Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B57/00—Other synthetic dyes of known constitution
  • C09B57/02—Coumarine dyes
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/133509—Filters, e.g. light shielding masks
  • G02F1/133514—Colour filters
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
  • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • 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
  • G03F7/075—Silicon-containing 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B47/00—Porphines; Azaporphines
  • C09B47/04—Phthalocyanines abbreviation: Pc
  • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
  • C09B47/10—Obtaining compounds having halogen atoms directly bound to the phthalocyanine skeleton

Definitions

• the present invention relates to a compound, a colorant containing the compound, a colored curable resin composition, and the like.
• Dyes are used for color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, ink jets, and the like.
• a dye coumarin 6 represented by the following formula is known.
• the present invention includes the following inventions. [1] A compound represented by the formula (Z).
• R 1 and R 2 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a group containing an acryloyl group, or a group containing a methacryloyl group. Or represents a group containing a silicon atom.
• R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a nitro group, or a carbon number of 1 to 20
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is a group containing an acryloyl group, a group containing a methacryloyl group, or It is a group containing a silicon atom.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is a group containing an acryloyl group, a group containing a methacryloyl group, or It is a group containing a silicon atom.
• Z1 The compound according to [1], wherein the group containing a silicon atom is a group represented by the formula (Z1).
• R 11A represents a single bond or an alkanediyl group having 1 to 10 carbon atoms
• —CH 2 — contained in the alkanediyl group represents —O—, —CO—, —NR 10 —, — OCO—, —COO—, —OCONH—, —CONH— or —NHCO—
• the hydrogen atom contained in the alkanediyl group may have a hydroxyl group of 1 to 4 carbon atoms.
• the alkyl group may be substituted.
• R 10 represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
• R 12A , R 13A and R 14A each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. * Represents a bond with a nitrogen atom or a carbon atom.
• the compound according to [1] or [2], wherein the group containing an acryloyl group or the group containing a methacryloyl group is a group represented by the formula (Z2).
• R 15A represents an alkanediyl group having 1 to 10 carbon atoms
• —CH 2 — contained in the alkanediyl group represents —O—, —CO—, —NR 11 —, —OCO—
• the hydrogen atom contained in the alkanediyl group may be substituted with —COO—, —OCONH—, —CONH— or —NHCO—, and the alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group May be substituted.
• R 11 represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
• R 16A represents an acryloyl group or a methacryloyl group.
• a colorant comprising the compound according to any one of [1] to [3].
• the green pigment is at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment.
• the green pigment is at least one selected from the group consisting of a chlorinated copper phthalocyanine pigment, a brominated copper phthalocyanine pigment, and a brominated zinc phthalocyanine pigment.
• the green pigment is C.I. I. Pigment green 36 and C.I. I.
• the colorant according to any one of [5] to [7], which is at least one selected from the group consisting of CI Pigment Green 58.
• a colored curable resin composition comprising the colorant, resin, polymerizable compound and polymerization initiator according to any one of [4] to [8].
• a liquid crystal display device including the color filter according to [10].
• R 1 and R 2 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a group containing an acryloyl group, or a group containing a methacryloyl group. Or represents a group containing a silicon atom.
• R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, a nitro group, or a carbon number of 1 to 20
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is a group containing an acryloyl group, a group containing a methacryloyl group, or It is a group containing a silicon atom.
• Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 1 and R 2 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group.
• a linear alkyl group having 1 to 20 carbon atoms such as n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group and icosyl group; isopropyl group A branched alkyl group having 3 to 20 carbon atoms such as isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; alkyl group having 1 to 20 carbon atoms such as Examples thereof include alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.
• Examples of the aryl group represented by R 1 and R 2 include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2, Alkyl such as 5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group Examples thereof include a phenyl group which may be substituted, preferably a tolyl group or a dimethylphenyl group.
• R 1 and R 2 are each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 5 to 10 carbon atoms, An ethyl group or 2-ethylhexyl group is more preferable, and an ethyl group is still more preferable.
• * —NR 1 R 2 (* represents a bond to a carbon atom) is preferably a group represented by the following formula.
• Examples of the alkyl group having 1 to 20 carbon atoms represented by R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 include a methyl group, ethyl group, n-propyl group, isopropyl Group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and methylcyclohexyl group Is mentioned.
• Examples of the alkoxy group having 1 to 20 carbon atoms represented by R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, Examples include a pentyloxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group.
• Examples of the halogen atom represented by R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 include a fluorine atom, a chlorine atom and a bromine atom.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is a group containing an acryloyl group, a group containing a methacryloyl group, or It is a group containing a silicon atom.
• a group containing an acryloyl group or a group containing a methacryloyl group represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 is a group structure.
• the unit means a group having at least one acryloyl group or methacryloyl group.
• the number of carbon atoms of the group containing an acryloyl group is usually 3 to 16, preferably 3 to 12, and more preferably 3 to 8.
• the number of carbon atoms of the group containing a methacryloyl group is usually 4 to 17, preferably 4 to 13, and more preferably 4 to 9.
• the group containing an acryloyl group is preferably a group containing an acryloyloxy group.
• the group containing a methacryloyl group is preferably a group containing a methacryloyloxy group.
• the group containing an acryloyl group or the group containing a methacryloyl group is preferably a group represented by the formula (Z2).
• R 15A represents an alkanediyl group having 1 to 10 carbon atoms
• —CH 2 — contained in the alkanediyl group represents —O—, —CO—, —NR 11 —, —OCO—
• the hydrogen atom contained in the alkanediyl group may be substituted with —COO—, —OCONH—, —CONH— or —NHCO—, and the alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group May be substituted.
• R 11 represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
• R 16A represents an acryloyl group or a methacryloyl group. * Represents a bond with a nitrogen atom or a carbon atom.
• Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R 15A include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene group, isobutylene group, 2-methyltrimethyl group.
• Examples include a methylene group, an isopentylene group, an isohexylene group, an isooctylene group, and a 2-ethylhexylene group, preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.
• the alkanediyl group having 1 to 10 carbon atoms represented by R 15A is preferably a group in which —CH 2 — contained in the alkanediyl group is substituted with —O—.
• the number of —O— in R 15A is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. At least one of the —O— may be bonded to R 16A .
• -CH 2 - a nitrogen atom or a bond carbon atoms * -CH 2 of the - is, -O -, - CO -, - NR 11 -, - OCO -, - COO -, - OCONH -, - It is preferably not substituted with CONH- and -NHCO-.
• the alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
• a methyl group, an ethyl group, a propyl group or a butyl group is preferable, and an ethyl group is more preferable.
• Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 11 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group.
• An alkyl group having 1 to 20 carbon atoms such as a group, dodecyl group, hexadecyl group, icosyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; Examples thereof include alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.
• R 11 is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a methyl group or a hydrogen atom.
• Examples of the group containing an acryloyl group or a methacryloyl group include a group represented by (ii-1) to a group represented by (ii-42), preferably a group represented by (ii-1) A group represented by (ii-8) and a group represented by (ii-13) to a group represented by (ii-22), more preferably a group represented by (ii-1) to ( a group represented by ii-8), more preferably a group represented by (ii-1) or a group represented by (ii-5).
• * represents a bond.
• the group containing a silicon atom represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 includes a silicon atom as a component of the group. Means group.
• the number of carbon atoms of the group containing a silicon atom is usually 1 to 30, preferably 1 to 20, and more preferably 1 to 10.
• the group containing a silicon atom is preferably a group represented by the formula (Z1).
• R 11A represents a single bond or an alkanediyl group having 1 to 10 carbon atoms
• —CH 2 — contained in the alkanediyl group represents —O—, —CO—, —NR 10 —, — OCO—, —COO—, —OCONH—, —CONH— or —NHCO—
• the hydrogen atom contained in the alkanediyl group may have a hydroxyl group of 1 to 4 carbon atoms.
• the alkyl group may be substituted.
• R 10 represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
• R 12A , R 13A and R 14A each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. * Represents a bond with a nitrogen atom or a carbon atom. ]
• Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R 11A include the same as the alkanediyl group having 1 to 10 carbon atoms represented by R 15A .
• R 11A is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.
• Examples of the alkyl group having 1 to 4 carbon atoms that may replace the hydrogen atom of the alkanediyl group of R 11A include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a tert group. -Butoxy group.
• Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 10 include the same as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R 11 .
• Examples of the alkyl group having 1 to 4 carbon atoms represented by R 12A , R 13A and R 14A include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Group, cyclopropyl group and cyclobutyl group.
• Examples of the alkoxy group having 1 to 4 carbon atoms represented by R 12A , R 13A and R 14A include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group and a tert-butoxy group.
• R 12A , R 13A and R 14A are preferably all the same group.
• R 12A , R 13A and R 14A are each independently preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and an alkyl group having 1 to 2 carbon atoms or 1 carbon atom An alkoxy group of ⁇ 2 is more preferred, and a methyl group is still more preferred.
• Examples of the group containing a silicon atom include the groups described below. Examples of the group in which R 11A is not a single bond or —CH 2 — contained in R 11A are substituted include the groups shown below (* represents a bond).
• Examples of the group in which —CH 2 — contained in R 11A is substituted with —O— include the groups shown below (* represents a bond).
• Examples of the group in which —CH 2 — contained in R 11A is substituted with —CO— include the groups shown below (* represents a bond).
• the group in which —CH 2 — contained in R 11A is substituted with —NR 10 — is preferably —NH—, —NCH 3 —, —NC 2 H 5 —, and preferred groups are the groups shown below: (* Represents a bond).
• Examples of the group in which —CH 2 — contained in R 11A is substituted with —OCO— include the groups shown below (* represents a bond).
• Examples of the group in which —CH 2 — contained in R 11A is substituted with —COO— include the groups shown below (* represents a bond).
• Examples of the group in which —CH 2 — contained in R 11A is substituted with —OCONH— include the following groups (* represents a bond).
• Examples of the group in which —CH 2 — contained in R 11A is substituted with —CONH— include the groups shown below (* represents a bond).
• Examples of the group in which —CH 2 — contained in R 11A is substituted with —NHCO— include the groups shown below (* represents a bond).
• Examples of the group in which the hydrogen atom contained in the alkanediyl group contained in R 11A may be substituted with an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group include the following groups: (* Represents a bond).
• the group containing a silicon atom is represented by the formula (Z1) in which —CH 2 — contained in the alkanediyl group represented by R 11A is substituted with —OCO—, —COO— or —OCONH—.
• a group represented by the formula (Z1) in which —CH 2 — contained in the alkanediyl group represented by R 11A is substituted with —COO— is more preferred.
• the group containing a silicon atom is preferably a group represented below.
• R 3 , R 4 , R 5 and R 6 are each independently preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. More preferably, it is more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
• R 7 , R 8 , R 9 and R 10 are each independently preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a carboxyl group, and preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or a carboxyl group. It is more preferably a group, and further preferably a hydrogen atom or a carboxyl group.
• R 7 , R 8 , R 9 and R 10 is a group containing an acryloyl group, a group containing a methacryloyl group or a group containing a silicon atom
• R 7 , R 8 , R 9 and R It is preferable that any one of 10 is a group containing an acryloyl group, a group containing a methacryloyl group, or a group containing a silicon atom.
• the at least one of R 8 and R 9, a group containing an acryloyl group is preferably a group containing a group or a silicon atom containing methacryloyl group
• R 7 and R 10 are hydrogen atoms
• the compound (Z) include a compound represented by the formula (Z-1) to a compound represented by the formula (Z-56).
• the reaction temperature is preferably 0 ° C. to 200 ° C., more preferably 100 ° C. to 150 ° C.
• the reaction time is preferably 1 hour to 24 hours, more preferably 8 hours to 16 hours.
• the solvent include methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, and N-methylpyrrolidone, and 1-pentanol is preferable.
• R 1 to R 4 and R 6 to R 10 each have the same meaning as described above.
• the amount of the compound represented by the formula (2-A) to be used is preferably 1 mol to 10 mol, more preferably 1 to 5 mol, relative to 1 mol of the compound represented by the formula (2-B). And more preferably 1 mole.
• the amount of ethyl cyanoacetate to be used is preferably 1 to 10 mol, more preferably 1 to 5 mol, still more preferably 1 mol with respect to 1 mol of the compound represented by the formula (2-B). It is.
• the amount of benzoic acid to be used is preferably 0.1 mol to 3 mol, more preferably 0.3 to 0.4 mol, per 1 mol of the compound represented by the formula (2-B).
• Examples of the method for obtaining the compound represented by the formula (Z), which is the target compound, from the reaction mixture include a method of appropriately adjusting the temperature of the reaction mixture to precipitate crystals and collecting the crystals by filtration.
• the crystals collected by filtration were water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, N, N-dimethylformamide. It is preferable to wash with a solvent such as N-methylpyrrolidone or a mixture thereof and then dry. Moreover, you may refine
• the compound (Z) in which R 9 is a group containing a silicon atom can be obtained by reacting a compound represented by the formula (z5a) with a compound represented by the formula (z6).
• the compound represented by the formula (z5a) can be produced by diazo coupling a compound represented by the formula (2-A) and a compound represented by the formula (z4a).
• the compound (Z) in which R 8 is a group containing a silicon atom can be obtained by reacting a compound represented by the formula (z5b) with a compound represented by the formula (z6).
• the compound represented by the formula (z5b) can be produced by diazo coupling the compound represented by the formula (2-A) and the compound represented by the formula (z4b).
• the compound represented by the formula (z5a) and the compound represented by the formula (z5b) may be collectively referred to as a compound represented by the formula (z5).
• R 113 represents a divalent linking group.
• R 114 and R 115 each independently represent a hydrophilic group.
• R 116 represents a group containing a silicon atom.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 represent the same meaning as described above.
• Examples of the divalent linking group represented by R 113 include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene group, isobutylene group, 2-methyltrimethylene group, isopentylene. And an alkanediyl group having 1 to 10 carbon atoms such as an isohexylene group, an isooctylene group and a 2-ethylhexylene group.
• R 10 represents the same meaning as described above.
• Examples of the hydrophilic group represented by R 114 and R 115 include a hydroxy group and a carboxy group. However, R 114 and R 115 do not represent the same group, and it is preferable that R 114 is a carboxyl group and R 115 is a hydroxyl group.
• the group containing a silicon atom represented by R 116 represents a group containing a silicon atom as a component of the group, and is preferably a group represented by the formula (Z1).
• R 11A , R 12A , R 13A and R 14A represent the same meaning as described above.
• * represents a bond to R 115.
• a group represented by * —R 113 —R 116 (* represents a bond to a carbon atom) corresponds to R 8 and R 9 in the compound (Z).
• the reaction between the compound represented by the formula (z5) and the compound represented by the formula (z6) is preferably performed in the presence of a halogenated solvent such as chloroform.
• the reaction temperature is preferably ⁇ 10 ° C. to 100 ° C., more preferably 0 ° C. to 50 ° C.
• the reaction time is preferably 1 to 12 hours, more preferably 1 to 4 hours.
• the usage-amount of the compound represented by a formula (z6) is 1 mol or more and 8 mol or less normally with respect to 1 mol of compounds represented by a formula (z5), Preferably they are 1 mol or more and 4 mol or less.
• an acidic catalyst examples include mineral acids such as sulfuric acid and hydrochloric acid.
• the amount of these catalysts to be used is arbitrary, but is preferably 0.01 to 4 mol, more preferably 0.8 to 2 mol, relative to 1 mol of the compound represented by the formula (z6).
• Examples of the method for obtaining the target compound of the present invention from the reaction mixture include a method in which the reaction mixture is mixed with an acid (for example, acetic acid) and water, and the precipitated crystals are collected by filtration.
• the acid is preferably prepared by preparing an aqueous solution of the acid in advance, and then adding the reaction mixture to the aqueous solution.
• the temperature when adding the reaction mixture is usually 10 ° C. or higher and 50 ° C. or lower, preferably 20 ° C. or higher and 50 ° C. or lower, more preferably 20 ° C. or higher and 30 ° C. or lower.
• After adding the reaction mixture to the aqueous acid solution it is preferable to stir at the same temperature for about 0.5 to 2 hours.
• the crystal collected by filtration is preferably washed with water or the like and then dried. Moreover, you may refine
• the compound (Z) in which R 9 is a group containing an acryloyl group or a group containing a methacryloyl group is obtained by reacting a compound represented by the formula (z8a) with a compound represented by the formula (z9).
• the compound represented by the formula (z8a) can be produced by reacting the compound represented by the formula (2-A) with the compound represented by the formula (z7a).
• the compound (Z) in which R 9 is a group containing an acryloyl group or a group containing a methacryloyl group can be obtained by reacting a compound represented by the formula (z8b) with a compound represented by the formula (z9). it can.
• the compound represented by the formula (z8b) can be produced by reacting the compound represented by the formula (2-A) with the compound represented by the formula (z7b). Note that in this specification, the compound represented by the formula (z8a) and the compound represented by the formula (z8b) may be collectively referred to as a compound represented by the formula (z8).
• R 111 represents a divalent linking group.
• R 110 represents a group containing an acryloyl group or a group containing a methacryloyl group.
• R 112 represents a halogen atom.
• R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 represent the same meaning as described above.
• Examples of the divalent linking group represented by R 111 include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, isopropylene group, isobutylene group, 2-methyltrimethylene group, isopentylene. And an alkanediyl group having 1 to 10 carbon atoms such as an isohexylene group, an isooctylene group and a 2-ethylhexylene group.
• R 11 represents the same meaning as described above.
• examples of the halogen atom represented by R 112 include a chlorine atom and a bromine atom.
• the group containing an acryloyl group or a group containing a methacryloyl group represented by R 110 include a group having at least one acryloyl group or methacryloyl group as a structural unit of the group.
• a group represented by * —R 111 —R 110 (* represents a bond to a carbon atom) corresponds to R 8 and R 9 in the compound (Z).
• the reaction between the compound represented by the formula (z8) and the compound represented by the formula (z9) is preferably performed in the presence of a halogenated solvent such as chloroform.
• the reaction temperature is preferably ⁇ 10 ° C. to 100 ° C., more preferably 0 ° C. to 50 ° C.
• the reaction time is preferably 1 to 12 hours, more preferably 1 to 4 hours.
• the usage-amount of the compound represented by a formula (z9) is 1 mol or more and 8 mol or less normally with respect to 1 mol of compounds represented by a formula (z8), Preferably they are 1 mol or more and 4 mol or less.
• an acidic catalyst examples include mineral acids such as sulfuric acid and hydrochloric acid.
• the amount of these catalysts to be used is arbitrary, but is preferably 0.01 to 4 mol, more preferably 0.8 to 2 mol, relative to 1 mol of the compound represented by the formula (z9).
• Examples of the method for obtaining the compound of the present invention that is the target compound from the reaction mixture include the same methods as those for obtaining the compound (Z) in which R 8 or R 9 is a group containing a silicon atom.
• the compound (Z) of the present invention can be used as a dye.
• the colored curable resin composition of the present invention includes a colorant (A) containing the compound (Z), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
• a colorant (A) containing the compound (Z), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
• the colorant (A) may use a dye other than the compound (Z) or a green pigment (P).
• the colored curable resin composition of the present invention preferably further contains at least one selected from the group consisting of a solvent (E) and a leveling agent (F).
• the colored curable resin composition of the present invention may further contain a polymerization initiation assistant (D1).
• the compound illustrated as each component can be used individually or in combination of multiple types.
• a yellow dye or a red dye is preferable, and a yellow dye is particularly preferable.
• yellow dyes include dyes having a pyridone skeleton.
• halogenated copper phthalocyanine pigments such as fluorinated copper phthalocyanine pigments, chlorinated copper phthalocyanine pigments, brominated copper phthalocyanine pigments; fluorinated zinc phthalocyanine pigments, chlorinated zinc phthalocyanine pigments, brominated zinc phthalocyanine pigments Zinc halide phthalocyanine pigments such as C.I. I. And green pigments such as CI Pigment Green 7, 10, 15, 25, 36, 47, and 58.
• the green pigment (P) is preferably at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment, More preferably, it is at least one selected from the group consisting of chlorinated copper phthalocyanine pigments, brominated copper phthalocyanine pigments and brominated zinc phthalocyanine pigments, C. I. More preferably, it is at least one selected from the group consisting of CI Pigment Green 36 and 58.
• the green pigment (P) is preferably a halogenated copper phthalocyanine pigment, more preferably at least one selected from the group consisting of a chlorinated copper phthalocyanine pigment and a brominated copper phthalocyanine pigment. , C.I. I. Pigment Green 36 is more preferable.
• the colorant (A) may contain other pigments, for example, Specifically, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 180, 194, 214; C. I. And blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, and the like.
• the content of the compound (Z) is preferably 0.01% by mass or more and 90% by mass or less, more preferably 0.1% by mass or more and 80% by mass or less, with respect to the total amount of the colorant (A). More preferably, it is 1 mass% or more and 65 mass% or less, More preferably, it is 2 mass% or more and 60 mass% or less.
• the content is preferably 10% by mass or more and 99.99% by mass or less, and more preferably 20% by mass or more and 99.9% by mass with respect to the total amount of the colorant (A).
• the content ratio of the compound (Z) and the green pigment (P) [compound (Z): green pigment (P)] is preferably 1:99 to 50:50, more preferably 2:98 to 30:70, more preferably 3:97 to 20:80.
• the total content of the compound (Z) and the green pigment (P) is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 50% by mass or more with respect to the total amount of the colorant (A). Further, it is more preferably 70% by mass or more, particularly preferably 80% by mass or more, and the upper limit is 100% by mass or less, and may be 95% by mass or less.
• the content of the colorant (A) is usually 1% by mass or more and 99% by mass or less, preferably 2% by mass or more and 90% by mass or less, with respect to the total solid content of the colored curable resin composition. More preferably, it is 3 mass% or more and 80 mass% or less, More preferably, it is 5 mass% or more and 70 mass% or less, More preferably, it is 5 mass% or more and 60 mass% or less, Most preferably, it is 5 mass%. It is 50 mass% or less. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.
• total amount of solids refers to the total amount of components obtained by removing the solvent (E) from the colored curable resin composition of the present invention.
• the total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.
• the resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and an addition polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. More preferred.
• examples of such resins include the following resins [K1] to [K6].
• Resin [K1] At least one (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), a cyclic ether structure having 2 to 4 carbon atoms, A copolymer with a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”); Resin [K2] (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) In some cases) Resin [K3] Copolymer of (a) and (c); Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c); Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c); Resin [K6] A
• (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid; Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbic
• (B) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond.
• (B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
• (meth) acrylic acid represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.
• Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond.
• Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.
• Examples of (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).
• (B1-1) includes glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, ⁇ -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, ⁇ -methyl-o-vinylbenzyl glycidyl ether, ⁇ -methyl-m-vinylbenzyl glycidyl ether, ⁇ -methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (g
• Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a formula Examples thereof include a compound represented by (I) and a compound represented by formula (II).
• R a and R b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
• X a and X b is a single bond, * - R c -, * - R c -O -, * - represents the R c -S- or * -R c -NH-.
• R c represents an alkanediyl group having 1 to 6 carbon atoms. * Represents a bond with O.
• alkyl group having 1 to 4 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.
• Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a 1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
• R a and R b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.
• alkanediyl groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
• X a and X b are preferably a single bond, a methylene group, an ethylene group, * —CH 2 —O— and * —CH 2 CH 2 —O—, more preferably a single bond, * —CH 2. CH 2 —O— (* represents a bond with O).
• Examples of the compound represented by the formula (I) include compounds represented by any one of the formulas (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) A compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferred.
• Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) A compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferred.
• the compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination with the compound represented by formula (I) and the compound represented by formula (II). May be.
• the content ratio of the compound represented by formula (I) and the compound represented by formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, more preferably 20:80 to 80:20.
• (B2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.
• (B2) includes 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-acryloyloxymethyl oxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.
• (B3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group.
• Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.
• (B) is preferably (b1) in that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.
• Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth).
• tricyclodecyl (meth) acrylate There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate” as trivial name.) [5.2.1.0 2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc.
• (Meth) acrylic acid esters of Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate; Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2
• styrene vinyltoluene
• benzyl (meth) acrylate tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate
• N from the viewpoint of copolymerization reactivity and heat resistance.
• -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable.
• the ratio of the structural unit derived from each is the total structural unit constituting the resin [K1] Structural unit derived from (a); 2 to 60 mol% Structural unit derived from (b); 40 to 98 mol% It is preferable that Structural unit derived from (a); 10-50 mol% Structural unit derived from (b); 50 to 90 mol% It is more preferable that When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter are excellent. Tend.
• Resin [K1] is, for example, a method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document Can be produced with reference to the cited references described in 1.
• a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere, with stirring, The method of heating and heat retention is mentioned.
• the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used.
• polymerization initiators azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.)
• the solvent any solvent that dissolves each monomer may be used.
• the solvent (E) for the colored curable resin composition of the present invention include a solvent described later.
• the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used.
• a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used.
• the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.
• Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].
• Resin [K4] is obtained by obtaining a copolymer of (a) and (c), and (b) a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms which (b) has It can manufacture by adding to.
• a copolymer of (a) and (c) is produced in the same manner as described in the method for producing resin [K1]. In this case, it is preferable that the ratio of the structural units derived from each is the same as that described for the resin [K3].
• the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms which (b) has.
• the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4].
• a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether for example, tris ( Dimethylaminomethyl) phenol, etc.
• a polymerization inhibitor eg, hydroquinone, etc.
• the amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By making it within this range, the storage stability of the colored curable resin composition, the developability when forming the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern are improved. Tend. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used in the resin [K4], and (b1-1) is more preferable.
• the amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
• the amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
• the reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization.
• the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.
• Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above.
• the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
• the ratio of the structural units derived from (b) and (c) is respectively based on the total number of moles of all the structural units constituting the copolymer.
• the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a).
• Resin [K5] can be obtained by reacting the product.
• the amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol per 100 mol of (b). Since (b) used in the resin [K5] is preferably (b1), and (b1-1) is more preferable because the cyclic ether has high reactivity and it is difficult for unreacted (b) to remain.
• Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5].
• Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
• Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like.
• the amount of carboxylic acid anhydride used is preferably 0.5 to 1 mole per mole of (a) used.
• the resin (B) specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 2,6 ] Resin such as decyl (meth) acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3 , 4-epoxytricyclo [5.2.1.0 2,6] decyl (meth) acrylate / (meth) acrylic acid /
• the resin (B) is preferably a kind selected from the group consisting of a resin [K1], a resin [K2] and a resin [K3], and more preferably from a group consisting of a resin [K2] and a resin [K3]. It is the kind chosen. When these resins are used, the colored curable resin composition is excellent in developability. Resin [K2] is more preferable from the viewpoint of adhesion between the coloring pattern and the substrate.
• the polystyrene equivalent weight average molecular weight of the resin (B) is usually 3,000 to 100,000, preferably 5,000 to 50,000, more preferably 5,000 to 35,000, Preferably it is 5,000 to 30,000, and particularly preferably 6,000 to 30,000.
• the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.
• the acid value of the resin (B) is usually 20 mg-KOH / g to 170 mg-KOH / g, preferably 30 mg-KOH / g to 170 mg-KOH / g, more preferably 40 mg-KOH / g to 170 mg.
• -KOH / g more preferably 50 mg-KOH / g to 170 mg-KOH / g.
• 50 mg-KOH / g to 150 mg-KOH / g is preferable
• 60 mg-KOH / g to 150 mg-KOH / g is more preferable
• 60 mg-KOH / g to 135 mg-KOH / g is more preferable
• 70 mg-KOH / g is usually 20 mg-KOH / g to 170 mg-KOH / g, preferably 30 mg-KOH / g to 170 mg-KOH / g, more preferably 40 mg-KOH / g to 170 mg
• the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.
• the content of the resin (B) is preferably 7% by mass to 65% by mass, more preferably 10% by mass to 60% by mass, and further preferably 13% by mass to 60% by mass with respect to the total amount of the solid content. % By mass, particularly preferably 17% by mass to 55% by mass.
• the polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.
• Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinyl pyrrolidone. And the above-mentioned (a), (a) and (c).
• Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol diester.
• a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds.
• examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) I
• the weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, more preferably from 250 to 1,500.
• the content of the polymerizable compound (C) is preferably 1 to 70% by mass, more preferably 2 to 65% by mass, and more preferably 5 to 65% by mass, based on the total amount of the solid content. It is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. is there.
• the content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20, more preferably on a mass basis. Is from 35:65 to 80:20. When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.
• the polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
• Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.
• O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one -2-Imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- ⁇ 2-methyl-4- (3,3-dimethyl-2,4-dioxa) Cyclopentanylmethyloxy) benzoyl ⁇ -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl
• O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred.
• Alkylphenone compounds include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- ( 4-isopropenylphenyl) propan-1-one oligomer, ⁇ , ⁇ -diethoxyacetophenone, benzyldimethyl ketal, Irgacure 369, 907, 379 (above, manufactured by BASF) and the like.
• Biimidazole compounds are 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′.
• triazine compounds examples include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-
• acylphosphine oxide compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly
• the polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and more preferably Is a polymerization initiator containing an O-acyloxime compound.
• the content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 1 to 30 parts by mass, and more preferably 1 to 30 parts by mass.
• the polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
• Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.
• amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone, and the like, among which 4,4′-bis (diethylamino) benzophenone is preferred.
• Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.
• alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy.
• Anthracene, 2-ethyl-9,10-dibutoxyanthracene and the like can be mentioned.
• thioxanthone compound examples include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.
• Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.
• the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).
• the amount is preferably 1 to 20 parts by mass.
• a solvent (E) is not specifically limited, The solvent normally used in the said field
• ester solvents solvents containing —COO— in the molecule and not containing —O—
• ether solvents solvents containing —O— in the molecule and not containing —COO—
• ether ester solvents intramolecular Solvent containing -COO- and -O-
• ketone solvent solvent containing -CO- in the molecule and not containing -COO-
• alcohol solvent containing OH in the molecule, -O-,- Solvent containing no CO- and -COO-
• aromatic hydrocarbon solvent amide solvent, dimethyl sulfoxide and the like.
• Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, ⁇ -butyrolactone, and the like.
• Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, die Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.
• ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate Le acetate, propylene glycol monopropyl ether
• ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.
• Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
• Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
• Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
• solvents may be used alone or in combination of two or more.
• the content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition.
• the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass.
• Leveling agent (F) examples include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
• silicone surfactant examples include a surfactant having a siloxane bond in the molecule.
• Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) Can be mentioned.
• fluorosurfactant examples include surfactants having a fluorocarbon chain in the molecule.
• Florard registered trademark
• FC430 FC431
• MegaFac registered trademark
• F142D F171, F172, F173, F177, F183, F183, F554, R30
• RS-718-K manufactured by DIC Corporation
• EFTOP registered trademark
• EF301 EF301
• EF303 EF351
• EF352 manufactured by Mitsubishi Materials Electronic Chemicals
• Surflon registered trademark
• SC101 SC105
• SC105 Asahi Glass Co., Ltd.
• E5844 Daikin Fine Chemical Laboratory Co., Ltd.
• silicone surfactant having a fluorine atom examples include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule.
• Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.
• the content of the leveling agent (F) is preferably 0.0005% by mass or more and 0.6% by mass or less, more preferably 0.001% by mass or more and 0.000% by mass or more based on the total amount of the colored curable resin composition. 5 mass% or less, more preferably 0.001 mass% or more and 0.2 mass% or less, preferably 0.002 mass% or more and 0.1 mass% or less, more preferably 0.005 mass% or more and 0 or less. 0.07% by mass or less.
• the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.
• the colored curable resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.
• the colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary. It can be prepared by mixing the leveling agent (F), the polymerization initiation assistant (D1) and other components.
• the pigment in the case of containing the pigment (P) is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 ⁇ m or less. .
• pigment dispersant commercially available surfactants can be used, and silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and other surface activities. Agents and the like.
• surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines.
• the desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
• a solution by dissolving the compound (Z) in part or all of the solvent (E) in advance.
• the solution is preferably filtered with a filter having a pore size of about 0.01 to 1 ⁇ m.
• the colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 ⁇ m.
• Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable.
• the photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed.
• a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure.
• the colored pattern and the colored coating film thus formed are the color filter of the present invention.
• the film thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted according to the purpose and application, for example, 0.1 to 30 ⁇ m, preferably 0.1 to 20 ⁇ m, and more preferably 0.5. ⁇ 6 ⁇ m.
• resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon
• aluminum, silver, or a silver / copper / palladium alloy thin film is used.
• another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.
• Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows. First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained. Examples of the coating method include spin coating, slit coating, and slit and spin coating.
• the temperature for heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C.
• the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When drying under reduced pressure, it is preferably performed at a temperature of 20 to 25 ° C. under a pressure of 50 to 150 Pa.
• the film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.
• the coloring composition layer is exposed through a photomask for forming a target coloring pattern.
• the pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
• the light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
• Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.
• a colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer.
• a developer for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable.
• concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, and even more preferably 0.03 to 5% by mass.
• the developer may contain a surfactant.
• the developing method may be any of paddle method, dipping method, spray method and the like.
• the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.
• the post bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C.
• the post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.
• Example 1 3-amino-4-hydroxybenzoic acid (Tokyo Chemical Industry Co., Ltd.) 10 parts, 4- (diethylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.) 12.8 parts, benzoic acid (Tokyo Chemical Industry Co., Ltd.) 2.73 parts), 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 157 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 7.43 parts are mixed and stirred at 120 ° C. for 3 hours. To obtain a mixture (1).
• the obtained mixture (1) and mixture (2) were mixed, and further 3.76 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.41 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) Then, 52.5 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.35 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 120 ° C. for 8 hours. The reaction solution was cooled to room temperature, and the precipitated crystals were obtained as a residue of suction filtration.
• Example 2 Example 1 was synthesized in the same manner as in Example 1 except that a compound represented by the following formula (d-1) was used instead of 3-amino-4-hydroxybenzoic acid, and the compound represented by formula (Ad1-2) The compound represented was obtained.
• Synthesis example 1 An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Then, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 2,6 ] decan-9-yl acrylate mixture (content ratio is 50:50 in molar ratio) 171 parts dissolved in propylene glycol monomethyl ether acetate 40 parts using a dropping pump over about 5 hours And dripped.
• Example 3 Colorant (A): C.I. I. Pigment Green 58 (pigment) 27 parts; 12 parts acrylic pigment dispersant; Resin (B): Resin B1 (solid content conversion) 9.5 parts; and Solvent (E): Propylene glycol monomethyl ether acetate 180 parts; And a pigment dispersion (3) in which the pigment was sufficiently dispersed using a bead mill was obtained.
• Colorant (A) 2.0 parts of the compound represented by formula (Z-1); Resin (B): Resin B1 (solid content conversion) 40 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts; Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 9.8 parts; Solvent (E): 670 parts of propylene glycol monomethyl ether acetate; Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts; and Pigment dispersion (3) 228.5 parts; Were mixed to obtain a colored curable resin composition
• a colored curable resin composition (J2) was obtained in the same manner as in Example 3 except that the pigment green 36 (pigment) was used instead.
• Example 5 In the same manner as in Example 3 except that the compound represented by the formula (Z-1) of the colorant (A) is replaced with the compound represented by the formula (Z-41), a colored curable resin composition (J3 )
• a colored curable resin composition (J4) was obtained in the same manner as in Example 5 except that it was replaced with CI Pigment Green 36 (pigment).
• Example 7 [Preparation of colored pattern and evaluation of sublimation]
• the colored curable resin composition (J1) obtained in Example 3 was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by spin coating, and then prebaked at 100 ° C. for 3 minutes for coloring. A composition layer was formed. After cooling, the distance between the substrate on which the colored composition layer is formed and the photomask made of quartz glass is set to 200 ⁇ m, and an exposure machine (TME-150RSK; manufactured by Topcon Corporation) is used, and 80 mJ / cm 2 in the atmosphere. The exposure amount (standard on 365 nm) was used. A photomask having a 100 ⁇ m line and space pattern was used.
• the colored composition layer after the exposure was developed by being immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 70 seconds, and washed with water.
• the film thickness was measured.
• Table 1 The colored coating film and the resin coating film for sublimation test (SJSM) obtained above were opposed to each other with an interval of 70 ⁇ m, and a post-baking was performed at 230 ° C. for 10 minutes to obtain a colored pattern. .
• the color difference ( ⁇ Eab *) before and after heating of the resin coating film for sublimation test (SJSM) was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS).
• the color difference ( ⁇ Eab *) was 4.0.
• a color difference ( ⁇ Eab *) of 5.0 or more indicates that the colorant has sublimability.
• Table 1 In Table 1, “ ⁇ ” indicates that the colorant does not have sublimability, and “x” indicates that the colorant has sublimability.
• Example 8 to 10 and Comparative Example 2 Except for replacing the colored curable resin composition (J1) obtained in Example 3 with the colored curable resin composition (J2) to the colored curable resin composition (J5), respectively, Example 7 and Similarly, a colored pattern was obtained and evaluated for sublimation. The results are shown in Table 1.
• the color filter using the colored curable resin composition containing the compound of the present invention is suitably used for a display device such as a liquid crystal display device.

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