses a photo radical generator made of a specific oxime ester compound
  • JP-A 2003-156842 discloses the use of a photopolymerization initiator composed of aacetophenone compound and a triazine compound and a photopolymerization initiation assistant composed of an amine.
  • the present invention provides a photosensitive coloring composition that gives an excellent pattern shape with high sensitivity even when the colorant content is high or when it is applied with a thick film, and a color filter using the same.
  • the purpose is to provide.
  • the photosensitive coloring composition is highly sensitive and uses a photopolymerization initiator represented by the following general formula (1) in order to obtain an excellent pattern shape.
  • a photosensitive coloring containing a colorant carrier comprising a transparent resin and its precursor, a colorant and a photopolymerization initiator represented by the following general formula (1)
  • a composition is provided.
  • a color filter comprising a filter segment formed from the photosensitive coloring composition of the present invention.
  • a color filter comprising a black matrix formed from the photosensitive coloring composition of the present invention.
  • a and B each independently represent a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed polycyclic hydrocarbon group, and X represents a monovalent organic residue.
  • the photosensitive coloring composition of the present invention contains a colorant carrier composed of a transparent resin and a precursor thereof, a colorant, and a photopolymerization initiator represented by the above general formula (1).
  • the photopolymerization initiator represented by the general formula (1) forms a filter segment and a black matrix having an excellent pattern shape when the photosensitive coloring composition having high sensitivity contains the photopolymerization initiator. be able to.
  • the photopolymerization initiator represented by the general formula (1) is characterized in that ⁇ 1, ⁇ 1 -diketoxime is characterized by having a heterocyclic group or a condensed polycyclic hydrocarbon group at the 1-position and 3-position. It is an ester compound.
  • the photopolymerization initiator used in the present invention has an absorption band from the near ultraviolet to the visible region due to the introduction of a heterocyclic group or a condensed polycyclic hydrocarbon group into ⁇ and ⁇ . It is possible to have activity up to a long wavelength region, and active radicals can be efficiently generated by irradiation with energy rays, particularly light.
  • a and B each independently represent a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted condensed polycyclic hydrocarbon group.
  • the heterocyclic ring in the substituted or unsubstituted heterocyclic group represented by A or B in the general formula (1) is an aromatic group containing a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom. Examples include aliphatic heterocycles.
  • Specific examples include 2-Chenyl group, 2-Benzoenyl group, Naphtho [2,3-b] Chenolinole group, 3 Thianthrenyl group, 2 Thianthrenyl group, 2— Furyl group, 2-benzofuryl group, biranyl group, isobenzofuranyl group, chromenyl group, xanthur group, phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazyl group, Pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H—indolyl group, 2 indolinole group, 3 indolinole group, 1H indazolyl group, purinyl group, 4H—key Lysinyl group, isoquinolyl group, quinolyl group, phthaladyl group
  • the position where the substituted or unsubstituted heterocyclic group is bonded to the adjacent carbonyl carbon is the position of the heterocyclic group exemplified above by specifying the specific position (for example, in the 2-chenyl group). Is not limited to the 2-position, but may be any position where the heterocyclic group can be bonded to the carbonyl group next to it (for example, the Cheninore group includes 2 Chenyl, 3 Chenyl, 4 Chenyl). Or it can be 5 Cenyl.
  • the condensed polycyclic hydrocarbon in the substituted or unsubstituted condensed polycyclic hydrocarbon group represented by A or B in the general formula (1) is a condensed polycyclic ring formed of 7 or more carbon atoms.
  • Specific examples include cyclic hydrocarbons such as indul, 1,3-indandionyl, naphthyl, / 3-tetralonyl, ⁇ -naphthoquinolyl, pentarenyl, azulenyl, heptaenyl, fluorenyl, and fluorenonyl.
  • a condensed polycyclic hydrocarbon group in which two or three rings are condensed is preferable, but is not limited thereto.
  • the position where the substituted or unsubstituted condensed polycyclic hydrocarbon group is bonded to the adjacent carbonyl carbon is any position as long as the condensed polycyclic hydrocarbon group can be bonded to the adjacent force sulfonyl group. Good.
  • Examples of the substituent that the heterocyclic group and the condensed polycyclic hydrocarbon group described above may have include a hydroxyl group, a mercapto group, a cyano group, a nitro group, a halogen atom, an alkyl group, an aryl group, a heterocyclic group.
  • Cyclic group acyl group, alkoxyl group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, allylthio group, heterocyclic thio group, amino group, alkylamino group, dialkylamino group, aryleno amino group, diarino Examples thereof include a reamino group, an alkylaryl amino group, a benzylamino group, and a dibenzylamino group.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /,
  • the alkyl group as a substituent includes a linear, branched or monocyclic group having 1 to 18 carbon atoms.
  • a condensed polycyclic alkyl group is included. Specific examples thereof include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, Noel group, decyl group, dodecinole group, octadecyl group, isopropyl group, isobutyl group.
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /
  • the aryl group as a substituent includes a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms. . Specific examples thereof include, for example, phenyl group, 1 naphthyl group, 2 naphthyl group, 9 anthryl group, 9 phenanthryl group, 1-pyrenyl group, 5 naphthacenyl group, 1 induryl group, 2 azulenyl group, 1-acenaphthyl group, 9 fluorenyl group. It is a group.
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the heterocyclic group as a substituent includes a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom. Ring or A condensed polycyclic heterocyclic group is included. Specific examples thereof include, for example, 2-furanyl group, 2-cenyl group, 2 indolinole group, 3 indolinole group, 2 benzofurinole group, 2 benzocenyl group, 2 rubazolyl group, 3-canolebasolinol group, 4 canolebasolinole group, 9 ataridinyl group Group
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the acyl group as a substituent may be a hydrogen atom or a linear or branched chain having 1 to 18 carbon atoms; A carbonyl group to which a monocyclic or condensed polycyclic aliphatic group is bonded, or a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, a nitrogen atom, an oxygen atom, a sulfur atom, and And / or a carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 18 to 18 carbon atoms including a phosphorus atom is bonded, and these may have an unsaturated bond in the structure.
  • Specific examples thereof include, for example, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, bivaloyl group, lauroyl group, myristoyl group, nonremitinole group, stearoyl group, cyclopentylcarbonyl group, cyclohexane Hexylcarbonyl, Atalylyl, Methacryloyl, Crotonyl, Isocrotonyl, Oleoinole, Benzoyl, 2 Methylbenzoyl, 4-Methoxybenzoyl, 1 Naphthoyl, 2 Naphthoyl, Cinnamoyl, 3 Froyl Group, 2 tenol group, nicotinol group, isonicotinoyl group, 9 anthroyl group, 5-naphthaceneol group and the like.
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /,
  • the alkoxy group as a substituent may be a linear, branched or monocyclic group having 1 to 18 carbon atoms.
  • a condensed polycyclic alkoxyl group is included.
  • Specific examples thereof include, for example, methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, iso Propoxy group, isobutoxy group, isopentyloxy group, sec butoxy group, t-butoxy group, sec pentyloxy group, t pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, A cyclopentyloxy group, a cyclohexyloxy group, an adamantyloxy group, a norbornyloxy group, a polonyloxy group, a 4-decylcyclohexyloxy group, a 2 tetra
  • the aryloxy group as a substituent that the heterocyclic group and the condensed polycyclic hydrocarbon group may have includes a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms. Specific examples thereof include, for example, phenoxy group, 1 naphthyloxy group, 2-naphthyloxy group, 9 anthryloxy group, 9 phenanthryloxy group, 1-pyrenyloxy group, 5 naphthacenyloxy group, 1 induroxy group, 2-azlenenyloxy Group, 1-cenaphthyloxy group, 9-fluorenyloxy group.
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the heterocyclic oxy group as a substituent includes a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom.
  • Monocyclic or condensed polycyclic heterocyclic oxy groups are included. Specific examples thereof include, for example, 2-furanyloxy group, 2 enyloxy group, 2 indolyloxy group, 3 indolyloxy group, 2 monobenzofuryloxy group, 2-benzozonyloxy group, 2 force rubazolyloxy group, 3 force Rubazolyloxy group, 4 rubazolyloxy group, 9 ataridinyloxy group
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /
  • the acyloxy group as a substituent may be a hydrogen atom or a linear or branched chain having 1 to 18 carbon atoms;
  • a carbonyloxy group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms including an atom and / or a phosphorus atom is bonded is included.
  • Specific examples thereof include, for example, acetoxy group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, bivalyloxy group, lauroyloxy group, myristyloxy group, palmitoyloxy group.
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, Alkyl as a substituent
  • the thio group includes a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms. Specific examples thereof include, for example, methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, and octadecylthio group.
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /
  • the arylo group as a substituent includes a monocyclic or condensed polycyclic arylothio group having 6 to 18 carbon atoms. Specific examples thereof include a phenylthio group, a 1 naphthylthio group, a 2 naphthylthio group, a 9-anthrylthio group, a 9 phenanthrylthio group, and the like.
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /, And the heterocyclic thio group as a substituent includes a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom.
  • Monocyclic or fused polycyclic heterocyclic thio groups are included. Specific examples thereof include, for example, 2-furylthio group, 2 phenylthio group, 2 pyrrolylthio group, 6 indolylthio group, 2 benzofurylthio group, 2 benzochelylthio group, 2 force rubazolylthio group, 3 force rubazolylthio group, 4 A rubazolylthio group.
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /
  • the alkylamino group as a substituent includes, for example, a methylamino group, an ethylamino group, a propylamino group, a butylamino group, and a pentylamino group.
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /
  • the dialkylamino group as a substituent includes, for example, a dimethylamino group, a jetylamino group, a dipropylamino group, a dibutylamino group, Dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, Includes methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutyramino group, cyclopropylamino group, pyrrolidino group, piperidino group, piperazin
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /
  • the arylarylamino group as a substituent includes, for example, an Narylamino group, an anilino group, a 1-naphthylamino group, and a 2-naphthylamino group.
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /
  • the diarylamino group as a substituent includes, for example, a diaryreamino group, a diphenylamino group, a ditolylamino group, N —Includes phenyl 1-naphthylamino group, N-phenyl 2-naphthylamino group.
  • the heterocyclic group and the condensed polycyclic hydrocarbon group may have! /,
  • an alkylarylamino group as a substituent includes, for example, an N methylanilino group, an N methyl-2-pyridino group, an N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropylinole, N-pentylanilino group, N-ethylanilino group, N-methyl-1-naphthylamino group are included.
  • the hydrogen atom of the substituent that the heterocyclic group and the condensed polycyclic hydrocarbon group may have may be further substituted with another substituent.
  • the group include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group, an aryloxy group such as a phenoxy group and a p-trioxy group, and a methoxycarbonyl group.
  • Butoxycarbonyl groups alkoxycarbonyl groups such as phenoxycarbonyl groups, etc., acetoxy groups, propionyloxy groups, benzyloxy groups, etc., acylyl groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, methoxalyl groups, etc.
  • Alkyls such as acyl, methylsulfanyl and tert-butylsulfanyl Faniru group, Hue Nils Alpha sulfonyl group, p-tolylsulfanyl ⁇ reel sulfanyl group such as, Mechiruamino group, an alkylamino group such Kishinore amino cyclohexane, Jimechiruamino group, Jechiruamino group, a morpholino group, Pi Dialkylamino groups such as peridino group, arylamino groups such as phenylamino group, p-tolylamino group, alkyl groups such as methyl group, ethyl group, tert butyl group, dodecyl group, phenyl group, ptolyl group, xylyl group, In addition to aryl groups such as tamenyl group, naphthyl group, anthryl group, phen
  • a substituent structure S in A and B, another substituent, or a carbon atom on the ring may be combined to form a cyclic structure.
  • a and B may be integrated to form a ring structure.
  • X in the general formula (1) represents a monovalent organic residue.
  • the monovalent organic residue may have an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent.
  • Alkynyl group optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted heterocyclic oxy group, optionally substituted acyloxy group, substituted An alkyl sulfanyl group that may have a group, an arylsulfanyl group that may have a substituent, an alkylsulfiel group that may have a substituent, and an arylsulfur group that may have a substituent Group, alkylsulfonyl group which may have a substituent, arylarylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl group which may have a substituent A canole which may have a substituent A moyl group, a sulfamoyl group which may have a substituent, an amino group which may have a substituent, a phosphinoyl group which may have a substituent, and a heterocyclic group
  • the alkyl group which may have a substituent as the monovalent organic residue is preferably an alkyl group having from 30 to 30 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, Butyl group, Hexyl group, Octyl group, Decyl group, Dodecyl group, Okudadecyl group, Isopropyl group, Isobutyl group, sec Butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl Group, 2-ethylhexyl group, phenacyl Group, 1 naphthoylmethyl group, 2 naphthoylmethyl group, 4-methylsulfaurphenacinole group, 4 phenylsulfaurphenacyl group, 4-dimethylaminophenacyl group, 4 cyanophenacyl group, 4 methyl
  • the aryl group that may have a substituent as the monovalent organic residue is preferably a phenyl group, a biphenyl group, a 1 naphthyl group, preferably an aryl group having 6 to 30 carbon atoms, 2-naphthinole group, 9 anthrinole group, 9 phenanthrinole group, 1-pyrenyl group, 5 naphthacenyl group, 1 indur group, 2 azulenyl group, 9 fluorenyl group, terphenyl group, quarter terphenyl group, o-, m-, And p-trinole group, xylinole group, o-, m-, and p cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quaternarynaphthalenyl group, heptaenyl group, biphenylenyl group, mes
  • the alkenyl group which may have a substituent as the monovalent organic residue is preferably an alkenyl group having 2 to 10 carbon atoms, such as a bur group, a allyl group, and a styryl group. Are listed.
  • the monovalent organic residue may have a substituent! /
  • the alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, for example, an ethur group, a propynyl group, a propanolol group. Gill group etc. are mentioned.
  • the alkoxy group which may have a substituent as the monovalent organic residue is preferably an alkoxy group having 1 to 30 carbon atoms.
  • the aryloxy group which may have a substituent as the monovalent organic residue is preferably an aryloxy group having 6 to 30 carbon atoms.
  • the heterocyclic oxy group which may have a substituent as the monovalent organic residue is a monocyclic or condensed polyoxy group containing a nitrogen atom, an oxygen atom, a sulfur atom and / or a phosphorus atom.
  • Specific examples include cyclic heterocyclic oxy groups such as 2-furanyloxy group, 2-phenyloxy group, 2 indoloxy group, 3 indoloxy group, 2 force rubazolyloxy group, 2 benzofuryloxy group, 2 benzocenyloxy group. Examples thereof include a xyl group, a tri-strand rubazolyloxy group, a 4-canoleverzolyloxy group, and a 9-ataridinyloxy group.
  • the acyloxy group which may have a substituent as the monovalent organic residue is preferably an acyloxy group having 2 to 20 carbon atoms, for example, an acetyloxy group, a propanoxy group, a butanoyloxy group, Examples include a pentanoyloxy group, a trifluoromethylcarbonyloxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, and a 2-naphthylcarbonyloxy group.
  • alkylsulfanyl group which may have a substituent as the monovalent organic residue
  • an alkylsulfanyl group having 1 to 20 carbon atoms is preferred, for example, a methylsulfanol group, ethyl Sulfanyl, propylsulfanyl, isopropylsulfanyl, butylsulfanyl, hexylsulfanyl, cyclohexylsulfanyl, octylsulfanyl, 2-ethylhexylsulfanyl, decanolsulfanyl, dodecanol
  • sulfanyl group octadecanol sulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group and the like.
  • aryl sulfanyl group which may have a substituent as the monovalent organic residue
  • an aryl sulfanyl group having 6 to 30 carbon atoms is preferable.
  • a phenylsulfaninole group 1 Naphtylsulfanyl group, 2-Naphtylsulfanyl group, 2-Chlorophenylsulfanyl group, 2-Methylphenylsulfanyl group, 2-Methoxyphenylsulfanyl group, 2-Butoxyphenylsulfanyl group, 3-Chlorophenyl Sulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-diphenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfaneyl group, 4-methoxyphenyl Sulfanyl group, 4-methyls
  • an alkylsulfier group having 1 to 20 carbon atoms is preferred.
  • Examples thereof include a neutral sulfiel group, a dodecanol sulfiel group, an octadecanol sulfiel group, a cyanomethyl sulfinyl group, and a methoxymethyl sulfier group.
  • aryl sulfiel group which may have a substituent as the monovalent organic residue
  • an aryl sulfiel group having 6 to 30 carbon atoms is preferable. Nore group, 1 Naphthyl sulfier group, 2-Naphthyl sulfier group, 2-Chronophenyl sulfier group, 2-Methylphenyl sulfier group, 2-Methoxyphenyl sulfier group Group, 2 butoxyphenyl sulfier group, 3 cyclophenyl sulfiel group, 3 trifluoromethylphenyl sulfinyl group, 3-cyanophenyl sulfinyl group, 3-diphenyl phenyl sulfier group, 4 Fluorophenyl sulfier group, 4-cyanophenole sulfinyl group, 4-methoxyphenyl sulfinyl group, 4-methylsulfau
  • alkylsulfonyl group which may have a substituent as the monovalent organic residue
  • an alkylsulfonyl group having 1 to 20 carbon atoms is preferred.
  • a rusulfonyl group a dodecanolylsulfonyl group, an octadecanolsulfonyl group, a cyanomethylsulfonyl group, and a methoxy
  • the arylsulfonyl group which may have a substituent as the monovalent organic residue is preferably an arylsulfonyl group having 6 to 30 carbon atoms.
  • an acyl group having 2 to 20 carbon atoms is preferable.
  • the alkoxycarbonyl group which may have a substituent as the monovalent organic residue is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, a methoxycarbonyl group, ethoxy Carbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyl Oxycarbonyl group, 1 naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfurylphenyloxycarbonyl group, 4 phenylsulfanyl phenyloxycarbonyl group, 4-dimethylaminophenyl Oxycarbonyl group, 4 jetylaminophenyloxycarbonyl group, 2-carbonyl group Oral phenyloxycarbonyl
  • a rubamoyl group having 1 to 30 carbon atoms is preferred.
  • the sulfamoyl group which may have a substituent as the monovalent organic residue is preferably a sulfamoyl group having 0 to 30 carbon atoms.
  • the amino group which may have a substituent as the monovalent organic residue is preferably an amino group having 0 to 50 carbon atoms, for example, -NH, N-alkylamino group, Examples include N arylamino group, N acylamino group, N sulfonylamino group, N, N dialkylamino group, N, N diarylamino group, N alkyl mono-N arylamino group, N, N disulfonino amino group and the like.
  • the phosphinoyl group which may have a substituent as the monovalent organic residue is preferably a phosphinoyl group having 2 to 50 total carbon atoms, for example, a dimethylphosphinoyl group, a dimethyl ester Phosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis ( 2, 4, 6 trimethylphenyl) phosphinoyl group and the like.
  • a phosphinoyl group having 2 to 50 total carbon atoms for example, a dimethylphosphinoyl group, a dimethyl ester Phosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group,
  • the monovalent organic residue may have a substituent! / ⁇ heterocyclic group includes an aromatic or aliphatic group containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. Heterocycles are preferred.
  • alkyl group which may have a substituent described above an aryl group which may have a substituent, an alkenyl group which may have a substituent, and an alkynyl group which may have a substituent
  • An alkoxy group which may have a substituent an aryloxy group which may have a substituent
  • an acyloxy group which may have a substituent
  • an alkylsulfanyl group which may have a substituent
  • Arylsulfanyl group may have a substituent!
  • the hydrogen atom of the moyl group, the amino group which may have a substituent, or the heterocyclic group which may have a substituent may be further substituted with another substituent.
  • substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p-tolyloxy group and other aryloxy groups, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl groups such as phenoxycarbonyl group, acetoxy group, propionyloxy group, and acyloxy groups such as benzoyloxy group, acetyl group, benzoyl group, Isobutyryl group, atarylloyl group, methacryloyl group, metylyl group and other isyl groups, methylsulfanyl group, alkylsulfanyl group such as tert-butylsulfanyl group, phenylsulfanyl group, and arylsulfanyl group such as p
  • X is preferably an alkyl group that may have a substituent, an aryl group that may have a substituent, an acyl group that may have a substituent, or a phosphier that may have a substituent.
  • X is more preferably an alkyl group which may have a substituent or an aryl group which may have a substituent. Specific examples thereof include a methyl group, an ethynole group, a propyl group, Forces including butyl group, t-butyl group, trifluoromethyl group, phenyl group, benzyl group, etc. It is not limited to these examples.
  • a and B in the general formula (1) are not the same from the viewpoint of solubility or sensitivity.
  • a in the general formula (1) is a substituted or unsubstituted carbazolyl group, or a substituted or unsubstituted group. It is a photopolymerization initiator for naphthyl groups.
  • the carbazolyl group and the naphthyl group may be bonded at any substitution position as long as they can form a covalent bond with the adjacent carbon atom of the general formula (1).
  • the substituent that the canolazolyl group or naphthyl group may have include the same substituents as those mentioned for the substituent that A and B may have.
  • the partial force of the substituents on the carbazolyl group and naphthyl group is bonded to the carbon atom of the carbazolyl group or naphthyl group or a part of other substituents to form a ring structure as a unit! Moyo!
  • a in the general formula (1) is represented by the following general formula (2), which is substituted or unsubstituted. Group or substituted or not It is a photopolymerization initiator representing a group represented by the following general formula (3).
  • the group represented by the general formula (2) and the general formula (3) is bonded to the carbonyl carbon atom at any substitution position that can form a covalent bond with the adjacent carbonyl carbon atom.
  • Y represents a monovalent organic residue, and examples thereof include the same monovalent organic residues as X in the general formula (1). Because of its low weight, a substituted or unsubstituted alkyl group is preferred.
  • photopolymerization initiators represented by the general formula (1) a group represented by the general formula (2) in which A in the general formula (1) is substituted or unsubstituted is preferable.
  • B is a photopolymerization initiator of the group represented by the general formula (3), which is substituted or unsubstituted.
  • the hydrogen atoms of the groups represented by the general formula (2) and the general formula (3) may be substituted with substituents.
  • substituents include A and B And the same substituents as mentioned for the substituents that may have.
  • the substituent in formula (2) is preferably a acyl group, more preferably a substituted or unsubstituted benzoyl group or a substituted or unsubstituted alkylcarbonyl group.
  • the specific structure of the photopolymerization initiator represented by the general formula (1) in the present invention is shown in Table 1A N. The structure of the force photopolymerization initiator is not limited thereto.
  • the starting material for synthesizing the photopolymerization initiator represented by the general formula (1) is an oxime represented by the following general formula (4).
  • a and B have the same meanings as A and B in the general formula (1).
  • the oxime represented by the general formula (4) is, for example, Org. React., 7, 1953>, 327, edited by the Chemical Society of Japan, 4th edition, Experimental Chemistry Course, Vol. 14, p. 1316 (Maruzen) ) Can be obtained in various ways. Further, it can be obtained from a method for synthesizing oxime described in commercially available chemistry texts (for example, J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992).
  • One of the most convenient methods of synthesizing oximes is nitrosation of active methylene groups with nitrous acid or alkyl nitrites.
  • the reaction conditions are, for example, Organic Syntheses Coil. Vol. VI, pp 840, Organic Syntheses Coll. Vol. III, p 191 and 51 «5, Organic 3 ⁇ 4ynth eses Coll. Vol. II, pp 202, 204 and 363, J. Am. Chem. Soc, 47, 1925>, 2033, J. Chem. Soc, 117, 1920>, 590, J. Am. Chem. Soc, 51, 1929>, 2264 Suitable for the manufacture of oxime.
  • Nitrous acid is usually produced from sodium nitrite.
  • the nitrite alkyl ester is, for example, nitrite methyl ester, isopropyl nitrite ester, butyl nitrite ester, isoamyl nitrite ester.
  • the photopolymerization initiator represented by the general formula (1) is a method described in the literature, for example, an oxime obtained by the above-described method, and a silk silk starting from the oxime represented by the general formula (4).
  • an inert solvent such as tetrahydrofuran, benzene or dimethylformamide
  • a base for example a tertiary amine such as triethylamine, or in a basic solvent such as pyridine. Produced by reacting.
  • Such a reaction is known to those skilled in the art and is generally performed at 15 ° C to + 50 ° C, preferably 0 to 30 ° C.
  • the photopolymerization initiator represented by the general formula (1) of the present invention can be identified by elemental analysis values and 1 H-NMR.
  • the photopolymerization initiator represented by the general formula (1) is used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, with respect to 100 parts by weight of the colorant in the photosensitive coloring composition. Can be used
  • photopolymerization initiator represented by the general formula (1) In addition to the photopolymerization initiator represented by the general formula (1), other photopolymerization initiators can be used in combination with the photosensitive coloring composition of the present invention.
  • photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4 isopropylinophenenole) 2-hydroxy 2-methyl Propane 1-one, 1-hydroxycyclohexyl phenyl ketone, 2 Benzylue 2 Dimethylamino 1- (4 morpholinophenyl) Acetophenone compounds such as butane 1-on, benzoin, benzoin methyl ether, benzoin ether, benzoin Benzoin compounds such as isopropyl ether, benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methinole, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4 benzoyl 4 ' -Methyl Diph Disulfide, 3, 3 ', 4, 4'-Te
  • Phosphine compounds such as oxime ester compounds, bis (2, 4, 6 trimethylbenzoinole) phenylphosphine oxide, 2, 4, 6 trimethylbenzoyl diphenylphosphine oxide, 9, 10 phenanthrenequinone Quinone compounds such as camphorquinone and ethylanthraquinone, borate compounds, strong rubazole compounds, imidazole compounds Compounds, titanocene compounds and the like.
  • These photopolymerization initiators can be used alone or as a mixture of two or more at any ratio as required.
  • the other photopolymerization initiator can be used in an amount of 5 200 parts by weight, preferably 10 150 parts by weight, based on 100 parts by weight of the colorant in the photosensitive coloring composition.
  • the photosensitive coloring composition of the present invention may contain a sensitizer.
  • the sensitizer is used in an amount of 0.;! 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the coloring composition.
  • Sensitizers include unsaturated ketones represented by chalcone derivatives such as dibenzalacetone, 1,2-diketone derivatives represented by benzylyacamphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone, and the like.
  • anthraquinone derivatives xanthene derivatives, thixanthene derivatives, xanthone derivatives, thixanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, atalidine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin Conductor, tetravirazinoporphyrazine derivative, phthalocyanine derivative, tetraazaborfilazine derivative, tetraquinoxalyloborphyrazine derivative, naphthalocyanine derivative, subphthal
  • Two or more kinds of sensitizers may be used in an optional ratio as necessary.
  • examples of the sensitizer capable of particularly suitably sensitizing the photopolymerization initiator represented by the general formula (1) include thixanthone derivatives and Michler ketone derivatives. More specifically, 2, 4 Getinorethioxanthone, 2 Chlorothioxanthone, 2, 4 Diclochio thixanthone, 2 Isopropylthioxanthone, 4 Isopropylthioxanthone, 1 Chloro-4 propoxythioxanthone, 4, 4 'bis (Dimethylamino) benzophenone, 4, 4, 1-bis (jetylamino) benzophenone, 4, 4, 1-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoylru N-ethylcarbazole, 3, 6 dibenzoyl Nethylcarbazole and the like are preferably used.
  • the photosensitive coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen.
  • Examples of such amine compounds include triethanolamine, methyljetanolamine, triisopropanolamine, 4-dimethylenoreaminobenzoic acid methinole, 4-dimethylenoreaminobenzoic acid ethyl, 4-dimethylamino.
  • Examples include isoamyl benzoate, 2 dimethylaminoethyl benzoate, 2-ethylamino 4-benzoylaminobenzoate, and N, N dimethylbalatluidine.
  • the colorant carrier contained in the photosensitive coloring composition of the present invention is composed of a transparent resin and a precursor thereof.
  • the transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.
  • Transparent resins include thermoplastic resins, thermosetting resins, and photosensitive resins.
  • the precursor includes a monomer or an oligomer that is cured by irradiation with radiation to form a transparent resin, and these can be used alone or in admixture of two or more.
  • the transparent resin can be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.
  • the transparent resin precursor can be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the colorant in the coloring composition.
  • thermoplastic resin examples include petital resin, styrene monomaleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polychlorinated butyl, chlorinated butyl-vinyl acetate copolymer, polyacetic butyl, polyurethane series. Resins, polyester resins, acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like.
  • thermosetting resin examples include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.
  • the photosensitive resin has a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group in a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group or an amino group (meth).
  • a resin in which a photocrosslinkable group such as a (meth) atalyloyl group, a styryl group or the like is introduced into the polymer by reacting an acrylic compound or keihylic acid is used.
  • a linear polymer containing an acid anhydride such as styrene maleic anhydride copolymer or ⁇ -olefin maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate.
  • Half-esterified products are also used.
  • Monomers and oligomers that are precursors of the transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate.
  • the ratio M / P between the weight (P) of the transparent resin and the weight (M) of the precursor is preferably 0.10 to 1.20. 20 to 1.00 is more preferable, and 0.25 to 0.60 is particularly preferable. If the M / P force is less than 0.10, the sensitivity will be low, and if the M / P exceeds 1.20, the pattern shape will have poor linearity or tack.
  • the ratio I / M between the weight (I) of the photopolymerization initiator and the weight (M) of the precursor of the transparent resin is preferably 0.20 to 1.50, preferably 0.25 to 1. 40 is more preferred, 0.30 to 1.30 is particularly preferred.
  • the ratio between the total weight (I) of the photopolymerization initiator and the sensitizer and the weight (M) of the precursor of the transparent resin I / M is 0.20 ⁇ ; 1. 50 bb
  • It is preferably 0.23 to; 1.00, more preferably 0.25 to 0.60, and particularly preferably 0.25 to 0.60.
  • organic or inorganic pigments may be used alone or in admixture of two or more.
  • organic pigments are usually used because pigments with high color developability and high heat resistance, particularly pigments with high heat decomposition resistance are preferred.
  • organic pigments that can be used in the photosensitive coloring composition of the present invention are as follows. Indicated by index number.
  • Red photosensitive coloring compositions for forming red filter segments include, for example, C Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81 : 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, Red pigments such as 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272, and 279 can be used.
  • a red pigment and an orange pigment can be used in combination in the red light sensitive composition.
  • Yellow photosensitive coloring compositions for forming yellow color filter segments include, for example, C ⁇ Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16 , 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 6 0, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, pan, 104, 106, 108, 109, 110, 113, 1 14, 115, 116, 1 17, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 15 3, 154, 155, 156, dishes, 162, 164 , 166, 167, 168, 169, 170, 171, 172, 1 73, 174, 175, 176, 177,
  • orange photosensitive coloring composition for forming the orange filter segment for example, orange pigments such as Pigment orange 36, 43, 51, 55, 59, 61, 71, 73 are used. Touch with force S.
  • green pigments such as C Pigment Green 7, 10, 36, and 37 can be used.
  • a yellow pigment can be used in combination with the green photosensitive coloring composition.
  • Examples of the blue photosensitive coloring composition for forming the blue filter segment include C ⁇ Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22 Blue pigments such as 60, 64 and 80 can be used. Purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination with the blue photosensitive coloring composition.
  • Examples of the cyan photosensitive coloring composition for forming the cyan filter segment include C ⁇ Pigment Bluel 5: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 mag blue pigment Use with power S.
  • Purple and red pigments such as Pigment Violet 1, 19, CI Pigment Red 81, 144, 146, 177, 169 are used for the magenta photosensitive coloring composition for forming the magenta color filter segment. be able to.
  • a yellow pigment can be used in combination with the magenta photosensitive coloring composition.
  • the black photosensitive coloring composition for forming the black matrix includes, for example, carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically C pigment black 1, 6,
  • the power S can be used with 7, 12, 20, 31 etc.
  • a mixture of a red pigment, a blue pigment, and a green pigment can also be used for the black photosensitive coloring composition.
  • carbon black which is preferred from the viewpoint of price and light shielding property, may be surface-treated with a resin or the like.
  • a blue pigment and a purple pigment can be used together with a black photosensitive coloring composition.
  • carbon black having a specific surface area by the BET method of 50 to 200 m 2 / g is preferable.
  • the black matrix shape is deteriorated.
  • the dispersion aid is excessively adsorbed on the carbon black. This is because it is necessary to add a large amount of a dispersion aid in order to express various physical properties.
  • carbon black having an oil absorption of 120 ml / 100 g or less of dibutyl phthalate (hereinafter referred to as “DBP”) is preferably as small as possible.
  • the average primary particle size of carbon black is preferably 20 to 50 nm. Carbon black with an average primary particle size of less than 20 nm is difficult to disperse at a high concentration, and it is difficult to obtain a photosensitive black composition with good stability over time. This is because the black matrix shape may be deteriorated.
  • inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red beryllium (red iron (III) oxide), cadmium red, ultramarine blue, bituminous, chromium oxide green, cobalt Metal oxide powder such as green, amber, titanium black, synthetic iron black, titanium oxide, iron tetroxide, metal sulfide Examples include powders and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness.
  • the photosensitive coloring composition of the present invention may contain a dye within a range that does not lower the heat resistance for color matching.
  • the coloring agent is sufficiently dispersed in the coloring agent carrier so that the dry film thickness is 0.2 to 10 m on a transparent substrate such as a glass substrate.
  • a solvent In order to make it easy to form filter segments and black matrix by applying to the solvent, it is possible to add a solvent.
  • Solvents include, for example, cyclohexanone, ethyl acetate sorb acetate, butyl acetate sorb acetate, 1-methoxy-2-propyl acetate, diethylene glycoresin methinore ethenore, ethino benzene, ethylene glycono lesino ethenore, xylene, ethyl ce
  • Examples include sorb, methyl n-amyl ketone, propylene glycol monomethyl mono-tertonolene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, and petroleum solvents. These may be used alone or in combination. Use.
  • the photosensitive coloring composition of the present invention comprises one or two or more colorants, together with the photopolymerization initiator, in a colorant carrier and a solvent, a three roll mill, a two roll mill, a sand mill, a kneader, It can be finely dispersed using various dispersing means such as an attritor.
  • a photosensitive coloring composition containing two or more colorants can also be produced by mixing each colorant separately in a colorant carrier and a solvent and finely dispersing them.
  • a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained.
  • the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, a photosensitive coloring composition obtained by dispersing the pigment in a colorant carrier and a solvent using the dispersion aid.
  • a color filter having excellent transparency can be obtained.
  • the dispersion aid can be used in an amount of 0.;! To 40 parts by weight, preferably 0.;! To 30 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition. .
  • the resin-type pigment dispersant has a pigment affinity part having a property of adsorbing to the pigment and a part compatible with the colorant carrier, and adsorbs to the pigment to disperse the pigment in the colorant carrier.
  • Specific examples of the resin-type pigment dispersant include polyurethanes, polycarboxylic acid esters such as polyatarylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkyls.
  • Noreamine salts polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters and their modified products, amides formed by the reaction of poly (lower alkylene imines) with polyesters having free carboxyl groups
  • oil-based dispersants such as (meth) acrylic acid styrene copolymer, (meth) acrylic acid (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polybulualcohol, polybulupyrrolidone, etc.
  • Water-soluble resin, water-soluble polymer compound, polyester System, modified poly Atari rate system, an ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.
  • Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, and lauryl sulfate.
  • a dye derivative is a compound in which a substituent is introduced into an organic dye, and the organic dye is a light yellow aromatic polycyclic compound such as naphthalene or anthraquinone that is not generally called a dye. Is also included.
  • the dye derivative include JP-A-63-305173 and JP-B-57. — Those described in Japanese Patent Publication No. 15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469, etc. can be used alone or in combination of two or more. Can be used.
  • the photosensitive coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time of the composition, and also a silane coupling agent in order to improve adhesion to the transparent substrate.
  • An adhesion improver such as can also be contained.
  • Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and jetylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butyl pyroteol, tetraethylphosphine, and tetraphenyl.
  • Organic phosphines such as phosphine, phosphites and the like can be mentioned.
  • silane coupling agent Byurutorisu (13 methoxyethoxy) silane, Byurueto Kishishiran, Byurushiran such as Bulle trimethoxysilane, I - methacryloxydiethoxyphenyl Cipro built trimethoxysilane, etc. (meth) acrylic silanes, ( 3 -— (3,4 epoxy cyclohexyl)
  • the silane coupling agent can be used in an amount of 0.1 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the photosensitive coloring composition. .
  • the photosensitive coloring composition of the present invention can be prepared in the form of a solvent development type or alkali development type colored resist material.
  • the colored resist material is deposited in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and a solvent.
  • a colorant is dispersed.
  • the colorant is preferably contained in a proportion of 5 to 70% by weight based on the total solid content of the photosensitive coloring composition. More preferably, it is contained in a proportion of 20 to 50% by weight, and the remainder consists essentially of a resinous binder provided by the colorant carrier.
  • the photosensitive coloring composition is obtained by means of centrifugation, sintered filter, membrane filter, etc.
  • coarse particles of 5 ⁇ m or more preferably coarse particles of 1 m or more, more preferably coarse particles of 0.5 ⁇ m or more and mixed dust.
  • the color filter of the present invention comprises a filter segment or a black matrix formed from the photosensitive coloring composition of the present invention on a transparent substrate, and a general color filter has at least one red color.
  • a glass plate such as soda lime glass, low alkali borosilicate glass or non-alkali alumino borosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.
  • a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after paneling.
  • the dry film thickness of the filter segment and the black matrix is preferably 0.2-2; more preferably lO ⁇ m, more preferably 0.2-5111.
  • a vacuum dryer, a competition oven, an IR oven, a hot plate or the like may be used.
  • each color filter segment and black matrix by a photolithography method is performed by the following method. That is, a photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, or the like. Apply to 2-10111. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact or non-contact with the film. Then solvent Alternatively, the developer is not sprayed with a force immersed in an alkaline developer or sprayed.
  • a coating method such as spray coating, spin coating, slit coating, roll coating, or the like. Apply to 2-10111. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact or non-contact with the film. Then solvent Alternatively, the developer is not sprayed with a force immersed in an alkaline developer or sprayed.
  • an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used.
  • an antifoamer and surfactant can also be added to a developing solution.
  • a shower development method As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid buildup) development method, or the like can be applied.
  • the molecular weight of the resin is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography).
  • the mixture was further reacted at 80 ° C for 3 hours, and then a solution in which 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone was added, and further at 80 ° C for 1 hour. The reaction was continued to obtain an acryl resin solution.
  • a solution in which 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone was added, and further at 80 ° C for 1 hour.
  • the reaction was continued to obtain an acryl resin solution.
  • about 2 g of the acrylic resin solution was sampled and heated and dried at 180 ° C for 20 minutes to measure the non-volatile content. Based on the measured value, the non-volatile content was added to the previously synthesized acrylic resin solution. Cyclohexanone was added so as to be 20% by weight.
  • the obtained attalinole resin had a weight average molecular weight of 40000.
  • 1,3-bis (4-methoxymononaphthalene 1 yl) propane 1,3-dione is changed to 1,3-bis (4 ethoxy naphthalene 1 yl) 1 propane 1 1,3-dione Except that, Photopolymerization Initiator A-2 was obtained in the same manner as Photoinitiator A-1.
  • Photopolymerization initiator A-6 was obtained in the same manner as initiator A-1.
  • Photopolymerization initiator A-7 was obtained in the same manner as photopolymerization initiator A-1, except that it was changed to 3-dione.
  • Photopolymerization initiator A-8 was obtained in the same manner as photopolymerization initiator A-1, except that it was changed to naphthalene-1-ylpropane 1,3-dione.
  • Diketopyrrolopyrrole pigment (C ⁇ Pigment Red 254) ("Ilga Four Red B-CF” manufactured by Chinoku 'Specialty' Chemicals) 11.0 parts, Diketopyrrolopyrrole pigment derivative 1.0
  • Eiger mill Eiger Japan "Mini Model M-250 MKIIJ"
  • a halogenated copper phthalocyanine pigment (Cment Pigment Green 36; “Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.) 7. 1 part and a monoazo pigment (C ⁇ Pigment Y ellow 150; manufactured by LANXESS “E4GN — GT ”) 3.
  • a green pigment dispersion was prepared in the same manner as the red pigment dispersion except that 9 parts were used and the pigment derivative was changed to the following triazine pigment derivative.
  • a black pigment dispersion was prepared in the same manner as the red pigment dispersion except that 12.0 parts of carbon black (“MA77” manufactured by Mitsubishi Chemical Corporation) was used as the pigment.
  • Trimethylolpropane tritalylate (Shin Nakamura Chemical "NK Este Nore ATMPTJ")
  • Photoinitiator A Compound A— 1
  • Photoinitiator B Compound A— 2
  • Photoinitiator C Compound A— 3
  • Photoinitiator D Compound A— 4
  • Photoinitiator E Compound A— 5
  • Photoinitiator F Compound A— 6
  • Photoinitiator G Compound A— 7
  • Photoinitiator H Compound A— 8
  • Photoinitiator I 2 Benzyl 2-dimethylamino-14 morpholinophyl) 1-butanone 1 (“Irgacure 369” manufactured by Chinoku “Specialty” Chemicals)
  • the formed filter segment or black matrix pattern The sensitivity of the resist was determined by the amount of irradiation exposure completed according to the image dimensions.
  • the rank of evaluation is as follows.
  • the shape of the formed filter segment or black matrix pattern was evaluated by (1) pattern linearity and (2) pattern cross-sectional shape.
  • the linearity (1) of the pattern was evaluated by observation with an optical microscope.
  • the rank of evaluation is as follows.
  • the cross-sectional shape (2) of the pattern was evaluated by observation with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • ⁇ Forward tapered shape.
  • ⁇ Non-tapered shape.
  • Film thickness Film thickness of each color filter segment and black matrix
  • Colorant content Ratio of colorant based on the total solid content of the photosensitive coloring composition
  • I / M (Weight of photoinitiator) / (Weight of transparent resin precursor)
  • I / M (total weight of photopolymerization initiator and sensitizer) / (weight of transparent resin precursor).
  • the photosensitive coloring composition of 22 had high sensitivity, and the linearity and cross-sectional shape of the obtained pattern were also good.
  • a in the general formula (1) is a group represented by the substituted or unsubstituted general formula (2)
  • B is a group represented by the substituted or unsubstituted general formula (3).
  • the photosensitive coloring compositions of Examples 8 to 22 using the compound had higher sensitivity and good solubility in solvents.
  • the photosensitive coloring composition of the present invention has a high colorant content or forms each color filter segment and black matrix by using a specific compound as a photopolymerization initiator. Even if the film thickness is large, it is possible to form high-sensitivity and excellent color filter segments and black matrix patterns. Therefore, a high quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

Abstract

L'invention concerne une composition de coloration photosensible comportant : un support pour un agent de coloration, qui comporte une résine transparente et un précurseur de celle-ci ; un agent de coloration ; et un initiateur de photopolymérisation représenté par la formule générale (1). Un filtre de couleur comporte un substrat transparent et un segment de filtre ou de matrice noire faite avec la composition de coloration photosensible. [Formule Générale (1)], dans laquelle A et B représentent indépendamment un groupe hétérocyclique substitué ou non substitué ou un groupe hydrocarboné polycyclique réuni par fusion substitué ou non substitué ; et X représente un résidu organique univalent.
PCT/JP2007/068082 2006-09-22 2007-09-18 Composition de coloration photosensible et filtre de couleur WO2008035671A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2105792A1 (fr) * 2008-03-28 2009-09-30 FUJIFILM Corporation Composition de résine photosensible, filtre de couleur opaque à la lumière, son procédé de production, et capteur d'image
EP2169463A3 (fr) * 2008-09-29 2010-09-15 FUJIFILM Corporation Composition durcissable colorée, filtre de couleur, et son procédé de production
WO2020252628A1 (fr) * 2019-06-17 2020-12-24 湖北固润科技股份有限公司 Photo-initiateurs à base d'ester d'oxime contenant une structure cyclique hétéroaromatique à cinq chaînons, leur préparation et leur utilisation

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5315909B2 (ja) * 2008-10-08 2013-10-16 東洋インキＳｃホールディングス株式会社 重合性組成物およびそれを用いたネガ型レジストおよびそれを用いた画像パターン形成方法。
JP2010128344A (ja) * 2008-11-28 2010-06-10 Fujifilm Corp 着色硬化性組成物、カラーフィルタ、および液晶表示装置
JP5493381B2 (ja) * 2009-02-20 2014-05-14 東洋インキＳｃホールディングス株式会社 カラーフィルタ用着色組成物、及びそれを用いたカラーフィルタ
JP6621643B2 (ja) * 2015-10-22 2019-12-18 株式会社Adeka オキシムエステル化合物及び該化合物を含有する重合開始剤

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07278214A (ja) * 1994-02-15 1995-10-24 Hitachi Chem Co Ltd 光開始剤、感光性組成物、感光材料およびパターンの製造法
JP2001233842A (ja) * 1999-12-15 2001-08-28 Ciba Specialty Chem Holding Inc オキシムエステルの光開始剤
WO2004050653A2 (fr) * 2002-12-03 2004-06-17 Ciba Specialty Chemicals Holding Inc. Photo-initiateurs a base d'ester d'oxime comportant des groupes heteroaromatiques
JP2005187678A (ja) * 2003-12-26 2005-07-14 Toyo Ink Mfg Co Ltd 光重合性組成物
JP2006162784A (ja) * 2004-12-03 2006-06-22 Toppan Printing Co Ltd 感光性着色組成物、及びそれを用いたカラーフィルタ
JP2007210991A (ja) * 2006-01-13 2007-08-23 Toyo Ink Mfg Co Ltd オキシムエステル化合物、ラジカル重合開始剤および重合性組成物
JP2007241231A (ja) * 2006-02-10 2007-09-20 Toyo Ink Mfg Co Ltd 重合性組成物およびそれを用いたネガ型レジストおよびそれを用いた画像パターン形成方法。

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2129438B (en) * 1982-10-29 1987-04-29 Hri Inc Coal slurry drying and deoxygenating process for coal liquefaction
JPS60147692A (ja) * 1984-01-13 1985-08-03 株式会社東芝 シュラウドヘッドの耐震装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07278214A (ja) * 1994-02-15 1995-10-24 Hitachi Chem Co Ltd 光開始剤、感光性組成物、感光材料およびパターンの製造法
JP2001233842A (ja) * 1999-12-15 2001-08-28 Ciba Specialty Chem Holding Inc オキシムエステルの光開始剤
WO2004050653A2 (fr) * 2002-12-03 2004-06-17 Ciba Specialty Chemicals Holding Inc. Photo-initiateurs a base d'ester d'oxime comportant des groupes heteroaromatiques
JP2005187678A (ja) * 2003-12-26 2005-07-14 Toyo Ink Mfg Co Ltd 光重合性組成物
JP2006162784A (ja) * 2004-12-03 2006-06-22 Toppan Printing Co Ltd 感光性着色組成物、及びそれを用いたカラーフィルタ
JP2007210991A (ja) * 2006-01-13 2007-08-23 Toyo Ink Mfg Co Ltd オキシムエステル化合物、ラジカル重合開始剤および重合性組成物
JP2007241231A (ja) * 2006-02-10 2007-09-20 Toyo Ink Mfg Co Ltd 重合性組成物およびそれを用いたネガ型レジストおよびそれを用いた画像パターン形成方法。

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2105792A1 (fr) * 2008-03-28 2009-09-30 FUJIFILM Corporation Composition de résine photosensible, filtre de couleur opaque à la lumière, son procédé de production, et capteur d'image
US8110324B2 (en) 2008-03-28 2012-02-07 Fujifilm Corporation Photosensitive resin composition, light-shielding color filter and production process therefor, and image sensor
EP2169463A3 (fr) * 2008-09-29 2010-09-15 FUJIFILM Corporation Composition durcissable colorée, filtre de couleur, et son procédé de production
WO2020252628A1 (fr) * 2019-06-17 2020-12-24 湖北固润科技股份有限公司 Photo-initiateurs à base d'ester d'oxime contenant une structure cyclique hétéroaromatique à cinq chaînons, leur préparation et leur utilisation

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