WO2013146322A1 - Colored curable composition, color filter and method for producing color filter, and display device - Google Patents

Colored curable composition, color filter and method for producing color filter, and display device Download PDF

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WO2013146322A1
WO2013146322A1 PCT/JP2013/057293 JP2013057293W WO2013146322A1 WO 2013146322 A1 WO2013146322 A1 WO 2013146322A1 JP 2013057293 W JP2013057293 W JP 2013057293W WO 2013146322 A1 WO2013146322 A1 WO 2013146322A1
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group
carbon atoms
curable composition
colored curable
colored
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PCT/JP2013/057293
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French (fr)
Japanese (ja)
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晃男 片山
一成 八木
新居　一巳
福重　裕一
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments

Definitions

  • the present invention relates to a colored curable composition containing a dye as a coloring compound, a color filter, a method for producing a color filter, and a display device.
  • a pigment dispersion method is widely used as one of methods for producing a color filter used for a liquid crystal display device, a solid-state imaging device, or the like.
  • a pigment dispersion method there is a method of producing a color filter by a photolithography method using a colored curable composition in which a pigment is dispersed in various photosensitive compositions. This method is stable against light and heat because it contains a pigment, and is patterned by a photolithographic method, so that the positional accuracy is sufficiently secured, and used for a liquid crystal display device, an EL display device, etc.
  • the method is suitable for producing a color filter or the like.
  • coloring compounds used in the production of color filters not only pigments but also coloring compounds other than pigments such as dyes have been widely studied.
  • dyes compounds having a wide variety of dye bases such as pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes, triarylmethane dyes are known (for example, Japanese Patent No. 3387541, JP 2009-265641 and JP-A 2009-186657).
  • an object of the present invention is to provide a colored curable composition useful for forming a colored pattern of a color filter, which can form a colored cured film having high contrast while increasing luminance.
  • the present invention also provides a color filter capable of displaying a high-brightness and high-contrast image using the colored curable composition of the present invention, a method for producing the same, and an image quality using the color filter. It is an object to provide a display device capable of displaying a good image.
  • R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or a group having 6 to 10 carbon atoms.
  • R 5 represents an aromatic hydrocarbon group
  • R 5 represents —SO 3 ⁇ , —SO 3 H, —SO 3 M, —CO 2 H, —CO 2 R 6 , —SO 3 R 6 , —SO 2 NHR 8 , Or —SO 2 NR 8 R 9 , where R 6 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and R 8 and R 9 each independently represent a hydrogen atom or a straight chain having 1 to 10 carbon atoms.
  • a branched alkyl group, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic heterocyclic group having 5 to 10 carbon atoms, and R 8 and R 9 are They may combine with each other to form a heterocyclic ring having 1 to 10 carbon atoms, and M represents a sodium atom or a potassium atom.
  • R 101 , R 102 , R 103 , R 104 , R 105 , and R 106 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or Represents an aromatic hydrocarbon group having 6 to 10 carbon atoms
  • R 107 and R 108 each independently represent a hydrogen atom or a saturated hydrocarbon group having 4 to 8 carbon atoms
  • R 107 and R 108 are R 109 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms
  • X represents a halogen atom, BF 4 , PF 6 , ClO 4 , N (SO 2 CF 3 ) 2 or ArSO 3
  • Ar represents an aromatic hydrocarbon group having 6 to 10 carbon atoms
  • a represents an integer of 0 or 1.
  • Z 1 , Z 2 , Z 3 and Z 4 are all N, or any one of Z 1 and Z 3 , Z 2 and Z 4 is N
  • Each of the other groups represents C—R, each R independently representing a hydrogen atom, an alkyl group, or an aryl group
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 are each independently an alkyl group, alkenyl group, aryl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, halogen atom, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group Carbamoyl group, sulfamoyl group, acyl group, silyloxy group, cyano group, nitro group, or heterocyclic group, A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 Each May be
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M are the same as A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M are respectively synonymous.
  • the content of the compound represented by the general formula (II) (B) is from 0.1% by mass to 50% by mass with respect to the total amount of the colored compounds.
  • a 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 all form a ring structure.
  • the total content of the coloring compound is any one of ⁇ 1> to ⁇ 5>, in which the total solid content of the colored curable composition is 0.2% by mass or more and 50% by mass or less.
  • a color filter comprising a colored film obtained by curing the colored curable composition according to any one of ⁇ 1> to ⁇ 6>.
  • a method for producing a color filter comprising: an exposure step of exposing in a similar manner; and a development step of developing a colored layer after exposure to form a colored pattern.
  • a display device comprising the color filter according to ⁇ 7> or the color filter obtained by the production method according to ⁇ 8>.
  • the present invention provides at least one dye selected from the group consisting of a xanthene dye represented by the general formula (I-1) and a triarylmethane compound represented by the general formula (I-2) as the coloring compound.
  • a compound and a porphyrin compound represented by the general formula (II) are combined. Thereby, the quenching performance is improved, and a colored cured film having high contrast and high brightness can be formed.
  • luminance can be provided.
  • a color filter capable of displaying a high-brightness and high-contrast image, a manufacturing method thereof, and the color filter are used.
  • a display device capable of displaying an image with good image quality can be provided.
  • the colored curable composition of the present invention comprises (A) one or more dye compounds selected from the compounds represented by the general formulas (I-1) and (I-2) as a coloring compound, and (B) And a porphyrin compound represented by the general formula (II).
  • the composition further contains (C) a polymerizable compound and (D) a photopolymerization initiator and has photosensitivity.
  • the colored curable composition according to the present invention includes (A) one or more dye compounds selected from the compounds represented by formulas (I-1) and (I-2), (B) In addition to the porphyrin compound represented by the general formula (II), other colored compounds such as other organic dyes and pigments may be included as long as the effects of the present invention are not impaired.
  • organic dyes examples include pyrazole azo, anilinoazo, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, squarylium And dyes such as phthalocyanine, benzopyran, and indigo.
  • the colored curable composition of the present invention may further contain a binder resin such as an alkali-soluble binder, an organic solvent, and various additives as long as the effects of the present invention are not impaired as necessary.
  • the colored curable composition of the present invention may be simply referred to as “colored composition of the present invention” or “colored composition”.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the “alkyl group” is a general term for “linear, branched and cyclic” alkyl groups.
  • the substituent (atomic group) in this specification is used by the meaning including the thing which has an unsubstituted thing and a substituent further. That is, in the present specification, the “alkyl group” is used in a meaning including an unsubstituted alkyl group and a substituted alkyl group, and the same applies to other substituents.
  • the colored curable composition of the present invention comprises (A) one or more dye compounds selected from the group consisting of compounds represented by general formulas (I-1) and (I-2), and (B) general And a porphyrin compound represented by the formula (II).
  • the colored compounds will be sequentially described.
  • the colored compound of the present invention comprises (A) one or more pigment compounds selected from the group consisting of compounds represented by formulas (I-1) and (I-2) (hereinafter referred to as “specific dye (A ) ").
  • the colored curable composition according to the present invention contains at least one xanthene dye represented by the following general formula (I-1) so that the present invention is applied when subjected to alkali treatment (for example, alkali development after exposure).
  • alkali treatment for example, alkali development after exposure
  • the colored curable composition exhibits excellent alkali solubility.
  • R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic group having 6 to 10 carbon atoms. Represents a group hydrocarbon group.
  • saturated hydrocarbon group having 1 to 10 carbon atoms examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, 2-ethylhexyl.
  • preferred is an alkyl group having 1 to 9 carbon atoms, and more preferred is an alkyl group having 1 to 8 carbon atoms.
  • Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include groups such as phenyl and naphthyl.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms includes a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR 6 , —SO 3 — , —SO 3 H, —SO 3 M, — It may be substituted with CO 2 H, —CO 2 R 6 , —SO 3 R 6 , —SO 2 NHR 8 or —SO 2 NR 8 R 9 .
  • R 6 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and is synonymous with the “saturated hydrocarbon group having 1 to 10 carbon atoms” in the above R 1 to R 4 , and the preferred embodiment is also the same. Details of R 8 , R 9 , and M will be described later.
  • Examples of the halogen atom include fluorine, chlorine, bromine and the like.
  • Examples of the “—SO 3 R 6 ” include methanesulfonyl, ethanesulfonyl, hexanesulfonyl, decanesulfonyl and the like.
  • Examples of the “—CO 2 R 6 ” include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl.
  • R 8 and R 9 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, Alternatively, it represents an aromatic heterocyclic group having 5 to 10 carbon atoms, and R 8 and R 9 may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms.
  • the aromatic hydrocarbon group and the aromatic heterocyclic group represented by R 8 and R 9 are —OH, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OR 6 , —NO 2 , —CH ⁇ CH 2 , —CH ⁇ CHR 6 , or a halogen atom may be substituted.
  • R 6 represents a saturated hydrocarbon group having 1 to 10 carbon atoms.
  • the saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the “saturated hydrocarbon group having 1 to 10 carbon atoms” in R 1 to R 4 , and the preferred embodiment is also the same.
  • the linear or branched alkyl group having 1 to 10 carbon atoms represented by R 8 and R 9 may be unsubstituted or substituted, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Examples include pentyl, isopentyl, hexyl, 2-ethylhexyl, 1,5-dimethylhexyl, octyl and the like. Of these, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable.
  • the cycloalkyl group having 3 to 30 carbon atoms represented by R 8 and R 9 may be unsubstituted or substituted, and examples thereof include groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. Is mentioned. Of these, a cycloalkyl group having 3 to 15 carbon atoms is preferable.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 8 and R 9 include groups such as phenyl and naphthyl.
  • Examples of the aromatic heterocyclic group having 5 to 10 carbon atoms represented by R 8 and R 9 include aromatic heterocyclic groups having an oxygen atom, a nitrogen atom, etc.
  • hetero atom such as a pyrrole ring group and a pyrazine ring.
  • the linear or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms may be substituted.
  • substituent when they are substituted include a hydroxyl group, a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aromatic heterocyclic group having 5 to 10 carbon atoms, —CH ⁇ CH 2 , Or —CH ⁇ CHR 6 (R 6 : a saturated hydrocarbon group having 1 to 10 carbon atoms).
  • the methylene group contained in the cycloalkyl group may be substituted with an oxygen atom, a carbonyl group, or —NR 6 — (R 6 : a saturated hydrocarbon group having 1 to 10 carbon atoms).
  • the saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the “saturated hydrocarbon group having 1 to 10 carbon atoms” in R 1 to R 4 , and the preferred embodiment is also the same.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted.
  • substituent in the case of substitution for example, ethyl, propyl, phenyl, dimethylphenyl, —SO 3 R 6 (R 6 : saturated hydrocarbon group having 1 to 10 carbon atoms) or —SO 2 NHR 8 is preferable. .
  • Examples of the substituted aromatic hydrocarbon group having 6 to 10 carbon atoms include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, hexylphenyl, decanylphenyl, fluorophenyl, chlorophenyl, bromophenyl, hydroxyphenyl, Examples include methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decanyloxyphenyl, and trifluoromethylphenyl.
  • the heterocyclic ring having 1 to 10 carbon atoms is a saturated hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group , An aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic heterocyclic group having 5 to 10 carbon atoms may be substituted.
  • R 8 and R 9 are each a branched alkyl group having 6 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, carbon A hydroxyl group-containing alkyl group having 2 to 8 carbon atoms, a hydroxyl group-containing aryl group having 2 to 8 carbon atoms, or an alkoxyl group-containing alkyl group having 2 to 8 carbon atoms, an alkoxyl group-containing aryl group having 2 to 8 carbon atoms is preferable, and 2-ethylhexyl is preferable. Particularly preferred.
  • Examples of the “—SO 2 NHR 8 ” include sulfamoyl, methanesulfamoyl, ethanesulfamoyl, propanesulfamoyl, isopropanesulfamoyl, butanesulfamoyl, isobutanesulfamoyl, pentanessulfamoyl, Isopentanesulfamoyl, neopentanesulfamoyl, cyclopentanesulfamoyl, hexanesulfamoyl, cyclohexanesulfamoyl, heptanesulfamoyl, cycloheptanesulfamoyl, octanessulfamoyl, 2-ethylhexanesulfamoyl 1,5-dimethylhexanesulfamoyl, cyclooctanesulfamoyl, nonanesul
  • examples of the “—SO 2 NHR 8 ” and “—SO 2 NR 8 R 9 ” further include groups represented by the following structural formulas.
  • X 1 to X 3 in the structural formulas shown below are as follows.
  • X 1 represents a halogen atom.
  • Examples of the halogen atom for X 1 include a fluorine atom, a chlorine atom, and a bromine atom.
  • X 2 represents an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a halogen atom, or a nitro group, and the alkyl group and the alkoxy group may be substituted with a halogen atom.
  • Examples of the halogen atom for X 2 include a fluorine atom, a chlorine atom and a bromine atom.
  • Examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, propyl, isopropyl, perfluoromethyl and the like.
  • Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy, propoxy and the like.
  • X 3 represents an alkyl group having 1 to 3 carbon atoms or an alkoxyl group having 1 to 3 carbon atoms, and the alkyl group and the alkoxy group may be substituted with a halogen atom.
  • alkyl group having 1 to 3 carbon atoms examples include methyl, ethyl, propyl, isopropyl, perfluoromethyl and the like.
  • alkoxy group having 1 to 3 carbon atoms examples include methoxy, ethoxy, propoxy and the like.
  • M represents a sodium atom or a potassium atom.
  • R 5 represents —SO 3 — , —SO 3 H, —SO 3 M, —CO 2 H, —CO 2 R 6 , —SO 3 R 6 , —SO 2 NHR 8 , or —SO 2 NR 8 R 9.
  • R 6 , R 8 , R 9 and M are as described above, and the preferred embodiments are also the same.
  • R 5 is —CO 2 H, ethyloxycarbonyl, sulfoxyl, 2-ethylhexyloxypropane sulfamoyl, 1,5-dimethylhexanesulfamoyl, 3-phenyl-1-methylpropanesulfamoyl, iso
  • An embodiment that is propoxypropane sulfamoyl is preferred.
  • M represents an integer of 0 to 5.
  • n1, n2, n3 and n4 each independently represents 0 or 1.
  • X represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
  • a represents an integer of 0 or 1.
  • R 1 and R 2 or at least one of R 3 and R 4 is an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferable. More preferably, at least one of R 1 and R 2 and at least one of R 3 and R 4 are an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, An embodiment in which at least one of R 1 and R 2 and at least one of R 3 and R 4 is an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred.
  • the compound represented by the formula (I-1-5) includes a salt thereof.
  • R 11 to R 14 each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms includes a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR 6 , —SO 3 — , —SO 3 H, —SO 3 Na, — It may be substituted with CO 2 H, —CO 2 R 6 , —SO 3 R 6 , —SO 2 NHR 8 or —SO 2 NR 8 R 9 .
  • R 15 represents a hydrogen atom, —SO 3 ⁇ , —SO 3 H, —SO 2 NHR 8 or —SO 2 NR 8 R 9
  • R 16 represents —SO 3 ⁇ , —SO 3 H, —SO 2 NHR 8 or —SO 2 NR 8 R 9
  • the saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the saturated hydrocarbon group having 1 to 10 carbon atoms represented by R 6 in the general formula (I-1), and preferred embodiments thereof are also the same.
  • R 11 to R 14 have the same meanings as R 1 to R 4 in the compound represented by the general formula (I-1), and preferred embodiments thereof are also the same.
  • R 6 , R 8 , R 9 , X, and a have the same meanings as R 6 , R 8 , R 9 , X, and a of the compound represented by the general formula (I-1). It is the same.
  • R 21 to R 24 each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms includes a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR 26 , —SO 3 — , —SO 3 Na, —CO 2 H, — It may be substituted with CO 2 R 26 , —SO 3 H, —SO 3 R 26, or —SO 2 NHR 28 .
  • R 25 represents —SO 3 — , —SO 3 Na, —CO 2 H, —CO 2 R 26 , —SO 3 H, or SO 2 NHR 28
  • R 26 represents a saturated carbonization having 1 to 10 carbon atoms.
  • R 28 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • the saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the saturated hydrocarbon group having 1 to 10 carbon atoms represented by R 6 in the general formula (I-1), and the preferred embodiment is also the same. It may be substituted with OR 26 or a halogen atom.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms has the same meaning as the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 1 to R 4 in the general formula (I-1). It is the same, and may be substituted by -R 26 or -OR 26 .
  • R 21 to R 24 have the same meanings as R 1 to R 4 in the compound represented by the general formula (I-1), and preferred embodiments thereof are also the same.
  • M, X, and a have the same meanings as m, X, and a in (I-1), respectively, and the preferred embodiments are also the same.
  • R 31 and R 32 each independently represent a phenyl group.
  • the phenyl group may be substituted with a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OR 26 , —CO 2 R 26 , —SO 3 R 26, or —SO 2 NHR 28 .
  • R 33 represents —SO 3 — or —SO 2 NHR 28
  • R 34 represents a hydrogen atom, —SO 3 — or —SO 2 NHR 28 .
  • R 26, R 28, X and a are the formula (I-1-2) has the same meaning as R 26, R 28, X and a of, preferred embodiment is also the same.
  • R 41 and R 42 each independently represent a phenyl group.
  • the phenyl group may be substituted with R 26 or —SO 2 NHR 28 .
  • R 43 represents —SO 3 — or —SO 2 NHR 28 .
  • R 26, R 28, X and a are the formula (I-1-2) has the same meaning as R 26, R 28, X and a of, preferred embodiment is also the same.
  • R 50 , R 51 , R 52 , and R 53 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 54 , R 55 , and R 56 each independently represents a sulfo group or a group represented by the following formula (a1).
  • R 57 represents an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, An alkyl group having 2 to 12 carbon atoms substituted with an alkoxyl group having 2 to 12, an alkylcarboxylalkyl group represented by the following formula (a2), an alkyloxycarbonylalkyl group represented by the following formula (a3), or carbon It represents a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms, or an alkyl group with 1 to 20 carbon atoms substituted with a phenyl group.
  • R 60 CO—O—R 61 — Formula (a2)
  • R 70 O—CO—R 71 ⁇ ...
  • Formula (a3) [In Formula (a2) and Formula (a3), R 60 and R 70 each independently represents an alkyl group having 2 to 12 carbon atoms, and R 61 and R 71 each independently represent 2 to 12 carbon atoms. Represents an alkylene group. ]
  • examples of the alkyl group having 1 to 3 carbon atoms represented by R 50 , R 51 , R 52 , and R 53 include a methyl group, an ethyl group, and a propyl group. Can be mentioned.
  • Examples of the alkyl group having 2 to 20 carbon atoms represented by R 57 include an ethyl group, a propyl group, an n-hexyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, and a 2-ethylhexyl group. 1,3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group and the like.
  • Examples of the “cyclohexyl alkyl group having 2 to 12 carbon atoms in the alkyl chain” represented by R 57 include a cyclohexylethyl group, a 3-cyclohexylpropyl group, and an 8-cyclohexyloctyl group.
  • Examples of the “alkyl cycloalkyl group having 1 to 4 carbon atoms in the alkyl chain” represented by R 57 include 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2- (n-butyl) cyclohexyl group and the like. Can be mentioned.
  • Examples of the “alkyl group having 2 to 12 carbon atoms substituted by an alkoxyl group having 2 to 12 carbon atoms” represented by R 57 include a 3-ethoxy-n-propyl group, a propoxypropyl group, and 4-propoxy-n. -Butyl group, 3-methyl-n-hexyloxyethyl group, 3- (2-ethylhexyloxy) propyl group and the like can be mentioned.
  • Examples of the “phenyl group substituted with an alkyl group having 1 to 20 carbon atoms” represented by R 57 include an o-isopropylphenyl group.
  • Examples of the “alkyl group having 1 to 20 carbon atoms substituted with a phenyl group” represented by R 57 include a DL-1-phenylethyl group, a benzyl group, and a 3-phenyl-n-butyl group. It is done.
  • Examples of the alkyl group having 2 to 12 carbon atoms in R 60 and R 70 include an ethyl group, a propyl group, an n-hexyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, 2- Examples include ethylhexyl group, 1,3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group.
  • Examples of the alkylene group having 2 to 12 carbon atoms in R 61 and R 71 include a dimethylene group and a hexamethylene group.
  • the compound represented by the formula (I-1-5) may be a salt.
  • the salt include alkali metal salts of alkali metals such as sodium and potassium, and amine salts such as triethylamine and 1-amino-3-phenylbutane.
  • amine salts such as triethylamine and 1-amino-3-phenylbutane.
  • R 54 , R 55 , and R 56 of the compound represented by the formula (I-1-5) are sulfo groups, a salt is formed at the sulfo group. .
  • Specific examples of the compound represented by the formula (I-1-5) include C.I. I. Acid Red 289 and the like.
  • the compounds represented by the above formulas (I-1-1) to (I-1-5) may be used singly or in combination of two or more.
  • the xanthene dye represented by the general formula (I-1) include the following compounds (1) to (2) and C.I. I. Acid Red 289, and the following compounds (1a) to (1f) and the like can be mentioned.
  • the xanthene dye represented by the general formula (I-1) may have a tautomer, for example, the compound (1b) is a tautomer of the compound (1b-1). .
  • Rb and Rc each independently represent a hydrogen atom, —SO 3 ⁇ , —CO 2 H or —SO 2 NHRa.
  • Ra represents 2-ethylhexyl.
  • X and a are as described above.
  • Rd, Re and Rf each independently represent —SO 3 ⁇ , —SO 3 Na or —SO 2 NHRa.
  • Ra represents 2-ethylhexyl.
  • Rg, Rh and Ri each independently represent a hydrogen atom, —SO 3 ⁇ , —SO 3 H or —SO 2 NHRa.
  • Ra represents 2-ethylhexyl.
  • the compound represented by the general formula (I-1) is obtained by, for example, chlorinating a dye or dye intermediate containing —SO 3 H by a conventional method, and obtaining the obtained dye or dye intermediate containing —SO 2 Cl. It can be produced by reacting with an amine represented by R 8 —NH 2 .
  • the dye produced by the method described in JP-A-3-78702 can also be produced by chlorination in the same manner as described above and then reacting with an amine.
  • the content of the xanthene dye represented by the general formula (I-1) in the colored curable composition is 0.1% by mass to 40.0% by mass with respect to the solid content of the colored curable composition. And more preferably 1.0 to 30.0% by mass.
  • a desired color density and hue can be obtained when the content of the xanthene dye is 0.1% by mass or more.
  • content of a xanthene dye is 40.0 mass% or less, it is advantageous to ensuring the relative amount of hardening components, such as a resin component and a polymeric compound.
  • R 101 , R 102 , R 103 , R 104 , R 105 , and R 106 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or carbon Represents an aromatic hydrocarbon group of formula 6-10.
  • saturated hydrocarbon group having 1 to 10 carbon atoms examples include alkyl groups (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, Octyl, 2-ethylhexyl, cyclooctyl, nonyl, decanyl, tricyclodecanyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, ethoxypropyl, etc.), alkenyl group (for example, butenyl group, Straight-chain alkenyl groups such as hexenyl group, pentenyl group, octenyl group).
  • Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include groups such as phenyl and naphthyl.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms is a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR 111 , —SO 3 —. , —SO 3 H, —SO 3 M, —CO 2 H, —CO 2 R 111 , —SO 3 R 111 , —SO 2 NHR 111 may be substituted.
  • R 111 represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or a saturated hydrocarbon group having 1 to 10 carbon atoms, and the “aromatic hydrocarbon group having 6 to 10 carbon atoms” in the above R 101 to R 106 , “Saturated hydrocarbon group having 1 to 10 carbon atoms”, and preferred embodiments are also the same. Further, the “aromatic hydrocarbon group having 6 to 10 carbon atoms” and the “saturated hydrocarbon group having 1 to 10 carbon atoms” represented by R 111 may be substituted with a halogen atom. The methylene group contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an oxygen atom, a carbonyl group, or —NR 111 —.
  • Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
  • Examples of the “—SO 3 R 111 ” include methanesulfonyl, ethanesulfonyl, hexanesulfonyl, decanesulfonyl and the like.
  • Examples of the “—CO 2 R 111 ” include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl.
  • Examples of the “—SO 2 NHR 111 ” include sulfamoyl, methanesulfamoyl, ethanesulfamoyl, propanesulfamoyl, isopropanesulfamoyl, butanesulfamoyl, isobutanesulfamoyl, pentanessulfamoyl, Isopentanesulfamoyl, neopentanesulfamoyl, cyclopentanesulfamoyl, hexanesulfamoyl, cyclohexanesulfamoyl, heptanesulfamoyl, cycloheptanesulfamoyl, octanessulfamoyl, 2-ethylhexanesulfamoyl 1,5-dimethylhexanesulfamoyl, cyclooctanesulfamoyl, nonanes
  • Preferred substituents when the aromatic hydrocarbon group having 6 to 10 carbon atoms is substituted include ethyl, propyl, phenyl, dimethylphenyl, —SO 3 R 111 , —SO 2 NHR 111 and the like. —SO 3 R 111 and —SO 2 NHR 111 are as described above.
  • substituted aromatic hydrocarbon group having 6 to 10 carbon atoms include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, hexylphenyl, decanylphenyl, fluorophenyl, chlorophenyl, bromophenyl, and hydroxyphenyl. , Methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decanyloxyphenyl, trifluoromethylphenyl and the like.
  • M represents a sodium atom or a potassium atom.
  • R 107 and R 108 each independently represents a hydrogen atom or a saturated hydrocarbon group having 4 to 8 carbon atoms.
  • saturated hydrocarbon group having 4 to 8 carbon atoms include butyl group, heptyl group, hexyl group, octyl group and the like.
  • R 107 and R 108 may be bonded to each other to form an aromatic hydrocarbon ring.
  • Preferred examples of the aromatic hydrocarbon ring in this case include a benzene ring and a naphthalene ring.
  • R 109 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.
  • the saturated hydrocarbon group having 1 to 10 carbon atoms represented by R 109 has the same meaning as the “saturated hydrocarbon group having 1 to 10 carbon atoms” in R 101 to R 106 .
  • R 109 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • X represents a halogen atom, BF 4 , PF 6 , ClO 4 , N (SO 2 CF 3 ) 2 , or ArSO 3 .
  • Ar in ArSO 3 represents an aromatic hydrocarbon group having 6 to 10 carbon atoms.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms has the same meaning as the “aromatic hydrocarbon group having 6 to 10 carbon atoms” in R 101 to R 106 , and the preferred embodiment is also the same.
  • halogen atom represented by X examples include a fluorine atom, a chlorine atom, and a bromine atom.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by Ar is synonymous with the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 101 to R 106 , and the preferred embodiments are also the same.
  • the aromatic hydrocarbon group having 6 to 10 carbon atoms is a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR 111 , —SO 3 —.
  • —SO 3 H, —SO 3 M, —CO 2 H, —CO 2 R 111 , —SO 3 R 111 , —SO 2 NHR 111 , —SO 2 N (R 111 ) 2 may be substituted. .
  • Ar a phenyl group and a naphthyl group are preferable.
  • R 206 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, which may be unsubstituted or substituted.
  • the saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the “saturated hydrocarbon group having 1 to 10 carbon atoms” in R 101 to R 106 of the general formula (I-2).
  • R 206 is preferably an alkyl group having 4 to 20 carbon atoms and an alkenyl group having 4 to 20 carbon atoms, which may be unsubstituted or substituted.
  • R 209 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • Y represents SO 3 H or SO 3 M
  • M represents a sodium atom or a potassium atom.
  • R 206 is, for example, a linear alkyl group having 4 to 10 carbon atoms such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isobutyl group, isopentyl group, isohexyl group, 2 -Branched alkyl groups having 4 to 10 carbon atoms such as ethylhexyl group.
  • examples of the substituted alkyl group include a hydroxy-substituted alkyl group, a cyano-substituted alkyl group, a halogen-substituted alkyl group, an alkoxy-substituted alkyl group, and an alkoxyalkoxy-substituted alkyl group.
  • examples of the hydroxy-substituted alkyl group include a 4-hydroxybutyl group.
  • Examples of the cyano-substituted alkyl group include cyano-substituted alkyl groups having 4 to 6 carbon atoms such as 4-cyanobutyl group and 6-cyanohexyl.
  • Examples of the halogen atom-substituted alkyl group include halogen atom-substituted alkyl groups having 4 to 6 carbon atoms such as a 4-chlorobutyl group, a 5-bromopentyl group, and a hexafluorobutyl group.
  • alkoxy-substituted alkyl group examples include 2-ethoxyethyl group, 2- (n) propoxyethyl group, 2- (iso) propoxyethyl group, 2- (n) butoxyethyl group, 2- (iso) butoxyethyl group, (C1-C8) alkoxy substituted (C2-C4) alkyl groups such as 2- (2-ethylhexyloxy) ethyl group, 3-methoxypropyl group, 4-methoxybutyl group, 2-methoxypropyl group It is done.
  • alkoxyalkoxy-substituted alkyl group examples include 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2- (n) propoxyethoxy) ethyl group, 2- (2- (Iso) propoxyethoxy) ethyl group, 2- (2- (n) butoxyethoxy) ethyl group, 2- (2- (iso) butoxyethoxy) ethyl group, 2- ⁇ 2- (2-ethylhexyloxy) ethoxy ⁇
  • Examples include (1-C8) alkoxy (C1-C8) alkoxy-substituted (C2-C4) alkyl groups such as ethyl group.
  • alkenyl group represented by R 206 for example, butenyl, hexenyl, pentenyl group, and a linear alkenyl group such as octenyl groups.
  • R 206 is an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, or the like.
  • a linear alkyl group is an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, or the like.
  • R 209 includes a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.
  • the compound represented by the general formula (I-2-1) can be obtained by alkylating or alkenylating a known dye by a known method.
  • C.I. I. Acid Blue 83 and C.I. I. It can be obtained by alkylating or alkenylating the —NH— moiety in the molecular structure of Acid Blue90.
  • a method of alkylation or alkenylation a method of reacting an alkyl halide (alkene) with an alkali in a solvent and a method of using an alkyl tosyl (alkenyl) ester and an alkali are common.
  • R 301 , R 302 , R 303 , and R 304 each independently represents an alkyl group.
  • R 305 represents an alkyl group or an aryl group which may have a substituent.
  • X ⁇ represents Cl ⁇ , BF 4 ⁇ , PF 6 ⁇ , or ArSO 3 ⁇ .
  • Ar represents an aromatic hydrocarbon group, and the aromatic hydrocarbon group may be substituted with an amino group which may have a substituent.
  • alkyl group represented by R 301 to R 304 an alkyl group generally found in triarylmethane dyes is preferable, and an alkyl group having 1 to 4 carbon atoms is preferable.
  • the alkyl group is more preferably a methyl group or an ethyl group.
  • R 301 , R 302 , R 303 , and R 304 may be the same or different, but are preferably the same from the viewpoint of dye production.
  • R 305 is preferably an alkyl group or an aryl group generally found in triarylmethane dyes, and examples thereof include an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted with the alkyl group.
  • R 305 is more preferably an ethyl group, a phenyl group, or a p-tolyl group, and more preferably an ethyl group.
  • X ⁇ is preferably BF 4 ⁇ , PF 6 ⁇ or ArSO 3 ⁇ from the viewpoint of heat resistance of the compound.
  • the aromatic hydrocarbon group represented by Ar may be substituted with an amino group which may have a substituent.
  • Examples of the aromatic hydrocarbon group include an aromatic ring group formed by ring formation using only carbon atoms, or an aromatic ring group containing a hetero atom, and may have a condensed ring structure. A monocyclic ring or a double condensed ring is preferable. Of these, an aromatic ring formed only by carbon atoms is preferable, and a benzene ring or a naphthalene ring is more preferable.
  • Ar is a naphthalene ring, the substitution position may be either the 1-position or the 2-position.
  • the aromatic hydrocarbon group may be substituted with an amino group which may have a substituent.
  • substituent of the amino group include an alkyl group having 1 to 4 carbon atoms, an aryl group which is a 5-membered or 6-membered monocyclic or bicondensed ring, and the like.
  • the compound represented by the general formula (I-2-2), the X - is Cl - in the case of may be a commercially available product as it is marketed, be synthesized by known methods Good. The synthesis method is described in “Review Synthetic Dyes” (Horiguchi Hiroshi, Sankyo Publishing, 1968).
  • the content of the triarylmethane dye represented by the general formula (I-2) in the colored curable composition is 0.1% by mass to 50.0% with respect to the solid content of the colored curable composition. % By mass is preferable, and 1.0% by mass to 30.0% by mass is more preferable. A desired color density and hue can be obtained when the content of the triarylmethane dye is 0.1% by mass or more. Further, when the content of the triarylmethane dye is 50.0% by mass or less, it is advantageous to secure a relative amount of a curing component such as a resin component or a polymerizable compound.
  • a curing component such as a resin component or a polymerizable compound.
  • the colored compound of the present invention includes (B) a porphyrin compound represented by the following general formula (II) (hereinafter referred to as “porphyrin compound” or “specific dye (B)” as appropriate) together with the specific dye (A) described above. Need to be contained).
  • Z 1 , Z 2 , Z 3 and Z 4 all represent N, or any one of Z 1 and Z 3 or Z 2 and Z 4 is both N And the remaining one set represents both C—R, and each R independently represents a hydrogen atom, an alkyl group, or an aryl group.
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an alkoxy group.
  • Alkylthio group, aryloxy group, arylthio group, halogen atom, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, carbamoyl group, sulfamoyl group, acyl group, silyloxy group, cyano group, nitro group, or hetero represents a cyclic group.
  • Each of A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 may further have a substituent.
  • a 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 may be bonded to each other to form a ring structure, At least one of these does not form a ring structure.
  • an alicyclic structure may be formed, but it is preferable not to form an aromatic ring structure, and more preferably A 1 and A 2 , A 3 and A 4 , A 5 and A 6 and any one of A 7 and A 8 does not form a ring structure.
  • M represents a divalent metal atom or a divalent atomic group containing a metal atom.
  • the colored curable composition of the present invention contains the specific dye (A) and the specific dye (B), so that the reason and the reason is not clear, but the brightness and contrast of the formed colored cured film are effective. Can be increased.
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms.
  • alkenyl group is preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms.
  • the aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group.
  • the alkoxy group is preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, and an isopropoxy group.
  • Group, t-butoxy group, dodecyloxy group and cycloalkyloxy group include, for example, cyclopentyloxy group, cyclohexyloxy group and the like.
  • the alkylthio group is preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and specific examples include a methylthio group, an ethylthio group, an octylthio group, and a cyclohexylthio group.
  • the aryloxy group is preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms. Specific examples include a phenoxy group and a 1-naphthoxy group.
  • the arylthio group is preferably an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and specific examples include a phenylthio group.
  • a halogen atom Preferably, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably a fluorine atom, a chlorine atom, and a bromine atom are mentioned.
  • the alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms.
  • Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, and a cyclohexyloxycarbonyl group. And a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group.
  • the aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, and specific examples include a phenoxycarbonyl group.
  • the amino group is preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms. Specific examples include an amino group, a methylamino group, an N, N-dibutylamino group, and a tetradecylamino group. 2-ethylhexylamino group, cyclohexylamino group and the like.
  • the carbamoyl group is preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples include a carbamoyl group, an N, N-diethylcarbamoyl group, and an N-ethyl-N group. -Octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group and the like.
  • the sulfamoyl group is preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms. Specific examples thereof include a sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecyl group. Examples thereof include a sulfamoyl group, an N-ethyl-N-phenylsulfamoyl group, and an N-cyclohexylsulfamoyl group.
  • the acyl group is preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms.
  • the silyloxy group is preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms.
  • Specific examples include a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, and a diphenylmethylsilyloxy group.
  • the heterocyclic group is preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms.
  • Examples include a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, Examples include 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group and the like.
  • substituents represented by A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 may be further substituted.
  • substituents that can be introduced include halogen atoms (for example, A fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (preferably a straight chain, branched chain or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms).
  • alkenyl groups specifically, for example, vinyl group, allyl group, 3-buten-1-yl group, etc., aryl group (preferably having 6 to 48 carbon atoms, more preferably having 6 to 48 carbon atoms).
  • aryl groups specifically, for example, a phenyl group, a naphthyl group, etc., a heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group).
  • silyl groups preferably silyl groups having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms. Specific examples include trimethylsilyl group, triethyl group, and the like. Rusilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group,
  • An alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms), specifically, for example, a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an iso In the case of propoxy group, t-butoxy group, dodecyloxy group, and cycloalkyloxy group, for example, cyclopentyloxy group, cyclohexyloxy group, etc., aryloxy group (preferably having 6 to 48 carbon atoms, more preferably carbon Examples thereof include aryloxy groups having 6 to 24, specifically, for example, phenoxy group, 1-naphthoxy group and the like, and heterocyclic oxy groups (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms).
  • acyloxy group preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, specifically, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group , Dodecanoyloxy group, etc.
  • an alkoxycarbonyloxy group preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, specifically, for example, an ethoxycarbonyloxy group, t-butoxycarbony
  • a carbamoyloxy group preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms
  • a carbamoyloxy group specifically, for example, N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group, etc.
  • sulfamoyloxy group preferably having 1 to 32 carbon atoms, more preferably Is a sulfamoyloxy group having 1 to 24 carbon atoms.
  • N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group and the like alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably 1 carbon atom)
  • alkylsulfonyloxy group preferably having 1 to 38 carbon atoms, more preferably 1 carbon atom
  • specific examples include methylsulfonyloxy group, hexadecylsulfonyloxy group, cyclohexylsulfonyloxy group, etc.
  • arylsulfonyloxy group preferably having 6 to 32 carbon atoms, and more.
  • Preferred examples thereof include arylsulfonyloxy groups having 6 to 24 carbon atoms.
  • phenylsulfonyloxy groups and the like acyl groups (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms).
  • Acyl group specifically, for example, formyl group, acetyl group, pivaloyl group, Nzoyl group, tetradecanoyl group, cyclohexanoyl group, etc.
  • alkoxycarbonyl group preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms.
  • Methoxycarbonyl group ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group, etc.
  • aryloxycarbonyl group preferably having 7 to 32 carbon atoms
  • an aryloxycarbonyl group having 7 to 24 carbon atoms specifically, for example, a phenoxycarbonyl group
  • a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, specifically, for example, carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N— Octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group, etc.), amino group (preferably Is an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms.
  • an amino group preferably having 6 to 32 carbon atoms, more preferred
  • anilino group preferably having 6 to 32 carbon atoms, more preferred
  • an anilino group having 6 to 24 specifically, for example, an anilino group, an N-methylanilino group and the like, a heterocyclic amino group (preferably having a carbon number of 1 to 32, more preferably 1 to 18).
  • a 4-pyridylamino group and the like and a carbonamido group (preferably a carbon number group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms).
  • a carbonamido group preferably a carbon number group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms.
  • an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexaneamide group, etc. a ureido group (preferably a ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms)
  • imide group preferably having a carbon number
  • N-succinimide group, N-phthalimide group, etc. alkoxycarbonylamino groups (preferably having 2 to 48 carbon atoms, more Preferred examples thereof include an alkoxycarbonylamino group having 2 to 24 carbon atoms. Specific examples include a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an octadecyloxycarbonylamino group, and a cyclohexyloxycarbonylamino group.
  • an aryloxycarbonylamino group preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, specifically, for example, a phenoxycarbonylamino group
  • Sulfonamide group preferably carbon Examples thereof include a sulfonamide group having 1 to 48, more preferably 1 to 24 carbon atoms. Specific examples include a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide group, and a cyclohexanesulfone.
  • An amide group a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms), specifically, for example, N, N-dipropyls Rufamoylamino group, N-ethyl-N-dodecylsulfamoylamino group and the like) and azo groups (preferably azo groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms).
  • phenylazo group, 3-pyrazolylazo group
  • alkylthio group preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, specifically, for example, a methylthio group, an ethylthio group, an octylthio group, a cyclohexylthio group, etc.
  • an arylthio group Preferably an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, specifically, for example, a phenylthio group
  • a heterocyclic thio group preferably having 1 to 32 carbon atoms, more Preferred examples include a heterocyclic thio group having 1 to 18 carbon atoms, and specific examples include 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group and the like, alkylsulfinyl group ( Preferred are alkylsulfinyl groups having 1 to 32 carbon
  • Dodecanesulfinyl group arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, specifically, for example, phenylsulfinyl group), alkylsulfonyl group (Preferably includes an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
  • sulfamoyl group preferably sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, specifically, for example, sulfamoyl group, N N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group, etc.), sulfo group, phosphonyl group (preferably Is a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms.
  • phosphinoyl Amino group preferably phosphinoyla having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms
  • a mino group specifically, a diethoxyphosphinoylamino group, a dioctyloxyphosphinoylamino group, and the like.
  • alkyl group and aryl group represented by R are A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7. and alkyl groups described as the substituent a 8 represents, and is synonymous with an aryl group.
  • specific examples of the metal atom in the “divalent metal atom or divalent atomic group containing a metal atom” represented by M are preferably Al, Si, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Mo, Ru, Rh, Pd, In, Sn, Pt, Pb, Mg are mentioned, more preferably Al, V, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, Mg are mentioned, More preferably, Al, V, Mn, Fe, Co, Ni, Cu, Zn, Mg are mentioned, Especially preferably, V, Co, Ni, Cu and Zn are mentioned.
  • divalent atomic group containing a metal atom represented by M in the general formula (II)
  • metal halide atoms for example, Al—F, Al—Cl, Al—Br, Al—I, In-F, In-Cl, Fe-Cl, In-Br, In-I, SiF 2, SiCl 2, SiBr 2, SiI 2, TiF 2, TiCl 2, TiBr 2, TiI 2 like
  • alkyl for example, Al—F, Al—Cl, Al—Br, Al—I, In-F, In-Cl 2, SiBr 2, SiI 2, TiF 2, TiCl 2, TiBr 2, TiI 2 like
  • aryl A metal atom to which a substituent such as a group, a naphthyl group, an alkoxy group or a hydroxyl group is bonded specifically, for example, Si (CH 3 ) 2 , Si (C 2 H 5 ) 2 , Al—C 6 H 5 , In— C 6 H 5 , Al (OH), Mn
  • the porphyrin compound used in the present invention is preferably a tetraazaporphyrin compound in which Z 1 , Z 2 , Z 3 and Z 4 all represent N, preferably a compound represented by the general formula (II-2) .
  • a 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M are the same as A 1 , A 2 , A in the general formula (II).
  • 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M have the same meanings.
  • the maximum value of the absorption spectrum of the compound represented by the general formula (II) used in the present invention is preferably from 550 nm to 650 nm, more preferably from 570 nm to 630 nm, particularly preferably from 570 nm to 610 nm, from the viewpoint of the transmittance of the color filter. Is preferred.
  • X 1 , X 2 , X 3 , X 4 , Y 1 , Y 2 , Y 3 , and Y 4 are respectively synonymous with the groups described for A 1 to A 8 in the general formula (II-2). It is. If X 1 and Y 1 , X 2 and Y 2 , X 3 and Y 3 , X 4 and Y 4 are not the same, the above four isomers can be formed.
  • the content of the said specific dye (B) it is preferable that it is 0.1 mass% or more with respect to the total amount of the coloring compound contained in a colored curable composition, and it is more preferable that it is 0.5 mass% or more. It is preferably 1% by mass or more. Since the compound of the present invention can obtain good chromaticity and contrast when used as a color filter even in a trace amount, it is excellent in cost reduction effect.
  • the upper limit of the content of the specific dye (B) is not particularly limited as long as it satisfies the user's requirements such as chromaticity requirements and resist performance when the color filter is used, but with the specific dye (A) Considering the balance, it is preferably 50% by mass or less with respect to the total amount of the coloring compound.
  • the colored curable composition of the present invention may contain a known dye other than the specific dye (A) and the specific dye (B) as a coloring compound.
  • Other dyes that may be included in the colored curable composition of the present invention include pyrazole azo series, anilino azo series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, It is a dye such as phenothiazine, pyrrolopyrazole azomethine, squarylium, quinophthalone, benzopyran, or indigo.
  • the total content of the specific dye (A) and the specific dye (B) contained in the colored curable composition of the present invention is preferably 1% by mass or more and 90% by mass or less, preferably 10% by mass or more. More preferably, it is 70 mass% or less, More preferably, it is 10 mass% or more and 50 mass% or less.
  • a pigment may be used in combination as the colored compound.
  • a pigment having an average primary particle size of 10 nm or more and 30 nm or less is preferable.
  • a colored curable composition having excellent brightness and contrast can be obtained in the above embodiment.
  • organic pigments are preferably used from the viewpoint of reliability.
  • organic pigments in the present invention include organic pigments described in paragraph [0093] of JP-A-2009-256572.
  • the following pigments are suitable from the viewpoint of color reproducibility, but are not limited to these in the present invention.
  • These organic pigments can be used alone or in various combinations in order to increase color purity.
  • the content of the pigment in the colored curable composition of the present invention is preferably 0.5% by mass to 50% by mass with respect to the total solid content of the composition, and is preferably 1% by mass. More preferable is 30% by mass.
  • the pigment content is within the above range, it is effective to ensure excellent color characteristics.
  • the pigment is preferably used as a pigment dispersion composition by dispersing the pigment using at least one dispersant.
  • a coated pigment is used.
  • the dispersant for example, a known pigment dispersant or surfactant can be appropriately selected and used.
  • the content of the dispersant is preferably 1% by mass to 100% by mass and more preferably 3% by mass to 70% by mass with respect to the mass of the pigment.
  • the total content of the coloring compound is preferably 0.2% by mass or more and 50% by mass or less, and preferably 1% by mass or more and 50% by mass or less, based on the total solid content of the colored curable composition. More preferably, it is 10 mass% or more and 50 mass% or less.
  • the colored curable composition of the present invention preferably contains at least one polymerizable compound.
  • the polymerizable compound is, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected and used from components constituting a known composition, as disclosed in JP-A-2006-23696. Examples include the components described in paragraph numbers [0010] to [0020] and the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921.
  • the polymerizable compound is preferably a compound having a terminal ethylenically unsaturated bond, and more preferably selected from compounds having two or more terminal ethylenically unsaturated bonds.
  • Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof.
  • a urethane-added polymerizable compound produced by an addition reaction between an isocyanate and a hydroxyl group is also suitable, such as JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765.
  • Urethane compounds having them are also suitable.
  • Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490.
  • pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate.
  • Pentaerythritol tetra (meth) acrylate EO modified products dipentaerythritol hexa (meth) acrylate EO modified products, etc., and commercially available products include NK ester A-TMMT, NK ester A-TMM-3, and NK oligo UA.
  • NK Oligo UA-7200 manufactured by Shin-Nakamura Chemical Co., Ltd.
  • examples of the polymerizable compound (C) include components described in paragraphs [0031] to [0061] of JP-A-2009-265630 from the viewpoint of low-temperature curability.
  • the polymerizable compound (C) the following (1) to (20) and (M-1) to (M-8) are preferable.
  • a colored film formed using a polymerizable monomer having two ethylenically unsaturated bonds in the molecule is excellent from the viewpoint of low-temperature curability.
  • These polymerizable compounds can be used alone or in combination of two or more.
  • the content of the polymerizable compound in the total solid content is preferably 10% by mass to 80% by mass, and 15% by mass. % To 75% by mass is more preferable, and 20% to 60% by mass is particularly preferable.
  • the colored curable composition of the present invention preferably contains at least one photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
  • the photopolymerization initiator is a compound that is exposed to exposure light and starts and accelerates polymerization of the polymerizable compound.
  • a compound that responds to actinic rays having a wavelength of 300 nm or longer and initiates and accelerates polymerization of the polymerizable compound is preferable.
  • a photopolymerization initiator that does not directly respond to actinic rays having a wavelength of 300 nm or longer can also be preferably used in combination with a sensitizer.
  • oxime ester compounds organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexa
  • examples thereof include arylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxide) compounds, benzophenone compounds, acetophenone compounds, benzimidazole compounds, and derivatives thereof.
  • oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity.
  • Examples of the oxime ester compound include JP 2000-80068, JP 2001-233842, JP 2004-534797, WO 2005/080337, WO 2006/018933, JP
  • JP The compounds described in JP 2007-210991 A, JP 2007-231000 A, JP 2007-2699779 A, JP 2009-191061 A, and International Publication No. 2009/131189 can be used.
  • a compound represented by the following general formula (A) is also suitable as an oxime ester compound that is a photopolymerization initiator.
  • X 1 , X 2 , and X 3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group
  • R 1 represents —R, —OR, —COR, —SR, —CONRR 'Or -CN
  • R 2 and R 3 each independently represent -R, -OR, -COR, -SR, or -NRR'.
  • R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group.
  • one or more carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. May form a ring.
  • halogen atom examples include fluorine, chlorine, bromine, and iodine, and X 1 , X 2 , and X 3 are alkyl.
  • alkyl group in the case of representing a group examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2- Ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxypropyl, Monofluoromethyl, difluoromethyl, Fluoromethyl, trifluor
  • X ⁇ 1 >, X ⁇ 2 > and X ⁇ 3 > represent a hydrogen atom, or X ⁇ 1 > represents an alkyl group and X ⁇ 2 > and X ⁇ 3 > both represent a hydrogen atom.
  • examples of the alkyl group represented by R and R ′ include methyl, Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, Vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl,
  • Examples of the aryl group represented by R and R ′ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like.
  • Examples of the aralkyl group represented by R and R ′ include benzyl, chlorobenzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl, phenylethenyl and the like.
  • Examples of the heterocyclic group represented by R and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl and the like.
  • Examples of the ring formed by bonding R and R ′ to each other include a piperidine ring and a morpholine ring.
  • R 2 and R 3 including R and R ′ are each independently a methyl group, a hexyl group, a cyclohexyl group, —S—Ph, —S—Ph—Cl, and —S—Ph—.
  • Br is a particularly preferred embodiment.
  • X 1 , X 2 , and X 3 are all hydrogen atoms;
  • R 1 is an alkyl group, particularly a methyl group;
  • R 2 is alkyl
  • Particularly preferred as photoinitiators are those which are groups, in particular methyl groups; those in which R 3 is an alkyl group, in particular ethyl group.
  • photopolymerization initiator represented by the general formula (A) include compounds A to F exemplified below.
  • present invention is not limited by the following compounds.
  • the photopolymerization initiator represented by the general formula (A) can be synthesized, for example, by the method described in JP-A-2005-220097.
  • the compound represented by the general formula (A) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferable examples include those having an absorption wavelength in the wavelength region of 300 nm to 380 nm. In particular, those having high absorbance at 308 nm and 355 nm are preferable.
  • a compound represented by the following general formula (B) is also suitable as an oxime ester compound that is a photopolymerization initiator.
  • R 22 represents a monovalent substituent.
  • a 22 represents a divalent linking group, and Ar represents an aryl group.
  • n is an integer of 0 to 5.
  • X 22 represents a monovalent substituent, and when n is an integer of 2 to 5, a plurality of X 22 may be the same or different.
  • the monovalent substituent represented by R 22 is preferably a monovalent nonmetallic atomic group shown below.
  • the monovalent nonmetallic atomic group represented by R 22 has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent.
  • the alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms.
  • the aryl group that may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • the alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group and an ethylsulfonyl group.
  • the arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group.
  • the acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms.
  • acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group benzoyl group, 1-naphthoyl Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl group
  • the heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom.
  • a thienyl group, a furyl group, a pyranyl group, etc. are mentioned.
  • R 22 is more preferably an unsubstituted or substituted acyl group from the viewpoint of increasing sensitivity, and specifically, an unsubstituted or substituted acetyl group or propionyl.
  • Group, benzoyl group and toluyl group are preferred.
  • Examples of the substituent include groups represented by the following structural formula, and among these, any of (d-1), (d-4) and (d-5) is preferable.
  • the divalent linking group represented by A 22 includes an alkylene having 1 to 12 carbon atoms which may have a substituent, cyclohexylene which may have a substituent, and a substituent.
  • Alkynylene which may have Examples of the substituent that can be introduced into these groups include halogen atoms 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- Examples include aryloxy groups such as a tolyloxy group, alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group.
  • a 22 is an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, from the viewpoint of increasing the sensitivity and suppressing the coloration due to heating.
  • Alkylene group substituted with alkenyl group for example, vinyl group, allyl group
  • aryl group for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group
  • An alkylene group substituted with an anthryl group, a phenanthryl group, or a styryl group is preferred.
  • the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.
  • Ar is phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m -, P-cumenyl group, mesityl group and the like.
  • a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.
  • the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy such as a methoxy group, an ethoxy group and a tert-butoxy group.
  • aryloxy group such as phenoxy group, p-tolyloxy group, alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy group such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, Benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methacrylyl group and other acyl groups, methylamino group, cyclohexylamino group and other alkylamino groups, dimethylamino group, diethylamino group, morpholino group, piperidino group and other dialkylamino groups, F Niruamino group, a methyl group, an ethyl group, tert- butyl group, an alkyl group such as a dodecyl group, a hydroxy group, a carboxy group, and the like
  • the monovalent substituent represented by X 22 may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent.
  • the alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms.
  • a methyl group an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, a trifluoromethyl group.
  • the aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms.
  • a phenyl group a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a terphenyl group, a quarterphenyl group, o-, m-, and p-tolyl groups, xylyl groups, and the like.
  • the alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.
  • the alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.
  • the alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and a benzyloxy group. .
  • the aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, Examples include 2-methylphenyloxy group, 2-methoxyphenyloxy group, and the like.
  • the alkylthiooxy group which may have a substituent is preferably an alkylthiooxy group having 1 to 30 carbon atoms.
  • the arylthiooxy group which may have a substituent is preferably an arylthiooxy group having 6 to 30 carbon atoms, such as a phenylthiooxy group, a 1-naphthylthiooxy group, a 2-naphthylthiooxy group, 2 -Chlorophenylthiooxy group, 2-methylphenylthiooxy group, 2-methoxyphenylthiooxy group, 2-butoxyphenylthiooxy group, 3-chlorophenylthiooxy group, 3-trifluoromethylphenylthiooxy group, 3-cyano Phenylthiooxy group, 3-nitrophenylthiooxy group, 4-fluorophenylthiooxy group, 4-cyanophenylthiooxy group, 4-methoxyphenylthiooxy group, 4-dimethylaminophenylthiooxy group, 4-methylsulfanyl Phenylthiooxy group, 4-phenylsulfanylphenol There is Ruchio
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the amide group which may have a substituent on N include N, N-dimethylamide group and N, N-diethylamide group.
  • X 22 may have an alkyl group which may have a substituent or a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region.
  • An amide group which may have a substituent is preferable, and an alkyl group which may have a substituent is more preferable.
  • n in the general formula (B) represents an integer of 0 to 5, and is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, from the viewpoint of ease of synthesis.
  • X 22 there are a plurality the plurality of X 22 may be the same, May be different.
  • the compound represented by the general formula (B) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferable examples include those having an absorption wavelength in the wavelength region of 300 nm to 380 nm. In particular, those having high absorbance at 308 nm and 355 nm are preferable.
  • organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.
  • hexaarylbiimidazole compounds include, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286.
  • Various compounds described in the specification specifically 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o- Bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′,
  • the photopolymerization initiator can be used alone or in combination of two or more.
  • multiple types of compounds represented by general formula (A) may be used, and multiple types of compounds represented by general formula (B) may be used.
  • at least one compound represented by the general formulas (A) and (B) and an oxime compound other than the compounds represented by the general formulas (A) and (B) or a photopolymerization initiator other than the oxime compound are used. It may be used.
  • the total content of the photopolymerization initiator is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to 10% by mass with respect to the total solid content in the colored curable composition. More preferably, 1% by mass to 5% by mass is most preferable. Within this range, the sensitivity during exposure is high and the color characteristics are also good.
  • a binder resin may be used for improving the film-forming property.
  • an alkali-soluble binder is preferably used from the viewpoint of pattern formation.
  • the alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
  • the alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent and developable with a weak alkaline aqueous solution.
  • linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.
  • alkali-soluble binders include those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful.
  • the linear organic high molecular polymer may be a copolymer of hydrophilic monomers.
  • Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth) Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight
  • Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like.
  • hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.
  • the alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain.
  • Polymers and the like are also useful. Examples of the above-described polymer containing a polymerizable group include a dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co.
  • polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control.
  • acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control.
  • acrylic resin examples include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, the Photomer 6173, and the KS resist-106. Cyclomer P series and the like are preferable.
  • the alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 ⁇ 10 5 from the viewpoint of developability, liquid viscosity, and the like, and a weight of 2000 to 1 ⁇ 10 5 is preferable. Polymers are more preferred, and polymers of 5000 to 5 ⁇ 10 4 are particularly preferred.
  • the alkali-soluble binder can be used alone or in combination of two or more.
  • the colored curable composition of the present invention may contain a polyfunctional thiol compound.
  • the colored curable composition of the present invention includes a polyfunctional thiol compound to increase sensitivity, suppress ion elution caused by a coloring material such as a dye, and the like. When the composition is used, it is possible to prevent deterioration of image quality such as crosstalk and display a clear image with high image quality.
  • polyfunctional thiol compound means a compound having two or more thiol groups in the molecule.
  • the polyfunctional thiol compound is preferably a low molecular compound having a molecular weight of 100 or more, specifically, preferably having a molecular weight of 100 to 1500, and more preferably 150 to 1000.
  • the polyfunctional thiol compound preferably has 2 to 10 thiol groups in the molecule, more preferably 2 to 6, and particularly preferably 2 to 4. In addition, these compounds are preferably used as a system that is used auxiliary when the radical polymerizable monomer is polymerized.
  • the addition amount of the polyfunctional thiol compound is 1 to 20% by mass with respect to the total solid content of the composition, or is less than the addition amount of the radical polymerizable monomer contained at the same time. It is preferable to make it an addition amount.
  • Propionate dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trifunctional, etc. It mentioned as compound. Particularly preferred is a compound containing secondary SH, and it is preferred to have a triazine skeleton from the viewpoint of liquid stability. Specific examples include Karenz MT series (manufactured by Showa Denko KK).
  • the content of the polyfunctional thiol compound is preferably 0.01% by mass to 20% by mass, and preferably 0.1% by mass to 10% by mass with respect to the total solid content in the colored curable composition. Further preferred. When the content of the polyfunctional thiol compound is in this range, the sensitivity of the colored curable composition is good, the storage stability is good, the pixel adhesion in the obtained color filter is good, and there is no pattern defect. When used in a liquid crystal display device, a colored curable composition having good electrical characteristics can be provided.
  • sensitizer A sensitizer can also be added to the colored curable composition of the present invention.
  • Typical sensitizers used in the present invention include Krivello [J. V. Crivello, Adv. in Polymer Sci, 62, 1 (1984)]. Specific examples include pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10. -Dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like.
  • the sensitizer is preferably added in a proportion of 50 to 200% by mass with respect to the photopolymerization initiator.
  • a chain transfer agent can also be added to the colored curable composition of the present invention.
  • the chain transfer agent used in the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercapto.
  • Examples include mercapto compounds having a heterocyclic ring such as benzimidazole and N-phenylmercaptobenzimidazole.
  • a chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
  • the addition amount of the chain transfer agent is preferably in the range of 0.01% by mass to 15% by mass with respect to the total solid content of the colored curable composition of the present invention, from the viewpoint of reducing sensitivity variation, 0.1% by mass to 10% by mass is more preferable, and 0.5% by mass to 5% by mass is particularly preferable.
  • the colored curable composition of the present invention may contain a polymerization inhibitor.
  • the polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to polymerization initiation species such as radicals generated in the colored curable composition by light or heat. , Electron donation) and the like to deactivate the polymerization initiating species and to prevent unintentional initiation of polymerization.
  • the polymerization inhibitors described in paragraphs [0154] to [0173] of JP-A-2007-334322 can be used. Among these, p-methoxyphenol is preferably used as the polymerization inhibitor.
  • the content of the polymerization inhibitor in the colored curable composition of the present invention is preferably 0.0001% by mass to 5% by mass and more preferably 0.001% by mass to 5% by mass with respect to the total mass of the polymerizable compound. 0.001% by mass to 1% by mass is particularly preferable.
  • the colored curable composition of the present invention can contain an organic solvent.
  • the organic solvent is basically not particularly limited as long as it can satisfy the solubility of each side-by-side component and the coating property when a colored curable composition is used, and in particular, the solubility and coating property of the solid content. In view of safety, it is preferably selected.
  • organic solvents examples include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate.
  • Oxyacetic acid alkyl esters eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate).
  • ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl methyl ether.
  • ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
  • aromatic hydrocarbons include toluene and xylene.
  • organic solvents are also preferably mixed in a combination of two or more from the viewpoints of the solubility of each of the aforementioned components and, when an alkali-soluble binder is included, the solubility of the components and the improvement of the coated surface.
  • It is a mixed solution composed of two or more selected from cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
  • the content of the organic solvent in the colored curable composition is preferably such that the total solid concentration in the colored curable composition is 10% by mass to 80% by mass, and the amount is 15% by mass to 60% by mass. Is more preferable.
  • the colored curable composition of the present invention may contain a surfactant.
  • a surfactant any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Specific examples include nonionic surfactants described in paragraph 0058 of JP-A-2009-098616, and among them, fluorine surfactants are preferable.
  • Other surfactants that can be used in the present invention include, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, and F554.
  • F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC -170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105,7000,950,7600, Surflon S-112, S-113, S-131 S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Footgent 250 (manufactured by Neos Co., Ltd.), etc.
  • the structural unit A and the structural unit B represented by the following formula (W) are included, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent is 1, A copolymer having a molecular weight of 000 or more and 10,000 or less can be given as a preferred example.
  • R 1 and R 3 each independently represent a hydrogen atom or a methyl group
  • R 2 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 4 represents a hydrogen atom or carbon number
  • 1 represents an alkyl group having 4 or less
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p represents a numerical value of 10% to 80% by mass
  • Q represents a numerical value of 20% to 90% by mass
  • r represents an integer of 1 to 18, and n represents an integer of 1 to 10.
  • L is preferably a branched alkylene group represented by the following formula (W-2).
  • R 5 in Formula (W-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. Two or three alkyl groups are more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • the addition amount of the surfactant in the colored curable composition of the present invention is preferably 0.01 to 2.0% by mass, particularly 0.02 to 1.0% by mass, based on the total solid content of the colored curable composition. preferable. Within this range, the coatability and the uniformity of the cured film are good.
  • the colored curable composition of the present invention may contain an adhesion improving agent.
  • the adhesion improver improves the adhesion between the inorganic material serving as the support, for example, a silicon compound such as glass, silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, and the cured film of the colored curable composition layer.
  • a compound for example, a silicon compound such as glass, silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, and the cured film of the colored curable composition layer.
  • a compound include silane coupling agents.
  • the silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
  • silane coupling agent a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
  • the content of the adhesion improving agent in the colored curable composition of the present invention is preferably 0.1% by mass to 20% by mass, and preferably 0.2% by mass to 5% by mass with respect to the total solid content of the colored curable composition. % Is more preferable.
  • Crosslinking agent A supplementary crosslinking agent may be used in the colored curable composition of the present invention to further increase the hardness of the colored layer obtained by curing the colored curable composition.
  • the crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group.
  • a development accelerator can also be added in order to promote the alkali solubility of the non-exposed region when the colored curable composition layer is exposed and to further improve the developability of the colored curable composition.
  • the development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less.
  • aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, is
  • the colored curable composition of the present invention may further contain various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, antioxidants and the like. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
  • the colored curable composition of the present invention may contain a light stabilizer described in paragraph [0078] of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph [0081] of the same publication. .
  • the colored curable composition of the present invention is prepared by mixing the above-described components and optional components as necessary.
  • the components constituting the colored curable composition may be combined at once, or may be sequentially added after each component is dissolved and dispersed in a solvent.
  • the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a colored curable composition.
  • the colored curable composition prepared as described above can be used after being preferably filtered using a filter having a pore size of about 0.01 ⁇ m to 3.0 ⁇ m.
  • the colored curable composition of the present invention can form a colored cured film having excellent brightness and contrast, it can be used for forming colored pixels such as color filters used in liquid crystal display devices, as well as printing inks and inkjet inks. And can be suitably used as a production application for paints and the like.
  • the color filter of the present invention includes a substrate and a colored pixel composed of a colored film formed on the substrate by the colored curable composition of the present invention.
  • the colored region on the substrate is composed of colored layers such as red (R), green (G), and blue (B) that form each pixel of the color filter.
  • the method for producing a color filter of the present invention includes a colored layer forming step (A) in which a colored layer (colored curable composition layer) is formed by applying the above-described colored curable composition on a support, and a step ( The exposure process (B) which carries out pattern-like exposure with respect to the colored layer formed in A), and the image development process (C) which develops the said exposed colored layer and forms a pattern are included.
  • the exposure process (B) which carries out pattern-like exposure with respect to the colored layer formed in A
  • the image development process (C) which develops the said exposed colored layer and forms a pattern are included.
  • the aspect which further provided the post-baking (post-heating process) (D) which heat-processes with respect to the coloring pattern obtained at the process (C) is preferable.
  • COA color filter on array
  • the support examples include soda glass, alkali-free glass, borosilicate glass, quartz glass, silicon substrate, and resin substrate used in liquid crystal display devices.
  • a driving substrate for a thin film transistor (TFT) liquid crystal display device is used.
  • an undercoat layer, an interlayer insulating film, or the like may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface.
  • the pre-baking condition examples include a condition of heating at 70 to 130 ° C. for about 0.5 to 15 minutes using a hot plate or an oven.
  • the thickness of the colored layer formed with a colored curable composition is suitably selected according to the objective.
  • the range of 0.2 ⁇ m to 5.0 ⁇ m is preferable, and the range of 1.0 ⁇ m to 4.0 ⁇ m is more preferable.
  • the pixel film thickness is preferably in the range of 0.3 ⁇ m to 5.0 ⁇ m, and more preferably in the range of 0.5 ⁇ m to 3.5 ⁇ m.
  • the thickness of a colored layer is a film thickness after prebaking.
  • ultrahigh pressure, high pressure, medium pressure, and low pressure mercury lamps chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser light sources, and the like can be used.
  • the irradiation light is preferably an ultraviolet laser having a wavelength range of 300 nm to 410 nm, and more preferably a wavelength of 300 nm to 360 nm.
  • the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used.
  • the pattern exposure from the viewpoint of productivity, preferably in the range of 1mJ / cm 2 ⁇ 100mJ / cm 2, the range of 1mJ / cm 2 ⁇ 50mJ / cm 2 is more preferable.
  • the colored layer after exposure is developed with a developer.
  • a developer dissolves the uncured portion of the colored layer and does not dissolve the cured portion
  • a combination of various organic solvents or an alkaline aqueous solution can be used.
  • the alkali concentration is preferably adjusted to pH 10-13.
  • alkaline aqueous solution examples include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl.
  • alkaline aqueous solutions such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene.
  • an organic alkaline developer is particularly desirable as the developer from the viewpoint of not causing damage to the underlying circuit.
  • the development time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 120 seconds.
  • the development temperature is preferably 20 ° C. to 40 ° C., more preferably 20 ° C. to 30 ° C.
  • Development can be performed by a paddle method, a shower method, a spray method, or the like. Moreover, after developing using alkaline aqueous solution, it is preferable to wash
  • a color filter of the present invention it is also preferable to perform post-exposure by ultraviolet irradiation on a colored pattern (pixel) formed using a colored curable composition.
  • -Process (D)- It is preferable to further heat-treat the colored pattern after development or the colored pattern subjected to post-exposure by ultraviolet irradiation as described above.
  • the color pattern By heating the formed color pattern (so-called post-bake process), the color pattern can be further cured.
  • This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
  • the temperature during the heat treatment is preferably 100 ° C. to 300 ° C., more preferably 150 ° C. to 250 ° C.
  • the heating time is preferably about 10 minutes to 120 minutes.
  • the colored pattern thus obtained constitutes a pixel in the color filter.
  • the above-described step (A), step (B), step (C), and step (D) may be repeated according to the desired number of colors.
  • the step (D) may be performed, or formation, exposure, and formation of all colored layers having a desired number of colors. After the development is completed, the step (D) may be performed collectively.
  • a color filter constituted by using the colored curable composition of the present invention a color filter which is a more preferable aspect, a production method thereof, and details relating to production of a COA using these will be described.
  • the color filter of the present invention can be manufactured as follows. After applying the colored curable composition of the present invention containing a colorant on the TFT substrate to form a coated film of the colored curable composition, the coated film is subjected to pattern exposure, alkali development, post-baking treatment, etc. Each pixel is formed. Next, after sputtering a transparent electrode (ITO) film on each pixel, a positive photoresist coating film is formed, pattern exposure is performed on the photoresist film, development is performed, and further, necessary ITO is etched to form a pixel electrode pattern. After the formation, the photoresist film remaining on the pixel electrode pattern is removed with a remover to obtain a COA color filter.
  • ITO transparent electrode
  • a coating method such as spin coating, spin coating, casting coating, roll coating, etc., on a substrate directly or via another layer.
  • the colored curable composition layer applied on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, oven or the like.
  • slit coating is also effective as a method for forming a coating film, and this coating method is becoming common.
  • the pattern exposure of the coating film can be performed by exposing through a predetermined mask pattern and curing only the coating film portion irradiated with light.
  • radiation that can be used in exposure ultraviolet rays such as g-line and i-line are particularly preferably used.
  • an alkali development treatment in the case of the negative type, the uncured portion that has not been exposed is eluted in the alkaline aqueous solution, and only the photocured portion remains.
  • an organic alkali developer that does not damage the underlying circuit or the like is desirable.
  • the development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.
  • alkali examples include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-
  • An alkaline aqueous solution obtained by diluting an organic alkaline compound such as undecene with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass can be used.
  • a developer composed of such an alkaline aqueous solution the developer is generally washed (rinsed) with pure water after development. Next, excess developer is washed away and dried, followed by heat treatment (post-bake).
  • the said process can be repeated sequentially for every color, and a hardened film can be manufactured. Thereby, a color filter is obtained.
  • the post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 200 ° C. to 240 ° C. is performed.
  • This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so as to satisfy the above conditions for the coated film after development. Can be done.
  • a transparent electrode (ITO) film is formed on the formed pixel by sputtering, a positive photoresist film is further formed thereon, pattern exposure and development are performed, and unnecessary with chemicals such as hydrofluoric acid. ITO is etched to form pixel electrodes.
  • a positive photoresist having etching resistance is required.
  • a well-known method can be normally used for pattern exposure, image development, and etching without a restriction
  • the positive resist remaining on the formed pixel electrode is quickly stripped and removed with a stripping solution. There is no restriction
  • a typical stripping solution includes a mixed solvent of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO).
  • MEA monoethanolamine
  • DMSO dimethyl sulfoxide
  • the color filter of the present invention is usually used in various display devices such as a TFT liquid crystal display device having the structure disclosed in FIG. 1 of JP-A-9-31347.
  • the color filter obtained as described above is suitable for a COA type image display device because it can be easily aligned and can increase the aperture ratio.
  • the pixel is formed using the colored curable composition of the present invention, the resistance to the stripping solution is high, so that the yield rate is high and the production efficiency is also high.
  • heat discoloration, low dielectric constant, film thickness uniformity, resolution, voltage holding ratio, light resistance and the like normally required for color filters are also good.
  • the structure of the color filter may be a form in which the pixel is composed of only one layer, or a pixel film formed of a coating film of a colored curable composition for pixels and a pixel formed on the pixel film.
  • substrate and a pixel electrode may be sufficient.
  • the film thickness of the pixel film is preferably 0.3 ⁇ m to 5.0 ⁇ m, and more preferably 0.5 ⁇ m to 3.5 ⁇ m. The higher the coating thickness, the higher the chromaticity can be achieved. However, the thicker the coating thickness, the lower the resolution of the contact hole.
  • the film thickness of the pixel protective film is preferably 0.2 ⁇ m to 5.0 ⁇ m, and more preferably 0.2 ⁇ m to 3.0 ⁇ m. Further, it is desirable that the unevenness of the underlying pixel is flattened so that the surface is smooth.
  • COA COA type image display device
  • a normal color filter is provided on a glass substrate and bonded to a TFT substrate.
  • the COA technique directly forms a color filter on a TFT substrate, and it is necessary to consider the following points (i) to (iii) as compared with a normal color filter material.
  • (I) Low dielectric constant In the COA, since the pixel electrode is directly provided on the TFT, the voltage is directly applied to the color filter. Therefore, the color filter material is required to be a low dielectric constant material.
  • the COA since the COA is provided with pixels directly on the TFT, there is no concern about positional displacement, and a substrate on which ITO is sputtered over the entire surface may be prepared as a counter substrate sandwiching the liquid crystal. For this reason, the necessity of alignment becomes about the position of the sealing agent, and the working efficiency is dramatically improved.
  • the COA technology does not require alignment accuracy (it is gradual), the line width of the black matrix can be made very narrow, the aperture ratio can be increased, and the power consumption of the backlight can be increased. There is a merit that can be kept low. In this way, various studies have been made on COA, which may become an essential technology for future LCD large-sized substrates.
  • the risk of producing a color filter on the TFT and the color filter material that can meet the requirements (i) to (iii) are not provided, so that the adoption is advanced. The current situation was not.
  • the colored curable composition of the present invention can solve the problems caused by the color filter material for COA, and the method of use thereof can be used depending on the purpose. That is, the most desirable method is a method for producing a color filter using the colored curable composition of the present invention containing a colorant. Further, when the flatness cannot be satisfied by producing a color filter on the TFT, various required characteristics can be obtained by using the colored curable composition of the present invention which does not further contain a colorant as a flattening film. Can be satisfied. Naturally, the planarization layer has good compatibility with the underlying color filter, so that the adhesion is good and the defect rate from the COA material surface can be minimized.
  • the color filter obtained by the method for producing a color filter of the present invention is excellent in luminance and contrast because the colored curable composition of the present invention is used.
  • the display device of the present invention includes the color filter of the present invention.
  • a liquid crystal display liquid crystal display device; LCD
  • organic EL display organic EL display device
  • a liquid crystal projector liquid crystal projector
  • display device for a game machine a display device for a portable terminal such as a mobile phone.
  • Display devices such as digital camera display devices and car navigation display devices, particularly color display devices are suitable.
  • the color filter of the present invention is used in an organic EL display device, a liquid crystal display device or the like, it is possible to display an image with high luminance and excellent spectral characteristics and contrast.
  • ⁇ Liquid crystal display device> A liquid crystal display device using the color filter of the present invention will be described.
  • organic EL display devices and liquid crystal display devices and details of each display device refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho (issued in 1989) ”.
  • the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”.
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
  • the color filter of the present invention is particularly effective for a color TFT liquid crystal display device.
  • the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can.
  • the color filter of the present invention can also be used for a COA (Color-filter On Array) system.
  • the color filter of the present invention When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, but further, red, green and blue LED light sources (RGB-LED).
  • RGB-LED red, green and blue LED light sources
  • Example 1-1 Preparation of colored curable composition- The following components were mixed and dissolved to prepare a colored curable composition.
  • Organic solvent 1 propylene glycol monomethyl ether acetate
  • Organic solvent 2 diethylene glycol ethyl methyl ether
  • Alkali-soluble binder 1 cyclohexyl methacrylate / methacrylic acid / glycidyl methacrylate and methacrylic acid adduct (30/30 / 40 [molar ratio], 45% propylene glycol monomethyl ether solution)
  • polymerizable compound 1 Nippon Kayaku Co., Ltd., KAYARAD DPHA 5 parts Polymerizable compound 2 (Toa Gosei Co., Ltd., Aronix TO-2349) 2 parts Polymerization inhibitor (p-me
  • the blue pigment dispersion was prepared as follows. C. I. 12.8 parts of Pigment Blue 15: 6 and 7.2 parts of a dispersant (Solsperse 5500 manufactured by Nippon Lubrizol Co., Ltd.) are mixed with 80.0 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently mixed using a bead mill. A blue pigment dispersion was prepared by dispersing.
  • the dye solution 1 was prepared by mixing and dissolving the following components.
  • the dye concentration of the dye solution 1 was 0.1% with respect to the color material in the colored curable composition.
  • Organic solvent 1 propylene glycol monomethyl ether acetate
  • the dye solution 2 was prepared by mixing and dissolving the following components.
  • Organic solvent 1 propylene glycol monomethyl ether acetate
  • Specific dye (A) (Compound 1) 2.6 parts
  • dye solution 1 P-26, a specific dye (B)
  • dye solution 2 Includes Compound 1 as the specific dye (A).
  • the colored layer on which the latent image was formed was developed with an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%) at 26 ° C. for 45 seconds, and then rinsed with running water for 20 seconds. And dried with a spray to obtain a fine line pattern image.
  • the obtained fine line pattern image was post-baked at 230 ° C. for 20 minutes to obtain a colored layer (colored cured film) B having a thickness of 2 ⁇ m.
  • Contrast The obtained substrate having each colored layer B is sandwiched between two polarizing films, and the luminance value is measured when the polarization axes of the two polarizing films are parallel and perpendicular. (Topcon Co., Ltd., model number: BM-5A), and the value obtained by dividing the luminance when the polarization axes of the two polarizing films are parallel by the luminance when perpendicular is obtained. Obtained as contrast. The higher the contrast, the better the performance as a color filter for a liquid crystal display device.
  • Example 1-1 the amount of the specific dye (B) used was changed as shown in Table 1, and other than that, a colored curable composition was prepared in the same manner as in Example 1-1. A colored layer was formed and evaluated. The evaluation results are also shown in Table 2.
  • the obtained colored curable composition was evaluated in the same manner as in Example 1-1. The evaluation results are shown in Table 2.
  • the dye solution 3 was prepared by mixing and dissolving the following components.
  • the dye concentration of the dye solution 3 was 0.1% with respect to the color material in the colored curable composition.
  • Organic solvent 1 propylene glycol monomethyl ether acetate
  • Specific dye (B) (P-32) 2.4 parts
  • Dye solution 2 is the same dye solution as used in Example 1-1. ⁇ Organic solvent 1 (propylene glycol monomethyl ether acetate) 48.0 parts ⁇ Specific dye (A) (compound 1) 2.6 parts In dye solution 3, specific dye (B) (P-32) is dye The solution 2 contains (Compound 1) which is the specific dye (A).
  • Example 1-5 the amount of the specific dye (B) used in the dye solution 3 was changed as shown in Table 1, and other than that, the colored curable composition was the same as Example 1-5. Were prepared to form a colored layer and evaluated. The evaluation results are shown in Table 2.
  • Example 1-9 to 1-12 the type of the specific dye (B) in the dye solution 1 was changed as shown in Table 1, and a colored curable composition was prepared in the same manner as in Example 1-3 except that. Then, a colored layer was formed and evaluated. The evaluation results are shown in Table 2 below.
  • Example 1-13 to 1-15 the specific dye (A) in the dye solution 2 was changed as shown in Table 1, except that a colored curable composition was prepared in the same manner as in Example 1-3. A colored layer was formed and evaluated. The evaluation results are shown in Table 2 below.
  • Example 1-7 the specific dye (A) in the dye solution 2 was changed as shown in Table 1, except that a colored curable composition was prepared in the same manner as in Example 1-7. A colored layer was formed and evaluated. The evaluation results are shown in Table 2 below.
  • the dye solution 4 was prepared by mixing and dissolving the following components. ⁇ Organic solvent 1 (propylene glycol monomethyl ether acetate) 44.6 parts ⁇ Exemplary compound CB-34 described in JP-A-2008-292970 2.4 parts After evaluation, evaluation was performed in the same manner as in Example 1-1. The results are shown in Table 2.
  • the porphyrin compound contained in the dye solution 4 has an aromatic ring structure in which A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 are all in the general formula (II). It is a dye that is out of the scope of the present invention.
  • the evaluation results shown in Table 2 revealed the following. Coloration formed by the colored curable composition according to the present invention, in which a specific dye (A) selected from the group consisting of xanthene compounds and triarylmethane compounds of Examples 1-1 to 1-18 and a porphyrin compound are combined
  • the cured film has both high contrast and spectral characteristics. As shown in Examples 1-1 and 1-5, even if the content of the specific dye (B) is very small, this is used. It can be seen that it has higher contrast and brightness improvement effect than the comparative example 1-1. As shown in Comparative Example 1-1, when the porphyrin compound was not used, the contrast of the colored curable composition was low and the performance was not sufficient.
  • a colored curable composition having good chromaticity and contrast can be obtained by using the specific dye (A) and the specific dye (B) in combination.
  • phthalocyanine compounds that are analogs of porphyrin compounds that is, all of A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 in the general formula (II)
  • the luminance and contrast are slightly lower than those of the Examples, and the performance is not sufficient.
  • the compound having a porphyrin structure represented by the general formula (II) according to the present invention has a smaller molecular structure and higher mobility than a comparative dye having a phthalocyanine structure. It is presumed that the effect of suppressing aggregation between the pigment particles is high.
  • ⁇ Preparation of red colored curable resin composition R> Ingredients having the following composition were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. For 3 hours.
  • the mixed solution thus obtained was further subjected to a dispersion treatment for 12 hours using a bead disperser disperse mat (made by GETZMANN) using 0.3 mm ⁇ zirconia beads, and then further a high-pressure disperser NANO-3000 with a decompression mechanism.
  • Dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using -10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.
  • Red colored curable resin composition R Components of the following composition were further added to the obtained pigment dispersion to prepare a red colored curable resin composition R.
  • Photopolymerization initiator (2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer) 3.1 parts.4 , 4'-bis (diethylamino) benzophenone (sensitizing dye) 4.2 parts, 2-mercaptobenzothiazole (hydrogen donating compound) 2.1 parts, polymerization inhibitor: p-methoxyphenol 0.001 part, fluorine-based Surfactant (trade name: Megafac 08 manufactured by DIC (Ltd.)) 0.5 parts Propylene glycol monomethyl ether acetate 60 parts
  • a black colored curable resin composition K was prepared with the following composition.
  • Surfactant the following compound
  • ⁇ Formation of color filter> ⁇ Formation of black matrix>
  • the alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water.
  • the substrate was heat treated at 120 ° C. for 3 minutes to stabilize the surface state, and then the substrate was cooled and adjusted to 23 ° C.
  • the black colored curable resin composition K was applied to the substrate using a glass substrate coater (trade name: MH-1600, manufactured by FS Asia Co., Ltd.) having a slit nozzle.
  • KOH containing nonionic surfactant, trade names: CDK-1, Fuji
  • the film was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image.
  • ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image K was obtained.
  • heat treatment was performed at 220 ° C. for 30 minutes to form a black matrix.
  • Spacer formation> A spacer was formed on the ITO transparent electrode produced above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.
  • liquid crystal alignment control protrusions were formed on the ITO transparent electrode on which the spacers were formed.
  • the following methods were used for exposure, development, and baking.
  • a proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 ⁇ m from the surface of the curable resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm 2 .
  • a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C.
  • the liquid crystal alignment control protrusion made of the curable resin layer patterned into a desired shape is formed on the color filter side substrate.
  • a display device substrate was obtained.
  • the liquid crystal display device substrate on which the liquid crystal alignment control protrusions were formed was baked at 230 ° C. for 30 minutes to form cured liquid crystal alignment control protrusions on the liquid crystal display device substrate.
  • an LED light source (a liquid crystal television manufactured by Sony Corporation, a backlight light source of KDL-40ZX1) was disposed as a light source on the side of the liquid crystal cell provided with the polarizing plate, thereby obtaining a liquid crystal display (LCD).
  • the liquid crystal display device produced as described above has high contrast and brightness, and is suitable as a display device.
  • the MVA mode liquid crystal display device was evaluated.
  • the colored curable composition of the present invention is used for a liquid crystal display device of another mode or a color filter of an organic EL display, the same applies. It seems that good image quality can be obtained.
  • Example 2-1 The following components were mixed and dissolved to prepare a colored curable composition 2-1, which was evaluated.
  • Organic solvent propylene glycol monomethyl ether acetate
  • Organic solvent diethylene glycol ethyl methyl ether
  • Part block isocyanate B1 (Asahi Kasei Chemicals Corporation, TPA-B80X) 2.2 parts monomer (M-1) 3.3 parts polymerizable compound 1 (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 3 2 parts
  • Polymerization inhibitor p-methoxyphenol
  • Photopolymerization initiator 1 (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazole)
  • the dye solution 1 was prepared by mixing and dissolving the following components.
  • Organic solvent 1 (propylene glycol monomethyl ether acetate) 44.6 parts Specific dye (B) (P-26) 2.4 parts
  • Dye solution 2 was prepared by mixing and dissolving the following components.
  • ⁇ Organic solvent 1 (propylene glycol monomethyl ether acetate) 48.0 parts
  • Specific dye (A) (compound 1) 2.6 parts
  • specific dye (B) (P-26) is dye
  • the solution 2 contains (Compound 1) which is the specific dye (A).
  • the chromium-coated glass substrate on which the coating film was formed was heated and cured (post-baked) at 180 ° C. for 60 minutes using a hot air circulation dryer to prepare a test piece.
  • the coating film at one corner of the test piece was scraped to expose the chromium surface.
  • a silver paste was spin-coated on the back surface of the test piece and air-dried. Thereafter, the chromium exposed surface on the front surface and the silver paste coated surface on the back surface were electrically connected (connected) with the silver paste.
  • Example 2-2 to 2-4 Colored curable compositions 2-2 to 2-4 were prepared in the same manner as in Example 2-1, except that the specific dye A (compound 1) used in Example 2-1 was changed to compounds 2 to 4. Evaluation was performed in the same manner as in Example 2-1. The evaluation results are shown in Table 3.
  • the colored curable composition comprising the combination of the specific dye A and the specific dye B of the present invention shows suitable performance even when used for a color filter for COA.

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Abstract

This colored curable composition contains a colored compound containing: (A) at least one type of dye compound selected from a group of compounds represented by general formulas (I-1) and (I-2); and (B) a porphyrin compound represented by general formula (II).

Description

着色硬化性組成物、カラーフィルタ、カラーフィルタの製造方法、および表示装置Colored curable composition, color filter, method for producing color filter, and display device
　本発明は、染料を着色化合物として含む着色硬化性組成物、カラーフィルタ、カラーフィルタの製造方法、および表示装置に関する。 The present invention relates to a colored curable composition containing a dye as a coloring compound, a color filter, a method for producing a color filter, and a display device.
　液晶表示装置や固体撮像素子等に用いられるカラーフィルタを作製する方法の１つとして、顔料分散法が広く利用されている。顔料分散法としては、顔料を種々の感光性組成物に分散させた着色硬化性組成物を用い、フォトリソ法によってカラーフィルタを作製する方法がある。この方法は、顔料を含有するために光や熱に対して安定であると共に、フォトリソ法によってパターニングするため、位置精度が充分に確保され、液晶表示装置、ＥＬ表示装置等に用いられるカラーディスプレー用カラーフィルタなどの作製に好適な方法とされている。 A pigment dispersion method is widely used as one of methods for producing a color filter used for a liquid crystal display device, a solid-state imaging device, or the like. As a pigment dispersion method, there is a method of producing a color filter by a photolithography method using a colored curable composition in which a pigment is dispersed in various photosensitive compositions. This method is stable against light and heat because it contains a pigment, and is patterned by a photolithographic method, so that the positional accuracy is sufficiently secured, and used for a liquid crystal display device, an EL display device, etc. The method is suitable for producing a color filter or the like.
　カラーフィルタの作製に用いられる着色化合物としては、顔料だけでなく、染料などの顔料以外の色素化合物も広く検討されている。そのうち、染料としては、ピリミジンアゾ系染料、ピラゾールアゾ系染料、キサンテン系染料、トリアリールメタン染料など、多種多様な色素母体を持つ化合物が知られている（例えば、特許第３３８７５４１号公報、特開２００９－２６５６４１号公報、および特開２００９－１８６６５７号公報参照）。 As coloring compounds used in the production of color filters, not only pigments but also coloring compounds other than pigments such as dyes have been widely studied. Among them, as dyes, compounds having a wide variety of dye bases such as pyrimidine azo dyes, pyrazole azo dyes, xanthene dyes, triarylmethane dyes are known (for example, Japanese Patent No. 3387541, JP 2009-265641 and JP-A 2009-186657).
　着色化合物として染料を使用すると、染料自体の色純度やその色相の鮮やかさにより、画像表示させたときの表示画像の色相や輝度を高めることができる点で有用とされてはいるものの、しかしながら、染料を使用したカラーフィルタの画像特性には、なお改良の余地があり、コントラスト、輝度性能において更なる改良が求められているのが現状である。 When a dye is used as a coloring compound, although it is considered useful because it can increase the hue and brightness of a display image when an image is displayed due to the color purity of the dye itself and the vividness of the hue, There is still room for improvement in the image characteristics of color filters using dyes, and there is a need for further improvements in contrast and luminance performance.
　本発明は、上記従来の技術に鑑みなされたものである。すなわち、本発明は、輝度を高めつつ、高いコントラストを有する着色硬化膜を形成し得る、カラーフィルタの着色パターンの形成に有用な着色硬化性組成物を提供することを課題とする。
　また、本発明は、前記本発明の着色硬化性組成物を用いた、高輝度でコントラストの高い画像の表示が可能なカラーフィルタ、およびその製造方法、並びに該カラーフィルタを用いてなる、画質の良好な画像表示が可能な表示装置を提供することを課題とする。 The present invention has been made in view of the above prior art. That is, an object of the present invention is to provide a colored curable composition useful for forming a colored pattern of a color filter, which can form a colored cured film having high contrast while increasing luminance.
The present invention also provides a color filter capable of displaying a high-brightness and high-contrast image using the colored curable composition of the present invention, a method for producing the same, and an image quality using the color filter. It is an object to provide a display device capable of displaying a good image.
　本発明者らは前記課題を解決すべく鋭意検討を行なった結果、特定染料と特定のポルフィリン構造を持つ染料とを組み合わせて用いることにより非常に高い輝度と高いコントラストを両立できることを見出し、本発明を完成した。
　即ち、前記課題を達成するための具体的手段は以下の通りである。
＜１＞（Ａ）下記一般式（Ｉ－１）及び（Ｉ－２）で表される化合物からなる群より選択される１種以上の色素化合物と、（Ｂ）下記一般式（ＩＩ）で表されるポルフィリン化合物と、を含む着色化合物を含有する着色硬化性組成物。 As a result of intensive studies to solve the above problems, the present inventors have found that a combination of a specific dye and a dye having a specific porphyrin structure can achieve both extremely high luminance and high contrast, and the present invention. Was completed.
That is, specific means for achieving the above-described problem are as follows.
<1> (A) one or more dye compounds selected from the group consisting of compounds represented by the following general formulas (I-1) and (I-2); and (B) the following general formula (II): The coloring curable composition containing the coloring compound containing the porphyrin compound represented.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（前記一般式（Ｉ－１）において、Ｒ１、Ｒ２、Ｒ３、及びＲ４は、各々独立に、水素原子、炭素数１～１０の飽和炭化水素基、又は炭素数６～１０の芳香族炭化水素基を表す。Ｒ５は、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３Ｍ、－ＣＯ２Ｈ、－ＣＯ２Ｒ６、－ＳＯ３Ｒ６、－ＳＯ２ＮＨＲ８、又は－ＳＯ２ＮＲ８Ｒ９を表す。Ｒ６は、炭素数１～１０の飽和炭化水素基を表す。Ｒ８及びＲ９は、各々独立に、水素原子、炭素数１～１０の直鎖又は分岐のアルキル基、炭素数３～３０のシクロアルキル基、炭素数６～１０の芳香族炭化水素基、又は炭素数５～１０の芳香族複素環基を表し、Ｒ８とＲ９とは互いに結合して炭素数１～１０の複素環を形成してもよい。Ｍは、ナトリウム原子又はカリウム原子を表す。ｍは、０～５の整数を表し、ｍが２以上の整数である場合、複数のＲ５は同一でも異なっていてもよい。ｎ１、ｎ２、ｎ３、及びｎ４は、各々独立に０又は１を表す。Ｘは、ハロゲン原子を表す。ａは、０又は１の整数を表す。ただし、ｎ１～ｎ４の全てが１を表しかつＲ５が－ＳＯ３ －以外の基を表す場合はａ＝１であり、ｎ１～ｎ４の少なくとも１つが０を表す場合はａ＝０である。） (In the general formula (I-1), R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or a group having 6 to 10 carbon atoms. R 5 represents an aromatic hydrocarbon group, R 5 represents —SO 3 − , —SO 3 H, —SO 3 M, —CO 2 H, —CO 2 R 6 , —SO 3 R 6 , —SO 2 NHR 8 , Or —SO 2 NR 8 R 9 , where R 6 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and R 8 and R 9 each independently represent a hydrogen atom or a straight chain having 1 to 10 carbon atoms. Or a branched alkyl group, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic heterocyclic group having 5 to 10 carbon atoms, and R 8 and R 9 are They may combine with each other to form a heterocyclic ring having 1 to 10 carbon atoms, and M represents a sodium atom or a potassium atom. Represents an integer of 0 to 5, when m is an integer of 2 or more, the plurality of R 5 may be the same or different .n1, n2, n3, and n4 are each independently 0 or 1 X represents a halogen atom, a represents an integer of 0 or 1, provided that when n1 to n4 all represent 1 and R 5 represents a group other than —SO 3 — , a = 1 And when at least one of n1 to n4 represents 0, a = 0.)
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
（前記一般式（Ｉ－２）において、Ｒ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５、及びＲ１０６は、各々独立に、水素原子、炭素数１～１０の飽和炭化水素基、又は炭素数６～１０の芳香族炭化水素基を表す。Ｒ１０７及びＲ１０８は、各々独立に、水素原子又は炭素数４～８の飽和炭化水素基を表す、あるいは、Ｒ１０７とＲ１０８は互いに結合して芳香族炭化水素環を形成している。Ｒ１０９は、水素原子又は炭素数１～１０の飽和炭化水素基を表す。Ｘは、ハロゲン原子、ＢＦ４、ＰＦ６、ＣｌＯ４、Ｎ（ＳＯ２ＣＦ３）２、又はＡｒＳＯ３を表し、Ａｒは、炭素数６～１０の芳香族炭化水素基を表す。ａは、０又は１の整数を表す。） (In the general formula (I-2), R 101 , R 102 , R 103 , R 104 , R 105 , and R 106 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or Represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, R 107 and R 108 each independently represent a hydrogen atom or a saturated hydrocarbon group having 4 to 8 carbon atoms, or R 107 and R 108 are R 109 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, and X represents a halogen atom, BF 4 , PF 6 , ClO 4 , N (SO 2 CF 3 ) 2 or ArSO 3 , Ar represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a represents an integer of 0 or 1.)
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
（前記一般式（ＩＩ）中、Ｚ１、Ｚ２、Ｚ３及びＺ４はすべてがＮを表すか、若しくは、Ｚ１とＺ３、Ｚ２とＺ４のいずれか１組が双方ともにＮを表し、他の一組が双方ともにＣ－Ｒを表し、Ｒは、各々独立に水素原子、アルキル基、又はアリール基を表す。Ａ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７及びＡ８は各々独立にアルキル基、アルケニル基、アリール基、アルコキシ基、アルキルチオ基、アリールオキシ基、アリールチオ基、ハロゲン原子、ヒドロキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アミノ基、カルバモイル基、スルファモイル基、アシル基、シリルオキシ基、シアノ基、ニトロ基、又はヘテロ環基を表す。Ａ１とＡ２、Ａ３とＡ４、Ａ５とＡ６、及びＡ７とＡ８は、各々互いに結合して環構造を形成してもよいが、これらのうち少なくとも１組は環構造を形成しない。Ｍは２価の金属原子、又は金属原子を含む２価の原子団を表す。 (In the general formula (II), Z 1 , Z 2 , Z 3 and Z 4 are all N, or any one of Z 1 and Z 3 , Z 2 and Z 4 is N Each of the other groups represents C—R, each R independently representing a hydrogen atom, an alkyl group, or an aryl group, A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 are each independently an alkyl group, alkenyl group, aryl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, halogen atom, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group Carbamoyl group, sulfamoyl group, acyl group, silyloxy group, cyano group, nitro group, or heterocyclic group, A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 Each May be bonded together to form a ring structure, at least one pair of these do not form a ring structure .M represents a divalent atomic group containing a divalent metal atom or a metal atom.
＜２＞　前記（Ｂ）一般式（ＩＩ）で表される化合物が、下記一般式（ＩＩ－２）で表される化合物である＜１＞に記載の着色硬化性組成物。 <2> The colored curable composition according to <1>, wherein the compound represented by (B) the general formula (II) is a compound represented by the following general formula (II-2).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（前記一般式（ＩＩ－２）中、Ａ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７、Ａ８及びＭは、一般式（ＩＩ）におけるＡ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７、Ａ８及びＭと各々同義である。） (In the general formula (II-2), A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M are the same as A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M are respectively synonymous.)
＜３＞　さらに、（Ｃ）重合性化合物、及び（Ｄ）光重合開始剤を含有する＜１＞又は＜２＞に記載の着色硬化性組成物。
＜４＞　前記（Ｂ）一般式（ＩＩ）で表される化合物の含有量が、前記着色化合物の総量に対して０．１質量％以上５０質量％以下である＜１＞～＜３＞のいずれか１つに記載の着色硬化性組成物。
＜５＞　前記一般式（ＩＩ）で表される化合物中、Ａ１とＡ２、Ａ３とＡ４、Ａ５とＡ６、及びＡ７とＡ８のいずれもが環構造を形成していない＜１＞～＜４＞のいずれか１つに記載の着色硬化性組成物。
＜６＞　前記着色化合物の総含有量が、着色硬化性組成物の全固形分に対して、０．２質量％以上５０質量％以下である＜１＞～＜５＞のいずれか１つに記載の着色硬化性組成物。
＜７＞　＜１＞～＜６＞のいずれか１つに記載の着色硬化性組成物を硬化して得られた着色膜を備えるカラーフィルタ。
＜８＞　＜１＞～＜６＞のいずれか１つに記載の着色硬化性組成物を、支持体上に付与して着色層を形成する着色層形成工程と、形成された着色層をパターン様に露光する露光工程と、露光後の着色層を現像して着色パターンを形成する現像工程と、を有するカラーフィルタの製造方法。
＜９＞　＜７＞に記載のカラーフィルタ又は＜８＞に記載の製造方法により得られたカラーフィルタを具備してなる表示装置。 <3> The colored curable composition according to <1> or <2>, further comprising (C) a polymerizable compound and (D) a photopolymerization initiator.
<4> The content of the compound represented by the general formula (II) (B) is from 0.1% by mass to 50% by mass with respect to the total amount of the colored compounds. The colored curable composition as described in any one.
<5> In the compound represented by the general formula (II), A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 all form a ring structure. The colored curable composition according to any one of <1> to <4>.
<6> The total content of the coloring compound is any one of <1> to <5>, in which the total solid content of the colored curable composition is 0.2% by mass or more and 50% by mass or less. The colored curable composition as described.
<7> A color filter comprising a colored film obtained by curing the colored curable composition according to any one of <1> to <6>.
<8> A colored layer forming step of forming a colored layer by applying the colored curable composition according to any one of <1> to <6> onto a support, and patterning the formed colored layer A method for producing a color filter comprising: an exposure step of exposing in a similar manner; and a development step of developing a colored layer after exposure to form a colored pattern.
<9> A display device comprising the color filter according to <7> or the color filter obtained by the production method according to <8>.
　本発明は、着色化合物として、一般式（Ｉ－１）で表されるキサンテン系染料及び一般式（Ｉ－２）で表されるトリアリールメタン化合物からなる群より選択される１種以上の色素化合物と、一般式（ＩＩ）で表されるポルフィリン化合物とを組み合わせたものである。これにより、消光性能が向上し、高いコントラストを有し、高輝度の着色硬化膜を形成し得る。 The present invention provides at least one dye selected from the group consisting of a xanthene dye represented by the general formula (I-1) and a triarylmethane compound represented by the general formula (I-2) as the coloring compound. A compound and a porphyrin compound represented by the general formula (II) are combined. Thereby, the quenching performance is improved, and a colored cured film having high contrast and high brightness can be formed.
　本発明によれば、輝度を高めつつ、高いコントラストを有する着色硬化膜を形成し得る、カラーフィルタの着色パターンの形成に有用な着色硬化性組成物を提供することができる。
　また、本発明によれば、前記本発明の着色硬化性組成物を用いた、高輝度でコントラストの高い画像の表示が可能なカラーフィルタ、およびその製造方法、並びに該カラーフィルタを用いてなる、良好な画質の画像表示が可能な表示装置を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the colored curable composition useful for formation of the colored pattern of a color filter which can form the colored cured film which has high contrast, improving a brightness | luminance can be provided.
Further, according to the present invention, using the colored curable composition of the present invention, a color filter capable of displaying a high-brightness and high-contrast image, a manufacturing method thereof, and the color filter are used. A display device capable of displaying an image with good image quality can be provided.
本発明の実施例における比誘電率の測定において作製した主電極及びガード電極を示す概略平面図である。It is a schematic plan view which shows the main electrode and guard electrode which were produced in the measurement of the dielectric constant in the Example of this invention.
　以下、本発明の着色硬化性組成物について詳細に説明すると共に、これを用いた本発明のカラーフィルタ及びその製造方法、並びに表示装置について詳細に説明する。 Hereinafter, the colored curable composition of the present invention will be described in detail, and the color filter of the present invention using the same, the manufacturing method thereof, and the display device will be described in detail.
＜＜着色硬化性組成物＞＞
　本発明の着色硬化性組成物は、着色化合物として、（Ａ）一般式（Ｉ－１）及び（Ｉ－２）で表される化合物から選択される１種以上の色素化合物と、（Ｂ）一般式（ＩＩ）で表されるポルフィリン化合物と、を含む着色化合物を少なくとも含有する組成物である。好ましくは、さらに、（Ｃ）重合性化合物、及び（Ｄ）光重合開始剤を含有し、感光性を有する組成物である。
　また、本発明にかかる着色硬化性組成物は、着色化合物としては、（Ａ）一般式（Ｉ－１）及び（Ｉ－２）で表される化合物から選択される１種以上の色素化合物と、（Ｂ）一般式（ＩＩ）で表されるポルフィリン化合物に加え、本発明の効果を損なわない限りにおいて、他の有機染料、顔料等の他の着色化合物を含んでいてもよい。他の有機染料の例としては、ピラゾールアゾ系、アニリノアゾ系、アントラキノン系、アンスラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、スクアリリウム系、フタロシアニン系、べンゾピラン系、インジゴ系等の染料が挙げられる。
　本発明の着色硬化性組成物は、必要に応じて、本発明の効果を損なわない限りにおいて、さらに、アルカリ可溶性バインダー等のバインダー樹脂、有機溶剤、及び各種添加剤を含有してもよい。 << Colored curable composition >>
The colored curable composition of the present invention comprises (A) one or more dye compounds selected from the compounds represented by the general formulas (I-1) and (I-2) as a coloring compound, and (B) And a porphyrin compound represented by the general formula (II). Preferably, the composition further contains (C) a polymerizable compound and (D) a photopolymerization initiator and has photosensitivity.
The colored curable composition according to the present invention includes (A) one or more dye compounds selected from the compounds represented by formulas (I-1) and (I-2), (B) In addition to the porphyrin compound represented by the general formula (II), other colored compounds such as other organic dyes and pigments may be included as long as the effects of the present invention are not impaired. Examples of other organic dyes include pyrazole azo, anilinoazo, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, squarylium And dyes such as phthalocyanine, benzopyran, and indigo.
The colored curable composition of the present invention may further contain a binder resin such as an alkali-soluble binder, an organic solvent, and various additives as long as the effects of the present invention are not impaired as necessary.
　以下、本発明の着色硬化性組成物を構成する各成分について、詳細に説明する。なお、以下において、本発明の着色硬化性組成物を単に「本発明の着色組成物」又は「着色組成物」と称することがある。
　なお、本明細書中において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　本明細書においては「アルキル基」は「直鎖、分岐及び環状」のアルキル基の総称である。また、本明細書における置換基（原子団）は、無置換のもの及び置換基をさらに有するものを包含する意味で使用される。即ち、本明細書において、「アルキル基」とは、無置換のアルキル基及び置換アルキル基を包含する意味で用いられ、他の置換基も同様である。 Hereinafter, each component which comprises the colored curable composition of this invention is demonstrated in detail. In the following, the colored curable composition of the present invention may be simply referred to as “colored composition of the present invention” or “colored composition”.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, the “alkyl group” is a general term for “linear, branched and cyclic” alkyl groups. Moreover, the substituent (atomic group) in this specification is used by the meaning including the thing which has an unsubstituted thing and a substituent further. That is, in the present specification, the “alkyl group” is used in a meaning including an unsubstituted alkyl group and a substituted alkyl group, and the same applies to other substituents.
　本発明の着色硬化性組成物は、（Ａ）一般式（Ｉ－１）及び（Ｉ－２）で表される化合物からなる群より選択される１種以上の色素化合物と、（Ｂ）一般式（ＩＩ）で表されるポルフィリン化合物と、を含む着色化合物を含有する。
　以下、着色化合物について順次説明する。
＜一般式（Ｉ）で表される色素化合物＞
　本発明の着色化合物は、（Ａ）一般式（Ｉ－１）及び（Ｉ－２）で表される化合物からなる群より選択される１種以上の色素化合物（以下、適宜「特定染料（Ａ）」とも称する。）を含有する。 The colored curable composition of the present invention comprises (A) one or more dye compounds selected from the group consisting of compounds represented by general formulas (I-1) and (I-2), and (B) general And a porphyrin compound represented by the formula (II).
Hereinafter, the colored compounds will be sequentially described.
<Dye Compound Represented by General Formula (I)>
The colored compound of the present invention comprises (A) one or more pigment compounds selected from the group consisting of compounds represented by formulas (I-1) and (I-2) (hereinafter referred to as “specific dye (A ) ").
（一般式（Ｉ－１）で表される化合物）
　本発明にかかる着色硬化性組成物が、下記一般式（Ｉ－１）で表されるキサンテン染料の少なくとも一種を含有することにより、アルカリ処理（例えば露光後のアルカリ現像）したときには本発明にかかる着色硬化性組成物は、優れたアルカリ溶解性を示す。 (Compound represented by formula (I-1))
The colored curable composition according to the present invention contains at least one xanthene dye represented by the following general formula (I-1) so that the present invention is applied when subjected to alkali treatment (for example, alkali development after exposure). The colored curable composition exhibits excellent alkali solubility.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　前記一般式（Ｉ－１）において、Ｒ１、Ｒ２、Ｒ３、及びＲ４は、各々独立に、水素原子、炭素数１～１０の飽和炭化水素基、又は炭素数６～１０の芳香族炭化水素基を表す。 In the general formula (I-1), R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic group having 6 to 10 carbon atoms. Represents a group hydrocarbon group.
　前記炭素数１～１０の飽和炭化水素基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ペンチル、イソペンチル、ネオペンチル、シクロペンチル、ヘキシル、シクロヘキシル、ヘプチル、シクロヘプチル、オクチル、２－エチルヘキシル、シクロオクチル、ノニル、デカニル、トリシクロデカニル、メトキシプロピル、エトキシプロピル、ヘキシロキシプロピル、２－エチルヘキシロキシプロピル、メトキシヘキシル、エトキシプロピル等の基が挙げられる。中でも、好ましくは炭素数１～９のアルキル基であり、より好ましくは炭素数１～８のアルキル基である。 Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, 2-ethylhexyl. , Cyclooctyl, nonyl, decanyl, tricyclodecanyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, ethoxypropyl, and the like. Among them, preferred is an alkyl group having 1 to 9 carbon atoms, and more preferred is an alkyl group having 1 to 8 carbon atoms.
　前記炭素数６～１０の芳香族炭化水素基としては、例えば、フェニル、ナフチル等の基が挙げられる。炭素数６～１０の芳香族炭化水素基は、ハロゲン原子、炭素数１～１０の飽和炭化水素基、－ＯＨ、－ＯＲ６、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３Ｍ、－ＣＯ２Ｈ、－ＣＯ２Ｒ６、－ＳＯ３Ｒ６、－ＳＯ２ＮＨＲ８又は－ＳＯ２ＮＲ８Ｒ９で置換されていてもよい。Ｒ６は、炭素数１～１０の飽和炭化水素基を表し、前記Ｒ１～Ｒ４における「炭素数１～１０の飽和炭化水素基」と同義であり、好ましい態様も同様である。Ｒ８、Ｒ９、及びＭの詳細については、後述する。 Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include groups such as phenyl and naphthyl. The aromatic hydrocarbon group having 6 to 10 carbon atoms includes a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR 6 , —SO 3 — , —SO 3 H, —SO 3 M, — It may be substituted with CO 2 H, —CO 2 R 6 , —SO 3 R 6 , —SO 2 NHR 8 or —SO 2 NR 8 R 9 . R 6 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and is synonymous with the “saturated hydrocarbon group having 1 to 10 carbon atoms” in the above R 1 to R 4 , and the preferred embodiment is also the same. Details of R 8 , R 9 , and M will be described later.
　前記ハロゲン原子としては、例えば、フッ素、塩素、臭素等が挙げられる。
　前記「－ＳＯ３Ｒ６」としては、例えば、メタンスルホニル、エタンスルホニル、ヘキサンスルホニル、デカンスルホニル等が挙げられる。
　前記「－ＣＯ２Ｒ６」としては、例えば、メチルオキシカルボニル、エチルオキシカルボニル、プロピルオキシカルボニル、イソプロピルオキシカルボニル、ブチルオキシカルボニル、イソブチルオキシカルボニル、ペンチルオキシカルボニル、イソペンチルオキシカルボニル、ネオペンチルオキシカルボニル、シクロペンチルオキシカルボニル、ヘキシルオキシカルボニル、シクロヘキシルオキシカルボニル、ヘプチルオキシカルボニル、シクロヘプチルオキシカルボニル、オクチルオキシカルボニル、２－エチルヘキシルオキシカルボニル、シクロオクチルオキシカルボニル、ノニルオキシカルボニル、デカニルオキシカルボニル、トリシクロデカニルオキシカルボニル、メトキシプロピルオキシカルボニル、エトキシプロピルオキシカルボニル、ヘキシロキシプロピルオキシカルボニル、２－エチルヘキシロキシプロピルオキシカルボニル、メトキシヘキシルオキシカルボニル等が挙げられる。 Examples of the halogen atom include fluorine, chlorine, bromine and the like.
Examples of the “—SO 3 R 6 ” include methanesulfonyl, ethanesulfonyl, hexanesulfonyl, decanesulfonyl and the like.
Examples of the “—CO 2 R 6 ” include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl. , Cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclooctyloxycarbonyl, nonyloxycarbonyl, decanyloxycarbonyl, tricyclodecanyl Oxycarbonyl, methoxypropyloxycarbonyl, ethoxypropyloxy Examples include carbonyl, hexyloxypropyloxycarbonyl, 2-ethylhexyloxypropyloxycarbonyl, methoxyhexyloxycarbonyl and the like.
　Ｒ８及びＲ９は、各々独立に、水素原子、炭素数１～１０の直鎖又は分岐のアルキル基、炭素数３～３０のシクロアルキル基、炭素数６～１０の芳香族炭化水素基、又は炭素数５～１０の芳香族複素環基を表し、Ｒ８とＲ９とは互いに結合して炭素数１～１０の複素環を形成してもよい。また、Ｒ８及びＲ９で表される前記芳香族炭化水素基及び前記芳香族複素環基は、－ＯＨ、炭素数１～１０の飽和炭化水素基、－ＯＲ６、－ＮＯ２、－ＣＨ＝ＣＨ２、－ＣＨ＝ＣＨＲ６、又はハロゲン原子で置換されていてもよい。Ｒ６は、炭素数１～１０の飽和炭化水素基を表す。炭素数１～１０の飽和炭化水素基は、前記Ｒ１～Ｒ４における「炭素数１～１０の飽和炭化水素基」と同義であり、好ましい態様も同様である。 R 8 and R 9 are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, Alternatively, it represents an aromatic heterocyclic group having 5 to 10 carbon atoms, and R 8 and R 9 may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms. In addition, the aromatic hydrocarbon group and the aromatic heterocyclic group represented by R 8 and R 9 are —OH, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OR 6 , —NO 2 , —CH ═CH 2 , —CH═CHR 6 , or a halogen atom may be substituted. R 6 represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the “saturated hydrocarbon group having 1 to 10 carbon atoms” in R 1 to R 4 , and the preferred embodiment is also the same.
　Ｒ８、Ｒ９で表される炭素数１～１０の直鎖又は分岐のアルキル基は、無置換でも置換基を有してもよく、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ペンチル、イソペンチル、ヘキシル、２－エチルヘキシル、１，５－ジメチルヘキシル、オクチル等の基が挙げられる。中でも、炭素数１～８の直鎖又は分岐のアルキル基が好ましい。
　Ｒ８、Ｒ９で表される炭素数３～３０のシクロアルキル基は、無置換でも置換基を有してもよく、例えば、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル、トリシクロデシル等の基が挙げられる。中でも、炭素数３～１５のシクロアルキル基が好ましい。
　Ｒ８、Ｒ９で表される炭素数６～１０の芳香族炭化水素基は、例えば、フェニル、ナフチル等の基が挙げられる。
　Ｒ８、Ｒ９で表される炭素数５～１０の芳香族複素環基は、複素原子として酸素原子、窒素原子等を有する芳香族複素環基が挙げられ、例えば、ピロール環基、ピラジン環、ピリジン環基、チアジン環基、トリアジン環基、ピラン環基、フラン環基、モルホリン環基、等が挙げられる。 The linear or branched alkyl group having 1 to 10 carbon atoms represented by R 8 and R 9 may be unsubstituted or substituted, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Examples include pentyl, isopentyl, hexyl, 2-ethylhexyl, 1,5-dimethylhexyl, octyl and the like. Of these, a linear or branched alkyl group having 1 to 8 carbon atoms is preferable.
The cycloalkyl group having 3 to 30 carbon atoms represented by R 8 and R 9 may be unsubstituted or substituted, and examples thereof include groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. Is mentioned. Of these, a cycloalkyl group having 3 to 15 carbon atoms is preferable.
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 8 and R 9 include groups such as phenyl and naphthyl.
Examples of the aromatic heterocyclic group having 5 to 10 carbon atoms represented by R 8 and R 9 include aromatic heterocyclic groups having an oxygen atom, a nitrogen atom, etc. as a hetero atom, such as a pyrrole ring group and a pyrazine ring. Pyridine ring group, thiazine ring group, triazine ring group, pyran ring group, furan ring group, morpholine ring group, and the like.
　前記炭素数１～１０の直鎖又は分岐のアルキル基、及び前記炭素数３～３０のシクロアルキル基は、置換されていてもよい。これらが置換されている場合の置換基としては、例えば、水酸基、ハロゲン原子、炭素数６～１０の芳香族炭化水素基、炭素数５～１０の芳香族複素環基、－ＣＨ＝ＣＨ２、又は－ＣＨ＝ＣＨＲ６（Ｒ６：炭素数１～１０の飽和炭化水素基）が挙げられる。前記シクロアルキル基に含まれるメチレン基は、酸素原子、カルボニル基、又は－ＮＲ６－（Ｒ６：炭素数１～１０の飽和炭化水素基）で置換されてもよい。炭素数１～１０の飽和炭化水素基は、前記Ｒ１～Ｒ４における「炭素数１～１０の飽和炭化水素基」と同義であり、好ましい態様も同様である。 The linear or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms may be substituted. Examples of the substituent when they are substituted include a hydroxyl group, a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aromatic heterocyclic group having 5 to 10 carbon atoms, —CH═CH 2 , Or —CH═CHR 6 (R 6 : a saturated hydrocarbon group having 1 to 10 carbon atoms). The methylene group contained in the cycloalkyl group may be substituted with an oxygen atom, a carbonyl group, or —NR 6 — (R 6 : a saturated hydrocarbon group having 1 to 10 carbon atoms). The saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the “saturated hydrocarbon group having 1 to 10 carbon atoms” in R 1 to R 4 , and the preferred embodiment is also the same.
　前記炭素数６～１０の芳香族炭化水素基は、置換されていてもよい。置換されている場合の置換基としては、例えば、エチル、プロピル、フェニル、ジメチルフェニル、－ＳＯ３Ｒ６（Ｒ６：炭素数１～１０の飽和炭化水素基）又は－ＳＯ２ＮＨＲ８が好ましい。 The aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted. As the substituent in the case of substitution, for example, ethyl, propyl, phenyl, dimethylphenyl, —SO 3 R 6 (R 6 : saturated hydrocarbon group having 1 to 10 carbon atoms) or —SO 2 NHR 8 is preferable. .
　置換されている炭素数６～１０の芳香族炭化水素基としては、例えば、メチルフェニル、ジメチルフェニル、トリメチルフェニル、エチルフェニル、ヘキシルフェニル、デカニルフェニル、フルオロフェニル、クロロフェニル、ブロモフェニル、ヒドロキシフェニル、メトキシフェニル、ジメトキシフェニル、エトキシフェニル、ヘキシロキシフェニル、デカニロキシフェニル、トリフルオロメチルフェニル等が挙げられる。 Examples of the substituted aromatic hydrocarbon group having 6 to 10 carbon atoms include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, hexylphenyl, decanylphenyl, fluorophenyl, chlorophenyl, bromophenyl, hydroxyphenyl, Examples include methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decanyloxyphenyl, and trifluoromethylphenyl.
　また、Ｒ８とＲ９とが互いに結合して炭素数１～１０の複素環を形成している場合、炭素数１～１０の複素環は、炭素数１～１０の飽和炭化水素基、水酸基、炭素数６～１０の芳香族炭化水素基、又は炭素数５～１０の芳香族複素環基で置換されていてもよい。 In addition, when R 8 and R 9 are bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms, the heterocyclic ring having 1 to 10 carbon atoms is a saturated hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group , An aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic heterocyclic group having 5 to 10 carbon atoms may be substituted.
　上記の中でも、Ｒ８及びＲ９としては、炭素数６～８の分枝状アルキル基、炭素数５～７のシクロアルキル基、アリル基、フェニル基、炭素数８～１０のアラルキル基、炭素数２～８の水酸基含有アルキル、炭素数２～８の水酸基含有アリール基、又は炭素数２～８のアルコキシル基含有アルキル、炭素数２～８のアルコキシル基含有アリール基が好ましく、２－エチルヘキシルが特に好ましい。 Among them, R 8 and R 9 are each a branched alkyl group having 6 to 8 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, carbon A hydroxyl group-containing alkyl group having 2 to 8 carbon atoms, a hydroxyl group-containing aryl group having 2 to 8 carbon atoms, or an alkoxyl group-containing alkyl group having 2 to 8 carbon atoms, an alkoxyl group-containing aryl group having 2 to 8 carbon atoms is preferable, and 2-ethylhexyl is preferable. Particularly preferred.
　前記「－ＳＯ２ＮＨＲ８」としては、例えば、スルファモイル、メタンスルファモイル、エタンスルファモイル、プロパンスルファモイル、イソプロパンスルファモイル、ブタンスルファモイル、イソブタンスルファモイル、ペンタンスルファモイル、イソペンタンスルファモイル、ネオペンタンスルファモイル、シクロペンタンスルファモイル、ヘキサンスルファモイル、シクロヘキサンスルファモイル、ヘプタンスルファモイル、シクロヘプタンスルファモイル、オクタンスルファモイル、２－エチルヘキサンスルファモイル、１，５－ジメチルヘキサンスルファモイル、シクロオクタンスルファモイル、ノナンスルファモイル、デカンスルファモイル、トリシクロデカンスルファモイル、メトキシプロパンスルファモイル、エトキシプロパンスルファモイル、プロポキシプロパンスルファモイル、イソプロポキシプロパンスルファモイル、ヘキシロキシプロパンスルファモイル、２－エチルヘキシロキシプロパンスルファモイル、メトキシヘキサンスルファモイル、３－フェニル－１－メチルプロパンスルファモイル等が挙げられる。 Examples of the “—SO 2 NHR 8 ” include sulfamoyl, methanesulfamoyl, ethanesulfamoyl, propanesulfamoyl, isopropanesulfamoyl, butanesulfamoyl, isobutanesulfamoyl, pentanessulfamoyl, Isopentanesulfamoyl, neopentanesulfamoyl, cyclopentanesulfamoyl, hexanesulfamoyl, cyclohexanesulfamoyl, heptanesulfamoyl, cycloheptanesulfamoyl, octanessulfamoyl, 2-ethylhexanesulfamoyl 1,5-dimethylhexanesulfamoyl, cyclooctanesulfamoyl, nonanesulfamoyl, decanesulfamoyl, tricyclodecanesulfamoyl, methoxypropanesulfamoyl, ethoxy Propanesulfamoyl, propoxypropanesulfamoyl, isopropoxypropanesulfamoyl, hexyloxypropane sulfamoyl, 2-ethylhexyloxypropane sulfamoyl, methoxyhexanesulfamoyl, 3-phenyl-1-methylpropanesulfur A famoyl etc. are mentioned.
　また、前記「－ＳＯ２ＮＨＲ８」及び「－ＳＯ２ＮＲ８Ｒ９」としては、更に下記の構造式で表される基が挙げられる。
　なお、以下に示す構造式中のＸ１～Ｘ３は、以下の通りである。
　Ｘ１は、ハロゲン原子を表す。Ｘ１におけるハロゲン原子としては、フッ素原子、塩素原子及び臭素原子が挙げられる。
　Ｘ２は、炭素数１～３のアルキル基、炭素数１～３のアルコキシル基、ハロゲン原子、又はニトロ基を表し、該アルキル基及びアルコキシ基はハロゲン原子で置換されていてもよい。Ｘ２におけるハロゲン原子としては、フッ素原子、塩素原子及び臭素原子が挙げられる。炭素数１～３のアルキル基としては、メチル、エチル、プロピル、イソプロピル、パーフルオロメチル等が挙げられる。炭素数１～３のアルコキシ基としては、メトキシ、エトキシ、プロポキシ等が挙げられる。
　Ｘ３は、炭素数１～３のアルキル基又は炭素数１～３のアルコキシル基を表し、該アルキル基及びアルコキシ基はハロゲン原子で置換されていてもよい。炭素数１～３のアルキル基としては、メチル、エチル、プロピル、イソプロピル、パーフルオロメチル等が挙げられる。炭素数１～３のアルコキシ基としては、メトキシ、エトキシ、プロポキシ等が挙げられる。 Further, examples of the “—SO 2 NHR 8 ” and “—SO 2 NR 8 R 9 ” further include groups represented by the following structural formulas.
X 1 to X 3 in the structural formulas shown below are as follows.
X 1 represents a halogen atom. Examples of the halogen atom for X 1 include a fluorine atom, a chlorine atom, and a bromine atom.
X 2 represents an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a halogen atom, or a nitro group, and the alkyl group and the alkoxy group may be substituted with a halogen atom. Examples of the halogen atom for X 2 include a fluorine atom, a chlorine atom and a bromine atom. Examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, propyl, isopropyl, perfluoromethyl and the like. Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy, propoxy and the like.
X 3 represents an alkyl group having 1 to 3 carbon atoms or an alkoxyl group having 1 to 3 carbon atoms, and the alkyl group and the alkoxy group may be substituted with a halogen atom. Examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, propyl, isopropyl, perfluoromethyl and the like. Examples of the alkoxy group having 1 to 3 carbon atoms include methoxy, ethoxy, propoxy and the like.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　－ＳＯ３Ｍ中、Ｍは、ナトリウム原子又はカリウム原子を表す。
　Ｒ５は、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３Ｍ、－ＣＯ２Ｈ、－ＣＯ２Ｒ６、－ＳＯ３Ｒ６、－ＳＯ２ＮＨＲ８、又は－ＳＯ２ＮＲ８Ｒ９を表す。Ｒ６、Ｒ８、Ｒ９、及びＭは、上記の通りであり、好ましい態様も同様である。
　中でも、Ｒ５は、－ＣＯ２Ｈ、エチルオキシカルボニル、スルホキシル、２－エチルヘキシロキシプロパンスルファモイル、１，５－ジメチルヘキサンスルファモイル、３－フェニル－１－メチルプロパンスルファモイル、イソプロポキシプロパンスルファモイルである態様が好ましい。 In —SO 3 M, M represents a sodium atom or a potassium atom.
R 5 represents —SO 3 — , —SO 3 H, —SO 3 M, —CO 2 H, —CO 2 R 6 , —SO 3 R 6 , —SO 2 NHR 8 , or —SO 2 NR 8 R 9. Represents. R 6 , R 8 , R 9 and M are as described above, and the preferred embodiments are also the same.
Among them, R 5 is —CO 2 H, ethyloxycarbonyl, sulfoxyl, 2-ethylhexyloxypropane sulfamoyl, 1,5-dimethylhexanesulfamoyl, 3-phenyl-1-methylpropanesulfamoyl, iso An embodiment that is propoxypropane sulfamoyl is preferred.
　また、ｍは、０～５の整数を表す。ｍが２以上の整数である場合、複数のＲ５は同一でも異なっていてもよい。ｎ１、ｎ２、ｎ３及びｎ４は、各々独立に、０又は１を表す。
　Ｘは、ハロゲン原子を表す。ハロゲン原子としては、フッ素原子、塩素原子、及び臭素原子などが挙げられる。
　ａは、０又は１の整数を表す。ｎ１～ｎ４の全てが１を表しかつＲ５が－ＳＯ３ －以外の基を表す場合はａ＝１であり、ｎ１～ｎ４の少なくとも１つが０を表す場合はａ＝０である。ａ＝０のとき、Ｒ１、Ｒ２、Ｒ３、Ｒ４、及びＲ５の少なくとも１つの基は、水素原子が１つ外れたアニオン基として存在していてもよい。 M represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R 5 may be the same or different. n1, n2, n3 and n4 each independently represents 0 or 1.
X represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
a represents an integer of 0 or 1. When all of n1 to n4 represent 1 and R 5 represents a group other than —SO 3 — , a = 1, and when at least one of n1 to n4 represents 0, a = 0. When a = 0, at least one group of R 1 , R 2 , R 3 , R 4 , and R 5 may be present as an anion group from which one hydrogen atom is removed.
　上記のうち、Ｒ１及びＲ２の少なくとも１つ又はＲ３及びＲ４の少なくとも１つが、炭素数１～４のアルキル基、又は炭素数６～１０の芳香族炭化水素基である態様が好ましく、Ｒ１及びＲ２の少なくとも１つ及びＲ３及びＲ４の少なくとも１つが、炭素数１～４のアルキル基又は炭素数６～１０の芳香族炭化水素基である態様がより好ましく、更には、Ｒ１及びＲ２の少なくとも１つ及びＲ３及びＲ４の少なくとも１つが、炭素数６～１０の芳香族炭化水素基である態様が好ましい。 Among the above, an embodiment in which at least one of R 1 and R 2 or at least one of R 3 and R 4 is an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferable. More preferably, at least one of R 1 and R 2 and at least one of R 3 and R 4 are an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms, An embodiment in which at least one of R 1 and R 2 and at least one of R 3 and R 4 is an aromatic hydrocarbon group having 6 to 10 carbon atoms is preferred.
　前記一般式（Ｉ－１）で表される化合物の中でも、式（Ｉ－１－１）～式（Ｉ－１－５）で表される化合物が好適に挙げられる。式（Ｉ－１－５）で表される化合物には、その塩も含まれる。 Among the compounds represented by the general formula (I-1), compounds represented by the formulas (I-1-1) to (I-1-5) are preferable. The compound represented by the formula (I-1-5) includes a salt thereof.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　前記式（Ｉ－１－１）において、Ｒ１１～Ｒ１４は、各々独立に、水素原子、炭素数１～１０の飽和炭化水素基、又は炭素数６～１０の芳香族炭化水素基を表す。炭素数６～１０の芳香族炭化水素基は、ハロゲン原子、炭素数１～１０の飽和炭化水素基、－ＯＨ、－ＯＲ６、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３Ｎａ、－ＣＯ２Ｈ、－ＣＯ２Ｒ６、－ＳＯ３Ｒ６、－ＳＯ２ＮＨＲ８又は－ＳＯ２ＮＲ８Ｒ９で置換されていてもよい。Ｒ１５は、水素原子、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ２ＮＨＲ８又は－ＳＯ２ＮＲ８Ｒ９を表し、Ｒ１６は、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ２ＮＨＲ８又は－ＳＯ２ＮＲ８Ｒ９を表す。炭素数１～１０の飽和炭化水素基は、前記一般式（Ｉ－１）のＲ６で表される炭素数１～１０の飽和炭化水素基と同義であり、好ましい態様も同様である。
　Ｒ１１～Ｒ１４は、前記一般式（Ｉ－１）で表される化合物のＲ１～Ｒ４と同義であり、好ましい態様も同様である。Ｒ６、Ｒ８、Ｒ９、Ｘ、及びａは、前記一般式（Ｉ－１）で表される化合物のＲ６、Ｒ８、Ｒ９、Ｘ、及びａと同義であり、好ましい態様も同様である。 In the formula (I-1-1), R 11 to R 14 each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. . The aromatic hydrocarbon group having 6 to 10 carbon atoms includes a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR 6 , —SO 3 — , —SO 3 H, —SO 3 Na, — It may be substituted with CO 2 H, —CO 2 R 6 , —SO 3 R 6 , —SO 2 NHR 8 or —SO 2 NR 8 R 9 . R 15 represents a hydrogen atom, —SO 3 − , —SO 3 H, —SO 2 NHR 8 or —SO 2 NR 8 R 9 , and R 16 represents —SO 3 − , —SO 3 H, —SO 2 NHR 8 or —SO 2 NR 8 R 9 is represented. The saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the saturated hydrocarbon group having 1 to 10 carbon atoms represented by R 6 in the general formula (I-1), and preferred embodiments thereof are also the same.
R 11 to R 14 have the same meanings as R 1 to R 4 in the compound represented by the general formula (I-1), and preferred embodiments thereof are also the same. R 6 , R 8 , R 9 , X, and a have the same meanings as R 6 , R 8 , R 9 , X, and a of the compound represented by the general formula (I-1). It is the same.
　前記式（Ｉ－１－２）において、Ｒ２１～Ｒ２４は、各々独立に、水素原子、炭素数１～１０の飽和炭化水素基、又は炭素数６～１０の芳香族炭化水素基を表す。炭素数６～１０の芳香族炭化水素基は、ハロゲン原子、炭素数１～１０の飽和炭化水素基、－ＯＨ、－ＯＲ２６、－ＳＯ３ －、－ＳＯ３Ｎａ、－ＣＯ２Ｈ、－ＣＯ２Ｒ２６、－ＳＯ３Ｈ、－ＳＯ３Ｒ２６又は－ＳＯ２ＮＨＲ２８で置換されていてもよい。Ｒ２５は、－ＳＯ３ －、－ＳＯ３Ｎａ、－ＣＯ２Ｈ、－ＣＯ２Ｒ２６、－ＳＯ３Ｈ、又はＳＯ２ＮＨＲ２８を表し、Ｒ２６は、炭素数１～１０の飽和炭化水素基を表す。Ｒ２８は、水素原子、炭素数１～１０の飽和炭化水素基、又は炭素数６～１０の芳香族炭化水素基を表す。
　炭素数１～１０の飽和炭化水素基は、前記一般式（Ｉ－１）のＲ６で表される炭素数１～１０の飽和炭化水素基と同義であり、好ましい態様も同様であり、－ＯＲ２６又はハロゲン原子で置換されていてもよい。炭素数６～１０の芳香族炭化水素基は、前記一般式（Ｉ－１）のＲ１～Ｒ４で表される炭素数６～１０の芳香族炭化水素基と同義であり、好ましい態様も同様であり、－Ｒ２６又は－ＯＲ２６で置換されていてもよい。
　Ｒ２１～Ｒ２４は、前記一般式（Ｉ－１）で表される化合物のＲ１～Ｒ４と同義であり、好ましい態様も同様である。また、ｍ、Ｘ、及びａは、（Ｉ－１）のｍ、Ｘ、及びａとそれぞれ同義であり、好ましい態様も同様である。 In the formula (I-1-2), R 21 to R 24 each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. . The aromatic hydrocarbon group having 6 to 10 carbon atoms includes a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR 26 , —SO 3 — , —SO 3 Na, —CO 2 H, — It may be substituted with CO 2 R 26 , —SO 3 H, —SO 3 R 26, or —SO 2 NHR 28 . R 25 represents —SO 3 — , —SO 3 Na, —CO 2 H, —CO 2 R 26 , —SO 3 H, or SO 2 NHR 28 , and R 26 represents a saturated carbonization having 1 to 10 carbon atoms. Represents a hydrogen group. R 28 represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.
The saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the saturated hydrocarbon group having 1 to 10 carbon atoms represented by R 6 in the general formula (I-1), and the preferred embodiment is also the same. It may be substituted with OR 26 or a halogen atom. The aromatic hydrocarbon group having 6 to 10 carbon atoms has the same meaning as the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 1 to R 4 in the general formula (I-1). It is the same, and may be substituted by -R 26 or -OR 26 .
R 21 to R 24 have the same meanings as R 1 to R 4 in the compound represented by the general formula (I-1), and preferred embodiments thereof are also the same. M, X, and a have the same meanings as m, X, and a in (I-1), respectively, and the preferred embodiments are also the same.
　前記式（Ｉ－１－３）において、Ｒ３１及びＲ３２は、各々独立に、フェニル基を表す。フェニル基は、ハロゲン原子、炭素数１～１０の飽和炭化水素基、－ＯＲ２６、－ＣＯ２Ｒ２６、－ＳＯ３Ｒ２６又は－ＳＯ２ＮＨＲ２８で置換されていてもよい。Ｒ３３は、－ＳＯ３ －又は－ＳＯ２ＮＨＲ２８を表し、Ｒ３４は、水素原子、－ＳＯ３ －又は－ＳＯ２ＮＨＲ２８を表す。Ｒ２６、Ｒ２８、Ｘ及びａは、前記式（Ｉ－１－２）のＲ２６、Ｒ２８、Ｘ及びａと同義であり、好ましい態様も同様である。 In the formula (I-1-3), R 31 and R 32 each independently represent a phenyl group. The phenyl group may be substituted with a halogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OR 26 , —CO 2 R 26 , —SO 3 R 26, or —SO 2 NHR 28 . R 33 represents —SO 3 — or —SO 2 NHR 28 , and R 34 represents a hydrogen atom, —SO 3 — or —SO 2 NHR 28 . R 26, R 28, X and a are the formula (I-1-2) has the same meaning as R 26, R 28, X and a of, preferred embodiment is also the same.
　前記式（Ｉ－１－４）において、Ｒ４１及びＲ４２は、各々独立に、フェニル基を表す。フェニル基は、Ｒ２６、又は－ＳＯ２ＮＨＲ２８で置換されていてもよい。Ｒ４３は、－ＳＯ３ －又は－ＳＯ２ＮＨＲ２８を表す。Ｒ２６、Ｒ２８、Ｘ及びａは、前記式（Ｉ－１－２）のＲ２６、Ｒ２８、Ｘ及びａと同義であり、好ましい態様も同様である。 In the formula (I-1-4), R 41 and R 42 each independently represent a phenyl group. The phenyl group may be substituted with R 26 or —SO 2 NHR 28 . R 43 represents —SO 3 — or —SO 2 NHR 28 . R 26, R 28, X and a are the formula (I-1-2) has the same meaning as R 26, R 28, X and a of, preferred embodiment is also the same.
　前記式（Ｉ－１－５）において、Ｒ５０、Ｒ５１、Ｒ５２、及びＲ５３は、各々独立に、水素原子又は炭素数１～３のアルキル基を表し、Ｒ５４、Ｒ５５、及びＲ５６は、各々独立に、スルホ基、又は下記式（ａ１）で表される基を表す。
　　　Ｒ５７ＨＮＳＯ２－　・・・式（ａ１）
　〔式（ａ１）中、Ｒ５７は、炭素数２～２０のアルキル基、アルキル鎖の炭素数が２～１２のシクロヘキシルアルキル基、アルキル鎖の炭素数が１～４のアルキルシクロヘキシル基、炭素数２～１２のアルコキシル基で置換された炭素数２～１２のアルキル基、下記式（ａ２）で表されるアルキルカルボキシルアルキル基、下記式（ａ３）で表されるアルキルオキシカルボニルアルキル基、又は炭素数１～２０のアルキル基で置換されたフェニル基、又はフェニル基で置換された炭素数１～２０のアルキル基を表す。〕
　　　Ｒ６０－ＣＯ－Ｏ－Ｒ６１－　・・・式（ａ２）
　　　Ｒ７０－Ｏ－ＣＯ－Ｒ７１－　・・・式（ａ３）
　〔式（ａ２）及び式（ａ３）中、Ｒ６０及びＲ７０は、各々独立に、炭素数２～１２のアルキル基を表し、Ｒ６１及びＲ７１は、各々独立に、炭素数２～１２のアルキレン基を表す。〕 In the formula (I-1-5), R 50 , R 51 , R 52 , and R 53 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 54 , R 55 , and R 56 each independently represents a sulfo group or a group represented by the following formula (a1).
R 57 HNSO 2 −... Formula (a1)
[In the formula (a1), R 57 represents an alkyl group having 2 to 20 carbon atoms, a cyclohexylalkyl group having 2 to 12 carbon atoms in the alkyl chain, an alkylcyclohexyl group having 1 to 4 carbon atoms in the alkyl chain, An alkyl group having 2 to 12 carbon atoms substituted with an alkoxyl group having 2 to 12, an alkylcarboxylalkyl group represented by the following formula (a2), an alkyloxycarbonylalkyl group represented by the following formula (a3), or carbon It represents a phenyl group substituted with an alkyl group having 1 to 20 carbon atoms, or an alkyl group with 1 to 20 carbon atoms substituted with a phenyl group. ]
R 60 —CO—O—R 61 — Formula (a2)
R 70 —O—CO—R 71 −... Formula (a3)
[In Formula (a2) and Formula (a3), R 60 and R 70 each independently represents an alkyl group having 2 to 12 carbon atoms, and R 61 and R 71 each independently represent 2 to 12 carbon atoms. Represents an alkylene group. ]
　前記式（Ｉ－１－５）において、Ｒ５０、Ｒ５１、Ｒ５２、及びＲ５３で表される炭素数１～３のアルキル基としては、例えば、メチル基、エチル基、プロピル基などが挙げられる。 In the formula (I-1-5), examples of the alkyl group having 1 to 3 carbon atoms represented by R 50 , R 51 , R 52 , and R 53 include a methyl group, an ethyl group, and a propyl group. Can be mentioned.
　前記Ｒ５７で表される炭素数２～２０のアルキル基としては、例えば、エチル基、プロピル基、ｎ－ヘキシル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ドデシル基、２－エチルヘキシル基、１，３－ジメチルブチル基、１－メチルブチル基、１，５－ジメチルヘキシル基、１，１，３，３－テトラメチルブチル基などが挙げられる。
　前記Ｒ５７で表される「アルキル鎖の炭素数が２～１２のシクロヘキシルアルキル基」としては、例えば、シクロヘキシルエチル基、３－シクロヘキシルプロピル基、８－シクロヘキシルオクチル基などが挙げられる。
　前記Ｒ５７で表される「アルキル鎖の炭素数が１～４のアルキルシクロヘキシル基」としては、例えば、２－エチルシクロヘキシル基、２－プロピルシクロヘキシル基、２－（ｎ－ブチル）シクロヘキシル基などが挙げられる。
　前記Ｒ５７で表される「炭素数２～１２のアルコキシル基で置換された炭素数２～１２のアルキル基」としては、３－エトキシ－ｎ－プロピル基、プロポキシプロピル基、４－プロポキシ－ｎ－ブチル基、３－メチル－ｎ－ヘキシルオキシエチル基、３－（２－エチルヘキシルオキシ）プロピル基などが挙げられる。
　前記Ｒ５７で表される「炭素数１～２０のアルキル基で置換されたフェニル基」としては、例えば、ｏ－イソプロピルフェニル基などが挙げられる。
　前記Ｒ５７で表される「フェニル基で置換された炭素数１～２０のアルキル基」としては、例えば、ＤＬ－１－フェニルエチル基、ベンジル基、３－フェニル－ｎ－ブチル基などが挙げられる。 Examples of the alkyl group having 2 to 20 carbon atoms represented by R 57 include an ethyl group, a propyl group, an n-hexyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, and a 2-ethylhexyl group. 1,3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group and the like.
Examples of the “cyclohexyl alkyl group having 2 to 12 carbon atoms in the alkyl chain” represented by R 57 include a cyclohexylethyl group, a 3-cyclohexylpropyl group, and an 8-cyclohexyloctyl group.
Examples of the “alkyl cycloalkyl group having 1 to 4 carbon atoms in the alkyl chain” represented by R 57 include 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2- (n-butyl) cyclohexyl group and the like. Can be mentioned.
Examples of the “alkyl group having 2 to 12 carbon atoms substituted by an alkoxyl group having 2 to 12 carbon atoms” represented by R 57 include a 3-ethoxy-n-propyl group, a propoxypropyl group, and 4-propoxy-n. -Butyl group, 3-methyl-n-hexyloxyethyl group, 3- (2-ethylhexyloxy) propyl group and the like can be mentioned.
Examples of the “phenyl group substituted with an alkyl group having 1 to 20 carbon atoms” represented by R 57 include an o-isopropylphenyl group.
Examples of the “alkyl group having 1 to 20 carbon atoms substituted with a phenyl group” represented by R 57 include a DL-1-phenylethyl group, a benzyl group, and a 3-phenyl-n-butyl group. It is done.
　また、前記Ｒ６０、Ｒ７０における炭素数２～１２のアルキル基としては、例えば、エチル基、プロピル基、ｎ－ヘキシル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ドデシル基、２－エチルヘキシル基、１，３－ジメチルブチル基、１－メチルブチル基、１，５－ジメチルヘキシル基、１，１，３，３－テトラメチルブチル基などが挙げられる。
　前記Ｒ６１、Ｒ７１における炭素数２～１２のアルキレン基としては、例えば、ジメチレン基、ヘキサメチレン基などが挙げられる。 Examples of the alkyl group having 2 to 12 carbon atoms in R 60 and R 70 include an ethyl group, a propyl group, an n-hexyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, 2- Examples include ethylhexyl group, 1,3-dimethylbutyl group, 1-methylbutyl group, 1,5-dimethylhexyl group, 1,1,3,3-tetramethylbutyl group.
Examples of the alkylene group having 2 to 12 carbon atoms in R 61 and R 71 include a dimethylene group and a hexamethylene group.
　式（Ｉ－１－５）で表される化合物は、塩であってもよい。塩としては、例えば、ナトリウム、カリウムなどのアルカリ金属のアルカリ金属塩、トリエチルアミン、１－アミノ－３－フェニルブタンなどのアミン塩などが挙げられる。具体的には、例えば、式（Ｉ－１－５）で表される化合物の置換基Ｒ５４、Ｒ５５、及びＲ５６がスルホ基である場合には、該スルホ基において塩が形成される。 The compound represented by the formula (I-1-5) may be a salt. Examples of the salt include alkali metal salts of alkali metals such as sodium and potassium, and amine salts such as triethylamine and 1-amino-3-phenylbutane. Specifically, for example, when the substituents R 54 , R 55 , and R 56 of the compound represented by the formula (I-1-5) are sulfo groups, a salt is formed at the sulfo group. .
　前記式（Ｉ－１－５）で表される化合物の具体例としては、Ｃ．Ｉ．Ａｃｉｄ Ｒｅｄ ２８９などが挙げられる。 Specific examples of the compound represented by the formula (I-1-5) include C.I. I. Acid Red 289 and the like.
　上記の式（Ｉ－１－１）～式（Ｉ－１－５）で表される化合物（塩を含む）は、一種単独で用いるほか、二種以上を混合して用いてもよい。 The compounds represented by the above formulas (I-1-1) to (I-1-5) (including salts) may be used singly or in combination of two or more.
　前記一般式（Ｉ－１）で表されるキサンテン系染料の具体例としては、下記化合物（１）～（２）及びＣ．Ｉ．Ａｃｉｄ　Ｒｅｄ　２８９、並びに以下に示す化合物（１ａ）～（１ｆ）などが挙げられる。
　なお、一般式（Ｉ－１）で表されるキサンテン系染料は、互変異性体を有していてもよく、例えば化合物（１ｂ）は、化合物（１ｂ－１）の互変異性体である。 Specific examples of the xanthene dye represented by the general formula (I-1) include the following compounds (1) to (2) and C.I. I. Acid Red 289, and the following compounds (1a) to (1f) and the like can be mentioned.
The xanthene dye represented by the general formula (I-1) may have a tautomer, for example, the compound (1b) is a tautomer of the compound (1b-1). .
　下記化合物（１ａ）、（１ｂ）及び（１ｂ－１）中、Ｒｂ及びＲｃは、各々独立に、水素原子、－ＳＯ３ －、－ＣＯ２Ｈ又は－ＳＯ２ＮＨＲａを表す。Ｒａは、２－エチルヘキシルを表す。Ｘ及びａは、既述の通りである。
　下記化合物（１ｃ）及び（１ｄ）中、Ｒｄ、Ｒｅ及びＲｆは、各々独立に、－ＳＯ３ －、－ＳＯ３Ｎａ又は－ＳＯ２ＮＨＲａを表す。Ｒａは、２－エチルヘキシルを表す。
　下記化合物（１ｅ）及び（１ｆ）中、Ｒｇ、Ｒｈ及びＲｉは、各々独立に、水素原子、－ＳＯ３ －、－ＳＯ３Ｈ又は－ＳＯ２ＮＨＲａを表す。Ｒａは、２－エチルヘキシルを表す。 In the following compounds (1a), (1b) and (1b-1), Rb and Rc each independently represent a hydrogen atom, —SO 3 − , —CO 2 H or —SO 2 NHRa. Ra represents 2-ethylhexyl. X and a are as described above.
In the following compounds (1c) and (1d), Rd, Re and Rf each independently represent —SO 3 − , —SO 3 Na or —SO 2 NHRa. Ra represents 2-ethylhexyl.
In the following compounds (1e) and (1f), Rg, Rh and Ri each independently represent a hydrogen atom, —SO 3 − , —SO 3 H or —SO 2 NHRa. Ra represents 2-ethylhexyl.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　前記一般式（Ｉ－１）で表される化合物は、例えば、－ＳＯ３Ｈを含む色素又は色素中間体を常法により塩素化し、得られた－ＳＯ２Ｃｌを含む色素又は色素中間体をＲ８－ＮＨ２で表されるアミンと反応させることにより製造できる。また、特開平３－７８７０２号公報に記載の方法により製造された色素を、上記と同様に塩素化した後、アミンと反応させることで製造することもできる。 The compound represented by the general formula (I-1) is obtained by, for example, chlorinating a dye or dye intermediate containing —SO 3 H by a conventional method, and obtaining the obtained dye or dye intermediate containing —SO 2 Cl. It can be produced by reacting with an amine represented by R 8 —NH 2 . In addition, the dye produced by the method described in JP-A-3-78702 can also be produced by chlorination in the same manner as described above and then reacting with an amine.
　前記一般式（Ｉ－１）で表されるキサンテン染料の着色硬化性組成物中における含有量としては、着色硬化性組成物の固形分に対して、０．１質量％～４０．０質量％が好ましく、１．０質量％～３０．０質量％がより好ましい。キサンテン染料の含有量が０．１質量％以上であることで、所望とする色濃度及び色相が得られる。また、キサンテン染料の含有量が４０．０質量％以下であると、樹脂成分や重合性化合物等の硬化成分の相対量を確保するのに有利である。 The content of the xanthene dye represented by the general formula (I-1) in the colored curable composition is 0.1% by mass to 40.0% by mass with respect to the solid content of the colored curable composition. And more preferably 1.0 to 30.0% by mass. A desired color density and hue can be obtained when the content of the xanthene dye is 0.1% by mass or more. Moreover, when content of a xanthene dye is 40.0 mass% or less, it is advantageous to ensuring the relative amount of hardening components, such as a resin component and a polymeric compound.
（一般式（Ｉ－２）で表される化合物）
　本発明にかかる着色硬化性組成物が、下記一般式（Ｉ－２）で表されるトリアリールメタン染料の少なくとも一種を含有することにより、アルカリ処理（例えば露光後のアルカリ現像）したときには本発明にかかる着色硬化性組成物は、優れたアルカリ溶解性を示す。 (Compound represented by formula (I-2))
When the colored curable composition according to the present invention contains at least one triarylmethane dye represented by the following general formula (I-2) and is subjected to alkali treatment (for example, alkali development after exposure), the present invention The colored curable composition according to the present invention exhibits excellent alkali solubility.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　前記一般式（Ｉ－２）において、Ｒ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５、及びＲ１０６は、各々独立に、水素原子、炭素数１～１０の飽和炭化水素基、又は炭素数６～１０の芳香族炭化水素基を表す。
　前記炭素数１～１０の飽和炭化水素基としては、例えば、アルキル基（例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ペンチル、イソペンチル、ネオペンチル、シクロペンチル、ヘキシル、シクロヘキシル、ヘプチル、シクロヘプチル、オクチル、２－エチルヘキシル、シクロオクチル、ノニル、デカニル、トリシクロデカニル、メトキシプロピル、エトキシプロピル、ヘキシロキシプロピル、２－エチルヘキシロキシプロピル、メトキシヘキシル、エトキシプロピル等）、アルケニル基（例えばブテニル基、ヘキセニル基、ペンテニル基、オクテニル基等の直鎖状のアルケニル基）が挙げられる。中でも、好ましくは炭素数１～１０のアルキル基であり、より好ましくは炭素数１～９のアルキル基であり、更に好ましくは炭素数１～８のアルキル基である。 In the general formula (I-2), R 101 , R 102 , R 103 , R 104 , R 105 , and R 106 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or carbon Represents an aromatic hydrocarbon group of formula 6-10.
Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms include alkyl groups (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, Octyl, 2-ethylhexyl, cyclooctyl, nonyl, decanyl, tricyclodecanyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, ethoxypropyl, etc.), alkenyl group (for example, butenyl group, Straight-chain alkenyl groups such as hexenyl group, pentenyl group, octenyl group). Among them, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 9 carbon atoms is more preferable, and an alkyl group having 1 to 8 carbon atoms is still more preferable.
　前記炭素数６～１０の芳香族炭化水素基としては、例えば、フェニル、ナフチル等の基が挙げられる。炭素数６～１０の芳香族炭化水素基は、ハロゲン原子、炭素数６～１０の芳香族炭化水素基、炭素数１～１０の飽和炭化水素基、－ＯＨ、－ＯＲ１１１、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３Ｍ、－ＣＯ２Ｈ、－ＣＯ２Ｒ１１１、－ＳＯ３Ｒ１１１、－ＳＯ２ＮＨＲ１１１で置換されていてもよい。 Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include groups such as phenyl and naphthyl. The aromatic hydrocarbon group having 6 to 10 carbon atoms is a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR 111 , —SO 3 —. , —SO 3 H, —SO 3 M, —CO 2 H, —CO 2 R 111 , —SO 3 R 111 , —SO 2 NHR 111 may be substituted.
　Ｒ１１１は、炭素数６～１０の芳香族炭化水素基、又は炭素数１～１０の飽和炭化水素基を表し、前記Ｒ１０１～Ｒ１０６における「炭素数６～１０の芳香族炭化水素基」、「炭素数１～１０の飽和炭化水素基」とそれぞれ同義であり、好ましい態様も同様である。また、Ｒ１１１で表される「炭素数６～１０の芳香族炭化水素基」及び「炭素数１～１０の飽和炭化水素基」は、ハロゲン原子で置換されていてもよい。炭素数１～１０の飽和炭化水素基に含まれるメチレン基は、酸素原子、カルボニル基、又は－ＮＲ１１１－で置換されていてもよい。 R 111 represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or a saturated hydrocarbon group having 1 to 10 carbon atoms, and the “aromatic hydrocarbon group having 6 to 10 carbon atoms” in the above R 101 to R 106 , “Saturated hydrocarbon group having 1 to 10 carbon atoms”, and preferred embodiments are also the same. Further, the “aromatic hydrocarbon group having 6 to 10 carbon atoms” and the “saturated hydrocarbon group having 1 to 10 carbon atoms” represented by R 111 may be substituted with a halogen atom. The methylene group contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an oxygen atom, a carbonyl group, or —NR 111 —.
　前記ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子などが挙げられる。
　前記「－ＳＯ３Ｒ１１１」としては、例えば、メタンスルホニル、エタンスルホニル、ヘキサンスルホニル、デカンスルホニル等が挙げられる。
　前記「－ＣＯ２Ｒ１１１」としては、例えば、メチルオキシカルボニル、エチルオキシカルボニル、プロピルオキシカルボニル、イソプロピルオキシカルボニル、ブチルオキシカルボニル、イソブチルオキシカルボニル、ペンチルオキシカルボニル、イソペンチルオキシカルボニル、ネオペンチルオキシカルボニル、シクロペンチルオキシカルボニル、ヘキシルオキシカルボニル、シクロヘキシルオキシカルボニル、ヘプチルオキシカルボニル、シクロヘプチルオキシカルボニル、オクチルオキシカルボニル、２－エチルヘキシルオキシカルボニル、シクロオクチルオキシカルボニル、ノニルオキシカルボニル、デカニルオキシカルボニル、トリシクロデカニルオキシカルボニル、メトキシプロピルオキシカルボニル、エトキシプロピルオキシカルボニル、ヘキシロキシプロピルオキシカルボニル、２－エチルヘキシロキシプロピルオキシカルボニル、メトキシヘキシルオキシカルボニル等が挙げられる。
　前記「－ＳＯ２ＮＨＲ１１１」としては、例えば、スルファモイル、メタンスルファモイル、エタンスルファモイル、プロパンスルファモイル、イソプロパンスルファモイル、ブタンスルファモイル、イソブタンスルファモイル、ペンタンスルファモイル、イソペンタンスルファモイル、ネオペンタンスルファモイル、シクロペンタンスルファモイル、ヘキサンスルファモイル、シクロヘキサンスルファモイル、ヘプタンスルファモイル、シクロヘプタンスルファモイル、オクタンスルファモイル、２－エチルヘキサンスルファモイル、１，５－ジメチルヘキサンスルファモイル、シクロオクタンスルファモイル、ノナンスルファモイル、デカンスルファモイル、トリシクロデカンスルファモイル、メトキシプロパンスルファモイル、エトキシプロパンスルファモイル、プロポキシプロパンスルファモイル、イソプロポキシプロパンスルファモイル、ヘキシロキシプロパンスルファモイル、２－エチルヘキシロキシプロパンスルファモイル、メトキシヘキサンスルファモイル、３－フェニル－１－メチルプロパンスルファモイル等が挙げられる。
　前記「－ＯＲ１１１」としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ヘキシロキシ基等が挙げられる。 Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the “—SO 3 R 111 ” include methanesulfonyl, ethanesulfonyl, hexanesulfonyl, decanesulfonyl and the like.
Examples of the “—CO 2 R 111 ” include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl. , Cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclooctyloxycarbonyl, nonyloxycarbonyl, decanyloxycarbonyl, tricyclodecanyl Oxycarbonyl, methoxypropyloxycarbonyl, ethoxypropylo Examples include xycarbonyl, hexyloxypropyloxycarbonyl, 2-ethylhexyloxypropyloxycarbonyl, methoxyhexyloxycarbonyl and the like.
Examples of the “—SO 2 NHR 111 ” include sulfamoyl, methanesulfamoyl, ethanesulfamoyl, propanesulfamoyl, isopropanesulfamoyl, butanesulfamoyl, isobutanesulfamoyl, pentanessulfamoyl, Isopentanesulfamoyl, neopentanesulfamoyl, cyclopentanesulfamoyl, hexanesulfamoyl, cyclohexanesulfamoyl, heptanesulfamoyl, cycloheptanesulfamoyl, octanessulfamoyl, 2-ethylhexanesulfamoyl 1,5-dimethylhexanesulfamoyl, cyclooctanesulfamoyl, nonanesulfamoyl, decanesulfamoyl, tricyclodecanesulfamoyl, methoxypropanesulfamoyl, etho Xypropanesulfamoyl, propoxypropane sulfamoyl, isopropoxypropane sulfamoyl, hexyloxypropane sulfamoyl, 2-ethylhexyloxypropane sulfamoyl, methoxyhexanesulfamoyl, 3-phenyl-1-methylpropane And sulfamoyl.
Examples of the “—OR 111 ” include a methoxy group, an ethoxy group, a propoxy group, and a hexyloxy group.
　前記炭素数６～１０の芳香族炭化水素基が置換されている場合の好ましい置換基としては、エチル、プロピル、フェニル、ジメチルフェニル、－ＳＯ３Ｒ１１１、又は－ＳＯ２ＮＨＲ１１１などである。－ＳＯ３Ｒ１１１及び－ＳＯ２ＮＨＲ１１１は、既述の通りである。 Preferred substituents when the aromatic hydrocarbon group having 6 to 10 carbon atoms is substituted include ethyl, propyl, phenyl, dimethylphenyl, —SO 3 R 111 , —SO 2 NHR 111 and the like. —SO 3 R 111 and —SO 2 NHR 111 are as described above.
　置換されている炭素数６～１０の芳香族炭化水素基の具体例としては、メチルフェニル、ジメチルフェニル、トリメチルフェニル、エチルフェニル、ヘキシルフェニル、デカニルフェニル、フルオロフェニル、クロロフェニル、ブロモフェニル、ヒドロキシフェニル、メトキシフェニル、ジメトキシフェニル、エトキシフェニル、ヘキシロキシフェニル、デカニロキシフェニル、トリフルオロメチルフェニル等が挙げられる。 Specific examples of the substituted aromatic hydrocarbon group having 6 to 10 carbon atoms include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, hexylphenyl, decanylphenyl, fluorophenyl, chlorophenyl, bromophenyl, and hydroxyphenyl. , Methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decanyloxyphenyl, trifluoromethylphenyl and the like.
　前記－ＳＯ３Ｍ中、Ｍは、ナトリウム原子又はカリウム原子を表す。 In the —SO 3 M, M represents a sodium atom or a potassium atom.
　Ｒ１０７及びＲ１０８は、各々独立に、水素原子、又は炭素数４～８の飽和炭化水素基を表す。
　炭素数４～８の飽和炭化水素基としては、ブチル基、ヘプチル基、ヘキシル基、オクチル基などが挙げられる。 R 107 and R 108 each independently represents a hydrogen atom or a saturated hydrocarbon group having 4 to 8 carbon atoms.
Examples of the saturated hydrocarbon group having 4 to 8 carbon atoms include butyl group, heptyl group, hexyl group, octyl group and the like.
　Ｒ１０７とＲ１０８は、互いに結合して芳香族炭化水素環を形成していてもよい。この場合の芳香族炭化水素環としては、ベンゼン環、ナフタレン環などが好適に挙げられる。 R 107 and R 108 may be bonded to each other to form an aromatic hydrocarbon ring. Preferred examples of the aromatic hydrocarbon ring in this case include a benzene ring and a naphthalene ring.
　Ｒ１０９は、水素原子、又は炭素数１～１０の飽和炭化水素基を表す。Ｒ１０９で表される炭素数１～１０の飽和炭化水素基は、前記Ｒ１０１～Ｒ１０６における「炭素数１～１０の飽和炭化水素基」と同義である。Ｒ１０９は、好ましくは、水素原子又は炭素数１～３のアルキル基である。 R 109 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. The saturated hydrocarbon group having 1 to 10 carbon atoms represented by R 109 has the same meaning as the “saturated hydrocarbon group having 1 to 10 carbon atoms” in R 101 to R 106 . R 109 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
　Ｘは、ハロゲン原子、ＢＦ４、ＰＦ６、ＣｌＯ４、Ｎ（ＳＯ２ＣＦ３）２、又はＡｒＳＯ３を表す。ＡｒＳＯ３中のＡｒは、炭素数６～１０の芳香族炭化水素基を表す。炭素数６～１０の芳香族炭化水素基は、前記Ｒ１０１～Ｒ１０６における「炭素数６～１０の芳香族炭化水素基」と同義であり、好ましい態様も同様である。 X represents a halogen atom, BF 4 , PF 6 , ClO 4 , N (SO 2 CF 3 ) 2 , or ArSO 3 . Ar in ArSO 3 represents an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic hydrocarbon group having 6 to 10 carbon atoms has the same meaning as the “aromatic hydrocarbon group having 6 to 10 carbon atoms” in R 101 to R 106 , and the preferred embodiment is also the same.
　Ｘで表されるハロゲン原子としては、フッ素原子、塩素原子、及び臭素原子などが挙げられる。
　Ａｒで表される炭素数６～１０の芳香族炭化水素基は、Ｒ１０１～Ｒ１０６で表される炭素数６～１０の芳香族炭化水素基と同義であり、好ましい態様も同様である。炭素数６～１０の芳香族炭化水素基は、ハロゲン原子、炭素数６～１０の芳香族炭化水素基、炭素数１～１０の飽和炭化水素基、－ＯＨ、－ＯＲ１１１、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３Ｍ、－ＣＯ２Ｈ、－ＣＯ２Ｒ１１１、－ＳＯ３Ｒ１１１、－ＳＯ２ＮＨＲ１１１、－ＳＯ２Ｎ（Ｒ１１１）２で置換されていてもよい。
　中でも、Ａｒとしては、フェニル基、ナフチル基が好ましい。 Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, and a bromine atom.
The aromatic hydrocarbon group having 6 to 10 carbon atoms represented by Ar is synonymous with the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R 101 to R 106 , and the preferred embodiments are also the same. The aromatic hydrocarbon group having 6 to 10 carbon atoms is a halogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a saturated hydrocarbon group having 1 to 10 carbon atoms, —OH, —OR 111 , —SO 3 —. , —SO 3 H, —SO 3 M, —CO 2 H, —CO 2 R 111 , —SO 3 R 111 , —SO 2 NHR 111 , —SO 2 N (R 111 ) 2 may be substituted. .
Among these, as Ar, a phenyl group and a naphthyl group are preferable.
　また、ａは、０又は１の整数を表し、Ｒ１０１～Ｒ１０６のいずれかが－ＳＯ３ －を含むときはａ＝０であり、Ｒ１０１～Ｒ１０６がいずれも－ＳＯ３ －を含まないときはａ＝１である。 A represents an integer of 0 or 1, and when any of R 101 to R 106 includes —SO 3 — , a = 0, and each of R 101 to R 106 includes —SO 3 — . If not, a = 1.
　前記一般式（Ｉ－２）で表される化合物の中でも、下記一般式（Ｉ－２－１）又は（Ｉ－２－２）で表される化合物が好ましい。 Among the compounds represented by the general formula (I-2), compounds represented by the following general formula (I-2-1) or (I-2-2) are preferable.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　前記一般式（Ｉ－２－１）において、Ｒ２０６は、炭素数１～１０の飽和炭化水素基を表し、無置換でも置換されていてもよい。炭素数１～１０の飽和炭化水素基は、前記一般式（Ｉ－２）のＲ１０１～Ｒ１０６における「炭素数１～１０の飽和炭化水素基」と同義である。中でも、Ｒ２０６は、炭素数４～２０のアルキル基、炭素数４～２０のアルケニル基が好ましく、これらは無置換でも置換されていてもよい。
　Ｒ２０９は、水素原子、又は炭素数１～３のアルキル基を表す。Ｙは、ＳＯ３Ｈ又はＳＯ３Ｍを表し、Ｍはナトリウム原子又はカリウム原子を表す。 In the general formula (I-2-1), R 206 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, which may be unsubstituted or substituted. The saturated hydrocarbon group having 1 to 10 carbon atoms has the same meaning as the “saturated hydrocarbon group having 1 to 10 carbon atoms” in R 101 to R 106 of the general formula (I-2). Among these, R 206 is preferably an alkyl group having 4 to 20 carbon atoms and an alkenyl group having 4 to 20 carbon atoms, which may be unsubstituted or substituted.
R 209 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Y represents SO 3 H or SO 3 M, and M represents a sodium atom or a potassium atom.
　Ｒ２０６は、例えば、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等の炭素数４～１０の直鎖状アルキル基、イソブチル基、イソペンチル基、イソヘキシル基、２－エチルヘキシル基等の炭素数４～１０の分岐状アルキル基が挙げられる。 R 206 is, for example, a linear alkyl group having 4 to 10 carbon atoms such as butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isobutyl group, isopentyl group, isohexyl group, 2 -Branched alkyl groups having 4 to 10 carbon atoms such as ethylhexyl group.
　アルキル基が置換基を有している場合、置換アルキル基としては、例えば、ヒドロキシ置換アルキル基、シアノ置換アルキル基、ハロゲン置換アルキル基、アルコキシ置換アルキル基、アルコキシアルコキシ置換アルキル基等が挙げられる。但し、これらに限定されるものではない。ヒドロキシ置換アルキル基としては、例えば４－ヒドロキシブチル基が挙げられる。シアノ置換アルキル基としては、例えば４－シアノブチル基、６－シアノヘキシル等の炭素数４～６のシアノ置換アルキル基が挙げられる。ハロゲン原子置換アルキル基としては、例えば４－クロロブチル基、５－ブロモペンチル基、ヘキサフロロブチル基等の炭素数４～６のハロゲン原子置換アルキル基が挙げられる。アルコキシ置換アルキル基としては、例えば２－エトキシエチル基、２－（ｎ）プロポキシエチル基、２－（ｉｓｏ）プロポキシエチル基、２－（ｎ）ブトキシエチル基、２－（ｉｓｏ）ブトキシエチル基、２－（２－エチルヘキシルオキシ）エチル基、３－メトキシプロピル基、４－メトキシブチル基、２－メトキシプロピル基等の（炭素数１～８）アルコキシ置換（炭素数２～４）アルキル基が挙げられる。アルコキシアルコキシ置換アルキル基としては、例えば２－（２－メトキシエトキシ）エチル基、２－（２－エトキシエトキシ）エチル基、２－（２－（ｎ）プロポキシエトキシ）エチル基、２－（２－（ｉｓｏ）プロポキシエトキシ）エチル基、２－（２－（ｎ）ブトキシエトキシ）エチル基、２－（２－（ｉｓｏ）ブトキシエトキシ）エチル基、２－｛２－（２－エチルヘキシルオキシ）エトキシ｝エチル基等の（炭素数１～８）アルコキシ（炭素数１～８）アルコキシ置換（炭素数２～４）アルキル基が挙げられる。 When the alkyl group has a substituent, examples of the substituted alkyl group include a hydroxy-substituted alkyl group, a cyano-substituted alkyl group, a halogen-substituted alkyl group, an alkoxy-substituted alkyl group, and an alkoxyalkoxy-substituted alkyl group. However, it is not limited to these. Examples of the hydroxy-substituted alkyl group include a 4-hydroxybutyl group. Examples of the cyano-substituted alkyl group include cyano-substituted alkyl groups having 4 to 6 carbon atoms such as 4-cyanobutyl group and 6-cyanohexyl. Examples of the halogen atom-substituted alkyl group include halogen atom-substituted alkyl groups having 4 to 6 carbon atoms such as a 4-chlorobutyl group, a 5-bromopentyl group, and a hexafluorobutyl group. Examples of the alkoxy-substituted alkyl group include 2-ethoxyethyl group, 2- (n) propoxyethyl group, 2- (iso) propoxyethyl group, 2- (n) butoxyethyl group, 2- (iso) butoxyethyl group, (C1-C8) alkoxy substituted (C2-C4) alkyl groups such as 2- (2-ethylhexyloxy) ethyl group, 3-methoxypropyl group, 4-methoxybutyl group, 2-methoxypropyl group It is done. Examples of the alkoxyalkoxy-substituted alkyl group include 2- (2-methoxyethoxy) ethyl group, 2- (2-ethoxyethoxy) ethyl group, 2- (2- (n) propoxyethoxy) ethyl group, 2- (2- (Iso) propoxyethoxy) ethyl group, 2- (2- (n) butoxyethoxy) ethyl group, 2- (2- (iso) butoxyethoxy) ethyl group, 2- {2- (2-ethylhexyloxy) ethoxy} Examples include (1-C8) alkoxy (C1-C8) alkoxy-substituted (C2-C4) alkyl groups such as ethyl group.
　また、Ｒ２０６で表されるアルケニル基としては、例えば、ブテニル基、ヘキセニル基、ペンテニル基、オクテニル基等の直鎖状のアルケニル基が挙げられる。 As the alkenyl group represented by R 206, for example, butenyl, hexenyl, pentenyl group, and a linear alkenyl group such as octenyl groups.
　上記のうち、好ましいＲ２０６は、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基等の炭素数４～１０の直鎖状アルキル基である。 Among the above, preferable R 206 is an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, or the like. A linear alkyl group.
　Ｒ２０９としては、水素原子、又は炭素数１～３のアルキル基が挙げられ、好ましくはメチル基である。 R 209 includes a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a methyl group.
　前記一般式（Ｉ－２－１）で表される化合物は、公知の色素を公知の方法によりアルキル化又はアルケニル化することで得られる。例えばＣ．Ｉ．　Ａｃｉｄ　Ｂｌｕｅ８３やＣ．Ｉ．　Ａｃｉｄ　Ｂｌｕｅ９０の分子構造中の－ＮＨ－部位をアルキル化又はアルケニル化することで得ることができる。ここで、アルキル化又はアルケニル化の方法は、溶剤中でハロゲン化アルキル（アルケン）とアルカリを用い反応させる方法やトシル酸アルキル（アルケニル）エステルとアルカリを用いる方法が一般的である。 The compound represented by the general formula (I-2-1) can be obtained by alkylating or alkenylating a known dye by a known method. For example, C.I. I. Acid Blue 83 and C.I. I. It can be obtained by alkylating or alkenylating the —NH— moiety in the molecular structure of Acid Blue90. Here, as a method of alkylation or alkenylation, a method of reacting an alkyl halide (alkene) with an alkali in a solvent and a method of using an alkyl tosyl (alkenyl) ester and an alkali are common.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　前記一般式（Ｉ－２－２）において、Ｒ３０１、Ｒ３０２、Ｒ３０３、及びＲ３０４は、各々独立に、アルキル基を表す。Ｒ３０５は、アルキル基、又は置換基を有してもよいアリール基を表す。Ｘ－は、Ｃｌ－、ＢＦ４ －、ＰＦ６ －、又はＡｒＳＯ３ －を表す。Ａｒは、芳香族炭化水素基を表し、該芳香族炭化水素基は置換基を有していてもよいアミノ基で置換されていてもよい。 In the general formula (I-2-2), R 301 , R 302 , R 303 , and R 304 each independently represents an alkyl group. R 305 represents an alkyl group or an aryl group which may have a substituent. X − represents Cl − , BF 4 − , PF 6 − , or ArSO 3 − . Ar represents an aromatic hydrocarbon group, and the aromatic hydrocarbon group may be substituted with an amino group which may have a substituent.
　Ｒ３０１～Ｒ３０４で表されるアルキル基としては、トリアリールメタン系色素に一般にみられるアルキル基が好適であり、炭素数１～４のアルキル基が好ましい。中でも、アルキル基は、メチル基、エチル基がより好ましい。 As the alkyl group represented by R 301 to R 304 , an alkyl group generally found in triarylmethane dyes is preferable, and an alkyl group having 1 to 4 carbon atoms is preferable. Among these, the alkyl group is more preferably a methyl group or an ethyl group.
　前記Ｒ３０１、Ｒ３０２、Ｒ３０３、及びＲ３０４は、それぞれ同一であっても異なってもよいが、色素製造の観点からは、同一であることが好ましい。 R 301 , R 302 , R 303 , and R 304 may be the same or different, but are preferably the same from the viewpoint of dye production.
　Ｒ３０５は、トリアリールメタン系色素に一般にみられるアルキル基、アリール基が好適であり、炭素数１～４のアルキル基、又は該アルキル基で置換されていてもよいフェニル基などが挙げられる。中でも、Ｒ３０５は、エチル基、フェニル基、又はｐ－トリル基がより好ましく、エチル基が更に好ましい。 R 305 is preferably an alkyl group or an aryl group generally found in triarylmethane dyes, and examples thereof include an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted with the alkyl group. Among these, R 305 is more preferably an ethyl group, a phenyl group, or a p-tolyl group, and more preferably an ethyl group.
　前記一般式（Ｉ－２－２）中、Ｘ－は、化合物の耐熱性の点で、ＢＦ４ －、ＰＦ６ －、ＡｒＳＯ３ －が好ましい。Ａｒで表される芳香族炭化水素基は、置換基を有していてもよいアミノ基で置換されていてもよい。芳香族炭化水素基としては、炭素原子のみで環形成された芳香族環基、又はヘテロ原子を含む芳香族環基が挙げられ、縮環構造を有してもよく、５員又は６員環の単環又は２縮合環が好ましい。中でも、炭素原子のみで環形成された芳香族環が好ましく、ベンゼン環又はナフタレン環がより好ましい。Ａｒがナフタレン環の場合、置換位置は１位又は２位のいずれでもよい。 In the general formula (I-2-2), X − is preferably BF 4 − , PF 6 − or ArSO 3 − from the viewpoint of heat resistance of the compound. The aromatic hydrocarbon group represented by Ar may be substituted with an amino group which may have a substituent. Examples of the aromatic hydrocarbon group include an aromatic ring group formed by ring formation using only carbon atoms, or an aromatic ring group containing a hetero atom, and may have a condensed ring structure. A monocyclic ring or a double condensed ring is preferable. Of these, an aromatic ring formed only by carbon atoms is preferable, and a benzene ring or a naphthalene ring is more preferable. When Ar is a naphthalene ring, the substitution position may be either the 1-position or the 2-position.
　前記芳香族炭化水素基は、置換基を有していてもよいアミノ基で、置換されていてもよい。アミノ基の置換基としては、例えば炭素数１～４のアルキル基、５員又は６員環の単環又は２縮合環であるアリール基等が挙げられる。 The aromatic hydrocarbon group may be substituted with an amino group which may have a substituent. Examples of the substituent of the amino group include an alkyl group having 1 to 4 carbon atoms, an aryl group which is a 5-membered or 6-membered monocyclic or bicondensed ring, and the like.
　前記一般式（Ｉ－２－２）で表される化合物は、Ｘ－がＣｌ－である場合には、上市されている市販品を使用してもよいし、公知の方法で合成してもよい。合成法については、「総説合成染料」（堀口博著、三共出版、１９６８年）に記載されている。 The compound represented by the general formula (I-2-2), the X - is Cl - in the case of may be a commercially available product as it is marketed, be synthesized by known methods Good. The synthesis method is described in “Review Synthetic Dyes” (Horiguchi Hiroshi, Sankyo Publishing, 1968).
　前記一般式（Ｉ－２）で表される化合物（一般式（Ｉ－２－１）又は（Ｉ－２－２）で表される化合物を含む）の具体例（例示化合物１～２２、例示化合物３１～３７等）を示す。但し、本発明は、これら化合物に限定されるものではない。 Specific examples (Exemplary Compounds 1 to 22, Exemplified Compounds 1 to 22) of the compound represented by the general formula (I-2) (including the compound represented by the general formula (I-2-1) or (I-2-2)) Compounds 31-37 and the like). However, the present invention is not limited to these compounds.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　前記一般式（Ｉ－２）で表されるトリアリールメタン染料の着色硬化性組成物中における含有量としては、着色硬化性組成物の固形分に対して、０．１質量％～５０．０質量％が好ましく、１．０質量％～３０．０質量％がより好ましい。トリアリールメタン染料の含有量が０．１質量％以上であることで、所望とする色濃度及び色相が得られる。また、トリアリールメタン染料の含有量が５０．０質量％以下であると、樹脂成分や重合性化合物等の硬化成分の相対量を確保するのに有利である。 The content of the triarylmethane dye represented by the general formula (I-2) in the colored curable composition is 0.1% by mass to 50.0% with respect to the solid content of the colored curable composition. % By mass is preferable, and 1.0% by mass to 30.0% by mass is more preferable. A desired color density and hue can be obtained when the content of the triarylmethane dye is 0.1% by mass or more. Further, when the content of the triarylmethane dye is 50.0% by mass or less, it is advantageous to secure a relative amount of a curing component such as a resin component or a polymerizable compound.
＜（Ｂ）下記一般式（ＩＩ）で表されるポルフィリン化合物＞
　本発明の着色化合物には、既述の特定染料（Ａ）とともに、（Ｂ）下記一般式（ＩＩ）で表されるポルフィリン化合物（以下、適宜「ポルフィリン化合物」又は「特定染料（Ｂ）」と称する）を含有することを要する。 <(B) Porphyrin compound represented by the following general formula (II)>
The colored compound of the present invention includes (B) a porphyrin compound represented by the following general formula (II) (hereinafter referred to as “porphyrin compound” or “specific dye (B)” as appropriate) together with the specific dye (A) described above. Need to be contained).
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　前記一般式（ＩＩ）中、Ｚ１、Ｚ２、Ｚ３およびＺ４は全てがＮを表すか、若しくは、Ｚ１とＺ３、又はＺ２とＺ４のいずれか１組が双方ともにＮを表し、残りの１組が双方ともにＣ－Ｒを表し、Ｒは各々独立に水素原子、アルキル基、又はアリール基を表す。
　前記一般式（ＩＩ）中、Ａ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７及びＡ８は、各々独立に水素原子、アルキル基、アルケニル基、アリール基、アルコキシ基、アルキルチオ基、アリールオキシ基、アリールチオ基、ハロゲン原子、ヒドロキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アミノ基、カルバモイル基、スルファモイル基、アシル基、シリルオキシ基、シアノ基、ニトロ基、又は、ヘテロ環基を表す。Ａ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７およびＡ８は各々さらに置換基を有するものであってもよい。
　前記一般式（ＩＩ）中、Ａ１とＡ２、Ａ３とＡ４、Ａ５とＡ６、及びＡ７とＡ８とは、各々互いに結合して環構造を形成してもよいが、これらのうち少なくとも１組は環構造を形成しない。
　また環構造を形成する組においても、脂環構造を形成してもよいが芳香環構造を形成しないことが好ましく、より好ましくは、Ａ１とＡ２、Ａ３とＡ４、Ａ５とＡ６、及びＡ７とＡ８のいずれもが環構造を形成しない態様である。
　前記一般式（ＩＩ）中、Ｍは２価の金属原子、又は金属原子を含む２価の原子団を表す。 In the general formula (II), Z 1 , Z 2 , Z 3 and Z 4 all represent N, or any one of Z 1 and Z 3 or Z 2 and Z 4 is both N And the remaining one set represents both C—R, and each R independently represents a hydrogen atom, an alkyl group, or an aryl group.
In the general formula (II), A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or an alkoxy group. , Alkylthio group, aryloxy group, arylthio group, halogen atom, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, carbamoyl group, sulfamoyl group, acyl group, silyloxy group, cyano group, nitro group, or hetero Represents a cyclic group. Each of A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 may further have a substituent.
In the general formula (II), A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 may be bonded to each other to form a ring structure, At least one of these does not form a ring structure.
In the group forming the ring structure, an alicyclic structure may be formed, but it is preferable not to form an aromatic ring structure, and more preferably A 1 and A 2 , A 3 and A 4 , A 5 and A 6 and any one of A 7 and A 8 does not form a ring structure.
In the general formula (II), M represents a divalent metal atom or a divalent atomic group containing a metal atom.
　本発明の着色硬化性組成物は、前記特定染料（Ａ）と、特定染料（Ｂ）とを含有することにより、理由は定かではないが、形成された着色硬化膜の輝度とコントラストを効果的に高めることができる。 The colored curable composition of the present invention contains the specific dye (A) and the specific dye (B), so that the reason and the reason is not clear, but the brightness and contrast of the formed colored cured film are effective. Can be increased.
　Ａ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７及びＡ８が表す置換基について説明する。
　アルキル基としては好ましくは、炭素数１～４８、より好ましくは炭素数１～２４の、直鎖、分岐鎖、又は環状のアルキル基が挙げられ、具体的には例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、２－エチルヘキシル基、ドデシル基、ヘキサデシル基、シクロプロピル基、シクロペンチル基、シクロヘキシル基、１－ノルボルニル基、１－アダマンチル基などが挙げられる。アルケニル基として好ましくは炭素数２～４８、より好ましくは炭素数２～１８のアルケニル基が挙げられ、具体的には例えば、ビニル基、アリル基、３－ブテン－１－イル基などが挙げられる。アリール基として好ましくは炭素数６～４８、より好ましくは炭素数６～２４のアリール基が挙げられ、具体的には例えば、フェニル基、ナフチル基などが挙げられる。アルコキシ基として好ましくは炭素数１～４８、より好ましくは炭素数１～２４のアルコキシ基が挙げられ、具体的には例えば、メトキシ基、エトキシ基、１－ブトキシ基、２－ブトキシ基、イソプロポキシ基、ｔ－ブトキシ基、ドデシルオキシ基、また、シクロアルキルオキシ基であれば、例えば、シクロペンチルオキシ基、シクロヘキシルオキシ基など挙げられる。アルキルチオ基としては好ましくは炭素数１～４８、より好ましくは炭素数１～２４のアルキルチオ基が挙げられ、具体的には例えば、メチルチオ基、エチルチオ基、オクチルチオ基、シクロヘキシルチオ基など挙げられる。アリールオキシ基として好ましくは炭素数６～４８、より好ましくは炭素数６～２４のアリールオキシ基が挙げられ、具体的には例えば、フェノキシ基、１－ナフトキシ基など挙げられる。アリールチオ基として好ましくは炭素数６～４８、より好ましくは炭素数６～２４のアリールチオ基が挙げられ、具体的には例えば、フェニルチオ基などが挙げられる。ハロゲン原子としては、好ましくは、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、好ましくはフッ素原子、塩素原子、臭素原子が挙げられる。アルコキシカルボニル基として好ましくは炭素数２～４８、より好ましくは炭素数２～２４のアルコキシカルボニル基が挙げられ、具体的には例えば、メトキシカルボニル基、エトキシカルボニル基、オクタデシルオキシカルボニル基、シクロヘキシルオキシカルボニル基、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルシクロヘキシルオキシカルボニル基などが挙げられる。 The substituents represented by A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 will be described.
The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples include a methyl group, an ethyl group, Propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl Group, 1-adamantyl group and the like. The alkenyl group is preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms. Specific examples include a vinyl group, an allyl group, and a 3-buten-1-yl group. . The aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and specific examples thereof include a phenyl group and a naphthyl group. The alkoxy group is preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, and an isopropoxy group. Group, t-butoxy group, dodecyloxy group and cycloalkyloxy group include, for example, cyclopentyloxy group, cyclohexyloxy group and the like. The alkylthio group is preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and specific examples include a methylthio group, an ethylthio group, an octylthio group, and a cyclohexylthio group. The aryloxy group is preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms. Specific examples include a phenoxy group and a 1-naphthoxy group. The arylthio group is preferably an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and specific examples include a phenylthio group. As a halogen atom, Preferably, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably a fluorine atom, a chlorine atom, and a bromine atom are mentioned. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, and a cyclohexyloxycarbonyl group. And a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group.
　アリールオキシカルボニル基として好ましくは炭素数７～３２、より好ましくは炭素数７～２４のアリールオキシカルボニル基が挙げられ、具体的には例えば、フェノキシカルボニル基などが挙げられる。アミノ基として好ましくは炭素数３２以下、より好ましくは炭素数２４以下のアミノ基が挙げられ、具体的には、例えば、アミノ基、メチルアミノ基、Ｎ，Ｎ－ジブチルアミノ基、テトラデシルアミノ基、２－エチルへキシルアミノ基、シクロヘキシルアミノ基などが挙げられる。カルバモイル基としては好ましくは炭素数１～４８、より好ましくは炭素数１～２４のカルバモイル基が挙げられ、具体的には、例えば、カルバモイル基、Ｎ，Ｎ－ジエチルカルバモイル基、Ｎ－エチル－Ｎ－オクチルカルバモイル基、Ｎ，Ｎ－ジブチルカルバモイル基、Ｎ－プロピルカルバモイル基、Ｎ－フェニルカルバモイル基、Ｎ－メチル－Ｎ－フェニルカルバモイル基、Ｎ，Ｎ－ジシクロへキシルカルバモイル基などが挙げられる。スルファモイル基として好ましくは炭素数３２以下、より好ましくは炭素数２４以下のスルファモイル基が挙げられ、具体的には例えば、スルファモイル基、Ｎ，Ｎ－ジプロピルスルファモイル基、Ｎ－エチル－Ｎ－ドデシルスルファモイル基、Ｎ－エチル－Ｎ－フェニルスルファモイル基、Ｎ－シクロヘキシルスルファモイル基などが挙げられる。アシル基として好ましくは炭素数１～４８、より好ましくは炭素数１～２４のアシル基が挙げられ、具体的には、例えば、ホルミル基、アセチル基、ピバロイル基、ベンゾイル基、テトラデカノイル基、シクロヘキサノイル基などが挙げられる。シリルオキシ基として好ましくは炭素数１～３２、より好ましくは炭素数１～１８のシリルオキシ基が挙げられ、具体的には、例えば、トリメチルシリルオキシ基、ｔ－ブチルジメチルシリルオキシ基、ジフェニルメチルシリルオキシ基などが挙げられる。ヘテロ環基として好ましくは炭素数１～３２、より好ましくは炭素数１～１８のヘテロ環基が挙げられ、具体的には、例えば、２－チエニル基、４－ピリジル基、２－フリル基、２－ピリミジニル基、１－ピリジル基、２－ベンゾチアゾリル基、１－イミダゾリル基、１－ピラゾリル基、ベンゾトリアゾール－１－イル基などが挙げられる。 The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, and specific examples include a phenoxycarbonyl group. The amino group is preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms. Specific examples include an amino group, a methylamino group, an N, N-dibutylamino group, and a tetradecylamino group. 2-ethylhexylamino group, cyclohexylamino group and the like. The carbamoyl group is preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples include a carbamoyl group, an N, N-diethylcarbamoyl group, and an N-ethyl-N group. -Octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group and the like. The sulfamoyl group is preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms. Specific examples thereof include a sulfamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecyl group. Examples thereof include a sulfamoyl group, an N-ethyl-N-phenylsulfamoyl group, and an N-cyclohexylsulfamoyl group. The acyl group is preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples include a formyl group, an acetyl group, a pivaloyl group, a benzoyl group, a tetradecanoyl group, A cyclohexanoyl group etc. are mentioned. The silyloxy group is preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms. Specific examples include a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, and a diphenylmethylsilyloxy group. Etc. The heterocyclic group is preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms. Specific examples include a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, Examples include 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group and the like.
　これら、Ａ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７及びＡ８が表す置換基はさらに置換されていてもよく、導入可能な置換基としては例えばハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子など）、アルキル基（好ましくは炭素数１～４８、より好ましくは炭素数１～２４の、直鎖、分岐鎖、又は環状のアルキル基が挙げられ、具体的には、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、２－エチルヘキシル基、ドデシル基、ヘキサデシル基、シクロプロピル基、シクロペンチル基、シクロヘキシル基、１－ノルボルニル基、１－アダマンチル基など）、アルケニル基（好ましくは炭素数２～４８、より好ましくは炭素数２～１８のアルケニル基が挙げられ、具体的には、例えば、ビニル基、アリル基、３－ブテン－１－イル基など）、アリール基（好ましくは炭素数６～４８、より好ましくは炭素数６～２４のアリール基が挙げられ、具体的には、例えば、フェニル基、ナフチル基など）、ヘテロ環基（好ましくは炭素数１～３２、より好ましくは炭素数１～１８のヘテロ環基が挙げられ、具体的には、例えば、２－チエニル基、４－ピリジル基、２－フリル基、２－ピリミジニル基、１－ピリジル基、２－ベンゾチアゾリル基、１－イミダゾリル基、１－ピラゾリル基、ベンゾトリアゾール－１－イル基など）、シリル基（好ましくは炭素数３～３８、より好ましくは炭素数３～１８のシリル基が挙げられ、具体的には、例えば、トリメチルシリル基、トリエチルシリル基、トリブチルシリル基、ｔ－ブチルジメチルシリル基、ｔ－ヘキシルジメチルシリル基など）、ヒドロキシル基、シアノ基、ニトロ基、 These substituents represented by A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 may be further substituted. Examples of the substituents that can be introduced include halogen atoms (for example, A fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (preferably a straight chain, branched chain or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). For example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl Group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group, etc.), alkenyl group (preferably having 2 to 48 carbon atoms, more preferably 2 carbon atoms). 18 alkenyl groups, specifically, for example, vinyl group, allyl group, 3-buten-1-yl group, etc., aryl group (preferably having 6 to 48 carbon atoms, more preferably having 6 to 48 carbon atoms). 24 aryl groups, specifically, for example, a phenyl group, a naphthyl group, etc., a heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group). Specifically, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazole -1-yl group, etc.), silyl groups (preferably silyl groups having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms). Specific examples include trimethylsilyl group, triethyl group, and the like. Rusilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group), hydroxyl group, cyano group, nitro group,
アルコキシ基（好ましくは炭素数１～４８、より好ましくは炭素数１～２４のアルコキシ基が挙げられ、具体的には、例えば、メトキシ基、エトキシ基、１－ブトキシ基、２－ブトキシ基、イソプロポキシ基、ｔ－ブトキシ基、ドデシルオキシ基、また、シクロアルキルオキシ基であれば、例えば、シクロペンチルオキシ基、シクロヘキシルオキシ基など）、アリールオキシ基（好ましくは炭素数６～４８、より好ましくは炭素数６～２４のアリールオキシ基が挙げられ、具体的には、例えば、フェノキシ基、１－ナフトキシ基など）、ヘテロ環オキシ基（好ましくは炭素数１～３２、より好ましくは炭素数１～１８のヘテロ環オキシ基が挙げられ、具体的には、例えば、１－フェニルテトラゾール－５－オキシ基、２－テトラヒドロピラニルオキシ基など）、シリルオキシ基（好ましくは炭素数１～３２、より好ましくは炭素数１～１８のシリルオキシ基が挙げられ、具体的には、例えば、トリメチルシリルオキシ基、ｔ－ブチルジメチルシリルオキシ基、ジフェニルメチルシリルオキシ基など）、アシルオキシ基（好ましくは炭素数２～４８、より好ましくは炭素数２～２４のアシルオキシ基が挙げられ、具体的には、例えば、アセトキシ基、ピバロイルオキシ基、ベンゾイルオキシ基、ドデカノイルオキシ基など）、アルコキシカルボニルオキシ基（好ましくは炭素数２～４８、より好ましくは炭素数２～２４のアルコキシカルボニルオキシ基が挙げられ、具体的には、例えば、エトキシカルボニルオキシ基、ｔ－ブトキシカルボニルオキシ基、また、シクロアルキルオキシカルボニルオキシ基であれば、例えば、シクロヘキシルオキシカルボニルオキシ基など）、アリールオキシカルボニルオキシ基（好ましくは炭素数７～３２、より好ましくは炭素数７～２４のアリールオキシカルボニルオキシ基が挙げられ、具体的には、例えば、フェノキシカルボニルオキシ基など）、カルバモイルオキシ基（好ましくは炭素数１～４８、より好ましくは炭素数１～２４のカルバモイルオキシ基が挙げられ、具体的には、例えば、Ｎ，Ｎ－ジメチルカルバモイルオキシ基、Ｎ－ブチルカルバモイルオキシ基、Ｎ－フェニルカルバモイルオキシ基、Ｎ－エチル－Ｎ－フェニルカルバモイルオキシ基など）、スルファモイルオキシ基（好ましくは炭素数１～３２、より好ましくは炭素数１～２４のスルファモイルオキシ基が挙げられ、具体的には、例えば、Ｎ，Ｎ－ジエチルスルファモイルオキシ基、Ｎ－プロピルスルファモイルオキシ基など）、アルキルスルホニルオキシ基（好ましくは炭素数１～３８、より好ましくは炭素数１～２４のアルキルスルホニルオキシ基が挙げられ、具体的には、例えば、メチルスルホニルオキシ基、ヘキサデシルスルホニルオキシ基、シクロヘキシルスルホニルオキシ基など）、アリールスルホニルオキシ基（好ましくは炭素数６～３２、より好ましくは炭素数６～２４のアリールスルホニルオキシ基が挙げられ、具体的には、例えば、フェニルスルホニルオキシ基など）、アシル基（好ましくは炭素数１～４８、より好ましくは炭素数１～２４のアシル基が挙げられ、具体的には、例えば、ホルミル基、アセチル基、ピバロイル基、ベンゾイル基、テトラデカノイル基、シクロヘキサノイル基など）、アルコキシカルボニル基（好ましくは炭素数２～４８、より好ましくは炭素数２～２４のアルコキシカルボニル基が挙げられ、具体的には、例えば、メトキシカルボニル基、エトキシカルボニル基、オクタデシルオキシカルボニル基、シクロヘキシルオキシカルボニル基、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルシクロヘキシルオキシカルボニル基など）、アリールオキシカルボニル基（好ましくは炭素数７～３２、より好ましくは炭素数７～２４のアリールオキシカルボニル基が挙げられ、具体的には、例えば、フェノキシカルボニル基など）、 An alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms), specifically, for example, a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an iso In the case of propoxy group, t-butoxy group, dodecyloxy group, and cycloalkyloxy group, for example, cyclopentyloxy group, cyclohexyloxy group, etc., aryloxy group (preferably having 6 to 48 carbon atoms, more preferably carbon Examples thereof include aryloxy groups having 6 to 24, specifically, for example, phenoxy group, 1-naphthoxy group and the like, and heterocyclic oxy groups (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms). Specific examples thereof include, for example, 1-phenyltetrazol-5-oxy group, 2-tetrahydropyrani group, and the like. Oxy group, etc.), silyloxy groups (preferably silyloxy groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, and specific examples include trimethylsilyloxy group, t-butyldimethylsilyloxy group, Diphenylmethylsilyloxy group, etc.), acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, specifically, for example, an acetoxy group, a pivaloyloxy group, a benzoyloxy group , Dodecanoyloxy group, etc.), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, specifically, for example, an ethoxycarbonyloxy group, t-butoxycarbonyloxy group and cycloalkyloxy Examples of the sulfonyloxy group include a cyclohexyloxycarbonyloxy group and the like, and an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms). Specifically, for example, a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms), specifically, for example, N, N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group, etc.), sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably Is a sulfamoyloxy group having 1 to 24 carbon atoms. Specifically, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group and the like, alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, more preferably 1 carbon atom) And specific examples include methylsulfonyloxy group, hexadecylsulfonyloxy group, cyclohexylsulfonyloxy group, etc., arylsulfonyloxy group (preferably having 6 to 32 carbon atoms, and more). Preferred examples thereof include arylsulfonyloxy groups having 6 to 24 carbon atoms. Specifically, for example, phenylsulfonyloxy groups and the like, acyl groups (preferably having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). Acyl group, specifically, for example, formyl group, acetyl group, pivaloyl group, Nzoyl group, tetradecanoyl group, cyclohexanoyl group, etc.), alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms). Methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group, etc.), aryloxycarbonyl group (preferably having 7 to 32 carbon atoms) More preferably, an aryloxycarbonyl group having 7 to 24 carbon atoms, specifically, for example, a phenoxycarbonyl group),
カルバモイル基（好ましくは炭素数１～４８、より好ましくは炭素数１～２４のカルバモイル基が挙げられ、具体的には、例えば、カルバモイル基、Ｎ，Ｎ－ジエチルカルバモイル基、Ｎ－エチル－Ｎ－オクチルカルバモイル基、Ｎ，Ｎ－ジブチルカルバモイル基、Ｎ－プロピルカルバモイル基、Ｎ－フェニルカルバモイル基、Ｎ－メチル－Ｎ－フェニルカルバモイル基、Ｎ，Ｎ－ジシクロへキシルカルバモイル基など）、アミノ基（好ましくは炭素数３２以下、より好ましくは炭素数２４以下のアミノ基が挙げられ、具体的には、例えば、アミノ基、メチルアミノ基、Ｎ，Ｎ－ジブチルアミノ基、テトラデシルアミノ基、２－エチルへキシルアミノ基、シクロヘキシルアミノ基など）、アニリノ基（好ましくは炭素数６～３２、より好ましくは６～２４のアニリノ基が挙げられ、具体的には、例えば、アニリノ基、Ｎ－メチルアニリノ基など）、ヘテロ環アミノ基（好ましくは炭素数１～３２、より好ましくは１～１８のヘテロ環アミノ基が挙げられ、具体的には、例えば、４－ピリジルアミノ基など）、カルボンアミド基（好ましくは炭素数２～４８、より好ましくは２～２４のカルボンアミド基が挙げられ、具体的には、例えば、アセトアミド基、ベンズアミド基、テトラデカンアミド基、ピバロイルアミド基、シクロヘキサンアミド基など）、ウレイド基（好ましくは炭素数１～３２、より好ましくは炭素数１～２４のウレイド基が挙げられ、具体的には、例えば、ウレイド基、Ｎ，Ｎ－ジメチルウレイド基、Ｎ－フェニルウレイド基など）、イミド基（好ましくは炭素数３６以下、より好ましくは炭素数２４以下のイミド基が挙げられ、具体的には、例えば、Ｎ－スクシンイミド基、Ｎ－フタルイミド基など）、アルコキシカルボニルアミノ基（好ましくは炭素数２～４８、より好ましくは炭素数２～２４のアルコキシカルボニルアミノ基が挙げられ、具体的には、例えば、メトキシカルボニルアミノ基、エトキシカルボニルアミノ基、ｔ－ブトキシカルボニルアミノ基、オクタデシルオキシカルボニルアミノ基、シクロヘキシルオキシカルボニルアミノ基など）、アリールオキシカルボニルアミノ基（好ましくは炭素数７～３２、より好ましくは炭素数７～２４のアリールオキシカルボニルアミノ基が挙げられ、具体的には、例えば、フェノキシカルボニルアミノ基など）、スルホンアミド基（好ましくは炭素数１～４８、より好ましくは炭素数１～２４のスルホンアミド基が挙げられ、具体的には、例えば、メタンスルホンアミド基、ブタンスルホンアミド基、ベンゼンスルホンアミド基、ヘキサデカンスルホンアミド基、シクロヘキサンスルホンアミド基など）、スルファモイルアミノ基（好ましくは炭素数１～４８、より好ましくは炭素数１～２４のスルファモイルアミノ基が挙げられ、具体的には、例えば、Ｎ，Ｎ－ジプロピルスルファモイルアミノ基、Ｎ－エチル－Ｎ－ドデシルスルファモイルアミノ基など）、アゾ基（好ましくは炭素数１～３２、より好ましくは炭素数１～２４のアゾ基が挙げられ、具体的には、例えば、フェニルアゾ基、３－ピラゾリルアゾ基など）、 A carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, specifically, for example, carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N— Octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group, etc.), amino group (preferably Is an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms. Specific examples include an amino group, a methylamino group, an N, N-dibutylamino group, a tetradecylamino group, and 2-ethyl. Hexylamino group, cyclohexylamino group, etc.), anilino group (preferably having 6 to 32 carbon atoms, more preferred) Includes an anilino group having 6 to 24, specifically, for example, an anilino group, an N-methylanilino group and the like, a heterocyclic amino group (preferably having a carbon number of 1 to 32, more preferably 1 to 18). Specific examples thereof include, for example, a 4-pyridylamino group and the like, and a carbonamido group (preferably a carbon number group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms). For example, an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexaneamide group, etc., a ureido group (preferably a ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms) For example, ureido group, N, N-dimethylureido group, N-phenylureido group, etc.), imide group (preferably having a carbon number) Examples thereof include imide groups having 6 or less, more preferably 24 or less carbon atoms. Specifically, for example, N-succinimide group, N-phthalimide group, etc., alkoxycarbonylamino groups (preferably having 2 to 48 carbon atoms, more Preferred examples thereof include an alkoxycarbonylamino group having 2 to 24 carbon atoms. Specific examples include a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an octadecyloxycarbonylamino group, and a cyclohexyloxycarbonylamino group. Group), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, specifically, for example, a phenoxycarbonylamino group), Sulfonamide group (preferably carbon Examples thereof include a sulfonamide group having 1 to 48, more preferably 1 to 24 carbon atoms. Specific examples include a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide group, and a cyclohexanesulfone. An amide group), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms), specifically, for example, N, N-dipropyls Rufamoylamino group, N-ethyl-N-dodecylsulfamoylamino group and the like) and azo groups (preferably azo groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms). For example, phenylazo group, 3-pyrazolylazo group),
アルキルチオ基（好ましくは炭素数１～４８、より好ましくは炭素数１～２４のアルキルチオ基が挙げられ、具体的には、例えば、メチルチオ基、エチルチオ基、オクチルチオ基、シクロヘキシルチオ基など）、アリールチオ基（好ましくは炭素数６～４８、より好ましくは炭素数６～２４のアリールチオ基が挙げられ、具体的には、例えば、フェニルチオ基など）、ヘテロ環チオ基（好ましくは炭素数１～３２、より好ましくは炭素数１～１８のヘテロ環チオ基が挙げられ、具体的には、例えば、２－ベンゾチアゾリルチオ基、２－ピリジルチオ基、１－フェニルテトラゾリルチオ基など）、アルキルスルフィニル基（好ましくは炭素数１～３２、より好ましくは炭素数１～２４のアルキルスルフィニル基が挙げられ、具体的には、例えば、ドデカンスルフィニル基など）、アリールスルフィニル基（好ましくは炭素数６～３２、より好ましくは炭素数６～２４のアリールスルフィニル基が挙げられ、具体的には、例えば、フェニルスルフィニル基など）、アルキルスルホニル基（好ましくは炭素数１～４８、より好ましくは炭素数１～２４のアルキルスルホニル基が挙げられ、具体的には、例えば、メチルスルホニル基、エチルスルホニル基、プロピルスルホニル基、ブチルスルホニル基、イソプロピルスルホニル基、２－エチルヘキシルスルホニル基、ヘキサデシルスルホニル基、オクチルスルホニル基、シクロヘキシルスルホニル基など）、アリールスルホニル基（好ましくは炭素数６～４８、より好ましくは炭素数６～２４のアリールスルホニル基が挙げられ、具体的には、例えば、フェニルスルホニル基、１－ナフチルスルホニル基など）、スルファモイル基（好ましくは炭素数３２以下、より好ましくは炭素数２４以下のスルファモイル基が挙げられ、具体的には、例えば、スルファモイル基、Ｎ，Ｎ－ジプロピルスルファモイル基、Ｎ－エチル－Ｎ－ドデシルスルファモイル基、Ｎ－エチル－Ｎ－フェニルスルファモイル基、Ｎ－シクロヘキシルスルファモイル基など）、スルホ基、ホスホニル基（好ましくは炭素数１～３２、より好ましくは炭素数１～２４のホスホニル基が挙げられ、具体的には、例えば、フェノキシホスホニル基、オクチルオキシホスホニル基、フェニルホスホニル基など）、ホスフィノイルアミノ基（好ましくは炭素数１～３２、より好ましくは炭素数１～２４のホスフィノイルアミノ基が挙げられ、具体的には、例えば、ジエトキシホスフィノイルアミノ基、ジオクチルオキシホスフィノイルアミノ基など）を表す。 An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, specifically, for example, a methylthio group, an ethylthio group, an octylthio group, a cyclohexylthio group, etc.), an arylthio group (Preferably an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, specifically, for example, a phenylthio group), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more Preferred examples include a heterocyclic thio group having 1 to 18 carbon atoms, and specific examples include 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group and the like, alkylsulfinyl group ( Preferred are alkylsulfinyl groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms. Dodecanesulfinyl group), arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, specifically, for example, phenylsulfinyl group), alkylsulfonyl group (Preferably includes an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group. Group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group, etc.), arylsulfonyl group (preferably having 6 to 48 carbon atoms, more preferably having 6 to 24 carbon atoms). , Specifically For example, phenylsulfonyl group, 1-naphthylsulfonyl group, etc.), sulfamoyl group (preferably sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, specifically, for example, sulfamoyl group, N N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group, etc.), sulfo group, phosphonyl group (preferably Is a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples thereof include phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group, etc.), phosphinoyl Amino group (preferably phosphinoyla having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms) And a mino group, specifically, a diethoxyphosphinoylamino group, a dioctyloxyphosphinoylamino group, and the like.
　Ｚ１、Ｚ２、Ｚ３およびＺ４が表すＣ－Ｒ中、Ｒが表すアルキル基、及びアリール基としては、Ａ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７及びＡ８が表す置換基として説明したアルキル基、及びアリール基と同義である。 In the CR represented by Z 1 , Z 2 , Z 3 and Z 4 , the alkyl group and aryl group represented by R are A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7. and alkyl groups described as the substituent a 8 represents, and is synonymous with an aryl group.
　前記一般式（ＩＩ）中、Ｍが表す「２価の金属原子、又は金属原子を含む２価の原子団」における金属原子の具体例としては、好ましくはＡｌ、Ｓｉ、Ｃａ、Ｔｉ、Ｖ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇｅ、Ｍｏ、Ｒｕ、Ｒｈ、Ｐｄ、Ｉｎ、Ｓｎ、Ｐｔ、Ｐｂ、Ｍｇが挙げられ、より好ましくはＡｌ、Ｖ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｒｕ、Ｒｈ、Ｐｄ、Ｐｔ、Ｍｇが挙げられ、さらに好ましくはＡｌ、Ｖ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｍｇが挙げられ、特に好ましくはＶ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎが挙げられる。
　前記一般式（ＩＩ）中、Ｍが表す「金属原子を含む２価の原子団」の具体例としては、ハロゲン化金属原子（例えばＡｌ-Ｆ、Ａｌ-Ｃｌ、Ａｌ-Ｂｒ、Ａｌ－Ｉ、Ｉｎ-Ｆ，Ｉｎ－Ｃｌ、Ｆｅ－Ｃｌ、Ｉｎ－Ｂｒ、Ｉｎ－Ｉ、ＳｉＦ２，ＳｉＣｌ２，ＳｉＢｒ２，ＳｉＩ２、ＴｉＦ２，ＴｉＣｌ２，ＴｉＢｒ２，ＴｉＩ２等）、アルキル基、アリール基、ナフチル基、アルコキシ基、水酸基等の置換基が結合した金属原子（具体的には、例えばＳｉ（ＣＨ３）２、Ｓｉ（Ｃ２Ｈ５）２、Ａｌ-Ｃ６Ｈ５、Ｉｎ－Ｃ６Ｈ５、Ａｌ（ＯＨ）、Ｍｎ（ＯＨ）、Ｓｉ（ＯＨ）２、Ｚｒ（ＯＨ）２、Ａｌ－ＯＣＨ３、Ａｌ－Ｏ（Ｃ６Ｈ５）等）、酸化金属原子（例えばＴｉＯ、ＭｎＯ、ＶＯ等）、が挙げられる。 In the general formula (II), specific examples of the metal atom in the “divalent metal atom or divalent atomic group containing a metal atom” represented by M are preferably Al, Si, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Mo, Ru, Rh, Pd, In, Sn, Pt, Pb, Mg are mentioned, more preferably Al, V, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, Mg are mentioned, More preferably, Al, V, Mn, Fe, Co, Ni, Cu, Zn, Mg are mentioned, Especially preferably, V, Co, Ni, Cu and Zn are mentioned.
Specific examples of the “divalent atomic group containing a metal atom” represented by M in the general formula (II) include metal halide atoms (for example, Al—F, Al—Cl, Al—Br, Al—I, In-F, In-Cl, Fe-Cl, In-Br, In-I, SiF 2, SiCl 2, SiBr 2, SiI 2, TiF 2, TiCl 2, TiBr 2, TiI 2 like) alkyl, aryl A metal atom to which a substituent such as a group, a naphthyl group, an alkoxy group or a hydroxyl group is bonded (specifically, for example, Si (CH 3 ) 2 , Si (C 2 H 5 ) 2 , Al—C 6 H 5 , In— C 6 H 5 , Al (OH), Mn (OH), Si (OH) 2 , Zr (OH) 2 , Al—OCH 3 , Al—O (C 6 H 5 ), etc.), metal oxide atoms (for example, TiO , MnO, VO, etc.).
　本発明で用いられるポルフィリン化合物は、Ｚ１、Ｚ２、Ｚ３及びＺ４は全てがＮを表すテトラアザポルフィリン化合物が好ましく、好ましくは一般式（ＩＩ－２）で表される化合物が挙げられる。 The porphyrin compound used in the present invention is preferably a tetraazaporphyrin compound in which Z 1 , Z 2 , Z 3 and Z 4 all represent N, preferably a compound represented by the general formula (II-2) .
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　前記一般式（ＩＩ－２）中、Ａ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７、Ａ８及びＭは、一般式（ＩＩ）におけるＡ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７、Ａ８及びＭと各々同義である。 In the general formula (II-2), A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M are the same as A 1 , A 2 , A in the general formula (II). 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M have the same meanings.
　本発明で用いられる一般式（ＩＩ）で表される化合物の吸収スペクトルの極大値は、カラーフィルタの透過率の観点から５５０ｎｍから６５０ｎｍが好ましく、より好ましくは５７０ｎｍから６３０ｎｍ、特に好ましくは５７０ｎｍから６１０ｎｍが好ましい。 The maximum value of the absorption spectrum of the compound represented by the general formula (II) used in the present invention is preferably from 550 nm to 650 nm, more preferably from 570 nm to 630 nm, particularly preferably from 570 nm to 610 nm, from the viewpoint of the transmittance of the color filter. Is preferred.
　以下、本発明における特定染料（Ｂ）の具体例を示す。但し、本発明においては、これらに制限されるものではない。下記具体例において、「ｔ－Ｂｕ」はｔ－ブチル基を表し、「Ｍｅ」はメチル基を表し、「Ｅｔ」はエチル基を表し、「ｎ－Ｐｒ」はｎ－プロピル基を表し、「ｉ－Ｐｒ」はｉ－プロピル基を表し、「Ｐｈ」はフェニル基を表す。
　なお、以下に示す化合物は異性体については記述していないが、実際には次の様にジシアノエチレン化合物を金属塩と反応させ環化させるため４つの異性体が存在し、それらの混合物である。 Specific examples of the specific dye (B) in the present invention are shown below. However, the present invention is not limited to these. In the specific examples below, “t-Bu” represents a t-butyl group, “Me” represents a methyl group, “Et” represents an ethyl group, “n-Pr” represents an n-propyl group, “ “i-Pr” represents an i-propyl group, and “Ph” represents a phenyl group.
In addition, although the compound shown below does not describe about an isomer, in fact, there exist four isomers in order to make a dicyanoethylene compound react with a metal salt and cyclize as follows, and it is a mixture thereof. .
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　前記スキームにおけるＸ１、Ｘ２、Ｘ３、Ｘ４、Ｙ１、Ｙ２、Ｙ３、およびＹ４は、一般式（ＩＩ－２）におけるＡ１からＡ８で説明された基とそれぞれ同義である。Ｘ１とＹ１、Ｘ２とＹ２、Ｘ３とＹ３、Ｘ４とＹ４が同じでない場合、上記の４つの異性体を形成し得る。 In the scheme, X 1 , X 2 , X 3 , X 4 , Y 1 , Y 2 , Y 3 , and Y 4 are respectively synonymous with the groups described for A 1 to A 8 in the general formula (II-2). It is. If X 1 and Y 1 , X 2 and Y 2 , X 3 and Y 3 , X 4 and Y 4 are not the same, the above four isomers can be formed.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
　前記特定染料（Ｂ）の含有量としては、着色硬化性組成物に含まれる着色化合物の総量に対して０．１質量％以上であることが好ましく、０．５質量％以上であることがより好ましく、１質量％以上であることが特に好ましい。本発明の化合物は、微量の使用であってもカラーフィルタにした際に良好な色度、コントラストを得ることが出来るため、コストダウン効果に優れる。前記特定染料（Ｂ）の含有量の上限は、カラーフィルタにした際の色度要求やレジスト性能等、ユーザーの要求に適合するものである限り特に限定されないが、前記特定染料（Ａ）とのバランスを考慮すれば、着色化合物の総量に対して５０質量％以下であることが好ましい。 As content of the said specific dye (B), it is preferable that it is 0.1 mass% or more with respect to the total amount of the coloring compound contained in a colored curable composition, and it is more preferable that it is 0.5 mass% or more. It is preferably 1% by mass or more. Since the compound of the present invention can obtain good chromaticity and contrast when used as a color filter even in a trace amount, it is excellent in cost reduction effect. The upper limit of the content of the specific dye (B) is not particularly limited as long as it satisfies the user's requirements such as chromaticity requirements and resist performance when the color filter is used, but with the specific dye (A) Considering the balance, it is preferably 50% by mass or less with respect to the total amount of the coloring compound.
（その他の染料）
　本発明の着色硬化性組成物には、着色化合物として、前記した特定染料（Ａ）及び特定染料（Ｂ）以外の公知の染料を含んでもよい。
　本発明の着色硬化性組成物に含んでもよいその他の染料としては、ピラゾールアゾ系、アニリノアゾ系、アントラキノン系、アンスラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、スクアリリウム系、キノフタロン系、ベンゾピラン系、インジゴ系等の染料である。
　本発明の着色硬化性組成物に含んでもよいその他の染料の具体例としては、例えば、特開昭６４－９０４０３号公報、特開昭６４－９１１０２号公報、特開平１－９４３０１号公報、特開平６－１１６１４号公報、特登２５９２２０７号、米国特許第４，８０８，５０１号明細書、米国特許第５，６６７，９２０号明細書、米国特許第５，０５９，５００号明細書、特開平５－３３３２０７号公報、特開平６－３５１８３号公報、特開平６－５１１１５号公報、特開平６－１９４８２８号公報、特開平８－２１１５９９号公報、特開平４－２４９５４９号公報、特開平１０－１２３３１６号公報、特開平１１－３０２２８３号公報、特開平７－２８６１０７号公報、特開２００１－４８２３号公報、特開平８－１５５２２号公報、特開平８－２９７７１号公報、特開平８－１４６２１５号公報、特開平１１－３４３４３７号公報、特開平８－６２４１６号公報、特開２００２－１４２２０号公報、特開２００２－１４２２１号公報、特開２００２－１４２２２号公報、特開２００２－１４２２３号公報、特開平８－３０２２２４号公報、特開平８－７３７５８号公報、特開平８－１７９１２０号公報、特開平８－１５１５３１号公報、特開平６－２３０２１０号公報等に記載の染料である。 (Other dyes)
The colored curable composition of the present invention may contain a known dye other than the specific dye (A) and the specific dye (B) as a coloring compound.
Other dyes that may be included in the colored curable composition of the present invention include pyrazole azo series, anilino azo series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, It is a dye such as phenothiazine, pyrrolopyrazole azomethine, squarylium, quinophthalone, benzopyran, or indigo.
Specific examples of other dyes that may be contained in the colored curable composition of the present invention include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, No. 6-11614, No. 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, JP-A-8-2111599, JP-A-4-249549, JP-A-10- No. 123316, JP-A-11-302283, JP-A-7-286107, JP-A-2001-4823, JP-A-8-15522, JP-A-8- No. 9771, No. 8-146215, No. 11-343437, No. 8-62416, No. 2002-14220, No. 2002-14221, No. 2002-14222 JP, 2002-14223, JP 8-302224, JP 8-73758, JP 8-179120, JP 8-151351, JP 6230210, etc. It is a dye as described in above.
　本発明の着色硬化性組成物に含まれる特定染料（Ａ）及び特定染料（Ｂ）の総含有量は、着色化合物中、１質量％以上９０質量％以下であることが好ましく、１０質量％以上７０質量％以下であることがより好ましく、１０質量％以上５０質量％以下であることがさらに好ましい。 The total content of the specific dye (A) and the specific dye (B) contained in the colored curable composition of the present invention is preferably 1% by mass or more and 90% by mass or less, preferably 10% by mass or more. More preferably, it is 70 mass% or less, More preferably, it is 10 mass% or more and 50 mass% or less.
（顔料）
　本発明の着色硬化性組成物には、前記着色化合物として顔料を併用することもできる。
　顔料としては平均一次粒子径が１０ｎｍ以上３０ｎｍ以下の顔料が好ましい。上記態様であると、輝度とコントラストに優れる着色硬化性組成物が得られる。 (Pigment)
In the colored curable composition of the present invention, a pigment may be used in combination as the colored compound.
As the pigment, a pigment having an average primary particle size of 10 nm or more and 30 nm or less is preferable. A colored curable composition having excellent brightness and contrast can be obtained in the above embodiment.
　顔料としては、従来公知の種々の無機顔料又は有機顔料を用いることができるが、信頼性の観点で有機顔料を用いることが好ましい。本発明において有機顔料として、例えば、特開２００９－２５６５７２号公報の段落〔００９３〕に記載の有機顔料が挙げられる。
　また特に、以下に示す顔料が、色再現性の観点で好適であるが、本発明においてはこれらに限定されるものではない。これら有機顔料は、単独で、または、色純度を上げるため種々組合せて用いることもできる。
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　１７７、２２４、２４２、２５４、２５５、２６４
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１３８、１３９、１５０、１８０、１８５
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｏｒａｎｇｅ　３６、３８、７１、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｇｒｅｅｎ　７、３６、５８、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６、
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３ Conventionally known various inorganic pigments or organic pigments can be used as the pigment, but organic pigments are preferably used from the viewpoint of reliability. Examples of the organic pigment in the present invention include organic pigments described in paragraph [0093] of JP-A-2009-256572.
In particular, the following pigments are suitable from the viewpoint of color reproducibility, but are not limited to these in the present invention. These organic pigments can be used alone or in various combinations in order to increase color purity.
C. I. Pigment Red 177, 224, 242, 254, 255, 264
C. I. Pigment Yellow 138, 139, 150, 180, 185
C. I. Pigment Orange 36, 38, 71,
C. I. Pigment Green 7, 36, 58,
C. I. Pigment Blue 15: 6,
C. I. Pigment Violet 23
　顔料を用いる場合、本発明の着色硬化性組成物中における顔料の含有量は、該組成物の全固形分に対して、０．５質量％～５０質量％であることが好ましく、１質量％～３０質量％がより好ましい。顔料の含有量が前記範囲内であると、優れた色特性を確保するのに有効である。 When a pigment is used, the content of the pigment in the colored curable composition of the present invention is preferably 0.5% by mass to 50% by mass with respect to the total solid content of the composition, and is preferably 1% by mass. More preferable is 30% by mass. When the pigment content is within the above range, it is effective to ensure excellent color characteristics.
　なお、本発明において、顔料は、分散剤の少なくとも１種を使用して顔料を分散し、顔料分散組成物として使用することが好ましい。被覆顔料を用いる場合でも同様である。この分散剤の使用により、顔料の分散性を向上させることができる。
　分散剤としては、例えば、公知の顔料分散剤や界面活性剤を適宜選択して用いることができる。
　分散剤の含有量としては、顔料の質量に対して、１質量％～１００質量％が好ましく、３質量％～７０質量％がより好ましい。 In the present invention, the pigment is preferably used as a pigment dispersion composition by dispersing the pigment using at least one dispersant. The same applies when a coated pigment is used. By using this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, for example, a known pigment dispersant or surfactant can be appropriately selected and used.
The content of the dispersant is preferably 1% by mass to 100% by mass and more preferably 3% by mass to 70% by mass with respect to the mass of the pigment.
　前記着色化合物の総含有量は、着色硬化性組成物の全固形分に対して、０．２質量％以上５０質量％以下であることが好ましく、１質量％以上５０質量％以下であることがより好ましく、１０質量％以上５０質量％以下であることがさらに好ましい。 The total content of the coloring compound is preferably 0.2% by mass or more and 50% by mass or less, and preferably 1% by mass or more and 50% by mass or less, based on the total solid content of the colored curable composition. More preferably, it is 10 mass% or more and 50 mass% or less.
＜（Ｃ）重合性化合物＞
　本発明の着色硬化性組成物は、少なくとも一種の重合性化合物を含有することが好ましい。
　重合性化合物としては、例えば少なくとも一個のエチレン性不飽和二重結合を有する重合性化合物であり、公知の組成物を構成する成分から選択して用いることができ、特開２００６－２３６９６号公報の段落番号［００１０］～［００２０］に記載の成分や、特開２００６－６４９２１号公報の段落番号［００２７］～［００５３］に記載の成分を挙げることができる。重合性化合物としては、好ましくは、末端エチレン性不飽和結合を有する化合物であり、より好ましくは末端エチレン性不飽和結合を２個以上有する化合物から選ばれる。
　このような化合物群は当該産業分野において広く知られているものであり、本発明においてはこれらを特に限定なく用いることができる。これらは、例えば、モノマー、プレポリマー、すなわち２量体、３量体及びオリゴマー、又はそれらの混合物並びにそれらの多量体などの化学的形態のいずれであってもよい。 <(C) Polymerizable compound>
The colored curable composition of the present invention preferably contains at least one polymerizable compound.
The polymerizable compound is, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected and used from components constituting a known composition, as disclosed in JP-A-2006-23696. Examples include the components described in paragraph numbers [0010] to [0020] and the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921. The polymerizable compound is preferably a compound having a terminal ethylenically unsaturated bond, and more preferably selected from compounds having two or more terminal ethylenically unsaturated bonds.
Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof.
　また、イソシアネートと水酸基との付加反応を用いて製造されるウレタン付加の重合性化合物も好適であり、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報に記載のエチレンオキサイド骨格を有するウレタン化合物類も好適である。
　その他の例としては、特開昭４８－６４１８３号公報、特公昭４９－４３１９１号公報、特公昭５２－３０４９０号公報の各公報に記載されているようなポリエステルアクリレート類、エポキシ樹脂と（メタ）アクリル酸とを反応させて得られるエポキシアクリレート類等の多官能のアクリレートやメタクリレートを挙げることができる。更に日本接着協会誌ｖｏｌ．２０、Ｎｏ．７、３００～３０８ページ（１９８４年）に光硬化性モノマー及びオリゴマーとして紹介されているものも使用することができる。 In addition, a urethane-added polymerizable compound produced by an addition reaction between an isocyanate and a hydroxyl group is also suitable, such as JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. And the ethylene oxide skeletons described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Urethane compounds having them are also suitable.
Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting with acrylic acid. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.
　具体例としては、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリ（（メタ）アクリロイルオキシエチル）イソシアヌレート、ペンタエリスリトールテトラ（メタ）アクリレートＥＯ変性体、ジペンタエリスリトールヘキサ（メタ）アクリレートＥＯ変性体などが、並びに、市販品としては、ＮＫエステル　Ａ－ＴＭＭＴ、ＮＫエステル　Ａ－ＴＭＭ－３、ＮＫオリゴＵＡ－３２Ｐ、ＮＫオリゴＵＡ－７２００（以上、新中村化学工業（株）製）、アロニックス　Ｍ－３０５、アロニックス　Ｍ－３０６、アロニックス　Ｍ－３０９、アロニックス　Ｍ－４５０、アロニックス　Ｍ－４０２、ＴＯ－１３８２、ＴＯ－２３４９（以上、東亞合成（株）製）、Ｖ＃８０２（大阪有機化学工業（株）製）、ＫＡＹＡＲＡＤ　Ｄ－３３０、Ｄ－３２０、Ｄ－３１０、ＤＰＨＡ（以上、日本化薬株式会社製）を好ましい例として挙げることができる。 Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate. , Pentaerythritol tetra (meth) acrylate EO modified products, dipentaerythritol hexa (meth) acrylate EO modified products, etc., and commercially available products include NK ester A-TMMT, NK ester A-TMM-3, and NK oligo UA. -32P, NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Allo M-402, TO-1382, TO-2349 (above, manufactured by Toagosei Co., Ltd.), V # 802 (produced by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD D-330, D-320, D-310, DPHA (made by Nippon Kayaku Co., Ltd.) can be mentioned as a preferred example.
　また、前記（Ｃ）重合性化合物としては、低温硬化性の観点から、特開２００９－２６５６３０号の段落番号〔００３１〕～〔００６１〕に記載の成分を挙げることができる。なかでも、前記（Ｃ）重合性化合物としては、以下に示す（１）～（２０）及び（Ｍ－１）～（Ｍ－８）が好ましい。特に分子内に２つのエチレン性不飽和結合を有する重合性モノマーを用いて形成された着色膜は、低温硬化性の観点から優れる。 In addition, examples of the polymerizable compound (C) include components described in paragraphs [0031] to [0061] of JP-A-2009-265630 from the viewpoint of low-temperature curability. Among these, as the polymerizable compound (C), the following (1) to (20) and (M-1) to (M-8) are preferable. In particular, a colored film formed using a polymerizable monomer having two ethylenically unsaturated bonds in the molecule is excellent from the viewpoint of low-temperature curability.
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　これらの重合性化合物は単独で、或いは２種以上の併用で用いることができる。 These polymerizable compounds can be used alone or in combination of two or more.
　着色硬化性組成物に重合性化合物を用いる場合、全固形分中における重合性化合物の含有量（２種以上の場合は総含有量）としては、１０質量％～８０質量％が好ましく、１５質量％～７５質量％がより好ましく、２０質量％～６０質量％が特に好ましい。 When a polymerizable compound is used in the colored curable composition, the content of the polymerizable compound in the total solid content (the total content in the case of 2 or more types) is preferably 10% by mass to 80% by mass, and 15% by mass. % To 75% by mass is more preferable, and 20% to 60% by mass is particularly preferable.
＜（Ｄ）光重合開始剤＞
　本発明の着色硬化性組成物は、少なくとも一種の光重合開始剤を含有することが好ましい。
　光重合開始剤は、前記重合性化合物を重合させ得るものであれば、特に制限はなく、特性、開始効率、吸収波長、入手性、コスト等の観点で選ばれるのが好ましい。
　光重合開始剤は、露光光により感光し、重合性化合物の重合を開始、促進する化合物である。波長３００ｎｍ以上の活性光線に感応し、重合性化合物の重合を開始、促進する化合物が好ましい。また、波長３００ｎｍ以上の活性光線に直接感応しない光重合開始剤についても、増感剤と組み合わせて好ましく用いることができる。 <(D) Photopolymerization initiator>
The colored curable composition of the present invention preferably contains at least one photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
The photopolymerization initiator is a compound that is exposed to exposure light and starts and accelerates polymerization of the polymerizable compound. A compound that responds to actinic rays having a wavelength of 300 nm or longer and initiates and accelerates polymerization of the polymerizable compound is preferable. In addition, a photopolymerization initiator that does not directly respond to actinic rays having a wavelength of 300 nm or longer can also be preferably used in combination with a sensitizer.
　具体的には例えば、オキシムエステル化合物、有機ハロゲン化化合物、オキシジアゾール化合物、カルボニル化合物、ケタール化合物、ベンゾイン化合物、アクリジン化合物、有機過酸化物、アゾ化合物、クマリン化合物、アジド化合物、メタロセン化合物、ヘキサアリールビイミダゾール化合物、有機ホウ酸化合物、ジスルホン酸化合物、オニウム塩化合物、アシルホスフィン（オキシド）化合物、ベンゾフェノン化合物、アセトフェノン化合物、ベンズイミダゾール化合物及びその誘導体等が挙げられる。
　これらの中でも、感度の点から、オキシムエステル化合物、ヘキサアリールビイミダゾール化合物が好ましい。 Specifically, for example, oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexa Examples thereof include arylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxide) compounds, benzophenone compounds, acetophenone compounds, benzimidazole compounds, and derivatives thereof.
Among these, oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity.
　オキシムエステル化合物としては、特開２０００－８００６８号公報、特開２００１－２３３８４２号公報、特表２００４－５３４７９７号公報、国際公開第２００５／０８０３３７号、国際公開第２００６／０１８９７３号明細書、特開２００７－２１０９９１号公報、特開２００７－２３１０００号公報、特開２００７－２６９７７９号公報、特開２００９－１９１０６１号公報、国際公開第２００９／１３１１８９号明細書に記載の化合物を使用できる。 Examples of the oxime ester compound include JP 2000-80068, JP 2001-233842, JP 2004-534797, WO 2005/080337, WO 2006/018933, JP The compounds described in JP 2007-210991 A, JP 2007-231000 A, JP 2007-2699779 A, JP 2009-191061 A, and International Publication No. 2009/131189 can be used.
　具体的な例としては、２－（Ｏ－ベンゾイルオキシム）－１－［４－（フェニルチオ）フェニル］－１，２－ブタンジオン、２－（Ｏ－ベンゾイルオキシム）－１－［４－（フェニルチオ）フェニル］－１，２－ペンタンジオン、２－（Ｏ－ベンゾイルオキシム）－１－［４－（フェニルチオ）フェニル］－１，２－ヘキサンジオン、２－（Ｏ－ベンゾイルオキシム）－１－［４－（フェニルチオ）フェニル］－１，２－ヘプタンジオン、２－（Ｏ－ベンゾイルオキシム）－１－［４－（フェニルチオ）フェニル］－１，２－オクタンジオン、２－（Ｏ－ベンゾイルオキシム）－１－［４－（メチルフェニルチオ）フェニル］－１，２－ブタンジオン、２－（Ｏ－ベンゾイルオキシム）－１－［４－（エチルフェニルチオ）フェニル］－１，２－ブタンジオン、２－（Ｏ－ベンゾイルオキシム）－１－［４－（ブチルフェニルチオ）フェニル］－１，２－ブタンジオン、１－（Ｏ－アセチルオキシム）－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン、１－（Ｏ－アセチルオキシム）－１－［９－メチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン、１－（Ｏ－アセチルオキシム）－１－［９－プロピル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン、１－（Ｏ－アセチルオキシム）－１－［９－エチル－６－（２－エチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン、１－（Ｏ－アセチルオキシム）－１－［９－エチル－６－（２－ブチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン、１－（Ｏ－アセチルオキシム）－１－［９－エチル－６－（チオフェノイル）－９Ｈ－カルバゾール－３－イル］プロパノンなどが挙げられる。但し、これらに限定されるものではない。 Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) Phenyl] -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4 -(Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime)- 1- [4- (Methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1 2-butanedione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Ethanone, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9 -Ethyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) -9H- carbazol-3-yl] ethanone, 1-(O-acetyl oxime) -1- [9-ethyl-6- (thiophenoyl) -9H- carbazol-3-yl] such as propanone and the like. However, it is not limited to these.
　また、本発明においては、感度、経時安定性、後加熱時の着色の観点から、光重合開始剤であるオキシムエステル化合物として、下記一般式（Ａ）で表される化合物も好適である。 In the present invention, from the viewpoint of sensitivity, stability over time, and coloring during post-heating, a compound represented by the following general formula (A) is also suitable as an oxime ester compound that is a photopolymerization initiator.
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
　一般式（Ａ）中、Ｘ１、Ｘ２、及びＸ３はそれぞれ独立に、水素原子、ハロゲン原子、又はアルキル基を表し、Ｒ１は－Ｒ、－ＯＲ、－ＣＯＲ、－ＳＲ、－ＣＯＮＲＲ’、又は－ＣＮを表し、Ｒ２及びＲ３はそれぞれ独立に、－Ｒ、－ＯＲ、－ＣＯＲ、－ＳＲ、又は－ＮＲＲ’を表す。Ｒ及びＲ’は、それぞれ独立に、アルキル基、アリール基、アラルキル基、又は、複素環基を表し、これらの基は、ハロゲン原子及び複素環基からなる群より選択される１以上で置換されていてもよく、該アルキル基、及びアラルキル基におけるアルキル鎖を構成する炭素原子の１以上が、不飽和結合、エーテル結合、又はエステル結合に置き換わっていてもよく、Ｒ及びＲ’は互いに結合して環を形成していてもよい。 In the general formula (A), X 1 , X 2 , and X 3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R 1 represents —R, —OR, —COR, —SR, —CONRR 'Or -CN, and R 2 and R 3 each independently represent -R, -OR, -COR, -SR, or -NRR'. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. And one or more carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. May form a ring.
　一般式（Ａ）中、Ｘ1、Ｘ２、及びＸ３がハロゲン原子を表す場合のハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられ、Ｘ1、Ｘ２、及びＸ３がアルキル基
を表す場合のアルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、第二ブチル、第三ブチル、アミル、イソアミル、第三アミル、ヘキシル、ヘプチル、オクチル、イソオクチル、２－エチルヘキシル、第三オクチル、ノニル、イソノニル、デシル、イソデシル、ビニル、アリル、ブテニル、エチニル、プロピニル、メトキシエチル、エトキシエチル、プロピロキシエチル、メトキシエトキシエチル、エトキシエトキシエチル、プロピロキシエトキシエチル、メトキシプロピル、モノフルオロメチル、ジフルオロメチル、トリフルオロメチル、トリフルオロエチル、パーフルオロエチル、２－（ベンゾオキサゾール－２’－イル）エテニル等が挙げられる。
　なかでも、Ｘ1、Ｘ２、及びＸ３がいずれも、水素原子を表すか、或いは、Ｘ1がアルキル基を表し、Ｘ２、及びＸ３がいずれも水素原子を表すことが好ましい。 In general formula (A), when X 1 , X 2 , and X 3 represent a halogen atom, examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and X 1 , X 2 , and X 3 are alkyl. Examples of the alkyl group in the case of representing a group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2- Ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxypropyl, Monofluoromethyl, difluoromethyl, Fluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2'-yl) ethenyl and the like.
Especially, it is preferable that all of X < 1 >, X < 2 > and X < 3 > represent a hydrogen atom, or X < 1 > represents an alkyl group and X < 2 > and X < 3 > both represent a hydrogen atom.
　一般式（Ａ）中、Ｒ及びＲ’で表されるアルキル基としては、例えば、メチル、
エチル、プロピル、イソプロピル、ブチル、イソブチル、第二ブチル、第三ブチル、アミル、イソアミル、第三アミル、ヘキシル、ヘプチル、オクチル、イソオクチル、２－エチルヘキシル、第三オクチル、ノニル、イソノニル、デシル、イソデシル、ビニル、アリル、ブテニル、エチニル、プロピニル、メトキシエチル、エトキシエチル、プロピロキシエチル、メトキシエトキシエチル、エトキシエトキシエチル、プロピロキシエトキシエチル、メトキシプロピル、モノフルオロメチル、ジフルオロメチル、トリフルオロメチル、トリフルオロエチル、パーフルオロエチル、２－（ベンゾオキサゾール－２’－イル）エテニル等が挙げられる。
　Ｒ及びＲ’で表されるアリール基としては、例えば、フェニル、トリル、キシリル、エチルフェニル、クロロフェニル、ナフチル、アンスリル、フェナンスレニル等が挙げられる。
　Ｒ及びＲ’で表されるアラルキル基としては、例えば、ベンジル、クロロベンジル、α－メチルベンジル、α、α－ジメチルベンジル、フェニルエチル、フェニルエテニル等が挙げられる。
　Ｒ及びＲ’で表される複素環基としては、例えば、ピリジル、ピリミジル、フリル、チオフェニル等が挙げられる。
　また、Ｒ及びＲ’は互いに結合して形成される環としては、例えば、ピペリジン環、モルホリン環等が挙げられる。 In general formula (A), examples of the alkyl group represented by R and R ′ include methyl,
Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, Vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl Perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like.
Examples of the aryl group represented by R and R ′ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like.
Examples of the aralkyl group represented by R and R ′ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylethenyl and the like.
Examples of the heterocyclic group represented by R and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl and the like.
Examples of the ring formed by bonding R and R ′ to each other include a piperidine ring and a morpholine ring.
　上記Ｒ及びＲ’を含んで構成されるＲ２及びＲ３としては、それぞれ独立に、メチル基、ヘキシル基、シクロヘキシル基、－Ｓ－Ｐｈ、－Ｓ－Ｐｈ－Ｃｌ、及び－Ｓ－Ｐｈ－Ｂｒが特に好ましい様態である。 R 2 and R 3 including R and R ′ are each independently a methyl group, a hexyl group, a cyclohexyl group, —S—Ph, —S—Ph—Cl, and —S—Ph—. Br is a particularly preferred embodiment.
　光重合開始剤の中でも、一般式（Ａ）において、Ｘ1、Ｘ２、及びＸ３がいずれも、水素原子であるもの；Ｒ１がアルキル基、特にメチル基であるもの；Ｒ２がアルキル基、特にメチル基であるもの；Ｒ３がアルキル基、特にエチル基であるものは、光重合開始剤として特に好適である。 Among the photopolymerization initiators, in general formula (A), X 1 , X 2 , and X 3 are all hydrogen atoms; R 1 is an alkyl group, particularly a methyl group; R 2 is alkyl Particularly preferred as photoinitiators are those which are groups, in particular methyl groups; those in which R 3 is an alkyl group, in particular ethyl group.
　従って、上記一般式（Ａ）で表される光重合開始剤の好ましい具体例としては、以下に例示する化合物Ａ～化合物Ｆが挙げられる。ただし、本発明は以下の化合物により何ら制限を受けるものではない。 Accordingly, preferred specific examples of the photopolymerization initiator represented by the general formula (A) include compounds A to F exemplified below. However, the present invention is not limited by the following compounds.
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
　一般式（Ａ）で表される光重合開始剤は、例えば、特開２００５－２２００９７号公報に記載の方法により合成することができる。 The photopolymerization initiator represented by the general formula (A) can be synthesized, for example, by the method described in JP-A-2005-220097.
　本発明に用いる一般式（Ａ）で表される化合物は、２５０ｎｍ～５００ｎｍの波長領域に吸収波長を有するものである。より好ましくは、３００ｎｍ～３８０ｎｍの波長領域に吸収波長を有するものを挙げることができる。特に、３０８ｎｍ及び３５５ｎｍの吸光度が高いものが好ましい。 The compound represented by the general formula (A) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferable examples include those having an absorption wavelength in the wavelength region of 300 nm to 380 nm. In particular, those having high absorbance at 308 nm and 355 nm are preferable.
　また、本発明においては、感度、経時安定性、後加熱時の着色の観点から、光重合開始剤であるオキシムエステル化合物として、下記一般式（Ｂ）で表される化合物も好適である。 In the present invention, from the viewpoint of sensitivity, stability over time, and coloring during post-heating, a compound represented by the following general formula (B) is also suitable as an oxime ester compound that is a photopolymerization initiator.
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
　一般式（Ｂ）中、Ｒ２２は１価の置換基を表す。Ａ２２は２価の連結基を表し、Ａｒは、アリール基を表す。ｎは、０～５の整数である。Ｘ２２は１価の置換基を表し、ｎが２～５の整数である場合複数存在するＸ２２は、同一であっても異なってもよい。 In the general formula (B), R 22 represents a monovalent substituent. A 22 represents a divalent linking group, and Ar represents an aryl group. n is an integer of 0 to 5. X 22 represents a monovalent substituent, and when n is an integer of 2 to 5, a plurality of X 22 may be the same or different.
　一般式（Ｂ）中、Ｒ２２で表される一価の置換基としては、以下に示す一価の非金属原子団であることが好ましい。
　一般式（Ｂ）中、Ｒ２２で表される一価の非金属原子団としては、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルキルスルホニル基、置換基を有してもよいアリールスルホニル基、置換基を有してもよいアシル基、置換基を有してもよい複素環基、等が挙げられる。 In the general formula (B), the monovalent substituent represented by R 22 is preferably a monovalent nonmetallic atomic group shown below.
In the general formula (B), the monovalent nonmetallic atomic group represented by R 22 has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent. And an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, a heterocyclic group which may have a substituent, and the like.
　置換基を有してもよいアルキル基としては、炭素数１～３０のアルキル基が好ましく、例えば、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基、トリフルオロメチル基、等が挙げられる。 The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, a trifluoromethyl group. Group, and the like.
　置換基を有してもよいアリール基としては、炭素数６～３０のアリール基が好ましく、例えば、フェニル基、ビフェニル基、１－ナフチル基、２－ナフチル基等が挙げられる。 The aryl group that may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.
　置換基を有してもよいアルキルスルホニル基としては、炭素数１～２０のアルキルスルホニル基が好ましく、例えば、メチルスルホニル基、エチルスルホニル基等が挙げられる。 The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group and an ethylsulfonyl group.
　置換基を有してもよいアリールスルホニル基としては、炭素数６～３０のアリールスルホニル基が好ましく、例えば、フェニルスルホニル基、１－ナフチルスルホニル基等が挙げられる。 The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group.
　置換基を有してもよいアシル基としては、炭素数２～２０のアシル基が好ましく、例えば、アセチル基、プロパノイル基、ブタノイル基、トリフルオロメチルカルボニル基、ペンタノイル基、ベンゾイル基、１－ナフトイル基、２－ナフトイル基、４－メチルスルファニルベンゾイル基、４－フェニルスルファニルベンゾイル基、４－ジメチルアミノベンゾイル基、４－ジエチルアミノベンゾイル基、２－クロロベンゾイル基、２－メチルベンゾイル基、２－メトキシベンゾイル基、２－ブトキシベンゾイル基、３－クロロベンゾイル基、３－トリフルオロメチルベンゾイル基、３－シアノベンゾイル基、３－ニトロベンゾイル基、４－フルオロベンゾイル基、４－シアノベンゾイル基、４－メトキシベンゾイル基等が挙げられる。 The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms. For example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.
　置換基を有してもよい複素環基としては、窒素原子、酸素原子、硫黄原子、リン原子を含む、芳香族或いは脂肪族の複素環が好ましい。例えば、チエニル基、フリル基、ピラニル基、等が挙げられる。 The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, a thienyl group, a furyl group, a pyranyl group, etc. are mentioned.
　一般式（Ｂ）中、Ｒ２２としては、高感度化の点から、無置換の又は置換基を有するアシル基がより好ましく、具体的には、無置換の又は置換基を有するアセチル基、プロピオニル基、ベンゾイル基、トルイル基が好ましい。
　前記置換基としては、例えば、下記の構造式で表される基が挙げられ、中でも、（ｄ－１）（ｄ－４）及び（ｄ－５）のいずれかが好ましい。 In general formula (B), R 22 is more preferably an unsubstituted or substituted acyl group from the viewpoint of increasing sensitivity, and specifically, an unsubstituted or substituted acetyl group or propionyl. Group, benzoyl group and toluyl group are preferred.
Examples of the substituent include groups represented by the following structural formula, and among these, any of (d-1), (d-4) and (d-5) is preferable.
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
　一般式（Ｂ）中、Ａ２２で表される二価の連結基としては、置換基を有してもよい炭素数１～１２のアルキレン、置換基を有してもよいシクロヘキシレン、置換基を有してもよいアルキニレンが挙げられる。
　これらの基に導入しうる置換基としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、メトキシ基、エトキシ基、ｔｅｒｔ－ブトキシ基等のアルコキシ基、フェノキシ基、ｐ－トリルオキシ基等のアリールオキシ基、メトキシカルボニル基、ブトキシカルボニル基、フェノキシカルボニル基等のアルコキシカルボニル基等が挙げられる。 In the general formula (B), the divalent linking group represented by A 22 includes an alkylene having 1 to 12 carbon atoms which may have a substituent, cyclohexylene which may have a substituent, and a substituent. Alkynylene, which may have
Examples of the substituent that can be introduced into these groups include halogen atoms 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- Examples include aryloxy groups such as a tolyloxy group, alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group.
　中でも、一般式（Ｂ）中、Ａ２２としては、感度を高め、加熱経時による着色を抑制する点から、無置換のアルキレン基、アルキル基（例えば、メチル基、エチル基、ｔｅｒｔ－ブチル基、ドデシル基）で置換されたアルキレン基、アルケニル基（例えば、ビニル基、アリル基）で置換されたアルキレン基、アリール基（例えば、フェニル基、ｐ－トリル基、キシリル基、クメニル基、ナフチル基、アンスリル基、フェナントリル基、スチリル基）で置換されたアルキレン基が好ましい。 Among them, in the general formula (B), A 22 is an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, from the viewpoint of increasing the sensitivity and suppressing the coloration due to heating. Alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group) An alkylene group substituted with an anthryl group, a phenanthryl group, or a styryl group is preferred.
　一般式（Ｂ）中、Ａｒで表されるアリール基としては、炭素数６～３０のアリール基が好ましく、また、置換基を有していてもよい。
　具体的にはＡｒは、フェニル基、ビフェニル基、１－ナフチル基、２－ナフチル基、ターフェニル基、クオーターフェニル基、ｏ－、ｍ－、及びｐ－トリル基、キシリル基、ｏ－、ｍ－、及びｐ－クメニル基、メシチル基等が挙げられる。中でも、感度を高め、加熱経時による着色を抑制する点から、置換又は無置換のフェニル基が好ましい。 In the general formula (B), the aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.
Specifically, Ar is phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m -, P-cumenyl group, mesityl group and the like. Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.
　上記フェニル基が置換基を有している場合、その置換基としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、メトキシ基、エトキシ基、ｔｅｒｔ－ブトキシ基等のアルコキシ基、フェノキシ基、ｐ－トリルオキシ基等のアリールオキシ基、メトキシカルボニル基、ブトキシカルボニル基、フェノキシカルボニル基等のアルコキシカルボニル基、アセトキシ基、プロピオニルオキシ基、ベンゾイルオキシ基等のアシルオキシ基、アセチル基、ベンゾイル基、イソブチリル基、アクリロイル基、メタクリロイル基、メトキサリル基等のアシル基、メチルアミノ基、シクロヘキシルアミノ基等のアルキルアミノ基、ジメチルアミノ基、ジエチルアミノ基、モルホリノ基、ピペリジノ基等のジアルキルアミノ基、フェニルアミノ基、メチル基、エチル基、ｔｅｒｔ－ブチル基、ドデシル基等のアルキル基、ヒドロキシ基、カルボキシ基、等が挙げられる。 When the phenyl group has a substituent, examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy such as a methoxy group, an ethoxy group and a tert-butoxy group. Group, aryloxy group such as phenoxy group, p-tolyloxy group, alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy group such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, Benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methacrylyl group and other acyl groups, methylamino group, cyclohexylamino group and other alkylamino groups, dimethylamino group, diethylamino group, morpholino group, piperidino group and other dialkylamino groups, F Niruamino group, a methyl group, an ethyl group, tert- butyl group, an alkyl group such as a dodecyl group, a hydroxy group, a carboxy group, and the like.
　一般式（Ｂ）においては、前記Ａｒと隣接するＳとで形成される「ＳＡｒ」の構造が
以下に示す構造であると、感度の点で好ましい。 In general formula (B), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure.
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
　一般式（Ｂ）中、Ｘ２２で表される一価の置換基としては、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオオキシ基、置換基を有してもよいアリールチオオキシ基、ハロゲン原子等が挙げられる。 In the general formula (B), the monovalent substituent represented by X 22 may have an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. A good alkenyl group, 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 alkylthiooxy group which may have a substituent, Examples include an arylthiooxy group which may have a substituent, a halogen atom, and the like.
　置換基を有してもよいアルキル基としては、炭素数１～３０のアルキル基が好ましく、例えば、メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基、トリフルオロメチル基、２－エチルヘキシル基、フェナシル基、等が挙げられる。 The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, a trifluoromethyl group. Group, 2-ethylhexyl group, phenacyl group, and the like.
　置換基を有してもよいアリール基としては、炭素数６～３０のアリール基が好ましく、例えば、フェニル基、ビフェニル基、１－ナフチル基、２－ナフチル基、ターフェニル基、クオーターフェニル基、ｏ－、ｍ－、及びｐ－トリル基、キシリル基、等がある。 The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms. For example, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a terphenyl group, a quarterphenyl group, o-, m-, and p-tolyl groups, xylyl groups, and the like.
　置換基を有してもよいアルケニル基としては、炭素数２～１０のアルケニル基が好ましく、例えば、ビニル基、アリル基、スチリル基等が挙げられる。 The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.
　置換基を有してもよいアルキニル基としては、炭素数２～１０のアルキニル基が好ましく、例えば、エチニル基、プロピニル基、プロパルギル基等が挙げられる。 The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.
　置換基を有してもよいアルコキシ基としては、炭素数１～３０のアルコキシ基が好ましく、例えば、メトキシ基、エトキシ基、プロピルオキシ基、イソプロピルオキシ基、ブトキシ基、ベンジルオキシ基等が挙げられる。 The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and a benzyloxy group. .
　置換基を有してもよいアリールオキシ基としては、炭素数６～３０のアリールオキシ基が好ましく、例えば、フェニルオキシ基、１－ナフチルオキシ基、２－ナフチルオキシ基、２－クロロフェニルオキシ基、２－メチルフェニルオキシ基、２－メトキシフェニルオキシ基、等が挙げられる。 The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, Examples include 2-methylphenyloxy group, 2-methoxyphenyloxy group, and the like.
　置換基を有してもよいアルキルチオオキシ基としては、炭素数１～３０のアルキルチオオキシ基が好ましく、例えば、メチルチオオキシ基、エチルチオオキシ基、プロピルチオオキシ基、イソプロピルチオオキシ基、ブチルチオオキシ基、イソブチルチオオキシ基、ｓｅｃ－ブチルチオオキシ基、ｔｅｒｔ－ブチルチオオキシ基、ペンチルチオオキシ基、イソペンチルチオオキシ基、ヘキシルチオオキシ基、ヘプチルチオオキシ基、オクチルチオオキシ基、２－エチルヘキシルチオオキシ基、デシルチオオキシ基、ドデシルチオオキシ基、オクタデシルチオオキシ基、ベンジルチオオキシ基等が挙げられる。 The alkylthiooxy group which may have a substituent is preferably an alkylthiooxy group having 1 to 30 carbon atoms. For example, a methylthiooxy group, an ethylthiooxy group, a propylthiooxy group, an isopropylthiooxy group, a butylthiooxy group Group, isobutylthiooxy group, sec-butylthiooxy group, tert-butylthiooxy group, pentylthiooxy group, isopentylthiooxy group, hexylthiooxy group, heptylthiooxy group, octylthiooxy group, 2-ethylhexyl Examples include a thiooxy group, a decylthiooxy group, a dodecylthiooxy group, an octadecylthiooxy group, and a benzylthiooxy group.
　置換基を有してもよいアリールチオオキシ基としては、炭素数６～３０のアリールチオオキシ基が好ましく、例えば、フェニルチオオキシ基、１－ナフチルチオオキシ基、２－ナフチルチオオキシ基、２－クロロフェニルチオオキシ基、２－メチルフェニルチオオキシ基、２－メトキシフェニルチオオキシ基、２－ブトキシフェニルチオオキシ基、３－クロロフェニルチオオキシ基、３－トリフルオロメチルフェニルチオオキシ基、３－シアノフェニルチオオキシ基、３－ニトロフェニルチオオキシ基、４－フルオロフェニルチオオキシ基、４－シアノフェニルチオオキシ基、４－メトキシフェニルチオオキシ基、４－ジメチルアミノフェニルチオオキシ基、４－メチルスルファニルフェニルチオオキシ基、４－フェニルスルファニルフェニルチオオキシ基等がある。 The arylthiooxy group which may have a substituent is preferably an arylthiooxy group having 6 to 30 carbon atoms, such as a phenylthiooxy group, a 1-naphthylthiooxy group, a 2-naphthylthiooxy group, 2 -Chlorophenylthiooxy group, 2-methylphenylthiooxy group, 2-methoxyphenylthiooxy group, 2-butoxyphenylthiooxy group, 3-chlorophenylthiooxy group, 3-trifluoromethylphenylthiooxy group, 3-cyano Phenylthiooxy group, 3-nitrophenylthiooxy group, 4-fluorophenylthiooxy group, 4-cyanophenylthiooxy group, 4-methoxyphenylthiooxy group, 4-dimethylaminophenylthiooxy group, 4-methylsulfanyl Phenylthiooxy group, 4-phenylsulfanylphenol There is Ruchiookishi group, and the like.
　ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子等がある。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
　置換基を有してもよいハロゲン化アルキル基としては、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、ジクロロメチル基、トリクロロメチル基、モノブロモメチル基、ジブロモメチル基、トリブロモメチル基等が挙げられる。 Examples of the halogenated alkyl group which may have a substituent include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group, and a tribromomethyl group. Etc.
　Ｎ上に置換基を有してもよいアミド基としては、Ｎ，Ｎ－ジメチルアミド基、Ｎ，Ｎ－ジエチルアミド基等が挙げられる。 Examples of the amide group which may have a substituent on N include N, N-dimethylamide group and N, N-diethylamide group.
　これらの中でも、一般式（Ｂ）中、Ｘ２２としては、溶剤溶解性と長波長領域の吸収効率向上の点から、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオオキシ基、置換基を有してもよいアリールチオオキシ基、置換基を有してもよいハロゲン化アルキル基、置換基を有してもよいアミノ基、又はＮ上に置換基を有してもよいアミド基が好ましく、中でも置換基を有してもよいアルキル基がより好ましい。 Among these, in the general formula (B), X 22 may have an alkyl group which may have a substituent or a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. Aryl group, alkenyl group optionally having substituent, alkynyl group optionally having substituent, alkoxy group optionally having substituent, aryloxy group optionally having substituent, substituent An alkylthiooxy group which may have a substituent, an arylthiooxy group which may have a substituent, a halogenated alkyl group which may have a substituent, an amino group which may have a substituent, or N An amide group which may have a substituent is preferable, and an alkyl group which may have a substituent is more preferable.
　また、一般式（Ｂ）におけるｎは０～５の整数を表すが、合成の容易さの観点で０～３の整数が好ましく、０～２の整数がより好ましい。
　一般式（Ｂ）において、Ｘ２２が複数存在する場合、複数のＸ２２は同じであっても、
異なっていてもよい。 Further, n in the general formula (B) represents an integer of 0 to 5, and is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, from the viewpoint of ease of synthesis.
In Formula (B), if X 22 there are a plurality, the plurality of X 22 may be the same,
May be different.
　上記した一般式（Ｂ）で表されるオキシム光重合開始剤の具体例を以下に示す。 Specific examples of the oxime photopolymerization initiator represented by the general formula (B) are shown below.
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
　本発明に用いる一般式（Ｂ）で表される化合物は、２５０ｎｍ～５００ｎｍの波長領域に吸収波長を有するものである。より好ましくは、３００ｎｍ～３８０ｎｍの波長領域に吸収波長を有するものを挙げることができる。特に、３０８ｎｍ及び３５５ｎｍの吸光度が高いものが好ましい。 The compound represented by the general formula (B) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferable examples include those having an absorption wavelength in the wavelength region of 300 nm to 380 nm. In particular, those having high absorbance at 308 nm and 355 nm are preferable.
　有機ハロゲン化化合物の例としては、具体的には、若林等、「Ｂｕｌｌ　Ｃｈｅｍ．Ｓｏｃ．Ｊａｐａｎ」４２、２９２４（１９６９）、米国特許第３，９０５，８１５号明細書、特公昭４６－４６０５号公報、特開昭４８－３６２８１号公報、特開昭５５－３２０７０号公報、特開昭６０－２３９７３６号公報、特開昭６１－１６９８３５号公報、特開昭６１－１６９８３７号公報、特開昭６２－５８２４１号公報、特開昭６２－２１２４０１号公報、特開昭６３－７０２４３号公報、特開昭６３－２９８３３９号公報、Ｍ．Ｐ．Ｈｕｔｔ“Ｊｏｕｒｎａｌ　ｏｆ　Ｈｅｔｅｒｏｃｙｃｌｉｃ　Ｃｈｅｍｉｓｔｒｙ”１（Ｎｏ３），（１９７０）等に記載の化合物が挙げられ、特に、トリハロメチル基が置換したオキサゾール化合物、ｓ－トリアジン化合物が挙げられる。 Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No. 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.
　ヘキサアリールビイミダゾール化合物の例としては、例えば、特公平６－２９２８５号公報、米国特許第３，４７９，１８５号、同第４，３１１，７８３号、同第４，６２２，２８６号等の各明細書に記載の種々の化合物、具体的には、２，２’－ビス（ｏ－クロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（ｏ－ブロモフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（ｏ，ｐ－ジクロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（ｏ－クロロフェニル）－４，４’，５，５’－テトラ（ｍ－メトキシフェニル）ビイミダゾール、２，２’－ビス（ｏ，ｏ’－ジクロロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（ｏ－ニトロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（ｏ－メチルフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール、２，２’－ビス（ｏ－トリフルオロフェニル）－４，４’，５，５’－テトラフェニルビイミダゾール等が挙げられる。 Examples of hexaarylbiimidazole compounds include, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Various compounds described in the specification, specifically 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o- Bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5'-Tetrapheny Biimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 , 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.
　光重合開始剤は、１種又は２種以上を組み合わせて用いることができる。２種以上用いる場合には、一般式（Ａ）で表される化合物を複数種使用してもよいし、一般式（Ｂ）で表される化合物を複数種使用してもよい。また、一般式（Ａ）及び（Ｂ）で表される化合物からそれぞれ少なくとも１種を用いてもよい。また、一般式（Ａ）及び（Ｂ）で表される化合物をそれぞれ少なくとも１種と一般式（Ａ）及び（Ｂ）で表される化合物以外のオキシム化合物あるいはオキシム化合物以外の光重合開始剤を用いてもよい。また、増感剤を併用してもよい。 The photopolymerization initiator can be used alone or in combination of two or more. When using 2 or more types, multiple types of compounds represented by general formula (A) may be used, and multiple types of compounds represented by general formula (B) may be used. Moreover, you may use at least 1 sort (s) from the compound represented by general formula (A) and (B), respectively. Further, at least one compound represented by the general formulas (A) and (B) and an oxime compound other than the compounds represented by the general formulas (A) and (B) or a photopolymerization initiator other than the oxime compound are used. It may be used. Moreover, you may use a sensitizer together.
　光重合開始剤の総含有量は、着色硬化性組成物中の全固形分に対して、０．１質量％～２０質量％であることが好ましく、０．５質量％～１０質量％であることがより好ましく、１質量％～５質量％が最も好ましい。この範囲内であると、露光時の感度が高く、また色特性も良好である。 The total content of the photopolymerization initiator is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to 10% by mass with respect to the total solid content in the colored curable composition. More preferably, 1% by mass to 5% by mass is most preferable. Within this range, the sensitivity during exposure is high and the color characteristics are also good.
＜（Ｅ）バインダー樹脂＞
　本発明の着色硬化性組成物には、被膜形成性向上のためにバインダー樹脂を用いてもよい。バインダー樹脂としては、パターン形成性の観点から、アルカリ可溶性のバインダーを用いることが好ましい。
（アルカリ可溶性バインダー）
　アルカリ可溶性バインダーは、アルカリ可溶性を有すること以外は、特に限定はなく、好ましくは、耐熱性、現像性、入手性等の観点から選択することができる。 <(E) Binder resin>
In the colored curable composition of the present invention, a binder resin may be used for improving the film-forming property. As the binder resin, an alkali-soluble binder is preferably used from the viewpoint of pattern formation.
(Alkali-soluble binder)
The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
　アルカリ可溶性バインダーとしては、線状有機高分子重合体であり、且つ、有機溶剤に可溶で、弱アルカリ水溶液で現像できるものが好ましい。このような線状有機高分子重合体としては、側鎖にカルボン酸を有するポリマー、例えば、特開昭５９－４４６１５号、特公昭５４－３４３２７号、特公昭５８－１２５７７号、特公昭５４－２５９５７号、特開昭５９－５３８３６号、特開昭５９－７１０４８号の各公報に記載されているような、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体等が挙げられ、同様に側鎖にカルボン酸を有する酸性セルロース誘導体が有用である。 The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.
　上述したものの他、アルカリ可溶性バインダーとしては、水酸基を有するポリマーに酸無水物を付加させたもの等や、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、ポリ（２－ヒドロキシエチル（メタ）アクリレート）、ポリビニルピロリドンやポリエチレンオキサイド、ポリビニルアルコール、等も有用である。また、線状有機高分子重合体は、親水性を有するモノマーを共重合したものであってもよい。この例としては、アルコキシアルキル（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、グリセロール（メタ）アクリレート、（メタ）アクリルアミド、Ｎ－メチロールアクリルアミド、２級若しくは３級のアルキルアクリルアミド、ジアルキルアミノアルキル（メタ）アクリレート、モルホリン（メタ）アクリレート、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム、ビニルイミダゾール、ビニルトリアゾール、メチル（メタ）アクリレート、エチル（メタ）アクリレート、分岐若しくは直鎖のプロピル（メタ）アクリレート、分岐若しくは直鎖のブチル（メタ）アクリレート、又は、フェノキシヒドロキシプロピル（メタ）アクリレート、等が挙げられる。その他、親水性を有するモノマーとしては、テトラヒドロフルフリル基、燐酸基、燐酸エステル基、４級アンモニウム塩基、エチレンオキシ鎖、プロピレンオキシ鎖、スルホン酸基及びその塩由来の基、モルホリノエチル基等を含んでなるモノマー等も有用である。 In addition to those described above, alkali-soluble binders include those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth) Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.
　また、アルカリ可溶性バインダーは、架橋効率を向上させるために、重合性基を側鎖に有してもよく、例えば、アリル基、（メタ）アクリル基、アリルオキシアルキル基等を側鎖に含有するポリマー等も有用である。上述の重合性基を含有するポリマーの例としては、ダイヤナ－ルＮＲシリーズ（三菱レイヨン株式会社製）、Ｐｈｏｔｏｍｅｒ６１７３（ＣＯＯＨ含有　ｐｏｌｙｕｒｅｔｈａｎｅ　ａｃｒｙｌｉｃ　ｏｌｉｇｏｍｅｒ．Ｄｉａｍｏｎｄ　Ｓｈａｍｒｏｃｋ　Ｃｏ．Ｌｔｄ．，製）、ビスコートＲ－２６４、ＫＳレジスト１０６（いずれも大阪有機化学工業株式会社製）、サイクロマーＰシリーズ、プラクセル　ＣＦ２００シリーズ（いずれもダイセル化学工業株式会社製）、Ｅｂｅｃｒｙｌ３８００（ダイセルユーシービー株式会社製）などが挙げられる。また、硬化皮膜の強度を上げるためにアルコール可溶性ナイロンや２，２－ビス－（４－ヒドロキシフェニル）－プロパンとエピクロルヒドリンとのポリエーテル等も有用である。 The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the above-described polymer containing a polymerizable group include a dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., biscort R-264, Examples thereof include KS resist 106 (all manufactured by Osaka Organic Chemical Industries, Ltd.), Cyclomer P series, Plaxel, CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Corporation), and the like. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
　これら各種アルカリ可溶性バインダーの中でも、耐熱性の観点からは、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、アクリル系樹脂、アクリルアミド系樹脂、アクリル／アクリルアミド共重合体樹脂が好ましく、現像性制御の観点からは、アクリル系樹脂、アクリルアミド系樹脂、アクリル／アクリルアミド共重合体樹脂が好ましい。 Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.
　前記アクリル系樹脂としては、ベンジル（メタ）アクリレート、（メタ）アクリル酸、ヒドロキシエチル（メタ）アクリレート、（メタ）アクリルアミド等から選ばれるモノマーからなる共重合体や、前記のＰｈｏｔｏｍｅｒ６１７３、ＫＳレジスト－１０６、サイクロマーＰシリーズ等が好ましい。 Examples of the acrylic resin include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, the Photomer 6173, and the KS resist-106. Cyclomer P series and the like are preferable.
　アルカリ可溶性バインダーは、現像性、液粘度等の観点から、重量平均分子量（ＧＰＣ法で測定されたポリスチレン換算値）が１０００～２×１０５の重合体が好ましく、２０００～１×１０５の重合体がより好ましく、５０００～５×１０４の重合体が特に好ましい。
　アルカリ可溶性バインダーは、単独で用いることも２種以上を併用することもできる。 The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 5 from the viewpoint of developability, liquid viscosity, and the like, and a weight of 2000 to 1 × 10 5 is preferable. Polymers are more preferred, and polymers of 5000 to 5 × 10 4 are particularly preferred.
The alkali-soluble binder can be used alone or in combination of two or more.
＜その他の成分＞
　本発明の着色硬化性組成物には、さらに必要に応じて、本発明の効果を損なわない限りにおいて、公知の添加剤、例えば、多官能チオール化合物、連鎖移動剤、重合禁止剤、有機溶剤、界面活性剤、密着改良剤、架橋剤、現像促進剤、およびその他の添加剤を含有することができる。
　以下に、これらの成分を説明する。 <Other ingredients>
In the colored curable composition of the present invention, if necessary, as long as the effects of the present invention are not impaired, known additives such as polyfunctional thiol compounds, chain transfer agents, polymerization inhibitors, organic solvents, A surfactant, an adhesion improving agent, a crosslinking agent, a development accelerator, and other additives can be contained.
Below, these components are demonstrated.
（多官能チオール化合物）
　本発明の着色硬化性組成物は、多官能チオール化合物を含有してもよい。
　本発明の着色硬化性組成物は、多官能チオール化合物を含むことで、感度を高め、染料等の色材起因のイオン溶出等が抑制され、液晶表示装置のカラーフィルタ作製に本発明の着色硬化性組成物を用いたとき、クロストーク等の画質の劣化を防止することができ、鮮明な高画質の表示が可能となる。 (Polyfunctional thiol compound)
The colored curable composition of the present invention may contain a polyfunctional thiol compound.
The colored curable composition of the present invention includes a polyfunctional thiol compound to increase sensitivity, suppress ion elution caused by a coloring material such as a dye, and the like. When the composition is used, it is possible to prevent deterioration of image quality such as crosstalk and display a clear image with high image quality.
　本発明において「多官能チオール化合物」とは、チオール基を分子内に２個以上有する化合物を意味する。上記多官能チオール化合物としては、分子量１００以上の低分子化合物が好ましく、具体的には、分子量１００～１５００であることが好ましく、１５０～１０００が更に好ましい。上記多官能チオール化合物はチオール基を分子内に２～１０個有することが好ましく、２～６個有することがさらに好ましく、2～4個有することが特に好ましい。また、これら化合物は上記ラジカル重合性モノマーが重合する際に補助的に用いられる系とされることが好ましい。具体的には、多官能チオール化合物の添加量を組成物の全固形分に対して１～２０質量％であるようにするか、若しくは、同時に含有する上記ラジカル重合性モノマーの添加量よりも少ない添加量とすることが好ましい。 In the present invention, “polyfunctional thiol compound” means a compound having two or more thiol groups in the molecule. The polyfunctional thiol compound is preferably a low molecular compound having a molecular weight of 100 or more, specifically, preferably having a molecular weight of 100 to 1500, and more preferably 150 to 1000. The polyfunctional thiol compound preferably has 2 to 10 thiol groups in the molecule, more preferably 2 to 6, and particularly preferably 2 to 4. In addition, these compounds are preferably used as a system that is used auxiliary when the radical polymerizable monomer is polymerized. Specifically, the addition amount of the polyfunctional thiol compound is 1 to 20% by mass with respect to the total solid content of the composition, or is less than the addition amount of the radical polymerizable monomer contained at the same time. It is preferable to make it an addition amount.
　本発明に用いうる多官能チオール化合物の具体例としては、例えば、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、テトラエチレングリコールビス（３－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（チオグリコレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ブタンジオールビス（３－メルカプトブチレート）、１,４-ビス（３－メルカプトブチルオキシ）ブタン、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５-トリアジン－２，４，６(１Ｈ，３Ｈ，５Ｈ)－トリオン、等が好適な多官能チオール化合物として挙げられる。特に好ましいのは2級SHを含む化合物であり、また、液安定性の観点からトリアジン骨格を有することが好ましい。具体的にはカレンズＭＴシリーズ（昭和電工(株)製）等を挙げることができる。 Specific examples of the polyfunctional thiol compound that can be used in the present invention include, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercapto). Propionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trifunctional, etc. It mentioned as compound. Particularly preferred is a compound containing secondary SH, and it is preferred to have a triazine skeleton from the viewpoint of liquid stability. Specific examples include Karenz MT series (manufactured by Showa Denko KK).
　多官能チオール化合物の含有量は、着色硬化性組成物中の全固形分に対して０．０１質量％～２０質量％であることが好ましく、０．１質量％～１０質量％であることが更に好ましい。多官能チオール化合物の含有量がこの範囲内にあると、着色硬化性組成物の感度が良好で、保存安定性が良好で、得られたカラーフィルタにおける画素の密着性が良好でパターン欠陥がなく、液晶表示装置に用いた場合に電気特性が良好な着色硬化性組成物を提供することができる。 The content of the polyfunctional thiol compound is preferably 0.01% by mass to 20% by mass, and preferably 0.1% by mass to 10% by mass with respect to the total solid content in the colored curable composition. Further preferred. When the content of the polyfunctional thiol compound is in this range, the sensitivity of the colored curable composition is good, the storage stability is good, the pixel adhesion in the obtained color filter is good, and there is no pattern defect. When used in a liquid crystal display device, a colored curable composition having good electrical characteristics can be provided.
（増感剤）
　本発明の着色硬化性組成物には増感剤を加えることもできる。本発明に用いる典型的な増感剤としては、クリベロ〔Ｊ．Ｖ．Ｃｒｉｖｅｌｌｏ，Ａｄｖ．ｉｎ　Ｐｏｌｙｍｅｒ　Ｓｃｉ，６２，１（１９８４）〕に開示しているものが挙げられ、具体的には、ピレン、ペリレン、アクリジン、チオキサントン、２－クロロチオキサントン、ベンゾフラビン、Ｎ－ビニルカルバゾール、９，１０－ジブトキシアントラセン、アントラキノン、ベンゾフェノン、クマリン、ケトクマリン、フェナントレン、カンファキノン、フェノチアジン誘導体などを挙げることができる。増感剤は、光重合開始剤に対し、５０～２００質量％の割合で添加することが好ましい。 (Sensitizer)
A sensitizer can also be added to the colored curable composition of the present invention. Typical sensitizers used in the present invention include Krivello [J. V. Crivello, Adv. in Polymer Sci, 62, 1 (1984)]. Specific examples include pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10. -Dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like. The sensitizer is preferably added in a proportion of 50 to 200% by mass with respect to the photopolymerization initiator.
（連鎖移動剤）
　本発明の着色硬化性組成物には連鎖移動剤を加えることもできる。本発明に用いる連鎖移動剤としては、例えば、Ｎ，Ｎ－ジメチルアミノ安息香酸エチルエステルなどのＮ，Ｎ－ジアルキルアミノ安息香酸アルキルエステル、２－メルカプトベンゾチアゾール、２－メルカプトベンゾオキサゾール、２－メルカプトベンゾイミダゾール、Ｎ－フェニルメルカプトベンゾイミダゾール、などの複素環を有するメルカプト化合物などが挙げられる。
　連鎖移動剤は、１種単独で用いてもよく、２種以上を併用してもよい。
　連鎖移動剤の添加量は、本発明の着色硬化性組成物の全固形分に対して、０．０１質量％～１５質量％の範囲であることが、感度ばらつきを低減するという観点から好ましく、０．１質量％～１０質量％がより好ましく、０．５質量％～５質量％が特に好ましい。 (Chain transfer agent)
A chain transfer agent can also be added to the colored curable composition of the present invention. Examples of the chain transfer agent used in the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercapto. Examples include mercapto compounds having a heterocyclic ring such as benzimidazole and N-phenylmercaptobenzimidazole.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
The addition amount of the chain transfer agent is preferably in the range of 0.01% by mass to 15% by mass with respect to the total solid content of the colored curable composition of the present invention, from the viewpoint of reducing sensitivity variation, 0.1% by mass to 10% by mass is more preferable, and 0.5% by mass to 5% by mass is particularly preferable.
（重合禁止剤）
　本発明の着色硬化性組成物は、重合禁止剤を含有してもよい。
　重合禁止剤とは、光や熱により着色硬化性組成物中に発生したラジカル等の重合開始種に対して水素供与（又は、水素授与）、エネルギー供与（又は、エネルギー授与）、電子供与（又は、電子授与）などを実施し、重合開始種を失活させ、重合が意図せず開始されることを抑制する役割をはたす物質である。特開２００７－３３４３２２号公報の段落〔０１５４〕～〔０１７３〕に記載された重合禁止剤などを用いることができる。
　これらの中でも、重合禁止剤としてはｐ－メトキシフェノールが好ましく挙げられる。
　本発明の着色硬化性組成物における重合禁止剤の含有量は、重合性化合物の全質量に対して、０．０００１質量％～５質量％が好ましく、０．００１質量％～５質量％がより好ましく、０．００１質量％～１質量％が特に好ましい。 (Polymerization inhibitor)
The colored curable composition of the present invention may contain a polymerization inhibitor.
The polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to polymerization initiation species such as radicals generated in the colored curable composition by light or heat. , Electron donation) and the like to deactivate the polymerization initiating species and to prevent unintentional initiation of polymerization. The polymerization inhibitors described in paragraphs [0154] to [0173] of JP-A-2007-334322 can be used.
Among these, p-methoxyphenol is preferably used as the polymerization inhibitor.
The content of the polymerization inhibitor in the colored curable composition of the present invention is preferably 0.0001% by mass to 5% by mass and more preferably 0.001% by mass to 5% by mass with respect to the total mass of the polymerizable compound. 0.001% by mass to 1% by mass is particularly preferable.
（有機溶剤）
　本発明の着色硬化性組成物は、有機溶剤を含有することができる。
　有機溶剤は、並存する各成分の溶解性や着色硬化性組成物としたときの塗布性を満足できるものであれば、基本的には特に制限はなく、特に、固形分の溶解性、塗布性、安全性を考慮して選ばれることが好ましい。 (Organic solvent)
The colored curable composition of the present invention can contain an organic solvent.
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each side-by-side component and the coating property when a colored curable composition is used, and in particular, the solubility and coating property of the solid content. In view of safety, it is preferably selected.
　有機溶剤としては、エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、オキシ酢酸アルキルエステル類（例：オキシ酢酸メチル、オキシ酢酸エチル、オキシ酢酸ブチル（具体的には、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等が挙げられる。））、３－オキシプロピオン酸アルキルエステル類、２－オキシプロピオン酸アルキルエステル類、２－オキシ－２－メチルプロピオン酸メチル、２－オキシ－２－メチルプロピオン酸エチル、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等が挙げられる。 Examples of organic solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and ethyl lactate. Oxyacetic acid alkyl esters (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate). )), 3-oxypropionic acid alkyl esters, 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate , Propyl pyruvate, Seto methyl acetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.
　また、エーテル類としては、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールエチルメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等が挙げられる。
　ケトン類としては、例えば、メチルエチルケトン、シクロヘキサノン、２－ヘプタノン、３－ヘプタノン等が挙げられる。
　芳香族炭化水素類としては、例えば、トルエン、キシレン等が好適に挙げられる。 Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl methyl ether. Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons include toluene and xylene.
　これらの有機溶剤は、前述の各成分の溶解性、及びアルカリ可溶性バインダーを含む場合はその溶解性、塗布面状の改良などの観点から、２種以上を混合することも好ましい。この場合、特に好ましくは、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテル、及びプロピレングリコールメチルエーテルアセテートから選択される２種以上で構成される混合溶液である。 These organic solvents are also preferably mixed in a combination of two or more from the viewpoints of the solubility of each of the aforementioned components and, when an alkali-soluble binder is included, the solubility of the components and the improvement of the coated surface. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, It is a mixed solution composed of two or more selected from cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
　有機溶剤の着色硬化性組成物中における含有量としては、着色硬化性組成物中の全固形分濃度が１０質量％～８０質量％になる量が好ましく、１５質量％～６０質量％になる量がより好ましい。 The content of the organic solvent in the colored curable composition is preferably such that the total solid concentration in the colored curable composition is 10% by mass to 80% by mass, and the amount is 15% by mass to 60% by mass. Is more preferable.
（界面活性剤）
　本発明の着色硬化性組成物は、界面活性剤を含有してもよい。
　界面活性剤としては、アニオン系、カチオン系、ノニオン系、又は、両性のいずれでも使用することができるが、好ましい界面活性剤はノニオン系界面活性剤である。具体的には、特開２００９－０９８６１６号公報の段落００５８に記載のノニオン系界面活性剤が挙げられ、中でもフッ素系界面活性剤が好ましい。
　本発明に用いることができるこの他の界面活性剤としては、例えば、市販品である、メガファックＦ１４２Ｄ、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１８３、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０、同Ｆ７８１、同Ｆ７８１－Ｆ、同Ｒ３０、同Ｒ０８、同Ｆ－４７２ＳＦ、同ＢＬ２０、同Ｒ－６１、同Ｒ－９０（ＤＩＣ（株）製）、フロラードＦＣ－１３５、同ＦＣ－１７０Ｃ、同ＦＣ－４３０、同ＦＣ－４３１、Ｎｏｖｅｃ　ＦＣ－４４３０（住友スリーエム（株）製）、アサヒガードＡＧ７１０５，７０００，９５０，７６００、サーフロンＳ－１１２、同Ｓ－１１３、同Ｓ－１３１、同Ｓ－１４１、同Ｓ－１４５、同Ｓ－３８２、同ＳＣ－１０１、同ＳＣ－１０２、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ－１０６（旭硝子（株）製）、エフトップＥＦ３５１、同３５２、同８０１、同８０２（三菱マテリアル電子化成（株）製）、フタージェント２５０（ネオス（株）製）などが挙げられる。
　また、界面活性剤として、下記式（Ｗ）で表される構成単位Ａ及び構成単位Ｂを含み、テトラヒドロフランを溶媒としてゲルパーミエーションクロマトグラフィで測定されるポリスチレン換算の重量平均分子量（Ｍｗ）が１，０００以上１０，０００以下である共重合体を好ましい例として挙げることができる。 (Surfactant)
The colored curable composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Specific examples include nonionic surfactants described in paragraph 0058 of JP-A-2009-098616, and among them, fluorine surfactants are preferable.
Other surfactants that can be used in the present invention include, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, and F554. F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC -170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105,7000,950,7600, Surflon S-112, S-113, S-131 S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Footgent 250 (manufactured by Neos Co., Ltd.), etc. Is mentioned.
Further, as the surfactant, the structural unit A and the structural unit B represented by the following formula (W) are included, and the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent is 1, A copolymer having a molecular weight of 000 or more and 10,000 or less can be given as a preferred example.
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
　（式（Ｗ）中、Ｒ1及びＲ3はそれぞれ独立に、水素原子又はメチル基を表し、Ｒ2は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ4は水素原子又は炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐ及びｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｎは１以上１０以下の整数を表す。） (In the formula (W), R 1 and R 3 each independently represent a hydrogen atom or a methyl group, R 2 represents a linear alkylene group having 1 to 4 carbon atoms, and R 4 represents a hydrogen atom or carbon number. 1 represents an alkyl group having 4 or less, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p represents a numerical value of 10% to 80% by mass. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and n represents an integer of 1 to 10.
　前記Ｌは、下記式（Ｗ－２）で表される分岐アルキレン基であることが好ましい。式（Ｗ－２）におけるＲ５は、炭素数１以上４以下のアルキル基を表し、相溶性と被塗布面に対する濡れ性の点で、炭素数１以上３以下のアルキル基が好ましく、炭素数２又は３のアルキル基がより好ましい。
　式（Ｗ）におけるｐとｑとの和（ｐ＋ｑ）は、ｐ＋ｑ＝１００、すなわち、１００質量％であることが好ましい。
　前記共重合体の重量平均分子量（Ｍｗ）は、１，５００以上５，０００以下がより好ましい。 L is preferably a branched alkylene group represented by the following formula (W-2). R 5 in Formula (W-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. Two or three alkyl groups are more preferred.
The sum (p + q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.
The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
　これら界面活性剤は、１種単独で又は２種以上を使用することができる。
　本発明の着色硬化性組成物における界面活性剤の添加量は、着色硬化性組成物の全固形分中０．０１～２．０質量％が好ましく、０．０２～１．０質量％が特に好ましい。この範囲であると、塗布性及び硬化膜の均一性が良好となる。 These surfactants can be used alone or in combination of two or more.
The addition amount of the surfactant in the colored curable composition of the present invention is preferably 0.01 to 2.0% by mass, particularly 0.02 to 1.0% by mass, based on the total solid content of the colored curable composition. preferable. Within this range, the coatability and the uniformity of the cured film are good.
（密着改良剤）
　本発明の着色硬化性組成物は、密着改良剤を含有してもよい。
　密着改良剤は、支持体となる無機物、例えば、ガラス、シリコン、酸化シリコン、窒化シリコン等のシリコン化合物、金、銅、アルミニウム等と着色硬化性組成物層の硬化膜との密着性を向上させる化合物である。具体的には、シランカップリング剤等が挙げられる。密着改良剤としてのシランカップリング剤は、界面の改質を目的とするものであり、特に限定することなく、公知のものを使用することができる。
　シランカップリング剤としては、特開２００９－９８６１６号公報の段落００４８に記載のシランカップリング剤が好ましく、中でもγ－グリシドキシプロピルトリアルコキシシランやγ－メタクリロキシプロピルトリアルコキシシランがより好ましい。これらは１種単独又は２種以上を併用できる。
　本発明の着色硬化性組成物における密着改良剤の含有量は、着色硬化性組成物の全固形分量に対して、０．１質量％～２０質量％が好ましく、０．２質量％～５質量％がより好ましい。 (Adhesion improver)
The colored curable composition of the present invention may contain an adhesion improving agent.
The adhesion improver improves the adhesion between the inorganic material serving as the support, for example, a silicon compound such as glass, silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, and the cured film of the colored curable composition layer. A compound. Specific examples include silane coupling agents. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable. These can be used alone or in combination of two or more.
The content of the adhesion improving agent in the colored curable composition of the present invention is preferably 0.1% by mass to 20% by mass, and preferably 0.2% by mass to 5% by mass with respect to the total solid content of the colored curable composition. % Is more preferable.
（架橋剤）
　本発明の着色硬化性組成物に補足的に架橋剤を用い、着色硬化性組成物を硬化させてなる着色層の硬度をより高めることもできる。
　架橋剤としては、架橋反応により膜硬化を行なえるものであれば、特に限定はなく、例えば、（ａ）エポキシ樹脂、（ｂ）メチロール基、アルコキシメチル基、及びアシロキシメチル基から選ばれる少なくとも１つの置換基で置換された、メラミン化合物、グアナミン化合物、グリコールウリル化合物又はウレア化合物、（ｃ）メチロール基、アルコキシメチル基、及びアシロキシメチル基から選ばれる少なくとも１つの置換基で置換された、フェノール化合物、ナフトール化合物又はヒドロキシアントラセン化合物、が挙げられる。
　中でも、エポキシ樹脂は硬化剤としてレジスト系中に存在する酸（樹脂、モノマー等）、ＳＨ化合物との反応により、より強固な膜を形成可能であるため、特に好ましい。低粘度、耐熱性、安定性の観点では脂環式エポキシが好ましい。
　架橋剤の具体例などの詳細については、特開２００４－２９５１１６号公報の段落〔０１３４〕～〔０１４７〕の記載を参照することができる。 (Crosslinking agent)
A supplementary crosslinking agent may be used in the colored curable composition of the present invention to further increase the hardness of the colored layer obtained by curing the colored curable composition.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, substituted with one substituent, Phenol compounds, naphthol compounds or hydroxyanthracene compounds are mentioned.
Among these, an epoxy resin is particularly preferable because a stronger film can be formed by a reaction with an acid (resin, monomer, etc.) present in the resist system as a curing agent and an SH compound. From the viewpoint of low viscosity, heat resistance, and stability, alicyclic epoxy is preferable.
For details such as specific examples of the crosslinking agent, the description in paragraphs [0134] to [0147] of JP-A No. 2004-295116 can be referred to.
（現像促進剤）
　着色硬化性組成物層を露光した場合の非露光領域のアルカリ溶解性を促進し、着色硬化性組成物の現像性の更なる向上を図る場合には、現像促進剤を添加することもできる。現像促進剤は好ましくは分子量１０００以下の低分子量有機カルボン酸化合物、分子量１０００以下の低分子量フェノール化合物である。
　具体的には、例えば、ギ酸、酢酸、プロピオン酸、酪酸、吉草酸、ピバル酸、カプロン酸、ジエチル酢酸、エナント酸、カプリル酸等の脂肪族モノカルボン酸；シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ブラシル酸、メチルマロン酸、エチルマロン酸、ジメチルマロン酸、メチルコハク酸、テトラメチルコハク酸、シトラコン酸等の脂肪族ジカルボン酸；トリカルバリル酸、アコニット酸、カンホロン酸等の脂肪族トリカルボン酸；安息香酸、トルイル酸、クミン酸、ヘメリト酸、メシチレン酸等の芳香族モノカルボン酸；フタル酸、イソフタル酸、テレフタル酸、トリメリト酸、トリメシン酸、メロファン酸、ピロメリト酸等の芳香族ポリカルボン酸；フェニル酢酸、ヒドロアトロパ酸、ヒドロケイ皮酸、マンデル酸、フェニルコハク酸、アトロパ酸、ケイ皮酸、ケイ皮酸メチル、ケイ皮酸ベンジル、シンナミリデン酢酸、クマル酸、ウンベル酸等が挙げられる。 (Development accelerator)
A development accelerator can also be added in order to promote the alkali solubility of the non-exposed region when the colored curable composition layer is exposed and to further improve the developability of the colored curable composition. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid.
（その他の添加物）
　本発明の着色硬化性組成物には、さらに必要に応じて、各種添加物、例えば、充填剤、上記以外の高分子化合物、紫外線吸収剤、酸化防止剤等を配合することができる。これらの添加物としては、特開２００４－２９５１１６号公報の段落〔０１５５〕～〔０１５６〕に記載のものを挙げることができる。
　本発明の着色硬化性組成物においては、特開２００４－２９５１１６号公報の段落〔００７８〕に記載の光安定剤、同公報の段落〔００８１〕に記載の熱重合防止剤を含有することができる。 (Other additives)
If necessary, the colored curable composition of the present invention may further contain various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, antioxidants and the like. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A No. 2004-295116.
The colored curable composition of the present invention may contain a light stabilizer described in paragraph [0078] of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph [0081] of the same publication. .
（着色硬化性組成物の調製方法）
　本発明の着色硬化性組成物は、前述の各成分と必要に応じて任意成分とを混合することで調製される。
　なお、着色硬化性組成物の調製に際しては、着色硬化性組成物を構成する各成分を一括配合してもよいし、各成分を溶剤に溶解・分散した後に逐次配合してもよい。また、配合する際の投入順序や作業条件は特に制約を受けない。例えば、全成分を同時に溶剤に溶解・分散して組成物を調製してもよいし、必要に応じては、各成分を適宜２つ以上の溶液・分散液としておいて、使用時（塗布時）にこれらを混合して着色硬化性組成物として調製してもよい。
　上記のようにして調製された着色硬化性組成物は、好ましくは、孔径０．０１μｍ～３．０μｍ程度のフィルタなどを用いて濾別した後、使用に供することができる。 (Method for preparing colored curable composition)
The colored curable composition of the present invention is prepared by mixing the above-described components and optional components as necessary.
In preparing the colored curable composition, the components constituting the colored curable composition may be combined at once, or may be sequentially added after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a colored curable composition.
The colored curable composition prepared as described above can be used after being preferably filtered using a filter having a pore size of about 0.01 μm to 3.0 μm.
　本発明の着色硬化性組成物は、輝度及びコントラストに優れた着色硬化膜を形成することができるため、液晶表示装置に用いられるカラーフィルタなどの着色画素形成用として、また、印刷インキ、インクジェットインキ、及び塗料などの作製用途として好適に用いることができる。 Since the colored curable composition of the present invention can form a colored cured film having excellent brightness and contrast, it can be used for forming colored pixels such as color filters used in liquid crystal display devices, as well as printing inks and inkjet inks. And can be suitably used as a production application for paints and the like.
＜＜カラーフィルタ及びその製造方法＞＞
　本発明のカラーフィルタは、基板と、該基板上に本発明の着色硬化性組成物により形成された着色膜からなる着色画素と、を備える。基板上の着色領域は、カラーフィルタの各画素をなす例えば赤（Ｒ）、緑（Ｇ）、青（Ｂ）等の着色層で構成されている。 << Color filter and manufacturing method thereof >>
The color filter of the present invention includes a substrate and a colored pixel composed of a colored film formed on the substrate by the colored curable composition of the present invention. The colored region on the substrate is composed of colored layers such as red (R), green (G), and blue (B) that form each pixel of the color filter.
　本発明のカラーフィルタの製造方法は、既述の着色硬化性組成物を支持体上に付与して着色層（着色硬化性組成物層）を形成する着色層形成工程（Ａ）と、工程（Ａ）にて形成された着色層に対してパターン様の露光をする露光工程（Ｂ）と、前記露光された着色層を現像してパターンを形成する現像工程（Ｃ）と、を含む。
　また、本発明のカラーフィルタの製造方法では、特に、工程（Ｃ）で得られた着色パターンに対して加熱処理を行なうポストベーク（後加熱工程）（Ｄ）を更に設けた態様が好ましい。
　さらに、前記現像工程と前記ポストベーク工程との間に、着色パターンに対して紫外線を照射する工程（後露光）を設けることも可能である。 The method for producing a color filter of the present invention includes a colored layer forming step (A) in which a colored layer (colored curable composition layer) is formed by applying the above-described colored curable composition on a support, and a step ( The exposure process (B) which carries out pattern-like exposure with respect to the colored layer formed in A), and the image development process (C) which develops the said exposed colored layer and forms a pattern are included.
Moreover, in the manufacturing method of the color filter of this invention, the aspect which further provided the post-baking (post-heating process) (D) which heat-processes with respect to the coloring pattern obtained at the process (C) is preferable.
Furthermore, it is also possible to provide a step (post-exposure) for irradiating the colored pattern with ultraviolet rays between the development step and the post-bake step.
　以下、本発明のカラーフィルタの製造方法について、より具体的に説明する。従来主に用いられてきた製造方法に加え、輝度および歩留まり向上の観点から有効とされるＣｏｌｏｒ　Ｆｉｌｔｅｒ　ｏｎ　Ａｒｒａｙ（ＣＯＡ）方式のカラーフィルタ製造方法についても説明する。 Hereinafter, the method for producing the color filter of the present invention will be described more specifically. A color filter on array (COA) type color filter manufacturing method that is effective from the viewpoint of improving luminance and yield will be described in addition to the manufacturing method that has been mainly used conventionally.
（従来型のカラーフィルタ製造方法）
－工程（Ａ）－
　本発明のカラーフィルタの製造方法では、まず、支持体上に、既述の本発明の着色硬化性組成物を回転塗布、スリット塗布、流延塗布、ロール塗布、バー塗布、インクジェット等の塗布方法により付与して着色層を形成し、その後、該着色層を加熱（プリベーク）又は真空乾燥などで乾燥させる。 (Conventional color filter manufacturing method)
-Process (A)-
In the method for producing a color filter of the present invention, first, the above-described colored curable composition of the present invention is applied onto a support by spin coating, slit coating, cast coating, roll coating, bar coating, ink jet, or the like. Is applied to form a colored layer, and then the colored layer is dried by heating (pre-baking) or vacuum drying.
　支持体としては、例えば、液晶表示装置に用いられるソーダガラス、無アルカリガラス、ホウケイ酸ガラス、石英ガラス、シリコン基板、樹脂基板などが挙げられる。
　また、ＣＯＡ方式の液晶表示装置用としては、薄膜トランジスター（ＴＦＴ）方式の液晶表示装置の駆動用基板が用いられる。
　また、これらの支持体上には、必要により、上部の層との密着改良、物質の拡散防止、或いは表面の平坦化のために、下塗り層、層間絶縁膜等を設けてもよい。 Examples of the support include soda glass, alkali-free glass, borosilicate glass, quartz glass, silicon substrate, and resin substrate used in liquid crystal display devices.
For a COA liquid crystal display device, a driving substrate for a thin film transistor (TFT) liquid crystal display device is used.
Further, an undercoat layer, an interlayer insulating film, or the like may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface.
　プリベークの条件としては、ホットプレートやオーブンを用いて、７０℃～１３０℃で、０．５分間～１５分間程度加熱する条件が挙げられる。
　また、着色硬化性組成物により形成される着色層の厚みは、目的に応じて適宜選択される。液晶表示装置用カラーフィルタにおいては、０．２μｍ～５．０μｍの範囲が好ましく、１．０μｍ～４．０μｍの範囲が更に好ましい。また、ＣＯＡ方式の液晶表示装置用カラーフィルタにおいては、画素膜の厚みは０．３μｍ～５．０μｍの範囲が好ましく、０．５μｍ～３．５μｍの範囲が更に好ましい。なお、着色層の厚みは、プリベーク後の膜厚である。 Examples of the pre-baking condition include a condition of heating at 70 to 130 ° C. for about 0.5 to 15 minutes using a hot plate or an oven.
Moreover, the thickness of the colored layer formed with a colored curable composition is suitably selected according to the objective. In the color filter for liquid crystal display devices, the range of 0.2 μm to 5.0 μm is preferable, and the range of 1.0 μm to 4.0 μm is more preferable. In the color filter for a liquid crystal display device of the COA type, the pixel film thickness is preferably in the range of 0.3 μm to 5.0 μm, and more preferably in the range of 0.5 μm to 3.5 μm. In addition, the thickness of a colored layer is a film thickness after prebaking.
－工程（Ｂ）－
　続いて、本発明のカラーフィルタの製造方法では、支持体上に形成された着色層に対して、パターン様の露光が行なわれる。露光に適用し得る光もしくは放射線としては、ｇ線、ｈ線、ｉ線、各種レーザー光が好ましく、特にｉ線が好ましい。照射光にｉ線を用いる場合、５ｍＪ／ｃｍ２～５００ｍＪ／ｃｍ２の露光量で照射することが好ましい。 -Process (B)-
Subsequently, in the method for producing a color filter of the present invention, pattern-like exposure is performed on the colored layer formed on the support. As light or radiation applicable to exposure, g-line, h-line, i-line and various laser beams are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is preferably irradiated at an exposure dose of 5mJ / cm 2 ~ 500mJ / cm 2.
　また、その他の露光光源としては、超高圧、高圧、中圧、低圧の各水銀灯、ケミカルランプ、カーボンアーク灯、キセノン灯、メタルハライド灯、各種レーザー光源、等が使用できる。 Also, as other exposure light sources, ultrahigh pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser light sources, and the like can be used.
～レーザー光源を用いた露光工程～
　レーザー光源を用いた露光方式では照射光は、波長が３００ｎｍ～４１０ｎｍの範囲である波長の範囲の紫外光レーザーが好ましく、さらに好ましくは３００ｎｍ～３６０ｎｍの範囲の波長である。具体的には、特に出力が大きく、比較的安価な固体レーザーのＮｄ：ＹＡＧレーザーの第三高調波（３５５ｎｍ）や、エキシマレーザーのＸｅＣｌ（３０８ｎｍ）、ＸｅＦ（３５３ｎｍ）を好適に用いることができる。パターン露光量としては、生産性の観点から、１ｍＪ／ｃｍ２～１００ｍＪ／ｃｍ２の範囲が好ましく、１ｍＪ／ｃｍ２～５０ｍＪ／ｃｍ２の範囲がより好ましい。 -Exposure process using laser light source-
In the exposure method using a laser light source, the irradiation light is preferably an ultraviolet laser having a wavelength range of 300 nm to 410 nm, and more preferably a wavelength of 300 nm to 360 nm. Specifically, the Nd: YAG laser third harmonic (355 nm), which is a relatively inexpensive solid output, and the excimer laser XeCl (308 nm), XeF (353 nm) can be suitably used. . The pattern exposure, from the viewpoint of productivity, preferably in the range of 1mJ / cm 2 ~ 100mJ / cm 2, the range of 1mJ / cm 2 ~ 50mJ / cm 2 is more preferable.
　露光装置としては、特に制限はないが市販されているものとしては、Ｃａｌｌｉｓｔｏ（ブイテクノロジー株式会社製）やＥＧＩＳ（ブイテクノロジー株式会社製）やＤＦ２２００Ｇ（大日本スクリーン株式会社製）などが使用可能である。また上記以外の装置も好適に用いられる。 There are no particular restrictions on the exposure apparatus, but commercially available devices such as Callisto (buoy technology), EGIS (buoy technology), and DF2200G (Dainippon Screen) can be used. is there. Further, devices other than those described above are also preferably used.
－工程（Ｃ）－
　続いて、露光後の着色層に対して、現像液にて現像が行なわれる。これにより、着色パターンを形成することができる。現像液は、着色層の未硬化部を溶解し、硬化部を溶解しないものであれば、種々の有機溶剤の組み合わせやアルカリ性水溶液を用いることができる。現像液がアルカリ性水溶液である場合、アルカリ濃度が好ましくはｐＨ１０～１３となるように調製するのがよい。前記アルカリ性水溶液としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、硅酸ナトリウム、メタ硅酸ナトリウム、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８-ジアザビシクロ-［５，４，０］-７-ウンデセン等のアルカリ性水溶液が挙げられる。
　ＣＯＡ方式の液晶表示装置に用いるカラーフィルタにおいては、現像液としては、下地の回路などにダメージを起さない観点から、有機アルカリ現像液が特に望ましい。
　現像時間は、３０秒～３００秒が好ましく、更に好ましくは３０秒～１２０秒である。現像温度は、２０℃～４０℃が好ましく、更に好ましくは２０℃～３０℃である。
　現像は、パドル方式、シャワー方式、スプレー方式等で行なうことができる。
　また、アルカリ性水溶液を用いて現像した後は、水で洗浄することが好ましい。 -Process (C)-
Subsequently, the colored layer after exposure is developed with a developer. Thereby, a colored pattern can be formed. As long as the developing solution dissolves the uncured portion of the colored layer and does not dissolve the cured portion, a combination of various organic solvents or an alkaline aqueous solution can be used. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 10-13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Examples include alkaline aqueous solutions such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene.
In a color filter used in a COA type liquid crystal display device, an organic alkaline developer is particularly desirable as the developer from the viewpoint of not causing damage to the underlying circuit.
The development time is preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 120 seconds. The development temperature is preferably 20 ° C. to 40 ° C., more preferably 20 ° C. to 30 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like.
Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water.
　本発明のカラーフィルタの製造方法では、特に、着色硬化性組成物を用いて形成された着色パターン（画素）に対して、紫外線照射による後露光を行なうことも好ましい。 In the method for producing a color filter of the present invention, it is also preferable to perform post-exposure by ultraviolet irradiation on a colored pattern (pixel) formed using a colored curable composition.
－工程（Ｄ）－
　現像後の着色パターンに対して、あるいは上記のような紫外線照射による後露光が行なわれた着色パターンに対して、さらに加熱処理を行なうことが好ましい。形成された着色パターンを加熱処理（いわゆるポストベーク処理）することにより、着色パターンを更に硬化させることができる。この加熱処理は、例えば、ホットプレート、各種ヒーター、オーブンなどにより行なうことができる。
　加熱処理の際の温度としては、１００℃～３００℃であることが好ましく、更に好ましくは、１５０℃～２５０℃である。また、加熱時間は、１０分～１２０分程度が好ましい。 -Process (D)-
It is preferable to further heat-treat the colored pattern after development or the colored pattern subjected to post-exposure by ultraviolet irradiation as described above. By heating the formed color pattern (so-called post-bake process), the color pattern can be further cured. This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
The temperature during the heat treatment is preferably 100 ° C. to 300 ° C., more preferably 150 ° C. to 250 ° C. The heating time is preferably about 10 minutes to 120 minutes.
　このようにして得られた着色パターンは、カラーフィルタにおける画素を構成する。複数の色相の画素を有するカラーフィルタの作製においては、上記の工程（Ａ）、工程（Ｂ）、工程（Ｃ）、および工程（Ｄ）を所望の色数に合わせて繰り返せばよい。
　なお、単色の着色層の形成、露光、現像が終了する毎に（１色毎に）、前記工程（Ｄ）を行なってもよいし、所望の色数の全ての着色層の形成、露光、現像が終了した後に、一括して前記工程（Ｄ）を行なってもよい。 The colored pattern thus obtained constitutes a pixel in the color filter. In manufacturing a color filter having a plurality of hue pixels, the above-described step (A), step (B), step (C), and step (D) may be repeated according to the desired number of colors.
In addition, whenever formation, exposure, and development of a single color layer are completed (for each color), the step (D) may be performed, or formation, exposure, and formation of all colored layers having a desired number of colors. After the development is completed, the step (D) may be performed collectively.
　以下、本発明の着色硬化性組成物を用いて構成されるカラーフィルタとして、より好適な態様であるカラーフィルタ、その作製方法、及びこれらを用いたＣＯＡの作製に関わる詳細について説明する。 Hereinafter, as a color filter constituted by using the colored curable composition of the present invention, a color filter which is a more preferable aspect, a production method thereof, and details relating to production of a COA using these will be described.
－ＣＯＡ方式カラーフィルタの製造方法及び使用方法－
　上述の通り、本発明のカラーフィルタは、以下のようにして製造することが出来る。ＴＦＴ基板上に着色剤を含む本発明の着色硬化性組成物を塗布して、着色硬化性組成物の塗布膜を形成後、該塗布膜にパターン露光、アルカリ現像、ポストベーク処理等を施して、各画素を形成する。次いで該各画素上に透明電極（ＩＴＯ）膜をスパッタリング後、ポジ型フォトレジスト塗布膜を形成し、該フォトレジスト膜にパターン露光、現像を施し、更に必要なＩＴＯをエッチングして画素電極パターンを形成した後に、該画素電極パターン上に残存しているフォトレジスト膜を剥離液で除去することにより、ＣＯＡ方式カラーフィルタを得る。 -Manufacturing method and usage of COA color filter-
As described above, the color filter of the present invention can be manufactured as follows. After applying the colored curable composition of the present invention containing a colorant on the TFT substrate to form a coated film of the colored curable composition, the coated film is subjected to pattern exposure, alkali development, post-baking treatment, etc. Each pixel is formed. Next, after sputtering a transparent electrode (ITO) film on each pixel, a positive photoresist coating film is formed, pattern exposure is performed on the photoresist film, development is performed, and further, necessary ITO is etched to form a pixel electrode pattern. After the formation, the photoresist film remaining on the pixel electrode pattern is removed with a remover to obtain a COA color filter.
　本発明の着色硬化性組成物を塗布して塗布膜を形成するには、直接又は他の層を介して基板に回転塗布（スピンコート）、スリット塗布、流延塗布、ロール塗布等の塗布方法により塗布、乾燥（プリベーク）する等すればよい。基板上に塗布された着色硬化性組成物層の乾燥（プリベーク）は、ホットプレート、オーブン等で５０℃～１４０℃の温度で１０～３００秒で行なうことができる。また、近年、基板の大型化が進んでいることから、塗布膜の形成方法としてはスリット塗布も有効であり、かかる塗布方法が一般的になりつつある。 In order to form a coating film by applying the colored curable composition of the present invention, a coating method such as spin coating, spin coating, casting coating, roll coating, etc., on a substrate directly or via another layer. Application, drying (pre-baking), etc. The colored curable composition layer applied on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, oven or the like. In recent years, since the substrate has been increased in size, slit coating is also effective as a method for forming a coating film, and this coating method is becoming common.
　また、塗布膜のパターン露光は、所定のマスクパターンを介して露光し、光照射された塗布膜部分だけを硬化させることにより行なうことができる。露光に際して用いることができる放射線としては、特にｇ線、ｉ線等の紫外線が好ましく用いられる。
　次いでアルカリ現像処理を行なうことにより、ネガ型の場合には前記露光がなされていない非硬化部をアルカリ水溶液に溶出させ、光硬化した部分だけが残る。現像液としては、下地の回路などにダメージを起さない、有機アルカリ現像液が望ましい。現像温度としては通常２０℃～３０℃であり、現像時間は２０～９０秒である。
　アルカリとしては、例えば、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、１，８－ジアザビシクロ－［５、４、０］－７－ウンデセンなどの有機アルカリ性化合物を濃度が０．００１質量％～１０質量％、好ましくは０．０１質量％～１質量％となるように純水で希釈したアルカリ性水溶液が使用できる。なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、一般に現像後純水で洗浄（リンス）が行なわれる。
　次いで、余剰の現像液を洗浄除去し、乾燥を施した後に加熱処理（ポストベーク）を行なう。このように各色ごとに前記工程を順次繰り返して硬化被膜を製造することができる。これによりカラーフィルタが得られる。 Further, the pattern exposure of the coating film can be performed by exposing through a predetermined mask pattern and curing only the coating film portion irradiated with light. As radiation that can be used in exposure, ultraviolet rays such as g-line and i-line are particularly preferably used.
Next, by carrying out an alkali development treatment, in the case of the negative type, the uncured portion that has not been exposed is eluted in the alkaline aqueous solution, and only the photocured portion remains. As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.
Examples of the alkali include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7- An alkaline aqueous solution obtained by diluting an organic alkaline compound such as undecene with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass can be used. In the case where a developer composed of such an alkaline aqueous solution is used, the developer is generally washed (rinsed) with pure water after development.
Next, excess developer is washed away and dried, followed by heat treatment (post-bake). Thus, the said process can be repeated sequentially for every color, and a hardened film can be manufactured. Thereby, a color filter is obtained.
　ポストベークは、硬化を完全なものとするための現像後の加熱処理であり、通常２００℃～２４０℃の熱硬化処理を行なう。
　このポストベーク処理は、現像後の塗布膜に対して、前記条件になるようにホットプレートやコンベクションオーブン（熱風循環式乾燥機）、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行なうことができる。 The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 200 ° C. to 240 ° C. is performed.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so as to satisfy the above conditions for the coated film after development. Can be done.
　そして、形成された画素上にスパッタリングで透明電極（ＩＴＯ）膜を形成し、さらにその上にポジ型フォトレジスト膜を形成し、パターン露光、現像を施した後、フッ酸などの薬品で不要なＩＴＯをエッチングして画素電極を形成する。この際用いられるフォトレジストとしては、エッチング耐性のあるポジ型フォトレジストが必要である。また、パターン露光や現像、エッチングは通常公知の手法を制限なく用いることができる。
　次に、形成された画素電極上に残っているポジ型レジストを剥離液で速やかに剥離除去する。この剥離液としては特に制限はなく従来公知の剥離液を使用することができる。例えば、特開昭５１－７２５０３号、特開昭５７－８４４５６号、特開平６－２２２５７３号等の各公報や米国特許第４１６５２９４号及び欧州特許第０１１９３３７号の各明細書に開示されている各種の有機溶剤が使用できる。代表的な剥離液としては、モノエタノールアミン（ＭＥＡ）とジメチルスルホキシド（ＤＭＳＯ）の混合溶媒が挙げられる。また、剥離液として６０℃以上に加熱した有機溶剤を使用することで、剥離工程を短時間にすることができ、さらにまた、現像残査の問題もなくすことができる。本発明における着色硬化性組成物は特に耐剥離液性が優れているので、６０℃以上に加熱した有機溶剤を使用してもカラーフィルタの塗膜が剥れたり、膨潤・膨張したりするようなことはなく、レジスト膜を除去することができる。 Then, a transparent electrode (ITO) film is formed on the formed pixel by sputtering, a positive photoresist film is further formed thereon, pattern exposure and development are performed, and unnecessary with chemicals such as hydrofluoric acid. ITO is etched to form pixel electrodes. As the photoresist used at this time, a positive photoresist having etching resistance is required. Moreover, a well-known method can be normally used for pattern exposure, image development, and etching without a restriction | limiting.
Next, the positive resist remaining on the formed pixel electrode is quickly stripped and removed with a stripping solution. There is no restriction | limiting in particular as this stripping solution, A conventionally well-known stripping solution can be used. For example, various publications disclosed in JP-A-51-72503, JP-A-57-84456, JP-A-6-222573, etc., and U.S. Pat. No. 4,165,294 and European Patent No. 0119337. These organic solvents can be used. A typical stripping solution includes a mixed solvent of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO). Further, by using an organic solvent heated to 60 ° C. or higher as the stripping solution, the stripping process can be shortened, and further, there can be no problem of development residue. Since the colored curable composition in the present invention is particularly excellent in peeling liquid resistance, even if an organic solvent heated to 60 ° C. or higher is used, the coating film of the color filter may be peeled off or swelled / expanded. There is nothing, and the resist film can be removed.
　本発明のカラーフィルタは、通常、特開平９－３１１３４７号公報の図１に開示されているような構造でＴＦＴ液晶表示装置などの各種表示装置に用いられる。
　上述のようにして得られたカラーフィルタは、位置合わせが容易で、開口率を高めることができるため、ＣＯＡ方式の画像表示装置に好適である。しかも、本発明の着色硬化性組成物を用いて画素を形成しているので、剥離液耐性が高く、そのため良品化率が高く、生産効率も高いものである。また、通常カラーフィルタに要求される耐熱変色性、低誘電率性、膜厚均一性、解像性、電圧保持率、耐光性なども良好である。 The color filter of the present invention is usually used in various display devices such as a TFT liquid crystal display device having the structure disclosed in FIG. 1 of JP-A-9-31347.
The color filter obtained as described above is suitable for a COA type image display device because it can be easily aligned and can increase the aperture ratio. In addition, since the pixel is formed using the colored curable composition of the present invention, the resistance to the stripping solution is high, so that the yield rate is high and the production efficiency is also high. In addition, heat discoloration, low dielectric constant, film thickness uniformity, resolution, voltage holding ratio, light resistance and the like normally required for color filters are also good.
　カラーフィルタの構造は、上記したように画素が１層のみからなる形態であってもよく、あるいは、画素用着色硬化性組成物の塗布膜からなる画素膜と該画素膜上に形成された画素保護膜用光熱重合性組成物からなる画素保護膜との２層を基板と画素電極との間に有する形態であってもよい。
　前記画素膜の膜厚は、０．３μｍ～５．０μｍが好ましく、０．５μｍ～３．５μｍがより好ましい。塗布厚みが厚い方が高色度を達成できるが、塗布厚みが厚いとコンタクトホールの解像性が悪くなるので、バランスが必要である。また、前記画素保護膜の膜厚は０．２μｍ～５．０μｍが好ましく、０．２μｍ～３．０μｍがより好ましい。また、下地の画素の凹凸を平坦化して、表面は平滑であることが望ましい。 As described above, the structure of the color filter may be a form in which the pixel is composed of only one layer, or a pixel film formed of a coating film of a colored curable composition for pixels and a pixel formed on the pixel film. The form which has two layers with the pixel protective film which consists of a photothermographic composition for protective films between a board | substrate and a pixel electrode may be sufficient.
The film thickness of the pixel film is preferably 0.3 μm to 5.0 μm, and more preferably 0.5 μm to 3.5 μm. The higher the coating thickness, the higher the chromaticity can be achieved. However, the thicker the coating thickness, the lower the resolution of the contact hole. The film thickness of the pixel protective film is preferably 0.2 μm to 5.0 μm, and more preferably 0.2 μm to 3.0 μm. Further, it is desirable that the unevenness of the underlying pixel is flattened so that the surface is smooth.
～本発明の着色硬化性組成物を用いたＣＯＡ方式の画像表示装置の製造方法～
　以下、本発明の着色硬化性組成物において最も好適なＣＯＡ方式の画像表示装置（以下、単に「ＣＯＡ」とも称する。）の例を示す。
　通常のカラーフィルタはガラス基板上に設けられ、ＴＦＴ基板と貼り合せられる。これに対し、ＣＯＡの技術はＴＦＴ基板に直接カラーフィルタを形成するもので、通常のカラーフィルタ材料と比較して下記（ｉ）～（ｉｉｉ）の点を考慮する必要がある。
（ｉ）低誘電率
　ＣＯＡではＴＦＴに直接画素電極を設けるため、電圧が直接カラーフィルタにかかることから、カラーフィルタの材料が低誘電率材料であることが求められる。
（ｉｉ）コンタクトホール
　ＣＯＡでは画素電極のＩＴＯ配線がその下に設けられるＴＦＴと接続される必要がある。このため、コンタクトホールが現像時に確実に形成されることが求められる。
（ｉｉｉ）剥離液耐性
　ＣＯＡでは画素毎に電極形成が必須となる。該電極の形成では、画素の上にＩＴＯをスパッタで付け、パターニング及びエッチングによる配線をポジ型レジストを用いて行ない、次いで、残ったポジ型レジストを、通常８０℃程度の高温の剥離液で除去する。このためＣＯＡではカラーフィルタ等がこの剥離液によって侵されないこと、及び剥離液によって膨潤し、ＩＴＯが追従できなくて断線することのないように低膨潤率が求められる。 -Method for producing COA type image display device using colored curable composition of the present invention-
Examples of the most suitable COA type image display device (hereinafter also simply referred to as “COA”) in the colored curable composition of the present invention will be shown below.
A normal color filter is provided on a glass substrate and bonded to a TFT substrate. On the other hand, the COA technique directly forms a color filter on a TFT substrate, and it is necessary to consider the following points (i) to (iii) as compared with a normal color filter material.
(I) Low dielectric constant In the COA, since the pixel electrode is directly provided on the TFT, the voltage is directly applied to the color filter. Therefore, the color filter material is required to be a low dielectric constant material.
(Ii) Contact hole In the COA, the ITO wiring of the pixel electrode needs to be connected to the TFT provided therebelow. For this reason, it is required that the contact hole be reliably formed during development.
(Iii) Resistance to stripping solution In COA, electrode formation is essential for each pixel. In forming the electrodes, ITO is sputtered on the pixels, wiring by patterning and etching is performed using a positive resist, and then the remaining positive resist is removed with a high-temperature stripping solution of about 80 ° C. To do. For this reason, in COA, a low swelling rate is required so that the color filter or the like is not attacked by the stripping solution and is swollen by the stripping solution so that the ITO cannot follow and disconnect.
　一方、ＴＦＴ基板の上にカラーフィルタを作製する際、カラーフィルタ作製工程における不良品の出現はＴＦＴ基板も含めて不良品となるため、非常にリスクが高い。しかし、近年液晶ＴＶに代表されるようにＬＣＤが大型化されるに伴い、製造基板サイズも年々大型化している。さらに液晶の注入時間も長くなるため、液晶注入方法が滴下方式へと変わりつつある。上述したように、このような基板サイズの大型化、液晶滴下方式の適用などに伴い、カラーフィルタとＴＦＴ基板を貼り合せる際に、カラーフィルタの画素とＴＦＴとの位置合せ精度がシビアになっており、基板の中心部と周辺部との位置ズレを修正することが非常に困難になりつつある。 On the other hand, when a color filter is manufactured on a TFT substrate, the appearance of defective products in the color filter manufacturing process is a defective product including the TFT substrate, which is very risky. However, as LCDs have recently become larger as typified by liquid crystal TVs, the size of the production substrate has also increased year by year. Furthermore, since the liquid crystal injection time becomes longer, the liquid crystal injection method is changing to the dropping method. As described above, with the increase in the substrate size and the application of the liquid crystal dropping method, when the color filter and the TFT substrate are bonded, the alignment accuracy between the color filter pixel and the TFT becomes severe. Therefore, it is becoming very difficult to correct the positional deviation between the central portion and the peripheral portion of the substrate.
　この点において、ＣＯＡはＴＦＴの上に直接画素を設けるために、位置ズレの心配はなく、また、液晶を挟んだ対向基板には、ＩＴＯを全面にスパッタした基板を用意すればよい。このため、位置合せの必要はシール剤の位置程度になり、飛躍的に作業効率が向上する。上述したように、ＣＯＡの技術は、位置合せ精度が必要ない（緩やかである）ことから、ブラックマトリックスの線幅を非常に狭くして、開口率を広げることができ、バックライトの電力消費を低く抑えられるメリットがある。このようにＣＯＡについては種々検討されており、今後のＬＣＤ大型基板への必須技術になる可能性がある。しかしながら、上述の通り、ＴＦＴの上にカラーフィルタを作製することによるリスクと、カラーフィルタ材料として前記（ｉ）～（ｉｉｉ）の要求に応えられるようなものが提供されていないため、採用が進んでいないのが現状であった。 In this respect, since the COA is provided with pixels directly on the TFT, there is no concern about positional displacement, and a substrate on which ITO is sputtered over the entire surface may be prepared as a counter substrate sandwiching the liquid crystal. For this reason, the necessity of alignment becomes about the position of the sealing agent, and the working efficiency is dramatically improved. As described above, since the COA technology does not require alignment accuracy (it is gradual), the line width of the black matrix can be made very narrow, the aperture ratio can be increased, and the power consumption of the backlight can be increased. There is a merit that can be kept low. In this way, various studies have been made on COA, which may become an essential technology for future LCD large-sized substrates. However, as described above, the risk of producing a color filter on the TFT and the color filter material that can meet the requirements (i) to (iii) are not provided, so that the adoption is advanced. The current situation was not.
　本発明の着色硬化性組成物は、上記に鑑み、ＣＯＡ用の前記カラーフィルタ材料に起因する問題点を解決し得るものであり、その使用方法は、それぞれ目的によって使い分けることができる。
　即ち、最も望ましい方法は、着色剤を含んだ本発明の着色硬化性組成物を用いてカラーフィルタを作製する方法である。更に、ＴＦＴ上にカラーフィルタを作製することによって平坦性が満足できない場合には、さらに着色剤を含まない本発明の着色硬化性組成物を平坦化膜として使用することで、種々の要求特性を満足することができる。当然、該平坦化層は下地のカラーフィルタとの相性も良いので、密着性も良くＣＯＡの材料面からの不良率を最少に抑えることができる。 In view of the above, the colored curable composition of the present invention can solve the problems caused by the color filter material for COA, and the method of use thereof can be used depending on the purpose.
That is, the most desirable method is a method for producing a color filter using the colored curable composition of the present invention containing a colorant. Further, when the flatness cannot be satisfied by producing a color filter on the TFT, various required characteristics can be obtained by using the colored curable composition of the present invention which does not further contain a colorant as a flattening film. Can be satisfied. Naturally, the planarization layer has good compatibility with the underlying color filter, so that the adhesion is good and the defect rate from the COA material surface can be minimized.
＜＜表示装置＞＞
　本発明のカラーフィルタの製造方法により得られたカラーフィルタ（本発明のカラーフィルタ）は、本発明の着色硬化性組成物を用いていることから、輝度及びコントラストに優れている。
　本発明の表示装置は、本発明のカラーフィルタを備えたものである。
　本発明の表示装置として、具体的には、液晶ディスプレイ（液晶表示装置；ＬＣＤ）、有機ＥＬディスプレイ（有機ＥＬ表示装置）、液晶プロジェクタ、ゲーム機用表示装置、携帯電話などの携帯端末用表示装置、デジタルカメラ用表示装置、カーナビ用表示装置などの表示装置、特にカラー表示装置が好適である。
　本発明のカラーフィルタを有機ＥＬ表示装置や、液晶表示装置等に用いた場合、高輝度で、分光特性及びコントラストに優れた画像の表示が可能になる。 << Display device >>
The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in luminance and contrast because the colored curable composition of the present invention is used.
The display device of the present invention includes the color filter of the present invention.
Specifically, as a display device of the present invention, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone. Display devices such as digital camera display devices and car navigation display devices, particularly color display devices are suitable.
When the color filter of the present invention is used in an organic EL display device, a liquid crystal display device or the like, it is possible to display an image with high luminance and excellent spectral characteristics and contrast.
＜液晶表示装置＞
　本発明のカラーフィルタを用いた液晶表示装置について説明する。有機ＥＬ表示装置や液晶表示装置の定義や各表示装置の詳細については、例えば「電子ディスプレイデバイス（佐々木　昭夫著、（株）工業調査会　１９９０年発行）」、「ディスプレイデバイス（伊吹　順章著、産業図書（株）平成元年発行）」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田　龍男編集、（株）工業調査会　１９９４年発行）」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。 <Liquid crystal display device>
A liquid crystal display device using the color filter of the present invention will be described. For the definition of organic EL display devices and liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho (issued in 1989) ”. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
　本発明のカラーフィルタは、中でも特に、カラーＴＦＴ方式の液晶表示装置に対して有効である。カラーＴＦＴ方式の液晶表示装置については、例えば「カラーＴＦＴ液晶ディスプレイ（共立出版（株）１９９６年発行）」に記載されている。更に、本発明はＩＰＳなどの横電界駆動方式、ＭＶＡなどの画素分割方式などの視野角が拡大された液晶表示装置や、ＳＴＮ、ＴＮ、ＶＡ、ＯＣＳ、ＦＦＳ、及びＲ－ＯＣＢ等にも適用できる。また、本発明のカラーフィルタは、ＣＯＡ（Ｃｏｌｏｒ－ｆｉｌｔｅｒ　Ｏｎ　Ａｒｒａｙ）方式にも供することが可能である。 The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can. The color filter of the present invention can also be used for a COA (Color-filter On Array) system.
　本発明のカラーフィルタを液晶表示装置に用いると、従来公知の冷陰極管の三波長管と組み合わせたときに高いコントラストを実現できるが、更に、赤、緑、青のＬＥＤ光源（ＲＧＢ－ＬＥＤ）をバックライトとすることによって輝度が高く、また、色純度の高い色再現性の良好な液晶表示装置を提供することができる。 When the color filter of the present invention is used in a liquid crystal display device, a high contrast can be realized when combined with a conventionally known three-wavelength tube of a cold cathode tube, but further, red, green and blue LED light sources (RGB-LED). By using as a backlight, a liquid crystal display device having high luminance and high color purity and good color reproducibility can be provided.
　以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「部」、「％」は質量基準である。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “part” and “%” are based on mass.
〔実施例１－１〕
－着色硬化性組成物の調製－
　下記の各成分を混合、溶解し、着色硬化性組成物を調製した。
・有機溶剤１（プロピレングリコールモノメチルエーテルアセテート）　　　　　　８部
・有機溶剤２（ジエチレングリコールエチルメチルエーテル）　　　　　　　　　２６部
・アルカリ可溶性バインダー１（シクロヘキシルメタクリレート／メタクリル酸／グリシジルメタクリレートとメタクリル酸の付加物（３０／３０／４０［モル比］、４５％プロピレングリコールモノメチルエーテル溶液）　　　　　　　　　　　　　　　　　　１部
・アルカリ可溶性バインダー２（アリルメタクリレート／メタクリル酸共重合体＝モル比７０／３０、重量平均分子量２６８００）　　　　　　　　　　　　　　　　　　　２部
・重合性化合物１（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＤＰＨＡ）　　　　　　　５部
・重合性化合物２（東亜合成（株）製、アロニックス　ＴＯ－２３４９）　　　　　２部
・重合禁止剤（ｐ－メトキシフェノール）　　　　　　　　　　　　　　　０．００３部
・光重合開始剤１（１－（Ｏ－アセチルオキシム）－１－［９－エチル－６－（チオフェノイル）－９Ｈ－カルバゾール－３－イル］プロパノン）　　　　　　　　　　０．５部
・光重合開始剤２（１，３－ジヒドロ－１－フェニル－２Ｈ－ベンズイミダゾール－２－チオン）　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．１部
・多官能チオール化合物１（１，４－ビス（３－メルカプトブチリルオキシ）ブタン）　０．３部
・密着改良剤（３－メタクリロキシプロピルトリメトキシシラン）　　　　　　０．２部
・フッ素系界面活性剤（ＤＩＣ社製　メガファックＦ－５５４、０．２％プロピレングリコールモノメチルエーテルアセテート溶液）　　　　　　　　　　　　　　　　５．１部
・青色顔料分散液１（Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６分散液）　　　　　　２５部
・染料溶液１　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．１部
・染料溶液２　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部 Example 1-1
-Preparation of colored curable composition-
The following components were mixed and dissolved to prepare a colored curable composition.
Organic solvent 1 (propylene glycol monomethyl ether acetate) 8 parts Organic solvent 2 (diethylene glycol ethyl methyl ether) 26 parts Alkali-soluble binder 1 (cyclohexyl methacrylate / methacrylic acid / glycidyl methacrylate and methacrylic acid adduct (30/30 / 40 [molar ratio], 45% propylene glycol monomethyl ether solution) 1 part alkali-soluble binder 2 (allyl methacrylate / methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 2 parts polymerizable compound 1 ( Nippon Kayaku Co., Ltd., KAYARAD DPHA 5 parts Polymerizable compound 2 (Toa Gosei Co., Ltd., Aronix TO-2349) 2 parts Polymerization inhibitor (p-methoxyphenone) ) 0.003 parts / photopolymerization initiator 1 (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] propanone) 0.5 parts / light Polymerization initiator 2 (1,3-dihydro-1-phenyl-2H-benzimidazol-2-thione) 0.1 part polyfunctional thiol compound 1 (1,4-bis (3-mercaptobutyryloxy) butane) 0.3 part, adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.2 part, fluorosurfactant (manufactured by DIC, MegaFuck F-554, 0.2% propylene glycol monomethyl ether acetate solution) 5 1 part blue pigment dispersion 1 (Pigment Blue 15: 6 dispersion) 25 parts dye solution 1 0.1 part dye solution 2 1.5 parts
　なお、前記青色顔料分散液は以下のようにして調製した。
　Ｃ．Ｉ．ピグメントブルー１５：６を１２．８部と分散剤（日本ルーブリゾール社製ソルスパース５５００）７．２部とを、プロピレングリコールモノメチルエーテルアセテート８０．０部と混合し、ビーズミルを用いて顔料を十分に分散させて、青色顔料分散液を調製した。 The blue pigment dispersion was prepared as follows.
C. I. 12.8 parts of Pigment Blue 15: 6 and 7.2 parts of a dispersant (Solsperse 5500 manufactured by Nippon Lubrizol Co., Ltd.) are mixed with 80.0 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently mixed using a bead mill. A blue pigment dispersion was prepared by dispersing.
　染料溶液１は下記の各成分を混合、溶解して作製した。実施例１－１において染料溶液１の染料濃度は、着色硬化性組成物中の色材に対して０．１％であった。
・有機溶剤１（プロピレングリコールモノメチルエーテルアセテート）　　　４４．６部
・特定染料（Ｂ）（Ｐ－２６）　　　　　　　　　　　　　　　　　　　　　　２．４部 The dye solution 1 was prepared by mixing and dissolving the following components. In Example 1-1, the dye concentration of the dye solution 1 was 0.1% with respect to the color material in the colored curable composition.
・ Organic solvent 1 (propylene glycol monomethyl ether acetate) 44.6 parts ・ Specific dye (B) (P-26) 2.4 parts
　染料溶液２は下記の各成分を混合、溶解して作製した。
・有機溶剤１（プロピレングリコールモノメチルエーテルアセテート）　　　４８．０部
・特定染料（Ａ）（化合物１）　　　　　　　　　　　　　　　　　　　　　　２．６部
　染料溶液１には、特定染料（Ｂ）であるＰ－２６が、染料溶液２には、特定染料（Ａ）である化合物１がそれぞれ含まれる。 The dye solution 2 was prepared by mixing and dissolving the following components.
Organic solvent 1 (propylene glycol monomethyl ether acetate) 48.0 parts Specific dye (A) (Compound 1) 2.6 parts In dye solution 1, P-26, a specific dye (B), is dye solution 2 Includes Compound 1 as the specific dye (A).
－着色硬化性組成物層（着色層）の形成－
　ガラス（＃１７３７；コーニング社製）基板上に、上記で調製した着色硬化性組成物をスピンコート法で塗布した後、室温で３０分間乾燥させることにより揮発成分を揮発させて、着色層Ａを形成した。この着色層Ａにｉ線（波長３６５ｎｍ）を照射し、潜像を形成させた。ｉ線の光源には超高圧水銀ランプを用い、平行光としてから照射するようにした。このとき、照射光量を４０ｍＪ／ｃｍ２とした。次いで、この潜像が形成された着色層に対して、炭酸ナトリウム／炭酸水素ナトリウムの水溶液（濃度２．４％）を用いて２６℃で４５秒間現像し、次いで、流水で２０秒間リンスした後、スプレーで乾燥して、細線パターン画像を得た。得られた細線パターン画像を２３０℃で２０分間、ポストベーク処理し、膜厚２μｍの着色層（着色硬化膜）Ｂを得た。 -Formation of colored curable composition layer (colored layer)-
After applying the colored curable composition prepared above on a glass (# 1737; manufactured by Corning) by spin coating, the volatile components are volatilized by drying at room temperature for 30 minutes to form the colored layer A. Formed. The colored layer A was irradiated with i rays (wavelength 365 nm) to form a latent image. An ultra-high pressure mercury lamp was used as the i-line light source, and it was irradiated as parallel light. At this time, the irradiation light quantity was 40 mJ / cm 2 . Next, the colored layer on which the latent image was formed was developed with an aqueous solution of sodium carbonate / sodium bicarbonate (concentration 2.4%) at 26 ° C. for 45 seconds, and then rinsed with running water for 20 seconds. And dried with a spray to obtain a fine line pattern image. The obtained fine line pattern image was post-baked at 230 ° C. for 20 minutes to obtain a colored layer (colored cured film) B having a thickness of 2 μm.
－評価－
　上記で得られた着色層のコントラスト及び分光特性について、以下に示す方法で評価した。評価結果は、下記表２に示す。
（１）コントラスト
　得られた各着色層Ｂを有する基板を２枚の偏光フィルムの間に挟み、２枚の偏光フィルムの偏光軸が平行な場合、及び垂直な場合の輝度の値を色彩輝度計（トプコン（株）製、型番：ＢＭ－５Ａ）を使用して測定し、２枚の偏光フィルムの偏光軸が平行な場合の輝度を垂直な場合の輝度で除して、得られた値をコントラストとして求めた。コントラストが高いほど、液晶表示装置用のカラーフィルタとして良好な性能を示す。
（２）分光特性(輝度）
　上記で得た着色層Ｂの透過スペクトルを、オリンパス（株）製の顕微分光測定装置ＯＳＰ－ＳＰ２００（商品名）を用いて測定した。得られた透過スペクトルより、ＣＩＥ１９３１表色系における色度座標ｘ値、ｙ値、Ｙ値を求めた。
　分光特性は、（ｘ、ｙ）＝（０．１３８、０．０８５）におけるＹ値（輝度）が高い場合、優れた分光特性を有していると言え、カラーフィルタにした際に良好な画像を得られる。 -Evaluation-
The contrast and spectral characteristics of the colored layer obtained above were evaluated by the following methods. The evaluation results are shown in Table 2 below.
(1) Contrast The obtained substrate having each colored layer B is sandwiched between two polarizing films, and the luminance value is measured when the polarization axes of the two polarizing films are parallel and perpendicular. (Topcon Co., Ltd., model number: BM-5A), and the value obtained by dividing the luminance when the polarization axes of the two polarizing films are parallel by the luminance when perpendicular is obtained. Obtained as contrast. The higher the contrast, the better the performance as a color filter for a liquid crystal display device.
(2) Spectral characteristics (luminance)
The transmission spectrum of the colored layer B obtained above was measured using a microspectrophotometer OSP-SP200 (trade name) manufactured by Olympus Corporation. From the obtained transmission spectrum, the chromaticity coordinate x value, y value, and Y value in the CIE 1931 color system were determined.
When the Y value (luminance) at (x, y) = (0.138, 0.085) is high, it can be said that the spectral characteristics have excellent spectral characteristics. Can be obtained.
〔実施例１－２～１－４〕
　実施例１－１において、特定染料（Ｂ）の使用量を、表１に記載のように変更し、それ以外は、実施例１－１と同様にして、着色硬化性組成物を調製し、着色層を形成すると共に、評価を行なった。評価結果は、表２に併記する。 [Examples 1-2 to 1-4]
In Example 1-1, the amount of the specific dye (B) used was changed as shown in Table 1, and other than that, a colored curable composition was prepared in the same manner as in Example 1-1. A colored layer was formed and evaluated. The evaluation results are also shown in Table 2.
〔実施例１－５〕
－着色硬化性組成物の調製－
　下記の各成分を混合、溶解し、着色硬化性組成物を調製した。
・有機溶剤１（プロピレングリコールモノメチルエーテルアセテート）　　　　　　８部
・有機溶剤２（ジエチレングリコールエチルメチルエーテル）　　　　　　　　　２６部
・アルカリ可溶性バインダー１（シクロヘキシルメタクリレート／メタクリル酸／グリシジルメタクリレートとメタクリル酸の付加物（３０／３０／４０［モル比］）、４５％プロピレングリコールモノメチルエーテル溶液）　　　　　　　　　　　　　　　　　１部
・アルカリ可溶性バインダー２（アリルメタクリレート／メタクリル酸共重合体＝モル比７０／３０、重量平均分子量２６８００）　　　　　　　　　　　　　　　　　　　２部
・重合性化合物１（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＤＰＨＡ）　　　　　　　５部
・重合性化合物２（東亜合成（株）製、アロニックス　ＴＯ－２３４９）　　　　　２部
・重合禁止剤（ｐ－メトキシフェノール）　　　　　　　　　　　　　　　０．００３部
・光重合開始剤１（１－（Ｏ－アセチルオキシム）－１－［９－エチル－６－（チオフェノイル）－９Ｈ－カルバゾール－３－イル］プロパノン）　　　　　　　　　　０．５部
・光重合開始剤２（１，３－ジヒドロ－１－フェニル－２Ｈ－ベンズイミダゾール－２－チオン）　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．１部
・多官能チオール化合物１（１，４－ビス（３－メルカプトブチリルオキシ）ブタン）　０．３部
・密着改良剤（３－メタクリロキシプロピルトリメトキシシラン）　　　　　　０．２部
・フッ素系界面活性剤（ＤＩＣ社製　メガファックＦ－５５４、０．２％プロピレングリコールモノメチルエーテルアセテート溶液）　　　　　　　　　　　　　　　　５．１部
・青色顔料分散液１（Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６分散液）　　　　　　２５部
・染料溶液３　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．１部
・染料溶液２　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部 [Example 1-5]
-Preparation of colored curable composition-
The following components were mixed and dissolved to prepare a colored curable composition.
Organic solvent 1 (propylene glycol monomethyl ether acetate) 8 parts Organic solvent 2 (diethylene glycol ethyl methyl ether) 26 parts Alkali-soluble binder 1 (cyclohexyl methacrylate / methacrylic acid / glycidyl methacrylate and methacrylic acid adduct (30/30 / 40 [molar ratio]), 45% propylene glycol monomethyl ether solution) 1 part alkali-soluble binder 2 (allyl methacrylate / methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 2 parts polymerizable compound 1 (Nippon Kayaku Co., Ltd., KAYARAD DPHA) 5 parts Polymerizable compound 2 (Toa Gosei Co., Ltd., Aronix TO-2349) 2 parts Polymerization inhibitor (p-methoxypheno 0.003 part ・ Photopolymerization initiator 1 (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] propanone) 0.5 part Photopolymerization initiator 2 (1,3-dihydro-1-phenyl-2H-benzimidazol-2-thione) 0.1 part polyfunctional thiol compound 1 (1,4-bis (3-mercaptobutyryloxy) butane ) 0.3 part ・ Adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.2 part ・ Fluorosurfactant (manufactured by DIC, MegaFuck F-554, 0.2% propylene glycol monomethyl ether acetate solution) 5.1 parts blue pigment dispersion 1 (Pigment Blue 15: 6 dispersion) 25 parts dye solution 0.1 parts dye solution 2 1.5 parts
　得られた着色硬化性組成物の評価を実施例１－１と同様にして行った。評価結果は表２に示す。 The obtained colored curable composition was evaluated in the same manner as in Example 1-1. The evaluation results are shown in Table 2.
　染料溶液３は下記の各成分を混合、溶解して作製した。実施例１－５において染料溶液３の染料濃度は、着色硬化性組成物中の色材に対して０．１％であった。
・有機溶剤１（プロピレングリコールモノメチルエーテルアセテート）　　　４４．６部
・特定染料（Ｂ）（Ｐ－３２）　　　　　　　　　　　　　　　　　　　　　　２．４部 The dye solution 3 was prepared by mixing and dissolving the following components. In Example 1-5, the dye concentration of the dye solution 3 was 0.1% with respect to the color material in the colored curable composition.
・ Organic solvent 1 (propylene glycol monomethyl ether acetate) 44.6 parts ・ Specific dye (B) (P-32) 2.4 parts
　また、染料溶液２は実施例１－１で用いたものと同じ染料溶液である。
・有機溶剤１（プロピレングリコールモノメチルエーテルアセテート）　　　４８．０部
・特定染料（Ａ）（化合物１）　　　　　　　　　　　　　　　　　　　　　　２．６部
　染料溶液３には、特定染料（Ｂ）である（Ｐ－３２）が、染料溶液２には、特定染料（Ａ）である（化合物１）がそれぞれ含まれる。 Dye solution 2 is the same dye solution as used in Example 1-1.
・ Organic solvent 1 (propylene glycol monomethyl ether acetate) 48.0 parts ・ Specific dye (A) (compound 1) 2.6 parts In dye solution 3, specific dye (B) (P-32) is dye The solution 2 contains (Compound 1) which is the specific dye (A).
〔実施例１－６～１－８〕
　実施例１－５において、染料溶液３における特定染料（Ｂ）の使用量を、表１に記載のように変更し、それ以外は、実施例１－５と同様にして、着色硬化性組成物を調製し、着色層を形成すると共に、評価を行なった。評価結果は、表２に示す。 [Examples 1-6 to 1-8]
In Example 1-5, the amount of the specific dye (B) used in the dye solution 3 was changed as shown in Table 1, and other than that, the colored curable composition was the same as Example 1-5. Were prepared to form a colored layer and evaluated. The evaluation results are shown in Table 2.
〔実施例１－９～１－１２〕
　実施例１－３において、染料溶液１における特定染料（Ｂ）の種類を表１に記載のように変更し、それ以外は、実施例１－３と同様にして、着色硬化性組成物を調製し、着色層を形成すると共に、評価を行なった。評価結果は、下記表２に示す。 [Examples 1-9 to 1-12]
In Example 1-3, the type of the specific dye (B) in the dye solution 1 was changed as shown in Table 1, and a colored curable composition was prepared in the same manner as in Example 1-3 except that. Then, a colored layer was formed and evaluated. The evaluation results are shown in Table 2 below.
〔実施例１－１３～１－１５〕
　実施例１－３において、染料溶液２における特定染料（Ａ）を表１に記載のように変更し、それ以外は、実施例１－３と同様にして、着色硬化性組成物を調製し、着色層を形成すると共に、評価を行なった。評価結果は、下記表２に示す。 [Examples 1-13 to 1-15]
In Example 1-3, the specific dye (A) in the dye solution 2 was changed as shown in Table 1, except that a colored curable composition was prepared in the same manner as in Example 1-3. A colored layer was formed and evaluated. The evaluation results are shown in Table 2 below.
〔実施例１－１６～１－１８〕
　実施例１－７において、染料溶液２における特定染料（Ａ）を表１に記載のように変更し、それ以外は、実施例１－７と同様にして、着色硬化性組成物を調製し、着色層を形成すると共に、評価を行なった。評価結果は、下記表２に示す。 [Examples 1-16 to 1-18]
In Example 1-7, the specific dye (A) in the dye solution 2 was changed as shown in Table 1, except that a colored curable composition was prepared in the same manner as in Example 1-7. A colored layer was formed and evaluated. The evaluation results are shown in Table 2 below.
〔比較例１－１〕
　下記の各成分を混合、溶解し、着色硬化性組成物を調製した。
・有機溶剤１（プロピレングリコールモノメチルエーテルアセテート）　　　　　　８部
・有機溶剤２（ジエチレングリコールエチルメチルエーテル）　　　　　　　　　２６部
・アルカリ可溶性バインダー１（シクロヘキシルメタクリレート／メタクリル酸／グリシジルメタクリレートとメタクリル酸の付加物（３０／３０／４０［モル比］）、４５％プロピレングリコールモノメチルエーテル溶液）　　　　　　　　　　　　　　　　　１部
・アルカリ可溶性バインダー２（アリルメタクリレート／メタクリル酸共重合体＝モル比７０／３０、重量平均分子量２６８００）　　　　　　　　　　　　　　　　　　　２部
・重合性化合物１（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＤＰＨＡ）　　　　　　　５部
・重合性化合物２（東亜合成（株）製、アロニックス　ＴＯ－２３４９）　　　　　２部
・重合禁止剤（ｐ－メトキシフェノール）　　　　　　　　　　　　　　　０．００３部
・光重合開始剤１（１－（Ｏ－アセチルオキシム）－１－［９－エチル－６－（チオフェノイル）－９Ｈ－カルバゾール－３－イル］プロパノン）　　　　　　　　　　０．５部
・光重合開始剤２（１，３－ジヒドロ－１－フェニル－２Ｈ－ベンズイミダゾール－２－チオン）　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．１部
・多官能チオール化合物１（１，４－ビス（３－メルカプトブチリルオキシ）ブタン）　０．３部
・密着改良剤（３－メタクリロキシプロピルトリメトキシシラン）　　　　　　０．２部
・フッ素系界面活性剤（ＤＩＣ社製　メガファックＦ－５５４、０．２％プロピレングリコールモノメチルエーテルアセテート溶液）　　　　　　　　　　　　　　　　５．１部
・青色顔料分散液（Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６分散液）　　　　　　　２８部
・染料溶液２　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１部
　調製後、実施例１－１と同様にして評価を行った。結果は表２に示す。 [Comparative Example 1-1]
The following components were mixed and dissolved to prepare a colored curable composition.
Organic solvent 1 (propylene glycol monomethyl ether acetate) 8 parts Organic solvent 2 (diethylene glycol ethyl methyl ether) 26 parts Alkali-soluble binder 1 (cyclohexyl methacrylate / methacrylic acid / glycidyl methacrylate and methacrylic acid adduct (30/30 / 40 [molar ratio]), 45% propylene glycol monomethyl ether solution) 1 part alkali-soluble binder 2 (allyl methacrylate / methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 2 parts polymerizable compound 1 (Nippon Kayaku Co., Ltd., KAYARAD DPHA) 5 parts Polymerizable compound 2 (Toa Gosei Co., Ltd., Aronix TO-2349) 2 parts Polymerization inhibitor (p-methoxypheno 0.003 part ・ Photopolymerization initiator 1 (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] propanone) 0.5 part Photopolymerization initiator 2 (1,3-dihydro-1-phenyl-2H-benzimidazol-2-thione) 0.1 part polyfunctional thiol compound 1 (1,4-bis (3-mercaptobutyryloxy) butane ) 0.3 part ・ Adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.2 part ・ Fluorosurfactant (manufactured by DIC, MegaFuck F-554, 0.2% propylene glycol monomethyl ether acetate solution) 5.1 parts blue pigment dispersion (Pigment Blue 15: 6 dispersion) 28 parts dye solution 2 After preparing 1 part, evaluation was performed in the same manner as in Example 1-1. The results are shown in Table 2.
〔比較例１－２〕
　下記の各成分を混合、溶解し、着色硬化性組成物を調製した。
・有機溶剤１（プロピレングリコールモノメチルエーテルアセテート）　　　　　　８部
・有機溶剤２（ジエチレングリコールエチルメチルエーテル）　　　　　　　　　２６部
・アルカリ可溶性バインダー１（シクロヘキシルメタクリレート／メタクリル酸／グリシジルメタクリレートとメタクリル酸の付加物（３０／３０／４０［モル比］）、４５％プロピレングリコールモノメチルエーテル溶液）　　　　　　　　　　　　　　　　　１部
・アルカリ可溶性バインダー２（アリルメタクリレート／メタクリル酸共重合体＝モル比７０／３０、重量平均分子量２６８００）　　　　　　　　　　　　　　　　　　　２部
・重合性化合物１（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＤＰＨＡ）　　　　　　　５部
・重合性化合物２（東亜合成（株）製、アロニックス　ＴＯ－２３４９）　　　　　２部
・重合禁止剤（ｐ－メトキシフェノール）　　　　　　　　　　　　　　　０．００３部
・光重合開始剤１（１－（Ｏ－アセチルオキシム）－１－［９－エチル－６－（チオフェノイル）－９Ｈ－カルバゾール－３－イル］プロパノン）　　　　　　　　　　０．５部
・光重合開始剤２（１，３－ジヒドロ－１－フェニル－２Ｈ－ベンズイミダゾール－２－チオン）　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．１部
・多官能チオール化合物１（１，４－ビス（３－メルカプトブチリルオキシ）ブタン）　０．３部
・密着改良剤（３－メタクリロキシプロピルトリメトキシシラン）　　　　　　０．２部
・フッ素系界面活性剤（ＤＩＣ社製　メガファックＦ－５５４、０．２％プロピレングリコールモノメチルエーテルアセテート溶液）　　　　　　　　　　　　　　　　５．１部
・青色顔料分散液（Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６分散液）　　　　　　　２５部
・染料溶液４　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　０．１部
・染料溶液２　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１．５部 [Comparative Example 1-2]
The following components were mixed and dissolved to prepare a colored curable composition.
Organic solvent 1 (propylene glycol monomethyl ether acetate) 8 parts Organic solvent 2 (diethylene glycol ethyl methyl ether) 26 parts Alkali-soluble binder 1 (cyclohexyl methacrylate / methacrylic acid / glycidyl methacrylate and methacrylic acid adduct (30/30 / 40 [molar ratio]), 45% propylene glycol monomethyl ether solution) 1 part alkali-soluble binder 2 (allyl methacrylate / methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 2 parts polymerizable compound 1 (Nippon Kayaku Co., Ltd., KAYARAD DPHA) 5 parts Polymerizable compound 2 (Toa Gosei Co., Ltd., Aronix TO-2349) 2 parts Polymerization inhibitor (p-methoxypheno 0.003 part ・ Photopolymerization initiator 1 (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] propanone) 0.5 part Photopolymerization initiator 2 (1,3-dihydro-1-phenyl-2H-benzimidazol-2-thione) 0.1 part polyfunctional thiol compound 1 (1,4-bis (3-mercaptobutyryloxy) butane ) 0.3 part ・ Adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.2 part ・ Fluorosurfactant (manufactured by DIC, MegaFuck F-554, 0.2% propylene glycol monomethyl ether acetate solution) 5.1 parts blue pigment dispersion (Pigment Blue 15: 6 dispersion) 25 parts dye solution 4 0.1 part dye solution 2 1.5 parts
　なお、染料溶液４は下記の各成分を混合、溶解して作製した。
・有機溶剤１（プロピレングリコールモノメチルエーテルアセテート）　　　４４．６部
・特開２００８－２９２９７０に記載の例示化合物ＣＢ－３４　　　　　　　　２．４部
　調製後、実施例１－１と同様にして評価を行った。結果は表２に示す。
　なお、染料溶液４に含まれるポルフィリン化合物は、一般式（ＩＩ）における、Ａ１とＡ２、Ａ３とＡ４、Ａ５とＡ６、及びＡ７とＡ８のすべてが芳香環構造を形成している本発明の範囲外の染料である。 The dye solution 4 was prepared by mixing and dissolving the following components.
・ Organic solvent 1 (propylene glycol monomethyl ether acetate) 44.6 parts ・ Exemplary compound CB-34 described in JP-A-2008-292970 2.4 parts After evaluation, evaluation was performed in the same manner as in Example 1-1. The results are shown in Table 2.
The porphyrin compound contained in the dye solution 4 has an aromatic ring structure in which A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 are all in the general formula (II). It is a dye that is out of the scope of the present invention.
Figure JPOXMLDOC01-appb-T000063
Figure JPOXMLDOC01-appb-T000063
　特定染料Ａである化合物１～化合物４の構造は以下に示すとおりである。 The structures of compounds 1 to 4 as specific dye A are as shown below.
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
　表２の評価結果より以下のことが明らかとなった。
　実施例１－１～１－１８のキサンテン化合物及びトリアリールメタン化合物からなる群より選ばれる特定染料（Ａ）と、ポルフィリン化合物とを組み合わせた本発明にかかる着色硬化性組成物により形成された着色硬化膜は、高いコントラストと分光特性を両立させており、実施例１－１や実施例１－５に示されるように、特定染料（Ｂ）の含有量は微量であっても、これを用いない比較例１－１に比べ、高いコントラストと輝度向上効果を持つことが分かる。
　比較例１－１に示されるように、ポルフィリン化合物を用いない場合は着色硬化性組成物のコントラストが低く、性能が十分ではなかった。
　前記各実施例に示される通り、特定染料（Ａ）と特定染料（Ｂ）との併用により良好な色度、コントラストを持つ着色硬化性組成物を得ることができるが、比較例１－２に示されるようにポルフィリン化合物の類縁化合物であるフタロシアニン系化合物、即ち、一般式（ＩＩ）におけるＡ１とＡ２、Ａ３とＡ４、Ａ５とＡ６、及びＡ７とＡ８のすべてが、互いに結合して環構造を形成している化合物を併用した場合には、輝度、コントラストが実施例群に対してやや低く、性能が十分でなかった。この理由は明確ではないが、本発明に係る一般式（ＩＩ）で表されるポルフィリン構造を有する化合物は、フタロシアニン構造を有する比較染料に比べて分子構造が小さく、移動性が高いため、染料分子同士、顔料粒子同士の凝集を抑制する効果が高いためと推定している。 The evaluation results shown in Table 2 revealed the following.
Coloration formed by the colored curable composition according to the present invention, in which a specific dye (A) selected from the group consisting of xanthene compounds and triarylmethane compounds of Examples 1-1 to 1-18 and a porphyrin compound are combined The cured film has both high contrast and spectral characteristics. As shown in Examples 1-1 and 1-5, even if the content of the specific dye (B) is very small, this is used. It can be seen that it has higher contrast and brightness improvement effect than the comparative example 1-1.
As shown in Comparative Example 1-1, when the porphyrin compound was not used, the contrast of the colored curable composition was low and the performance was not sufficient.
As shown in the above Examples, a colored curable composition having good chromaticity and contrast can be obtained by using the specific dye (A) and the specific dye (B) in combination. As shown, phthalocyanine compounds that are analogs of porphyrin compounds, that is, all of A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 in the general formula (II) In the case where the compounds which are bonded to each other to form a ring structure are used in combination, the luminance and contrast are slightly lower than those of the Examples, and the performance is not sufficient. Although the reason for this is not clear, the compound having a porphyrin structure represented by the general formula (II) according to the present invention has a smaller molecular structure and higher mobility than a comparative dye having a phthalocyanine structure. It is presumed that the effect of suppressing aggregation between the pigment particles is high.
〔実施例１－１９〕
＜液晶表示装置の作製＞
以下の手法によりカラーフィルタおよびそれを用いた液晶表示装置を作製し評価を行った。 [Example 1-19]
<Production of liquid crystal display device>
A color filter and a liquid crystal display device using the same were manufactured and evaluated by the following method.
＜赤色着色硬化性樹脂組成物Ｒの作製＞
　下記組成の成分を混合し、ホモジナイザーを用いて回転数３，０００ｒ．ｐ．ｍ．で３時間撹拌した。こうして得られた混合溶液に対して、更に０．３ｍｍφジルコニアビーズを用いたビーズ分散機ディスパーマット（ＧＥＴＺＭＡＮＮ社製）にて１２時間分散処理を行ない、その後更に、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー（株）製）を用いて、２０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／ｍｉｎとして分散処理を行なった。この分散処理を１０回繰り返し、顔料分散組成物を得た。 <Preparation of red colored curable resin composition R>
Ingredients having the following composition were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. For 3 hours. The mixed solution thus obtained was further subjected to a dispersion treatment for 12 hours using a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO-3000 with a decompression mechanism. Dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using -10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.
〔赤色顔料分散物組成〕
・Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４　　　　　　　　　　　　　　　　　　　　　７５部
・Ｐｉｇｍｅｎｔ　Ｒｅｄ　１７７　　　　　　　　　　　　　　　　　　　　　５０部
・ベンジルメタクリレート／メタクリル酸共重合体　　　　　　　　　　　　　　７０部
（共重合組成比７０／３０　　重量平均分子量３００００、酸価４０）
・プロピレングリコールモノメチルエーテルアセテート　　　　　　　　　　　８００部 [Red pigment dispersion composition]
Pigment Red 254 75 parts Pigment Red 177 50 parts Benzyl methacrylate / methacrylic acid copolymer 70 parts (copolymerization composition ratio 70/30 weight average molecular weight 30000, acid value 40)
・ Propylene glycol monomethyl ether acetate 800 parts
得られた顔料分散物にさらに下記組成の成分を添加し、赤色着色硬化性樹脂組成物Ｒを作製した。
〔赤色着色硬化性樹脂組成物Ｒ組成〕
・上記赤色顔料分散物　　　　　　　　　　　　　　　　　　　　　　　　　　１００部
・ベンジルメタクリレート／メタクリル酸（＝７０／３０［モル比］）共重合体（Ｍｗ：３０，０００）のプロピレングリコールモノメチルエーテルアセテート溶液（固形分５０％）　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　１２部
・重合性化合物１（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＤＰＨＡ）　　　　１２．１部
・光重合開始剤（２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾリル二量体）　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　３．１部
・４，４’－ビス（ジエチルアミノ）ベンゾフェノン（増感色素）　　　　　　４．２部
・２－メルカプトベンゾチアゾール（水素供与性化合物）　　　　　　　　　　２．１部
・重合禁止剤：ｐ－メトキシフェノール　　　　　　　　　　　　　　　　０．００１部
・フッソ系界面活性剤（商品名：Ｍｅｇａｆａｃ　Ｒ０８　ＤＩＣ（株）製）　０．５部
・プロピレングリコールモノメチルエーテルアセテート　　　　　　　　　　　　６０部 Components of the following composition were further added to the obtained pigment dispersion to prepare a red colored curable resin composition R.
[Red colored curable resin composition R composition]
・ 100 parts of the above red pigment dispersion ・ Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (Mw: 30,000) (solid content 50%) 12 parts Polymerizable compound 1 (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 12.1 parts. Photopolymerization initiator (2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer) 3.1 parts.4 , 4'-bis (diethylamino) benzophenone (sensitizing dye) 4.2 parts, 2-mercaptobenzothiazole (hydrogen donating compound) 2.1 parts, polymerization inhibitor: p-methoxyphenol 0.001 part, fluorine-based Surfactant (trade name: Megafac 08 manufactured by DIC (Ltd.)) 0.5 parts Propylene glycol monomethyl ether acetate 60 parts
＜緑色着色硬化性樹脂組成物Ｇの作製＞
　赤色着色硬化性樹脂組成物Ｒの作製において、Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４に代えてＰｉｇｍｅｎｔ　Ｇｒｅｅｎ　５８を１０３部、Ｐｉｇｍｅｎｔ　Ｒｅｄ　１７７に代えてＰｉｇｍｅｎｔ　Ｙｅｌｌｏｗ　１５０を１９部使用した他は同様にして、緑色着色硬化性樹脂組成物Ｇを作製した。 <Preparation of green colored curable resin composition G>
In the production of the red colored curable resin composition R, green colored curable resin was similarly used except that 103 parts of Pigment Green 58 were used instead of Pigment Red 254 and 19 parts of Pigment Yellow 150 were used instead of Pigment Red 177. Composition G was prepared.
＜黒色着色硬化性樹脂組成物Ｋの作製＞
　下記組成の混合物を調製し、赤色顔料分散物作製時と同様に分散処理を行って黒色顔料分散物を作製した。
〔黒色顔料分散物組成〕
・カーボンブラック（商品名：Ｎｉｐｅｘ３５、デグサジャパン（株）製）　１３．１部
・ポリマー（ベンジルメタクリレート／メタクリル酸＝７２／２８モル比のランダム共重合物、分子量３．７万）　　　　　　　　　　　　　　　　　　　　　　　　　６．７部
・プロピレングリコールモノメチルエーテルアセテート　　　　　　　　　　７９．１部
・分散剤（下記化合物）　　　　　　　　　　　　　　　　　　　　　　　　０．６５部 <Preparation of Black Colored Curable Resin Composition K>
A mixture having the following composition was prepared, and a dispersion treatment was performed in the same manner as in the preparation of the red pigment dispersion to prepare a black pigment dispersion.
[Black pigment dispersion composition]
Carbon black (trade name: Nippon 35, manufactured by Degussa Japan Co., Ltd.) 13.1 parts Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer, molecular weight 37,000) 6.7 parts Propylene glycol monomethyl ether acetate 79.1 partsDispersant (the following compound) 0.65 parts
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
　得られた黒色顔料分散組成物を用い、以下の組成で黒色着色硬化性樹脂組成物Ｋを調製した。
〔黒色着色硬化性樹脂組成物Ｋ組成〕
・上記黒色顔料分散物　　　　　　　　　　　　　　　　　　　　　　　　　　　２５部
・プロピレングリコールモノメチルエーテルアセテート　　　　　　　　　　　８．５部
・メチルエチルケトン　　　　　　　　　　　　　　　　　　　　　　　　　　　５３部
・バインダー（ポリマー（ベンジルメタクリレート／メタクリル酸＝７８／２２モル比のランダム共重合物、分子量３．８万）２７部とプロピレングリコールモノメチルエーテルアセテート７３部の混合物）　　　　　　　　　　　　　　　　　　　　　　　９．１部
・ヒドロキノンモノメチルエーテル　　　　　　　　　　　　　　　　　　０．００２部
・ＤＰＨＡ（日本化薬社製）　　　　　　　　　　　　　　　　　　　　　　　　１２部・２，４―ビス（トリクロロエチル）―６―［４’―（Ｎ，Ｎ－ビスエトキシカルボニルメチル）アミノ―３’―ブロモフェニル］―ｓ―トリアジン　　　　　　　　　０．１６部
・界面活性剤（下記化合物）のメチルエチルケトン３０質量％溶液　　　　０．０４２部 Using the obtained black pigment dispersion composition, a black colored curable resin composition K was prepared with the following composition.
[Black colored curable resin composition K composition]
-Black pigment dispersion 25 parts-Propylene glycol monomethyl ether acetate 8.5 parts-Methyl ethyl ketone 53 parts-Binder (Random copolymer of benzyl methacrylate / methacrylic acid = 78/22 molar ratio, molecular weight 38,000) A mixture of 27 parts and 73 parts of propylene glycol monomethyl ether acetate) 9.1 parts, hydroquinone monomethyl ether 0.002 parts, DPHA (manufactured by Nippon Kayaku Co., Ltd.) 12 parts, 2,4-bis (trichloroethyl) -6- [ 4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s-triazine 0.16 parts. Surfactant (the following compound) methyl ethyl ketone 30 % Solution of 0.042 parts
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000067
＜カラーフィルタの形成＞
＜ブラックマトリクスの形成＞
　無アルカリガラス基板を、ＵＶ洗浄装置で洗浄後、洗浄剤を用いてブラシ洗浄し、更に超純水で超音波洗浄した。該基板を１２０℃３分熱処理して表面状態を安定化させた後、該基板を冷却し２３℃に温調した。
　該基板にスリット状ノズルを有すガラス基板用コーター（エフ・エー・エス・アジア社製、商品名：ＭＨ－１６００）にて、前記の黒色着色硬化性樹脂組成物Ｋを塗布した。引き続きＶＣＤ（真空乾燥装置；東京応化工業（株）社製）で３０秒間、溶媒の一部を乾燥して塗布層の流動性を無くした後、１２０℃で３分間プリベークして膜厚２．４μｍの黒色硬化性樹脂層を得た。
　超高圧水銀灯を有すプロキシミティ型露光機（日立ハイテク電子エンジニアリング（株）社製）で、基板とマスク（画像パターンを有す石英露光マスク）を垂直に立てた状態で、露光マスク面と該硬化性樹脂層の間の距離を２００μｍに設定し、露光量３００ｍＪ／ｃｍ２でパターン露光した。 <Formation of color filter>
<Formation of black matrix>
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat treated at 120 ° C. for 3 minutes to stabilize the surface state, and then the substrate was cooled and adjusted to 23 ° C.
The black colored curable resin composition K was applied to the substrate using a glass substrate coater (trade name: MH-1600, manufactured by FS Asia Co., Ltd.) having a slit nozzle. Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm black curable resin layer was obtained.
In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the mask The distance between the curable resin layers was set to 200 μm, and pattern exposure was performed with an exposure amount of 300 mJ / cm 2 .
　次に、純水をシャワーノズルにて噴霧し、該黒色硬化性樹脂層の表面を均一に湿らせた後、ＫＯＨ系現像液（ＫＯＨ、ノニオン界面活性剤含有、商品名：ＣＤＫ－１、富士フイルムエレクトロニクスマテリアルズ社製）にて２３℃で８０秒、フラットノズル圧力０．０４ＭＰａでシャワー現像しパターニング画像を得た。引き続き、超純水を、超高圧洗浄ノズルにて９．８ＭＰａの圧力で噴射して残渣除去を行い、ブラック（Ｋ）の画像Ｋを得た。最後に２２０℃で３０分間熱処理し、ブラックマトリクスを形成した。 Next, pure water is sprayed with a shower nozzle to uniformly wet the surface of the black curable resin layer, and then a KOH developer (KOH, containing nonionic surfactant, trade names: CDK-1, Fuji) The film was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image K was obtained. Finally, heat treatment was performed at 220 ° C. for 30 minutes to form a black matrix.
＜ＲＧＢ画素の形成＞
　前記ブラックマトリクスを形成したガラス基板に、赤色着色硬化性樹脂組成物Ｒ、緑色着色硬化性樹脂組成物Ｇ、実施例１－１で作成した青色着色硬化性組成物を、それぞれ順にブラックマトリクス形成時と同様の工程にて積層およびパターニングし、ＲＧＢ３色画素のカラーフィルタを得た。このとき、ＲＧＢ各色の着色部膜厚は１．６μｍであった。 <Formation of RGB pixels>
When forming the black matrix, the red colored curable resin composition R, the green colored curable resin composition G, and the blue colored curable composition prepared in Example 1-1 were sequentially formed on the glass substrate on which the black matrix was formed. In the same process as above, lamination and patterning were performed to obtain a color filter of RGB three-color pixels. At this time, the thickness of the colored portion of each color of RGB was 1.6 μm.
＜ＩＴＯ電極の形成＞
　カラーフィルタが形成されたガラス基板をスパッタ装置に入れて、１００℃で１３００Å厚さのＩＴＯを全面真空蒸着した後、２４０℃で９０分間アニールしてＩＴＯを結晶化し、ＩＴＯ透明電極を形成した。 <Formation of ITO electrode>
The glass substrate on which the color filter was formed was placed in a sputtering apparatus, and 1300 mm thick ITO was vacuum-deposited at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO to form an ITO transparent electrode.
＜スペーサの形成＞
　特開２００４－２４０３３５号公報の［実施例１］に記載のスペーサ形成方法と同様の方法で、上記で作製したＩＴＯ透明電極上にスペーサを形成した。 <Spacer formation>
A spacer was formed on the ITO transparent electrode produced above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.
＜液晶配向制御用突起の形成＞
　下記のポジ型硬化性樹脂層用塗布液を用いて、前記スペーサを形成したＩＴＯ透明電極上に液晶配向制御用突起を形成した。
　但し、露光、現像、及び、ベーク工程は、以下の方法を用いた。
　所定のフォトマスクが硬化性樹脂層の表面から１００μｍの距離となるようにプロキシミティ露光機（日立ハイテク電子エンジニアリング株式会社製）を配置し、該フォトマスクを介して超高圧水銀灯により照射エネルギー１５０ｍＪ／ｃｍ２でプロキシミティ露光した。
　続いて、２．３８％テトラメチルアンモニウムヒドロキシド水溶液を、シャワー式現像装置にて３３℃で３０秒間基板に噴霧しながら現像した。こうして、硬化性樹脂層の不要部（露光部）を現像除去することにより、カラーフィルタ側基板上に、所望の形状にパターニングされた硬化性樹脂層よりなる液晶配向制御用突起が形成された液晶表示装置用基板を得た。
　次いで、該液晶配向制御用突起が形成された液晶表示装置用基板を２３０℃で３０分ベークすることにより、液晶表示装置用基板上に硬化された液晶配向制御用突起を形成した。 <Formation of projection for controlling liquid crystal alignment>
Using the following positive type curable resin layer coating solution, liquid crystal alignment control protrusions were formed on the ITO transparent electrode on which the spacers were formed.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the curable resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm 2 .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the curable resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusion made of the curable resin layer patterned into a desired shape is formed on the color filter side substrate. A display device substrate was obtained.
Next, the liquid crystal display device substrate on which the liquid crystal alignment control protrusions were formed was baked at 230 ° C. for 30 minutes to form cured liquid crystal alignment control protrusions on the liquid crystal display device substrate.
〔ポジ型硬化性樹脂層用塗布液処方〕
・ポジ型レジスト液（富士フイルムエレクトロニクスマテリアルズ（株）社製ＦＨ－２４１３Ｆ）　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　５３．０部
・メチルエチルケトン　　　　　　　　　　　　　　　　　　　　　　　　　４６．５部
・メガファックＦ－７８０Ｆ（ＤＩＣ（株）社製）　　　　　　　　　　　　０．０５部 [Coating liquid formulation for positive curable resin layer]
・ Positive resist solution (FH-2413F manufactured by Fujifilm Electronics Materials Co., Ltd.) 53.0 parts ・ Methyl ethyl ketone 46.5 parts ・ Megafac F-780F (manufactured by DIC Corporation) 0.05 parts
＜液晶表示装置の作製＞
　上記で得られた液晶表示装置用基板上に、さらにポリイミドよりなる配向膜を設けた。その後、カラーフィルタの画素群を取り囲むように周囲に設けられたブラックマトリックス外枠に相当する位置にエポキシ樹脂のシール剤を印刷すると共に、ＭＶＡモード用液晶を滴下し、対向基板と貼り合わせた後、貼り合わされた基板を熱処理してシール剤を硬化させた。
　このようにして得た液晶セルの両面に、（株）サンリツ社製の偏光板ＨＬＣ２－２５１８を貼り付けた。次いで、光源としてＬＥＤ光源（ＳＯＮＹ社製液晶テレビ、ＫＤＬ－４０ＺＸ１のバックライト光源）を前記偏光板が設けられた液晶セルの背面となる側に配置し、液晶表示装置（ＬＣＤ）とした。
　上記のようにして作成された液晶表示装置は、高いコントラストと輝度を持ち、表示装置として好適なものであった。なお、本実施例ではＭＶＡモード液晶表示装置での評価を行ったが、他のモードの液晶表示装置や、有機ＥＬディスプレイのカラーフィルタに本発明の着色硬化性組成物を用いても、同様に良好な画質を得られると思われる。 <Production of liquid crystal display device>
An alignment film made of polyimide was further provided on the liquid crystal display device substrate obtained above. After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant.
A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, an LED light source (a liquid crystal television manufactured by Sony Corporation, a backlight light source of KDL-40ZX1) was disposed as a light source on the side of the liquid crystal cell provided with the polarizing plate, thereby obtaining a liquid crystal display (LCD).
The liquid crystal display device produced as described above has high contrast and brightness, and is suitable as a display device. In this example, the MVA mode liquid crystal display device was evaluated. However, even when the colored curable composition of the present invention is used for a liquid crystal display device of another mode or a color filter of an organic EL display, the same applies. It seems that good image quality can be obtained.
［実施例２－１］
下記の各成分を混合、溶解し、着色硬化性組成物２－１を調製して評価を行なった。
・有機溶剤（プロピレングリコールモノメチルエーテルアセテート）　　　　　　２１部
・有機溶剤（ジエチレングリコールエチルメチルエーテル）　　　　　　　　　　２５部
・アルカリ可溶性樹脂１（アリルメタクリレート／メタクリル酸共重合体＝モル比７０／３０、重量平均分子量２６８００）　　　　　　　　　　　　　　　　　　　　　　１部
・ブロックイソシアネートＢ１（旭化成ケミカルズ(株)製、ＴＰＡ－Ｂ８０Ｘ）２．２部
・モノマー（Ｍ－１）　　　　　　　　　　　　　　　　　　　　　　　　　　３．３部
・重合性化合物１（日本化薬（株）製、ＫＡＹＡＲＡＤ　ＤＰＨＡ）　　　　　３．２部
・重合禁止剤（ｐ－メトキシフェノール）　　　　　　　　　　　　　　　０．００３部
・光重合開始剤１　（１－（Ｏ－アセチルオキシム）－１－［９－エチル－６－（チオフェノイル）－９Ｈ－カルバゾール－３－イル］プロパノン）　　　　　　　　　０．４部
・多官能ＳＨ化合物　Ｓ１　昭和電工（株）製　カレンズＭＴＢＤ１　　　　　０．４部
・密着改良剤（３－メタクリロキシプロピルトリメトキシシラン）　　　　　０．１５部
・フッ素系界面活性剤（ＤＩＣ社製　メガファックＦ－５５４、０．２％プロピレングリコールモノメチルエーテルアセテート溶液）　　　　　　　　　　　　　　　　５．５部
・青色顔料分散液（実施例１－１で用いた青色顔料分散液と同じもの、Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６分散液）　　　　　　　　　　　　　　　　　　　　　　　　２５部
・染料溶液１　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　６部
・染料溶液２　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　　２５部 [Example 2-1]
The following components were mixed and dissolved to prepare a colored curable composition 2-1, which was evaluated.
Organic solvent (propylene glycol monomethyl ether acetate) 21 parts Organic solvent (diethylene glycol ethyl methyl ether) 25 parts Alkali-soluble resin 1 (allyl methacrylate / methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 1 Part block isocyanate B1 (Asahi Kasei Chemicals Corporation, TPA-B80X) 2.2 parts monomer (M-1) 3.3 parts polymerizable compound 1 (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 3 2 parts ・ Polymerization inhibitor (p-methoxyphenol) 0.003 parts ・ Photopolymerization initiator 1 (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazole) 3-Il] propanone) 0 .4 parts ・ Polyfunctional SH compound S1 0.4 parts by Karenz MTBD1 manufactured by Showa Denko KK ・ 0.15 parts by adhesion improver (3-methacryloxypropyltrimethoxysilane) ・ Fluorosurfactant (Made by DIC) Fuchs F-554, 0.2% propylene glycol monomethyl ether acetate solution) 5.5 parts blue pigment dispersion (same as the blue pigment dispersion used in Example 1-1, Pigment Blue 15: 6 dispersion) 25 parts, dye solution 1 6 parts, dye solution 2 25 parts
　染料溶液１は下記の各成分を混合、溶解して作製した。
・有機溶剤１（プロピレングリコールモノメチルエーテルアセテート）　　　４４．６部
・特定染料（Ｂ）（Ｐ－２６）　　　　　　　　　　　　　　　　　　　　　　２．４部
　染料溶液２は下記の各成分を混合、溶解して作製した。
・有機溶剤１（プロピレングリコールモノメチルエーテルアセテート）　　　４８．０部
・特定染料（Ａ）（化合物１）　　　　　　　　　　　　　　　　　　　　　　２．６部
　染料溶液１には、特定染料（Ｂ）である（Ｐ－２６）が、染料溶液２には、特定染料（Ａ）である（化合物１）がそれぞれ含まれる。 The dye solution 1 was prepared by mixing and dissolving the following components.
Organic solvent 1 (propylene glycol monomethyl ether acetate) 44.6 parts Specific dye (B) (P-26) 2.4 parts Dye solution 2 was prepared by mixing and dissolving the following components.
・ Organic solvent 1 (propylene glycol monomethyl ether acetate) 48.0 parts ・ Specific dye (A) (compound 1) 2.6 parts In dye solution 1, specific dye (B) (P-26) is dye The solution 2 contains (Compound 1) which is the specific dye (A).
　得られた着色硬化性組成物２－１について、以下の評価を行なった。評価結果を表３に示す。 The following evaluation was performed on the obtained colored curable composition 2-1. The evaluation results are shown in Table 3.
（測定・評価）
－比誘電率の測定－
ａ）クロム被覆ガラス基板（１辺７５ｍｍ、クロム膜の厚さ０．３μｍ）上に、硬化後（ポストベーク後）の膜厚が３．０μｍになるように回転数を調整し、スピンコーターにて着色硬化性組成物２－１を塗布した。
ｂ）次いで、塗布膜が形成されたクロム被覆ガラス基板をホットプレート上で１００℃・１２０秒の条件でプリベークし、溶剤を乾燥させた。
ｃ）プリベーク後、２．５ｋＷの超高圧水銀灯を使用し、２００ｍＪ／ｃｍ２の露光量で塗布膜に光照射した。
ｄ）次いで、熱風循環式乾燥機にて、塗布膜が形成されたクロム被覆ガラス基板を１８０℃６０分の条件で加熱硬化（ポストベーク）し、試験片を作製した。
ｅ）ポストベーク後、試験片の角隅１ヶ所の塗膜を削り取り、クロム表面を露出させた。
ｆ）次いで、試験片の裏面に、銀ペーストをスピンコートし、風乾した。その後、表面のクロム露出面と裏面の銀ペースト塗布面とを前記銀ペーストで導通（接続）した。
ｇ）乾燥後、試験片の表塗膜面に対して真空蒸着装置（商品名：イオンスパッタＥ１０３０、日立（株）製）を用いて、図１に示すように、Ｐｔ・Ｐｄターゲット材で、試験片１上に蒸着厚みが約５０ｎｍの主電極２（内円）及びガード電極３（外円）を作製した。なお、試験片１上には、前記ｅ）において塗膜を削り取ったクロム表面４が露出している。
ｈ）電極作製後、試験片の電極のついていない部分の塗膜の厚みを触針式表面形状測定器（商品名：ＤＥＫＴＡＫ３、（株）アルバック製）で測定した。
ｉ）次いで、静電容量測定器（精密インピーダンスアナライザー４２９４Ａ、アジレント　テクノロジー（株）製）に誘電テストフィクスチャー１６４５１Ｂ及び電極を取り付け、更に前記ｇ）における試験片を装着して、１ｋＨｚ、０．５Ｖの交流電圧を印加したときの比誘電率ε’を測定した。評価結果を表３に示す。 (Measurement / Evaluation)
-Measurement of relative dielectric constant-
a) On a chrome-coated glass substrate (75 mm per side, chrome film thickness 0.3 μm), the rotation speed is adjusted so that the film thickness after curing (after post-baking) is 3.0 μm. Then, a colored curable composition 2-1 was applied.
b) Next, the chromium-coated glass substrate on which the coating film was formed was pre-baked on a hot plate at 100 ° C. for 120 seconds, and the solvent was dried.
c) After pre-baking, the coating film was irradiated with light at an exposure amount of 200 mJ / cm 2 using a 2.5 kW ultra-high pressure mercury lamp.
d) Next, the chromium-coated glass substrate on which the coating film was formed was heated and cured (post-baked) at 180 ° C. for 60 minutes using a hot air circulation dryer to prepare a test piece.
e) After post-baking, the coating film at one corner of the test piece was scraped to expose the chromium surface.
f) Next, a silver paste was spin-coated on the back surface of the test piece and air-dried. Thereafter, the chromium exposed surface on the front surface and the silver paste coated surface on the back surface were electrically connected (connected) with the silver paste.
g) After drying, using a vacuum vapor deposition apparatus (trade name: Ion Sputter E1030, manufactured by Hitachi, Ltd.) on the surface coating surface of the test piece, as shown in FIG. 1, with a Pt / Pd target material, A main electrode 2 (inner circle) and a guard electrode 3 (outer circle) having a deposition thickness of about 50 nm were prepared on the test piece 1. In addition, on the test piece 1, the chromium surface 4 from which the coating film has been removed in the above e) is exposed.
h) After electrode preparation, the thickness of the coating film of the test piece where no electrode was attached was measured with a stylus type surface shape measuring instrument (trade name: DEKTAK3, manufactured by ULVAC, Inc.).
i) Next, a dielectric test fixture 16451B and an electrode were attached to a capacitance measuring instrument (precision impedance analyzer 4294A, manufactured by Agilent Technologies), and the test piece in g) above was further attached, and 1 kHz, 0.5 V The relative dielectric constant ε ′ was measured when an AC voltage was applied. The evaluation results are shown in Table 3.
（評価基準）
Ａ：　比誘電率ε’＜３．０
Ｂ：　比誘電率ε’３．０～５．０
Ｃ：　比誘電率ε’＞５．０ (Evaluation criteria)
A: relative dielectric constant ε ′ <3.0
B: Relative permittivity ε′3.0 to 5.0
C: relative dielectric constant ε ′> 5.0
－剥離液耐性－
　以下の手順ａ）～ｅ）で試験片の膜厚みを測定して膨潤率を算出し、その算出値を、剥離液耐性を評価する指標とした。但し、剥離液耐性が悪いものは剥離液への浸漬時に、塗膜が剥離液中に溶解したり、基板から剥れたりして、膜厚を測定できないものがある。このようなものは「×」の評価とした。評価結果を表３に示す。 -Resistance to stripping solution-
In the following procedures a) to e), the film thickness of the test piece was measured to calculate the swelling ratio, and the calculated value was used as an index for evaluating the stripping solution resistance. However, those with poor stripping solution resistance cannot be measured for film thickness because the coating film dissolves in the stripping solution or peels off from the substrate when immersed in the stripping solution. Such a thing was evaluated as "x". The evaluation results are shown in Table 3.
ａ）前記〔比誘電率の測定〕のｄ）にて得た試験片の膜厚（ＦＴ０）を測定した。
ｂ）測定後、剥離液として、モノエタノールアミン（ＭＥＡ）とジメチルスルフォキシド（ＤＭＳＯ）との混合物（ＭＥＡ／ＤＭＳＯ＝７／３質量比）を用い、上記の試験片を剥離液に８０℃・１２０秒浸漬した。
ｃ）バットにＭＥＡ／ＤＭＳＯ＝７／３の液を満たし、前記ｂ）の浸漬後の試験片を更に漬け、その後、触針式表面形状測定器（商品名：ＤＥＫＴＡＫ３、（株）アルバック製）の試験片支持台に剥離液に表面を覆われた状態の試験片を載せて、塗膜厚み（ＦＴ１）を測定した（剥離液による膨潤状態の膜厚測定）。
ｄ）別のバットに純水を満たし、前記ｃ）において膨潤した試験片を浸漬し、１晩静置して塗膜に含まれる剥離液と水を置換した後、試験片を２００℃・３０分で乾燥し、再度塗膜厚（ＦＴ２）を測定した。
ｅ）上記により測定したＦＴ０、ＦＴ１、ＦＴ２を用いて、下記式から試験片の膨潤率及び膜減り率を算出し、下記基準に基づいて剥離液耐性を評価した。なお、（ＦＴ１－ＦＴ０）は、剥離液による見掛の膨潤を測定しているため、剥離液によって侵食された膜減り分（ＦＴ２－ＦＴ０）で補正し、真の膨潤率を算出した。
　真の膨潤率（％）＝１００×（ＦＴ１－ＦＴ２）／ＦＴ０
　膜減り率（％）＝１００×（ＦＴ２－ＦＴ０）／ＦＴ０ a) The film thickness (FT0) of the test piece obtained in d) of [Measurement of relative dielectric constant] was measured.
b) After measurement, a mixture of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO) (MEA / DMSO = 7/3 mass ratio) was used as the stripping solution, and the above test piece was used as the stripping solution at 80 ° C. -Soaked for 120 seconds.
c) Fill the bat with a solution of MEA / DMSO = 7/3, soak the test piece after dipping in b) above, and then stylus type surface shape measuring instrument (trade name: DEKTAK3, ULVAC, Inc.) A test piece having a surface covered with a stripping solution was placed on the test piece support, and the coating thickness (FT1) was measured (measurement of the film thickness in a swollen state with the stripping solution).
d) Fill another vat with pure water, immerse the test piece swollen in c) above, leave it overnight, and replace the stripping solution and water contained in the coating film. The coating thickness (FT2) was measured again.
e) Using FT0, FT1, and FT2 measured as described above, the swelling rate and film reduction rate of the test piece were calculated from the following formulas, and the stripping solution resistance was evaluated based on the following criteria. Since (FT1-FT0) was measured for apparent swelling due to the stripping solution, the true swelling ratio was calculated by correcting the film loss (FT2-FT0) eroded by the stripping solution.
True swelling ratio (%) = 100 × (FT1-FT2) / FT0
Film reduction rate (%) = 100 × (FT2-FT0) / FT0
（評価基準）
Ａ：　真の膨潤率≦４０％、膜減り率≦５％であり、剥離液耐性は良好であった。
Ｂ：　真の膨潤率≦４０％、膜減り率＞５％であり、剥離液耐性は許容の範囲内であった。
Ｃ：　塗膜が溶解又は剥離してしまい、剥離液耐性に劣っていた。 (Evaluation criteria)
A: True swelling rate ≦ 40%, film reduction rate ≦ 5%, and resistance to stripping solution was good.
B: True swelling rate ≦ 40%, film reduction rate> 5%, and resistance to stripping solution was within an allowable range.
C: The coating film was dissolved or peeled off, and the stripping solution resistance was poor.
［実施例２－２～２－４］
　実施例２－１で用いた特定染料Ａ（化合物１）を、化合物２～４に変更した以外は、実施例２－１と同様にして着色硬化性組成物２－２～２－４を調製し、実施例２－１と同様に評価した。評価結果は表３に示す。 [Examples 2-2 to 2-4]
Colored curable compositions 2-2 to 2-4 were prepared in the same manner as in Example 2-1, except that the specific dye A (compound 1) used in Example 2-1 was changed to compounds 2 to 4. Evaluation was performed in the same manner as in Example 2-1. The evaluation results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000068
Figure JPOXMLDOC01-appb-T000068
　表３より、本発明の特定染料Ａ及び特定染料Ｂの組合せからなる着色硬化性組成物は、ＣＯＡ用途のカラーフィルタに用いても好適な性能を示すことがわかった。 From Table 3, it was found that the colored curable composition comprising the combination of the specific dye A and the specific dye B of the present invention shows suitable performance even when used for a color filter for COA.
　日本出願２０１２－０８２２１２の開示はその全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosure of Japanese application 2012-082212 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

Claims (9)

  1. 　（Ａ）下記一般式（Ｉ－１）及び（Ｉ－２）で表される化合物からなる群より選択される１種以上の色素化合物と、（Ｂ）下記一般式（ＩＩ）で表されるポルフィリン化合物と、を含む着色化合物を含有する着色硬化性組成物。
    Figure JPOXMLDOC01-appb-C000001
    （前記一般式（Ｉ－１）において、Ｒ１、Ｒ２、Ｒ３、及びＲ４は、各々独立に、水素原子、炭素数１～１０の飽和炭化水素基、又は炭素数６～１０の芳香族炭化水素基を表す。Ｒ５は、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３Ｍ、－ＣＯ２Ｈ、－ＣＯ２Ｒ６、－ＳＯ３Ｒ６、－ＳＯ２ＮＨＲ８、又は－ＳＯ２ＮＲ８Ｒ９を表す。Ｒ６は、炭素数１～１０の飽和炭化水素基を表す。Ｒ８及びＲ９は、各々独立に、水素原子、炭素数１～１０の直鎖又は分岐のアルキル基、炭素数３～３０のシクロアルキル基、炭素数６～１０の芳香族炭化水素基、又は炭素数５～１０の芳香族複素環基を表し、Ｒ８とＲ９とは互いに結合して炭素数１～１０の複素環を形成してもよい。Ｍは、ナトリウム原子又はカリウム原子を表す。ｍは、０～５の整数を表し、ｍが２以上の整数である場合、複数のＲ５は同一でも異なっていてもよい。ｎ１、ｎ２、ｎ３、及びｎ４は、各々独立に０又は１を表す。Ｘは、ハロゲン原子を表す。ａは、０又は１の整数を表す。ただし、ｎ１～ｎ４の全てが１を表しかつＲ５が－ＳＯ３ －以外の基を表す場合はａ＝１であり、ｎ１～ｎ４の少なくとも１つが０を表す場合はａ＝０である。）
    Figure JPOXMLDOC01-appb-C000002
    （前記一般式（Ｉ－２）において、Ｒ１０１、Ｒ１０２、Ｒ１０３、Ｒ１０４、Ｒ１０５、及びＲ１０６は、各々独立に、水素原子、炭素数１～１０の飽和炭化水素基、又は炭素数６～１０の芳香族炭化水素基を表す。Ｒ１０７及びＲ１０８は、各々独立に、水素原子又は炭素数４～８の飽和炭化水素基を表す、あるいは、Ｒ１０７とＲ１０８は互いに結合して芳香族炭化水素環を形成している。Ｒ１０９は、水素原子又は炭素数１～１０の飽和炭化水素基を表す。Ｘは、ハロゲン原子、ＢＦ４、ＰＦ６、ＣｌＯ４、Ｎ（ＳＯ２ＣＦ３）２、又はＡｒＳＯ３を表し、Ａｒは、炭素数６～１０の芳香族炭化水素基を表す。ａは、０又は１の整数を表す。）
    Figure JPOXMLDOC01-appb-C000003
     （前記一般式（ＩＩ）中、Ｚ１、Ｚ２、Ｚ３及びＺ４はすべてがＮを表すか、若しくは、Ｚ１とＺ３、Ｚ２とＺ４のいずれか１組が双方ともにＮを表し、他の一組が双方ともにＣ－Ｒを表し、Ｒは、各々独立に水素原子、アルキル基、又はアリール基を表す。Ａ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７及びＡ８は各々独立にアルキル基、アルケニル基、アリール基、アルコキシ基、アルキルチオ基、アリールオキシ基、アリールチオ基、ハロゲン原子、ヒドロキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アミノ基、カルバモイル基、スルファモイル基、アシル基、シリルオキシ基、シアノ基、ニトロ基、又はヘテロ環基を表す。Ａ１とＡ２、Ａ３とＡ４、Ａ５とＡ６、及びＡ７とＡ８は、各々互いに結合して環構造を形成してもよいが、これらのうち少なくとも１組は環構造を形成しない。Ｍは２価の金属原子、又は金属原子を含む２価の原子団を表す。     (A) one or more dye compounds selected from the group consisting of compounds represented by the following general formulas (I-1) and (I-2); and (B) represented by the following general formula (II): A colored curable composition containing a coloring compound comprising a porphyrin compound.
    Figure JPOXMLDOC01-appb-C000001
    (In the general formula (I-1), R 1 , R 2 , R 3 , and R 4 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or a group having 6 to 10 carbon atoms. R 5 represents an aromatic hydrocarbon group, R 5 represents —SO 3 − , —SO 3 H, —SO 3 M, —CO 2 H, —CO 2 R 6 , —SO 3 R 6 , —SO 2 NHR 8 , Or —SO 2 NR 8 R 9 , where R 6 represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and R 8 and R 9 each independently represent a hydrogen atom or a straight chain having 1 to 10 carbon atoms. Or a branched alkyl group, a cycloalkyl group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic heterocyclic group having 5 to 10 carbon atoms, and R 8 and R 9 are They may combine with each other to form a heterocyclic ring having 1 to 10 carbon atoms, and M represents a sodium atom or a potassium atom. Represents an integer of 0 to 5, when m is an integer of 2 or more, the plurality of R 5 may be the same or different .n1, n2, n3, and n4 are each independently 0 or 1 X represents a halogen atom, a represents an integer of 0 or 1, provided that when n1 to n4 all represent 1 and R 5 represents a group other than —SO 3 — , a = 1 And when at least one of n1 to n4 represents 0, a = 0.)
    Figure JPOXMLDOC01-appb-C000002
    (In the general formula (I-2), R 101 , R 102 , R 103 , R 104 , R 105 , and R 106 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or Represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, R 107 and R 108 each independently represent a hydrogen atom or a saturated hydrocarbon group having 4 to 8 carbon atoms, or R 107 and R 108 are R 109 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, and X represents a halogen atom, BF 4 , PF 6 , ClO 4 , N (SO 2 CF 3 ) 2 or ArSO 3 , Ar represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, and a represents an integer of 0 or 1.)
    Figure JPOXMLDOC01-appb-C000003
     (In the general formula (II), Z 1 , Z 2 , Z 3 and Z 4 are all N, or any one of Z 1 and Z 3 , Z 2 and Z 4 is N Each of the other groups represents C—R, each R independently representing a hydrogen atom, an alkyl group, or an aryl group, A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 and A 8 are each independently an alkyl group, alkenyl group, aryl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, halogen atom, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group Carbamoyl group, sulfamoyl group, acyl group, silyloxy group, cyano group, nitro group, or heterocyclic group, A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 Each May be bonded together to form a ring structure, at least one pair of these do not form a ring structure .M represents a divalent atomic group containing a divalent metal atom or a metal atom.
  2. 　前記（Ｂ）一般式（ＩＩ）で表される化合物が、下記一般式（ＩＩ－２）で表される化合物である請求項１に記載の着色硬化性組成物。
    Figure JPOXMLDOC01-appb-C000004
     （前記一般式（ＩＩ－２）中、Ａ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７、Ａ８及びＭは、一般式（ＩＩ）におけるＡ１、Ａ２、Ａ３、Ａ４、Ａ５、Ａ６、Ａ７、Ａ８及びＭと各々同義である。）     The colored curable composition according to claim 1, wherein the compound represented by the general formula (II) is a compound represented by the following general formula (II-2).
    Figure JPOXMLDOC01-appb-C000004
     (In the general formula (II-2), A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M are the same as A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 and M are respectively synonymous.)
  3. 　さらに、（Ｃ）重合性化合物、及び（Ｄ）光重合開始剤を含有する請求項１又は請求項２に記載の着色硬化性組成物。 The colored curable composition according to claim 1 or 2, further comprising (C) a polymerizable compound and (D) a photopolymerization initiator.
  4. 　前記（Ｂ）一般式（ＩＩ）で表される化合物の含有量が、前記着色化合物の総量に対して０．１質量％以上５０質量％以下である請求項１～請求項３のいずれか１項に記載の着色硬化性組成物。 The content of the compound represented by (B) the general formula (II) is from 0.1% by mass to 50% by mass with respect to the total amount of the colored compounds. The colored curable composition according to Item.
  5. 　前記一般式（ＩＩ）で表される化合物中、Ａ１とＡ２、Ａ３とＡ４、Ａ５とＡ６、及びＡ７とＡ８のいずれもが環構造を形成していない請求項１～請求項４のいずれか１項に記載の着色硬化性組成物。 In the compound represented by the general formula (II), none of A 1 and A 2 , A 3 and A 4 , A 5 and A 6 , and A 7 and A 8 form a ring structure. The colored curable composition according to any one of claims 1 to 4.
  6. 　前記着色化合物の総含有量が、着色硬化性組成物の全固形分に対して、０．２質量％以上５０質量％以下である請求項１～請求項５のいずれか１項に記載の着色硬化性組成物。 The coloring according to any one of claims 1 to 5, wherein the total content of the coloring compound is 0.2% by mass or more and 50% by mass or less based on the total solid content of the colored curable composition. Curable composition.
  7. 　請求項１～請求項６のいずれか１項に記載の着色硬化性組成物を硬化して得られた着色膜を備えるカラーフィルタ。 A color filter comprising a colored film obtained by curing the colored curable composition according to any one of claims 1 to 6.
  8. 　請求項１～請求項６のいずれか１項に記載の着色硬化性組成物を、支持体上に付与して着色層を形成する着色層形成工程と、形成された着色層をパターン様に露光する露光工程と、露光後の着色層を現像して着色パターンを形成する現像工程と、を有するカラーフィルタの製造方法。 A colored layer forming step of forming a colored layer by applying the colored curable composition according to any one of claims 1 to 6 on a support, and exposing the formed colored layer in a pattern A method for producing a color filter, comprising: an exposing step for developing; and a developing step for developing a colored layer after exposure to form a colored pattern.
  9. 　請求項７に記載のカラーフィルタ又は請求項８に記載の製造方法により得られたカラーフィルタを具備してなる表示装置。 A display device comprising the color filter according to claim 7 or the color filter obtained by the production method according to claim 8.
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