WO2016056511A1 - Colored curable composition, colored cured film, color filter, method for producing color filter, solid-state imagine element and image display device - Google Patents

Colored curable composition, colored cured film, color filter, method for producing color filter, solid-state imagine element and image display device Download PDF

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Publication number
WO2016056511A1
WO2016056511A1 PCT/JP2015/078203 JP2015078203W WO2016056511A1 WO 2016056511 A1 WO2016056511 A1 WO 2016056511A1 JP 2015078203 W JP2015078203 W JP 2015078203W WO 2016056511 A1 WO2016056511 A1 WO 2016056511A1
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group
curable composition
colored curable
carbon atoms
compound
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PCT/JP2015/078203
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French (fr)
Japanese (ja)
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藤田　明徳
晃男 片山
孝太郎 岡部
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富士フイルム株式会社
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Priority to KR1020177009124A priority Critical patent/KR101892968B1/en
Publication of WO2016056511A1 publication Critical patent/WO2016056511A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • 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
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • 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
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • C09B11/16—Preparation from diarylketones or diarylcarbinols, e.g. benzhydrol
    • 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
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/12—Amino derivatives of triarylmethanes without any OH group bound to an aryl nucleus
    • C09B11/20—Preparation from other triarylmethane derivatives, e.g. by substitution, by replacement of substituents
    • 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
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • 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
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C09B69/06—Dyestuff salts, e.g. salts of acid dyes with basic dyes of cationic dyes with organic acids or with inorganic complex acids
    • 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
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate

Definitions

  • the present invention relates to a colored curable composition, a colored cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device.
  • a color filter uses a colored curable composition containing a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed and a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components as necessary.
  • a colored pattern by a photolithography method or an ink jet method.
  • color filters have been used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications.
  • color filters are required to have high color characteristics in terms of chromaticity and contrast.
  • color filters for image sensors solid-state imaging devices
  • color characteristics such as reduction of color unevenness and improvement of color resolution.
  • Triarylmethane dyes have attracted attention as dyes used in blue color filters.
  • triarylmethane dyes have a problem of low light stability and thermal stability. In addition, the stability may decrease due to the interaction between the triarylmethane dye and the contaminants in the colored curable composition, and the panel reliability is not sufficient.
  • triarylmethane dyes having various triarylmethane structures have been proposed.
  • a colorant that mixes triarylmethane dyes (or their lake pigments) and copper phthalocyanine blue pigments is proposed. (For example, Patent Documents 2 to 4).
  • a dispersant When a pigment is contained in the colorant, a dispersant is used.
  • the dispersant has a pigment adsorption group, and an ionic adsorption group such as a quaternary ammonium salt structure is known as the adsorption group.
  • Dispersants having an ionic adsorption group are highly compatible with finely divided copper phthalocyanine pigments, and have recently been put into practical use due to their high adsorption stability and their own high transparency.
  • Patent Documents 5 to 12 there are many proposals relating to an adsorbing group having a quaternary ammonium salt structure (for example, Patent Documents 5 to 12).
  • the adsorption group of the dispersant is an adsorption group having a quaternary ammonium salt structure (for example, Patent Document 13). And 14).
  • the counter anion of the quaternary ammonium salt and the triarylmethane are used. It has been clarified by the present inventors that the counter anion of the dye interacts (in the extreme example, salt exchange), the triarylmethane dye becomes unstable, and the heat resistance of the colored cured film is significantly reduced.
  • an object of the present invention is to provide a colored curable composition containing a highly stable triarylmethane dye and capable of forming a colored cured film having high heat resistance.
  • the present inventors have found that the above-described problems can be solved by enhancing the ion-pairing property between the cation and the counter-anion of the triarylmethane dye. Furthermore, the present inventors have found that the conductivity when the triarylmethane dye is dissolved in a specific solvent can be adopted as an ion pair index, and the stability of the triarylmethane dye can be improved by keeping the conductivity within a specific range. It was clarified that sex can be improved. And it discovered that the colored cured film formed from the colored curable composition containing the said triarylmethane dye had the outstanding heat resistance, and came to complete this invention. Specifically, the present invention has the following configuration.
  • the colored curable composition according to [1] further including a pigment and a dispersant, wherein the adsorption group of the dispersant contains at least one of an acidic adsorption group and a basic adsorption group.
  • TP3 general formula (TP3), Rtp 23 and Rtp 24 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Rtp 25 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
  • L 1 Represents a divalent linking group having 2 to 30 carbon atoms, P 1 represents a polymerizable group, and X represents an anion.
  • Forming a colored cured film, and a method for producing a color filter further comprising the following step (a) or step (b): (A) including a step of forming a photoresist layer on the colored cured film and a step of patterning the photoresist layer by exposure and development to obtain a resist pattern; (B) A step of dry etching the colored cured film to obtain a resist pattern.
  • a solid-state imaging device having the color filter according to [13] or [15].
  • An image display device having the color filter according to [13] or [15].
  • the stability of the triarylmethane dye in the colored curable composition can be increased, the heat resistance of the colored cured film formed from the colored curable composition can be increased.
  • a colored cured film with high heat resistance can be manufactured also from the colored curable composition which mixed the triarylmethane dye, the pigment, and the dispersing agent. Furthermore, by using such a colored curable composition, it is possible to provide a color filter, a solid-state imaging device, and a liquid crystal display device having high heat resistance.
  • 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 notation which does not describe substitution and non-substitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
  • light means actinic rays or radiation.
  • exposure in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
  • (meth) acrylate represents both and / or acrylate and methacrylate
  • (meth) acryl represents both and / or acryl and “(meth) acrylic”
  • Acryloyl represents both and / or acryloyl and methacryloyl.
  • “monomer” and “monomer” are synonymous.
  • the monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
  • the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer.
  • the polymerizable functional group refers to a group that participates in a polymerization reaction.
  • Me in the chemical formula represents a methyl group
  • Et represents an ethyl group
  • Pr represents a propyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group
  • AC represents an acetyl group.
  • the weight average molecular weight in the present invention refers to that measured by gel permeation chromatography (GPC) unless otherwise specified.
  • GPC gel permeation chromatography
  • HLC-8020 GPC manufactured by Tosoh Corporation
  • the column can be measured by connecting three TSKgel Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) in series.
  • the conditions can be performed using a RI (Refractive Index) detector with a sample concentration of 0.35 mass%, a flow rate of 0.35 mL / min, a sample injection amount of 10 ⁇ L, and a measurement temperature of 40 ° C.
  • RI Refractive Index
  • the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
  • the present invention relates to a colored curable composition
  • a colored curable composition comprising a triarylmethane dye having a triarylmethane structure containing a cation and a counter anion, and a polymerizable compound.
  • the conductivity at 23 ° C. of a solution obtained by dissolving the triarylmethane dye used in the colored curable composition of the present invention in 3 ml of a mixed solvent having a volume ratio of methanol / water of 2/1 is less than 20 ⁇ s / cm. .
  • the electric conductivity of the solution in which the triarylmethane dye is dissolved is synonymous with the ionization degree of the triarylmethane dye. It shows that the ion pair property of the cation and counteranion of a triarylmethane dye is so high that the electrical conductivity of the solution which dissolved the triarylmethane dye is small. In the present invention, if the electric conductivity of the above solution is less than 20 ⁇ s / cm, the ion pair property of the cation and the counter anion of the triarylmethane dye is good, and the triarylmethane dye exhibits stable performance. Can do.
  • the solution in which the triarylmethane dye is dissolved is prepared by mixing 10 mg of the triarylmethane dye with 3 ml of a mixed solvent of methanol / water and stirring for 20 minutes. In the present invention, the solution thus prepared is adjusted to 23 ° C., and the electrical conductivity is measured.
  • the mixed solvent of methanol / water is a mixed solvent having a volume ratio of methanol / water of 2/1.
  • the electric conductivity of the solution in which the triarylmethane dye is dissolved can be measured using an electric conductivity meter (LAQUATwin, manufactured by Horiba, Ltd.). That is, the electric conductivity in this specification means the electric conductivity measured by the method described in the examples.
  • the electrical conductivity measured under the above conditions may be less than 20 ⁇ s / cm, preferably 16 ⁇ s / cm or less, more preferably 12 ⁇ s / cm or less, and 10 ⁇ s / cm or less. More preferably, it is particularly preferably 8 ⁇ s / cm or less.
  • the lower limit is not particularly defined and may be 0 ⁇ s / cm.
  • the electrical conductivity of the solution in which the triarylmethane dye is dissolved is not available or cannot be measured except for LAQUATwin manufactured by HORIBA, Ltd.
  • the solubility was lowered, and the surface state of the coating film (resist compatibility) was deteriorated by microphase separation.
  • the heat resistance of the colored curable composition is increased by suppressing the conductivity of the solution obtained by dissolving the triarylmethane dye contained in the colored curable composition under predetermined conditions to be within the above range. be able to.
  • the coating film surface state (resist compatibility) Can also be improved.
  • the colored cured film and the color filter formed from the colored curable composition of the present invention are excellent in heat resistance.
  • an element including the color filter of the present invention has a high voltage holding ratio.
  • the colored curable composition of the present invention has an advantage of high compatibility.
  • the colored curable composition of the present invention contains a triarylmethane dye.
  • the triarylmethane dye used in the present invention has a conductivity of 20 ⁇ s / cm at 23 ° C. when dissolved in 3 ml of a mixed solvent having a methanol / water volume ratio of 2/1. There is no particular limitation as long as the conductivity is within the above range.
  • low molecular type triarylmethane dye used in the present invention include compounds represented by the following general formula (TP1).
  • Rtp 21 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Rtp 22 independently represents an aryl group having 6 to 10 carbon atoms
  • R 1 represents a substituent
  • X represents an anion.
  • Rtp 21 is preferably an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear.
  • the alkyl group preferably has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. Examples of the substituent that the alkyl group may have include the substituents mentioned in the section of Substituent Group A described later.
  • Rtp 22 represents an aryl group having 6 to 10 carbon atoms.
  • Rtp 22 is preferably an aryl group having a substituent at least in the ortho position.
  • Examples of the substituent that the aryl group may have include the substituents described in the section of Substituent Group A described later, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. By setting it as such a structure, heat resistance can be improved more.
  • R 1 represents a substituent and is preferably a substituent having a polymerizable group at the terminal.
  • R 1 is more preferably a substituent containing a linking group and a polymerizable group.
  • the linking group is preferably an alkylene group, a cycloalkylene group, a phenylene group, —NH—, —C ( ⁇ O) O—, —OC ( ⁇ O) —, —O—, or a combination thereof.
  • the alkylene group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • the cycloalkylene group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the carbon number of the phenylene group is preferably 6 to 12, and more preferably 6 to 10.
  • a known polymerizable group that can be crosslinked by a radical, acid, or heat can be used.
  • a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), or a methylol group can be used.
  • a group containing an ethylenically unsaturated bond is preferable, a (meth) acryloyl group, a (meth) acryloyloxy group or a vinyl group is more preferable, and a (meth) acryloyl group or a (meth) acryloyloxy group is further preferable.
  • X represents an anion, and the anion will be described later.
  • X is preferably a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a perfluoromethanesulfonic acid anion.
  • Substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfa Moylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfony
  • a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom
  • a linear or branched alkyl group a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms
  • a cycloalkyl group preferably substituted with 3 to 30 carbon atoms or Examples thereof include unsubstituted cycloalkyl groups such as cyclohexyl and cyclopentyl, and polycycloalkyl groups such as bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms
  • Linear or branched alkenyl group (straight or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl A group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as bicyclo An alkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] Octo-2-en-4-yl) and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred.
  • Cycloalkenyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl group),
  • An aryl group preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl
  • a heterocyclic group preferably 5 to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-constituting atom is selected from carbon atom, nitrogen atom and sulfur atom
  • a heterocyclic group having at least one hetero atom of any one of a nitrogen atom, an oxygen atom and a sulfur atom more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms
  • alkoxy group preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy
  • aryloxy group preferably Is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy
  • silyloxy group preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, tert-butyldimethylsilyloxy
  • a heterocyclic oxy group preferably having a carbon number of 2 to 30 substituted or unsubstituted heterocyclic oxy groups , Heterocyclic portion is preferably described
  • An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituent having 2
  • amino group preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms
  • amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino acylamino group (preferably formylamino group, carbon number A substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3, 4,5-tri-n-oc
  • Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino)
  • Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino Sulfonylamino), alkyl or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atom
  • alkylthio group preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, ethylthio, n-hexadecylthio
  • arylthio group preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms
  • the heterocyclic portion described in the above is preferably, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfur Moil, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N- (
  • alkyl or arylsulfinyl group preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl
  • an alkyl or arylsulfonyl group preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl
  • alkoxycarbonyl group preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl
  • a carbamoyl group preferably having a carbon number 1-30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or hetero
  • a ring azo group preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocycle portion is the heterocycle
  • a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substitution having 3 to 30 carbon atoms) Or, an unsubstituted silyl group, for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).
  • substituent group A a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a chloro atom, and
  • the cation is delocalized as follows, and the following structures are synonymous, and both are included in the present invention.
  • the cation moiety may be at any position in the molecule.
  • the triarylmethane dye is preferably a compound represented by the following general formula (TP2).
  • Rtp 21 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • Rtp 22 each independently represents an aryl group having 6 to 10 carbon atoms
  • L 1 represents a divalent linking group having 2 to 30 carbon atoms
  • P 1 represents a polymerizable group
  • X represents an anion.
  • L 1 represents a divalent linking group having 2 to 30 carbon atoms, and includes an alkylene group having 2 to 30 carbon atoms, a cycloalkylene group, a phenylene group, —C ( ⁇ O) O—, — A group consisting of OC ( ⁇ O) —, —O— or a combination thereof is preferred.
  • the alkylene group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • the cycloalkylene group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the carbon number of the phenylene group is preferably 6 to 12, and more preferably 6 to 10.
  • P 1 represents a polymerizable group, and examples thereof include a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), a methylol group, and the like.
  • the containing group is preferable, an acryloyl group, a methacryloyl group or a vinyl group is more preferable, and an acryloyl group or a methacryloyl group is more preferable.
  • X represents an anion, and the anion will be described later.
  • X is preferably a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a perfluoromethanesulfonate anion.
  • the triarylmethane dye is preferably a compound represented by the following general formula (TP3).
  • Rtp 23 and Rtp 24 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • Rtp 25 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • L 1 represents a divalent linking group having 2 to 30 carbon atoms
  • P 1 represents a polymerizable group
  • X represents an anion.
  • Rtp 23 and Rtp 24 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and preferably having 1 to 3 carbon atoms. It is more preferable to represent the alkyl group. Among them, Rtp 24 is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
  • the alkyl group may be either linear or branched, but is preferably linear.
  • Rtp 25 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably represents an alkyl group having 1 to 3 carbon atoms, more preferably represents a methyl group or an ethyl group, A methyl group is particularly preferred.
  • L 1 in the general formula (TP3) is the general formula (TP2) in a L 1 and synonymous, and preferred ranges are also the same.
  • P 1 in the general formula (TP3) is the general formula (TP2) in the same meaning as P 1, and preferred ranges are also the same.
  • X represents an anion, and the anion will be described later. X is preferably a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a perfluoromethanesulfonate anion.
  • the triarylmethane dye has an anion X at least either inside or outside the molecule.
  • the triarylmethane dye preferably has an anion X outside the molecule, and by having the anion X outside the molecule, the heat resistance of the colored cured film using the colored curable composition of the present invention is more effectively improved. Can be increased.
  • the anion X is contained according to the valence of the cation contained in the triarylmethane dye.
  • the cation is usually monovalent or divalent, and monovalent is preferable. Having an anion X in the molecule means that an anion site and a cation site are present in the triarylmethane dye via one or more covalent bonds.
  • Having an anion X outside the molecule means a case other than the above.
  • the anion X in the present invention is not particularly defined, but a low nucleophilic anion is preferable.
  • the low nucleophilic anion indicates an anion structure in which an organic acid having a pKa lower than that of sulfuric acid is dissociated.
  • the case where the anion X is in the molecule is a case where the anion X is in the same molecule as the triarylmethane dye. Specifically, the cation and the anion are bonded via a covalent bond in the repeating unit having a dye structure. This is the case where they are combined.
  • the anion moiety is at least selected from —SO 3 ⁇ , —COO ⁇ , —PO 3 ⁇ , a structure represented by the following general formula (A1), and a structure represented by the following general formula (A2).
  • A1 —SO 3 ⁇
  • A1 a structure represented by the following general formula (A2)
  • R 1 and R 2 each independently represents —SO 2 — or —CO—.
  • at least one of R 1 and R 2 -SO 2 - preferably represents an, both R 1 and R 2 are -SO 2 - and more preferably represents.
  • the general formula (A1) is more preferably represented by the following general formula (A1-1).
  • Formula (A1-1) is more preferably represented by the following general formula (A1-1).
  • R 1 and R 2 each independently represents —SO 2 — or —CO—.
  • X 1 and X 2 each independently represent an alkylene group or an arylene group.
  • R 1 and R 2 of the general formula (A1) in the same meaning as R 1 and R 2, and preferred ranges are also the same.
  • X 1 represents an alkylene group
  • the alkylene group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • the carbon number of the arylene group is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6.
  • X 1 has a substituent, it is preferably substituted with a fluorine atom.
  • X 2 represents an alkyl group or an aryl group, and an alkyl group is preferable.
  • the alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1.
  • X 2 has a substituent, it is preferably substituted with a fluorine atom.
  • R 3 represents —SO 2 — or —CO—.
  • R 4 and R 5 each independently represents —SO 2 —, —CO— or —CN.
  • Preferably representing the at least two R 3 ⁇ R 5 is -SO 2 - -
  • at least one of R 3 ⁇ R 5 -SO 2 more preferably represents.
  • the case where the anion X is a different molecule is a case where the anion X is outside the same repeating unit, and the cation and the anion are not bonded via a covalent bond but are present as separate molecules.
  • the anion X in this case include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, and a low nucleophilic anion, and a low nucleophilic anion, and a low nucleophilic anion is preferable.
  • the low nucleophilic anion may be an organic anion or an inorganic anion, and an organic anion is preferred.
  • Examples of the anion used in the present invention include known low nucleophilic anions described in paragraph No. 0075 of JP-A-2007-310315, the contents of which are incorporated herein.
  • the bis (sulfonyl) imide anion which is a low nucleophilic anion
  • a structure represented by the following general formula (AN-1) is preferable, and a bistrifluoromethanesulfonylimide anion is more preferable.
  • X 1 and X 2 each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom.
  • X 1 and X 2 may combine with each other to form a ring.
  • X 1 and X 2 each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, More preferred is a perfluoroalkyl group of ⁇ 10, more preferred is a perfluoroalkyl group having 1 to 4 carbon atoms, and a trifluoromethyl group is particularly preferred.
  • tris (sulfonyl) methide anion which is a low nucleophilic anion
  • a structure represented by the following general formula (AN-2) is preferable, and a tris (trifluoromethanesulfonyl) methion anion is more preferable.
  • X 3 , X 4 and X 5 each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms.
  • X 3 , X 4 and X 5 are each independently synonymous with X 1 and X 2 , and a preferred range is also synonymous.
  • the perfluorosulfonic acid anion is preferably a compound represented by the following general formula (AN3), more preferably a perfluoromethanesulfonic acid anion.
  • the tetraarylborate anion which is a low nucleophilic anion is preferably a compound represented by the following general formula (AN-5).
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represents an aryl group.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further an aryl group having 6 to 10 carbon atoms preferable.
  • the aryl group represented by Ar 1 , Ar 2 , Ar 3 and Ar 4 may have a substituent.
  • a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, a nitro group and the like can be mentioned, and a halogen atom and an alkyl group are preferable, A fluorine atom and an alkyl group are more preferable, and a fluorine atom and a perfluoroalkyl group having 1 to 4 carbon atoms are more preferable.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently more preferably a phenyl group having at least one selected from a halogen atom and an alkyl group having a halogen atom, and selected from a fluorine atom and an alkyl group having fluorine. More preferred is a phenyl group having at least one of the following.
  • the low nucleophilic anion also represents —B (CN) n1 (OR a ) 4-n1 (R a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 is 1 Represents an integer of 4).
  • Ra as the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • R a as the aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.
  • n1 is preferably 1 to 3, and more preferably 1 to 2.
  • the low nucleophilic anion is further represented by —PF 6 R P (6-n2) ⁇ (R P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents an integer of 1 to 6).
  • R P is preferably an alkyl group having a fluorine atom having 1 to 6 carbon atoms, more preferably an alkyl group having a fluorine having 1 to 4 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.
  • n2 is preferably an integer of 1 to 4, and more preferably 1 or 2.
  • the mass per molecule of the low nucleophilic anion is preferably 100 to 1,000, and more preferably 200 to 500.
  • the triarylmethane dye used in the present invention may contain only one kind of low nucleophilic anion or may contain two or more kinds.
  • the anion X may be a multimer.
  • the multimer in this case is exemplified by a multimer containing a repeating unit containing an anion and not containing a repeating unit derived from a dye structure containing a cation.
  • a repeating unit containing an anion a repeating unit containing an anion described in the embodiment described later can be cited as a preferred example.
  • the multimer containing an anion may have a repeating unit other than the repeating unit containing an anion.
  • the other repeating unit which the triarylmethane dye mentioned later may contain is illustrated as a preferable example.
  • triarylmethane dyes preferably used in the present invention and represented by general formulas (TP1) to (TP3) are shown below, but are not limited thereto.
  • the triarylmethane dyes represented by the general formulas (TP1) to (TP3) may contain a multimeric structure.
  • the triarylmethane dye When the triarylmethane dye has a multimeric structure, the triarylmethane dye is referred to as a polymer type triarylmethane dye.
  • a polymer type triarylmethane dye is also preferably used.
  • the triarylmethane dye is a polymer type, the multimeric structure may be a triarylmethane structure or an anion X.
  • the triarylmethane dye when the triarylmethane dye is a polymer type, it may be referred to as a dye multimer.
  • the triarylmethane dye represented by the general formula (TP1) will be described as an example, but the triarylmethane dye represented by the general formula (TP2) and the general formula (TP3) are represented. The same applies to the triarylmethane dye.
  • the triarylmethane dye is a polymer type, any part of the triarylmethane dye represented by the general formula (TP1) is bonded to the polymer, and at least one group in the general formula (TP1) is a polymer. It is preferably a repeating unit constituting.
  • each substituent in the general formula (TP1) other than the group bonded to the repeating unit constituting the polymer is a triarylmethane dye having a multimeric structure (low molecular type bird arylmethane dye)
  • the preferred range is also the same.
  • Rtp 21 , Rtp 22 or P 1 is a binding site with a polymer main chain, and more preferable that P 1 is a binding site with a polymer main chain.
  • P 1 is a binding site with a polymer main chain.
  • TP3 it is preferable that at least one of Rtp 21 , Rtp 22 or P 1 is a bonding site with the polymer main chain, and more preferable that P 1 is a bonding site with the polymer main chain.
  • the skeleton structure of the repeating unit is not particularly defined, but the general formula (A), It is preferable that at least one of the structural units represented by formula (B) and general formula (C) is a skeleton, or a triarylmethane dye represented by general formula (TP1) is represented by general formula (D It is preferable that it is a pigment
  • the description of paragraph numbers 0252 to 0304 of JP 2013-28764 is incorporated in the present specification.
  • X 1 represents a linking group formed by polymerization
  • L 1 represents a single bond or a divalent linking group.
  • DyeI is any one of Rtp 21 , Rtp 22 and R 1 in the general formula (TP1), any of Rtp 21 , Rtp 22 and P 1 in the general formula (TP2), or Rtp 23 to Rtp in the general formula (TP3).
  • Either 25 or P 1 is a group bonded to L 1 .
  • the general formula (A) will be described in detail.
  • X 1 represents a linking group formed by polymerization. That is, it refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. Two sites represented by * are repeating units.
  • X 1 is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, but is particularly preferably a linking group represented by the following (XX-1) to (X-24), (XX -1) and (XX-2) (meth) acrylic linking chains, (XX-10) to (XX-17) styrenic linking chains, (XX-18) and (XX- 19), and more preferably selected from vinyl-based linking chains represented by (XX-24), (meth) acrylic linking chains represented by (XX-1) and (XX-2), More preferably, it is selected from styrenic linking chains represented by (XX-10) to (XX-17) and vinyl linking chains represented by (XX-24), and (XX-1) and (XX -2)
  • L 1 represents a single bond or a divalent linking group.
  • the divalent linking group includes a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group, butylene).
  • arylene group having 6 to 30 carbon atoms (eg, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, —CH ⁇ CH—, —O—, —S —, —C ( ⁇ O) —, —CO 2 —, —NR—, —CONR—, —O 2 C—, —SO—, —SO 2 — and a linkage formed by linking two or more thereof.
  • L 1 includes an anion is also preferable.
  • L 1 is more preferably a single bond or an alkylene group, and more preferably a single bond or — (CH 2 ) n— (n is an integer of 1 to 5).
  • R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently. An example of the case where L 1 contains an anion will be described later.
  • DyeI is any one of Rtp 21 , Rtp 22 and R 1 in general formula (TP1), any of Rtp 21 , Rtp 22 and P 1 in general formula (TP2), or general formula ( Any of Rtp 23 to Rtp 25 and P 1 in TP3) is a group bonded to L 1 .
  • the dye multimer having the structural unit represented by the general formula (A) includes (1) a method of synthesizing a monomer having a dye residue by addition polymerization, (2) an isocyanate group, an acid anhydride group or an epoxy group.
  • the dye multimer having the structural unit represented by the general formula (A) is a radical polymer obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond from the viewpoint of heat resistance. It is preferable that
  • the triarylmethane dye used in the present invention may have another functional group in the dye structure portion of the dye multimer described above.
  • Examples of other functional groups include polymerizable groups and alkali-soluble groups (preferably acid groups).
  • the triarylmethane dye used in the present invention may contain other repeating units in addition to the repeating unit including the above-described pigment structure.
  • Other repeating units may have a functional group.
  • the repeating unit containing at least 1 sort (s) of a polymeric group and an alkali-soluble group (preferably acid group) is illustrated.
  • the triarylmethane dye used in the present invention may have other repeating units in addition to the repeating units represented by the general formulas (A) to (C).
  • One type of other repeating unit may be contained in one triarylmethane dye, or two or more types may be contained.
  • the triarylmethane dye used in the present invention may have other functional groups in the dye multimer represented by the general formulas (A) to (D). Details of these will be described below.
  • the dye multimer may contain a polymerizable group.
  • One type of polymerizable group may be included, or two or more types may be included.
  • the dye structure may contain a polymerizable group, or may contain other parts.
  • the dye structure preferably includes a polymerizable group.
  • the polymerizable group is synonymous with the polymerizable group that the triarylmethane dyes represented by the above general formulas (TP1) to (TP3) may have, and the preferred range is also the same.
  • the polymerizable group is preferably contained as a repeating unit having a polymerizable group in the dye multimer, and more preferably as a repeating unit having an ethylenically unsaturated bond. That is, the triarylmethane dye used in the present invention may contain a repeating unit containing a pigment monomer and a repeating unit having a polymerizable group, and the repeating unit containing a pigment monomer. More preferably, it contains a repeating unit having an ethylenically unsaturated bond.
  • a method for introducing a polymerizable group (1) a method in which a dye multimer is modified and introduced with a polymerizable group-containing compound, and (2) a method in which a dye monomer and a polymerizable group-containing compound are copolymerized and introduced. Etc. Details will be described below.
  • a method of introducing a dye multimer after modifying it with a polymerizable group-containing compound As a method for introducing the dye multimer by modifying with a polymerizable group-containing compound, a known method can be used without any particular limitation. For example, (a) a method of reacting a carboxylic acid contained in a dye multimer with an unsaturated bond-containing epoxy compound, and (b) a method of reacting a hydroxyl group or amino group of the dye multimer with an unsaturated bond-containing isocyanate compound. (C) A method of reacting the epoxy compound of the dye multimer with the unsaturated bond-containing carboxylic acid compound is preferable from the viewpoint of production.
  • the unsaturated bond-containing epoxy compound in the method of reacting the carboxylic acid contained in the dye multimer with the unsaturated bond-containing epoxy compound includes glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and 3,4-epoxycyclohexyl. Examples thereof include methyl acrylate, 3,4-epoxy-cyclohexylmethyl methacrylate, and glycidyl methacrylate and 3,4-epoxy-cyclohexylmethyl methacrylate are particularly preferable because of excellent crosslinkability and storage stability.
  • Known conditions can be used as the reaction conditions.
  • 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl atacrylate examples include 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and 2-isocyanatoethyl methacrylate is preferable because of its excellent crosslinkability and storage stability.
  • Known conditions can be used as the reaction conditions.
  • the unsaturated bond-containing carboxylic acid compound in the method of reacting the epoxy compound of the dye multimer with the unsaturated bond-containing carboxylic acid compound is particularly a carboxylic acid compound having a known (meth) acryloyloxy group
  • methacrylic acid and acrylic acid are preferable, and methacrylic acid is particularly preferable because of excellent crosslinkability and storage stability.
  • Known conditions can be used as the reaction conditions.
  • a method in which a dye monomer and a polymerizable group-containing compound are copolymerized and introduced (2) As a method for copolymerizing and introducing a dye monomer and a polymerizable group-containing compound, known methods can be used without any particular limitation.
  • D A radically polymerizable dye monomer and a radical can be used.
  • a method of copolymerizing a polymerizable group-containing compound that can be polymerized, and a method (e) a method of copolymerizing a dye monomer capable of polyaddition and a polymerizable group-containing compound capable of polyaddition are preferred.
  • a radically polymerizable polymerizable group-containing compound in a method of copolymerizing a radically polymerizable dye monomer and a radically polymerizable polymerizable group-containing compound an allyl group-containing compound (for example, (meth)) Allyl acrylate), epoxy group-containing compounds (for example, glycidyl (meth) acrylate, 3,4-epoxy-cyclohexylmethyl (meth) acrylate, etc.), oxetane group-containing compounds (for example, 3-methyl-3-oxetanylmethyl (meth) ) Acrylate, etc.) and methylol group-containing compounds (for example, N- (hydroxymethyl) acrylamide etc.), and epoxy compounds and oxetane compounds are particularly preferred.
  • Known conditions can be used as the reaction conditions.
  • a method for introducing a polymerizable group a method in which a carboxylic acid contained in a dye multimer is reacted with an unsaturated bond-containing epoxy compound is particularly preferable.
  • the amount of polymerizable group possessed by the dye multimer is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol, and more preferably 0.3 to 1. Particularly preferred is 0 mmol.
  • the ratio of the repeating unit containing a repeating unit having a polymerizable group in the dye multimer is, for example, preferably 5 to 50 mol, and more preferably 10 to 20 mol with respect to 100 mol of all repeating units.
  • a method for introducing a polymerizable group a method in which a carboxylic acid contained in a dye multimer is reacted with an unsaturated bond-containing epoxy compound is particularly preferable.
  • repeating unit having a polymerizable group examples include the following. However, the present invention is not limited to these.
  • Alkali-soluble group of dye multimer An example of the alkali-soluble group that the dye multimer may have is an acid group, and examples of the acid group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • the alkali-soluble group (preferably an acid group) is preferably contained in the dye multimer as a repeating unit having an alkali-soluble group (acid group).
  • a method for introducing an alkali-soluble group into a dye multimer a method in which an alkali-soluble group is introduced into a dye monomer in advance, and a monomer other than a dye monomer having an alkali-soluble group ((meth) acrylic acid, acrylic Modified product of caprolactone of acid, modified product of succinic anhydride of 2-hydroxyethyl (meth) acrylate, modified product of phthalic anhydride of 2-hydroxyethyl (meth) acrylate, 1,2-hydroxyethyl (meth) acrylate 2-cyclohexanedicarboxylic acid anhydride modified product, carboxylic acid-containing monomer such as styrene carboxylic acid, itaconic acid, maleic acid, norbornene carboxylic acid, phosphoric acid-containing monomer such as acid phosphooxyethyl methacrylate, vinyl phosphonic acid, vinyl sulfonic acid, Such as 2-acrylamido-2-methylsulf
  • the amount of the alkali-soluble group possessed by the dye multimer is preferably 0.3 to 2.0 mmol, more preferably 0.4 to 1.5 mmol, more preferably 0.5 to 1. Particularly preferred is 0 mmol.
  • the ratio of the repeating unit containing a repeating unit having an acid group is 100 repeating units containing a dye monomer. For example, 5-70 mol is preferable with respect to mol, and 10-50 mol is more preferable.
  • Other functional groups possessed by the dye multimer include development accelerators such as lactones, acid anhydrides, amides, —COCH 2 CO—, cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups And an affinity adjusting group such as a hydroxyl group, a maleimide group, and an amino group, and the like, which can be appropriately introduced.
  • the introduction method include a method of introducing the dye monomer in advance and a method of copolymerizing the monomer having the functional group.
  • repeating unit having an alkali-soluble group or other functional group that the dye multimer may have are shown below, but the present invention is not limited thereto.
  • the triarylmethane dye used in the present invention is a polymer
  • specific examples of the repeating unit that may be included are at least one of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylic acid amide.
  • Examples are repeating units derived from species.
  • the weight average molecular weight (Mw) of the polymer type triarylmethane dye is preferably 2,000 to 50,000, more preferably 3,000 to 30,000, and 6,000 to 20,000. 000 is particularly preferred.
  • the ratio [(Mw) / (Mn)] of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer type triarylmethane dye is preferably 1.0 to 2.0. 1.1 to 1.8 is more preferable, and 1.1 to 1.5 is particularly preferable.
  • the glass transition temperature (Tg) of the polymer type triarylmethane dye is preferably 50 ° C. or higher, and more preferably 100 ° C. or higher.
  • the 5% weight loss temperature by thermogravimetric analysis (TGA measurement) is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher.
  • the polymer type triarylmethane dye contains a repeating unit having a pigment structure and another repeating unit, it is preferably a random compound of a polymerizable compound containing a pigment and another polymerizable compound.
  • the dye structure is present randomly in the triarylmethane dye, and the effects of the present invention are more effectively exhibited.
  • anion X is contained according to the valence of the cation contained in the triarylmethane dye.
  • the cation is usually monovalent or divalent, and monovalent is preferable.
  • the presence of an anion X in the molecule means that it is in the same repeating unit of the triarylmethane dye. That is, it means a case where a cation and an anion are bonded via a covalent bond within a repeating unit having a dye structure.
  • having an anion X outside the molecule means other than the above, and when the cation and the anion are not bonded via a covalent bond and exist as separate compounds, or the cation and the anion are triarylmethane dyes, respectively. The case where it is contained as an independent repeating unit.
  • the anion portion is the same as that of the first embodiment of the anion in the low molecular type, and the preferred range is also the same.
  • the anion when the anion X is a different molecule is the same as in the second embodiment of the anion in the low molecular type, and the preferred range is also the same.
  • the case where the cation and the anion are contained in separate repeating units of the triarylmethane dye refers to the case where the cation and the anion are contained in independent repeating units of the triarylmethane dye.
  • the anion may be present in the side chain of the triarylmethane dye, may be present in the main chain, or may have the anion X in both the main chain and the side chain. .
  • a side chain is preferred.
  • the repeating unit containing an anion X include a repeating unit represented by the general formula (C) and a repeating unit represented by the general formula (D).
  • X 1 represents a main chain of repeating units.
  • L 1 represents a single bond or a divalent linking group.
  • anion represents the anion.
  • X 1 represents a main chain of repeating units, usually represents a linking group formed by polymerization reaction, for example, (meth) acrylic, styrene, vinyl and the like are preferable, ( More preferred is a (meth) acrylic type.
  • Two sites represented by * are repeating units.
  • L 1 represents a divalent linking group
  • an alkylene group having 1 to 30 carbon atoms (methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), an arylene group having 6 to 30 carbon atoms (phenylene group, Naphthalene group, etc.), heterocyclic linking group, —CH ⁇ CH—, —O—, —S—, —C ( ⁇ O) —, —CO—, —NR—, —CONR—, —OC—, —SO —, —SO 2 — and a linking group obtained by combining two or more thereof are preferred.
  • R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
  • L 1 is a single bond or an alkylene group having 1 to 10 carbon atoms (preferably — (CH 2 ) n— (n is an integer of 5 to 10), an arylene group having 6 to 12 carbon atoms (preferably phenylene group, naphthalene group) is, - NH -, - CO 2 -, - O- and -SO 2 - is a divalent linking group formed by combining two or more preferred.
  • L 2 and L 3 each independently represent a single bond or a divalent linking group.
  • anion represents the anion X.
  • L 2 and L 3 represent a divalent linking group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH ⁇ CH— , —O—, —S—, —C ( ⁇ O) —, —CO 2 —, —NR—, —CONR—, —O 2 C—, —SO—, —SO 2 — and combinations of two or more thereof
  • the linking group is preferred.
  • R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
  • L 2 is preferably an arylene group having 6 to 12 carbon atoms (particularly a phenylene group).
  • the arylene group having 6 to 30 carbon atoms is preferably substituted with a fluorine atom.
  • L 3 is preferably a group comprising a combination of an arylene group having 6 to 12 carbon atoms (particularly a phenylene group) and —O—, and at least one kind of arylene group having 6 to 12 carbon atoms is substituted with a fluorine atom. It is preferable.
  • a homopolymer (homopolymer) composed only of a dye compound component having a polymerizable group or a copolymer (copolymer) with other polymerizable compound is preferably used.
  • a homopolymer (homopolymer) is more preferable.
  • the molecular weight of the anionic multimer is preferably a weight average molecular weight of 3,000 to 30,000 and a molecular weight distribution of Mw / Mn of 0.8 to 3.0, more preferably a weight average molecular weight of 5, The molecular weight distribution is 1 to 2.5 in terms of Mw / Mn.
  • a chain transfer agent When forming an anionic multimer, a chain transfer agent may be added.
  • the chain transfer agent is preferably an alkyl mercaptan, and is preferably an alkyl mercaptan having 10 or less carbon atoms or an alkyl mercaptan substituted with an ether group / ester group. In particular, an alkyl mercaptan having a log P value of 5 or less is more preferable.
  • the amount of the anionic monomer compound having a polymerizable group that is a raw material of the anionic multimer contained in the anionic multimer is preferably 5% or less, more preferably 1% or less.
  • the halogen ion content contained in the anionic multimer is preferably 10 to 3000 ppm, more preferably 10 to 2000 ppm, and even more preferably 10 to 1000 ppm.
  • repeating unit containing the anion X Specific examples of the repeating unit containing the anion X are shown below, but the present invention is not limited thereto.
  • repeating units that are preferably used in accordance with the high molecular type triarylmethane dye are shown below. Examples of other repeating units are not limited to these repeating units.
  • repeating unit of the polymer type triarylmethane dye include the following structures, but the present invention is not limited thereto.
  • the content of the triarylmethane dye contained in the colored curable composition of the present invention is preferably 1.0 to 50% by mass, and preferably 5.0 to 30% by mass with respect to the total solid content in the colored curable composition. % Is more preferable, and 8 to 25% by mass is particularly preferable.
  • the content of the triarylmethane dye is the total amount of the two or more triarylmethane compounds.
  • the mass ratio of the content of the triarylmethane dye and the pigment in the colored curable composition is 1.0: 0.05. To 1.0: 1.0 is preferable, and 1.0: 0.1 to 1.0: 0.6 is more preferable.
  • the colored curable composition of the present invention may contain only a triarylmethane dye as a colorant, but may further contain a pigment. Moreover, when a pigment is contained in the colored curable composition, a dispersant is preferably contained. That is, the colored curable composition of the present invention may contain a triarylmethane dye having a triarylmethane structure containing a cation and a counter anion, a polymerizable compound, a pigment, and a dispersant. .
  • the dispersant has an adsorption group, and the adsorption group of the dispersant preferably includes at least one of an acidic adsorption group and a basic adsorption group.
  • Examples of the pigment mixed with the colored curable composition of the present invention include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, and triarylcarbonium. , Dioxazine, aminoanthraquinone, diketopyrrolopyrrole, indigo, thioindigo, isoindoline, isoindolinone, pyranthrone, or isoviolanthrone.
  • perylene compound pigments such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29, perinone compound pigments such as Pigment Orange 43, and Pigment Red 194, Pigment Violet 19, and Pigment Violet. 42, quinacridone such as Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 207, or Pigment Red 209, quinacridone compound pigment, Pigment Red 206, Pigment Orange 48, or Pigment Orange 49 Quinone compound pigment, anthraquinone compound pigment such as pigment yellow 147, anthanthrone compound pigment such as pigment red 168, pigment Benzimidazolone compound pigments such as Pigment Brown 25, Pigment Violet 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185; Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144
  • the pigment used in the present invention is preferably a green to cyan colorant, and includes Pigment Green 7, Pigment Green 36, Pigment Green 37, Pigment Green 58, Pigment Blue 16, Pigment Blue 75, or Pigment.
  • -A phthalocyanine compound pigment such as Blue 15; a triarylcarbonium compound pigment such as Pigment Blue 56 or Pigment Blue 61; a dioxazine compound pigment such as Pigment Violet 23 or Pigment Violet 37; Pigment Red 177 Aminoanthraquinone compound pigment, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 272, Pigment Orange 71, or Pigment Red Diketopyrrolopyrrole compound pigments such as Range 73, thioindigo compound pigments such as Pigment Red 88, isoindoline compound pigments such as Pigment Yellow 139 and Pigment Orange 66, and Iso Yellows such as Pigment Yellow 109 or Pigment Orange 61
  • indolinone compound pigments pyran
  • the colored curable composition of the present invention preferably contains at least one of an oxazine pigment and a phthalocyanine compound pigment.
  • the phthalocyanine compound pigment is preferably a copper phthalocyanine blue pigment, and the colored curable composition of the present invention more preferably contains a copper phthalocyanine blue pigment.
  • the colored curable composition of the present invention may contain a dye compound in addition to a triarylmethane dye having a triarylmethane structure containing a cation and a counter anion.
  • the dye compound include azo compounds (for example, Solvent Yellow 162), anthraquinone compounds (for example, anthraquinone compounds described in JP-A-2001-10881), and phthalocyanine compounds (for example, phthalocyanine described in US 2008 / 0076044A1).
  • Compound xanthene series (for example, C.I. Acid Red 289), triarylmethane series (for example, C.I.
  • Acid Blue 7 CI Acid Blue 83 (CI Acid Blue 83), CI Acid Blue 90 (CI Acid Blue 90), CI Solvent Blue 38 (CI Solvent Blue 38), Sea Eye Acid Iolet 17 (CI Acid Violet 17), C.I. Acid Violet 49, C.I. Acid Green 3 (C.I. Acid Green 3), methine dye, xanthene dye (For example, JP 2010-32999 A), dipyrromethene metal complex compounds (for example, JP 2012-237985 A) and the like.
  • the dye compound may contain at least one of a xanthene dye compound and a dipyrromethene metal complex compound.
  • a xanthene dye compound (hereinafter also referred to as xanthene dye) is a dye containing a compound having a xanthene skeleton in the molecule.
  • xanthene dyes include C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. Others are also the same), 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic violet 10, 11, 25, C.I.
  • xanthene dyes described in JP 2010-32999 A xanthene dyes described in Japanese Patent No. 4492760, and the like.
  • the xanthene dye is preferably dissolved in an organic solvent.
  • a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable.
  • Compound (1a) may be a tautomer thereof.
  • the content of the compound (1a) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye.
  • R 1 to R 4 each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent.
  • R 1 and R 2 may combine with each other to form a ring containing a nitrogen atom.
  • R 3 and R 4 may combine with each other to form a ring containing a nitrogen atom.
  • R 5 is, -OH, -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO 2 represents NR 9 R 10
  • R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • m represents an integer of 0 to 5. When m is 2 or more, the plurality of R 5 may be the same or different.
  • a represents 0 or 1;
  • X represents a halogen atom.
  • n represents the total number of anions in the compound (1a).
  • Z + represents N + (R 11 ) 4 , Na + or K + , and the four R 11 may be the same or different.
  • R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
  • R 9 and R 10 each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and is included in the saturated aliphatic hydrocarbon group— CH 2 — may be substituted with —O—, —CO—, —NH—, or —NR 8 —, and R 9 and R 10 are bonded to each other to form a 3- to 10-membered ring containing a nitrogen atom.
  • a heterocycle may be formed.
  • R 11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
  • Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 1 to R 4 include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group.
  • a toluyl group, a xylyl group, a mesityl group, and a propylphenyl group are preferable, and a toluyl group and a xylyl group are particularly preferable, and among these, a 2,6-disubstituted xylyl group is preferable.
  • the aromatic hydrocarbon group substituent which may have a halogen atom, -R 8, -OH, -OR 8 , -SO 3 -, - SO 3 H, -SO 3 - Z +, -CO 2 H, —CO 2 R 8 , —SR 8 , —SO 2 R 8 , —SO 3 R 8, or —SO 2 NR 9 R 10 may be mentioned.
  • substituent -SO 3 -, - SO 3 H, -SO 3 - Z + and -SO 2 NR 9 R 10 is preferably, -SO 3 - Z + and -SO 2 NR 9 R 10 Is more preferable.
  • N + (R 11) 4 are preferred.
  • R 1 to R 4 are these groups, a color filter with less generation of foreign matters and excellent heat resistance can be formed from the colored curable composition of the present invention containing the compound (1a).
  • Examples of the ring formed by combining R 1 and R 2 with each other and the ring formed by combining R 3 and R 4 with each other include the following.
  • the following structures are preferable from the viewpoint of compound stability.
  • Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 8 to R 11 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group.
  • Linear alkyl groups such as decyl group, dodecyl group, hexadecyl group, icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.
  • a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group are preferable, and a propyl group, an isopropyl group, a butyl group, a hexyl group, A 2-ethylhexyl group is preferred.
  • the hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.
  • Examples of —OR 8 include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group. Of these, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferable.
  • Examples of —CO 2 R 8 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group. Of these, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group are preferable.
  • Examples of —SR 8 include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
  • Examples of —SO 2 R 8 include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
  • Examples of —SO 3 R 8 include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.
  • —SO 2 NR 9 R 10 includes, for example, a sulfamoyl group; N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (2
  • N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-pentylsulfamoyl group, N -(2-ethylhexyl) sulfamoyl group is preferred, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N- (2-ethylhexyl) A sulfamoyl group is more preferred.
  • the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 9 and R 10 may have a substituent, and examples of the substituent include a hydroxy group and a halogen atom.
  • R 5 is, -OH, -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO 2 represents NR 9 R 10
  • R 5 is, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -CO 2 NHR 9, -SO 3 -, -SO 3 - Z +, -SO 3 H, -SO 2 R 8
  • —SO 2 NHR 9 is preferred, —SO 3 ⁇ , —SO 3 — Z + , —SO 3 H or —SO 2 NHR 9 is more preferred.
  • m is preferably an integer of 1 to 4, and more preferably 1 or 2.
  • Examples of the alkyl group having 1 to 6 carbon atoms in R 6 and R 7 include the alkyl groups having 1 to 6 carbon atoms among the alkyl groups mentioned as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. It is done.
  • Examples of the aralkyl group having 7 to 10 carbon atoms for R 11 include a benzyl group, a phenylethyl group, and a phenylbutyl group.
  • Z + is N + (R 11 ) 4 , Na + or K + , preferably N + (R 11 ) 4 .
  • N + (R 11 ) 4 is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms, at least two of the four R 11 . Further, the total number of carbon atoms of the four R 11 is preferably 20 to 80, and more preferably 20 to 60.
  • N + (R 11 ) 4 is present in the compound (1a), the color filter containing less foreign matter from the colored curable composition of the present invention containing the compound (1a) can be obtained when R 11 is these groups. Can be formed.
  • compound (3a) a compound represented by the formula (3a) (hereinafter sometimes referred to as “compound (3a)”) is also preferable.
  • Compound (3a) may be a tautomer thereof.
  • R 31 and R 32 each independently represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms.
  • the hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.
  • a hydrogen atom contained in an aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted with an alkoxy group having 1 to 3 carbon atoms, and is contained in a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms.
  • —CH 2 — may be substituted with —O—, —CO— or —NR 11 —.
  • R 33 and R 34 each independently represents an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
  • R 31 and R 33 may be bonded to each other to form a ring containing a nitrogen atom
  • R 32 and R 34 may be bonded to each other to form a ring containing a nitrogen atom.
  • p and q each independently represents an integer of 0 to 5. When p is 2 or more, the plurality of R 33 may be the same or different. When q is 2 or more, the plurality of R 34 may be the same or different.
  • R 11 has the same meaning as R 11 in the formula (1a).
  • the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R 31 and R 32 is the number of carbon atoms among the monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms described for R 8 in formula (1a). Examples thereof include 1 to 10 monovalent saturated hydrocarbon groups. Of these, methyl, ethyl, propyl, butyl, hexyl and 2-ethylhexyl are preferred.
  • Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be present as a substituent include the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms described for R 1 in formula (1a). It is done.
  • alkoxy group having 1 to 3 carbon atoms in which the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted include a methoxy group, an ethoxy group, and a propoxy group.
  • R 31 and R 32 are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.
  • Examples of the alkyl group having 1 to 4 carbon atoms in R 33 and R 34 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. Of these, a methyl group, an ethyl group, and a propyl group are preferable.
  • Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R 33 and R 34 include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.
  • Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R 33 and R 34 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
  • P and q are preferably integers of 0 to 2, preferably 0 or 1.
  • Examples of the compound (1a) include compounds represented by the formulas (1-1) to (1-43).
  • R represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.
  • C.I. I. Acid red 289 sulfonamidation product C.I. I. Quaternary ammonium salt of Acid Red 289, C.I. I. Acid violet 102 sulfonamidate or C.I. I.
  • the quaternary ammonium salt of Acid Violet 102 is preferred.
  • examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), or formula (1-12).
  • a compound represented by any one of formulas (1-24) to (1-33) is also preferable from the viewpoint of excellent solubility in an organic solvent.
  • xanthene pigment As the xanthene pigment, a commercially available xanthene dye (for example, “Chugai Aminol Fast Pin RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) can be used. . Alternatively, a commercially available xanthene dye can be used as a starting material and synthesized with reference to Japanese Patent Application Laid-Open No. 2010-32999, the contents of which are incorporated herein.
  • Dipyrromethene-based metal complex compound examples include compounds in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound.
  • R 1 to R 6 each independently represents a hydrogen atom or a monovalent substituent listed in the above-mentioned substituent group A, and R 7 represents a hydrogen atom, a halogen atom, an alkyl group, Represents an aryl group or a heterocyclic group.
  • R 1 and R 2 , R 2 and R 3 , R 4 and R 5 , and R 5 and R 6 are each independently bonded to each other to form 5-membered, 6-membered or 7-membered
  • a ring may be formed.
  • the ring formed include a saturated ring and an unsaturated ring.
  • Examples of the 5-membered, 6-membered or 7-membered saturated ring or unsaturated ring include a pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, Examples include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
  • the 5-membered, 6-membered and 7-membered rings formed are further substitutable groups, they may be substituted with any of the above-mentioned substituent group A, and two or more substituents In the case where the substituent is substituted, the substituents may be the same or different.
  • the preferred range of R 7 in the general formula (I) is synonymous with the case where R 1 to R 6 are a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and the preferred range is also the same. .
  • R 1 and R 6 are preferably an alkylamino group, an arylamino group, a carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, or a sulfonamido group, and a carbonamido group, a ureido group,
  • An alkoxycarbonylamino group and a sulfonamide group are more preferable, a carbonamide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are more preferable, and a carbonamide group and a ureido group are particularly preferable.
  • R 2 and R 5 are preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, or a carbamoylsulfonyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, An alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
  • R 3 and R 4 are preferably
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, such as methyl group, ethyl Group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, tert-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and benzyl group.
  • a branched or cyclic alkyl group having 1 to 12 carbon atoms is preferred, and examples thereof include isopropyl group, cyclopropyl group, i-butyl group, tert-butyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group.
  • a secondary or tertiary alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof include an isopropyl group, a cyclopropyl group, an i-butyl group, a tert-butyl group, a cyclobutyl group, and a cyclohexyl group.
  • the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
  • the heterocyclic group includes a 2-thienyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 2 -A benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group or benzotriazol-1-yl group is preferred, and a 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group or 1-pyridyl group is more preferred. preferable.
  • the metal or metal compound may be any metal atom or metal compound capable of forming a complex, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or 2 Valent metal chlorides are included.
  • metal chlorides such as GeCl 2
  • metal oxides such as TiO and VO
  • metal hydroxides such as Si (OH) 2 are also included.
  • R 1 and R 6 are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy Group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone An amide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulf
  • R 1 and R 6 are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group.
  • R 2 and R 5 are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group , Alkylsulfonyl group, arylsulfonyl group, or sulfo
  • R 3 and R 4 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group
  • dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound is described in paragraphs 0153 to 0176 of JP2012-237985A.
  • the complex compounds represented by 1), (I-2) or (I-3) can be taken into account, the contents of which are incorporated herein.
  • the general formula (I-1), (I-2) or (I-3) is a preferred embodiment of the dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound.
  • the complex compound represented by formula (I-3) is particularly preferred.
  • dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound, the description in paragraphs 0179 to 0186 of JP2012-237985A can be referred to. This content is incorporated herein. Further, specific examples of the dipyrromethene-based metal complex compound include the following compounds.
  • the pigment or dye compound When the pigment or dye compound is blended as a dispersion, it can be prepared according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.
  • the pigment or dye compound can be used as long as the effects of the present invention are not impaired, and the content of the pigment or dye compound is 0.5 to 70 mass based on the total solid content of the colored curable composition of the present invention. % Is preferred. Further, it is preferably added to the colored curable composition so that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05.
  • the mass ratio of the content of the triarylmethane dye and the pigment or dye compound in the colored curable composition is 1.0: 0. 10 to 1.0: 2.0 is preferable, and 1.0: 0.2 to 1.0: 0.8 is more preferable.
  • the total mass of the pigment and the dye compound is preferably within the above range.
  • the colored curable composition of the present invention preferably contains a dispersant.
  • the dispersant used in the coloring composition of the present invention is a polymer compound having an acidic group, a basic group and / or any one thereof as a pigment adsorbing group.
  • the dispersant used in the coloring composition of the present invention preferably contains 5 mol% or less of a so-called ionic dispersant (also expressed as a polyelectrolyte) in which the adsorbing group forms a salt structure with its counter ion in the polymer composition. More preferably, the polymer composition does not contain an ionic dispersant.
  • ionic dispersants are represented by amine salts, quaternary ammonium salts, carboxylates and phosphates, and these are available as commercially available dispersants.
  • the dispersant has a main chain structure of the polymer compound and an adsorption group, and the adsorption group of the dispersant used in the present invention preferably contains at least one of an acidic adsorption group and a basic adsorption group.
  • the dispersant having both acidic and basic adsorbing groups refers to a dispersant having both acidic and basic adsorbing groups.
  • the triarylmethane dye when the colored curable composition contains a dispersant, is further stabilized by making the adsorption group of the dispersant an acidic adsorption group, a basic adsorption group, or both. And the heat resistance of the colored curable composition can be increased. Furthermore, in a color filter or device formed from a colored curable composition, the voltage holding ratio is increased, and the compatibility of the colored curable composition is increased.
  • the present invention in addition to stabilizing the structure of the triarylmethane dye itself, by combining a triarylmethane dye and a dispersant having an adsorption group containing at least one of an acidic adsorption group and a basic adsorption group, Even when a triarylmethane dye, a pigment, and a dispersant are mixed, the structural stability of the triarylmethane dye is not impaired.
  • the acid value of the dispersing agent is preferably 10 to 100 mg / KOH, more preferably 10 to 80 mg / KOH, and 10 to 60 mg / KOH. Is more preferably 10 to 55 mg / KOH.
  • the amine value is preferably 3 to 100 mg / KOH, more preferably 10 to 100 mg / KOH, and further preferably 10 to 80 mg / KOH. It is preferably 10 to 50 mg / KOH, more preferably 10 to 40 mg / KOH.
  • the acid value and amine value of the dispersing agent are preferably within the above ranges.
  • the stability of the triarylmethane dye is further improved.
  • the main chain structure of the polymer compound includes, as addition polymerization polymers, vinyl polymers such as polystyrene, polymethacrylic acid ester, polyacrylic acid ester, polyvinyl polyalkylate, polyacrylamide, polyacrylonitrile, polyvinyl chloride, and polyvinyl alcohol.
  • Vinyl polymers such as polystyrene, polymethacrylic acid ester, polyacrylic acid ester, polyvinyl polyalkylate, polyacrylamide, polyacrylonitrile, polyvinyl chloride, and polyvinyl alcohol.
  • Polyolefin polymers such as polyethylene, polypropylene and polyisobutylene, diene polymers such as polybutadiene and polyisoprene, polyethyleneimine and the like
  • condensation polymers such as polyester, polyamide, polyether, polyurethane resin, epoxy resin, melamine resin Etc. are used respectively.
  • various polymers can be copolymerized with various monomers in order to develop the desired performance.
  • monomers to be copolymerized include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) ) Acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylic esters such as tetrahydrofurfuryl (meth) acrylate, sty
  • the structure of the polymer compound formed by polymerization may be any of a random polymer, a block polymer, and a graft polymer.
  • condensation polymers include urethane resin structures: tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and cyclized trimerized oligomers of these isocyanate groups, ethylene glycol, propylene glycol, tetramethylene glycol, hexanediol, decane Diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone, etc.
  • urethane resin structures tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and cyclized trimerized oligomers of these isocyanate groups, ethylene glycol, propylene glycol, tetramethylene glycol, hexanediol, decane Diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone, etc.
  • the acidic adsorbing group, the basic adsorbing group or both adsorbing groups are preferably bonded to the above-described polymer compound as a substituent.
  • the acidic adsorption group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.
  • Examples of basic adsorption groups include amino groups, alkylamino groups, imidazole groups, oxazole groups, pyridine groups, and morpholino groups.
  • alkyl group corresponding to the alkyl portion of the alkylamino group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and the like, Preferably, a linear or branched alkyl group having 1 to 4 carbon atoms can be used. In addition, a cyclic alkyl group having 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms, such as a cyclopropyl group and a cyclobutyl group, can also be used.
  • the above-mentioned acidic adsorbing group, basic adsorbing group or both adsorbing groups are nonionic adsorbing groups.
  • a dispersant having an acidic adsorbing group, a basic adsorbing group, or both adsorbing groups may be synthesized, or a commercially available dispersant may be used.
  • examples of commercially available dispersants include BYK-182, 161, 162, 163, 2155, 2164, and 9077 manufactured by BYK Chemie as amine dispersants, and BYK-190 manufactured by BYK Chemie as carboxylic acid dispersants, Examples of 191 include BYK-110 and 111 manufactured by Big Chemie as phosphoric acid dispersants.
  • Examples of commercially available dispersants include Solsperse 13240, 20000, 24000, 26000, 28000 manufactured by Avicia.
  • the dispersant can be used within a range not impairing the effects of the present invention, and the content of the dispersant is 0.5 to 30% by mass with respect to the total solid content of the colored curable composition of the present invention. Is more preferable, and 1.0 to 20% by mass is more preferable. Further, the mass ratio of the pigment and the dispersant contained in the colored curable composition is preferably 1: 5 to 5: 1, and more preferably 1: 3 to 1: 1. Furthermore, the mass ratio of the triarylmethane dye and the dispersant contained in the colored curable composition is preferably 10: 1 to 1: 1, and more preferably 5: 1 to 1: 1.
  • the colored curable composition of the present invention contains a polymerizable compound.
  • the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond.
  • compound groups are widely known in this industrial field, and in the present invention, these compounds can be used without any particular limitation. These may be in any chemical form such as, for example, monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and their (co) polymers.
  • Examples of monomers and their (co) polymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and these (co) polymers It is a polymer.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters amides
  • these (Co) polymers preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and these (co) polymers It is a polymer
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • an ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetra Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate Chryrate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate
  • methacrylic acid esters examples include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol.
  • itaconic acid esters for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol Diitaconate, sorbitol tetritaconate, etc., and crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, etc.
  • ethylene glycol diisocrotonate pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc.
  • Le for example, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetra malate, and the like.
  • esters examples include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are preferably used. Furthermore, the ester monomers described above can also be used as a mixture.
  • urethane-based addition-polymerizable compounds produced by the addition reaction of isocyanate and hydroxyl group.
  • Specific examples thereof include, for example, one molecule described in JP-B-48-41708.
  • Vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Compounds and the like.
  • CH 2 C (R) COOCH 2 CH (R ′) OH (A)
  • R and R ′ each independently represent H or CH 3 .
  • dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) Company-made) dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues.
  • These oligomer types can also be used.
  • the structure, details of usage such as single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the colored curable composition.
  • a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable.
  • those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) are used in combination.
  • a method of adjusting both sensitivity and intensity is also effective.
  • the selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment), binder polymer, etc.) contained in the colored curable composition.
  • the method of use is an important factor.
  • the compatibility may be improved by using a low-purity compound or using two or more kinds in combination.
  • a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.
  • the content of the polymerizable compound in the total solid content of the colored curable composition is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, from the viewpoint of more effectively obtaining the effects of the present invention. From 60% to 60% by weight is particularly preferred.
  • the colored curable composition of this invention may contain only 1 type of polymeric compounds, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.
  • the colored curable composition of the present invention preferably contains a polymerization initiator, and preferably contains at least one photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable compound or a triarylmethane dye containing a polymerizable group, and is selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. Preferably.
  • the photopolymerization initiator examples include at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like.
  • Specific examples of the photopolymerization initiator include those described in paragraphs 0070 to 0077 of JP-A No. 2004-295116. Among these, an oxime compound or a biimidazole compound is preferable from the viewpoint of rapid polymerization reaction.
  • Examples of commercially available photopolymerization initiators include IRGACURE OXE-02 (manufactured by BASF Japan).
  • the oxime compound (hereinafter also referred to as “oxime photopolymerization initiator”) is not particularly limited, and examples thereof include Japanese Patent Application Laid-Open No. 2000-80068, International Publication WO2002 / 100903A1, and Japanese Patent Application Laid-Open No. 2001-233842. Examples thereof include oxime compounds described in publications and the like. As specific examples of the oxime compound, the description in paragraph 0053 of JP2013-182215A can be referred to, and the contents thereof are incorporated in the present specification.
  • the compound represented by the following formula (1) or (2) is more preferable as the oxime compound from the viewpoints of sensitivity, stability with time, and coloring during post-heating.
  • R and X each represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group.
  • n is an integer of 1 to 5.
  • R is preferably an acyl group from the viewpoint of high sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.
  • A is an unsubstituted alkylene group, an alkylene group substituted with an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating,
  • An alkylene group substituted with an alkenyl group for example, vinyl group, allyl group
  • aryl group for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group
  • a substituted alkylene group is preferred.
  • Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating.
  • the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
  • X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region.
  • An arylthioxy group which may have an amino group and an amino group which may have a substituent are preferable.
  • n is preferably an integer of 1 to 2.
  • R 101 represents an alkyl group, an alkanoyl group, an alkenoyl group, an aryloyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a heteroaryloxycarbonyl group, an alkylthiocarbonyl group, an arylthiocarbonyl group.
  • Rf represents a carbocyclic aromatic group or a heterocyclic aromatic group.
  • R 102 represents an alkyl group, an aryl group, or a heterocyclic group, and these may be substituted.
  • R 103 and R 104 each independently represents an alkyl group, an aryl group or a heterocyclic group, and these groups are further substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonyl group or the like. Also good.
  • R 105 to R 111 are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloyl group, a heteroaryloyl group, an alkylthio group, an aryloylthio group, or a heteroaryloyl group.
  • One or two of R 105 to R 111 is an electron-withdrawing substituent, that is, a nitro group, a cyano group, a halogeno group, an alkylcarbonyl group or an arylcarbonyl group, which has a much higher curability. Since a colored curable composition is obtained, it is preferable.
  • the compound having a fluorene structure represented by the general formula (2) can be synthesized according to a synthesis method described in, for example, International Publication WO2014-050738.
  • biimidazole compound As specific examples of the biimidazole compound, the description in paragraphs 0061 to 0070 of JP2013-182213A can be referred to, and the contents thereof are incorporated herein.
  • the content of the photopolymerization initiator in the total solid content of the colored curable composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 19% by mass from the viewpoint of more effectively obtaining the effects of the present invention. Is more preferable, and 0.1 to 18% by mass is particularly preferable.
  • the lower limit may be 3% by mass or more, 4% by mass or more, and 5% by mass or more.
  • the colored curable composition of the present invention may contain only one type or two or more types of photopolymerization initiators. When two or more types are included, the total amount is preferably within the above range.
  • the colored curable composition of the present invention preferably contains at least one organic solvent.
  • the organic solvent is basically not particularly limited as long as it can satisfy the solubility of each of the coexisting components and the coating property when the colored curable composition is used, and in particular, the solubility of the binder, the coating property, It is preferable to select in consideration of safety.
  • organic solvent examples include esters, ethers, ketones, and aromatic hydrocarbons, and specific examples include those described in paragraph numbers 0161 to 0162 of JP2012-032754A.
  • organic solvents are preferably mixed in two or more types from the viewpoints of the solubility of each of the above-mentioned components and, when an alkali-soluble polymer is included, the solubility of the components and the improvement of the coated surface.
  • the content of the organic solvent in the colored curable composition is preferably such that the total solid concentration in the composition is 10 to 80% by mass, more preferably 15 to 60% by mass.
  • the colored curable composition of the present invention may contain only one type of organic solvent or two or more types of organic solvents. When two or more types are included, the total amount is preferably within the above range.
  • the colored curable composition of the present invention preferably contains a resin, and preferably contains an alkali-soluble resin as the resin.
  • the alkali-soluble resin 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 resin 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.
  • the alkali-soluble resin in the present invention includes those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meta) ) Acrylate), polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like 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 chain butyl (meth) acrylate, 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.
  • alkali-soluble resin a copolymer of benzyl methacrylate and methacrylic acid is also preferable.
  • alkali-soluble resin a copolymer of maleimide and ethylene oxide as shown in the following formulas (b1) and (b2) can also be preferably used.
  • R 1 represents a hydrogen atom, an aryl group, or an alkyl group.
  • alkyl group examples include a linear alkyl group having 1 to 10 carbon atoms, an alkyl group having a branched chain having 3 to 10 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group and the like can be mentioned.
  • the alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, an alkoxy group, a hydroxy group, and an amino group.
  • R 1 represents an aryl group
  • examples of the aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring aryl group, a heteroaryl group containing a hetero atom, and the like. More specifically, a phenyl group, a naphthyl group, a biphenyl group, a benzimidazolyl group, a pyridyl group, a furyl group, and the like can be given.
  • the aryl group may have a substituent, and examples of the substituent that can be introduced into the aryl group include an alkyl group such as a methyl group, an ethyl group, a t-butyl group, and a cyclohexyl group, an alkoxy group such as a methoxy group, Examples thereof include a carboxy group, a hydroxy group, an amino group, a nitro group, a chloro group, and a bromo group.
  • R 2 represents a hydrogen atom or a methyl group.
  • R 3 is an alkylene group having 2 or 3 carbon atoms,
  • R 4 represents a hydrogen atom, an aryl group, or an alkyl group, and
  • m represents an integer of 1 to 15.
  • Examples of the alkyl group when R 4 represents an alkyl group include a linear alkyl group having 1 to 20 carbon atoms, an alkyl group having a branched chain having 1 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group, a 2-ethylhexyl group, and the like can be given.
  • the alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, and an alkoxy group.
  • Examples of the aryl group when R 4 represents an aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring aryl group, a heteroaryl group containing a heteroatom, and the like. More specifically, a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, a benzimidazolyl group, an indolyl group, an imidazolyl group, an oxazolyl group, a carbazolyl group, a pyridyl group, a furyl group, and the like can be given.
  • the aryl group may have a substituent, and examples of the substituent that can be introduced into the aryl group include a nonyl group, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group and other alkyl groups, and a methoxy group. Examples thereof include an alkoxy group, a carboxy group, a hydroxy group, an amino group, a nitro group, a chloro group, and a bromo group.
  • the alkali-soluble resin 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-mentioned polymer containing a polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like.
  • alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful.
  • 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 resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.
  • a copolymer having a repeating unit represented by the following general formula (2) and an acidic group is preferred, and more preferably a structural unit represented by the general formula (3) in addition to the general formula (2) and the acidic group.
  • R 20 represents a hydrogen atom or a methyl group
  • R 21 to R 25 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an aryl group.
  • R 11 represents a hydrogen atom or a methyl group.
  • R 12 and R 13 each independently represents a hydrogen atom or a carbonyl group having 3 to 20 carbon atoms containing an unsaturated double bond as a partial structure, and both of R 12 and R 13 are hydrogen atoms. Absent. When at least one of R 12 and R 13 represents a carbonyl group having 3 to 20 carbon atoms containing an unsaturated double bond as a partial structure, it may further contain a carboxy group as a partial structure.
  • acrylic resins include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and commercially available KS resist 106 (Osaka).
  • benzyl (meth) acrylate (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like
  • commercially available KS resist 106 Osaka.
  • Organic Chemical Industry Co., Ltd.), Cyclomer P Series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.
  • alkali-soluble resin may contain the structural unit derived from the ethylenically unsaturated monomer shown by following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a hydrogen atom or a benzene ring that may contain a benzene ring.
  • n represents an integer of 1 to 15.
  • the alkylene group of R 2 preferably has 2 to 3 carbon atoms.
  • the alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R 3 may contain a benzene ring.
  • Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
  • the alkali-soluble resin is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1,000 to 200,000 from the viewpoint of developability, liquid viscosity and the like, and 2,000 to 100,000. More preferred is a polymer of 5,000 to 50,000.
  • the blending amount of the alkali-soluble resin is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, based on the total solid content of the colored curable composition.
  • the acid value of the alkali-soluble resin is preferably 10 to 1000 mg / KOH, more preferably 50 to 300 mg / KOH, still more preferably 50 to 200 mg / KOH, and particularly preferably 90 to 200 mg / KOH.
  • the colored curable composition of the present invention may contain only one type or two or more types of alkali-soluble resins. When two or more types are included, the total amount is preferably within the above range.
  • the colored curable composition of the present invention may further contain a crosslinking agent.
  • the crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction.
  • at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group.
  • the colored curable composition of the present invention may contain a surfactant.
  • the surfactant may be nonionic, cationic, or anionic, but a surfactant having an ethylene oxide structure and a fluorosurfactant are preferred.
  • a surfactant having an ethylene oxide structure having an HLB (Hydrophile-Lipophile Balance) value in the range of 9.2 to 15.5 or a fluorosurfactant described in JP-A-2-54202 is preferred.
  • HLB Hydrodrophile-Lipophile Balance
  • Examples of commercially available surfactants include Megafac F554 (manufactured by DIC Corporation).
  • the addition amount of the surfactant is preferably 0.0001 to 2.0% by mass with respect to the total solid content of the colored curable composition, More preferably, the content is 0.005 to 1.0% by mass.
  • the colored curable composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.
  • the colored curable composition of the present invention further contains various additives such as a thermal acid generator, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a sensitizer and a light stabilizer, as necessary. You can leave.
  • various additives such as a thermal acid generator, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a sensitizer and a light stabilizer, as necessary. You can leave.
  • ⁇ Dye stabilizer> In addition to the dye cation, it is preferable to add a dye stabilizer to the colored curable composition of the present invention.
  • a dye stabilizer for example, cationic, anionic, nonionic, amphoteric, silicon-based, fluorine-based surfactants can be used.
  • the surfactants a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed.
  • polymer dispersant examples include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salt and (partial) alkylamine salt; (co) polymer of hydroxyl group-containing unsaturated carboxylic acid ester such as hydroxyl group-containing polyacrylic acid ester or knitted product thereof; sulfonic acid or phosphoric acid having a crosslinkable group And the like.
  • the crosslinkable group a crosslinkable group that can be crosslinked by a radical, an acid, or heat can be used.
  • the colored curable composition of the present invention may contain an antioxidant.
  • the antioxidant include a radical scavenger, a peroxide decomposer, an ultraviolet absorber, and a singlet oxygen quencher.
  • examples of commercially available antioxidants include AO-60 (ADK STAB AO-60 (manufactured by ADEKA)).
  • radical scavenger examples include phenolic antioxidants and hindered amine antioxidants.
  • phenolic antioxidants include hydroxyphenylpropionate compounds, hydroxybenzyl compounds, thiobisphenol compounds, thiomethylphenol compounds, alkanediylphenol compounds, and the like. Of these, hydroxyphenylpropionate compounds are preferred from the viewpoint of the stability of color characteristics.
  • compounds described in paragraphs 0013 to 0034 of JP2012-155243A and paragraphs 0030 to 0042 of JP2013-14748A can be preferably used.
  • a peroxide decomposer is a compound that decomposes peroxides generated by exposure to light into harmless substances and prevents the generation of new radicals.
  • phosphorus antioxidants for example, sulfur antioxidants, sulfur And system antioxidants.
  • sulfur-based antioxidants are preferable from the viewpoint of the stability of color characteristics.
  • ultraviolet absorbers examples include salicylate-based antioxidants and benzophenone-based antioxidants.
  • a singlet oxygen quencher is a compound that can deactivate singlet oxygen by energy transfer from oxygen in a singlet state.
  • an ethylenic compound such as tetramethylethylene and cyclopentene, diethylamine, triethylamine, 1,4- Amines such as diazabicyclooctane (DABCO) and N-ethylimidazole, condensed polycyclic aromatic compounds such as optionally substituted naphthalene, dimethylnaphthalene, dimethoxyanthracene, anthracene and diphenylanthracene; 1,3-diphenylisobenzofuran
  • aromatic compounds such as 1,2,3,4-tetraphenyl-1,3-cyclopentadiene and pentaphenylcyclopentadiene, Harry H.
  • a metal complex having a sulfur atom-containing compound as a ligand can be exemplified.
  • such compounds include transition metal chelate compounds such as nickel complexes, cobalt complexes, copper complexes, manganese complexes, and platinum complexes having bisdithio- ⁇ -diketone, bisphenyldithiol, and thiobisphenol as ligands.
  • the sulfur antioxidant include thiopropionate compounds and mercaptobenzimidazole compounds. Of these, thiopropionate compounds are preferred from the viewpoint of the stability of color characteristics.
  • the antioxidants can be used alone or in admixture of two or more.
  • the content of the antioxidant is preferably 0.01 to 20% by mass, particularly preferably 0.1 to 10% by mass, based on the total solid content of the colored curable composition.
  • the colored curable composition of the present invention can contain a compound that functions as a curing agent.
  • a compound that functions as a curing agent For example, at least one compound selected from the group consisting of aromatic amine compounds, tertiary amine compounds, amine salts, phosphonium salts, amidine salts, amide compounds, thiol compounds, blocked isocyanate compounds, and imidazole ring-containing compounds can be used.
  • the colored curable composition contains such a curing agent, the low-temperature curing of the colored pattern can be more effectively realized. In addition, the storage stability of the colored curable composition can be further improved.
  • a compound that is more easily reduced than the above dye may be added as a dye reduction inhibitor.
  • dye reduction fading can be further suppressed during ITO (Indium Tin Oxide) sputtering after pixel formation.
  • a quinone compound is preferable, and a quinone compound having a molecular weight of about 100 to 800 and having the following structure is preferable.
  • the colored curable composition of the present invention may further contain various additives such as fillers, ultraviolet absorbers, anti-aggregation agents, sensitizers, and light stabilizers as necessary.
  • the acid generator may be a photoacid generator or a thermal acid generator, but a thermal acid generator is preferred.
  • a thermal acid generator is used, the heat resistance of the cured film tends to be further improved. This is based on the fact that one of the causes of the decrease in heat resistance is a decrease in acidity due to the penetration of the alkali developer into the cured film. In other words, the acidity of the cured film has been lowered in the baking treatment step after curing, and the heat resistance is inferior, but by adding a thermal acid generator, acid is generated at the time of baking, and the alkali developer is cured. A decrease in acidity due to penetration into the membrane can be suppressed.
  • the thermal acid generator refers to an acid generator that generates an acid when heated at 100 to 250 ° C. at 101.25 hPa.
  • the acid generated is preferably an acid having a pKa of 5 or less.
  • Specific examples of the acid generated include sulfonic acid, carboxylic acid, phosphoric acid and the like, and sulfonic acid is more preferable.
  • the photoacid generator the description in paragraphs 0103 to 0113 of JP-A-2006-259002 can be referred to, and the contents thereof are incorporated herein.
  • Thermal acid generators include ionic compounds (onium salts) and nonionic compounds.
  • ionic compound those containing no heavy metal or halogen ion are preferable, and onium salts of sulfonic acid are preferable.
  • ionic thermal acid generator include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, 1-dimethylthio-4,7-dihydroxynaphthalene, 4-hydroxyphenyldimethyl.
  • Sulfonium benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, these Examples include methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, hexafluorophosphonate and the like.
  • the colored curable composition of the present invention may contain a photosensitizer.
  • a photosensitizer As the sensitizer, 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 photosensitizer is preferably contained in an amount of 50 to 200% by mass with respect to the photopolymerization initiator.
  • the colored curable composition of the present invention may contain a chain transfer agent.
  • the chain transfer agent include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N -Heterocycles such as phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione And an aliphatic polyfunctional mercapto compound such as pentaerythritol tetrakis (3-mercaptobutyrate) and 1,4-bis (3-mercaptobutyryloxy) butane.
  • a chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
  • the content of the chain transfer agent is preferably 0.01 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, and preferably 0.1 to 10% by mass is more preferable, and 0.5 to 5% by mass is particularly preferable.
  • the colored curable composition of the present invention may contain a polymerization inhibitor.
  • a 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 composition by light or heat. ) And the like, inactivate the polymerization initiating species, and play a role of suppressing unintentional initiation of polymerization.
  • the polymerization inhibitors described in paragraphs 0154 to 0173 of JP 2007-334322 A 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 from 0.0001 to 5% by mass, more preferably from 0.001 to 5% by mass, based on the total mass of the polymerizable compound. 001 to 1 mass is particularly preferred.
  • the colored curable composition of the present invention may contain an adhesion improving agent.
  • the adhesion improver is a compound that improves the adhesion between a cured film and an inorganic substance serving as a substrate, for example, a silicon compound such as glass, silicon, silicon oxide, or silicon nitride, gold, copper, aluminum, or the like.
  • Specific examples include silane coupling agents and thiol compounds.
  • 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 to 20% by mass, more preferably 0.2 to 5% by mass with respect to the total solid content of the colored curable composition. .
  • a development accelerator can be added in order to promote alkali solubility in the non-exposed area and 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 contain various additives, for example, a filler, a polymer compound other than the above, an ultraviolet absorber, an anti-aggregation agent, and the like, if necessary. 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 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 composition.
  • the colored curable composition prepared as described above is preferably filtered using a filter having a pore diameter of 0.01 to 3.0 ⁇ m, more preferably a pore diameter of about 0.05 to 0.5 ⁇ m. Can be used for use.
  • the colored curable composition of the present invention can form a colored cured film excellent in hue and contrast
  • a color filter used in a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.) It can be suitably used for forming colored pixels such as printing inks, inkjet inks, and paints. In particular, it is suitable for use in forming colored pixels for liquid crystal display devices.
  • the colored curable composition of the present invention is preferably a colored curable composition for forming a colored layer of a color filter.
  • the present invention also relates to a colored cured film formed by curing the above-described colored curable composition.
  • the color filter has a colored cured film.
  • the color filter of the present invention is configured by providing a substrate and a colored region made of the colored curable composition of the present invention on the substrate.
  • the colored region on the substrate is composed of colored films 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 comprises a step (A) of applying a colored curable composition of the present invention on a support to form a colored layer (also referred to as a colored curable composition layer), and colored curing. And a step of forming a colored cured film by curing the conductive composition layer, and includes the following step (a) or step (b).
  • (B) A step of dry etching the colored cured film to obtain a resist pattern.
  • the manufacturing method of the color filter of this invention apply
  • the colored curable composition layer formed in the step (A) may be exposed to a pattern and developed to form a colored region (colored pattern) (B).
  • the step (C) of irradiating the colored pattern formed in the step (B) with ultraviolet rays and the colored pattern irradiated with the ultraviolet rays in the step (C) are applied.
  • the aspect which further provided the process (D) which heat-processes is preferable.
  • the method for producing a color filter of the present invention comprises a step of applying the above-described colored curable composition of the present invention on a support to form a colored curable composition layer, and the above colored curable composition layer. It is also preferable to include a step of exposing in a pattern and a step of developing and removing unexposed portions to form a colored pattern.
  • the manufacturing method of the color filter of the present invention will be described more specifically.
  • the support examples include soda glass, alkali-free glass, borosilicate glass, quartz glass, silicon substrate, and resin substrate used for liquid crystal display devices and the like. Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.
  • Examples of the pre-baking conditions include 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 curable composition layer formed from the colored curable composition is appropriately selected according to the purpose.
  • the range of 0.2 to 5.0 ⁇ m is preferable, and the range of 1.0 to 4.0 ⁇ m is more preferable.
  • the range of 0.2 to 5.0 ⁇ m is preferable, and the range of 0.3 to 2.5 ⁇ m is more preferable.
  • the thickness of a colored curable composition layer is a film thickness after drying.
  • 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 in the range of 300 to 410 nm, more preferably in the range of 300 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 amount is preferably in the range of 1 to 100 mJ / cm 2 from the viewpoint of productivity, and more preferably in the range of 1 to 50 mJ / cm 2 .
  • the colored curable composition layer after exposure is developed with a developer.
  • a developer dissolves the uncured portion of the colored curable composition 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.
  • the development time is preferably 30 to 300 seconds, more preferably 30 to 120 seconds.
  • the development temperature is preferably 20 to 40 ° C, more preferably 23 ° 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 post-exposure by ultraviolet irradiation can be performed on a colored pattern (pixel) formed using a colored curable composition.
  • the colored pattern can be further cured by subjecting the formed colored pattern to heat treatment (so-called post-bake treatment).
  • 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 to 300 ° C., more preferably 150 to 250 ° C.
  • the heating time is preferably about 10 to 120 minutes.
  • the colored pattern thus obtained constitutes a pixel in the color filter.
  • the above steps (A), (B), and if necessary, the steps (C) and (D) are repeated according to the desired number of colors. Good.
  • the color filter obtained by the method for producing a color filter of the present invention uses the colored curable composition of the present invention
  • the color filter is excellent in heat resistance
  • the element having the color filter is a voltage. Excellent retention.
  • the color filter of the present invention is excellent in hue and contrast. When used in a liquid crystal display device, it is possible to display an image having excellent spectral characteristics and contrast while achieving a good hue.
  • a film thickness of the colored pattern (colored pixel) in the color filter of the present invention 3.0 ⁇ m or less is preferable, and 2.5 ⁇ m or less is more preferable.
  • the color filter of the present invention can be used in an image display device such as a liquid crystal display device or an organic EL (Electro-Luminescence) display device, and is particularly suitable for use in a liquid crystal display device.
  • the liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics.
  • the image display device of the present invention preferably has at least three color filters of red, green and blue, and the blue color filter preferably uses the above-described colored curable composition.
  • liquid crystal display devices For the definition of liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Sangyo Tosho) Issued in 1989).
  • the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 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 (thin film transistor) type 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.)”.
  • the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), a STN (Super-Twist Nematic).
  • IPS In Plane Switching
  • MVA Multi-domain Vertical Alignment
  • STN Super-Twist Nematic
  • the color filter of the present invention can also be used for a bright and high-definition 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 element, 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 Light Emitting Diode)) as a backlight, a liquid crystal display device with high luminance and high color purity and good color reproducibility can be provided.
  • RGB-LED Light Emitting Diode
  • the colored curable composition of the present invention can be preferably used as a solid-state imaging device.
  • the configuration of the solid-state imaging device is a configuration provided with a color filter manufactured using the colored curable composition of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. The following configurations are listed.
  • a transfer electrode composed of a plurality of photodiodes, polysilicon, and the like constituting a light receiving area of a solid-state imaging device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) on a support.
  • CCD charge coupled device
  • CMOS complementary metal oxide semiconductor
  • a light-shielding film made of tungsten or the like that is open only on the light-receiving part of the photodiode on the photodiode and the transfer electrode, and is formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part.
  • the device has a device protective film made of silicon nitride or the like, and has the color filter for a solid-state imaging device of the present invention on the device protective film. Further, a configuration having light collecting means (for example, a microlens, etc., the same applies hereinafter) on the device protective film and below the color filter (on the side close to the support), or a structure having the light collecting means on the color filter. Etc.
  • TAM001-A 2.6 g, sodium hydride (oil mixture, 60% by mass, Tokyo Chemical Industry Co., Ltd.) 0.63 g, N-methylpyrrolidone 25 mL mixed solution with 1-iodopropane (Kanto Chemical Co., Ltd.) ) 14 g was added dropwise at room temperature. The solution after dropping was stirred at 75 ° C. for 2 hours. After cooling the reaction solution to room temperature, 100 mL of water was added. The pH of the solution was adjusted to 6-7 with hydrochloric acid, and the precipitated crude crystals were filtered. The crude crystals were suspended and washed with n-hexane to obtain 2.0 g of TAM001-B crystals.
  • TAM001-C (60 g), 38 g of triethylamine, 300 mL of acetonitrile, and 50 mL of tetrahydrofuran were placed in a flask, and while cooling with ice water, 32 g of acrylic acid chloride was added dropwise so that the internal temperature did not exceed 5 degrees. After stirring for 2 hours while cooling with ice, the solvent was concentrated and removed, water and ethyl acetate were added for extraction, and the resulting organic layer was concentrated and purified by silica gel column chromatography to obtain 44 g of TAM001-D. .
  • TAM001-B 5.3 parts by mass
  • TAM001-D 3.4 parts by mass
  • phosphorus oxychloride 3.1 parts by mass
  • toluene 50 parts by mass
  • Hexane 100 parts by mass
  • methanol 100 parts by mass
  • lithium bistrifluoromethanesulfonylimide 5 parts by mass
  • Water 200 parts by mass
  • the obtained crude product was purified by silica gel column chromatography to obtain 4.8 parts by mass of TAM001.
  • ⁇ max ethyl acetate solution
  • ⁇ ethyl acetate solution
  • TAM002 was synthesized by the same method as TAM001.
  • TAM003 was synthesized according to the following route in the same manner as TAM001. ⁇ max (ethyl acetate solution) of the absorption spectrum was 580 nm, and ⁇ (ethyl acetate solution) was 77000.
  • TAM004 was synthesized according to the following route in the same manner as TAM001.
  • the absorption spectrum had a ⁇ max (ethyl acetate solution) of 579 nm and ⁇ (ethyl acetate solution) of 78000.
  • TAM005 was synthesized by the same method as TAM004.
  • TAM006 was synthesized according to the following route in the same manner as TAM001. In the absorption spectrum, ⁇ max (ethyl acetate solution) was 580 nm, and ⁇ (ethyl acetate solution) was 80000.
  • TAM007 was synthesized according to the following route in the same manner as TAM001.
  • the absorption spectrum had a ⁇ max (ethyl acetate solution) of 579 nm and ⁇ (ethyl acetate solution) of 78000.
  • TAM008 was synthesized according to the following route in the same manner as TAM001. ⁇ max (ethyl acetate solution) of the absorption spectrum was 578 nm, and ⁇ (ethyl acetate solution) was 79000.
  • TAM009 was synthesized according to the following route in the same manner as TAM001.
  • ⁇ max ethyl acetate solution
  • ⁇ ethyl acetate solution
  • TAM010 was synthesized according to the following route in the same manner as TAM001.
  • ⁇ max ethyl acetate solution
  • ⁇ ethyl acetate solution
  • TAM011 was synthesized according to the following route in the same manner as TAM001. In the absorption spectrum, ⁇ max (ethyl acetate solution) was 580 nm, and ⁇ (ethyl acetate solution) was 79000.
  • TAM005P was synthesized in the same manner as TAM004P.
  • TAM006P was synthesize
  • the intermediate of Dye001 and Dye001 used in the present invention can be synthesized using the synthesis method described in paragraph 0159 of JP2013-144724A and paragraphs 0062 to 0064 of JP2013-116955A.
  • the xanthene dye 1-32 was obtained by introducing a propyl group into the following xanthene dye A using propyl bromide in the presence of sodium hydride.
  • the molar extinction coefficient of Dye001 in methanol was 68,000, and the maximum absorption wavelength was 567 nm.
  • Dye002 (dipyrromethene metal complex compound)
  • Dye002 can be synthesized by a method for synthesizing a dipyrromethene metal complex compound described in paragraphs 0131 to 0157 of JP-A-2008-292970.
  • TAM012 was synthesized according to the following route.
  • TAM013 was synthesized by the same method as TAM012.
  • TAM016-A was synthesized by the same method except that aniline was used instead of 2,4,6-trimethylaniline in the synthesis of TAM001-A.
  • Dye901 was synthesized according to the following procedure.
  • Dye904 was synthesized in the same procedure as Dye903 using the following compounds.
  • Dye905-A was synthesized in the same manner except that ethylaniline was used instead of N-ethyl-p-toluidine.
  • TAM001-Ds were synthesized in the same manner as the synthesis of TAM001.
  • Dye905 was synthesized according to the following procedure.
  • Dye008-A was synthesized by the same method except that p-toluidine was used instead of 2,4,6-trimethylaniline in the synthesis of TAM001-A.
  • Dye908 was synthesized in the same procedure as Dye903 using the following compounds.
  • Dye910 was synthesized in the same procedure as Dye903 using the following compound.
  • Pigment dispersion 1 was prepared as follows. The raw materials were mixed so that the composition described below was obtained, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. For 3 hours to prepare a mixed solution. Furthermore, the dispersion process was performed for 8 hours with a bead disperser Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) using 0.1 mm ⁇ zirconia beads.
  • the adsorption group of Disperbyk110 is a phosphate (acid value 53 mgKOH / g).
  • composition ⁇ C. I. Pigment Blue 15: 6 9.7 parts Dispersbyk110 manufactured by Big Chemie (non-volatile content 52%) 13.3 parts propylene glycol methyl ether acetate (hereinafter referred to as PGMEA) 77.0 parts
  • Pigment dispersion 2 was prepared in the same manner as pigment dispersion 1, except that the dispersant was changed to Disperbyk 162 (Bic Chemie, nonvolatile content 38%). The amount of PGMEA added was adjusted so that the non-volatile content of the dispersant in the pigment dispersion was equal to that of the pigment dispersion 1.
  • the adsorption group of Disperbyk162 is an amine (amine value 13 mgKOH / g).
  • Pigment dispersion 3 was prepared in the same manner as pigment dispersion 1 except that the dispersant was changed to Disperbyk 191 (by Big Chemie, non-volatile content 98%). The amount of PGMEA added was adjusted so that the non-volatile content of the dispersant in the pigment dispersion was equal to that of the pigment dispersion 1.
  • the adsorption group of Disperbyk 191 is a carboxylic acid adsorption group (acid value 30 mgKOH / g).
  • Pigment dispersion 4 was prepared as follows. The raw materials were mixed so that the composition described below was obtained, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. For 3 hours to prepare a mixed solution. Furthermore, the dispersion process was performed for 8 hours with a bead disperser Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) using 0.1 mm ⁇ zirconia beads.
  • the adsorption group of Disperbyk2000 is quaternary ammonium (amine value 4 mgKOH / g).
  • composition ⁇ C. I. Pigment Blue 15: 6 9.7 parts ⁇ Disperbyk2000 manufactured by Big Chemie (nonvolatile content 40%) 17.3 parts propylene glycol methyl ether acetate (PGMEA) 73.0 parts
  • a pigment dispersion 5 was prepared in the same manner as the pigment dispersion 4 except that the dispersant was changed to Disperbyk 140 (Bic Chemie, non-volatile content 52%).
  • the amount of PGMEA added was adjusted so that the non-volatile content of the dispersant in the pigment dispersion was equal to that of the pigment dispersion 4.
  • the adsorption group of Disperbyk140 is an alkylammonium salt adsorption group (acid value 73 mgKOH / g, amine value 76 mgKOH / g).
  • a pigment dispersion 5 was prepared in the same manner as the pigment dispersion 4 except that the dispersant was changed to Disperbyk 142 (by Big Chemie, nonvolatile content 60%). The amount of PGMEA added was adjusted so that the non-volatile content of the dispersant in the pigment dispersion was equal to that of the pigment dispersion 4.
  • the adsorption group of Disperbyk142 is a phosphate adsorption group (acid value 46 mgKOH / g, amine value 43 mgKOH / g).
  • Example 1 Preparation of colored curable composition
  • a colored curable composition was prepared so as to have the following composition 1.
  • TAM001 was used as the dye compound, and the content of TAM001 was 3.2 parts by mass.
  • composition 1 Details of each component of composition 1 are as follows. Polymerizable compound (T-1): KAYARAD DPHA (Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) Alkali-soluble resin (U-2): allyl methacrylate / methacrylic acid (77/23 “mass ratio” copolymer, weight average molecular weight 37,000, acid value 137 mg KOH / g) -Photopolymerization initiator (V-4): IRGACURE OXE-02 (BASF Japan) ⁇ Crosslinking agent (V-5): Karenz MTBD-1 (Showa Denko KK) ⁇ Crosslinking agent (V-6): Celoxide 2021P (Daicel Chemical Co., Ltd.) Antioxidant (A-1): AO-60: ADK STAB AO-60 (manufactured by ADEKA) Solvent (X-1)
  • Example 2 A colored curable composition was prepared in the same manner as in Example 1 except that the dye compound was a compound described in Table 1 below.
  • Example 15 A colored curable composition was prepared so as to have the following composition 2.
  • TAM001 was used as the dye compound, and the content of TAM001 was 3.2 parts by mass.
  • the pigment dispersion liquid 1 described above was used as the pigment dispersion liquid.
  • Example 16 to 74 A colored curable composition was prepared in the same manner as in Example 15 except that the dye compound was a compound described in Table 2 or 3 below and the pigment dispersion was a pigment dispersion described in Table 2 or 3 below.
  • Example 75 to 101 A colored curable composition was prepared in the same manner as in Example 15 except that the dye compound was a combination of the compounds described in Table 4 below and the pigment dispersion was a pigment dispersion described in Table 4 below.
  • a colored curable composition was prepared in the same manner as in Example 15 except that the dye compound was a compound described in Table 6 or 7 below and the pigment dispersion was a pigment dispersion described in Table 6 or 7 below.
  • the colored layer on which the latent image was formed was developed with an aqueous solution of sodium carbonate / sodium bicarbonate (concentration of 2.4% by mass) at 26 ° C. for 45 seconds, and then rinsed with running water for 20 seconds. After that, it was dried with a spray. The dried film was baked at 230 ° C. for 20 minutes in a clean oven to obtain a blue colored layer A.
  • the surface state of the colored layer A was observed and the resist compatibility was evaluated.
  • an optical microscope manufactured by Olympus Corporation, MX50
  • the resist compatibility was evaluated according to the following evaluation criteria.
  • color unevenness occurs when the dye distribution on the coated surface becomes non-uniform due to the gradual phase separation when the compatibility between the dye and impurities (for example, initiator, monomer, resin component) is poor.
  • Color unevenness is recognized when observed with an optical microscope. When the phase separation is significant, only the same components are gathered at a high concentration and recognized as an aggregate. However, in the following table or standard, such an aggregate is also defined as color unevenness.
  • A Color unevenness is not observed on the surface of the colored layer A, and the resist compatibility is good.
  • B Slightly uneven color unevenness is observed in the periphery of the colored layer A. Resist compatibility is generally good.
  • C Color unevenness is observed on the surface of the colored layer A. There is a problem with resist compatibility.
  • ⁇ Eab (Heat-resistant) A color difference ⁇ Eab between the transmission spectrum of the colored layer A and the transmission spectrum when the colored layer A was further baked at 230 ° C. for 60 minutes was calculated.
  • the ⁇ Eab value is a value obtained from the following color difference formula according to the CIE 1976 (L *, a *, b *) space color system (Japanese Color Society edited by New Color Science Handbook (Showa 60) p.266).
  • a chromaticity meter manufactured by Otsuka Electronics Co., Ltd., MCPD3700 was used for measurement of the transmission spectrum.
  • ⁇ Eab ⁇ ( ⁇ L *) 2 + ( ⁇ a *) 2 + ( ⁇ b *) 2 ⁇ 1/2
  • the heat resistance is good when ⁇ Eab is less than 3.0, and generally good when it is 3.0 or more and less than 5.0.
  • a colored curable composition was applied onto a glass substrate with ITO electrodes (Corning, product name: 1737) so that the film thickness after drying was 2.0 ⁇ m, and dried in an oven at 90 ° C. for 60 seconds (prebaked). )did. Then, exposure was performed at 100 mJ / cm 2 without using a mask (illuminance was 20 mW / cm 2 ), and a 1% aqueous solution of an alkaline developer (product name: CDK-1 manufactured by Fuji Film Electronics Materials Co., Ltd.) was used. It was developed at 25 ° C., washed with water and dried. The dried coating film was heat-treated (post-baked) for 30 minutes in an oven at 230 ° C.
  • the glass substrate on which the colored cured film is formed and the glass substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealant mixed with 5 ⁇ m glass beads, and then a liquid crystal (manufactured by Merck & Co., Ltd.) is bonded between the substrates. , Product name: MJ971189) was injected to produce a liquid crystal cell. Next, after putting the liquid crystal cell in a constant temperature layer at 70 ° C.
  • the colored layer using the colored curable composition of the example has a small ⁇ Eab value and excellent heat resistance. That is, it turned out that in this invention, the colored curable composition excellent in heat resistance can be provided. Moreover, in the element containing the color filter formed using the colored curable composition of an Example, it turned out that the voltage retention is also excellent.
  • the colored curable composition of an Example is excellent also in resist compatibility.
  • a cationic dye if the ion-pairing property with the counter-anion is weak, a part of the cationic dye is present as a cation, so that the compatibility with a hydrophobic polymer, monomer, or solvent tends to deteriorate.
  • the cationic dyes of the examples have high ion-pair properties and high compatibility with hydrophobic polymers, monomers, and solvents. This was found to correlate generally with the low conductivity of the dye solution.

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Abstract

The present invention addresses the problem of providing: a colored curable composition having high heat resistance; a colored cured film; a color filter; a method for producing a color filter; a solid-state imaging element; and an image display device. The present invention relates to a colored curable composition which contains a polymerizable compound and a triarylmethane dye having a triarylmethane structure containing a cation and a counter anion. With respect to this colored curable composition, the conductivity of a solution that is obtained by dissolving 10 mg of the triarylmethane dye into 3 ml of a mixed solvent having a methanol/water volume ratio of 2/1 is less than 20 μs/cm at 23°C.

Description

着色硬化性組成物、着色硬化膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子および画像表示装置Colored curable composition, colored cured film, color filter, method for producing color filter, solid-state imaging device, and image display device
　本発明は、着色硬化性組成物、着色硬化膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子および画像表示装置に関する。 The present invention relates to a colored curable composition, a colored cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device.
　従来、カラーフィルタは、有機顔料や無機顔料を分散させた顔料分散組成物と、多官能モノマー、重合開始剤、アルカリ可溶性樹脂、および必要に応じその他の成分とを含む着色硬化性組成物を用いて、フォトリソグラフィ法やインクジェット法などによって着色パターンを形成することで製造されている。
　近年、カラーフィルタは、液晶表示素子（ＬＣＤ）用途においてモニターのみならずテレビ（ＴＶ）へと用途が拡大している。この用途拡大に伴い、カラーフィルタには、色度やコントラストなどにおいて高度の色特性が要求されている。また、イメージセンサ（固体撮像素子）用途のカラーフィルタにおいても、同様に色ムラの低減、色分解能の向上など色特性の更なる向上が求められるようになっている。 Conventionally, a color filter uses a colored curable composition containing a pigment dispersion composition in which an organic pigment or an inorganic pigment is dispersed and a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin, and other components as necessary. Thus, it is manufactured by forming a colored pattern by a photolithography method or an ink jet method.
In recent years, color filters have been used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this expansion of applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. Similarly, color filters for image sensors (solid-state imaging devices) are required to further improve color characteristics such as reduction of color unevenness and improvement of color resolution.
　ところが、従来の顔料分散系では、顔料の粗大粒子による散乱の発生、分散安定性不良による粘度上昇等の問題が起きやすく、コントラストや輝度をさらに向上させることは困難であることが多い。そこで、着色剤には、顔料だけでなく、染料を用いることが検討されている（例えば、特許文献１）。着色剤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、かつ粗大粒子がなくなるためコントラストを向上させられる点で有用とされている。 However, in conventional pigment dispersion systems, problems such as the occurrence of scattering due to coarse pigment particles and the increase in viscosity due to poor dispersion stability tend to occur, and it is often difficult to further improve contrast and brightness. Therefore, it has been studied to use not only pigments but also dyes as colorants (for example, Patent Document 1). When a dye is used as a colorant, the hue and brightness of a display image when an image is displayed can be increased due to the color purity of the dye itself and the vividness of the hue, and contrast can be improved because coarse particles are eliminated. It is useful in terms.
　ブルー用のカラーフィルタに用いられる染料としては、トリアリールメタン染料が注目されている。しかし、トリアリールメタン染料には、光安定性や熱安定性が低いという課題がある。また、トリアリールメタン染料と着色硬化性組成物中における共雑物が相互作用することにより安定性が低下する場合があり、パネル信頼性が十分ではなかった。このような課題を解決するために、種々のトリアリールメタン構造を有するがトリアリールメタン染料が提案されている。
　また、トリアリールメタン染料の良好な分光特性と顔料系の高耐熱性・高信頼性を両立する手段としてトリアリールメタン染料（またはそのレーキ顔料）と銅フタロシアニン系青色顔料を混合した着色剤の提案がなされている（例えば、特許文献２～４）。 Triarylmethane dyes have attracted attention as dyes used in blue color filters. However, triarylmethane dyes have a problem of low light stability and thermal stability. In addition, the stability may decrease due to the interaction between the triarylmethane dye and the contaminants in the colored curable composition, and the panel reliability is not sufficient. In order to solve such a problem, triarylmethane dyes having various triarylmethane structures have been proposed.
In addition, as a means to achieve both the good spectral characteristics of triarylmethane dyes and the high heat resistance and high reliability of pigments, a colorant that mixes triarylmethane dyes (or their lake pigments) and copper phthalocyanine blue pigments is proposed. (For example, Patent Documents 2 to 4).
　着色剤に顔料が含有されている場合、分散剤が用いられる。分散剤は顔料吸着基を有しており、吸着基として４級アンモニウム塩構造などのイオン性吸着基が知られている。イオン性吸着基を有する分散剤は、微粒化銅フタロシアニン系顔料との相溶性が高く、吸着安定性の高さやそれ自身の高い透明性から近年実用化が進んでいる。特に４級アンモニウム塩構造を有する吸着基に関する提案は数多く存在する（例えば、特許文献５～１２）。また、トリアリールメタン染料などの染料と顔料を混合して用いる場合においても、分散剤の吸着基を、４級アンモニウム塩構造を有する吸着基とすることが提案されている（例えば、特許文献１３および１４）。 When a pigment is contained in the colorant, a dispersant is used. The dispersant has a pigment adsorption group, and an ionic adsorption group such as a quaternary ammonium salt structure is known as the adsorption group. Dispersants having an ionic adsorption group are highly compatible with finely divided copper phthalocyanine pigments, and have recently been put into practical use due to their high adsorption stability and their own high transparency. In particular, there are many proposals relating to an adsorbing group having a quaternary ammonium salt structure (for example, Patent Documents 5 to 12). Further, even when a mixture of a dye such as a triarylmethane dye and a pigment is used, it has been proposed that the adsorption group of the dispersant is an adsorption group having a quaternary ammonium salt structure (for example, Patent Document 13). And 14).
特開平６－７５３７５号公報JP-A-6-75375 特開２０１４－７１３２２号公報JP 2014-71322 A 特開２０１３－１４４７２４号公報JP 2013-144724 A 特開２０１２－１１３２１８号公報JP 2012-113218 A 特開２０１２－６８５５９号公報JP 2012-68559 A 特開２０１１－２１５１８６号公報JP 2011-215186 A 特開２０１２－１２８０１２号公報JP 2012-128012 A 特開２０１１－５７９７４号公報JP 2011-57974 A 特開２０１１－２２５４２号公報JP 2011-22542 A 特開２００１－２８８３８５号公報JP 2001-288385 A 特開２００６－３３８０４３号公報JP 2006-338043 A 特開２００４－３３９３６８号公報JP 2004-339368 A 特開２０１２－２０７１５８号公報JP 2012-207158 A 特開２０１２－２０８１６５号公報JP 2012-208165 A
　しかしながら、トリアリールメタン染料などの染料と顔料を混合して用いる場合において、例えば、４級アンモニウム塩のような塩構造を有する分散剤を用いた場合、４級アンモニウム塩の対アニオンとトリアリールメタン染料の対アニオンが相互作用（極端な例では塩交換）し、トリアリールメタン染料が不安定化し、着色硬化膜の耐熱性を著しく低下させることが本発明者らの検討により明らかとなった。 However, in the case of using a mixture of a dye such as a triarylmethane dye and a pigment, for example, when a dispersant having a salt structure such as a quaternary ammonium salt is used, the counter anion of the quaternary ammonium salt and the triarylmethane are used. It has been clarified by the present inventors that the counter anion of the dye interacts (in the extreme example, salt exchange), the triarylmethane dye becomes unstable, and the heat resistance of the colored cured film is significantly reduced.
　そこで本発明者らは、このような従来技術の課題を解決するために、トリアリールメタン染料を顔料および分散剤と混ぜ合わせた場合であっても、不安定化しないトリアリールメタン染料を提供することを目的として検討を進めた。すなわち、本発明は、安定性の高いトリアリールメタン染料を含む着色硬化性組成物であって、耐熱性の高い着色硬化膜を形成し得る着色硬化性組成物を提供することを課題とする。 Accordingly, the present inventors provide a triarylmethane dye that does not destabilize even when the triarylmethane dye is mixed with a pigment and a dispersant in order to solve such problems of the prior art. We proceeded with a study for this purpose. That is, an object of the present invention is to provide a colored curable composition containing a highly stable triarylmethane dye and capable of forming a colored cured film having high heat resistance.
　上記の課題を解決するために鋭意検討を行った結果、本発明者らは、トリアリールメタン染料のカチオンと対アニオンのイオンペア性を高めることで上述した課題を解決できることを見出した。さらに本発明者らは、イオンペア性の指標として、トリアリールメタン染料を特定溶媒に溶かしたときの電導度を採用できることを見出し、電導度を特定の範囲内とすることでトリアリールメタン染料の安定性を高め得ることを明らかにした。そして、上記トリアリールメタン染料を含む着色硬化性組成物から形成された着色硬化膜は優れた耐熱性を有することを見出し、本発明を完成するに至った。
　具体的に、本発明は、以下の構成を有する。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-described problems can be solved by enhancing the ion-pairing property between the cation and the counter-anion of the triarylmethane dye. Furthermore, the present inventors have found that the conductivity when the triarylmethane dye is dissolved in a specific solvent can be adopted as an ion pair index, and the stability of the triarylmethane dye can be improved by keeping the conductivity within a specific range. It was clarified that sex can be improved. And it discovered that the colored cured film formed from the colored curable composition containing the said triarylmethane dye had the outstanding heat resistance, and came to complete this invention.
Specifically, the present invention has the following configuration.
［１］カチオンを含むトリアリールメタン構造と対アニオンとを有するトリアリールメタン染料と、重合性化合物と、を含む着色硬化性組成物であって、トリアリールメタン染料１０ｍｇを、メタノール／水の体積比が２／１の混合溶媒３ｍｌに溶解させた溶解液の２３℃における電導度が２０μｓ／ｃｍ未満である着色硬化性組成物。
［２］さらに顔料と分散剤とを含み、分散剤の吸着基は、酸性吸着基および塩基性吸着基の少なくとも一方を含む［１］に記載の着色硬化性組成物。
［３］顔料は、銅フタロシアニン系青色顔料である［２］に記載の着色硬化性組成物。
［４］トリアリールメタン染料は、下記一般式（ＴＰ１）で表される化合物を含む［１］～［３］のいずれかに記載の着色硬化性組成物；
Figure JPOXMLDOC01-appb-C000004
 一般式（ＴＰ１）中、Ｒｔｐ２１はそれぞれ独立して水素原子または炭素数１～６のアルキル基を表し、Ｒｔｐ２２は、それぞれ独立して炭素数６～１０のアリール基を表す；Ｒ１は、置換基を表す；Ｘはアニオンを示す。
［５］トリアリールメタン染料は、下記一般式（ＴＰ２）で表される化合物を含む［１］～［４］のいずれかに記載の着色硬化性組成物；
Figure JPOXMLDOC01-appb-C000005
 一般式（ＴＰ２）中、Ｒｔｐ２１はそれぞれ独立して水素原子または炭素数１～６のアルキル基を表し、Ｒｔｐ２２は、それぞれ独立して炭素数６～１０のアリール基を表す；Ｌ１は炭素数２～３０の２価の連結基を表し、Ｐ１は重合性基を表す；Ｘはアニオンを示す。
［６］トリアリールメタン染料は、下記一般式（ＴＰ３）で表される化合物を含む［１］～［５］のいずれかに記載の着色硬化性組成物；
Figure JPOXMLDOC01-appb-C000006
 　一般式（ＴＰ３）中、Ｒｔｐ２３およびＲｔｐ２４はそれぞれ独立して水素原子または炭素数１～４のアルキル基を表し、Ｒｔｐ２５は水素原子または炭素数１～３のアルキル基を表す；Ｌ１は炭素数２～３０の２価の連結基を表し、Ｐ１は重合性基を表す；Ｘはアニオンを示す。
［７］一般式（ＴＰ３）において、Ｌ１は、炭素数６～１０のシクロアルキレン基を含む基である［６］に記載の着色硬化性組成物。
［８］一般式（ＴＰ３）において、Ｐ１はアクリロイル基またはメタクリロイル基である［６］または［７］に記載の着色硬化性組成物。
［９］一般式（ＴＰ３）において、Ｘは、ビストリフルオロメタンスルホニルイミドアニオン、トリストリフルオロメタンスルホニルメチドアニオンまたはパーフルオロメタンスルホン酸アニオンを表す［６］～［８］のいずれかに記載の着色硬化性組成物。
［１０］トリアリールメタン染料は、多量体構造を含む［１］～［９］のいずれかに記載の着色硬化性組成物。
［１１］カラーフィルタの着色層形成用である［１］～［１０］のいずれかに記載の着色硬化性組成物。
［１２］［１］～［１１］のいずれかに記載の着色硬化性組成物を硬化させてなる着色硬化膜。
［１３］［１２］に記載の着色硬化膜を有するカラーフィルタ。
［１４］［１］～［１１］のいずれかに記載の着色硬化性組成物を支持体上に適用して着色硬化性組成物層を形成する工程と、着色硬化性組成物層を硬化させて着色硬化膜を形成する工程と、を有し、さらに下記（ａ）工程または（ｂ）工程を有するカラーフィルタの製造方法；
　（ａ）着色硬化膜上にフォトレジスト層を形成する工程と、露光および現像することによりフォトレジスト層をパターニングしてレジストパターンを得る工程とを含む工程；
（ｂ）着色硬化膜をドライエッチングしてレジストパターンを得る工程。
［１５］［１４］に記載のカラーフィルタの製造方法によって製造されたカラーフィルタ。
［１６］［１３］または［１５］に記載のカラーフィルタを有する固体撮像素子。
［１７］［１３］または［１５］に記載のカラーフィルタを有する画像表示装置。 [1] A colored curable composition containing a triarylmethane dye having a triarylmethane structure containing a cation and a counter anion and a polymerizable compound, wherein 10 mg of the triarylmethane dye is added to a volume of methanol / water. A colored curable composition having a conductivity at 23 ° C. of less than 20 μs / cm in a solution dissolved in 3 ml of a mixed solvent having a ratio of 2/1.
[2] The colored curable composition according to [1], further including a pigment and a dispersant, wherein the adsorption group of the dispersant contains at least one of an acidic adsorption group and a basic adsorption group.
[3] The colored curable composition according to [2], wherein the pigment is a copper phthalocyanine blue pigment.
[4] The colored curable composition according to any one of [1] to [3], wherein the triarylmethane dye contains a compound represented by the following general formula (TP1);
Figure JPOXMLDOC01-appb-C000004
 In the general formula (TP1), Rtp 21 each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Rtp 22 each independently represents an aryl group having 6 to 10 carbon atoms; R 1 is Represents a substituent; X represents an anion.
[5] The colored curable composition according to any one of [1] to [4], wherein the triarylmethane dye contains a compound represented by the following general formula (TP2);
Figure JPOXMLDOC01-appb-C000005
 In the general formula (TP2), Rtp 21 each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Rtp 22 each independently represents an aryl group having 6 to 10 carbon atoms; L 1 is Represents a divalent linking group having 2 to 30 carbon atoms, P 1 represents a polymerizable group, and X represents an anion.
[6] The colored curable composition according to any one of [1] to [5], wherein the triarylmethane dye includes a compound represented by the following general formula (TP3);
Figure JPOXMLDOC01-appb-C000006
 In general formula (TP3), Rtp 23 and Rtp 24 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Rtp 25 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; L 1 Represents a divalent linking group having 2 to 30 carbon atoms, P 1 represents a polymerizable group, and X represents an anion.
[7] The colored curable composition according to [6], wherein in the general formula (TP3), L 1 is a group containing a cycloalkylene group having 6 to 10 carbon atoms.
[8] The colored curable composition according to [6] or [7], wherein in general formula (TP3), P 1 is an acryloyl group or a methacryloyl group.
[9] The coloring according to any one of [6] to [8], wherein in the general formula (TP3), X represents a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a perfluoromethanesulfonic acid anion. Curable composition.
[10] The colored curable composition according to any one of [1] to [9], wherein the triarylmethane dye includes a multimeric structure.
[11] The colored curable composition according to any one of [1] to [10], which is used for forming a colored layer of a color filter.
[12] A colored cured film obtained by curing the colored curable composition according to any one of [1] to [11].
[13] A color filter having the colored cured film according to [12].
[14] A step of applying the colored curable composition according to any one of [1] to [11] onto a support to form a colored curable composition layer, and curing the colored curable composition layer. Forming a colored cured film, and a method for producing a color filter further comprising the following step (a) or step (b):
(A) including a step of forming a photoresist layer on the colored cured film and a step of patterning the photoresist layer by exposure and development to obtain a resist pattern;
(B) A step of dry etching the colored cured film to obtain a resist pattern.
[15] A color filter manufactured by the method for manufacturing a color filter according to [14].
[16] A solid-state imaging device having the color filter according to [13] or [15].
[17] An image display device having the color filter according to [13] or [15].
　本発明によれば、着色硬化性組成物中のトリアリールメタン染料の安定性を高めることができるため、着色硬化性組成物から形成される着色硬化膜の耐熱性を高めることができる。また、本発明によれば、トリアリールメタン染料と顔料および分散剤を混合した着色硬化性組成物からも耐熱性の高い着色硬化膜を製造することができる。さらに、このような着色硬化性組成物を用いることによって、耐熱性の高いカラーフィルタ、固体撮像素子および液晶表示装置を提供することが可能となる。 According to the present invention, since the stability of the triarylmethane dye in the colored curable composition can be increased, the heat resistance of the colored cured film formed from the colored curable composition can be increased. Moreover, according to this invention, a colored cured film with high heat resistance can be manufactured also from the colored curable composition which mixed the triarylmethane dye, the pigment, and the dispersing agent. Furthermore, by using such a colored curable composition, it is possible to provide a color filter, a solid-state imaging device, and a liquid crystal display device having high heat resistance.
　以下において、本発明について詳細に説明する。以下に記載する構成要件の説明は、代表的な実施形態や具体例に基づいてなされることがあるが、本発明はそのような実施形態に限定されない。なお、本明細書において「～」を用いて表される数値範囲は「～」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。 Hereinafter, the present invention will be described in detail. The constituent elements described below may be described based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. 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.
　本明細書における基（原子団）の表記に於いて、置換および無置換を記していない表記は、置換基を有さない基（原子団）と共に置換基を有する基（原子団）をも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　また、本明細書中における「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等を意味する。また、本発明において光とは、活性光線または放射線を意味する。
　本明細書中における「露光」とは、特に断らない限り、水銀灯、エキシマレーザーに代表される遠紫外線、Ｘ線、ＥＵＶ光などによる露光のみならず、電子線、イオンビーム等の粒子線による描画も露光に含める。
　また、本明細書において、“（メタ）アクリレート”はアクリレートおよびメタクリレートの双方、または、いずれかを表し、“（メタ）アクリル”はアクリルおよびメタクリルの双方、または、いずれかを表し、“（メタ）アクリロイル”はアクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
　また、本明細書において、“単量体”と“モノマー”とは同義である。
　本明細書における単量体は、オリゴマーおよびポリマーと区別され、重量平均分子量が２，０００以下の化合物をいう。
　本明細書において、重合性化合物とは、重合性官能基を有する化合物のことをいい、単量体であっても、ポリマーであってもよい。重合性官能基とは、重合反応に関与する基を言う。
　本明細書において、化学式中のＭｅはメチル基を、Ｅｔはエチル基を、Ｐｒはプロピル基を、Ｂｕはブチル基を、Ｐｈはフェニル基を、ＡＣはアセチル基を示す。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
　本発明における重量平均分子量は、特に述べない限り、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）で測定したものをいう。ＧＰＣは、得られたポリマーについて、溶媒を除去することによって単離し、得られた固形分をテトラヒドロフランにて０．１質量％に希釈して、ＨＬＣ－８０２０ＧＰＣ（東ソー（株）製）にて、ＴＳＫｇｅｌ Ｓｕｐｅｒ Ｍｕｌｔｉｐｏｒｅ ＨＺ－Ｈ（東ソー（株）製、４．６ｍｍＩＤ×１５ｃｍ）を３本直列につないだものをカラムとして測定することができる。条件は、試料濃度を０．３５質量％、流速を０．３５ｍＬ／ｍｉｎ、サンプル注入量を１０μＬ、測定温度を４０℃とし、ＲＩ（Ｒｅｆｒａｃｔｉｖｅ　Ｉｎｄｅｘ）検出器を用いて行うことができる。
　本明細書において、全固形分とは、組成物の全組成から溶剤を除いた成分の総質量をいう。 In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent. To do. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.
Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous.
The monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
In the present specification, the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, Ph represents a phenyl group, and AC represents an acetyl group.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
The weight average molecular weight in the present invention refers to that measured by gel permeation chromatography (GPC) unless otherwise specified. GPC was isolated by removing the solvent from the obtained polymer, and the obtained solid content was diluted to 0.1% by mass with tetrahydrofuran, and HLC-8020 GPC (manufactured by Tosoh Corporation) was used. The column can be measured by connecting three TSKgel Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) in series. The conditions can be performed using a RI (Refractive Index) detector with a sample concentration of 0.35 mass%, a flow rate of 0.35 mL / min, a sample injection amount of 10 μL, and a measurement temperature of 40 ° C.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition.
[着色硬化性組成物]
　本発明は、カチオンを含むトリアリールメタン構造と対アニオンとを有するトリアリールメタン染料と、重合性化合物を含む着色硬化性組成物に関する。本発明の着色硬化性組成物に用いられるトリアリールメタン染料を、メタノール／水の体積比が２／１の混合溶媒３ｍｌに溶解させた溶解液の２３℃における電導度は２０μｓ／ｃｍ未満である。 [Colored curable composition]
The present invention relates to a colored curable composition comprising a triarylmethane dye having a triarylmethane structure containing a cation and a counter anion, and a polymerizable compound. The conductivity at 23 ° C. of a solution obtained by dissolving the triarylmethane dye used in the colored curable composition of the present invention in 3 ml of a mixed solvent having a volume ratio of methanol / water of 2/1 is less than 20 μs / cm. .
　トリアリールメタン染料を溶解させた溶解液の電導度とは、トリアリールメタン染料の電離度と同義である。トリアリールメタン染料を溶解させた溶解液の電導度が小さいほどトリアリールメタン染料のカチオンと対アニオンのイオンペア性が高いことを示す。本発明においては、上記の溶解液の電導度が２０μｓ／ｃｍ未満であれば、トリアリールメタン染料のカチオンと対アニオンのイオンペア性が良好であり、トリアリールメタン染料が安定した性能を発揮することができる。 The electric conductivity of the solution in which the triarylmethane dye is dissolved is synonymous with the ionization degree of the triarylmethane dye. It shows that the ion pair property of the cation and counteranion of a triarylmethane dye is so high that the electrical conductivity of the solution which dissolved the triarylmethane dye is small. In the present invention, if the electric conductivity of the above solution is less than 20 μs / cm, the ion pair property of the cation and the counter anion of the triarylmethane dye is good, and the triarylmethane dye exhibits stable performance. Can do.
　トリアリールメタン染料を溶解させた溶解液は、３ｍｌのメタノール／水の混合溶媒に、１０ｍｇのトリアリールメタン染料を混合し、２０分間撹拌することで作製される。本発明では、このように作製された溶解液を２３℃となるように調整し、電導度を測定する。なお、メタノール／水の混合溶媒は、メタノール／水の体積比が２／１の混合溶媒である。トリアリールメタン染料を溶解させた溶解液の電導度は、電導度計（堀場製作所（株）製、ＬＡＱＵＡｔｗｉｎ ）を用いて測定することができる。すなわち、本明細書中の電導度とは、実施例に記載した方法で測定した電導度のことをいう。
　本発明では、上記の条件で測定した電導度が、２０μｓ／ｃｍ未満であればよく、１６μｓ／ｃｍ以下であることが好ましく、１２μｓ／ｃｍ以下であることがより好ましく、１０μｓ／ｃｍ以下であることがさらに好ましく、８μｓ／ｃｍ以下であることが特に好ましい。下限値については、特に定めるものでは無く、０μｓ／ｃｍであってもよい。 The solution in which the triarylmethane dye is dissolved is prepared by mixing 10 mg of the triarylmethane dye with 3 ml of a mixed solvent of methanol / water and stirring for 20 minutes. In the present invention, the solution thus prepared is adjusted to 23 ° C., and the electrical conductivity is measured. The mixed solvent of methanol / water is a mixed solvent having a volume ratio of methanol / water of 2/1. The electric conductivity of the solution in which the triarylmethane dye is dissolved can be measured using an electric conductivity meter (LAQUATwin, manufactured by Horiba, Ltd.). That is, the electric conductivity in this specification means the electric conductivity measured by the method described in the examples.
In the present invention, the electrical conductivity measured under the above conditions may be less than 20 μs / cm, preferably 16 μs / cm or less, more preferably 12 μs / cm or less, and 10 μs / cm or less. More preferably, it is particularly preferably 8 μs / cm or less. The lower limit is not particularly defined and may be 0 μs / cm.
　トリアリールメタン染料を溶解させた溶解液の電導度は、堀場製作所（株）製のＬＡＱＵＡｔｗｉｎ以外が入手不可能または測定不可能な場合、順に、堀場製作所（株）製のｐＨ電極　６３７７－１０Ｄ、１０７６Ａ－１０Ｃ、メトラートレド（株）製のＳ４７０　ｓｅｖｅｎ　ｅｘｃｅｌｌｅｎｃｅ　ｐＨ／導電率メーター、メトロームジャパン株）製のＳ８５６導電率計、東亜ディーケーケー（株）製の電気伝導度計　ＣＭ－３０Ｒを用いて測定することが可能である。 The electrical conductivity of the solution in which the triarylmethane dye is dissolved is not available or cannot be measured except for LAQUATwin manufactured by HORIBA, Ltd. In order, pH electrode 6377-10D manufactured by HORIBA, Ltd. 1076A-10C, S470 conductivity excelence manufactured by METTLER TOLEDO Co., Ltd., pH / conductivity meter, S856 conductivity meter manufactured by Metrohm Japan Co., Ltd., conductivity meter CM-30R manufactured by Toa DKK Co., Ltd. It is possible.
　従来、着色硬化性組成物にトリアリールメタン染料と分散剤が混合されている場合、分散剤の吸着基としては、４級アンモニウム塩構造などのイオン性吸着基が多用されていた。しかし、このような場合、４級アンモニウム塩の対アニオンとトリアリールメタン染料の対アニオンが相互作用することでトリアリールメタン染料が不安定化し、着色硬化性組成物が十分に耐熱性を発揮できないという問題があった。さらに、このような場合、着色硬化性組成物から形成される素子の電気特性（電圧保持率）が著しく低下することや、染料がイオン性となることでカラーレジスト中の共雑物との相溶性を低下させ、ミクロ相分離により塗膜面状（レジスト相溶性）を悪化させることがあった。本発明では、着色硬化性組成物に含まれるトリアリールメタン染料を所定条件で溶解させた溶解液の電導度を上記範囲内となるように抑えることにより、着色硬化性組成物の耐熱性を高めることができる。さらに、本発明では、電導度を上記範囲内となるように抑えることにより、着色硬化性組成物の電気特性（電圧保持率）の低下を抑制することに加え、塗膜面状（レジスト相溶性）も向上させることができる。すなわち、本発明では、トリアリールメタン染料が安定化されているため、本発明の着色硬化性組成物から形成される着色硬化膜およびカラーフィルタは耐熱性に優れる。また、本発明のカラーフィルタを含む素子は電圧保持率が高い。さらに、本発明の着色硬化性組成物は相溶性が高いという利点を有する。 Conventionally, when a triarylmethane dye and a dispersant are mixed in a colored curable composition, an ionic adsorption group such as a quaternary ammonium salt structure has been frequently used as the adsorption group of the dispersant. However, in such a case, the triarylmethane dye becomes unstable due to the interaction between the counter anion of the quaternary ammonium salt and the counter anion of the triarylmethane dye, and the colored curable composition cannot sufficiently exhibit heat resistance. There was a problem. Furthermore, in such a case, the electrical characteristics (voltage holding ratio) of the element formed from the colored curable composition are remarkably lowered, or the dye becomes ionic so that it is compatible with the contaminants in the color resist. In some cases, the solubility was lowered, and the surface state of the coating film (resist compatibility) was deteriorated by microphase separation. In the present invention, the heat resistance of the colored curable composition is increased by suppressing the conductivity of the solution obtained by dissolving the triarylmethane dye contained in the colored curable composition under predetermined conditions to be within the above range. be able to. Furthermore, in the present invention, by suppressing the electrical conductivity to be within the above range, in addition to suppressing a decrease in the electrical properties (voltage holding ratio) of the colored curable composition, the coating film surface state (resist compatibility) ) Can also be improved. That is, in the present invention, since the triarylmethane dye is stabilized, the colored cured film and the color filter formed from the colored curable composition of the present invention are excellent in heat resistance. In addition, an element including the color filter of the present invention has a high voltage holding ratio. Furthermore, the colored curable composition of the present invention has an advantage of high compatibility.
＜トリアリールメタン染料（低分子タイプ）＞
　本発明の着色硬化性組成物はトリアリールメタン染料を含有する。本発明で用いるトリアリールメタン染料は、トリアリールメタン染料１０ｍｇを、メタノール／水の体積比が２／１の混合溶媒３ｍｌに溶解させた際に、溶解液の２３℃における電導度が２０μｓ／ｃｍ未満となるものであればよく、電導度が上記範囲内のものであれば特に制限はない。 <Triarylmethane dye (low molecular weight type)>
The colored curable composition of the present invention contains a triarylmethane dye. The triarylmethane dye used in the present invention has a conductivity of 20 μs / cm at 23 ° C. when dissolved in 3 ml of a mixed solvent having a methanol / water volume ratio of 2/1. There is no particular limitation as long as the conductivity is within the above range.
　本発明で用いる低分子タイプのトリアリールメタン染料の具体例としては、下記一般式（ＴＰ１）で表される化合物を挙げることができる。
Figure JPOXMLDOC01-appb-C000007
 Specific examples of the low molecular type triarylmethane dye used in the present invention include compounds represented by the following general formula (TP1).
Figure JPOXMLDOC01-appb-C000007
　一般式（ＴＰ１）中、Ｒｔｐ２１はそれぞれ独立して水素原子または炭素数１～６のアルキル基を表し、Ｒｔｐ２２は、それぞれ独立して炭素数６～１０のアリール基を表す。Ｒ１は、置換基を表す。Ｘはアニオンを示す。 In general formula (TP1), Rtp 21 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rtp 22 independently represents an aryl group having 6 to 10 carbon atoms. R 1 represents a substituent. X represents an anion.
　一般式（ＴＰ１）中、Ｒｔｐ２１は炭素数１～６のアルキル基が好ましい。アルキル基は、直鎖状、分岐状および環状のいずれであってもよいが、直鎖状が好ましい。アルキル基の炭素数は１～４が好ましく、１～３がより好ましい。アルキル基が有していてもよい置換基としては、後述する置換基群Ａの項で挙げた置換基が挙げられる。
　一般式（ＴＰ１）中、Ｒｔｐ２２は、炭素数６～１０のアリール基を表す。Ｒｔｐ２２は、少なくともオルト位に置換基を有するアリール基であることが好ましい。アリール基が有していてもよい置換基は、後述する置換基群Ａの項で挙げた置換基が挙げられ、炭素数１～３のアルキル基が好ましく、メチル基またはエチル基がさらに好ましい。このような構成とすることにより、耐熱性をより向上させることができる。 In general formula (TP1), Rtp 21 is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear. The alkyl group preferably has 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. Examples of the substituent that the alkyl group may have include the substituents mentioned in the section of Substituent Group A described later.
In General Formula (TP1), Rtp 22 represents an aryl group having 6 to 10 carbon atoms. Rtp 22 is preferably an aryl group having a substituent at least in the ortho position. Examples of the substituent that the aryl group may have include the substituents described in the section of Substituent Group A described later, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group. By setting it as such a structure, heat resistance can be improved more.
　一般式（ＴＰ１）中、Ｒ１は、置換基を表し、末端に重合性基を有する置換基であることが好ましい。また、Ｒ１は、連結基と重合性基を含む置換基であることがさらに好ましい。連結基は、アルキレン基、シクロアルキレン基、フェニレン基、－ＮＨ－、－Ｃ（＝Ｏ）Ｏ－、－ＯＣ（＝Ｏ）－、－Ｏ－またはこれらの組合せからなる基であることが好ましい。アルキレン基の炭素数は、１～８が好ましく、１～６がより好ましい。シクロアルキレン基の炭素数は６～１２が好ましく、６～１０がより好ましい。また、フェニレン基の炭素数は６～１２が好ましく、６～１０がより好ましい。
　重合性基としては、ラジカル、酸、熱により架橋可能な公知の重合性基を用いることができ、例えば、エチレン性不飽和結合を含む基、環状エーテル基（エポキシ基、オキセタン基）、メチロール基等が挙げられ、特にエチレン性不飽和結合を含む基が好ましく、（メタ）アクリロイル基、（メタ）アクリロイルオキシ基またはビニル基がより好ましく、（メタ）アクリロイル基または（メタ）アクリロイルオキシ基がさらに好ましい。
　一般式（ＴＰ１）中、Ｘはアニオンを表し、アニオンについては後述するが、Ｘはビストリフルオロメタンスルホニルイミドアニオン、トリストリフルオロメタンスルホニルメチドアニオンまたはパーフルオロメタンスルホン酸アニオンであることが好ましい。 In General Formula (TP1), R 1 represents a substituent and is preferably a substituent having a polymerizable group at the terminal. R 1 is more preferably a substituent containing a linking group and a polymerizable group. The linking group is preferably an alkylene group, a cycloalkylene group, a phenylene group, —NH—, —C (═O) O—, —OC (═O) —, —O—, or a combination thereof. . The alkylene group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The cycloalkylene group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The carbon number of the phenylene group is preferably 6 to 12, and more preferably 6 to 10.
As the polymerizable group, a known polymerizable group that can be crosslinked by a radical, acid, or heat can be used. For example, a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), or a methylol group. In particular, a group containing an ethylenically unsaturated bond is preferable, a (meth) acryloyl group, a (meth) acryloyloxy group or a vinyl group is more preferable, and a (meth) acryloyl group or a (meth) acryloyloxy group is further preferable.
In general formula (TP1), X represents an anion, and the anion will be described later. X is preferably a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a perfluoromethanesulfonic acid anion.
置換基群Ａ：
　置換基としては、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、カルボキシル基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アミノ基（アルキルアミノ基、アニリノ基を含む）、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキルまたはアリールスルホニルアミノ基、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、スルホ基、アルキルまたはアリールスルフィニル基、アルキルまたはアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、アリールまたはヘテロ環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、シリル基などが挙げられる。以下詳細に記述する。 Substituent group A:
Substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfa Moylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group Groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl or heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, etc. It is done. Details are described below.
　ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子）、直鎖もしくは分岐のアルキル基（直鎖または分岐の置換もしくは無置換のアルキル基で、好ましくは炭素数１～３０のアルキル基であり、例えばメチル、エチル、ｎ－プロピル、イソプロピル、ｔｅｒｔ－ブチル、ｎ－オクチル、２－クロロエチル、２－シアノエチル、２－エチルヘキシル）、シクロアルキル基（好ましくは、炭素数３～３０の置換または無置換のシクロアルキル基、例えば、シクロヘキシル、シクロペンチルが挙げられ、多シクロアルキル基、例えば、ビシクロアルキル基（好ましくは、炭素数５～３０の置換もしくは無置換のビシクロアルキル基で、例えば、ビシクロ［１，２，２］ヘプタン－２－イル、ビシクロ［２，２，２］オクタン－３－イル）やトリシクロアルキル基等の多環構造の基が挙げられる。好ましくは単環のシクロアルキル基、ビシクロアルキル基であり、単環のシクロアルキル基が特に好ましい。）、 A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms) For example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably substituted with 3 to 30 carbon atoms or Examples thereof include unsubstituted cycloalkyl groups such as cyclohexyl and cyclopentyl, and polycycloalkyl groups such as bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms such as bicyclo [ 1,2,2] heptan-2-yl, bicyclo [2,2,2] octane- - yl) or group of polycyclic structures such as tricycloalkyl groups is preferably a monocyclic cycloalkyl group, a bicycloalkyl group, a monocyclic cycloalkyl group is particularly preferred),..
　直鎖もしくは分岐のアルケニル基（直鎖または分岐の置換もしくは無置換のアルケニル基で、好ましくは炭素数２～３０のアルケニル基であり、例えば、ビニル、アリル、プレニル、ゲラニル、オレイル）、シクロアルケニル基（好ましくは、炭素数３～３０の置換もしくは無置換のシクロアルケニル基で、例えば、２－シクロペンテン－１－イル、２－シクロヘキセン－１－イルが挙げられ、多シクロアルケニル基、例えば、ビシクロアルケニル基（好ましくは、炭素数５～３０の置換もしくは無置換のビシクロアルケニル基で、例えば、ビシクロ［２，２，１］ヘプト－２－エン－１－イル、ビシクロ［２，２，２］オクト－２－エン－４－イル）やトリシクロアルケニル基であり、単環のシクロアルケニル基が特に好ましい。）アルキニル基（好ましくは、炭素数２～３０の置換または無置換のアルキニル基、例えば、エチニル、プロパルギル、トリメチルシリルエチニル基）、 Linear or branched alkenyl group (straight or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl A group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as bicyclo An alkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] Octo-2-en-4-yl) and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred. Cycloalkenyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl group),
　アリール基（好ましくは炭素数６～３０の置換もしくは無置換のアリール基で、例えばフェニル、ｐ－トリル、ナフチル、ｍ－クロロフェニル、ｏ－ヘキサデカノイルアミノフェニル）、ヘテロ環基（好ましくは５～７員の置換もしくは無置換、飽和もしくは不飽和、芳香族もしくは非芳香族、単環もしくは縮環のヘテロ環基であり、より好ましくは、環構成原子が炭素原子、窒素原子および硫黄原子から選択され、かつ窒素原子、酸素原子および硫黄原子のいずれかのヘテロ原子を少なくとも一個有するヘテロ環基であり、さらに好ましくは、炭素数３～３０の５もしくは６員の芳香族のヘテロ環基である。例えば、２－フリル、２－チエニル、２－ピリジル、４－ピリジル、２－ピリミジニル、２－ベンゾチアゾリル）、シアノ基、ヒドロキシル基、ニトロ基、カルボキシル基、 An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-constituting atom is selected from carbon atom, nitrogen atom and sulfur atom And a heterocyclic group having at least one hetero atom of any one of a nitrogen atom, an oxygen atom and a sulfur atom, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, Rokishiru group, a nitro group, a carboxyl group,
　アルコキシ基（好ましくは、炭素数１～３０の置換もしくは無置換のアルコキシ基で、例えば、メトキシ、エトキシ、イソプロポキシ、ｔｅｒｔ－ブトキシ、ｎ－オクチルオキシ、２－メトキシエトキシ）、アリールオキシ基（好ましくは、炭素数６～３０の置換もしくは無置換のアリールオキシ基で、例えば、フェノキシ、２－メチルフェノキシ、２，４－ジ－ｔｅｒｔ－アミルフェノキシ、４－ｔｅｒｔ－ブチルフェノキシ、３－ニトロフェノキシ、２－テトラデカノイルアミノフェノキシ）、シリルオキシ基（好ましくは、炭素数３～２０のシリルオキシ基で、例えば、トリメチルシリルオキシ、ｔｅｒｔ－ブチルジメチルシリルオキシ）、ヘテロ環オキシ基（好ましくは、炭素数２～３０の置換もしくは無置換のヘテロ環オキシ基で、ヘテロ環部は前述のヘテロ環基で説明されたヘテロ環部が好ましく、例えば、１－フェニルテトラゾール－５－オキシ、２－テトラヒドロピラニルオキシ）、 An alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably Is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having a carbon number of 2 to 30 substituted or unsubstituted heterocyclic oxy groups , Heterocyclic portion is preferably described in the heterocyclic portion described above heterocyclic group, e.g., 1-phenyl-5-oxy, 2-tetrahydropyranyloxy),
　アシルオキシ基（好ましくはホルミルオキシ基、炭素数２～３０の置換もしくは無置換のアルキルカルボニルオキシ基、炭素数６～３０の置換もしくは無置換のアリールカルボニルオキシ基であり、例えば、ホルミルオキシ、アセチルオキシ、ピバロイルオキシ、ステアロイルオキシ、ベンゾイルオキシ、ｐ－メトキシフェニルカルボニルオキシ）、カルバモイルオキシ基（好ましくは、炭素数１～３０の置換もしくは無置換のカルバモイルオキシ基で、例えば、Ｎ，Ｎ－ジメチルカルバモイルオキシ、Ｎ，Ｎ－ジエチルカルバモイルオキシ、モルホリノカルボニルオキシ、Ｎ，Ｎ－ジ－ｎ－オクチルアミノカルボニルオキシ、Ｎ－ｎ－オクチルカルバモイルオキシ）、アルコキシカルボニルオキシ基（好ましくは、炭素数２～３０の置換もしくは無置換アルコキシカルボニルオキシ基で、例えばメトキシカルボニルオキシ、エトキシカルボニルオキシ、ｔｅｒｔ－ブトキシカルボニルオキシ、ｎ－オクチルカルボニルオキシ）、アリールオキシカルボニルオキシ基（好ましくは、炭素数７～３０の置換もしくは無置換のアリールオキシカルボニルオキシ基で、例えば、フェノキシカルボニルオキシ、ｐ－メトキシフェノキシカルボニルオキシ、ｐ－ｎ－ヘキサデシルオキシフェノキシカルボニルオキシ）、 An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituent having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms). Substituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),
　アミノ基（好ましくは、アミノ基、炭素数１～３０の置換もしくは無置換のアルキルアミノ基、炭素数６～３０の置換もしくは無置換のアリールアミノ基、炭素数０～３０のヘテロ環アミノ基であり、例えば、アミノ、メチルアミノ、ジメチルアミノ、アニリノ、Ｎ－メチル－アニリノ、ジフェニルアミノ、Ｎ－１，３，５－トリアジン－２－イルアミノ）、アシルアミノ基（好ましくは、ホルミルアミノ基、炭素数１～３０の置換もしくは無置換のアルキルカルボニルアミノ基、炭素数６～３０の置換もしくは無置換のアリールカルボニルアミノ基であり、例えば、ホルミルアミノ、アセチルアミノ、ピバロイルアミノ、ラウロイルアミノ、ベンゾイルアミノ、３，４，５－トリ－ｎ－オクチルオキシフェニルカルボニルアミノ）、アミノカルボニルアミノ基（好ましくは、炭素数１～３０の置換もしくは無置換のアミノカルボニルアミノ基、例えば、カルバモイルアミノ、Ｎ，Ｎ－ジメチルアミノカルボニルアミノ、Ｎ，Ｎ－ジエチルアミノカルボニルアミノ、モルホリノカルボニルアミノ）、アルコキシカルボニルアミノ基（好ましくは炭素数２～３０の置換もしくは無置換アルコキシカルボニルアミノ基で、例えば、メトキシカルボニルアミノ、エトキシカルボニルアミノ、ｔｅｒｔ－ブトキシカルボニルアミノ、ｎ－オクタデシルオキシカルボニルアミノ、Ｎ－メチル－メトキシカルボニルアミノ）、 An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic amino group having 0 to 30 carbon atoms); For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino), acylamino group (preferably formylamino group, carbon number A substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3, 4,5-tri-n-octyloxyphenylcarbonylamino), amino A carbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms such as methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),
　アリールオキシカルボニルアミノ基（好ましくは、炭素数７～３０の置換もしくは無置換のアリールオキシカルボニルアミノ基で、例えば、フェノキシカルボニルアミノ、ｐ－クロロフェノキシカルボニルアミノ、ｍ－ｎ－オクチルオキシフェノキシカルボニルアミノ）、スルファモイルアミノ基（好ましくは、炭素数０～３０の置換もしくは無置換のスルファモイルアミノ基で、例えば、スルファモイルアミノ、Ｎ，Ｎ－ジメチルアミノスルホニルアミノ、Ｎ－ｎ－オクチルアミノスルホニルアミノ）、アルキルまたはアリールスルホニルアミノ基（好ましくは炭素数１～３０の置換もしくは無置換のアルキルスルホニルアミノ基、炭素数６～３０の置換もしくは無置換のアリールスルホニルアミノ基であり、例えば、メチルスルホニルアミノ、ブチルスルホニルアミノ、フェニルスルホニルアミノ、２，３，５－トリクロロフェニルスルホニルアミノ、ｐ－メチルフェニルスルホニルアミノ）、メルカプト基、 Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino Sulfonylamino), alkyl or arylsulfonylamino group (preferably substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methyl Sulfonyl Mino, butyl sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyl sulfonylamino, p- methylphenyl sulfonylamino), a mercapto group,
　アルキルチオ基（好ましくは、炭素数１～３０の置換もしくは無置換のアルキルチオ基で、例えばメチルチオ、エチルチオ、ｎ－ヘキサデシルチオ）、アリールチオ基（好ましくは炭素数６～３０の置換もしくは無置換のアリールチオ基で、例えば、フェニルチオ、ｐ－クロロフェニルチオ、ｍ－メトキシフェニルチオ）、ヘテロ環チオ基（好ましくは炭素数２～３０の置換または無置換のヘテロ環チオ基で、ヘテロ環部は前述のヘテロ環基で説明されたヘテロ環部が好ましく、例えば、２－ベンゾチアゾリルチオ、１－フェニルテトラゾール－５－イルチオ）、スルファモイル基（好ましくは炭素数０～３０の置換もしくは無置換のスルファモイル基で、例えば、Ｎ－エチルスルファモイル、Ｎ－（３－ドデシルオキシプロピル）スルファモイル、Ｎ，Ｎ－ジメチルスルファモイル、Ｎ－アセチルスルファモイル、Ｎ－ベンゾイルスルファモイル、Ｎ－（Ｎ’－フェニルカルバモイル）スルファモイル）、スルホ基、 An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms). , For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, wherein the heterocyclic moiety is the aforementioned heterocyclic group The heterocyclic portion described in the above is preferably, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfur Moil, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), a sulfo group,
　アルキルまたはアリールスルフィニル基（好ましくは、炭素数１～３０の置換または無置換のアルキルスルフィニル基、６～３０の置換または無置換のアリールスルフィニル基であり、例えば、メチルスルフィニル、エチルスルフィニル、フェニルスルフィニル、ｐ－メチルフェニルスルフィニル）、アルキルまたはアリールスルホニル基（好ましくは、炭素数１～３０の置換または無置換のアルキルスルホニル基、６～３０の置換または無置換のアリールスルホニル基であり、例えば、メチルスルホニル、エチルスルホニル、フェニルスルホニル、ｐ－メチルフェニルスルホニル）、アシル基（好ましくはホルミル基、炭素数２～３０の置換または無置換のアルキルカルボニル基、炭素数７～３０の置換もしくは無置換のアリールカルボニル基であり、例えば、アセチル、ピバロイル、２－クロロアセチル、ステアロイル、ベンゾイル、ｐ－ｎ－オクチルオキシフェニルカルボニル）、アリールオキシカルボニル基（好ましくは、炭素数７～３０の置換もしくは無置換のアリールオキシカルボニル基で、例えば、フェノキシカルボニル、ｏ－クロロフェノキシカルボニル、ｍ－ニトロフェノキシカルボニル、ｐ－ｔｅｒｔ－ブチルフェノキシカルボニル）、 An alkyl or arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbocycle having 7 to 30 carbon atoms) For example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryl having 7 to 30 carbon atoms) An oxycarbonyl group, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl),
　アルコキシカルボニル基（好ましくは、炭素数２～３０の置換もしくは無置換アルコキシカルボニル基で、例えば、メトキシカルボニル、エトキシカルボニル、ｔｅｒｔ－ブトキシカルボニル、ｎ－オクタデシルオキシカルボニル）、カルバモイル基（好ましくは、炭素数１～３０の置換もしくは無置換のカルバモイル、例えば、カルバモイル、Ｎ－メチルカルバモイル、Ｎ，Ｎ－ジメチルカルバモイル、Ｎ，Ｎ－ジ－ｎ－オクチルカルバモイル、Ｎ－（メチルスルホニル）カルバモイル）、アリールまたはヘテロ環アゾ基（好ましくは炭素数６～３０の置換もしくは無置換のアリールアゾ基、炭素数３～３０の置換もしくは無置換のヘテロ環アゾ基（ヘテロ環部は前述のヘテロ環基で説明されたヘテロ環部が好ましい）、例えば、フェニルアゾ、ｐ－クロロフェニルアゾ、５－エチルチオ－１，３，４－チアジアゾール－２－イルアゾ）、イミド基（好ましくは、炭素数２～３０の置換もしくは無置換のイミド基で、例えばＮ－スクシンイミド、Ｎ－フタルイミド）、ホスフィノ基（好ましくは、炭素数２～３０の置換もしくは無置換のホスフィノ基、例えば、ジメチルホスフィノ、ジフェニルホスフィノ、メチルフェノキシホスフィノ）、ホスフィニル基（好ましくは、炭素数２～３０の置換もしくは無置換のホスフィニル基で、例えば、ホスフィニル、ジオクチルオキシホスフィニル、ジエトキシホスフィニル）、 An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having a carbon number) 1-30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or hetero A ring azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocycle portion is the heterocycle described in the above heterocyclic group); Ring portion is preferred), for example, phenyl Azo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms such as N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably having 2 carbon atoms) Up to 30 substituted or unsubstituted phosphinyl groups such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),
　ホスフィニルオキシ基（好ましくは、炭素数２～３０の置換もしくは無置換のホスフィニルオキシ基で、例えば、ジフェノキシホスフィニルオキシ、ジオクチルオキシホスフィニルオキシ）、ホスフィニルアミノ基（好ましくは、炭素数２～３０の置換もしくは無置換のホスフィニルアミノ基で、例えば、ジメトキシホスフィニルアミノ、ジメチルアミノホスフィニルアミノ）、シリル基（好ましくは、炭素数３～３０の置換もしくは無置換のシリル基で、例えば、トリメチルシリル、ｔｅｒｔ－ブチルジメチルシリル、フェニルジメチルシリル）が挙げられる。
　置換基Ａ群としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、クロロ原子、メトキシ基が特に好ましい。 A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), a phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substitution having 3 to 30 carbon atoms) Or, an unsubstituted silyl group, for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).
As the substituent group A, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a chloro atom, and a methoxy group are particularly preferable.
　カチオンを含むトリアリールメタン構造は、カチオンが以下のように非局在化して存在しており、下記の構造は同義であり、いずれも本発明に含まれるものとする。なお、カチオン部位は、分子中のどの位置にあってもよい。
Figure JPOXMLDOC01-appb-C000008
 In the triarylmethane structure containing a cation, the cation is delocalized as follows, and the following structures are synonymous, and both are included in the present invention. The cation moiety may be at any position in the molecule.
Figure JPOXMLDOC01-appb-C000008
　トリアリールメタン染料は、下記一般式（ＴＰ２）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000009
 The triarylmethane dye is preferably a compound represented by the following general formula (TP2).
Figure JPOXMLDOC01-appb-C000009
　一般式（ＴＰ２）中、Ｒｔｐ２１はそれぞれ独立して水素原子または炭素数１～６のアルキル基を表し、Ｒｔｐ２２は、それぞれ独立して炭素数６～１０のアリール基を表す。Ｌ１は炭素数２～３０の２価の連結基を表し、Ｐ１は重合性基を表す。Ｘはアニオンを示す。 In general formula (TP2), Rtp 21 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Rtp 22 each independently represents an aryl group having 6 to 10 carbon atoms. L 1 represents a divalent linking group having 2 to 30 carbon atoms, and P 1 represents a polymerizable group. X represents an anion.
　一般式（ＴＰ２）中、Ｒｔｐ２１およびＲｔｐ２２は一般式（ＴＰ１）中のＲｔｐ２１およびＲｔｐ２２と同義であり、好ましい範囲も同様である。
　一般式（ＴＰ２）中、Ｌ１は炭素数２～３０の２価の連結基を表し、炭素数２～３０のアルキレン基、シクロアルキレン基、フェニレン基、－Ｃ（＝Ｏ）Ｏ－、－ＯＣ（＝Ｏ）－、－Ｏ－またはこれらの組合せからなる基であることが好ましい。アルキレン基の炭素数は、１～８が好ましく、１～６がより好ましい。シクロアルキレン基の炭素数は６～１２が好ましく、６～１０がより好ましい。また、フェニレン基の炭素数は６～１２が好ましく、６～１０がより好ましい。
　一般式（ＴＰ２）中、Ｐ１は重合性基を表し、エチレン性不飽和結合を含む基、環状エーテル基（エポキシ基、オキセタン基）、メチロール基等が挙げられ、特にエチレン性不飽和結合を含む基が好ましく、アクリロイル基、メタクリロイル基またはビニル基がより好ましく、アクリロイル基またはメタクリロイル基がさらに好ましい。
　一般式（ＴＰ２）中、Ｘはアニオンを表し、アニオンについては後述するが、Ｘはビストリフルオロメタンスルホニルイミドアニオン、トリストリフルオロメタンスルホニルメチドアニオンまたはパーフルオロメタンスルホン酸アニオンであることが好ましい。 In the general formula (TP2), Rtp 21 and Rtp 22 the general formula (TP1) in the same meaning as Rtp 21 and Rtp 22 of, and preferred ranges are also the same.
In General Formula (TP2), L 1 represents a divalent linking group having 2 to 30 carbon atoms, and includes an alkylene group having 2 to 30 carbon atoms, a cycloalkylene group, a phenylene group, —C (═O) O—, — A group consisting of OC (═O) —, —O— or a combination thereof is preferred. The alkylene group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The cycloalkylene group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The carbon number of the phenylene group is preferably 6 to 12, and more preferably 6 to 10.
In general formula (TP2), P 1 represents a polymerizable group, and examples thereof include a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), a methylol group, and the like. The containing group is preferable, an acryloyl group, a methacryloyl group or a vinyl group is more preferable, and an acryloyl group or a methacryloyl group is more preferable.
In general formula (TP2), X represents an anion, and the anion will be described later. X is preferably a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a perfluoromethanesulfonate anion.
　トリアリールメタン染料は、下記一般式（ＴＰ３）で表される化合物であることが好ましい。
Figure JPOXMLDOC01-appb-C000010
 The triarylmethane dye is preferably a compound represented by the following general formula (TP3).
Figure JPOXMLDOC01-appb-C000010
　一般式（ＴＰ３）中、Ｒｔｐ２３およびＲｔｐ２４はそれぞれ独立して水素原子または炭素数１～４のアルキル基を表し、Ｒｔｐ２５は水素原子または炭素数１～３のアルキル基を表す。Ｌ１は炭素数２～３０の２価の連結基を表し、Ｐ１は重合性基を表す。Ｘはアニオンを示す。 In General Formula (TP3), Rtp 23 and Rtp 24 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Rtp 25 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. L 1 represents a divalent linking group having 2 to 30 carbon atoms, and P 1 represents a polymerizable group. X represents an anion.
　一般式（ＴＰ３）中、Ｒｔｐ２３およびＲｔｐ２４はそれぞれ独立して水素原子または炭素数１～４のアルキル基を表し、炭素数１～４のアルキル基を表すことが好ましく、炭素数１～３のアルキル基を表すことがより好ましい。中でも、Ｒｔｐ２４はメチル基またはエチル基であることがさらに好ましく、メチル基であることが特に好ましい。なお、アルキル基は、直鎖状および分岐状のいずれであってもよいが、直鎖状が好ましい。　
　一般式（ＴＰ３）中、Ｒｔｐ２５は水素原子または炭素数１～３のアルキル基を表し、炭素数１～３のアルキル基を表すことが好ましく、メチル基またはエチル基を表すことがより好ましく、メチル基であることが特に好ましい。
　一般式（ＴＰ３）中のＬ１は一般式（ＴＰ２）中のＬ１と同義であり、好ましい範囲も同様である。また、一般式（ＴＰ３）中のＰ１は一般式（ＴＰ２）中のＰ１と同義であり、好ましい範囲も同様である。
　一般式（ＴＰ３）中、Ｘはアニオンを表し、アニオンについては後述するが、Ｘはビストリフルオロメタンスルホニルイミドアニオン、トリストリフルオロメタンスルホニルメチドアニオンまたはパーフルオロメタンスルホン酸アニオンであることが好ましい。 In general formula (TP3), Rtp 23 and Rtp 24 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and preferably having 1 to 3 carbon atoms. It is more preferable to represent the alkyl group. Among them, Rtp 24 is more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkyl group may be either linear or branched, but is preferably linear.
In general formula (TP3), Rtp 25 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably represents an alkyl group having 1 to 3 carbon atoms, more preferably represents a methyl group or an ethyl group, A methyl group is particularly preferred.
L 1 in the general formula (TP3) is the general formula (TP2) in a L 1 and synonymous, and preferred ranges are also the same. Also, P 1 in the general formula (TP3) is the general formula (TP2) in the same meaning as P 1, and preferred ranges are also the same.
In general formula (TP3), X represents an anion, and the anion will be described later. X is preferably a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a perfluoromethanesulfonate anion.
＜＜アニオンＸ＞＞
　トリアリールメタン染料は、分子内および分子外の少なくともいずれかにアニオンＸを有する。中でも、トリアリールメタン染料は、分子外にアニオンＸを有することが好ましく、分子外にアニオンＸを有することで本発明の着色硬化性組成物を用いた着色硬化膜の耐熱性をより効果的に高めることができる。
　アニオンＸは、トリアリールメタン染料に含まれるカチオンの価数に応じて含まれる。カチオンは、通常、１価または２価であり、１価が好ましい。分子内にアニオンＸを有するとは、１つ以上の共有結合を介してアニオン部位とカチオン部位がトリアリールメタン染料内に存在していることをいう。分子外にアニオンＸを有するとは、上記以外の場合をいう。
　また、本発明におけるアニオンＸは特に定めるものではないが、低求核性アニオンが好ましい。低求核性アニオンとは、硫酸のｐＫａより低いｐＫａを有する有機酸が解離したアニオン構造を示す。 << Anion X >>
The triarylmethane dye has an anion X at least either inside or outside the molecule. Among these, the triarylmethane dye preferably has an anion X outside the molecule, and by having the anion X outside the molecule, the heat resistance of the colored cured film using the colored curable composition of the present invention is more effectively improved. Can be increased.
The anion X is contained according to the valence of the cation contained in the triarylmethane dye. The cation is usually monovalent or divalent, and monovalent is preferable. Having an anion X in the molecule means that an anion site and a cation site are present in the triarylmethane dye via one or more covalent bonds. Having an anion X outside the molecule means a case other than the above.
Further, the anion X in the present invention is not particularly defined, but a low nucleophilic anion is preferable. The low nucleophilic anion indicates an anion structure in which an organic acid having a pKa lower than that of sulfuric acid is dissociated.
　アニオンＸが分子内にある場合とは、アニオンＸがトリアリールメタン染料と同一分子内にある場合であり、具体的には、色素構造を有する繰り返し単位内で、カチオンとアニオンが共有結合を介して結合している場合である。
　この場合のアニオン部としては、－ＳＯ３ －、－ＣＯＯ－、－ＰＯ３ －、下記一般式（Ａ１）で表される構造および下記一般式（Ａ２）で表される構造から選択される少なくとも１種が好ましい。 The case where the anion X is in the molecule is a case where the anion X is in the same molecule as the triarylmethane dye. Specifically, the cation and the anion are bonded via a covalent bond in the repeating unit having a dye structure. This is the case where they are combined.
In this case, the anion moiety is at least selected from —SO 3 − , —COO − , —PO 3 − , a structure represented by the following general formula (A1), and a structure represented by the following general formula (A2). One is preferred.
一般式（Ａ１）
Figure JPOXMLDOC01-appb-C000011
 General formula (A1)
Figure JPOXMLDOC01-appb-C000011
　一般式（Ａ１）中、Ｒ１およびＲ２はそれぞれ独立して－ＳＯ２－または－ＣＯ－を表す。一般式（Ａ１）中、Ｒ１およびＲ２の少なくとも１つが－ＳＯ２－を表すことが好ましく、Ｒ１およびＲ２の両方が－ＳＯ２－を表すことがより好ましい。 In general formula (A1), R 1 and R 2 each independently represents —SO 2 — or —CO—. In formula (A1), at least one of R 1 and R 2 -SO 2 - preferably represents an, both R 1 and R 2 are -SO 2 - and more preferably represents.
　上記一般式（Ａ１）は、下記一般式（Ａ１－１）で表されることがより好ましい。
一般式（Ａ１－１）
Figure JPOXMLDOC01-appb-C000012
 The general formula (A1) is more preferably represented by the following general formula (A1-1).
Formula (A1-1)
Figure JPOXMLDOC01-appb-C000012
　一般式（Ａ１－１）中、Ｒ１およびＲ２はそれぞれ独立して－ＳＯ２－または－ＣＯ－を表す。Ｘ１およびＸ２は、それぞれ独立してアルキレン基またはアリーレン基を表す。）
　一般式（Ａ１－１）中、Ｒ１およびＲ２は、一般式（Ａ１）中のＲ１およびＲ２と同義であり、好ましい範囲も同様である。
　Ｘ１がアルキレン基を表す場合、アルキレン基の炭素数は、１～８が好ましく、１～６がより好ましい。Ｘ１がアリーレン基を表す場合、アリーレン基の炭素数は、６～１８が好ましく、６～１２がより好ましく、６がさらに好ましい。Ｘ１が置換基を有する場合、フッ素原子で置換されていることが好ましい。
　Ｘ２は、アルキル基またはアリール基を表し、アルキル基が好ましい。アルキル基の炭素数は、１～８が好ましく、１～６がより好ましく、１～３がさらに好ましく、１が特に好ましい。Ｘ２が置換基を有する場合、フッ素原子で置換されていることが好ましい。 In general formula (A1-1), R 1 and R 2 each independently represents —SO 2 — or —CO—. X 1 and X 2 each independently represent an alkylene group or an arylene group. )
In formula (A1-1), R 1 and R 2 of the general formula (A1) in the same meaning as R 1 and R 2, and preferred ranges are also the same.
When X 1 represents an alkylene group, the alkylene group preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. When X 1 represents an arylene group, the carbon number of the arylene group is preferably 6 to 18, more preferably 6 to 12, and still more preferably 6. When X 1 has a substituent, it is preferably substituted with a fluorine atom.
X 2 represents an alkyl group or an aryl group, and an alkyl group is preferable. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1. When X 2 has a substituent, it is preferably substituted with a fluorine atom.
一般式（Ａ２）
Figure JPOXMLDOC01-appb-C000013
 General formula (A2)
Figure JPOXMLDOC01-appb-C000013
　一般式（Ａ２）中、Ｒ３は、－ＳＯ２－または－ＣＯ－を表す。Ｒ４およびＲ５はそれぞれ独立して－ＳＯ２－、－ＣＯ－または－ＣＮを表す。
　一般式（Ａ２）中、Ｒ３～Ｒ５の少なくとも１つが－ＳＯ２－を表すことが好ましく、Ｒ３～Ｒ５の少なくとも２つが－ＳＯ２－を表すことがより好ましい。 In general formula (A2), R 3 represents —SO 2 — or —CO—. R 4 and R 5 each independently represents —SO 2 —, —CO— or —CN.
Preferably representing the at least two R 3 ~ R 5 is -SO 2 - - In formula (A2), at least one of R 3 ~ R 5 -SO 2 more preferably represents.
　アニオンＸが別分子の場合とは、アニオンＸが同一繰り返し単位外にある場合であって、カチオンとアニオンが共有結合を介して結合せず、別分子として存在している場合である。
　この場合のアニオンＸとしては、フッ素アニオン、塩素アニオン、臭素アニオン、ヨウ素アニオン、シアン化物イオン、過塩素酸アニオン等や低求核性アニオンが例示され、低求核性アニオンが好ましい。
　低求核性のアニオンは、有機アニオンであっても、無機アニオンであってもよく、有機アニオンが好ましい。本発明で用いられるアニオンの例として、特開２００７－３１０３１５号公報の段落番号００７５に記載の公知の低求核性アニオンが挙げられ、これらの内容は本明細書に組み込まれる。
　好ましくは、ビス（スルホニル）イミドアニオン、トリス（スルホニル）メチドアニオン、テトラアリールボレートアニオン、Ｂ－（ＣＮ）ｎ１（ＯＲａ）４－ｎ１（Ｒａは炭素数１～１０のアルキル基または炭素数６～１０のアリール基を表し、ｎ１は１～４を表す）およびＰＦｎ２ＲＰ （６－ｎ２） -（ＲＰは炭素数１～１０のフッ素化アルキル基を表し、ｎ２は１～６の整数を表す）が挙げられ、ビス（スルホニル）イミドアニオン、トリス（スルホニル）メチドアニオン、パーフルオロスルホン酸アニオンおよびテトラアリールボレートアニオンから選択されることがより好ましく、ビス（スルホニル）イミドアニオンであることがさらに好ましい。 The case where the anion X is a different molecule is a case where the anion X is outside the same repeating unit, and the cation and the anion are not bonded via a covalent bond but are present as separate molecules.
Examples of the anion X in this case include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, and a low nucleophilic anion, and a low nucleophilic anion is preferable.
The low nucleophilic anion may be an organic anion or an inorganic anion, and an organic anion is preferred. Examples of the anion used in the present invention include known low nucleophilic anions described in paragraph No. 0075 of JP-A-2007-310315, the contents of which are incorporated herein.
Preferably, bis (sulfonyl) imide anion, tris (sulfonyl) methide anion, tetraarylborate anion, B − (CN) n1 (OR a ) 4-n1 (R a is an alkyl group having 1 to 10 carbon atoms or carbon number 6 And PF n2 R P (6-n2) − (R P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents 1 to 6) It is more preferably selected from bis (sulfonyl) imide anion, tris (sulfonyl) methide anion, perfluorosulfonate anion and tetraarylborate anion, and is a bis (sulfonyl) imide anion. Further preferred.
　低求核性のアニオンであるビス（スルホニル）イミドアニオンとしては、下記一般式（ＡＮ－１）で表される構造が好ましく、ビストリフルオロメタンスルホニルイミドアニオンがより好ましい。
い。 As the bis (sulfonyl) imide anion which is a low nucleophilic anion, a structure represented by the following general formula (AN-1) is preferable, and a bistrifluoromethanesulfonylimide anion is more preferable.
Yes.
一般式（ＡＮ－１）
Figure JPOXMLDOC01-appb-C000014
 General formula (AN-1)
Figure JPOXMLDOC01-appb-C000014
　式（ＡＮ－１）中、Ｘ１およびＸ２は、それぞれ独立に、フッ素原子またはフッ素原子を有する炭素数１～１０のアルキル基を表す。Ｘ１およびＸ２は互いに結合して環を形成しても良い。 In formula (AN-1), X 1 and X 2 each independently represent a fluorine atom or a C 1-10 alkyl group having a fluorine atom. X 1 and X 2 may combine with each other to form a ring.
　Ｘ１およびＸ２は、それぞれ独立に、フッ素原子またはフッ素原子を有する炭素数１～１０のアルキル基を表し、フッ素原子またはフッ素原子を有する炭素数１～１０のアルキル基が好ましく、炭素数１～１０のペルフルオロアルキル基であることがより好ましく、炭素数１～４のペルフルオロアルキル基であることがさらに好ましく、トリフルオロメチル基が特に好ましい。 X 1 and X 2 each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, preferably a fluorine atom or an alkyl group having 1 to 10 carbon atoms having a fluorine atom, More preferred is a perfluoroalkyl group of ˜10, more preferred is a perfluoroalkyl group having 1 to 4 carbon atoms, and a trifluoromethyl group is particularly preferred.
　低求核性のアニオンであるトリス（スルホニル）メチドアニオンとしては、下記一般式（ＡＮ－２）である構造が好ましく、トリストリフルオロメタンスルホニルメチドアニオンがより好ましい。 As the tris (sulfonyl) methide anion which is a low nucleophilic anion, a structure represented by the following general formula (AN-2) is preferable, and a tris (trifluoromethanesulfonyl) methion anion is more preferable.
一般式（ＡＮ－２）
Figure JPOXMLDOC01-appb-C000015
 General formula (AN-2)
Figure JPOXMLDOC01-appb-C000015
　式（ＡＮ－２）中、Ｘ３、Ｘ４およびＸ５はそれぞれ独立に、フッ素原子または炭素数１～１０のフッ素原子を有するアルキル基を表す。 In formula (AN-2), X 3 , X 4 and X 5 each independently represent a fluorine atom or an alkyl group having 1 to 10 carbon atoms.
　Ｘ３、Ｘ４およびＸ５は、それぞれ独立に、Ｘ１およびＸ２と同義であり、好ましい範囲も同義である。 X 3 , X 4 and X 5 are each independently synonymous with X 1 and X 2 , and a preferred range is also synonymous.
　パーフルオロスルホン酸アニオンは、下記一般式（ＡＮ３）で表される化合物が好ましく、パーフルオロメタンスルホン酸アニオンがより好ましい。
一般式（ＡＮ３）
Ｒ－ＳＯ３ －
　式（ＡＮ３）中、Ｒは、パーフルオロアルキル基またはパーフルオロアリール基を表す。Ｒがパーフルオロアルキル基を表す場合、炭素数は、１～６が好ましく、１～３がより好ましい。Ｒがパーフルオロアリール基を表す場合、炭素数は、６～１８が好ましく、６～１２がより好ましい。 The perfluorosulfonic acid anion is preferably a compound represented by the following general formula (AN3), more preferably a perfluoromethanesulfonic acid anion.
General formula (AN3)
R-SO 3 -
　 In formula (AN3), R represents a perfluoroalkyl group or a perfluoroaryl group. When R represents a perfluoroalkyl group, the carbon number is preferably 1 to 6, and more preferably 1 to 3. When R represents a perfluoroaryl group, the carbon number is preferably 6 to 18, and more preferably 6 to 12.
　低求核性のアニオンであるテトラアリールボレートアニオンとしては、下記一般式（ＡＮ－５）で表される化合物であることが好ましい。 The tetraarylborate anion which is a low nucleophilic anion is preferably a compound represented by the following general formula (AN-5).
一般式（ＡＮ－５）
Figure JPOXMLDOC01-appb-C000016
 General formula (AN-5)
Figure JPOXMLDOC01-appb-C000016
　式（ＡＮ－５）中、Ａｒ１、Ａｒ２、Ａｒ３およびＡｒ４は、それぞれ独立に、アリール基を表す。 In formula (AN-5), Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently represents an aryl group.
　Ａｒ１、Ａｒ２、Ａｒ３およびＡｒ４は、それぞれ独立に、炭素数６～２０のアリール基が好ましく、炭素数６～１４のアリール基がより好ましく、炭素数６～１０のアリール基がさらに好ましい。
　Ａｒ１、Ａｒ２、Ａｒ３およびＡｒ４が表わすアリール基は、置換基を有しても良い。置換基を有する場合、ハロゲン原子、アルキル基、アリール基、アルコキシ基、カルボニル基、カルボニルオキシ基、カルバモイル基、スルホ基、スルホンアミド基、ニトロ基等が挙げられ、ハロゲン原子およびアルキル基が好ましく、フッ素原子、アルキル基がより好ましく、フッ素原子、炭素数１～４のペルフルオロアルキル基がさらに好ましい。 Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further an aryl group having 6 to 10 carbon atoms preferable.
The aryl group represented by Ar 1 , Ar 2 , Ar 3 and Ar 4 may have a substituent. In the case of having a substituent, a halogen atom, an alkyl group, an aryl group, an alkoxy group, a carbonyl group, a carbonyloxy group, a carbamoyl group, a sulfo group, a sulfonamide group, a nitro group and the like can be mentioned, and a halogen atom and an alkyl group are preferable, A fluorine atom and an alkyl group are more preferable, and a fluorine atom and a perfluoroalkyl group having 1 to 4 carbon atoms are more preferable.
　Ａｒ１、Ａｒ２、Ａｒ３およびＡｒ４は、それぞれ独立に、ハロゲン原子およびハロゲン原子を有するアルキル基から選ばれる少なくともいずれかを有するフェニル基がより好ましく、フッ素原子およびフッ素を有するアルキル基から選ばれる少なくともいずれかを有するフェニル基がさらに好ましい。 Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently more preferably a phenyl group having at least one selected from a halogen atom and an alkyl group having a halogen atom, and selected from a fluorine atom and an alkyl group having fluorine. More preferred is a phenyl group having at least one of the following.
　低求核性のアニオンは、また、－Ｂ（ＣＮ）ｎ１（ＯＲａ）４－ｎ１（Ｒａは炭素数１～１０のアルキル基または炭素数６～１０のアリール基を表し、ｎ１は１～４の整数を表す）であることが好ましい。炭素数１～１０のアルキル基としてのＲａは、炭素数１～６のアルキル基が好ましく、炭素数１～４のアルキル基がより好ましい。炭素数６～１０のアリール基としてのＲａは、フェニル基、ナフチル基が好ましい。
　ｎ１は、１～３が好ましく、１～２がより好ましい。 The low nucleophilic anion also represents —B (CN) n1 (OR a ) 4-n1 (R a represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n1 is 1 Represents an integer of 4). Ra as the alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. R a as the aryl group having 6 to 10 carbon atoms is preferably a phenyl group or a naphthyl group.
n1 is preferably 1 to 3, and more preferably 1 to 2.
　低求核性のアニオンは、さらにまた、－ＰＦ６ＲＰ （６－ｎ２） -（ＲＰは炭素数１～１０のフッ素化アルキル基を表し、ｎ２は１～６の整数を表す）であることが好ましい。ＲＰは、炭素数１～６のフッ素原子を有するアルキル基が好ましく、炭素数１～４のフッ素を有するアルキル基がより好ましく、炭素数１～３のペルフルオロアルキル基がさらに好ましい。
　ｎ２は、１～４の整数が好ましく、１または２がより好ましい。 The low nucleophilic anion is further represented by —PF 6 R P (6-n2) − (R P represents a fluorinated alkyl group having 1 to 10 carbon atoms, and n2 represents an integer of 1 to 6). Preferably there is. R P is preferably an alkyl group having a fluorine atom having 1 to 6 carbon atoms, more preferably an alkyl group having a fluorine having 1 to 4 carbon atoms, more preferably a perfluoroalkyl group having 1 to 3 carbon atoms.
n2 is preferably an integer of 1 to 4, and more preferably 1 or 2.
　低求核性のアニオンの１分子あたりの質量は、１００～１，０００が好ましく、２００～５００がより好ましい。
　本発明に用いられるトリアリールメタン染料は、低求核性のアニオンを１種類のみ含んでいても良いし、２種類以上を含んでいても良い。 The mass per molecule of the low nucleophilic anion is preferably 100 to 1,000, and more preferably 200 to 500.
The triarylmethane dye used in the present invention may contain only one kind of low nucleophilic anion or may contain two or more kinds.
　以下に、低求核性のアニオンの具体例を示すが本発明はこれに限定されるものではない。
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
 Specific examples of the low nucleophilic anion are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　また、本発明では、アニオンＸが多量体であってもよい。この場合の多量体は、アニオンを含む繰り返し単位を含み、カチオンを含む色素構造由来の繰り返し単位を含まない多量体が例示される。ここで、アニオンを含む繰り返し単位は、後述する実施形態で述べるアニオンを含む繰り返し単位を好ましい例として挙げることができる。さらに、アニオンを含む多量体は、アニオンを含む繰り返し単位以外の繰り返し単位を有していてもよい。このような繰り返し単位としては、後述するトリアリールメタン染料が含んでいてもよい他の繰り返し単が好ましい例として例示される。 In the present invention, the anion X may be a multimer. The multimer in this case is exemplified by a multimer containing a repeating unit containing an anion and not containing a repeating unit derived from a dye structure containing a cation. Here, as the repeating unit containing an anion, a repeating unit containing an anion described in the embodiment described later can be cited as a preferred example. Furthermore, the multimer containing an anion may have a repeating unit other than the repeating unit containing an anion. As such a repeating unit, the other repeating unit which the triarylmethane dye mentioned later may contain is illustrated as a preferable example.
　以下に、本発明で好ましく用いられるトリアリールメタン染料であって、一般式（ＴＰ１）～（ＴＰ３）で表されるトリアリールメタン染料の例を示すが、これらに限定されるものではない。
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
 Examples of triarylmethane dyes preferably used in the present invention and represented by general formulas (TP1) to (TP3) are shown below, but are not limited thereto.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
＜トリアリールメタン染料（高分子タイプ）＞
　一般式（ＴＰ１）～（ＴＰ３）で表されるトリアリールメタン染料は、多量体構造を含んでいてもよい。トリアリールメタン染料が多量体構造を有する場合、トリアリールメタン染料は高分子タイプのトリアリールメタン染料という。本発明では、高分子タイプのトリアリールメタン染料も好ましく用いられる。トリアリールメタン染料が高分子タイプである場合、多量体構造は、トリアリールメタン構造が有していてもよいし、アニオンＸが有していても良い。なお、本明細書において、トリアリールメタン染料が高分子タイプである場合、色素多量体ということがある。 <Triarylmethane dye (polymer type)>
The triarylmethane dyes represented by the general formulas (TP1) to (TP3) may contain a multimeric structure. When the triarylmethane dye has a multimeric structure, the triarylmethane dye is referred to as a polymer type triarylmethane dye. In the present invention, a polymer type triarylmethane dye is also preferably used. When the triarylmethane dye is a polymer type, the multimeric structure may be a triarylmethane structure or an anion X. In the present specification, when the triarylmethane dye is a polymer type, it may be referred to as a dye multimer.
　以下の説明では、一般式（ＴＰ１）で表されるトリアリールメタン染料を例に挙げて説明するが、一般式（ＴＰ２）で表されるトリアリールメタン染料および一般式（ＴＰ３）で表されるトリアリールメタン染料についても同様である。
　トリアリールメタン染料が高分子タイプの場合、一般式（ＴＰ１）で表されるトリアリールメタン染料のいずれかの部位がポリマーと結合しており、一般式（ＴＰ１）における少なくとも１つの基がポリマーを構成する繰り返し単位であることが好ましい。ポリマーを構成する繰り返し単位と結合している基以外の一般式（ＴＰ１）中の各置換基の好ましい範囲は、多量体構造を有さないトリアリールメタン染料（低分子タイプの鳥アリールメタン染料）と同義であり、好ましい範囲も同様である。
　具体的には、一般式（ＴＰ１）において、Ｒｔｐ２１、Ｒｔｐ２２またはＲ１の少なくとも１つがポリマー主鎖との結合部位であることが好ましく、Ｒ１がポリマー主鎖との結合部位であることがより好ましい。
　一般式（ＴＰ２）においては、Ｒｔｐ２１、Ｒｔｐ２２またはＰ１の少なくとも１つがポリマー主鎖との結合部位であることが好ましく、Ｐ１がポリマー主鎖との結合部位であることがより好ましい。
　一般式（ＴＰ３）においては、Ｒｔｐ２１、Ｒｔｐ２２またはＰ１の少なくとも１つがポリマー主鎖との結合部位であることが好ましく、Ｐ１がポリマー主鎖との結合部位であることがより好ましい。
　トリアリールメタン染料が高分子である場合の、繰り返し単位の骨格構造としては、特に定めるものではないが、特開２０１３－２８７６４号の段落番号０２５２～０３０４に示される、一般式（Ａ）、一般式（Ｂ）、および、一般式（Ｃ）で表される構成単位の少なくとも一つを骨格とすることが好ましく、または、一般式（ＴＰ１）で表されるトリアリールメタン染料が一般式（Ｄ）で表される色素多量体であることが好ましい。特開２０１３－２８７６４号の段落番号０２５２～０３０４の記載は、本明細書に組み込まれる。 In the following description, the triarylmethane dye represented by the general formula (TP1) will be described as an example, but the triarylmethane dye represented by the general formula (TP2) and the general formula (TP3) are represented. The same applies to the triarylmethane dye.
When the triarylmethane dye is a polymer type, any part of the triarylmethane dye represented by the general formula (TP1) is bonded to the polymer, and at least one group in the general formula (TP1) is a polymer. It is preferably a repeating unit constituting. The preferred range of each substituent in the general formula (TP1) other than the group bonded to the repeating unit constituting the polymer is a triarylmethane dye having a multimeric structure (low molecular type bird arylmethane dye) The preferred range is also the same.
Specifically, in general formula (TP1), it is preferable that at least one of Rtp 21 , Rtp 22 or R 1 is a binding site with the polymer main chain, and R 1 is a binding site with the polymer main chain. Is more preferable.
In general formula (TP2), it is preferable that at least one of Rtp 21 , Rtp 22 or P 1 is a binding site with a polymer main chain, and more preferable that P 1 is a binding site with a polymer main chain.
In the general formula (TP3), it is preferable that at least one of Rtp 21 , Rtp 22 or P 1 is a bonding site with the polymer main chain, and more preferable that P 1 is a bonding site with the polymer main chain.
In the case where the triarylmethane dye is a polymer, the skeleton structure of the repeating unit is not particularly defined, but the general formula (A), It is preferable that at least one of the structural units represented by formula (B) and general formula (C) is a skeleton, or a triarylmethane dye represented by general formula (TP1) is represented by general formula (D It is preferable that it is a pigment | dye multimer represented by this. The description of paragraph numbers 0252 to 0304 of JP 2013-28764 is incorporated in the present specification.
＜＜一般式（Ａ）で表される構成単位＞＞
Figure JPOXMLDOC01-appb-C000024
 << Structural Unit Represented by General Formula (A) >>
Figure JPOXMLDOC01-appb-C000024
　一般式（Ａ）中、Ｘ１は重合によって形成される連結基を表し、Ｌ１は単結合または２価の連結基を表す。ＤｙｅＩは一般式（ＴＰ１）におけるＲｔｐ２１、Ｒｔｐ２２およびＲ１のいずれか、一般式（ＴＰ２）におけるＲｔｐ２１、Ｒｔｐ２２およびＰ１のいずれか、または、一般式（ＴＰ３）におけるＲｔｐ２３～Ｒｔｐ２５およびＰ１のいずれかが、Ｌ１と結合した基である。
　以下、一般式（Ａ）について詳細に説明する。 In general formula (A), X 1 represents a linking group formed by polymerization, and L 1 represents a single bond or a divalent linking group. DyeI is any one of Rtp 21 , Rtp 22 and R 1 in the general formula (TP1), any of Rtp 21 , Rtp 22 and P 1 in the general formula (TP2), or Rtp 23 to Rtp in the general formula (TP3). Either 25 or P 1 is a group bonded to L 1 .
Hereinafter, the general formula (A) will be described in detail.
　一般式（Ａ）中、Ｘ１は重合によって形成される連結基を表す。すなわち重合反応で形成される主鎖に相当する繰り返し単位を形成する部分を指す。なお、２つの＊で表された部位が繰り返し単位となる。Ｘ１としては、公知の重合可能なモノマーから形成される連結基であれば特に制限はないが、特に下記（ＸＸ－１）～（Ｘ－２４）で表される連結基が好ましく、（ＸＸ－１）および（ＸＸ－２）で表される（メタ）アクリル系連結鎖、（ＸＸ－１０）～（ＸＸ－１７）で表されるスチレン系連結鎖、（ＸＸ－１８）および（ＸＸ－１９）、並びに、（ＸＸ－２４）で表されるビニル系連結鎖から選択されることがより好ましく、（ＸＸ－１）および（ＸＸ－２）で表される（メタ）アクリル系連結鎖、（ＸＸ－１０）～（ＸＸ－１７）で表されるスチレン系連結鎖、（ＸＸ－２４）で表されるビニル系連結鎖から選択されることがより好ましく、（ＸＸ－１）および（ＸＸ－２）で表される（メタ）アクリル系連結鎖および（ＸＸ－１１）で表されるスチレン系連結鎖がより好ましい。
　（ＸＸ－１）～（Ｘ－２４）中、＊で示された部位でＬ１と連結していることを表す。Ｍｅはメチル基を表す。また、（ＸＸ－１８）および（ＸＸ－１９）中のＲは、水素原子、炭素数１～５のアルキル基またはフェニル基を表す。 In general formula (A), X 1 represents a linking group formed by polymerization. That is, it refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. Two sites represented by * are repeating units. X 1 is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, but is particularly preferably a linking group represented by the following (XX-1) to (X-24), (XX -1) and (XX-2) (meth) acrylic linking chains, (XX-10) to (XX-17) styrenic linking chains, (XX-18) and (XX- 19), and more preferably selected from vinyl-based linking chains represented by (XX-24), (meth) acrylic linking chains represented by (XX-1) and (XX-2), More preferably, it is selected from styrenic linking chains represented by (XX-10) to (XX-17) and vinyl linking chains represented by (XX-24), and (XX-1) and (XX -2) and a (meth) acrylic linking chain represented by (XX-11) A styrene-based connecting chain represented by
In (XX-1) to (X-24), it is linked to L 1 at the site indicated by *. Me represents a methyl group. R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　一般式（Ａ）中、Ｌ１は単結合または２価の連結基を表す。Ｌ１が２価の連結基を表す場合の上記２価の連結基としては、炭素数１～３０の置換もしくは無置換のアルキレン基（例えば、メチレン基、エチレン基、トリメチレン基、プロピレン基、ブチレン基など）、炭素数６～３０の置換もしくは無置換のアリーレン基（例えば、フェニレン基、ナフタレン基等）、置換もしくは無置換のヘテロ環連結基、－ＣＨ＝ＣＨ－、－Ｏ－、－Ｓ－、－Ｃ（＝Ｏ）－、－ＣＯ２－、－ＮＲ－、－ＣＯＮＲ－、－Ｏ２Ｃ－、－ＳＯ－、－ＳＯ２－およびこれらを２個以上連結して形成される連結基を表す。また、Ｌ１がアニオンを含む構成も好ましい。Ｌ１は、単結合またはアルキレン基がより好ましく、単結合または－（ＣＨ２）ｎ－（ｎは１～５の整数）がより好ましい。ここで、Ｒは、それぞれ独立に、水素原子、アルキル基、アリール基、またはヘテロ環基を表す。Ｌ１がアニオンを含む場合の例については、後述する。 In general formula (A), L 1 represents a single bond or a divalent linking group. In the case where L 1 represents a divalent linking group, the divalent linking group includes a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms (eg, methylene group, ethylene group, trimethylene group, propylene group, butylene). Group), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, phenylene group, naphthalene group, etc.), substituted or unsubstituted heterocyclic linking group, —CH═CH—, —O—, —S —, —C (═O) —, —CO 2 —, —NR—, —CONR—, —O 2 C—, —SO—, —SO 2 — and a linkage formed by linking two or more thereof. Represents a group. A configuration in which L 1 includes an anion is also preferable. L 1 is more preferably a single bond or an alkylene group, and more preferably a single bond or — (CH 2 ) n— (n is an integer of 1 to 5). Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently. An example of the case where L 1 contains an anion will be described later.
　一般式（Ａ）中、ＤｙｅＩは一般式（ＴＰ１）におけるＲｔｐ２１、Ｒｔｐ２２およびＲ１のいずれか、一般式（ＴＰ２）におけるＲｔｐ２１、Ｒｔｐ２２およびＰ１のいずれか、または、一般式（ＴＰ３）におけるＲｔｐ２３～Ｒｔｐ２５およびＰ１のいずれかが、Ｌ１と結合した基である。
　一般式（Ａ）で表される構成単位を有する色素多量体は、（１）色素残基を有するモノマーを付加重合により合成する方法、（２）イソシアネート基、酸無水物基またはエポキシ基等の高反応性官能基を有するポリマーと、高反応性基と反応可能な官能基（ヒドロキシル基、一級または二級アミノ基、カルボキシル基等）を有する色素とを反応させる方法により合成できる。
　付加重合には公知の付加重合（ラジカル重合、アニオン重合、カチオン重合）が適用できるが、このうち、特にラジカル重合により合成することが反応条件を穏和化でき、色素構造を分解させないため好ましい。ラジカル重合には、公知の反応条件を適用することができる。すなわち、本発明で用いるトリアリールメタン染料は、付加重合体であることが好ましい。
　中でも、一般式（Ａ）で表される構成単位を有する色素多量体は、耐熱性の観点から、エチレン性不飽和結合を有する色素単量体を用いてラジカル重合して得られたラジカル重合体であることが好ましい。 In general formula (A), DyeI is any one of Rtp 21 , Rtp 22 and R 1 in general formula (TP1), any of Rtp 21 , Rtp 22 and P 1 in general formula (TP2), or general formula ( Any of Rtp 23 to Rtp 25 and P 1 in TP3) is a group bonded to L 1 .
The dye multimer having the structural unit represented by the general formula (A) includes (1) a method of synthesizing a monomer having a dye residue by addition polymerization, (2) an isocyanate group, an acid anhydride group or an epoxy group. It can be synthesized by a method in which a polymer having a highly reactive functional group is reacted with a dye having a functional group (hydroxyl group, primary or secondary amino group, carboxyl group, etc.) capable of reacting with the highly reactive group.
Known addition polymerizations (radical polymerization, anionic polymerization, cationic polymerization) can be applied to the addition polymerization, but among these, synthesis by radical polymerization is particularly preferable because the reaction conditions can be moderated and the dye structure is not decomposed. Known reaction conditions can be applied to the radical polymerization. That is, the triarylmethane dye used in the present invention is preferably an addition polymer.
Among them, the dye multimer having the structural unit represented by the general formula (A) is a radical polymer obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond from the viewpoint of heat resistance. It is preferable that
＜＜他の官能基および繰り返し単位＞＞
　本発明で用いられるトリアリールメタン染料は、上述した色素多量体の色素構造部分に他の官能基を有していても良い。他の官能基としては、重合性基、アルカリ可溶性基（好ましくは酸基）等が例示される。
　また、本発明で用いられるトリアリールメタン染料は、上述した色素構造を含む繰り返し単位の他に、他の繰り返し単位を含んでいても良い。他の繰り返し単位は、官能基を有していても良い。
　また、他の繰り返し単位としては、重合性基、アルカリ可溶性基（好ましくは酸基）の少なくとも１種を含む繰り返し単位が例示される。
　すなわち、本発明で用いられるトリアリールメタン染料は、上記一般式（Ａ）～（Ｃ）で表される繰り返し単位のほかに、他の繰り返し単位を有していてもよい。他の繰り返し単位は、１つのトリアリールメタン染料中に、１種類のみ含まれていても良いし、２種類以上含まれていてもよい。
　また、本発明で用いられるトリアリールメタン染料は、上記一般式（Ａ）～（Ｄ）で表される色素多量体中に、他の官能基を有していても良い。以下、これらの詳細について説明する。 << Other functional groups and repeating units >>
The triarylmethane dye used in the present invention may have another functional group in the dye structure portion of the dye multimer described above. Examples of other functional groups include polymerizable groups and alkali-soluble groups (preferably acid groups).
Further, the triarylmethane dye used in the present invention may contain other repeating units in addition to the repeating unit including the above-described pigment structure. Other repeating units may have a functional group.
Moreover, as another repeating unit, the repeating unit containing at least 1 sort (s) of a polymeric group and an alkali-soluble group (preferably acid group) is illustrated.
That is, the triarylmethane dye used in the present invention may have other repeating units in addition to the repeating units represented by the general formulas (A) to (C). One type of other repeating unit may be contained in one triarylmethane dye, or two or more types may be contained.
The triarylmethane dye used in the present invention may have other functional groups in the dye multimer represented by the general formulas (A) to (D). Details of these will be described below.
＜＜色素多量体が有する重合性基＞＞
　色素多量体は重合性基を含んでいてもよい。重合性基は１種類のみ含んでいても良いし、２種類以上含んでいても良い。
　重合性基は、色素構造が重合性基を含んでいても良いし、他の部分が含んでいても良い。本発明では、色素構造が重合性基を含むことが好ましい。このような構成とすることにより耐熱性が向上する傾向にある。
　また、本発明では、色素構造以外の他の部分が重合性基を含む態様も好ましい。
　重合性基としては、上述した一般式（ＴＰ１）～（ＴＰ３）で表されるトリアリールメタン染料が有していてもよい重合性基と同義であり、好ましい範囲も同様である。
　重合性基は、色素多量体中に、重合性基を有する繰り返し単位として含まれることが好ましく、エチレン性不飽和結合を有する繰り返し単位として含まれることがより好ましい。すなわち、本発明で用いられるトリアリールメタン染料は、トリアリールメタン染料が色素単量体を含む繰り返し単位と重合性基を有する繰り返し単位を含有してもよく、色素単量体を含む繰り返し単位とエチレン性不飽和結合を有する繰り返し単位を含有することがより好ましい。 << Polymerizable group of dye multimer >>
The dye multimer may contain a polymerizable group. One type of polymerizable group may be included, or two or more types may be included.
As for the polymerizable group, the dye structure may contain a polymerizable group, or may contain other parts. In the present invention, the dye structure preferably includes a polymerizable group. By adopting such a configuration, the heat resistance tends to be improved.
Moreover, in this invention, the aspect in which other parts other than a pigment | dye structure contain a polymeric group is also preferable.
The polymerizable group is synonymous with the polymerizable group that the triarylmethane dyes represented by the above general formulas (TP1) to (TP3) may have, and the preferred range is also the same.
The polymerizable group is preferably contained as a repeating unit having a polymerizable group in the dye multimer, and more preferably as a repeating unit having an ethylenically unsaturated bond. That is, the triarylmethane dye used in the present invention may contain a repeating unit containing a pigment monomer and a repeating unit having a polymerizable group, and the repeating unit containing a pigment monomer. More preferably, it contains a repeating unit having an ethylenically unsaturated bond.
　重合性基の導入方法としては、（１）色素多量体を重合性基含有化合物で変性して導入する方法、（２）色素単量体と重合性基含有化合物を共重合して導入する方法等がある。以下、詳細に述べる。 As a method for introducing a polymerizable group, (1) a method in which a dye multimer is modified and introduced with a polymerizable group-containing compound, and (2) a method in which a dye monomer and a polymerizable group-containing compound are copolymerized and introduced. Etc. Details will be described below.
（１）色素多量体を重合性基含有化合物で変性して導入する方法：
　色素多量体を重合性基含有化合物で変性して導入する方法としては、特に制限なく公知の方法を用いることができる。例えば、（ａ）色素多量体が有するカルボン酸と不飽和結合含有エポキシ化合物とを反応させる方法、（ｂ）色素多量体が有するヒドロキシル基またはアミノ基と不飽和結合含有イソシアネート化合物とを反応させる方法、（ｃ）色素多量体が有するエポキシ化合物と不飽和結合含有カルボン酸化合物とを反応させる方法が製造上の観点から好ましい。 (1) A method of introducing a dye multimer after modifying it with a polymerizable group-containing compound:
As a method for introducing the dye multimer by modifying with a polymerizable group-containing compound, a known method can be used without any particular limitation. For example, (a) a method of reacting a carboxylic acid contained in a dye multimer with an unsaturated bond-containing epoxy compound, and (b) a method of reacting a hydroxyl group or amino group of the dye multimer with an unsaturated bond-containing isocyanate compound. (C) A method of reacting the epoxy compound of the dye multimer with the unsaturated bond-containing carboxylic acid compound is preferable from the viewpoint of production.
　（ａ）色素多量体が有するカルボン酸と不飽和結合含有エポキシ化合物とを反応させる方法における不飽和結合含有エポキシ化合物としては、メタクリル酸グリシジル、アクリル酸グリシジル、アリルグリシジルエーテル、３，４－エポキシーシクロヘキシルメチルアクリレート、３，４－エポキシーシクロヘキシルメチルメタクリレート等が挙げられうるが、特にメタクリル酸グリシジルおよび３，４－エポキシーシクロヘキシルメチルメタクリレートが、架橋性および保存安定性に優れ好ましい。反応条件は公知の条件を用いることができる。 (A) The unsaturated bond-containing epoxy compound in the method of reacting the carboxylic acid contained in the dye multimer with the unsaturated bond-containing epoxy compound includes glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, and 3,4-epoxycyclohexyl. Examples thereof include methyl acrylate, 3,4-epoxy-cyclohexylmethyl methacrylate, and glycidyl methacrylate and 3,4-epoxy-cyclohexylmethyl methacrylate are particularly preferable because of excellent crosslinkability and storage stability. Known conditions can be used as the reaction conditions.
　（ｂ）色素多量体が有するヒドロキシル基またはアミノ基と不飽和結合含有イソシアネート化合物とを反応させる方法における不飽和結合含有イソシアネート化合物として、２－イソシアナトエチルメタクリレート、２－イソシアナトエチルアタクリレート、１，１－ビス（アクリロイルオキシメチル）エチルイソシアネート等が挙げられるが、２－イソシアナトエチルメタクリレートが、架橋性および保存安定性に優れ好ましい。反応条件は公知の条件を用いることができる。 (B) As the unsaturated bond-containing isocyanate compound in the method of reacting the hydroxyl group or amino group of the dye multimer with the unsaturated bond-containing isocyanate compound, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl atacrylate, Examples include 1,1-bis (acryloyloxymethyl) ethyl isocyanate, and 2-isocyanatoethyl methacrylate is preferable because of its excellent crosslinkability and storage stability. Known conditions can be used as the reaction conditions.
　（ｃ）色素多量体が有するエポキシ化合物と不飽和結合含有カルボン酸化合物とを反応させる方法における不飽和結合含有カルボン酸化合物として、公知の（メタ）アクリロイルオキシ基を有するカルボン酸化合物であれば特に制限なく使用できるが、メタクリル酸およびアクリル酸が好ましく、特にメタクリル酸が架橋性および保存安定性に優れ好ましい。反応条件は公知の条件を用いることができる。 (C) The unsaturated bond-containing carboxylic acid compound in the method of reacting the epoxy compound of the dye multimer with the unsaturated bond-containing carboxylic acid compound is particularly a carboxylic acid compound having a known (meth) acryloyloxy group Although it can be used without limitation, methacrylic acid and acrylic acid are preferable, and methacrylic acid is particularly preferable because of excellent crosslinkability and storage stability. Known conditions can be used as the reaction conditions.
（２）色素モノマーと重合性基含有化合物を共重合して導入する方法：
　（２）色素単量体と重合性基含有化合物を共重合して導入する方法としては、特に制限なく公知の方法を用いることができるが、（ｄ）ラジカル重合可能な色素単量体とラジカル重合可能な重合性基含有化合物とを共重合する方法、（ｅ）重付加可能な色素単量体と重付加可能な重合性基含有化合物とを共重合する方法が好ましい。 (2) A method in which a dye monomer and a polymerizable group-containing compound are copolymerized and introduced:
(2) As a method for copolymerizing and introducing a dye monomer and a polymerizable group-containing compound, known methods can be used without any particular limitation. (D) A radically polymerizable dye monomer and a radical can be used. A method of copolymerizing a polymerizable group-containing compound that can be polymerized, and a method (e) a method of copolymerizing a dye monomer capable of polyaddition and a polymerizable group-containing compound capable of polyaddition are preferred.
　（ｄ）ラジカル重合可能な色素単量体とラジカル重合可能な重合性基含有化合物とを共重合する方法におけるラジカル重合可能な重合性基含有化合物として、特にアリル基含有化合物（例えば、（メタ）アクリル酸アリル等）、エポキシ基含有化合物（例えば、（メタ）アクリル酸グリシジル、３，４－エポキシーシクロヘキシルメチル（メタ）アクリレート等）、オキセタン基含有化合物（例えば、３－メチルー３－オキセタニルメチル（メタ）アクリレート等）、メチロール基含有化合物（例えば、Ｎ－（ヒドロキシメチル）アクリルアミド等）が挙げられ、特にエポキシ化合物、オキセタン化合物が好ましい。反応条件は公知の条件を用いることができる。 (D) As a radically polymerizable polymerizable group-containing compound in a method of copolymerizing a radically polymerizable dye monomer and a radically polymerizable polymerizable group-containing compound, an allyl group-containing compound (for example, (meth)) Allyl acrylate), epoxy group-containing compounds (for example, glycidyl (meth) acrylate, 3,4-epoxy-cyclohexylmethyl (meth) acrylate, etc.), oxetane group-containing compounds (for example, 3-methyl-3-oxetanylmethyl (meth) ) Acrylate, etc.) and methylol group-containing compounds (for example, N- (hydroxymethyl) acrylamide etc.), and epoxy compounds and oxetane compounds are particularly preferred. Known conditions can be used as the reaction conditions.
　（ｅ）重付加可能な色素単量体と重付加可能な重合性基含有化合物とを共重合する方法における重付加可能な重合性基含有化合物として、不飽和結合含有ジオール化合物（例えば、２，３－ジヒドロキシプロピル（メタ）アクリレート等）が挙げられる。反応条件は公知の条件を用いることができる。 (E) As a polymerizable group-containing compound capable of polyaddition in a method of copolymerizing a dye monomer capable of polyaddition and a polymerizable group-containing compound capable of polyaddition, an unsaturated bond-containing diol compound (eg, 3-dihydroxypropyl (meth) acrylate). Known conditions can be used as the reaction conditions.
　重合性基の導入方法として、色素多量体が有するカルボン酸と不飽和結合含有エポキシ化合物を反応させる方法が特に好ましい。 As a method for introducing a polymerizable group, a method in which a carboxylic acid contained in a dye multimer is reacted with an unsaturated bond-containing epoxy compound is particularly preferable.
　色素多量体が有する重合性基量は、色素多量体１ｇに対し０．１～２．０ｍｍｏｌであることが好ましく、０．２～１．５ｍｍｏｌであることがさらに好ましく、０．３～１．０ｍｍｏｌであることが特に好ましい。
　また、色素多量体が重合性基を有する繰り返し単位を含有する繰り返し単位の割合は、全繰り返し単位１００モルに対し、例えば、５～５０モルが好ましく、１０～２０モルがより好ましい。 The amount of polymerizable group possessed by the dye multimer is preferably 0.1 to 2.0 mmol, more preferably 0.2 to 1.5 mmol, and more preferably 0.3 to 1. Particularly preferred is 0 mmol.
In addition, the ratio of the repeating unit containing a repeating unit having a polymerizable group in the dye multimer is, for example, preferably 5 to 50 mol, and more preferably 10 to 20 mol with respect to 100 mol of all repeating units.
　重合性基の導入方法として、色素多量体が有するカルボン酸と不飽和結合含有エポキシ化合物を反応させる方法が特に好ましい。 As a method for introducing a polymerizable group, a method in which a carboxylic acid contained in a dye multimer is reacted with an unsaturated bond-containing epoxy compound is particularly preferable.
　重合性基を有する繰り返し単位としては、以下のような具体例が挙げられる。ただし、本発明はこれらに限定されるものではない。 Specific examples of the repeating unit having a polymerizable group include the following. However, the present invention is not limited to these.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
＜＜色素多量体が有するアルカリ可溶性基＞＞
　色素多量体が有していてもよいアルカリ可溶性基の一例は、酸基であり、酸基としては、カルボン酸基、スルホン酸基、リン酸基が例示される。
　アルカリ可溶性基（好ましくは酸基）は、アルカリ可溶性基（酸基）を有する繰り返し単位として、色素多量体中に含まれることが好ましい。 << Alkali-soluble group of dye multimer >>
An example of the alkali-soluble group that the dye multimer may have is an acid group, and examples of the acid group include a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
The alkali-soluble group (preferably an acid group) is preferably contained in the dye multimer as a repeating unit having an alkali-soluble group (acid group).
　色素多量体へのアルカリ可溶性基の導入方法としては、色素単量体にあらかじめアルカリ可溶性基を導入しておく方法およびアルカリ可溶性基を有する色素単量体以外のモノマー（（メタ）アクリル酸、アクリル酸のカプロラクトン変性物、（メタ）アクリル酸２－ヒドロキシエチルの無水こはく酸変性物、（メタ）アクリル酸２－ヒドロキシエチルの無水フタル酸変性物、（メタ）アクリル酸２－ヒドロキシエチルの１，２－シクロヘキサンジカルボン酸無水物変性物、スチレンカルボン酸、イタコン酸、マレイン酸、ノルボルネンカルボン酸等のカルボン酸含有モノマー、アシッドホスホオキシエチルメタクリレート、ビニルホスホン酸等のリン酸含有モノマー、ビニルスルホン酸、２－アクリルアミド－２－メチルスルホン酸等のスルホン酸含有モノマー）を共重合する方法が挙げられるが、双方の方法を用いることがさらに好ましい。 As a method for introducing an alkali-soluble group into a dye multimer, a method in which an alkali-soluble group is introduced into a dye monomer in advance, and a monomer other than a dye monomer having an alkali-soluble group ((meth) acrylic acid, acrylic Modified product of caprolactone of acid, modified product of succinic anhydride of 2-hydroxyethyl (meth) acrylate, modified product of phthalic anhydride of 2-hydroxyethyl (meth) acrylate, 1,2-hydroxyethyl (meth) acrylate 2-cyclohexanedicarboxylic acid anhydride modified product, carboxylic acid-containing monomer such as styrene carboxylic acid, itaconic acid, maleic acid, norbornene carboxylic acid, phosphoric acid-containing monomer such as acid phosphooxyethyl methacrylate, vinyl phosphonic acid, vinyl sulfonic acid, Such as 2-acrylamido-2-methylsulfonic acid A method of copolymerizing acid containing monomers) may be mentioned, more preferably to use both methods.
　色素多量体が有するアルカリ可溶性基量は、色素多量体１ｇに対し０．３～２．０ｍｍｏｌであることが好ましく、０．４～１．５ｍｍｏｌであることがさらに好ましく、０．５～１．０ｍｍｏｌであることが特に好ましい。
　また、色素多量体が色素単量体を含む繰り返し単位と酸基を有する繰り返し単位を含有する場合、酸基を有する繰り返し単位を含有する繰り返し単位の割合は、色素単量体を含む繰り返し単位１００モルに対し、例えば、５～７０モルが好ましく、１０～５０モルがより好ましい。 The amount of the alkali-soluble group possessed by the dye multimer is preferably 0.3 to 2.0 mmol, more preferably 0.4 to 1.5 mmol, more preferably 0.5 to 1. Particularly preferred is 0 mmol.
Further, when the dye multimer contains a repeating unit containing a dye monomer and a repeating unit having an acid group, the ratio of the repeating unit containing a repeating unit having an acid group is 100 repeating units containing a dye monomer. For example, 5-70 mol is preferable with respect to mol, and 10-50 mol is more preferable.
　色素多量体が有するその他の官能基として、ラクトン、酸無水物、アミド、－ＣＯＣＨ２ＣＯ－、シアノ基等の現像促進基、長鎖および環状アルキル基、アラルキル基、アリール基、ポリアルキレンオキシド基、ヒドロキシル基、マレイミド基、アミノ基等の親疏水性調整基等が挙げられ、適宜導入することができる。
　導入方法として、色素単量体にあらかじめ導入しておく方法、および上記官能基を有するモノマーを共重合する方法が挙げられる。 Other functional groups possessed by the dye multimer include development accelerators such as lactones, acid anhydrides, amides, —COCH 2 CO—, cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups And an affinity adjusting group such as a hydroxyl group, a maleimide group, and an amino group, and the like, which can be appropriately introduced.
Examples of the introduction method include a method of introducing the dye monomer in advance and a method of copolymerizing the monomer having the functional group.
　色素多量体が有してもよいアルカリ可溶性基その他の官能基を有する繰り返し単位の具体例を示すが、本発明はこれに限定されるものではない。 Specific examples of the repeating unit having an alkali-soluble group or other functional group that the dye multimer may have are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
 　
Figure JPOXMLDOC01-appb-C000031
 　
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　本発明で用いられるトリアリールメタン染料が高分子の場合、有していても良い繰り返し単位の具体例として、（メタ）アクリル酸、（メタ）アクリル酸エステルおよび（メタ）アクリル酸アミドの少なくとも１種に由来する繰り返し単位が例示される。
　高分子タイプのトリアリールメタン染料の重量平均分子量（Ｍｗ）は、２，０００～５０，０００であることが好ましく、３，０００～３０，０００であることがさらに好ましく、６，０００～２０，０００であることが特に好ましい。
　また、高分子タイプのトリアリールメタン染料の重量平均分子量（Ｍｗ）と、数平均分子量（Ｍｎ）との比〔（Ｍｗ）／（Ｍｎ）〕は１．０～２．０であることが好ましく、１．１～１．８であることがさらに好ましく、１．１～１．５であることが特に好ましい。 When the triarylmethane dye used in the present invention is a polymer, specific examples of the repeating unit that may be included are at least one of (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylic acid amide. Examples are repeating units derived from species.
The weight average molecular weight (Mw) of the polymer type triarylmethane dye is preferably 2,000 to 50,000, more preferably 3,000 to 30,000, and 6,000 to 20,000. 000 is particularly preferred.
Further, the ratio [(Mw) / (Mn)] of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer type triarylmethane dye is preferably 1.0 to 2.0. 1.1 to 1.8 is more preferable, and 1.1 to 1.5 is particularly preferable.
　高分子タイプのトリアリールメタン染料のガラス転移温度（Ｔｇ）は、５０℃以上であることが好ましく、１００℃以上であることがより好ましい。また、熱重量分析（ＴＧＡ測定）による５％重量減少温度が、１２０℃以上であることが好ましく、１５０℃以上であることがより好ましく、２００℃以上であることがさらに好ましい。この領域にあることで、本発明の着色硬化性組成物をカラーフィルタ等の作製に適用する際に、加熱プロセスに起因する濃度変化を低減する事ができるようになる。 The glass transition temperature (Tg) of the polymer type triarylmethane dye is preferably 50 ° C. or higher, and more preferably 100 ° C. or higher. Further, the 5% weight loss temperature by thermogravimetric analysis (TGA measurement) is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and further preferably 200 ° C. or higher. By being in this region, when applying the colored curable composition of the present invention to the production of a color filter or the like, it becomes possible to reduce the concentration change caused by the heating process.
　高分子タイプのトリアリールメタン染料が、色素構造を有する繰り返し単位と、他の繰り返し単位を含む場合、色素を含む重合性化合物と他の重合性化合物のランダム重合体であることが好ましい。ランダム重合体とすることにより、色素構造がトリアリールメタン染料にランダムに存在し、本発明の効果がより効果的に発揮される。 When the polymer type triarylmethane dye contains a repeating unit having a pigment structure and another repeating unit, it is preferably a random compound of a polymerizable compound containing a pigment and another polymerizable compound. By using a random polymer, the dye structure is present randomly in the triarylmethane dye, and the effects of the present invention are more effectively exhibited.
＜＜アニオンＸ＞＞
　トリアリールメタン染料が高分子タイプである場合においても、分子内および分子外の少なくともいずれかにアニオンＸを有する。中でも、分子外にアニオンＸを有することが好ましい。アニオンＸは、トリアリールメタン染料に含まれるカチオンの価数に応じて含まれる。カチオンは、通常、１価または２価であり、１価が好ましい。
　本発明において、分子内にアニオンＸがあるとは、トリアリールメタン染料の同一繰り返し単位内にあることを意味する。すなわち、色素構造を有する繰り返し単位内で、カチオンとアニオンが共有結合を介して結合している場合をいう。
　一方、分子外にアニオンＸを有するとは、上記以外をいい、カチオンとアニオンが共有結合を介して結合せず、別化合物として存在している場合や、カチオンとアニオンがトリアリールメタン染料のそれぞれ独立の繰り返し単位として含まれる場合をいう。 << Anion X >>
Even when the triarylmethane dye is of a polymer type, it has an anion X at least either inside or outside the molecule. Among these, it is preferable to have an anion X outside the molecule. The anion X is contained according to the valence of the cation contained in the triarylmethane dye. The cation is usually monovalent or divalent, and monovalent is preferable.
In the present invention, the presence of an anion X in the molecule means that it is in the same repeating unit of the triarylmethane dye. That is, it means a case where a cation and an anion are bonded via a covalent bond within a repeating unit having a dye structure.
On the other hand, having an anion X outside the molecule means other than the above, and when the cation and the anion are not bonded via a covalent bond and exist as separate compounds, or the cation and the anion are triarylmethane dyes, respectively. The case where it is contained as an independent repeating unit.
　アニオンＸが同一繰り返し単位内にある場合のアニオン部としては、上記低分子タイプにおけるアニオンの第一の実施形態と同様であり、好ましい範囲も同様である。 When the anion X is in the same repeating unit, the anion portion is the same as that of the first embodiment of the anion in the low molecular type, and the preferred range is also the same.
　アニオンＸが別分子の場合のアニオンとしては、上記低分子タイプにおけるアニオンの第二の実施形態と同様であり、好ましい範囲も同様である。 The anion when the anion X is a different molecule is the same as in the second embodiment of the anion in the low molecular type, and the preferred range is also the same.
　カチオンとアニオンがトリアリールメタン染料の別々の繰り返し単位に含まれる場合とは、カチオンとアニオンがトリアリールメタン染料のそれぞれ独立の繰り返し単位に含まれる場合をいう。
　この場合、アニオンは、トリアリールメタン染料の側鎖に有していてもよいし、主鎖に有していても良いし、主鎖および側鎖の両方にアニオンＸを有していてもよい。好ましくは側鎖である。
　アニオンＸを含む繰り返し単位の好ましい例としては、一般式（Ｃ）で表される繰り返し単位および一般式（Ｄ）で表される繰り返し単位が例示される。 The case where the cation and the anion are contained in separate repeating units of the triarylmethane dye refers to the case where the cation and the anion are contained in independent repeating units of the triarylmethane dye.
In this case, the anion may be present in the side chain of the triarylmethane dye, may be present in the main chain, or may have the anion X in both the main chain and the side chain. . A side chain is preferred.
Preferable examples of the repeating unit containing an anion X include a repeating unit represented by the general formula (C) and a repeating unit represented by the general formula (D).
一般式（Ｃ）
Figure JPOXMLDOC01-appb-C000034
 General formula (C)
Figure JPOXMLDOC01-appb-C000034
　一般式（Ｃ）中、Ｘ１は、繰り返し単位の主鎖を表す。Ｌ１は単結合または２価の連結基を表す。ａｎｉｏｎは、上記アニオンを表す。 In the general formula (C), X 1 represents a main chain of repeating units. L 1 represents a single bond or a divalent linking group. anion represents the anion.
　一般式（Ｃ）中、Ｘ１は、繰り返し単位の主鎖を表し、通常、重合反応で形成される連結基を表し、例えば、（メタ）アクリル系、スチレン系、ビニル系等が好ましく、（メタ）アクリル系がより好ましい。なお、２つの＊で表された部位が繰り返し単位となる。 In the general formula (C), X 1 represents a main chain of repeating units, usually represents a linking group formed by polymerization reaction, for example, (meth) acrylic, styrene, vinyl and the like are preferable, ( More preferred is a (meth) acrylic type. Two sites represented by * are repeating units.
　Ｌ１が２価の連結基を表す場合、炭素数１～３０のアルキレン基（メチレン基、エチレン基、トリメチレン基、プロピレン基、ブチレン基など）、炭素数６～３０のアリーレン基（フェニレン基、ナフタレン基等）、ヘテロ環連結基、－ＣＨ＝ＣＨ－、－Ｏ－、－Ｓ－、－Ｃ（＝Ｏ）－、－ＣＯ－、－ＮＲ－、－ＣＯＮＲ－、－ＯＣ－、－ＳＯ－、－ＳＯ２－およびこれらを２以上組み合わせた連結基が好ましい。ここで、Ｒは、それぞれ独立に、水素原子、アルキル基、アリール基、またはヘテロ環基を表す。
　特に、Ｌ１は、単結合、または、炭素数１～１０のアルキレン基（好ましくは、－（ＣＨ２）ｎ－（ｎは５～１０の整数）、炭素数６～１２のアリーレン基（好ましくはフェニレン基、ナフタレン基）、－ＮＨ－、－ＣＯ２－、－Ｏ－および－ＳＯ２－を２以上組み合わせた２価の連結基が好ましい。 When L 1 represents a divalent linking group, an alkylene group having 1 to 30 carbon atoms (methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), an arylene group having 6 to 30 carbon atoms (phenylene group, Naphthalene group, etc.), heterocyclic linking group, —CH═CH—, —O—, —S—, —C (═O) —, —CO—, —NR—, —CONR—, —OC—, —SO —, —SO 2 — and a linking group obtained by combining two or more thereof are preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
In particular, L 1 is a single bond or an alkylene group having 1 to 10 carbon atoms (preferably — (CH 2 ) n— (n is an integer of 5 to 10), an arylene group having 6 to 12 carbon atoms (preferably phenylene group, naphthalene group) is, - NH -, - CO 2 -, - O- and -SO 2 - is a divalent linking group formed by combining two or more preferred.
　Ｘ１の具体例としては、上記一般式（Ａ）におけるＸ１の例が好ましい例として例示される。 Specific examples of X 1, examples of X 1 in formula (A) are exemplified as preferable examples.
一般式（Ｄ）
Figure JPOXMLDOC01-appb-C000035
 Formula (D)
Figure JPOXMLDOC01-appb-C000035
　一般式（Ｄ）中、Ｌ２およびＬ３は、それぞれ独立して単結合または２価の連結基を表す。ａｎｉｏｎは、上記アニオンＸを表す。 In general formula (D), L 2 and L 3 each independently represent a single bond or a divalent linking group. anion represents the anion X.
　一般式（Ｄ）中、Ｌ２およびＬ３が２価の連結基を表す場合、炭素数１～３０のアルキレン基、炭素数６～３０のアリーレン基、ヘテロ環連結基、－ＣＨ＝ＣＨ－、－Ｏ－、－Ｓ－、－Ｃ（＝Ｏ）－、－ＣＯ２－、－ＮＲ－、－ＣＯＮＲ－、－Ｏ２Ｃ－、－ＳＯ－、－ＳＯ２－およびこれらを２以上組み合わせた連結基が好ましい。ここで、Ｒは、それぞれ独立に、水素原子、アルキル基、アリール基、またはヘテロ環基を表す。
　Ｌ２は、炭素数６～１２のアリーレン基（特にフェニレン基）が好ましい。炭素数６～３０のアリーレン基は、フッ素原子で置換されていることが好ましい。
　Ｌ３は、炭素数６～１２のアリーレン基（特にフェニレン基）と－Ｏ－との組み合わせからなる基が好ましく、少なくとも１種の炭素数６～１２のアリーレン基がフッ素原子で置換されていることが好ましい。 In the general formula (D), when L 2 and L 3 represent a divalent linking group, an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, —CH═CH— , —O—, —S—, —C (═O) —, —CO 2 —, —NR—, —CONR—, —O 2 C—, —SO—, —SO 2 — and combinations of two or more thereof The linking group is preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
L 2 is preferably an arylene group having 6 to 12 carbon atoms (particularly a phenylene group). The arylene group having 6 to 30 carbon atoms is preferably substituted with a fluorine atom.
L 3 is preferably a group comprising a combination of an arylene group having 6 to 12 carbon atoms (particularly a phenylene group) and —O—, and at least one kind of arylene group having 6 to 12 carbon atoms is substituted with a fluorine atom. It is preferable.
　アニオン多量体を形成する高分子としては、重合性基を有する染料化合物成分からのみ構成されるホモポリマー（単独重合体）でも、その他重合性化合物とのコポリマー（共重合体）でも好ましく用いることが出来るが、ホモポリマー（単独重合体）がより好ましい。
　アニオン多量体の分子量としては、重量平均分子量が３，０００～３０，０００かつ、分子量分布がＭｗ／Ｍｎで０．８～３．０であることが好ましく、より好ましくは重量平均分子量が５，０００～２０，０００かつ、分子量分布がＭｗ／Ｍｎで１～２．５である。 As a polymer forming an anion multimer, a homopolymer (homopolymer) composed only of a dye compound component having a polymerizable group or a copolymer (copolymer) with other polymerizable compound is preferably used. A homopolymer (homopolymer) is more preferable.
The molecular weight of the anionic multimer is preferably a weight average molecular weight of 3,000 to 30,000 and a molecular weight distribution of Mw / Mn of 0.8 to 3.0, more preferably a weight average molecular weight of 5, The molecular weight distribution is 1 to 2.5 in terms of Mw / Mn.
　アニオン多量体を形成する場合、連鎖移動剤を添加してもよい。連鎖移動剤としては、アルキルメルカプタンが好ましく、炭素数１０以下のアルキルメルカプタンまたはエーテル基・エステル基で置換されたアルキルメルカプタンが好ましい。特に、ｌｏｇＰ値が５以下のアルキルメルカプタンがより好ましい。
　アニオン多量体に含まれるアニオン多量体の原料である重合性基を有するアニオンモノマー化合物の量は、５％以下が好ましく、より好ましくは１％以下である。
　アニオン多量体に含まれるハロゲンイオン含有量としては、１０～３０００ｐｐｍ以下が好ましく、１０～２０００ｐｐｍがより好ましく、１０～１０００ｐｐｍがさらに好ましい。 When forming an anionic multimer, a chain transfer agent may be added. The chain transfer agent is preferably an alkyl mercaptan, and is preferably an alkyl mercaptan having 10 or less carbon atoms or an alkyl mercaptan substituted with an ether group / ester group. In particular, an alkyl mercaptan having a log P value of 5 or less is more preferable.
The amount of the anionic monomer compound having a polymerizable group that is a raw material of the anionic multimer contained in the anionic multimer is preferably 5% or less, more preferably 1% or less.
The halogen ion content contained in the anionic multimer is preferably 10 to 3000 ppm, more preferably 10 to 2000 ppm, and even more preferably 10 to 1000 ppm.
　アニオンＸを含む繰り返し単位の具体例を以下に示すが、本発明はこれらに限定されるものではない。
Figure JPOXMLDOC01-appb-C000036
 Specific examples of the repeating unit containing the anion X are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000036
　以下の具体例は、アニオン構造が解離していない状態を示しているが、アニオン構造が解離している状態も本発明の範囲内である。
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
 The following specific examples show the state where the anion structure is not dissociated, but the state where the anion structure is dissociated is also within the scope of the present invention.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　以下に、高分子タイプのトリアリールメタン染料により好ましく用いられる他の繰り返し単位の例を示す。他の繰り返し単位の例は、これらの繰り返し単位に限定されるものではない。
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
 Examples of other repeating units that are preferably used in accordance with the high molecular type triarylmethane dye are shown below. Examples of other repeating units are not limited to these repeating units.
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000043
　高分子タイプのトリアリールメタン染料の繰り返し単位の具体例として以下の構造を挙げることができるが、本発明はこれらに限定されるものではない。
Figure JPOXMLDOC01-appb-C000044
 Specific examples of the repeating unit of the polymer type triarylmethane dye include the following structures, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000044
＜＜トリアリールメタン染料の含有量＞＞
　本発明の着色硬化性組成物中に含まれるトリアリールメタン染料の含有量は、着色硬化性組成物中の全固形分に対して１．０～５０質量％が好ましく、５．０～３０質量％がさらに好ましく、８～２５質量％が特に好ましい。なお、トリアリールメタン染料にトリアリールメタン化合物が２種以上含まれる場合、トリアリールメタン染料の含有量は、２種以上のトリアリールメタン化合物の合計量となる。
　また、後述するように、本発明の着色硬化性組成物に顔料が含まれる場合、着色硬化性組成物中のトリアリールメタン染料と顔料の含有量の質量比は、１．０：０．０５～１．０：１．０が好ましく、１．０：０．１～１．０：０．６がより好ましい。 << Content of Triarylmethane Dye >>
The content of the triarylmethane dye contained in the colored curable composition of the present invention is preferably 1.0 to 50% by mass, and preferably 5.0 to 30% by mass with respect to the total solid content in the colored curable composition. % Is more preferable, and 8 to 25% by mass is particularly preferable. When the triarylmethane dye contains two or more triarylmethane compounds, the content of the triarylmethane dye is the total amount of the two or more triarylmethane compounds.
As will be described later, when the pigment is contained in the colored curable composition of the present invention, the mass ratio of the content of the triarylmethane dye and the pigment in the colored curable composition is 1.0: 0.05. To 1.0: 1.0 is preferable, and 1.0: 0.1 to 1.0: 0.6 is more preferable.
＜顔料＞
　本発明の着色硬化性組成物には、着色剤としてトリアリールメタン染料のみが含まれていてもよいが、さらに顔料が含有されてもよい。また、着色硬化性組成物に顔料が含有される場合は分散剤が含有されることが好ましい。すなわち、本発明の着色硬化性組成物には、カチオンを含むトリアリールメタン構造と対アニオンとを有するトリアリールメタン染料と、重合性化合物と、顔料と、分散剤とが含有されていてもよい。ここで、分散剤は吸着基を有するものであって、分散剤の吸着基は、酸性吸着基および塩基性吸着基の少なくとも一方を含むことが好ましい。 <Pigment>
The colored curable composition of the present invention may contain only a triarylmethane dye as a colorant, but may further contain a pigment. Moreover, when a pigment is contained in the colored curable composition, a dispersant is preferably contained. That is, the colored curable composition of the present invention may contain a triarylmethane dye having a triarylmethane structure containing a cation and a counter anion, a polymerizable compound, a pigment, and a dispersant. . Here, the dispersant has an adsorption group, and the adsorption group of the dispersant preferably includes at least one of an acidic adsorption group and a basic adsorption group.
　本発明の着色硬化性組成物に混合される顔料としては、ペリレン、ペリノン、キナクリドン、キナクリドンキノン、アントラキノン、アントアントロン、ベンズイミダゾロン、ジスアゾ縮合、ジスアゾ、アゾ、インダントロン、フタロシアニン、トリアリールカルボニウム、ジオキサジン、アミノアントラキノン、ジケトピロロピロール、インジゴ、チオインジゴ、イソインドリン、イソインドリノン、ピラントロンもしくはイソビオラントロン等が挙げられる。さらに詳しくは、例えば、ピグメント・レッド１９０、ピグメント・レッド２２４、ピグメント・バイオレット２９等のペリレン化合物顔料、ピグメント・オレンジ４３、もしくはピグメント・レッド１９４等のペリノン化合物顔料、ピグメント・バイオレット１９、ピグメント・バイオレット４２、ピグメント・レッド１２２、ピグメント・レッド１９２、ピグメント・レッド２０２、ピグメント・レッド２０７、もしくはピグメント・レッド２０９のキナクリドン化合物顔料、ピグメント・レッド２０６、ピグメント・オレンジ４８、もしくはピグメント・オレンジ４９等のキナクリドンキノン化合物顔料、ピグメント・イエロー１４７等のアントラキノン化合物顔料、ピグメント・レッド１６８等のアントアントロン化合物顔料、ピグメント・ブラウン２５、ピグメント・バイオレット３２、ピグメント・オレンジ３６、ピグメント・イエロー１２０、ピグメント・イエロー１８０、ピグメント・イエロー１８１、ピグメント・オレンジ６２、もしくはピグメント・レッド１８５等のベンズイミダゾロン化合物顔料、ピグメント・イエロー９３、ピグメント・イエロー９４、ピグメント・イエロー９５、ピグメント・イエロー１２８、ピグメント・イエロー１６６、ピグメント・オレンジ３４、ピグメント・オレンジ１３、ピグメント・オレンジ３１、ピグメント・レッド１４４、ピグメント・レッド１６６、ピグメント・レッド２２０、ピグメント・レッド２２１、ピグメント・レッド２４２、ピグメント・レッド２４８、ピグメント・レッド２６２、もしくはピグメント・ブラウン２３等のジスアゾ縮合化合物顔料、ピグメント・イエロー１３、ピグメント・イエロー８３、もしくはピグメント・イエロー１８８等のジスアゾ化合物顔料、ピグメント・レッド１８７、ピグメント・レッド１７０、ピグメント・イエロー７４、ピグメント・イエロー１５０、ピグメント・レッド４８、ピグメント・レッド５３、ピグメント・オレンジ６４、もしくはピグメント・レッド２４７等のアゾ化合物顔料、ピグメント・ブルー６０等のインダントロン化合物顔料、ピグメント・グリーン７、ピグメント・グリーン３６、ピグメント・グリーン３７、ピグメント・グリーン５８、ピグメント・ブルー１６、ピグメント・ブルー７５、もしくはピグメント・ブルー１５等のフタロシアニン化合物顔料、ピグメント・ブルー５６、もしくはピグメント・ブルー６１等のトリアリールカルボニウム化合物顔料、ピグメント・バイオレット２３、もしくはピグメント・バイオレット３７等のジオキサジン化合物顔料、ピグメント・レッド１７７等のアミノアントラキノン化合物顔料、ピグメント・レッド２５４、ピグメント・レッド２５５、ピグメント・レッド２６４、ピグメント・レッド２７２、ピグメント・オレンジ７１、もしくはピグメント・オレンジ７３等のジケトピロロピロール化合物顔料、ピグメント・レッド８８等のチオインジゴ化合物顔料、ピグメント・イエロー１３９、ピグメント・オレンジ６６等のイソインドリン化合物顔料、ピグメント・イエロー１０９、もしくはピグメント・オレンジ６１等のイソインドリノン化合物顔料、ピグメント・オレンジ４０、もしくはピグメント・レッド２１６等のピラントロン化合物顔料、またはピグメント・バイオレット３１等のイソビオラントロン化合物顔料が挙げられる。
　本発明で用いられる顔料は、緑からシアン色の色材が好ましく、ピグメント・グリーン７、ピグメント・グリーン３６、ピグメント・グリーン３７、ピグメント・グリーン５８、ピグメント・ブルー１６、ピグメント・ブルー７５、もしくはピグメント・ブルー１５等のフタロシアニン化合物顔料、ピグメント・ブルー５６、もしくはピグメント・ブルー６１等のトリアリールカルボニウム化合物顔料、ピグメント・バイオレット２３、もしくはピグメント・バイオレット３７等のジオキサジン化合物顔料、ピグメント・レッド１７７等のアミノアントラキノン化合物顔料、ピグメント・レッド２５４、ピグメント・レッド２５５、ピグメント・レッド２６４、ピグメント・レッド２７２、ピグメント・オレンジ７１、もしくはピグメント・オレンジ７３等のジケトピロロピロール化合物顔料、ピグメント・レッド８８等のチオインジゴ化合物顔料、ピグメント・イエロー１３９、ピグメント・オレンジ６６等のイソインドリン化合物顔料、ピグメント・イエロー１０９、もしくはピグメント・オレンジ６１等のイソインドリノン化合物顔料、ピグメント・オレンジ４０、もしくはピグメント・レッド２１６等のピラントロン化合物顔料、またはピグメント・バイオレット３１等のイソビオラントロン化合物顔料が好ましい。
　特に、本発明の着色硬化性組成物には、オキサジン顔料およびフタロシアニン化合物顔料の少なくとも１種が含まれることが好ましい。本発明では、フタロシアニン化合物顔料は、銅フタロシアニン系青色顔料であることが好ましく、本発明の着色硬化性組成物には、銅フタロシアニン系青色顔料が含まれることがより好ましい。 Examples of the pigment mixed with the colored curable composition of the present invention include perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, and triarylcarbonium. , Dioxazine, aminoanthraquinone, diketopyrrolopyrrole, indigo, thioindigo, isoindoline, isoindolinone, pyranthrone, or isoviolanthrone. More specifically, for example, perylene compound pigments such as Pigment Red 190, Pigment Red 224, and Pigment Violet 29, perinone compound pigments such as Pigment Orange 43, and Pigment Red 194, Pigment Violet 19, and Pigment Violet. 42, quinacridone such as Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 207, or Pigment Red 209, quinacridone compound pigment, Pigment Red 206, Pigment Orange 48, or Pigment Orange 49 Quinone compound pigment, anthraquinone compound pigment such as pigment yellow 147, anthanthrone compound pigment such as pigment red 168, pigment Benzimidazolone compound pigments such as Pigment Brown 25, Pigment Violet 32, Pigment Orange 36, Pigment Yellow 120, Pigment Yellow 180, Pigment Yellow 181, Pigment Orange 62, or Pigment Red 185; Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 166, Pigment Orange 34, Pigment Orange 13, Pigment Orange 31, Pigment Red 144, Pigment Red 166, Pigment Red Red 220, Pigment Red 221, Pigment Red 242, Pigment Red 248, Pigment Red 262, or Pigment Disazo condensation compound pigments such as Brown 23, Pigment Yellow 13, Pigment Yellow 83, or Disazo Compound Pigments such as Pigment Yellow 188, Pigment Red 187, Pigment Red 170, Pigment Yellow 74, Pigment Yellow 150, Pigment Red 48, Pigment Red 53, Pigment Orange 64, Pigment Red 247 and other azo compound pigments, Pigment Blue 60 and other indanthrone compound pigments, Pigment Green 7, Pigment Green 36, Pigment Green 37, phthalocyanine compound pigments such as Pigment Green 58, Pigment Blue 16, Pigment Blue 75, and Pigment Blue 15, Pigment Blue 56 Or triarylcarbonium compound pigments such as Pigment Blue 61, dioxazine compound pigments such as Pigment Violet 23 or Pigment Violet 37, aminoanthraquinone compound pigments such as Pigment Red 177, Pigment Red 254, Pigment Red 255, pigment red 264, pigment red 272, pigment orange 71, or diketopyrrolopyrrole compound pigment such as pigment orange 73, thioindigo compound pigment such as pigment red 88, pigment yellow 139, pigment orange 66 Isoindoline compound pigments such as Pigment Yellow 109, Pigment Orange 61, and Pigment Oren 40, or pyranthrone compound pigments such as Pigment Red 216 or isoviolanthrone compound pigments, such as Pigment Violet 31, and the like.
The pigment used in the present invention is preferably a green to cyan colorant, and includes Pigment Green 7, Pigment Green 36, Pigment Green 37, Pigment Green 58, Pigment Blue 16, Pigment Blue 75, or Pigment. -A phthalocyanine compound pigment such as Blue 15; a triarylcarbonium compound pigment such as Pigment Blue 56 or Pigment Blue 61; a dioxazine compound pigment such as Pigment Violet 23 or Pigment Violet 37; Pigment Red 177 Aminoanthraquinone compound pigment, Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 272, Pigment Orange 71, or Pigment Red Diketopyrrolopyrrole compound pigments such as Range 73, thioindigo compound pigments such as Pigment Red 88, isoindoline compound pigments such as Pigment Yellow 139 and Pigment Orange 66, and Iso Yellows such as Pigment Yellow 109 or Pigment Orange 61 Preference is given to indolinone compound pigments, pyrantron compound pigments such as Pigment Orange 40 or Pigment Red 216, or isoviolanthrone compound pigments such as Pigment Violet 31.
In particular, the colored curable composition of the present invention preferably contains at least one of an oxazine pigment and a phthalocyanine compound pigment. In the present invention, the phthalocyanine compound pigment is preferably a copper phthalocyanine blue pigment, and the colored curable composition of the present invention more preferably contains a copper phthalocyanine blue pigment.
＜染料化合物＞
　本発明の着色硬化性組成物には、カチオンを含むトリアリールメタン構造と対アニオンとを有するトリアリールメタン染料の他に染料化合物が含まれていてもよい。染料化合物としては、例えば、アゾ系（例えば、ソルベントイエロー１６２）、アントラキノン系（例えば、特開２００１－１０８８１号公報に記載のアントラキノン化合物）、フタロシアニン系（例えば、米国特許２００８／００７６０４４Ａ１に記載のフタロシアニン化合物）、キサンテン系（例えば、シー・アイ・アシッド・レッド２８９（Ｃ．Ｉ．Ａｃｉｄ．Ｒｅｄ　２８９））、トリアリールメタン系（例えば、シー・アイ・アシッドブルー７（Ｃ．Ｉ．Ａｃｉｄ　Ｂｌｕｅ７）、シー・アイ・アシッドブルー８３（Ｃ．Ｉ．Ａｃｉｄ　Ｂｌｕｅ８３）、シー・アイ・アシッドブルー９０（Ｃ．Ｉ．Ａｃｉｄ　Ｂｌｕｅ９０）、シー・アイ・ソルベント・ブルー３８（Ｃ．Ｉ．Ｓｏｌｖｅｎｔ　Ｂｌｕｅ３８）、シー・アイ・アシッド・バイオレット１７（Ｃ．Ｉ．Ａｃｉｄ　Ｖｉｏｌｅｔ１７）、シー・アイ・アシッド・バイオレット４９（Ｃ．Ｉ．Ａｃｉｄ　Ｖｉｏｌｅｔ４９）、シー・アイ・アシッド・グリーン３（Ｃ．Ｉ．Ａｃｉｄ　Ｇｒｅｅｎ３）、メチン染料、キサンテン色素（例えば特開２０１０－３２９９９号公報）、ジピロメテン金属錯体化合物（例えば特開２０１２－２３７９８５号公報）などが挙げられる。 <Dye compound>
The colored curable composition of the present invention may contain a dye compound in addition to a triarylmethane dye having a triarylmethane structure containing a cation and a counter anion. Examples of the dye compound include azo compounds (for example, Solvent Yellow 162), anthraquinone compounds (for example, anthraquinone compounds described in JP-A-2001-10881), and phthalocyanine compounds (for example, phthalocyanine described in US 2008 / 0076044A1). Compound), xanthene series (for example, C.I. Acid Red 289), triarylmethane series (for example, C.I. Acid Blue 7) CI Acid Blue 83 (CI Acid Blue 83), CI Acid Blue 90 (CI Acid Blue 90), CI Solvent Blue 38 (CI Solvent Blue 38), Sea Eye Acid Iolet 17 (CI Acid Violet 17), C.I. Acid Violet 49, C.I. Acid Green 3 (C.I. Acid Green 3), methine dye, xanthene dye (For example, JP 2010-32999 A), dipyrromethene metal complex compounds (for example, JP 2012-237985 A) and the like.
　染料化合物としては、キサンテン系染料化合物およびジピロメテン金属錯体化合物の少なくとも１種を含んでいてもよい。 The dye compound may contain at least one of a xanthene dye compound and a dipyrromethene metal complex compound.
＜＜キサンテン系染料化合物＞＞
　キサンテン系染料化合物（以下、キサンテン色素ともいう）は、分子内にキサンテン骨格を有する化合物を含む染料である。キサンテン色素としては、例えばＣ．Ｉ．アシッドレッド５１（以下、Ｃ．Ｉ．アシッドレッドの記載を省略し、番号のみの記載とする。他も同様である。）、５２、８７、９２、９４、２８９、３８８、Ｃ．Ｉ．アシッドバイオレット９、３０、１０２、Ｃ．Ｉ．ベーシックレッド１（ローダミン６Ｇ）、２、３、４、８、Ｃ．Ｉ．ベーシックレッド１０（ローダミンＢ）、１１、Ｃ．Ｉ．ベーシックバイオレット１０、１１、２５、Ｃ．Ｉ．ソルベントレッド２１８、Ｃ．Ｉ．モーダントレッド２７、Ｃ．Ｉ．リアクティブレッド３６（ローズベンガルＢ）、スルホローダミンＧ、特開２０１０－３２９９９号公報に記載のキサンテン染料および特許第４４９２７６０号公報に記載のキサンテン染料等が挙げられる。キサンテン色素は、有機溶剤に溶解するものが好ましい。 << Xanthene dye compound >>
A xanthene dye compound (hereinafter also referred to as xanthene dye) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of xanthene dyes include C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. Others are also the same), 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. And reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A, xanthene dyes described in Japanese Patent No. 4492760, and the like. The xanthene dye is preferably dissolved in an organic solvent.
　キサンテン色素としては、式（１ａ）で表される化合物（以下、「化合物（１ａ）」という場合がある。）を含む染料が好ましい。化合物（１ａ）は、その互変異性体であってもよい。化合物（１ａ）を用いる場合、キサンテン色素中の化合物（１ａ）の含有量は、５０質量％以上が好ましく、７０質量％以上がより好ましく、９０質量％以上がさらに好ましい。特に、キサンテン色素として、化合物（１ａ）のみを使用することが好ましい。 As the xanthene pigment, a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable. Compound (1a) may be a tautomer thereof. In the case of using the compound (1a), the content of the compound (1a) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye.
式（１ａ）
Figure JPOXMLDOC01-appb-C000045
 Formula (1a)
Figure JPOXMLDOC01-appb-C000045
　式（１ａ）中、Ｒ１～Ｒ４は、それぞれ独立に水素原子、置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基、または、置換基を有していてもよい炭素数６～１０の１価の芳香族炭化水素基を表し、上記飽和炭化水素基に含まれる－ＣＨ２－は、－Ｏ－、－ＣＯ－または－ＮＲ１１－で置換されていてもよい。
　Ｒ１およびＲ２は、互いに結合して窒素原子を含む環を形成してもよい。Ｒ３およびＲ４は、互いに結合して窒素原子を含む環を形成してもよい。
　Ｒ５は、－ＯＨ、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３ －Ｚ＋、－ＣＯ２Ｈ、－ＣＯ２ －Ｚ＋、－ＣＯ２Ｒ８、－ＳＯ３Ｒ８または－ＳＯ２ＮＲ９Ｒ１０を表す。
　Ｒ６およびＲ７は、それぞれ独立に、水素原子または炭素数１～６のアルキル基を表す。
　ｍは、０～５の整数を表す。ｍが２以上のとき、複数のＲ５は同一でも異なってもよい。
　ａは、０または１を表す。
　Ｘは、ハロゲン原子を表す。
　ｎは、化合物（１ａ）中のアニオンの合計数を表す。
　Ｚ＋は、Ｎ＋（Ｒ１１）４、Ｎａ＋またはＫ＋を表し、４つのＲ１１は同一でも異なってもよい。
　Ｒ８は、炭素数１～２０の１価の飽和炭化水素基を表し、上記飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
　Ｒ９およびＲ１０は、それぞれ独立に、水素原子または置換基を有していてもよい炭素数１～２０の１価の飽和炭化水素基を表し、上記飽和脂肪族炭化水素基に含まれる－ＣＨ２－は、－Ｏ－、－ＣＯ－、－ＮＨ－または－ＮＲ８－で置換されていてもよく、Ｒ９およびＲ１０は、互いに結合して窒素原子を含む３～１０員環の複素環を形成していてもよい。
　Ｒ１１は、水素原子、炭素数１～２０の１価の飽和炭化水素基または炭素数７～１０のアラルキル基を表す。 In formula (1a), R 1 to R 4 each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and —CH 2 — contained in the saturated hydrocarbon group is substituted with —O—, —CO— or —NR 11 —. May be.
R 1 and R 2 may combine with each other to form a ring containing a nitrogen atom. R 3 and R 4 may combine with each other to form a ring containing a nitrogen atom.
R 5 is, -OH, -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO 2 represents NR 9 R 10
R 6 and R 7 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, the plurality of R 5 may be the same or different.
a represents 0 or 1;
X represents a halogen atom.
n represents the total number of anions in the compound (1a).
Z + represents N + (R 11 ) 4 , Na + or K + , and the four R 11 may be the same or different.
R 8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R 9 and R 10 each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and is included in the saturated aliphatic hydrocarbon group— CH 2 — may be substituted with —O—, —CO—, —NH—, or —NR 8 —, and R 9 and R 10 are bonded to each other to form a 3- to 10-membered ring containing a nitrogen atom. A heterocycle may be formed.
R 11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.
　Ｒ１～Ｒ４における炭素数６～１０の１価の芳香族炭化水素基としては、例えば、フェニル基、トルイル基、キシリル基、メシチル基、プロピルフェニル基およびブチルフェニル基等が挙げられる。中でも、トルイル基、キシリル基、メシチル基、プロピルフェニル基が好ましく、特にトルイル基、キシリル基、中でも、２，６－ジ置換のキシリル基が好ましい。 Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R 1 to R 4 include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. Of these, a toluyl group, a xylyl group, a mesityl group, and a propylphenyl group are preferable, and a toluyl group and a xylyl group are particularly preferable, and among these, a 2,6-disubstituted xylyl group is preferable.
　芳香族炭化水素基が有していてもよい置換基としては、ハロゲン原子、－Ｒ８、－ＯＨ、－ＯＲ８、－ＳＯ３－、－ＳＯ３Ｈ、－ＳＯ３ －Ｚ＋、－ＣＯ２Ｈ、－ＣＯ２Ｒ８、－ＳＲ８、－ＳＯ２Ｒ８、－ＳＯ３Ｒ８または－ＳＯ２ＮＲ９Ｒ１０が挙げられる。これらの中でも、置換基としては、－ＳＯ３－、－ＳＯ３Ｈ、－ＳＯ３ －Ｚ＋および－ＳＯ２ＮＲ９Ｒ１０が好ましく、－ＳＯ３ －Ｚ＋および－ＳＯ２ＮＲ９Ｒ１０がより好ましい。この場合の－ＳＯ３ －Ｚ＋としては、－ＳＯ３ －　Ｎ＋（Ｒ１１）４が好ましい。　Ｒ１～Ｒ４がこれらの基であることにより、化合物（１ａ）を含む本発明の着色硬化性組成物から、異物の発生が少なく、且つ耐熱性により優れるカラーフィルタを形成できる。 The aromatic hydrocarbon group substituent which may have a halogen atom, -R 8, -OH, -OR 8 , -SO 3 -, - SO 3 H, -SO 3 - Z +, -CO 2 H, —CO 2 R 8 , —SR 8 , —SO 2 R 8 , —SO 3 R 8, or —SO 2 NR 9 R 10 may be mentioned. Among them, as the substituent, -SO 3 -, - SO 3 H, -SO 3 - Z + and -SO 2 NR 9 R 10 is preferably, -SO 3 - Z + and -SO 2 NR 9 R 10 Is more preferable. The Z +, -SO 3 - - -SO 3 in this case N + (R 11) 4 are preferred. When R 1 to R 4 are these groups, a color filter with less generation of foreign matters and excellent heat resistance can be formed from the colored curable composition of the present invention containing the compound (1a).
　Ｒ１およびＲ２が互いに結合して形成する環、並びにＲ３およびＲ４が互いに結合して形成する環としては、例えば以下のものが挙げられる。
Figure JPOXMLDOC01-appb-C000046
 Examples of the ring formed by combining R 1 and R 2 with each other and the ring formed by combining R 3 and R 4 with each other include the following.
Figure JPOXMLDOC01-appb-C000046
　これらの中でも、化合物安定性の観点から、以下に示す構造が好ましい。
Figure JPOXMLDOC01-appb-C000047
 Among these, the following structures are preferable from the viewpoint of compound stability.
Figure JPOXMLDOC01-appb-C000047
　Ｒ８～Ｒ１１における炭素数１～２０の１価の飽和炭化水素基としては、例えば、メチル基、エチル基、プロピル基、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、ドデシル基、ヘキサデシル基、イコシル基等の直鎖状アルキル基；イソプロピル基、イソブチル基、イソペンチル基、ネオペンチル基、２－エチルヘキシル基等の分岐鎖状アルキル基；シクロプロピル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、トリシクロデシル基等の炭素数３～２０の脂環式飽和炭化水素基が挙げられる。
　中でも、メチル基、エチル基、プロピル基、イソプロピル基、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、が好ましく、特にプロピル基、イソプロピル基、ブチル基、ヘキシル基、２－エチルヘキシル基が好ましい。
　炭素数１～２０の１価の飽和炭化水素基に含まれる水素原子は、例えば、炭素数６～１０の芳香族炭化水素基またはハロゲン原子で置換されていてもよい。 Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 8 to R 11 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Linear alkyl groups such as decyl group, dodecyl group, hexadecyl group, icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.
Among them, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group are preferable, and a propyl group, an isopropyl group, a butyl group, a hexyl group, A 2-ethylhexyl group is preferred.
The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.
　－ＯＲ８としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、２－エチルヘキシルオキシ基およびイコシルオキシ基等が挙げられる。中でもメトキシ基、エトキシ基、プロポキシ基、ブトキシ基が好ましい。 Examples of —OR 8 include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group. Of these, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferable.
　－ＣＯ２Ｒ８としては、例えば、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、ｔｅｒｔ－ブトキシカルボニル基、ヘキシルオキシカルボニル基およびイコシルオキシカルボニル基等が挙げられる。中でもメトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基が好ましい。 Examples of —CO 2 R 8 include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group. Of these, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group are preferable.
　－ＳＲ８としては、例えば、メチルスルファニル基、エチルスルファニル基、ブチルスルファニル基、ヘキシルスルファニル基、デシルスルファニル基およびイコシルスルファニル基等が挙げられる。
　－ＳＯ２Ｒ８としては、例えば、メチルスルホニル基、エチルスルホニル基、ブチルスルホニル基、ヘキシルスルホニル基、デシルスルホニル基およびイコシルスルホニル基等が挙げられる。
　－ＳＯ３Ｒ８としては、例えば、メトキシスルホニル基、エトキシスルホニル基、プロポキシスルホニル基、ｔｅｒｔ－ブトキシスルホニル基、ヘキシルオキシスルホニル基およびイコシルオキシスルホニル基等が挙げられる。 Examples of —SR 8 include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO 2 R 8 include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO 3 R 8 include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.
　－ＳＯ２ＮＲ９Ｒ１０としては、例えば、スルファモイル基；
Ｎ－メチルスルファモイル基、Ｎ－エチルスルファモイル基、Ｎ－プロピルスルファモイル基、Ｎ－イソプロピルスルファモイル基、Ｎ－ブチルスルファモイル基、Ｎ－イソブチルスルファモイル基、Ｎ－ｓｅｃ－ブチルスルファモイル基、Ｎ－ｔｅｒｔ－ブチルスルファモイル基、Ｎ－ペンチルスルファモイル基、Ｎ－（１－エチルプロピル）スルファモイル基、Ｎ－（１，１－ジメチルプロピル）スルファモイル基、Ｎ－（１，２－ジメチルプロピル）スルファモイル基、Ｎ－（２－エチルヘキシル）スルファモイル基、Ｎ－（２，２－ジメチルプロピル）スルファモイル基、Ｎ－（１－メチルブチル）スルファモイル基、Ｎ－（２－メチルブチル）スルファモイル基、Ｎ－（３－メチルブチル）スルファモイル基、Ｎ－シクロペンチルスルファモイル基、Ｎ－ヘキシルスルファモイル基、Ｎ－（１，３－ジメチルブチル）スルファモイル基、Ｎ－（３，３－ジメチルブチル）スルファモイル基、Ｎ－ヘプチルスルファモイル基、Ｎ－（１－メチルヘキシル）スルファモイル基、Ｎ－（１，４－ジメチルペンチル）スルファモイル基、Ｎ－オクチルスルファモイル基、Ｎ－（２－エチルヘキシル）スルファモイル基、Ｎ－（１，５－ジメチル）ヘキシルスルファモイル基、Ｎ－（１，１，２，２－テトラメチルブチル）スルファモイル基等のＮ－１置換スルファモイル基；
Ｎ，Ｎ－ジメチルスルファモイル基、Ｎ，Ｎ－エチルメチルスルファモイル基、Ｎ，Ｎ－ジエチルスルファモイル基、Ｎ，Ｎ－プロピルメチルスルファモイル基、Ｎ，Ｎ－イソプロピルメチルスルファモイル基、Ｎ，Ｎ－ｔｅｒｔ－ブチルメチルスルファモイル基、Ｎ，Ｎ－ブチルエチルスルファモイル基、Ｎ，Ｎ－ビス（１－メチルプロピル）スルファモイル基、Ｎ，Ｎ－ヘプチルメチルスルファモイル基等のＮ，Ｎ－２置換スルファモイル基等が挙げられる。
　中でもＮ－メチルスルファモイル基、Ｎ－エチルスルファモイル基、Ｎ－プロピルスルファモイル基、Ｎ－イソプロピルスルファモイル基、Ｎ－ブチルスルファモイル基、Ｎ－ペンチルスルファモイル基、Ｎ－（２－エチルヘキシル）スルファモイル基が好ましく、Ｎ－メチルスルファモイル基、Ｎ－エチルスルファモイル基、Ｎ－プロピルスルファモイル基、Ｎ－ブチルスルファモイル基、Ｎ－（２－エチルヘキシル）スルファモイル基がより好ましい。 —SO 2 NR 9 R 10 includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2 -Methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentyl Rufamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1- Methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group An N-1 substituted sulfamoyl group such as an N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group And N, N-2 substituted sulfamoyl groups such as a group.
Among them, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-pentylsulfamoyl group, N -(2-ethylhexyl) sulfamoyl group is preferred, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N- (2-ethylhexyl) A sulfamoyl group is more preferred.
　Ｒ９、Ｒ１０における炭素数１～２０の１価の飽和炭化水素基は、置換基を有していてもよく、置換基としては、ヒドロキシ基およびハロゲン原子が挙げられる。 The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R 9 and R 10 may have a substituent, and examples of the substituent include a hydroxy group and a halogen atom.
　Ｒ５は、－ＯＨ、－ＳＯ３ －、－ＳＯ３Ｈ、－ＳＯ３ －Ｚ＋、－ＣＯ２Ｈ、－ＣＯ２ －Ｚ＋、－ＣＯ２Ｒ８、－ＳＯ３Ｒ８または－ＳＯ２ＮＲ９Ｒ１０を表す。
　Ｒ５は、－ＣＯ２Ｈ、－ＣＯ２ －Ｚ＋、－ＣＯ２Ｒ８、－ＣＯ２ＮＨＲ９、－ＳＯ３ －、－ＳＯ３ －Ｚ＋、－ＳＯ３Ｈ、－ＳＯ２Ｒ８、または－ＳＯ２ＮＨＲ９が好ましく、－ＳＯ３ －、－ＳＯ３ －Ｚ＋、－ＳＯ３Ｈまたは－ＳＯ２ＮＨＲ９がより好ましい。
　ｍは、１～４の整数が好ましく、１または２がより好ましい。
　Ｒ６およびＲ７における炭素数１～６のアルキル基としては、上述した炭素数１～２０の１価の飽和炭化水素基で挙げたアルキル基のうち、炭素数１～６のアルキル基が挙げられる。
　Ｒ１１における炭素数７～１０のアラルキル基としては、ベンジル基、フェニルエチル基、フェニルブチル基等が挙げられる。 R 5 is, -OH, -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO 2 represents NR 9 R 10
R 5 is, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -CO 2 NHR 9, -SO 3 -, -SO 3 - Z +, -SO 3 H, -SO 2 R 8 Or —SO 2 NHR 9 is preferred, —SO 3 − , —SO 3 — Z + , —SO 3 H or —SO 2 NHR 9 is more preferred.
m is preferably an integer of 1 to 4, and more preferably 1 or 2.
Examples of the alkyl group having 1 to 6 carbon atoms in R 6 and R 7 include the alkyl groups having 1 to 6 carbon atoms among the alkyl groups mentioned as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. It is done.
Examples of the aralkyl group having 7 to 10 carbon atoms for R 11 include a benzyl group, a phenylethyl group, and a phenylbutyl group.
　Ｚ＋は、Ｎ＋（Ｒ１１）４、Ｎａ＋またはＫ＋であり、好ましくはＮ＋（Ｒ１１）４である。
　Ｎ＋（Ｒ１１）４は、４つのＲ１１のうち、少なくとも２つが炭素数５～２０の１価の飽和炭化水素基であることが好ましい。また、４つのＲ１１の合計炭素数は、２０～８０が好ましく、２０～６０がより好ましい。化合物（１ａ）中にＮ＋（Ｒ１１）４が存在する場合、Ｒ１１がこれらの基であることにより、化合物（１ａ）を含む本発明の着色硬化性組成物から、異物が少ないカラーフィルタを形成できる。 Z + is N + (R 11 ) 4 , Na + or K + , preferably N + (R 11 ) 4 .
N + (R 11 ) 4 is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms, at least two of the four R 11 . Further, the total number of carbon atoms of the four R 11 is preferably 20 to 80, and more preferably 20 to 60. When N + (R 11 ) 4 is present in the compound (1a), the color filter containing less foreign matter from the colored curable composition of the present invention containing the compound (1a) can be obtained when R 11 is these groups. Can be formed.
　化合物（１ａ）としては、式（３ａ）で表される化合物（以下「化合物（３ａ）」という場合がある。）も好ましい。化合物（３ａ）は、その互変異性体であってもよい。 As the compound (1a), a compound represented by the formula (3a) (hereinafter sometimes referred to as “compound (3a)”) is also preferable. Compound (3a) may be a tautomer thereof.
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
　式（３ａ）中、Ｒ３１およびＲ３２は、それぞれ独立に、炭素数１～１０の１価の飽和炭化水素基を表す。炭素数１～１０の１価の飽和炭化水素基に含まれる水素原子は、炭素数６～１０の芳香族炭化水素基また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に含まれる水素原子は、炭素数１～３のアルコキシ基で置換されていてもよく、炭素数１～１０の１価の飽和炭化水素基に含まれる－ＣＨ２－は、－Ｏ－、－ＣＯ－または－ＮＲ１１－で置換されていてもよい。
　Ｒ３３およびＲ３４は、それぞれ独立に、炭素数１～４のアルキル基、炭素数１～４のアルキルスルファニル基または炭素数１～４のアルキルスルホニル基を表す。
　Ｒ３１およびＲ３３は、互いに結合して窒素原子を含む環を形成してもよく、Ｒ３２およびＲ３４は、互いに結合して窒素原子を含む環を形成してもよい。
　ｐおよびｑは、それぞれ独立に、０～５の整数を表す。ｐが２以上のとき、複数のＲ３３は同一でも異なってもよい。ｑが２以上のとき、複数のＲ３４は同一でも異なってもよい。Ｒ１１は、式（１ａ）中のＲ１１と同義である。 In the formula (3a), R 31 and R 32 each independently represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. A hydrogen atom contained in an aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted with an alkoxy group having 1 to 3 carbon atoms, and is contained in a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. —CH 2 — may be substituted with —O—, —CO— or —NR 11 —.
R 33 and R 34 each independently represents an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
R 31 and R 33 may be bonded to each other to form a ring containing a nitrogen atom, and R 32 and R 34 may be bonded to each other to form a ring containing a nitrogen atom.
p and q each independently represents an integer of 0 to 5. When p is 2 or more, the plurality of R 33 may be the same or different. When q is 2 or more, the plurality of R 34 may be the same or different. R 11 has the same meaning as R 11 in the formula (1a).
　Ｒ３１およびＲ３２における炭素数１～１０の１価の飽和炭化水素基としては、式（１ａ）中のＲ８で説明した炭素数１～１０の１価の飽和炭化水素基のうち炭素数１～１０の１価の飽和炭化水素基が挙げられる。中でもメチル基、エチル基、プロピル基、ブチル基、ヘキシル基、２－エチルヘキシル基が好ましい。置換基として有していてもよい炭素数６～１０の芳香族炭化水素基としては、式（１ａ）中のＲ１で説明した炭素数６～１０の１価の芳香族炭化水素基が挙げられる。
　炭素数６～１０の芳香族炭化水素基に含まれる水素原子が置換されていてもよい炭素数１～３のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基等が挙げられる。
　Ｒ３１およびＲ３２は、それぞれ独立に、炭素数１～３の１価の飽和炭化水素基であることが好ましい。 The monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R 31 and R 32 is the number of carbon atoms among the monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms described for R 8 in formula (1a). Examples thereof include 1 to 10 monovalent saturated hydrocarbon groups. Of these, methyl, ethyl, propyl, butyl, hexyl and 2-ethylhexyl are preferred. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be present as a substituent include the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms described for R 1 in formula (1a). It is done.
Examples of the alkoxy group having 1 to 3 carbon atoms in which the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted include a methoxy group, an ethoxy group, and a propoxy group.
R 31 and R 32 are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.
　Ｒ３３およびＲ３４における炭素数１～４のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基等が挙げられる。中でもメチル基、エチル基、プロピル基が好ましい。
　Ｒ３３およびＲ３４における炭素数１～４のアルキルスルファニル基としては、メチルスルファニル基、エチルスルファニル基、プロピルスルファニル基、ブチルスルファニル基およびイソプロピルスルファニル基等が挙げられる。
　Ｒ３３およびＲ３４における炭素数１～４のアルキルスルホニル基としては、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およびイソプロピルスルホニル基等が挙げられる。 Examples of the alkyl group having 1 to 4 carbon atoms in R 33 and R 34 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. Of these, a methyl group, an ethyl group, and a propyl group are preferable.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R 33 and R 34 include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in R 33 and R 34 include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
　ｐおよびｑは、０～２の整数が好ましく、０または１が好ましい。 P and q are preferably integers of 0 to 2, preferably 0 or 1.
　化合物（１ａ）としては、例えば、式（１－１）～式（１－４３）で表される化合物が挙げられる。なお、式中、Ｒは、炭素数１～２０の１価の飽和炭化水素基を表し、炭素数６～１２の分岐状のアルキル基が好ましく、２－エチルヘキシル基がより好ましい。
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
 Examples of the compound (1a) include compounds represented by the formulas (1-1) to (1-43). In the formula, R represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
　上記例示化合物の中でも、Ｃ．Ｉ．アシッドレッド２８９のスルホンアミド化物、Ｃ．Ｉ．アシッドレッド２８９の４級アンモニウム塩、Ｃ．Ｉ．アシッドバイオレット１０２のスルホンアミド化物またはＣ．Ｉ．アシッドバイオレット１０２の第四級アンモニウム塩が好ましい。このような化合物としては、例えば、式（１－１）～式（１－８）、式（１－１１）または式（１－１２）で表される化合物等が挙げられる。
　また、有機溶剤への溶解性に優れる点で、式（１－２４）～式（１－３３）のいずれかで表される化合物も好ましい。 Among the above exemplified compounds, C.I. I. Acid red 289 sulfonamidation product, C.I. I. Quaternary ammonium salt of Acid Red 289, C.I. I. Acid violet 102 sulfonamidate or C.I. I. The quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), or formula (1-12).
In addition, a compound represented by any one of formulas (1-24) to (1-33) is also preferable from the viewpoint of excellent solubility in an organic solvent.
　キサンテン色素は、市販されているキサンテン染料（例えば、中外化成（株）製の「Ｃｈｕｇａｉ　Ａｍｉｎｏｌ　Ｆａｓｔ　Ｐｉｎｋ　Ｒ－Ｈ／Ｃ」、田岡化学工業（株）製の「Ｒｈｏｄａｍｉｎ　６Ｇ」）を用いることができる。また、市販されているキサンテン染料を出発原料として、特開２０１０－３２９９９号公報を参考に合成することもでき、この内容は本明細書に組み込まれる。 As the xanthene pigment, a commercially available xanthene dye (for example, “Chugai Aminol Fast Pin RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) can be used. . Alternatively, a commercially available xanthene dye can be used as a starting material and synthesized with reference to Japanese Patent Application Laid-Open No. 2010-32999, the contents of which are incorporated herein.
＜＜ジピロメテン系金属錯体化合物＞＞
　ジピロメテン系金属錯体化合物として、一般式（Ｉ）で表される化合物が金属原子または金属化合物に配位した化合物を挙げることができる。 << Dipyrromethene-based metal complex compound >>
Examples of the dipyrromethene-based metal complex compound include compounds in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound.
一般式（Ｉ）
Figure JPOXMLDOC01-appb-C000057
 Formula (I)
Figure JPOXMLDOC01-appb-C000057
　一般式（Ｉ）中、Ｒ１～Ｒ６は、各々独立に、水素原子または上述した置換基群Ａに挙げられる１価の置換基を表し、Ｒ７は水素原子、ハロゲン原子、アルキル基、アリール基またはヘテロ環基を表す。 In general formula (I), R 1 to R 6 each independently represents a hydrogen atom or a monovalent substituent listed in the above-mentioned substituent group A, and R 7 represents a hydrogen atom, a halogen atom, an alkyl group, Represents an aryl group or a heterocyclic group.
　上述した１価の基がさらに置換可能な基である場合には、上述した各基のいずれかによってさらに置換されていてもよい。なお、２個以上の置換基を有している場合には、それらの置換基は同一であっても異なっていてもよい。 When the above-described monovalent group is a further substitutable group, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different.
　一般式（Ｉ）中、Ｒ１とＲ２、Ｒ２とＲ３、Ｒ４とＲ５、およびＲ５とＲ６は、各々独立に、互いに結合して５員、６員または７員の環を形成していてもよい。形成される環としては、飽和環、または不飽和環が挙げられる。この５員、６員もしくは７員の飽和環、または、不飽和環としては、例えば、ピロール環、フラン環、チオフェン環、ピラゾール環、イミダゾール環、トリアゾール環、オキサゾール環、チアゾール環、ピロリジン環、ピペリジン環、シクロペンテン環、シクロヘキセン環、ベンゼン環、ピリジン環、ピラジン環、ピリダジン環が挙げられ、好ましくは、ベンゼン環、ピリジン環が挙げられる。
　なお、形成される５員、６員および７員の環が、さらに置換可能な基である場合には、上記置換基群Ａのいずれかで置換されていてもよく、２個以上の置換基で置換されている場合には、それらの置換基は同一であっても異なっていてもよい。
　また、一般式（Ｉ）中のＲ７の好ましい範囲は、前述のＲ１～Ｒ６がハロゲン原子、アルキル基、アリール基またはヘテロ環基である場合と同義であり、好ましい範囲も同様である。 In general formula (I), R 1 and R 2 , R 2 and R 3 , R 4 and R 5 , and R 5 and R 6 are each independently bonded to each other to form 5-membered, 6-membered or 7-membered A ring may be formed. Examples of the ring formed include a saturated ring and an unsaturated ring. Examples of the 5-membered, 6-membered or 7-membered saturated ring or unsaturated ring include a pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, Examples include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
In addition, when the 5-membered, 6-membered and 7-membered rings formed are further substitutable groups, they may be substituted with any of the above-mentioned substituent group A, and two or more substituents In the case where the substituent is substituted, the substituents may be the same or different.
In addition, the preferred range of R 7 in the general formula (I) is synonymous with the case where R 1 to R 6 are a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and the preferred range is also the same. .
　一般式（Ｉ）中、Ｒ１およびＲ６は、アルキルアミノ基、アリールアミノ基、カルボンアミド基、ウレイド基、イミド基、アルコキシカルボニルアミノ基、スルホンアミド基が好ましく、カルボンアミド基、ウレイド基、アルコキシカルボニルアミノ基、スルホンアミド基がより好ましく、カルボンアミド基、ウレイド基、アルコキシカルボニルアミノ基、スルホンアミド基がさらに好ましく、カルボンアミド基、ウレイド基が特に好ましい。 In general formula (I), R 1 and R 6 are preferably an alkylamino group, an arylamino group, a carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, or a sulfonamido group, and a carbonamido group, a ureido group, An alkoxycarbonylamino group and a sulfonamide group are more preferable, a carbonamide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are more preferable, and a carbonamide group and a ureido group are particularly preferable.
　一般式（Ｉ）中、Ｒ２およびＲ５は、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、ニトリル基、イミド基、カルバモイルスルホニル基が好ましく、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、ニトリル基、イミド基、カルバモイルスルホニル基がより好ましく、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、ニトリル基、イミド基、カルバモイルスルホニル基がさらに好ましく、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基が特に好ましい。
　一般式（Ｉ）中、Ｒ３およびＲ４は、アルキル基、アリール基またはヘテロ環基が好ましく、アルキル基またはアリール基が好ましい。 In general formula (I), R 2 and R 5 are preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, or a carbamoylsulfonyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, An alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
In general formula (I), R 3 and R 4 are preferably an alkyl group, an aryl group or a heterocyclic group, and more preferably an alkyl group or an aryl group.
　一般式（Ｉ）中、Ｒ３およびＲ４がアルキル基を表す場合、アルキル基としては、炭素数１～１２の直鎖状、分岐状または環状のアルキル基が好ましく、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、シクロプロピル基、ｎ－ブチル基、i－ブチル基、ｔｅｒｔ－ブチル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、および、ベンジル基が挙げられる。また、炭素数１～１２の分岐状または環状のアルキル基より好ましく、例えば、イソプロピル基、シクロプロピル基、i－ブチル基、ｔｅｒｔ－ブチル基、シクロブチル基、シクロペンチル基、シクロヘキシル基が挙げられる。さらに、炭素数１～１２の２級または３級のアルキル基が好ましく、例えば、イソプロピル基、シクロプロピル基、ｉ－ブチル基、ｔｅｒｔ－ブチル基、シクロブチル基、シクロヘキシル基等が挙げられる。 In the general formula (I), when R 3 and R 4 represent an alkyl group, the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, such as methyl group, ethyl Group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, tert-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and benzyl group. In addition, a branched or cyclic alkyl group having 1 to 12 carbon atoms is preferred, and examples thereof include isopropyl group, cyclopropyl group, i-butyl group, tert-butyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Further, a secondary or tertiary alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof include an isopropyl group, a cyclopropyl group, an i-butyl group, a tert-butyl group, a cyclobutyl group, and a cyclohexyl group.
　一般式（Ｉ）中、Ｒ３およびＲ４がアリール基を表す場合、アリール基としては、フェニル基およびナフチル基が好ましく、フェニル基がより好ましい。
　Ｒ３およびＲ４がヘテロ環基を表す場合、ヘテロ環基としては、２－チエニル基、４－ピリジル基、３－ピリジル基、２－ピリジル基、２－フリル基、２－ピリミジニル基、２－ベンゾチアゾリル基、１－イミダゾリル基、１－ピラゾリル基またはベンゾトリアゾール－１－イル基が好ましく、２－チエニル基、４－ピリジル基、２－フリル基、２－ピリミジニル基または１－ピリジル基がより好ましい。 In the general formula (I), when R 3 and R 4 represent an aryl group, the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
When R 3 and R 4 represent a heterocyclic group, the heterocyclic group includes a 2-thienyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 2 -A benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group or benzotriazol-1-yl group is preferred, and a 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group or 1-pyridyl group is more preferred. preferable.
　次に、ジピロメテン系金属錯体化合物を形成する金属原子または金属化合物について説明する。
　金属または金属化合物としては、錯体を形成可能な金属原子または金属化合物であればいずれであってもよく、２価の金属原子、２価の金属酸化物、２価の金属水酸化物、または２価の金属塩化物が含まれる。例えば、Ｚｎ、Ｍｇ、Ｓｉ、Ｓｎ、Ｒｈ、Ｐｔ、Ｐｄ、Ｍｏ、Ｍｎ、Ｐｂ、Ｃｕ、Ｎｉ、Ｃｏ、Ｆｅ、Ｂ等の他に、ＡｌＣｌ、ＩｎＣｌ、ＦｅＣｌ、ＴｉＣｌ２、ＳｎＣｌ２、ＳｉＣｌ２、ＧｅＣｌ２などの金属塩化物、ＴｉＯ、ＶＯ等の金属酸化物、Ｓｉ（ＯＨ）２等の金属水酸化物も含まれる。
　これらの中でも、錯体の安定性、分光特性、耐熱、耐光性、および製造適性等の観点から、Ｆｅ、Ｚｎ、Ｍｇ、Ｓｉ、Ｐｔ、Ｐｄ、Ｍｏ、Ｍｎ、Ｃｕ、Ｎｉ、Ｃｏ、ＴｉＯ、Ｂ、またはＶＯが好ましく、Ｆｅ、Ｚｎ、Ｍｇ、Ｓｉ、Ｐｔ、Ｐｄ、Ｃｕ、Ｎｉ、Ｃｏ、Ｂ、またはＶＯがさらに好ましく、Ｆｅ、Ｚｎ、Ｃｕ、Ｃｏ、Ｂ、またはＶＯ（Ｖ＝Ｏ）が特に好ましい。これらの中でも、特にＺｎが好ましい。 Next, the metal atom or metal compound that forms the dipyrromethene-based metal complex compound will be described.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or 2 Valent metal chlorides are included. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl, InCl, FeCl, TiCl 2 , SnCl 2 , SiCl 2 Further, metal chlorides such as GeCl 2 , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) 2 are also included.
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) is more preferable. Particularly preferred. Among these, Zn is particularly preferable.
　一般式（Ｉ）で表される化合物が金属原子または金属化合物に配位したジピロメテン系金属錯体化合物において、好ましい態様を以下に示す。すなわち、一般式（Ｉ）において、Ｒ１およびＲ６が、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、ヘテロ環基、シリル基、ヒドロキシル基、シアノ基、アルコキシ基、アリールオキシ基、ヘテロ環オキシ基、アシル基、アルコキシカルボニル基、カルバモイル基、アミノ基、アニリノ基、ヘテロ環アミノ基、カルボンアミド基、ウレイド基、イミド基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルホンアミド基、アゾ基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、アルキルスルホニル基、アリールスルホニル基、またはホスフィノイルアミノ基で表され、Ｒ２およびＲ５が、各々独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アリール基、ヘテロ環基、ヒドロキシル基、シアノ基、ニトロ基、アルコキシ基、アリールオキシ基、ヘテロ環オキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、イミド基、アルコキシカルボニルアミノ基、スルホンアミド基、アゾ基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、アルキルスルホニル基、アリールスルホニル基、またはスルファモイル基で表され、Ｒ３およびＲ４が、各々独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アリール基、ヘテロ環基、シリル基、ヒドロキシル基、シアノ基、アルコキシ基、アリールオキシ基、ヘテロ環オキシ基、アシル基、アルコキシカルボニル基、カルバモイル基、アニリノ基、カルボンアミド基、ウレイド基、イミド基、アルコキシカルボニルアミノ基、スルホンアミド基、アゾ基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、アルキルスルホニル基、アリールスルホニル基、スルファモイル基、またはホスフィノイルアミノ基で表され、Ｒ７が、水素原子、ハロゲン原子、アルキル基、アリール基、またはヘテロ環基で表され、金属原子または金属化合物が、Ｚｎ、Ｍｇ、Ｓｉ、Ｐｔ、Ｐｄ、Ｍｏ、Ｍｎ、Ｃｕ、Ｎｉ、Ｃｏ、ＴｉＯ、Ｂ、またはＶＯで表される態様が挙げられる。 In the dipyrromethene metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound, preferred embodiments are shown below. That is, in the general formula (I), R 1 and R 6 are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy Group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone An amide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, wherein R 2 and R 5 are each independently a hydrogen atom, a halogen atom, Atom, alkyl group, alkenyl group, aryl group, heterocyclic group, Droxyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group , An alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R 3 and R 4 are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, Aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamido group, ureido group, imide group , Alkoxycarbonyl Amino group, a sulfonamido group, represented by azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group or a phosphinoylamino group,, R 7 is a hydrogen atom, a halogen Represented by an atom, alkyl group, aryl group, or heterocyclic group, wherein the metal atom or metal compound is Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO; The aspect represented is mentioned.
　ジピロメテン系金属錯体化合物のより好ましい態様を以下に示す。すなわち、一般式（Ｉ）において、Ｒ１およびＲ６が、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、ヘテロ環基、シアノ基、アシル基、アルコキシカルボニル基、カルバモイル基、アミノ基、ヘテロ環アミノ基、カルボンアミド基、ウレイド基、イミド基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルホンアミド基、アゾ基、アルキルスルホニル基、アリールスルホニル基、またはホスフィノイルアミノ基で表され、Ｒ２およびＲ５が、各々独立に、アルキル基、アルケニル基、アリール基、ヘテロ環基、シアノ基、ニトロ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、イミド基、アルキルスルホニル基、アリールスルホニル基、またはスルファモイル基で表され、Ｒ３およびＲ４が、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、ヘテロ環基、シアノ基、アシル基、アルコキシカルボニル基、カルバモイル基、カルボンアミド基、ウレイド基、イミド基、アルコキシカルボニルアミノ基、スルホンアミド基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、アルキルスルホニル基、アリールスルホニル基、またはスルファモイル基で表され、Ｒ７が、水素原子、ハロゲン原子、アルキル基、アリール基、またはヘテロ環基で表され、金属原子または金属化合物が、Ｚｎ、Ｍｇ、Ｓｉ、Ｐｔ、Ｐｄ、Ｃｕ、Ｎｉ、Ｃｏ、ＢまたはＶＯで表される態様が挙げられる。 The more preferable aspect of a dipyrromethene type metal complex compound is shown below. That is, in the general formula (I), R 1 and R 6 are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group. Group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group R 2 and R 5 are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group , Alkylsulfonyl group, arylsulfonyl group, or sulfo R 3 and R 4 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a carbonamido group, It is represented by a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R 7 is a hydrogen atom or a halogen atom. , An alkyl group, an aryl group, or a heterocyclic group, and the metal atom or metal compound is represented by Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO.
　一般式（Ｉ）で表される化合物が金属原子または金属化合物に配位したジピロメテン系金属錯体化合物の好ましい態様は、特開２０１２－２３７９８５号公報の段落０１５３～０１７６に記載の一般式（Ｉ－１）、（Ｉ－２）または（Ｉ－３）で表される錯体化合物を参酌でき、この内容は本明細書に組み込まれる。 A preferred embodiment of the dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound is described in paragraphs 0153 to 0176 of JP2012-237985A. The complex compounds represented by 1), (I-2) or (I-3) can be taken into account, the contents of which are incorporated herein.
　一般式（Ｉ）で表される化合物が金属原子または金属化合物に配位したジピロメテン系金属錯体化合物の好ましい態様である、一般式（Ｉ－１）、（Ｉ－２）または（Ｉ－３）で表される錯体化合物のうち、一般式（Ｉ－３）で表される錯体化合物が、特に好ましい。 The general formula (I-1), (I-2) or (I-3) is a preferred embodiment of the dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound. Of the complex compounds represented by formula (I-3), the complex compound represented by formula (I-3) is particularly preferred.
　上記一般式（Ｉ）で表される化合物が金属原子または金属化合物に配位したジピロメテン系金属錯体化合物の具体例としては、特開２０１２－２３７９８５号公報の段落０１７９～０１８６の記載を参酌でき、この内容は本明細書に組み込まれる。
　また、ジピロメテン系金属錯体化合物の具体例として下記化合物も挙げられる。
Figure JPOXMLDOC01-appb-C000058
 As specific examples of the dipyrromethene-based metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound, the description in paragraphs 0179 to 0186 of JP2012-237985A can be referred to. This content is incorporated herein.
Further, specific examples of the dipyrromethene-based metal complex compound include the following compounds.
Figure JPOXMLDOC01-appb-C000058
　上記顔料または染料化合物を分散物として配合する場合、特開平９－１９７１１８号公報、特開２０００－２３９５４４号公報の記載に従って調製することができる。
　上記顔料または染料化合物は、本発明の効果を損なわない範囲で使用でき、顔料または染料化合物の含有量は、本発明の着色硬化性組成物の全固形分に対して、０．５～７０質量％であることが好ましい。また、吸収強度比（４５０ｎｍの吸収／６５０ｎｍの吸収）が、０．９５～１．０５の範囲となるように、着色硬化性組成物に添加されることが好ましい。
　また、本発明の着色硬化性組成物に顔料または染料化合物が含まれる場合、着色硬化性組成物中のトリアリールメタン染料と顔料または染料化合物の含有量の質量比は、１．０：０．１０～１．０：２．０が好ましく、１．０：０．２～１．０：０．８がより好ましい。着色硬化性組成物に顔料および染料化合物が含まれる場合、顔料および染料化合物の合計質量が上記範囲内であることが好ましい。 When the pigment or dye compound is blended as a dispersion, it can be prepared according to the descriptions in JP-A-9-197118 and JP-A-2000-239544.
The pigment or dye compound can be used as long as the effects of the present invention are not impaired, and the content of the pigment or dye compound is 0.5 to 70 mass based on the total solid content of the colored curable composition of the present invention. % Is preferred. Further, it is preferably added to the colored curable composition so that the absorption intensity ratio (absorption at 450 nm / absorption at 650 nm) is in the range of 0.95 to 1.05.
Moreover, when a pigment or dye compound is contained in the colored curable composition of the present invention, the mass ratio of the content of the triarylmethane dye and the pigment or dye compound in the colored curable composition is 1.0: 0. 10 to 1.0: 2.0 is preferable, and 1.0: 0.2 to 1.0: 0.8 is more preferable. When a pigment and a dye compound are contained in the colored curable composition, the total mass of the pigment and the dye compound is preferably within the above range.
＜分散剤＞
　本発明の着色硬化性組成物は、分散剤を含むことが好ましい。本発明の着色組成物に用いる分散剤は、顔料吸着基として酸性基、塩基性基およびまたはそのいずれか一つを有する高分子化合物である。本発明の着色組成物に用いる分散剤は、吸着基がその対イオンと塩構造を形成した、いわゆるイオン性分散剤（ポリ電解質とも表現される）をポリマー構成中に５ｍｏｌ％以下含むことが好ましく、ポリマー構成中にイオン性分散剤を含まないことがより好ましい。イオン性分散剤の例としては、アミン塩、４級アンモニウム塩、カルボン酸塩、リン酸塩に代表されるもので、これらは市販の分散剤として入手可能である。
　分散剤は高分子化合物の主鎖構造と吸着基を有し、本発明で用いる分散剤の吸着基は、酸性吸着基および塩基性吸着基の少なくとも一方を含むことが好ましい。ここで、酸性吸着基および塩基性吸着基の両方の吸着基を有する分散剤とは、酸性および塩基性の両方の吸着基を有する分散剤のことをいう。 <Dispersant>
The colored curable composition of the present invention preferably contains a dispersant. The dispersant used in the coloring composition of the present invention is a polymer compound having an acidic group, a basic group and / or any one thereof as a pigment adsorbing group. The dispersant used in the coloring composition of the present invention preferably contains 5 mol% or less of a so-called ionic dispersant (also expressed as a polyelectrolyte) in which the adsorbing group forms a salt structure with its counter ion in the polymer composition. More preferably, the polymer composition does not contain an ionic dispersant. Examples of ionic dispersants are represented by amine salts, quaternary ammonium salts, carboxylates and phosphates, and these are available as commercially available dispersants.
The dispersant has a main chain structure of the polymer compound and an adsorption group, and the adsorption group of the dispersant used in the present invention preferably contains at least one of an acidic adsorption group and a basic adsorption group. Here, the dispersant having both acidic and basic adsorbing groups refers to a dispersant having both acidic and basic adsorbing groups.
　本発明では、着色硬化性組成物が分散剤を含む場合に、分散剤の吸着基を酸性吸着基、塩基性吸着基またはその両方の吸着基とすることにより、トリアリールメタン染料をより安定化することが可能となり、着色硬化性組成物の耐熱性を高めることができる。さらに、着色硬化性組成物から形成されるカラーフィルタや素子においては、電圧保持率が高まり、着色硬化性組成物については相溶性が高まる。すなわち、本発明は、トリアリールメタン染料自体の構造を安定化させることに加え、トリアリールメタン染料と酸性吸着基および塩基性吸着基の少なくとも一方を含む吸着基を有する分散剤を組み合わせることによって、トリアリールメタン染料と顔料および分散剤を混合した場合であっても、トリアリールメタン染料の構造の安定性を損なわない点に特徴がある。 In the present invention, when the colored curable composition contains a dispersant, the triarylmethane dye is further stabilized by making the adsorption group of the dispersant an acidic adsorption group, a basic adsorption group, or both. And the heat resistance of the colored curable composition can be increased. Furthermore, in a color filter or device formed from a colored curable composition, the voltage holding ratio is increased, and the compatibility of the colored curable composition is increased. That is, the present invention, in addition to stabilizing the structure of the triarylmethane dye itself, by combining a triarylmethane dye and a dispersant having an adsorption group containing at least one of an acidic adsorption group and a basic adsorption group, Even when a triarylmethane dye, a pigment, and a dispersant are mixed, the structural stability of the triarylmethane dye is not impaired.
　分散剤の吸着基が酸性吸着基の場合、分散剤の酸価は、１０～１００ｍｇ／ＫＯＨであることが好ましく、１０～８０ｍｇ／ＫＯＨであることがより好ましく、１０～６０ｍｇ／ＫＯＨであることがさらに好ましく、１０～５５ｍｇ／ＫＯＨであることが特に好ましい。分散剤の吸着基が塩基性吸着基の場合、アミン価は、３～１００ｍｇ／ＫＯＨであることが好ましく、１０～１００ｍｇ／ＫＯＨであることがより好ましく、１０～８０ｍｇ／ＫＯＨであることがさらに好ましく、１０～５０ｍｇ／ＫＯＨであることがよりさらに好ましく、１０～４０ｍｇ／ＫＯＨであることが特に好ましい。分散剤の吸着基が酸性の吸着基および塩基性の吸着基である場合においても、分散剤の酸価とアミン価は上記範囲であることが好ましい。酸価とアミン価の比は、酸価：アミン価＝１：１～１：１０が好ましく、１：１～１：５がより好ましく、１：１～１：３が特に好ましい。酸価およびアミン価が上記範囲であれば、トリアリールメタン染料の安定性がより向上する。 When the adsorbing group of the dispersing agent is an acidic adsorbing group, the acid value of the dispersing agent is preferably 10 to 100 mg / KOH, more preferably 10 to 80 mg / KOH, and 10 to 60 mg / KOH. Is more preferably 10 to 55 mg / KOH. When the adsorbing group of the dispersant is a basic adsorbing group, the amine value is preferably 3 to 100 mg / KOH, more preferably 10 to 100 mg / KOH, and further preferably 10 to 80 mg / KOH. It is preferably 10 to 50 mg / KOH, more preferably 10 to 40 mg / KOH. Even when the adsorbing group of the dispersant is an acidic adsorbing group or a basic adsorbing group, the acid value and amine value of the dispersing agent are preferably within the above ranges. The ratio of acid value to amine value is preferably acid value: amine value = 1: 1 to 1:10, more preferably 1: 1 to 1: 5, and particularly preferably 1: 1 to 1: 3. When the acid value and the amine value are in the above ranges, the stability of the triarylmethane dye is further improved.
　高分子化合物の主鎖構造には、付加重合系ポリマーとして、ポリスチレン、ポリメタクリル酸エステル、ポリアクリル酸エステル、ポリアルキル酸ビニル、ポリアクリルアミド、ポリアクリロニトリル、ポリ塩化ビニル、ポリビニルアルコール等のビニル系ポリマー、ポリエチレン、ポリプロピレン、ポリイソブチレン等のポリオレフィン系ポリマー、ポリブタジエン、ポリイソプレン等のジエン系ポリマー、ポリエチレンイミン等が、また、縮合系ポリマーとして、ポリエステル、ポリアミド、ポリエーテル、ポリウレタン樹脂、エポキシ樹脂、メラミン樹脂等がそれぞれ用いられる。 The main chain structure of the polymer compound includes, as addition polymerization polymers, vinyl polymers such as polystyrene, polymethacrylic acid ester, polyacrylic acid ester, polyvinyl polyalkylate, polyacrylamide, polyacrylonitrile, polyvinyl chloride, and polyvinyl alcohol. Polyolefin polymers such as polyethylene, polypropylene and polyisobutylene, diene polymers such as polybutadiene and polyisoprene, polyethyleneimine and the like, and condensation polymers such as polyester, polyamide, polyether, polyurethane resin, epoxy resin, melamine resin Etc. are used respectively.
　上述の各種ポリマーは、目的とする性能を発現させるために、種々のモノマーと共重合させることができる。ビニル系ポリマーを例に取って、共重合させるモノマーを例示すると、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート等の（メタ）アクリル酸エステル類、スチレンおよびその誘導体、（無水）マレイン酸、イタコン酸、シトラコン酸等のジカルボン酸、α－メチルスチレン、酢酸ビニル、Ｎ－ビニルピロリドン、（メタ）アクリロニトリル、（メタ）アクリルアミド等の各種単量体、ポリメチルメタクリレートマクロモノマー、ポリスチレンマクロモノマー、ポリ２－ヒドロキシエチルメタクリレートマクロモノマー等のマクロモノマーが挙げられる。なお、これらの各種共重合モノマーを、複数種併用してもよい。 The above-mentioned various polymers can be copolymerized with various monomers in order to develop the desired performance. Taking a vinyl polymer as an example, examples of monomers to be copolymerized include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) ) Acrylate, tert-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, (Meth) acrylic esters such as tetrahydrofurfuryl (meth) acrylate, styrene and its derivatives, (carboxylic anhydride), dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, α-methyls Various monomers such as len, vinyl acetate, N-vinyl pyrrolidone, (meth) acrylonitrile, (meth) acrylamide, and other macromonomers such as polymethyl methacrylate macromonomer, polystyrene macromonomer, and poly-2-hydroxyethyl methacrylate macromonomer. It is done. In addition, you may use multiple types of these various copolymerization monomers together.
　なお、重合によって形成される高分子化合物の構造は、ランダム重合体、ブロック重合体、グラフト重合体の何れでも構わない。 The structure of the polymer compound formed by polymerization may be any of a random polymer, a block polymer, and a graft polymer.
　縮合系ポリマーの例としてウレタン樹脂の構造を例示すると、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネートおよびこれらのイソシアネート基の環化３量化オリゴマー、エチレングリコール、プロピレングリコール、テトラメチレングリコール、ヘキサンジオール、デカンジオール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ポリカプロラクトン等およびこれらの共重合体の両末端ヒドロキシ化合物、ならびに、メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、デカノール、メトキシポリエチレングリコール、エトキシポリエチレングリコール、メトキシポリプロピレングリコール、エトキシポリプロピレングリコール等の片末端ヒドロキシ化合物の重合体が挙げられる。 Examples of condensation polymers include urethane resin structures: tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and cyclized trimerized oligomers of these isocyanate groups, ethylene glycol, propylene glycol, tetramethylene glycol, hexanediol, decane Diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone, etc. and copolymers of both ends of these copolymers, and methanol, ethanol, propanol, butanol, hexanol, decanol, methoxy polyethylene glycol, ethoxy polyethylene glycol, Such as methoxy polypropylene glycol and ethoxy polypropylene glycol Polymers of terminal hydroxy compound.
　酸性吸着基、塩基性吸着基またはその両方の吸着基は、上述した高分子化合物に、置換基として結合させることが好ましい。酸性吸着基としては、カルボキシル基、リン酸基、スルホン酸基等が例示される。塩基性吸着基としては、例えばアミノ基、アルキルアミノ基、イミダゾール基、オキサゾール基、ピリジン基、モルホリノ基が例示される。アルキルアミノ基のアルキル部分に相当するアルキル基としては、例えばメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基等の、炭素数１～１０、好ましくは炭素数１～４の直鎖または分岐のアルキル基が用いることができる。また、例えばシクロプロピル基、シクロブチル基等の、炭素数３～１０、好ましくは炭素数３～６の環状のアルキル基も用いることができる。
　上述した酸性吸着基、塩基性吸着基またはその両方の吸着基は、非イオン性の吸着基であり、本発明では、非イオン性吸着基を有する分散剤を用いることが好ましい。 The acidic adsorbing group, the basic adsorbing group or both adsorbing groups are preferably bonded to the above-described polymer compound as a substituent. Examples of the acidic adsorption group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Examples of basic adsorption groups include amino groups, alkylamino groups, imidazole groups, oxazole groups, pyridine groups, and morpholino groups. Examples of the alkyl group corresponding to the alkyl portion of the alkylamino group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and the like, Preferably, a linear or branched alkyl group having 1 to 4 carbon atoms can be used. In addition, a cyclic alkyl group having 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms, such as a cyclopropyl group and a cyclobutyl group, can also be used.
The above-mentioned acidic adsorbing group, basic adsorbing group or both adsorbing groups are nonionic adsorbing groups. In the present invention, it is preferable to use a dispersant having a nonionic adsorbing group.
　酸性吸着基、塩基性吸着基またはその両方の吸着基を有する分散剤は、合成してもよいが、市販されている分散剤を用いてもよい。市販の分散剤としては、例えば、アミン系分散剤として、ビックケミー社製のＢＹＫ－１８２、１６１、１６２、１６３、２１５５、２１６４、９０７７を、カルボン酸系分散剤としてビックケミー社製のＢＹＫ－１９０、１９１を、リン酸系分散剤としてビックケミー社製のＢＹＫ－１１０、１１１を例示することができる。また、市販の分散剤としてアビシア社製のソルスパース１３２４０、２００００、２４０００、２６０００、２８０００等を例示することができる。 A dispersant having an acidic adsorbing group, a basic adsorbing group, or both adsorbing groups may be synthesized, or a commercially available dispersant may be used. Examples of commercially available dispersants include BYK-182, 161, 162, 163, 2155, 2164, and 9077 manufactured by BYK Chemie as amine dispersants, and BYK-190 manufactured by BYK Chemie as carboxylic acid dispersants, Examples of 191 include BYK-110 and 111 manufactured by Big Chemie as phosphoric acid dispersants. Examples of commercially available dispersants include Solsperse 13240, 20000, 24000, 26000, 28000 manufactured by Avicia.
＜＜分散剤の含有量＞＞
　上記分散剤は、本発明の効果を損なわない範囲で使用でき、分散剤の含有量は、本発明の着色硬化性組成物の全固形分に対して、０．５～３０質量％であることが好ましく、１．０～２０質量％であることがより好ましい。また、着色硬化性組成物に含まれる顔料と分散剤の質量比は、１：５～５：１であることが好ましく、１：３～１：１であることがより好ましい。さらに、着色硬化性組成物に含まれるトリアリールメタン染料と分散剤の質量比は、１０：１～１：１であることが好ましく、５：１～１：１であることがより好ましい。 << Content of Dispersant >>
The dispersant can be used within a range not impairing the effects of the present invention, and the content of the dispersant is 0.5 to 30% by mass with respect to the total solid content of the colored curable composition of the present invention. Is more preferable, and 1.0 to 20% by mass is more preferable. Further, the mass ratio of the pigment and the dispersant contained in the colored curable composition is preferably 1: 5 to 5: 1, and more preferably 1: 3 to 1: 1. Furthermore, the mass ratio of the triarylmethane dye and the dispersant contained in the colored curable composition is preferably 10: 1 to 1: 1, and more preferably 5: 1 to 1: 1.
＜重合性化合物＞
　本発明の着色硬化性組成物は、重合性化合物を含有する。重合性化合物としては、例えば、少なくとも１個のエチレン性不飽和二重結合を有する付加重合性化合物を挙げることができる。 <Polymerizable compound>
The colored curable composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond.
　具体的には、末端エチレン性不飽和結合を少なくとも１個、好ましくは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、この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量体およびオリゴマー、またはそれらの混合物並びにそれらの（共）重合体などの化学的形態のいずれであってもよい。 Specifically, it is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such compound groups are widely known in this industrial field, and in the present invention, these compounds can be used without any particular limitation. These may be in any chemical form such as, for example, monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and their (co) polymers.
　モノマーおよびその（共）重合体の例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など）やそのエステル類、アミド類、並びにこれらの（共）重合体が挙げられ、好ましくは、不飽和カルボン酸と脂肪族多価アルコール化合物とのエステル、および不飽和カルボン酸と脂肪族多価アミン化合物とのアミド類、並びにこれらの（共）重合体である。また、ヒドロキシル基やアミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能イソシアネート類或いはエポキシ類との付加反応物や、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基やエポキシ基等の親電子性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物、さらに、ハロゲン基やトシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン、ビニルエーテル等に置き換えた化合物群を使用することも可能である。 Examples of monomers and their (co) polymers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and these (co) polymers It is a polymer. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.
　脂肪族多価アルコール化合物と不飽和カルボン酸とのエステルのモノマーの具体例としては、アクリル酸エステルとして、例えば、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、１，３－ブタンジオールジアクリレート、テトラメチレングリコールジアクリレート、プロピレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリメチロールエタントリアクリレート、ヘキサンジオールジアクリレート、１，４－シクロヘキサンジオールジアクリレート、テトラエチレングリコールジアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールジアクリレート、ジペンタエリスリトールヘキサアクリレート、ソルビトールトリアクリレート、ソルビトールテトラアクリレート、ソルビトールペンタアクリレート、ソルビトールヘキサアクリレート、トリ（アクリロイルオキシエチル）イソシアヌレート、ポリエステルアクリレートオリゴマー、イソシアヌール酸ＥＯ（エチレンオキサイド）変性トリアクリレート等が挙げられる。 Specific examples of an ester monomer of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetra Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol Diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate Chryrate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanur Examples include acid EO (ethylene oxide) -modified triacrylate.
　また、メタクリル酸エステルとして、例えば、テトラメチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレート、トリメチロールプロパントリメタクリレート、トリメチロールエタントリメタクリレート、エチレングリコールジメタクリレート、１，３－ブタンジオールジメタクリレート、ヘキサンジオールジメタクリレート、ペンタエリスリトールジメタクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールジメタクリレート、ジペンタエリスリトールヘキサメタクリレート、ソルビトールトリメタクリレート、ソルビトールテトラメタクリレート、ビス〔ｐ－（３－メタクリルオキシ－２－ヒドロキシプロポキシ）フェニル〕ジメチルメタン、ビス－〔ｐ－（メタクリルオキシエトキシ）フェニル〕ジメチルメタン等が挙げられる。 Examples of methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2- Mud propoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and the like.
　さらに、イタコン酸エステルとして、例えば、エチレングリコールジイタコネート、プロピレングリコールジイタコネート、１，３－ブタンジオールジイタコネート、１，４－ブタンジオールジイタコネート、テトラメチレングリコールジイタコネート、ペンタエリスリトールジイタコネート、ソルビトールテトライタコネート等が、また、クロトン酸エステルとして、例えば、エチレングリコールジクロトネート、テトラメチレングリコールジクロトネート、ペンタエリスリトールジクロトネート、ソルビトールテトラジクロトネート等が、イソクロトン酸エステルとして、例えば、エチレングリコールジイソクロトネート、ペンタエリスリトールジイソクロトネート、ソルビトールテトライソクロトネート等が、また、マレイン酸エステルとして、例えば、エチレングリコールジマレート、トリエチレングリコールジマレート、ペンタエリスリトールジマレート、ソルビトールテトラマレート等が挙げられる。 Further, as itaconic acid esters, for example, ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol Diitaconate, sorbitol tetritaconate, etc., and crotonic acid esters such as ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetradicrotonate, etc. For example, ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, etc. As Le, for example, ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetra malate, and the like.
　その他のエステルの例として、例えば、特公昭５１－４７３３４号公報、特開昭５７－１９６２３１号公報記載の脂肪族アルコール系エステル類や、特開昭５９－５２４０号公報、特開昭５９－５２４１号公報、特開平２－２２６１４９号公報記載の芳香族系骨格を有するもの、特開平１－１６５６１３号公報記載のアミノ基を含有するもの等も好適に用いられる。さらに、前述のエステルモノマーは混合物としても使用することができる。 Examples of other esters include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613 are preferably used. Furthermore, the ester monomers described above can also be used as a mixture.
　また、イソシアネートと水酸基の付加反応を用いて製造されるウレタン系付加重合性化合物も好適であり、そのような具体例としては、例えば、特公昭４８－４１７０８号公報中に記載の、１分子に２個以上のイソシアネート基を有するポリイソシアネート化合物に、下記一般式（Ａ）で表される水酸基を含有するビニルモノマーを付加させた１分子中に２個以上の重合性ビニル基を含有するビニルウレタン化合物等が挙げられる。
　　ＣＨ２＝Ｃ（Ｒ）ＣＯＯＣＨ２ＣＨ（Ｒ’）ＯＨ　　・・・（Ａ）
　一般式（Ａ）中、ＲおよびＲ’は、それぞれ独立にＨまたはＣＨ３を表す。 Also suitable are urethane-based addition-polymerizable compounds produced by the addition reaction of isocyanate and hydroxyl group. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. Vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Compounds and the like.
CH 2 = C (R) COOCH 2 CH (R ′) OH (A)
In general formula (A), R and R ′ each independently represent H or CH 3 .
　また、重合性化合物としては、ジペンタエリスリトールトリアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬株式会社製）、ジペンタエリスリトールテトラアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬株式会社製）ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬株式会社製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬株式会社製）、およびこれらの（メタ）アクリロイル基がエチレングリコール、プロピレングリコール残基を介している構造も好ましい。これらのオリゴマータイプも使用できる。 Further, as the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercial product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) Company-made) dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.
　これらの重合性化合物について、その構造や、単独使用か併用か、添加量等の使用方法の詳細は、着色硬化性組成物の最終的な性能設計にあわせて任意に設定できる。例えば、感度の観点では、１分子あたりの不飽和基含量が多い構造が好ましく、多くの場合は２官能以上が好ましい。また、着色硬化膜の強度を高める観点では、３官能以上のものがよく、さらに、異なる官能数・異なる重合性基（例えばアクリル酸エステル、メタクリル酸エステル、スチレン化合物、ビニルエーテル化合物）のものを併用することで、感度と強度の両方を調節する方法も有効である。また、着色硬化性組成物に含有される他の成分（例えば、光重合開始剤、着色剤（顔料）、バインダーポリマー等）との相溶性、分散性に対しても、重合性化合物の選択・使用法は重要な要因であり、例えば、低純度化合物の使用や２種以上の併用により相溶性を向上させ得ることがある。また、基板などの硬質表面との密着性を向上させる観点で特定の構造を選択することもあり得る。 About these polymerizable compounds, the structure, details of usage such as single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the colored curable composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Also, from the viewpoint of increasing the strength of the colored cured film, those having three or more functionalities are preferable, and those having different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound) are used in combination. Thus, a method of adjusting both sensitivity and intensity is also effective. In addition, the selection of the polymerizable compound is also possible with respect to the compatibility and dispersibility with other components (for example, photopolymerization initiator, colorant (pigment), binder polymer, etc.) contained in the colored curable composition. The method of use is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected from the viewpoint of improving adhesion to a hard surface such as a substrate.
　着色硬化性組成物の全固形分中における重合性化合物の含有量は、本発明の効果をより効果的に得る観点から、１０～８０質量％が好ましく、１５～７５質量％がより好ましく、２０～６０質量％が特に好ましい。
　本発明の着色硬化性組成物は、重合性化合物を、１種類のみを含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 The content of the polymerizable compound in the total solid content of the colored curable composition is preferably 10 to 80% by mass, more preferably 15 to 75% by mass, from the viewpoint of more effectively obtaining the effects of the present invention. From 60% to 60% by weight is particularly preferred.
The colored curable composition of this invention may contain only 1 type of polymeric compounds, and may contain 2 or more types. When two or more types are included, the total amount is preferably within the above range.
＜重合開始剤＞
　本発明の着色硬化性組成物は、重合開始剤を含有することが好ましく、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、重合性化合物や重合性基を含むトリアリールメタン染料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。 <Polymerization initiator>
The colored curable composition of the present invention preferably contains a polymerization initiator, and preferably contains at least one photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it can polymerize a polymerizable compound or a triarylmethane dye containing a polymerizable group, and is selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like. Preferably.
　光重合開始剤としては、例えば、ハロメチルオキサジアゾール化合物およびハロメチル－ｓ－トリアジン化合物から選択される少なくとも１つの活性ハロゲン化合物、３－アリール置換クマリン化合物、ロフィン２量体、ベンゾフェノン化合物、アセトフェノン化合物およびその誘導体、シクロペンタジエン－ベンゼン－鉄錯体およびその塩、オキシム化合物、等が挙げられる。光重合開始剤の具体例については、特開２００４－２９５１１６号公報の段落００７０～００７７に記載のものが挙げられる。中でも、重合反応が迅速である点等から、オキシム系化合物またはビイミダゾール系化合物が好ましい。光重合開始剤の市販品としては、ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２（ＢＡＳＦジャパン社製）などを挙げることができる。 Examples of the photopolymerization initiator include at least one active halogen compound selected from halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl-substituted coumarin compounds, lophine dimers, benzophenone compounds, acetophenone compounds And derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, oxime compounds, and the like. Specific examples of the photopolymerization initiator include those described in paragraphs 0070 to 0077 of JP-A No. 2004-295116. Among these, an oxime compound or a biimidazole compound is preferable from the viewpoint of rapid polymerization reaction. Examples of commercially available photopolymerization initiators include IRGACURE OXE-02 (manufactured by BASF Japan).
　オキシム系化合物（以下、「オキシム系光重合開始剤」ともいう。）としては、特に限定はなく、例えば、特開２０００－８００６８号公報、国際公開ＷＯ２００２／１００９０３Ａ１号公報、特開２００１－２３３８４２号公報等に記載のオキシム系化合物が挙げられる。
　オキシム系化合物の具体的な例としては、特開２０１３－１８２２１５号公報の段落００５３の記載を参酌でき、この内容は本明細書に組み込まれる。 The oxime compound (hereinafter also referred to as “oxime photopolymerization initiator”) is not particularly limited, and examples thereof include Japanese Patent Application Laid-Open No. 2000-80068, International Publication WO2002 / 100903A1, and Japanese Patent Application Laid-Open No. 2001-233842. Examples thereof include oxime compounds described in publications and the like.
As specific examples of the oxime compound, the description in paragraph 0053 of JP2013-182215A can be referred to, and the contents thereof are incorporated in the present specification.
　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、オキシム系化合物として、下記式（１）または式（２）で表される化合物がより好ましい。 In the present invention, the compound represented by the following formula (1) or (2) is more preferable as the oxime compound from the viewpoints of sensitivity, stability with time, and coloring during post-heating.
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
　式（１）中、ＲおよびＸは、それぞれ、１価の置換基を表し、Ａは、２価の有機基を表し、Ａｒは、アリール基を表す。ｎは、１～５の整数である。 In formula (1), R and X each represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1 to 5.
　Ｒとしては、高感度化の点から、アシル基が好ましく、具体的には、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。 R is preferably an acyl group from the viewpoint of high sensitivity, and specifically, an acetyl group, a propionyl group, a benzoyl group, and a toluyl group are preferable.
　Ａ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。 A is an unsubstituted alkylene group, an alkylene group substituted with an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating, An alkylene group substituted with an alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) A substituted alkylene group is preferred.
　Ａｒ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、置換または無置換のフェニル基が好ましい。置換フェニル基の場合、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基が好ましい。 Ar is preferably a substituted or unsubstituted phenyl group from the viewpoint of increasing sensitivity and suppressing coloring due to heating. In the case of a substituted phenyl group, the substituent is preferably a halogen group such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
　Ｘ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キシ基、置換基を有してもよいアリールチオキシ基、置換基を有してもよいアミノ基が好ましい。また、式（１）におけるｎは１～２の整数が好ましい。 X is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl that may have a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. 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 alkylthioxy group which may have a substituent, a substituent An arylthioxy group which may have an amino group and an amino group which may have a substituent are preferable. In the formula (1), n is preferably an integer of 1 to 2.
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
　式（２）中、Ｒ１０１はアルキル基、アルカノイル基、アルケノイル基、アリーロイル基、アルコキシカルボニル基、アリーロキシカルボニル基、ヘテロ環オキシカルボニル基、ヘテロアリールオキシカルボニル基、アルキルチオカルボニル基、アリールチオカルボニル基、ヘテロ環チオカルボニル基、ヘテロアリールチオカルボニル基またはＣＯ－ＣＯ－Ｒｆを表す。Ｒｆは炭素環式芳香族基またはヘテロ環式芳香族基を表す。 In the formula (2), R 101 represents an alkyl group, an alkanoyl group, an alkenoyl group, an aryloyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a heteroaryloxycarbonyl group, an alkylthiocarbonyl group, an arylthiocarbonyl group. Represents a heterocyclic thiocarbonyl group, a heteroarylthiocarbonyl group, or CO—CO—Rf. Rf represents a carbocyclic aromatic group or a heterocyclic aromatic group.
　Ｒ１０２はアルキル基、アリール基またはヘテロ環基を示し、これらは置換されていても良い。
　Ｒ１０３およびＲ１０４は、それぞれ独立に、アルキル基、アリール基またはヘテロ環基を示し、これらの基は、さらにハロゲン原子、アルキル基、アリール基、アルコキシ基、アルキルカルボニル基等で置換されていても良い。 R 102 represents an alkyl group, an aryl group, or a heterocyclic group, and these may be substituted.
R 103 and R 104 each independently represents an alkyl group, an aryl group or a heterocyclic group, and these groups are further substituted with a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylcarbonyl group or the like. Also good.
　Ｒ１０５～Ｒ１１１は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アリール基、ヘテロ環基、アルコキシ基、アリーロイル基、ヘテロアリーロイル基、アルキルチオ基、アリーロイルチオ基、ヘテロアリーロイル基、アルキルカルボニル基、アリールカルボニル基、ヘテロアリールカルボニル基、アルコキシカルボニル基、アリーロキシカルボニル基、ヘテロ環オキシカルボニル基、ニトロ基、アミノ基、スルホン酸基、ヒドロキシ基、カルボン酸基、アミド基、カルバモイル基またはシアノ基を表す。
　Ｒ１０５～Ｒ１１１のうちの、一つまたは二つが電子吸引性の置換基、即ち、ニトロ基、シアノ基、ハロゲンノ基、アルキルカルボニル基またはアリールカルボニル基であることが、一段と高い硬化性を有する着色硬化性組成物が得られるので、好ましい。 R 105 to R 111 are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloyl group, a heteroaryloyl group, an alkylthio group, an aryloylthio group, or a heteroaryloyl group. , Alkylcarbonyl group, arylcarbonyl group, heteroarylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, nitro group, amino group, sulfonic acid group, hydroxy group, carboxylic acid group, amide group, carbamoyl Represents a group or a cyano group.
One or two of R 105 to R 111 is an electron-withdrawing substituent, that is, a nitro group, a cyano group, a halogeno group, an alkylcarbonyl group or an arylcarbonyl group, which has a much higher curability. Since a colored curable composition is obtained, it is preferable.
　上記一般式（２）で表されるフルオレン構造を有する化合物の具体例を以下に挙げる。ただし、これの化合物に限定されるものではない。 Specific examples of the compound having a fluorene structure represented by the general formula (2) are given below. However, it is not limited to these compounds.
　上記一般式（２）で表されるフルオレン構造を有する化合物は、例えば国際公開ＷＯ２０１４－０５０７３８号公報に記載された合成方法に準じて合成することができる。 The compound having a fluorene structure represented by the general formula (2) can be synthesized according to a synthesis method described in, for example, International Publication WO2014-050738.
　ビイミダゾール系化合物の具体例としては、特開２０１３－１８２２１３号公報段落００６１～００７０の記載を参酌でき、この内容は本明細書に組み込まれる。 As specific examples of the biimidazole compound, the description in paragraphs 0061 to 0070 of JP2013-182213A can be referred to, and the contents thereof are incorporated herein.
　また、本発明の着色硬化性組成物には、上記の光重合開始剤のほかに、特開２００４－２９５１１６号公報の段落番号００７９に記載の他の公知の光重合開始剤を使用してもよい。 In addition to the above photopolymerization initiator, other known photopolymerization initiators described in paragraph No. 0079 of JP-A No. 2004-295116 may be used in the colored curable composition of the present invention. Good.
　光重合開始剤の着色硬化性組成物の全固形分中における含有量は、本発明の効果をより効果的に得る観点から、０．１～２０質量％が好ましく、０．１～１９質量％がより好ましく、０．１～１８質量％が特に好ましい。下限は、３質量％以上とすることもでき、４質量％以上とすることもでき、５質量％以上とすることもできる。
　本発明の着色硬化性組成物は、光重合開始剤を、１種類のみを含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 The content of the photopolymerization initiator in the total solid content of the colored curable composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 19% by mass from the viewpoint of more effectively obtaining the effects of the present invention. Is more preferable, and 0.1 to 18% by mass is particularly preferable. The lower limit may be 3% by mass or more, 4% by mass or more, and 5% by mass or more.
The colored curable composition of the present invention may contain only one type or two or more types of photopolymerization initiators. When two or more types are included, the total amount is preferably within the above range.
＜有機溶剤＞
　本発明の着色硬化性組成物は、少なくとも一種の有機溶剤を含有することが好ましいい。
　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、バインダーの溶解性、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 preferably contains at least one organic solvent.
The organic solvent is basically not particularly limited as long as it can satisfy the solubility of each of the coexisting components and the coating property when the colored curable composition is used, and in particular, the solubility of the binder, the coating property, It is preferable to select in consideration of safety.
　有機溶剤としては、エステル類、エーテル類、ケトン類、芳香族炭化水素類が用いられ、具体的には、特開２０１２－０３２７５４号公報の段落番号０１６１～０１６２に記載のものが例示される。 Examples of the organic solvent include esters, ethers, ketones, and aromatic hydrocarbons, and specific examples include those described in paragraph numbers 0161 to 0162 of JP2012-032754A.
　これらの有機溶剤は、前述の各成分の溶解性、およびアルカリ可溶性ポリマ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、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、プロピレングリコールモノメチルエーテルアセテートおよびメチルエチルジグリコールから選択される２種以上で構成される混合溶液である。 These organic solvents are preferably mixed in two or more types from the viewpoints of the solubility of each of the above-mentioned components and, when an alkali-soluble polymer 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, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solution composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate and methyl ethyl diglycol.
　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、組成物中の全固形分濃度が１０～８０質量％になる量が好ましく、１５～６０質量％になる量がより好ましい。
　本発明の着色硬化性組成物は、有機溶剤を、１種類のみを含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 The content of the organic solvent in the colored curable composition is preferably such that the total solid concentration in the composition is 10 to 80% by mass, more preferably 15 to 60% by mass.
The colored curable composition of the present invention may contain only one type of organic solvent or two or more types of organic solvents. When two or more types are included, the total amount is preferably within the above range.
＜樹脂＞
　本発明の着色硬化性組成物は、樹脂を含むことが好ましく、樹脂としてアルカリ可溶性樹脂を含むことが好ましい。アルカリ可溶性樹脂は、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。 <Resin>
The colored curable composition of the present invention preferably contains a resin, and preferably contains an alkali-soluble resin as the resin. The alkali-soluble resin 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.
　アルカリ可溶性樹脂としては、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 resin 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.
　上述したものの他に、本発明におけるアルカリ可溶性樹脂としては、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、または、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、スルホン酸基およびその塩由来の基、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。
　アルカリ可溶性樹脂としては、ベンジルメタクリレートとメタクリル酸との共重合体も好ましい。 In addition to those described above, the alkali-soluble resin in the present invention includes those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meta) ) Acrylate), polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like 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 chain butyl (meth) acrylate, 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.
As the alkali-soluble resin, a copolymer of benzyl methacrylate and methacrylic acid is also preferable.
　アルカリ可溶性樹脂としては、下記式（ｂ１）および（ｂ２）に示すようなマレイミドとエチレンオキサイドの共重合体も好ましく用いることが出来る。 As the alkali-soluble resin, a copolymer of maleimide and ethylene oxide as shown in the following formulas (b1) and (b2) can also be preferably used.
式（ｂ１）
Figure JPOXMLDOC01-appb-C000062
 Formula (b1)
Figure JPOXMLDOC01-appb-C000062
　式（ｂ１）中、Ｒ１は、水素原子、アリール基、またはアルキル基を表す。）
　Ｒ１がアルキル基を表す場合のアルキル基としては、炭素数１～１０の直鎖状アルキル基、炭素数３～１０の分岐鎖を有するアルキル基、炭素数５～２０の環状アルキル基などが挙げられ、より具体的には、メチル基、エチル基、ｔ－ブチル基、シクロヘキシル基などが挙げられる。
　アルキル基は、置換基を有していてもよく、アルキル基に導入可能な置換基としては、フェニル基、カルボニル基、アルコキシ基、ヒドロキシ基、アミノ基などが挙げられる。
　Ｒ１がアリール基を表す場合のアリール基としては、単環構造のアリール基、多環構造のアリール基、縮環構造のアリール基、ヘテロ原子を含むヘテロアリール基などが挙げられる。より具体的には、フェニル基、ナフチル基、ビフェニル基、ベンゾイミダゾリル基、ピリジル基、フリル基などが挙げられる。
　アリール基は、置換基を有していてもよく、アリール基に導入可能な置換基としては、メチル基、エチル基、ｔ－ブチル基、シクロヘキシル基等のアルキル基、メトキシ基等のアルコキシ基、カルボキシ基、ヒドロキシ基、アミノ基、ニトロ基、クロロ基、ブロモ基などが挙げられる。 In formula (b1), R 1 represents a hydrogen atom, an aryl group, or an alkyl group. )
Examples of the alkyl group when R 1 represents an alkyl group include a linear alkyl group having 1 to 10 carbon atoms, an alkyl group having a branched chain having 3 to 10 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group and the like can be mentioned.
The alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, an alkoxy group, a hydroxy group, and an amino group.
When R 1 represents an aryl group, examples of the aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring aryl group, a heteroaryl group containing a hetero atom, and the like. More specifically, a phenyl group, a naphthyl group, a biphenyl group, a benzimidazolyl group, a pyridyl group, a furyl group, and the like can be given.
The aryl group may have a substituent, and examples of the substituent that can be introduced into the aryl group include an alkyl group such as a methyl group, an ethyl group, a t-butyl group, and a cyclohexyl group, an alkoxy group such as a methoxy group, Examples thereof include a carboxy group, a hydroxy group, an amino group, a nitro group, a chloro group, and a bromo group.
式（ｂ２）
Figure JPOXMLDOC01-appb-C000063
 Formula (b2)
Figure JPOXMLDOC01-appb-C000063
　式（ｂ２）中、Ｒ２は、水素原子またはメチル基を表す。Ｒ３は、炭素数２または３のアルキレン基であり、Ｒ４は、水素原子、アリール基、またはアルキル基を表し、ｍは、１～１５の整数を表す。 In formula (b2), R 2 represents a hydrogen atom or a methyl group. R 3 is an alkylene group having 2 or 3 carbon atoms, R 4 represents a hydrogen atom, an aryl group, or an alkyl group, and m represents an integer of 1 to 15.
　Ｒ４がアルキル基を表す場合のアルキル基としては、炭素数１～２０の直鎖状アルキル基、炭素数１～２０の分岐鎖を有するアルキル基、炭素数５～２０の環状アルキル基などが挙げられ、より具体的には、メチル基、エチル基、ｔ－ブチル基、シクロヘキシル基、２－エチルヘキシル基などが挙げられる。
　アルキル基は、置換基を有していてもよく、アルキル基に導入可能な置換基としては、フェニル基、カルボニル基、アルコキシ基などが挙げられる。
　Ｒ４がアリール基を表す場合のアリール基としては、単環構造のアリール基、多環構造のアリール基、縮環構造のアリール基、ヘテロ原子を含むヘテロアリール基などが挙げられる。より具体的には、フェニル基、ナフチル基、アントラニル基、ビフェニル基、ベンゾイミダゾリル基、インドリル基、イミダゾリル基、オキサゾリル基、カルバゾリル基、ピリジル基、フリル基などが挙げられる。
　アリール基は、置換基を有していてもよく、アリール基に導入可能な置換基としては、ノニル基、メチル基、エチル基、ｔ－ブチル基、シクロヘキシル基等のアルキル基、メトキシ基等のアルコキシ基、カルボキシ基、ヒドロキシ基、アミノ基、ニトロ基、クロロ基、ブロモ基などが挙げられる。 Examples of the alkyl group when R 4 represents an alkyl group include a linear alkyl group having 1 to 20 carbon atoms, an alkyl group having a branched chain having 1 to 20 carbon atoms, and a cyclic alkyl group having 5 to 20 carbon atoms. More specifically, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group, a 2-ethylhexyl group, and the like can be given.
The alkyl group may have a substituent, and examples of the substituent that can be introduced into the alkyl group include a phenyl group, a carbonyl group, and an alkoxy group.
Examples of the aryl group when R 4 represents an aryl group include a monocyclic aryl group, a polycyclic aryl group, a condensed ring aryl group, a heteroaryl group containing a heteroatom, and the like. More specifically, a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, a benzimidazolyl group, an indolyl group, an imidazolyl group, an oxazolyl group, a carbazolyl group, a pyridyl group, a furyl group, and the like can be given.
The aryl group may have a substituent, and examples of the substituent that can be introduced into the aryl group include a nonyl group, a methyl group, an ethyl group, a t-butyl group, a cyclohexyl group and other alkyl groups, and a methoxy group. Examples thereof include an alkoxy group, a carboxy group, a hydroxy group, an amino group, a nitro group, a chloro group, and a bromo group.
　また、アルカリ可溶性樹脂は、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、市販品のＫＳレジスト－１０６（大阪有機化学工業（株）製）、サイクロマーＰシリーズ（ダイセル化学工業（株）製）等が挙げられる。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ロヒドリンとのポリエーテル等も有用である。 Further, the alkali-soluble resin 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-mentioned polymer containing a polymerizable group include commercially available KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, etc. are also useful.
　これら各種アルカリ可溶性樹脂の中でも、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 resins, 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.
　特に、下記一般式（２）で示すような繰り返し単位と酸性基を有する共重合体が好ましく、より好ましくは一般式（２）と酸性基に加え、一般式（３）で表される構造単位を有する共重合体が挙げられる。 In particular, a copolymer having a repeating unit represented by the following general formula (2) and an acidic group is preferred, and more preferably a structural unit represented by the general formula (3) in addition to the general formula (2) and the acidic group. And a copolymer having.
一般式（２）
Figure JPOXMLDOC01-appb-C000064
 General formula (2)
Figure JPOXMLDOC01-appb-C000064
　一般式（２）中、Ｒ２０は、水素原子またはメチル基を表し、Ｒ２１～Ｒ２５は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、アルキル基、またはアリール基を表す。 In the general formula (2), R 20 represents a hydrogen atom or a methyl group, and R 21 to R 25 each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, or an aryl group.
一般式（３）
Figure JPOXMLDOC01-appb-C000065
 General formula (3)
Figure JPOXMLDOC01-appb-C000065
　一般式（３）中、Ｒ１１は、水素原子またはメチル基を表す。Ｒ１２およびＲ１３は、それぞれ独立して、水素原子または不飽和二重結合を部分構造として含む炭素数３～２０のカルボニル基を表し、Ｒ１２およびＲ１３の双方が水素原子であることはない。Ｒ１２およびＲ１３の少なくとも一方が不飽和二重結合を部分構造として含む炭素数３～２０のカルボニル基を表す場合、さらにカルボキシ基を部分構造として含んでいてもよい。 In General Formula (3), R 11 represents a hydrogen atom or a methyl group. R 12 and R 13 each independently represents a hydrogen atom or a carbonyl group having 3 to 20 carbon atoms containing an unsaturated double bond as a partial structure, and both of R 12 and R 13 are hydrogen atoms. Absent. When at least one of R 12 and R 13 represents a carbonyl group having 3 to 20 carbon atoms containing an unsaturated double bond as a partial structure, it may further contain a carboxy group as a partial structure.
　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、市販品のＫＳレジスト－１０６（大阪有機化学工業（株）製）、サイクロマーＰシリーズ（ダイセル化学工業（株）製）等が好ましい。 Examples of acrylic resins include copolymers composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and commercially available KS resist 106 (Osaka). Organic Chemical Industry Co., Ltd.), Cyclomer P Series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.
　また、アルカリ可溶性樹脂は、下記式（Ｘ）で示されるエチレン性不飽和単量体に由来する構造単位を含んでいてもよい。
一般式（Ｘ）
Figure JPOXMLDOC01-appb-C000066
 Moreover, alkali-soluble resin may contain the structural unit derived from the ethylenically unsaturated monomer shown by following formula (X).
Formula (X)
Figure JPOXMLDOC01-appb-C000066
　式（Ｘ）において、Ｒ1は、水素原子またはメチル基を表し、Ｒ2は炭素数２～１０のアルキレン基を表し、Ｒ3は、水素原子またはベンゼン環を含んでもよい炭素数１～２０のアルキル基を表す。ｎは１～１５の整数を表す。 In formula (X), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkylene group having 2 to 10 carbon atoms, and R 3 represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.
　上記式（Ｘ）において、Ｒ2のアルキレン基の炭素数は、２～３であることが好ましい。また、Ｒ3のアルキル基の炭素数は１～２０であるが、より好ましくは１～１０であり、Ｒ3のアルキル基はベンゼン環を含んでもよい。Ｒ3で表されるベンゼン環を含むアルキル基としては、ベンジル基、２－フェニル（イソ）プロピル基等を挙げることができる。 In the above formula (X), the alkylene group of R 2 preferably has 2 to 3 carbon atoms. The alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R 3 may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
　アルカリ可溶性樹脂は、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１,０００～２００，０００の重合体が好ましく、２，０００～１００，０００の重合体がより好ましく、５，０００～５０，０００の重合体が特に好ましい。 The alkali-soluble resin is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1,000 to 200,000 from the viewpoint of developability, liquid viscosity and the like, and 2,000 to 100,000. More preferred is a polymer of 5,000 to 50,000.
　アルカリ可溶性樹脂の配合量は、着色硬化性組成物の全固形分の１０～８０質量％であることが好ましく、２０～６０質量％であることがより好ましい。
　また、アルカリ可溶性樹脂の酸価は、１０～１０００ｍｇ／ＫＯＨが好ましく、５０～３００ｍｇ／ＫＯＨがより好ましく、５０～２００ｍｇ／ＫＯＨがさらに好ましく、９０～２００ｍｇ／ＫＯＨが特に好ましい。
　本発明の着色硬化性組成物は、アルカリ可溶性樹脂を、１種類のみを含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 The blending amount of the alkali-soluble resin is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, based on the total solid content of the colored curable composition.
The acid value of the alkali-soluble resin is preferably 10 to 1000 mg / KOH, more preferably 50 to 300 mg / KOH, still more preferably 50 to 200 mg / KOH, and particularly preferably 90 to 200 mg / KOH.
The colored curable composition of the present invention may contain only one type or two or more types of alkali-soluble resins. When two or more types are included, the total amount is preferably within the above range.
＜架橋剤＞
　本発明の着色硬化性組成物は、架橋剤をさらに含んでいてもよい。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、およ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またはウレア化合物、（ｃ）メチロール基、アルコキシメチル基、およ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、ナフトール化合物またはヒドロキシアントラセン化合物、が挙げられる。中でも、多官能エポキシ樹脂が好ましい。架橋剤の市販品としては、例えば、カレンズＭＴＢＤ－１（昭和電工株式会社製）、セロキサイド２０２１Ｐ　（ダイセル化学株式会社製）を挙げることができる。
　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、この内容は本明細書に組み込まれる。 <Crosslinking agent>
The colored curable composition of the present invention may further contain a crosslinking agent. 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, which is substituted with one substituent; Phenol compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred. Examples of commercially available cross-linking agents include Karenz MTBD-1 (manufactured by Showa Denko KK) and Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd.).
For details such as specific examples of the crosslinking agent, reference can be made to the description in paragraphs 0134 to 0147 of JP-A No. 2004-295116, the contents of which are incorporated herein.
＜界面活性剤＞
　本発明の着色硬化性組成物は、界面活性剤を含んでいても良い。界面活性剤は、ノニオン系、カチオン系、アニオン系のいずれでもよいが、エチレンオキサイド構造を持つ界面活性剤、フッ素系界面活性剤が好ましい。特にＨＬＢ（Ｈｙｄｒｏｐｈｉｌｅ－Ｌｉｐｏｐｈｉｌｅ　Ｂａｌａｎｃｅ）値が９．２～１５．５の範囲にあるエチレンオキサイド構造を持つ界面活性剤もしくは特開平２－５４２０２号公報記載のフッ素系界面活性剤が好ましい。界面活性剤の市販品としては、メガファックＦ５５４（ＤＩＣ（株）製）などを挙げることができる。
　本発明の着色硬化性組成物に界面活性剤を含有する場合、界面活性剤の添加量は、着色硬化性組成物の全固形分に対して、０．０００１～２．０質量％が好ましく、より好ましくは０．００５～１．０質量％である。
　本発明の着色硬化性組成物は、界面活性剤を、１種類のみを含んでいてもよいし、２種類以上含んでいてもよい。２種類以上含む場合は、その合計量が上記範囲となることが好ましい。 <Surfactant>
The colored curable composition of the present invention may contain a surfactant. The surfactant may be nonionic, cationic, or anionic, but a surfactant having an ethylene oxide structure and a fluorosurfactant are preferred. In particular, a surfactant having an ethylene oxide structure having an HLB (Hydrophile-Lipophile Balance) value in the range of 9.2 to 15.5 or a fluorosurfactant described in JP-A-2-54202 is preferred. Examples of commercially available surfactants include Megafac F554 (manufactured by DIC Corporation).
When the colored curable composition of the present invention contains a surfactant, the addition amount of the surfactant is preferably 0.0001 to 2.0% by mass with respect to the total solid content of the colored curable composition, More preferably, the content is 0.005 to 1.0% by mass.
The colored curable composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.
　本発明の着色硬化性組成物は、さらに必要に応じて、熱酸発生剤、充填材、酸化防止剤、紫外線吸収剤、凝集防止剤、増感剤や光安定剤等など各種添加剤を含んでいても良い。 The colored curable composition of the present invention further contains various additives such as a thermal acid generator, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a sensitizer and a light stabilizer, as necessary. You can leave.
＜染料安定化剤＞
　本発明の着色硬化性組成物には、染料カチオンとは別に、染料安定化剤を添加することが好ましい。安定化剤としては、例えば、カチオン系、アニオン系、ノニオン系、両性、シリコン系、フッ素系等の界面活性剤を使用できる。界面活性剤の中でも、均一に、微細に分散し得る点から、高分子界面活性剤（高分子分散剤）が好ましい。
　高分子分散剤としては、例えば、ポリアクリル酸エステル等の不飽和カルボン酸エステルの（共）重合体類；ポリアクリル酸等の不飽和カルボン酸の（共）重合体の（部分）アミン塩、（部分）アンモニウム塩や（部分）アルキルアミン塩類；水酸基含有ポリアクリル酸エステル等の水酸基含有不飽和カルボン酸エステルの（共）重合体やそれらの編成物；架橋性基を有するスルホン酸やリン酸の重合物等が挙げられる。
　架橋性基としては、ラジカル、酸、熱により架橋可能な架橋性基を用いることができる。具体的には（メタ）アクリル基、スチレン基、ビニル基、環状エーテル基、メチロール基が挙げられるが、（メタ）アクリル基、スチレン基、ビニル基が好ましく、（メタ）アクリル基およびスチレン基がより好ましい。
　またこれら界面活性剤のほかにビストリフルオロメタンスルホンイミドナトリウム塩や、下記アニオンの塩（ナトリウム塩、カリウム塩等）を加えることも有効である。
Figure JPOXMLDOC01-appb-C000067
 <Dye stabilizer>
In addition to the dye cation, it is preferable to add a dye stabilizer to the colored curable composition of the present invention. As the stabilizer, for example, cationic, anionic, nonionic, amphoteric, silicon-based, fluorine-based surfactants can be used. Among the surfactants, a polymer surfactant (polymer dispersant) is preferable because it can be uniformly and finely dispersed.
Examples of the polymer dispersant include (co) polymers of unsaturated carboxylic acid esters such as polyacrylic acid esters; (partial) amine salts of (co) polymers of unsaturated carboxylic acid such as polyacrylic acid; (Partial) ammonium salt and (partial) alkylamine salt; (co) polymer of hydroxyl group-containing unsaturated carboxylic acid ester such as hydroxyl group-containing polyacrylic acid ester or knitted product thereof; sulfonic acid or phosphoric acid having a crosslinkable group And the like.
As the crosslinkable group, a crosslinkable group that can be crosslinked by a radical, an acid, or heat can be used. Specific examples include (meth) acryl groups, styrene groups, vinyl groups, cyclic ether groups, and methylol groups, with (meth) acryl groups, styrene groups, and vinyl groups being preferred, and (meth) acryl groups and styrene groups being preferred. More preferred.
In addition to these surfactants, it is also effective to add bistrifluoromethanesulfonimide sodium salt and the following anion salts (sodium salt, potassium salt, etc.).
Figure JPOXMLDOC01-appb-C000067
＜酸化防止剤＞
　本発明の着色硬化性組成物は、酸化防止剤を含んでいてもよい。酸化防止剤としては、例えば、ラジカル捕捉剤、過酸化物分解剤、紫外線吸収剤、一重項酸素クエンチャー等を挙げることができる。酸化防止剤の市販品としては、例えば、ＡＯ－６０（アデカスタブＡＯ－６０（ＡＤＥＫＡ社製）などを挙げることができる。 <Antioxidant>
The colored curable composition of the present invention may contain an antioxidant. Examples of the antioxidant include a radical scavenger, a peroxide decomposer, an ultraviolet absorber, and a singlet oxygen quencher. Examples of commercially available antioxidants include AO-60 (ADK STAB AO-60 (manufactured by ADEKA)).
　ラジカル捕捉剤としては、例えば、フェノール系酸化防止剤、ヒンダードアミン系酸化防止剤等を挙げることができる。フェノール系酸化防止剤としては、例えば、ヒドロキシフェニルプロピオネート系化合物、ヒドロキシベンジル系化合物、チオビスフェノール系化合物、チオメチルフェノール系化合物、アルカンジイルフェノール系化合物等を挙げることができる。中でも、色特性の安定性の観点から、ヒドロキシフェニルプロピオネート系化合物が好ましい。
　例えば、特開２０１２－１５５２４３号公報の段落００１３～００３４、特開２０１３－１４７４８号公報の段落００３０～００４２に記載の化合物を好ましく用いることができる。 Examples of the radical scavenger include phenolic antioxidants and hindered amine antioxidants. Examples of phenolic antioxidants include hydroxyphenylpropionate compounds, hydroxybenzyl compounds, thiobisphenol compounds, thiomethylphenol compounds, alkanediylphenol compounds, and the like. Of these, hydroxyphenylpropionate compounds are preferred from the viewpoint of the stability of color characteristics.
For example, compounds described in paragraphs 0013 to 0034 of JP2012-155243A and paragraphs 0030 to 0042 of JP2013-14748A can be preferably used.
　過酸化物分解剤は、光に曝露されること等により発生した過酸化物を無害な物質に分解し、新たなラジカルが発生しないようにする化合物であり、例えば、リン系酸化防止剤、イオウ系酸化防止剤等を挙げることができる。中でも、色特性の安定性の観点から、イオウ系酸化防止剤が好ましい。 A peroxide decomposer is a compound that decomposes peroxides generated by exposure to light into harmless substances and prevents the generation of new radicals. For example, phosphorus antioxidants, sulfur And system antioxidants. Among these, sulfur-based antioxidants are preferable from the viewpoint of the stability of color characteristics.
　紫外線吸収剤としては、例えば、サルチル酸エステル系酸化防止剤、ベンゾフェノン系酸化防止剤を挙げることができる。 Examples of ultraviolet absorbers include salicylate-based antioxidants and benzophenone-based antioxidants.
　一重項酸素クエンチャーは、一重項状態の酸素からのエネルギー移動により一重項酸素を失活させ得る化合物であり、例えば、テトラメチルエチレン、シクロペンテン等のエチレン性化合物、ジエチルアミン、トリエチルアミン、１，４－ジアザビシクロオクタン（ＤＡＢＣＯ）、Ｎ－エチルイミダゾール等のアミン類、置換されても良いナフタレン、ジメチルナフタレン、ジメトキシアントラセン、アントラセン、ジフェニルアントラセン等の縮合多環芳香族化合物；１，３－ジフェニルイソベンゾフラン、１，２，３，４－テトラフェニル－１，３－シクロペンタジエン、ペンタフェニルシクロペンタジエン等の芳香族化合物の他、Ｈａｒｒｙ　Ｈ．ｗａｓｓｅｒｍａｎ，“Ｓｉｎｇｌｅｔ　Ｏｘｙｇｅｎ”，５章，Ａｃａｄｅｍｉｃ　Ｐｒｅｓｓ（１９７９）、Ｎｉｃｈｏｌａｓ　Ｊ．Ｔｕｒｒｏ，“”Ｍｏｄｅｒｎ　Ｍｏｌｅｃｕｌａｒ　Ｐｈｏｔｏｃｈｅｍｉｓｔｒｙ“”，１４章，Ｔｈｅ　Ｂｅｎｊａｍｉｎ　Ｃｕｍｍｉｎｇｓ　Ｐｕｂｌｉｓｈｉｎｇ　Ｃｏ．，Ｉｎｃ．（１９７８）、およびＣＭＣ社発行　カラー写真感光材料用高機能ケミカルス，７章（２００２）に、一重項酸素クエンチャーとして例示されている化合物を挙げることができる。 A singlet oxygen quencher is a compound that can deactivate singlet oxygen by energy transfer from oxygen in a singlet state. For example, an ethylenic compound such as tetramethylethylene and cyclopentene, diethylamine, triethylamine, 1,4- Amines such as diazabicyclooctane (DABCO) and N-ethylimidazole, condensed polycyclic aromatic compounds such as optionally substituted naphthalene, dimethylnaphthalene, dimethoxyanthracene, anthracene and diphenylanthracene; 1,3-diphenylisobenzofuran In addition to aromatic compounds such as 1,2,3,4-tetraphenyl-1,3-cyclopentadiene and pentaphenylcyclopentadiene, Harry H. et al. wasserman, “Single Oxygen”, Chapter 5, Academic Press (1979), Nicholas J. et al. Turro, “” Modern Molecular Photochemistry ””, Chapter 14, The Benjamin Cummings Publishing Co. , Inc. (1978), and CMC Corporation, High Performance Chemicals for Color Photosensitive Materials, Chapter 7 (2002) can include compounds exemplified as singlet oxygen quenchers.
　このほかに硫黄原子を有する化合物を配位子とする金属錯体を挙げることができる。このような化合物としてビスジチオ－α－ジケトン、ビスフェニルジチオール、およびチオビスフェノールを配位子とする、ニッケル錯体、コバルト錯体、銅錯体、マンガン錯体、白金錯体等の遷移金属キレート化合物を挙げることができる。
　イオウ系酸化防止剤としては、チオプロピオネート系化合物、メルカプトベンズイミダゾール系化合物を挙げることができる。中でも、色特性の安定性の観点から、チオプロピオネート系化合物が好ましい。 In addition, a metal complex having a sulfur atom-containing compound as a ligand can be exemplified. Examples of such compounds include transition metal chelate compounds such as nickel complexes, cobalt complexes, copper complexes, manganese complexes, and platinum complexes having bisdithio-α-diketone, bisphenyldithiol, and thiobisphenol as ligands. .
Examples of the sulfur antioxidant include thiopropionate compounds and mercaptobenzimidazole compounds. Of these, thiopropionate compounds are preferred from the viewpoint of the stability of color characteristics.
　本発明において、酸化防止剤は、単独でまたは２種以上を混合して使用することができる。酸化防止剤の含有量は、着色硬化性組成物の全固形分に対して、好ましくは０．０１～２０質量％、特に好ましくは０．１～１０質量％である。 In the present invention, the antioxidants can be used alone or in admixture of two or more. The content of the antioxidant is preferably 0.01 to 20% by mass, particularly preferably 0.1 to 10% by mass, based on the total solid content of the colored curable composition.
＜硬化剤＞
　本発明の着色硬化性組成物は、硬化剤として機能する化合物を含有することができる。例えば、芳香族アミン化合物、３級アミン化合物、アミン塩、ホスホニウム塩、アミジン塩、アミド化合物、チオール化合物、ブロックイソシアネート化合物およびイミダゾール環含有化合物からなる群より選ばれる少なくとも１つの化合物を用いることができる。
　着色硬化性組成物が、このような硬化剤を含有することにより、着色パターンの低温硬化をより効果的に実現することができる。併せて、着色硬化性組成物の保存安定性をより向上させることもできる。 <Curing agent>
The colored curable composition of the present invention can contain a compound that functions as a curing agent. For example, at least one compound selected from the group consisting of aromatic amine compounds, tertiary amine compounds, amine salts, phosphonium salts, amidine salts, amide compounds, thiol compounds, blocked isocyanate compounds, and imidazole ring-containing compounds can be used. .
When the colored curable composition contains such a curing agent, the low-temperature curing of the colored pattern can be more effectively realized. In addition, the storage stability of the colored curable composition can be further improved.
＜還元防止剤＞
　本発明の着色硬化性組成物は、上記染料よりも還元されやすい化合物を染料の還元防止剤として添加することもできる。これにより、画素形成後のＩＴＯ（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ）スパッタ時に染料還元褪色をより抑制することができる。具体的にはキノン化合物が好ましく、分子量１００～８００程度の以下構造のキノン化合物が好ましい。 <Reducing inhibitor>
In the colored curable composition of the present invention, a compound that is more easily reduced than the above dye may be added as a dye reduction inhibitor. Thereby, dye reduction fading can be further suppressed during ITO (Indium Tin Oxide) sputtering after pixel formation. Specifically, a quinone compound is preferable, and a quinone compound having a molecular weight of about 100 to 800 and having the following structure is preferable.
　本発明の着色硬化性組成物は、さらに必要に応じて、充填材、紫外線吸収剤、凝集防止剤、増感剤や光安定剤等など各種添加剤を含んでいても良い。 The colored curable composition of the present invention may further contain various additives such as fillers, ultraviolet absorbers, anti-aggregation agents, sensitizers, and light stabilizers as necessary.
＜酸発生剤＞
　酸発生剤は、光酸発生剤であっても、熱酸発生剤であってもよいが、熱酸発生剤が好ましい。熱酸発生剤を用いると硬化膜の耐熱性がより向上する傾向にある。これは、耐熱性低下の原因の１つに、アルカリ現像液の硬化膜への浸透による酸性度の低下があることに基づく。すなわち、硬化後のベーク処理工程で硬化膜の酸性度が低下してしまっており、耐熱性が劣るが、熱酸発生剤を配合することにより、ベーク時に酸が発生し、アルカリ現像液の硬化膜への浸透による酸性度の低下を抑制できる。
　熱酸発生剤は、１０１３．２５ｈＰａで１００～２５０℃で加熱したときに、酸を発生する酸発生剤をいう。発生する酸としては、ｐＫａ５以下の酸が好ましい。発生する酸の具体例としては、スルホン酸、カルボン酸、リン酸等が例示され、スルホン酸がより好ましい。
　光酸発生剤としては、特開２００６－２５９００２号公報の段落０１０３～０１１３の記載を参酌でき、これらの内容は本明細書に組み込まれる。
　熱酸発生剤には、イオン性化合物（オニウム塩）および非イオン性化合物が含まれる。
　イオン性化合物（オニウム塩）としては、重金属やハロゲンイオンを含まないものが好ましく、スルホン酸のオニウム塩が好ましい。
　イオン性の熱酸発生剤としては、具体的には、トリフェニルスルホニウム、１－ジメチルチオナフタレン、１－ジメチルチオ－４－ヒドロキシナフタレン、１－ジメチルチオ－４，７－ジヒドロキシナフタレン、４－ヒドロキシフェニルジメチルスルホニウム、ベンジル－４－ヒドロキシフェニルメチルスルホニウム、２－メチルベンジル－４－ヒドロキシフェニルメチルスルホニウム、２－メチルベンジル－４－アセチルフェニルメチルスルホニウム、２－メチルベンジル－４－ベンゾイルオキシフェニルメチルスルホニウム、これらのメタンスルホン酸塩、トリフルオロメタンスルホン酸塩、カンファースルホン酸塩、ｐ－トルエンスルホン酸塩、ヘキサフルオロホスホン酸塩等が挙げられる。 <Acid generator>
The acid generator may be a photoacid generator or a thermal acid generator, but a thermal acid generator is preferred. When a thermal acid generator is used, the heat resistance of the cured film tends to be further improved. This is based on the fact that one of the causes of the decrease in heat resistance is a decrease in acidity due to the penetration of the alkali developer into the cured film. In other words, the acidity of the cured film has been lowered in the baking treatment step after curing, and the heat resistance is inferior, but by adding a thermal acid generator, acid is generated at the time of baking, and the alkali developer is cured. A decrease in acidity due to penetration into the membrane can be suppressed.
The thermal acid generator refers to an acid generator that generates an acid when heated at 100 to 250 ° C. at 101.25 hPa. The acid generated is preferably an acid having a pKa of 5 or less. Specific examples of the acid generated include sulfonic acid, carboxylic acid, phosphoric acid and the like, and sulfonic acid is more preferable.
As the photoacid generator, the description in paragraphs 0103 to 0113 of JP-A-2006-259002 can be referred to, and the contents thereof are incorporated herein.
Thermal acid generators include ionic compounds (onium salts) and nonionic compounds.
As the ionic compound (onium salt), those containing no heavy metal or halogen ion are preferable, and onium salts of sulfonic acid are preferable.
Specific examples of the ionic thermal acid generator include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, 1-dimethylthio-4,7-dihydroxynaphthalene, 4-hydroxyphenyldimethyl. Sulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, these Examples include methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, hexafluorophosphonate and the like.
＜光増感剤＞
　本発明の着色硬化性組成物は、光増感剤を含有していてもよい。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。光増感剤は、光重合開始剤に対し、５０～２００質量％含むことが好ましい。 <Photosensitizer>
The colored curable composition of the present invention may contain a photosensitizer. As the sensitizer, 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 photosensitizer is preferably contained in an amount 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は、連鎖移動剤を含有してもよい。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、１，３，５－トリス（３－メルカブトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオンなどの複素環を有するメルカプト化合物、および、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）、１，４－ビス（３－メルカプトブチリルオキシ）ブタンなどの脂肪族多官能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。
　連鎖移動剤の含有量は、本発明の着色硬化性組成物の全固形分に対して、０．０１～１５質量％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、０．１～１０質量％がより好ましく、０．５～５質量％が特に好ましい。 <Chain transfer agent>
The colored curable composition of the present invention may contain a chain transfer agent. Examples of the chain transfer agent include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, N -Heterocycles such as phenylmercaptobenzimidazole, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione And an aliphatic polyfunctional mercapto compound such as pentaerythritol tetrakis (3-mercaptobutyrate) and 1,4-bis (3-mercaptobutyryloxy) butane.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
The content of the chain transfer agent is preferably 0.01 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, and preferably 0.1 to 10% by mass is more preferable, and 0.5 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（または、水素授与）、エネルギー供与（または、エネルギー授与）、電子供与（または、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、０．０００１～５質量％が好ましく、０．００１～５質量％がより好ましく、０．００１～１質量が特に好ましい。 <Polymerization inhibitor>
The colored curable composition of the present invention may contain a polymerization inhibitor. A 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 composition by light or heat. ) And the like, inactivate the polymerization initiating species, and play a role of suppressing unintentional initiation of polymerization. The polymerization inhibitors described in paragraphs 0154 to 0173 of JP 2007-334322 A 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 from 0.0001 to 5% by mass, more preferably from 0.001 to 5% by mass, based on the total mass of the polymerizable compound. 001 to 1 mass is particularly preferred.
＜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、基材となる無機物、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、チオール系化合物等が挙げられる。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種単独または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に対して、０．１～２０質量％が好ましく、０．２～５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 is a compound that improves the adhesion between a cured film and an inorganic substance serving as a substrate, for example, a silicon compound such as glass, silicon, silicon oxide, or silicon nitride, gold, copper, aluminum, or the like. Specific examples include silane coupling agents and thiol compounds. 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 to 20% by mass, more preferably 0.2 to 5% by mass with respect to the total solid content of the colored curable composition. .
＜現像促進剤＞
　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 be added in order to promote alkali solubility in the non-exposed area and 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、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、凝集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>
The colored curable composition of the present invention may contain various additives, for example, a filler, a polymer compound other than the above, an ultraviolet absorber, an anti-aggregation agent, and the like, if necessary. 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 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０．０１～３．０μｍ、より好ましくは孔径０．０５～０．５μｍ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 composition.
The colored curable composition prepared as described above is preferably filtered using a filter having a pore diameter of 0.01 to 3.0 μm, more preferably a pore diameter of about 0.05 to 0.5 μm. Can be used for use.
　本発明の着色硬化性組成物は、色相およ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（ＬＣＤ）や固体撮像素子（例えば、ＣＣＤ、ＣＭＯＳ等）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、およ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。特に、液晶表示装置用の着色画素形成用途に好適である。 Since the colored curable composition of the present invention can form a colored cured film excellent in hue and contrast, a color filter used in a liquid crystal display (LCD) or a solid-state imaging device (for example, CCD, CMOS, etc.) It can be suitably used for forming colored pixels such as printing inks, inkjet inks, and paints. In particular, it is suitable for use in forming colored pixels for liquid crystal display devices.
［着色硬化膜］
　本発明の着色硬化性組成物は、カラーフィルタの着色層形成用着色硬化性組成物であることが好ましい。また、本発明は、上述した着色硬化性組成物を硬化させることで形成される着色硬化膜に関するものでもある。カラーフィルタは、着色硬化膜を有する。 [Colored cured film]
The colored curable composition of the present invention is preferably a colored curable composition for forming a colored layer of a color filter. The present invention also relates to a colored cured film formed by curing the above-described colored curable composition. The color filter has a colored cured film.
［カラーフィルタおよびその製造方法］
　本発明のカラーフィルタは、基板と、上記基板上に本発明の着色硬化性組成物からなる着色領域とを設けて構成されたものである。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）等の着色膜で構成されている。 [Color filter and manufacturing method thereof]
The color filter of the present invention is configured by providing a substrate and a colored region made of the colored curable composition of the present invention on the substrate. The colored region on the substrate is composed of colored films 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、支持体上に本発明の着色硬化性組成物を塗布し、着色層（着色硬化性組成物層ともいう。）を形成する工程（Ａ）と、着色硬化性組成物層を硬化させて着色硬化膜を形成する工程とを有し、下記（ａ）工程または（ｂ）工程を有する。
（ａ）着色硬化膜上にフォトレジスト層を形成する工程と、露光および現像することによりフォトレジスト層をパターニングしてレジストパターンを得る工程とを含む工程；
（ｂ）着色硬化膜をドライエッチングしてレジストパターンを得る工程。 The method for producing a color filter of the present invention comprises a step (A) of applying a colored curable composition of the present invention on a support to form a colored layer (also referred to as a colored curable composition layer), and colored curing. And a step of forming a colored cured film by curing the conductive composition layer, and includes the following step (a) or step (b).
(A) including a step of forming a photoresist layer on the colored cured film and a step of patterning the photoresist layer by exposure and development to obtain a resist pattern;
(B) A step of dry etching the colored cured film to obtain a resist pattern.
　また、本発明のカラーフィルタの製造方法は、支持体上に本発明の着色硬化性組成物を塗布し、着色層（着色硬化性組成物層ともいう。）を形成する工程（Ａ）と、工程（Ａ）にて形成された着色硬化性組成物層をパターン状に露光し、現像して着色領域（着色パターン）を形成する工程（Ｂ）とを設けて構成されてもよい。また、本発明のカラーフィルタの製造方法では、特に、工程（Ｂ）で形成された着色パターンに対して紫外線を照射する工程（Ｃ）と、工程（Ｃ）で紫外線が照射された着色パターンに対して加熱処理を行なう工程（Ｄ）とをさらに設けた態様が好ましい。
　また、本発明のカラーフィルタの製造方法は、上述した本発明の着色硬化性組成物を支持体上に適用して着色硬化性組成物層を形成する工程と、上記着色硬化性組成物層をパターン状に露光する工程と、未露光部を現像除去して着色パターンを形成する工程とを含むことも好ましい。
　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。 Moreover, the manufacturing method of the color filter of this invention apply | coats the colored curable composition of this invention on a support body, and forms the colored layer (it is also called a colored curable composition layer) (A), The colored curable composition layer formed in the step (A) may be exposed to a pattern and developed to form a colored region (colored pattern) (B). In the method for producing a color filter of the present invention, in particular, the step (C) of irradiating the colored pattern formed in the step (B) with ultraviolet rays and the colored pattern irradiated with the ultraviolet rays in the step (C) are applied. On the other hand, the aspect which further provided the process (D) which heat-processes is preferable.
The method for producing a color filter of the present invention comprises a step of applying the above-described colored curable composition of the present invention on a support to form a colored curable composition layer, and the above colored curable composition layer. It is also preferable to include a step of exposing in a pattern and a step of developing and removing unexposed portions to form a colored pattern.
Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically.
－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塗布して着色硬化性組成物層を形成し、その後、上記着色硬化性組成物層を加熱（プリベーク）または真空乾燥などで乾燥させる。 -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 curable composition layer, and then the colored curable composition layer is dried by heating (prebaking) or vacuum drying.
　支持体としては、例えば、液晶表示装置等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、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 for liquid crystal display devices and the like. Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten 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、０．５～１５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硬化性組成物層の厚みは、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、０．２～５．０μｍの範囲が好ましく、１．０～４．０μｍの範囲がさらに好ましい。また、固体撮像素子用カラーフィルタにおいては、０．２～５．０μｍの範囲が好ましく、０．３～２．５μｍの範囲がさらに好ましい。なお、着色硬化性組成物層の厚みは、乾燥後の膜厚である。 Examples of the pre-baking conditions include 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 curable composition layer formed from the colored curable composition is appropriately selected according to the purpose. In the color filter for liquid crystal display devices, the range of 0.2 to 5.0 μm is preferable, and the range of 1.0 to 4.0 μm is more preferable. In the color filter for a solid-state image sensor, the range of 0.2 to 5.0 μm is preferable, and the range of 0.3 to 2.5 μm is more preferable. In addition, the thickness of a colored curable composition layer is a film thickness after drying.
－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硬化性組成物層に対して、パターン露光が行なわれる。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、５～５００ｍＪ／ｃｍ２の露光量で照射することが好ましい。 -Process (B)-
Then, in the manufacturing method of the color filter of this invention, pattern exposure is performed with respect to the colored curable composition layer formed on the support body. 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 i-line is used for irradiation light, it is preferable to irradiate with an exposure amount of 5 to 500 mJ / 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３００～４１０ｎｍ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３００～３６０ｎｍ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、１～１００ｍＪ／ｃｍ２の範囲が好ましく、１～５０ｍＪ／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 in the range of 300 to 410 nm, more preferably in the range of 300 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 amount is preferably in the range of 1 to 100 mJ / cm 2 from the viewpoint of productivity, and more preferably in the range of 1 to 50 mJ / cm 2 .
　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. In addition, devices other than those described above are also preferably used.
　続いて、露光後の着色硬化性組成物層に対して、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、着色硬化性組成物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となるように調整するのがよい。上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。
　現像時間は、３０～３００秒が好ましく、さらに好ましくは３０～１２０秒である。現像温度は、２０～４０℃が好ましく、さらに好ましくは２３℃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。 Subsequently, the colored curable composition 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 curable composition 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.
The development time is preferably 30 to 300 seconds, more preferably 30 to 120 seconds. The development temperature is preferably 20 to 40 ° C, more preferably 23 ° 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.
－工程（Ｃ）－
　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できる。 -Process (C)-
In the method for producing a color filter of the present invention, in particular, a post-exposure by ultraviolet irradiation can be performed on a colored pattern (pixel) formed using a colored curable composition.
－工程（Ｄ）－
　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、着色パターンをさら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、さらに好ましくは、１５０～２５０℃である。また、加熱時間は、１０～１２０分程度が好ましい。 -Process (D)-
It is preferable to further heat-treat the colored pattern that has been post-exposed by ultraviolet irradiation as described above. The colored pattern can be further cured by subjecting the formed colored pattern to heat treatment (so-called post-bake treatment). 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 to 300 ° C., more preferably 150 to 250 ° C. The heating time is preferably about 10 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）、および必要に応じて工程（Ｃ）や工程（Ｄ）を所望の色数に合わせて繰り返せばよい。
　なお、単色の着色硬化性組成物層の形成、露光、現像が終了する毎に（１色毎に）、上記工程（Ｃ）および工程（Ｄ）の少なくともいずれかを行なってもよいし、所望の色数の全ての着色硬化性組成物層の形成、露光、現像が終了した後に、一括して上記工程（Ｃ）および工程（Ｄ）の少なくともいずれかを行なってもよい。 The colored pattern thus obtained constitutes a pixel in the color filter. In the production of a color filter having a plurality of hue pixels, the above steps (A), (B), and if necessary, the steps (C) and (D) are repeated according to the desired number of colors. Good.
Each time the formation, exposure, and development of the monochromatic colored curable composition layer are completed (for each color), at least one of the above step (C) and step (D) may be performed. After the formation, exposure, and development of all the colored curable composition layers having the number of colors are completed, at least one of the step (C) and the step (D) may be performed collectively.
　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、耐熱性に優れ、カラーフィルタを有する素子は電圧保持に優れている。さらに、本発明のカラーフィルタは、色相およびコントラストに優れている。液晶表示装置に用いた場合、良好な色相を達成しながら、分光特性およびコントラストに優れた画像の表示が可能になる。 Since the color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) uses the colored curable composition of the present invention, the color filter is excellent in heat resistance, and the element having the color filter is a voltage. Excellent retention. Furthermore, the color filter of the present invention is excellent in hue and contrast. When used in a liquid crystal display device, it is possible to display an image having excellent spectral characteristics and contrast while achieving a good hue.
　なお、本発明のカラーフィルタにおける着色パターン（着色画素）の膜厚としては、３．０μｍ以下が好ましく、２．５μｍ以下がより好ましい。 In addition, as a film thickness of the colored pattern (colored pixel) in the color filter of the present invention, 3.0 μm or less is preferable, and 2.5 μm or less is more preferable.
［画像表示装置］
　本発明のカラーフィルタは、液晶表示装置や有機ＥＬ（Ｅｌｅｃｔｒｏ－Ｌｕｍｉｎｅｓｃｅｎｃｅ）表示装置などの、画像表示装置に用いることができ、特に液晶表示装置の用途に好適である。本発明のカラーフィルタを備えた液晶表示装置は、表示画像の色合いが良好で表示特性に優れた高画質画像を表示することができる。
　本発明の画像表示装置は、赤色、緑色および青色の少なくとも３色のカラーフィルタを有し、青色のカラーフィルタが、上述した着色硬化性組成物を用いていることが好ましい。 [Image display device]
The color filter of the present invention can be used in an image display device such as a liquid crystal display device or an organic EL (Electro-Luminescence) display device, and is particularly suitable for use in a liquid crystal display device. The liquid crystal display device provided with the color filter of the present invention can display a high-quality image with a good display image color and excellent display characteristics.
The image display device of the present invention preferably has at least three color filters of red, green and blue, and the blue color filter preferably uses the above-described colored curable composition.
　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。 For the definition of liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)”, “Display Device (Junsho Ibuki, Sangyo Tosho) Issued in 1989). The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 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（薄膜トランジスタ）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。さらに、本発明はＩＰＳ（Ｉｎ　Ｐｌａｎｅ　Ｓｗｉｔｃｈｉｎｇ）などの横電界駆動方式、ＭＶＡ（Ｍｕｌｔｉ－ｄｏｍａｉｎ　Ｖｅｒｔｉｃａｌ　Ａｌｉｇｎｍｅｎｔ）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（Ｓｕｐｅｒ－Ｔｗｉｓｔ　Ｎｅｍａｔｉｃ）、ＴＮ（ｔｗｉｓｔｅｄ　ｎｅｍａｔｉｃ）、ＶＡ（Ｖｅｒｔｉｃａｌ　Ａｌｉｇｎｍｅｎｔ）、ＯＣＳ（Ｏｎ－Ｃｈｉｐ　Ｓｐａｃｅｒ）、ＦＦＳ（Ｆｒｉｎｇｅ　Ｆｉｅｌｄ　Ｓｗｉｔｃｈｉｎｇ）、およびＲ－ＯＣＢ（Ｒｅｆｌｅｃｔｉｖｅ　Ｏｐｔｉｃａｌｌｙ　Ｃｏｍｐｅｎｓａｔｅｄ　Ｂｅｎｄ）等にも適用できる。
　また、本発明のカラーフィルタは、明るく高精細な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 (thin film transistor) type 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 relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), a STN (Super-Twist Nematic). ), TN (twisted nematic), VA (Vertical Alignment), OCS (On-Chip Spacer), FFS (Fringe Field Switching), and R-OCB (Reflective Optical Compensation).
The color filter of the present invention can also be used for a bright and high-definition COA (Color-filter On Array) system.
　本発明のカラーフィルタを液晶表示素子に用いると、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、さらに、赤、緑、青のＬＥＤ光源（ＲＧＢ－ＬＥＤ（Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ））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 element, 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 Light Emitting Diode)) as a backlight, a liquid crystal display device with high luminance and high color purity and good color reproducibility can be provided.
［固体撮像素子］
　本発明の着色硬化性組成物は、固体撮像素子用途としても好ましく用いることができる。固体撮像素子の構成としては、本発明の着色硬化性組成物を用いて製造されたカラーフィルタが備えられた構成であり、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。 [Solid-state imaging device]
The colored curable composition of the present invention can be preferably used as a solid-state imaging device. The configuration of the solid-state imaging device is a configuration provided with a color filter manufactured using the colored curable composition of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. The following configurations are listed.
　支持体上に、固体撮像素子（ＣＣＤ（電荷結合素子）イメージセンサ、ＣＭＯＳ（相補型金属酸化膜半導体）イメージセンサ、等）の受光エリアを構成する複数のフォトダイオードおよびポリシリコン等からなる転送電極を有し、上記フォトダイオードおよび上記転送電極上にフォトダイオードの受光部のみ開口したタングステン等からなる遮光膜を有し、遮光膜上に遮光膜全面およびフォトダイオード受光部を覆うように形成された窒化シリコン等からなるデバイス保護膜を有し、上記デバイス保護膜上に、本発明の固体撮像素子用カラーフィルタを有する構成である。
　更に、上記デバイス保護膜上であってカラーフィルタの下（支持体に近い側）に集光手段（例えば、マイクロレンズ等。以下同じ）を有する構成や、カラーフィルタ上に集光手段を有する構成等であってもよい。 A transfer electrode composed of a plurality of photodiodes, polysilicon, and the like constituting a light receiving area of a solid-state imaging device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) on a support. A light-shielding film made of tungsten or the like that is open only on the light-receiving part of the photodiode on the photodiode and the transfer electrode, and is formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part. The device has a device protective film made of silicon nitride or the like, and has the color filter for a solid-state imaging device of the present invention on the device protective film.
Further, a configuration having light collecting means (for example, a microlens, etc., the same applies hereinafter) on the device protective film and below the color filter (on the side close to the support), or a structure having the light collecting means on the color filter. Etc.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。なお、特に断りのない限り、「％」および「部」は質量基準である。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass.
＜合成例１＞
（ＴＡＭ００１の合成）
　４，４’－ジクロロベンゾフェノン（東京化成工業株式会社製）１２．５ｇ、２，４，６－トリメチルアニリン（東京化成工業株式会社製）１５．０ｇ、ｔｅｒｔ－ブトキシナトリウム１４．４ｇ、トルエン１５０ｍＬをフラスコに入れ、窒素雰囲気下において、室温で撹拌した。ここに、酢酸パラジウム（和光純薬工業株式会社製）５６ｍｇ、トリ－ｔｅｒｔ－ブチルホスホニウムテトラフルオロボラート（和光純薬工業株式会社製）２６６ｍｇを加えた後、加熱還流条件下で４時間撹拌した。冷却後、酢酸エチル２００ｍＬと水２００ｍＬを加えて、析出した結晶を濾取した。結晶を酢酸エチル１００ｍＬで加熱洗浄した後、得られたＴＡＭ００１－Ａの結晶８．０ｇを濾取した。 <Synthesis Example 1>
(Synthesis of TAM001)
4,4′-dichlorobenzophenone (Tokyo Chemical Industry Co., Ltd.) 12.5 g, 2,4,6-trimethylaniline (Tokyo Chemical Industry Co., Ltd.) 15.0 g, tert-butoxy sodium 14.4 g, toluene 150 mL Placed in flask and stirred at room temperature under nitrogen atmosphere. To this, 56 mg of palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and 266 mg of tri-tert-butylphosphonium tetrafluoroborate (manufactured by Wako Pure Chemical Industries, Ltd.) were added, followed by stirring for 4 hours under heating and reflux conditions. . After cooling, 200 mL of ethyl acetate and 200 mL of water were added, and the precipitated crystals were collected by filtration. The crystals were heated and washed with 100 mL of ethyl acetate, and 8.0 g of the obtained TAM001-A crystals were collected by filtration.
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
　ＴＡＭ００１－Ａ　２．６ｇ、水素化ナトリウム（オイル混合物、６０質量％含有、東京化成工業株式会社製）０．６３ｇ、Ｎ－メチルピロリドン２５ｍＬの混合溶液に、１－ヨウ化プロパン（関東化学社製）１４ｇを室温で滴下した。滴下後の溶液を７５℃で２時間撹拌した。反応溶液を室温まで冷却後、水１００ｍＬを加えた。塩酸にて溶液のｐＨを６～７にした後、析出した粗結晶をろ過した。粗結晶をｎ－ヘキサンで懸濁洗浄し、ＴＡＭ００１－Ｂの結晶２．０ｇを得た。 TAM001-A 2.6 g, sodium hydride (oil mixture, 60% by mass, Tokyo Chemical Industry Co., Ltd.) 0.63 g, N-methylpyrrolidone 25 mL mixed solution with 1-iodopropane (Kanto Chemical Co., Ltd.) ) 14 g was added dropwise at room temperature. The solution after dropping was stirred at 75 ° C. for 2 hours. After cooling the reaction solution to room temperature, 100 mL of water was added. The pH of the solution was adjusted to 6-7 with hydrochloric acid, and the precipitated crude crystals were filtered. The crude crystals were suspended and washed with n-hexane to obtain 2.0 g of TAM001-B crystals.
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000069
　１－アミノナフタレン５０ｇ、１，２－エポキシシクロヘキサン３８ｇ、１，３－ヘキサフロオロ－２－プロパノール１５０ｍＬをフラスコに加え、加熱還流下で５時間撹拌した。室温まで冷却後、溶媒を濃縮し、ヘキサン２００ｍＬで加熱懸濁洗浄し、得られた結晶をろ過、イソプロピルアルコールでさらに洗浄し、ＴＡＭ００１－Ｃ（５６ｇ）を得た。 50 g of 1-aminonaphthalene, 38 g of 1,2-epoxycyclohexane, and 150 mL of 1,3-hexafluoro-2-propanol were added to the flask, and the mixture was stirred for 5 hours under reflux with heating. After cooling to room temperature, the solvent was concentrated, washed with suspension by heating with 200 mL of hexane, and the resulting crystals were filtered and further washed with isopropyl alcohol to obtain TAM001-C (56 g).
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000070
　ＴＡＭ００１－Ｃ（６０ｇ）、トリエチルアミン３８ｇ、アセトニトリル３００ｍＬ、テトラヒドロフラン５０ｍＬをフラスコに入れ、氷水で冷却しながら、アクリル酸クロリド３２ｇを内温が５度を越えぬよう滴下した。２時間氷冷しながら撹拌した後、溶媒を濃縮除去し、水と酢酸エチルを加えて抽出し、得られた有機層を濃縮してシリカゲルカラムクロマトグラフィーで精製し、ＴＡＭ００１－Ｄを４４ｇ得た。 TAM001-C (60 g), 38 g of triethylamine, 300 mL of acetonitrile, and 50 mL of tetrahydrofuran were placed in a flask, and while cooling with ice water, 32 g of acrylic acid chloride was added dropwise so that the internal temperature did not exceed 5 degrees. After stirring for 2 hours while cooling with ice, the solvent was concentrated and removed, water and ethyl acetate were added for extraction, and the resulting organic layer was concentrated and purified by silica gel column chromatography to obtain 44 g of TAM001-D. .
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000071
　ＴＡＭ００１－Ｂ（５．３質量部）、ＴＡＭ００１－Ｄ（３．４質量部）、オキシ塩化リン（３．１質量部）、トルエン（５０質量部）の混合溶液を９０℃で３時間加熱撹拌した。反応液にヘキサン（１００質量部）を加え、上澄み液をデカンテーションにより除去した。次いで、メタノール（１００質量部）、リチウムビストリフルオロメタンスルホニルイミド（５質量部）を加え、溶解させた。この溶液に、水（２００質量部）を加え、粗体を得た。得られた粗体をシリカゲルカラムクロマトグラフィーにより精製することで、ＴＡＭ００１を４．８質量部得た。吸収スペクトルのλｍａｘ（酢酸エチル溶液）は５８７ｎｍ、ε（酢酸エチル溶液）は６５０００であった。 A mixed solution of TAM001-B (5.3 parts by mass), TAM001-D (3.4 parts by mass), phosphorus oxychloride (3.1 parts by mass), and toluene (50 parts by mass) is heated and stirred at 90 ° C. for 3 hours. did. Hexane (100 parts by mass) was added to the reaction solution, and the supernatant was removed by decantation. Subsequently, methanol (100 parts by mass) and lithium bistrifluoromethanesulfonylimide (5 parts by mass) were added and dissolved. Water (200 parts by mass) was added to this solution to obtain a crude product. The obtained crude product was purified by silica gel column chromatography to obtain 4.8 parts by mass of TAM001. In the absorption spectrum, λmax (ethyl acetate solution) was 587 nm, and ε (ethyl acetate solution) was 65000.
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000072
（ＴＡＭ００２の合成）
　ＴＡＭ００１と同様の手法でＴＡＭ００２を合成した。 (Synthesis of TAM002)
TAM002 was synthesized by the same method as TAM001.
Figure JPOXMLDOC01-appb-C000073
Figure JPOXMLDOC01-appb-C000073
（ＴＡＭ００３の合成）
　ＴＡＭ００１と同様の手法で下記ルートに従いＴＡＭ００３を合成した。吸収スペクトルのλｍａｘ（酢酸エチル溶液）は、５８０ｎｍ、ε（酢酸エチル溶液）は７７０００であった。 (Synthesis of TAM003)
TAM003 was synthesized according to the following route in the same manner as TAM001. Λmax (ethyl acetate solution) of the absorption spectrum was 580 nm, and ε (ethyl acetate solution) was 77000.
Figure JPOXMLDOC01-appb-C000074
Figure JPOXMLDOC01-appb-C000074
（ＴＡＭ００４の合成）
　ＴＡＭ００１と同様の手法で下記ルートに従いＴＡＭ００４を合成した。吸収スペクトルのλｍａｘ（酢酸エチル溶液）は、５７９ｎｍ、ε（酢酸エチル溶液）は７８０００であった。 (Synthesis of TAM004)
TAM004 was synthesized according to the following route in the same manner as TAM001. The absorption spectrum had a λmax (ethyl acetate solution) of 579 nm and ε (ethyl acetate solution) of 78000.
Figure JPOXMLDOC01-appb-C000075
Figure JPOXMLDOC01-appb-C000075
（ＴＡＭ００５の合成）
　ＴＡＭ００４と同様の手法でＴＡＭ００５を合成した。 (Synthesis of TAM005)
TAM005 was synthesized by the same method as TAM004.
Figure JPOXMLDOC01-appb-C000076
Figure JPOXMLDOC01-appb-C000076
（ＴＡＭ００６の合成）
　ＴＡＭ００１と同様の手法で下記ルートに従いＴＡＭ００６を合成した。吸収スペクトルのλｍａｘ（酢酸エチル溶液）は、５８０ｎｍ、ε（酢酸エチル溶液）は８００００であった。 (Synthesis of TAM006)
TAM006 was synthesized according to the following route in the same manner as TAM001. In the absorption spectrum, λmax (ethyl acetate solution) was 580 nm, and ε (ethyl acetate solution) was 80000.
Figure JPOXMLDOC01-appb-C000077
Figure JPOXMLDOC01-appb-C000077
（ＴＡＭ００７の合成）
　ＴＡＭ００１と同様の手法で下記ルートに従いＴＡＭ００７を合成した。吸収スペクトルのλｍａｘ（酢酸エチル溶液）は、５７９ｎｍ、ε（酢酸エチル溶液）は７８０００であった。 (Synthesis of TAM007)
TAM007 was synthesized according to the following route in the same manner as TAM001. The absorption spectrum had a λmax (ethyl acetate solution) of 579 nm and ε (ethyl acetate solution) of 78000.
Figure JPOXMLDOC01-appb-C000078
Figure JPOXMLDOC01-appb-C000078
（ＴＡＭ００８の合成）
　ＴＡＭ００１と同様の手法で下記ルートに従いＴＡＭ００８を合成した。吸収スペクトルのλｍａｘ（酢酸エチル溶液）は、５７８ｎｍ、ε（酢酸エチル溶液）は７９０００であった。 (Synthesis of TAM008)
TAM008 was synthesized according to the following route in the same manner as TAM001. Λmax (ethyl acetate solution) of the absorption spectrum was 578 nm, and ε (ethyl acetate solution) was 79000.
Figure JPOXMLDOC01-appb-C000079
Figure JPOXMLDOC01-appb-C000079
（ＴＡＭ００９の合成）
　ＴＡＭ００１と同様の手法で下記ルートに従いＴＡＭ００９を合成した。吸収スペクトルのλｍａｘ（酢酸エチル溶液）は、５７８ｎｍ、ε（酢酸エチル溶液）は７７０００であった。 (Synthesis of TAM009)
TAM009 was synthesized according to the following route in the same manner as TAM001. In the absorption spectrum, λmax (ethyl acetate solution) was 578 nm, and ε (ethyl acetate solution) was 77000.
Figure JPOXMLDOC01-appb-C000080
Figure JPOXMLDOC01-appb-C000080
（ＴＡＭ０１０の合成）
　ＴＡＭ００１と同様の手法で下記ルートに従いＴＡＭ０１０を合成した。吸収スペクトルのλｍａｘ（酢酸エチル溶液）は、５７７ｎｍ、ε（酢酸エチル溶液）は８００００であった。 (Synthesis of TAM010)
TAM010 was synthesized according to the following route in the same manner as TAM001. In the absorption spectrum, λmax (ethyl acetate solution) was 777 nm, and ε (ethyl acetate solution) was 80000.
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000081
（ＴＡＭ０１１の合成）
　ＴＡＭ００１と同様の手法で下記ルートに従いＴＡＭ０１１を合成した。吸収スペクトルのλｍａｘ（酢酸エチル溶液）は、５８０ｎｍ、ε（酢酸エチル溶液）は７９０００であった。 (Synthesis of TAM011)
TAM011 was synthesized according to the following route in the same manner as TAM001. In the absorption spectrum, λmax (ethyl acetate solution) was 580 nm, and ε (ethyl acetate solution) was 79000.
Figure JPOXMLDOC01-appb-C000082
Figure JPOXMLDOC01-appb-C000082
（ＴＡＭ００４Ｐの合成）
　窒素雰囲気下、メチルエチルケトン３０ｇを入れ７０℃に加熱した。この溶液にＴＡＭ００４　１７．９ｇ、メタクリル酸０．２６ｇ、シクロヘキシルメタクリレート
０．５ｇおよびＡＩＢＮ（０．１６ｇ）のメチルエチルケトン２０ｍＬ溶液を３時間かけて滴下した。滴下終了後１５時間攪拌し、メチルエチルケトンを濃縮後、ヘキサンに反応液を投入した。得られた個体を乾固することでＴＡＭ００４Ｐを得た。 (Synthesis of TAM004P)
Under a nitrogen atmosphere, 30 g of methyl ethyl ketone was added and heated to 70 ° C. To this solution, 17.9 g of TAM004, 0.26 g of methacrylic acid, 0.5 g of cyclohexyl methacrylate and 20 mL of methyl ethyl ketone in AIBN (0.16 g) were added dropwise over 3 hours. After completion of the dropwise addition, the mixture was stirred for 15 hours. After concentrating methyl ethyl ketone, the reaction solution was added to hexane. The obtained solid was dried to obtain TAM004P.
Figure JPOXMLDOC01-appb-C000083
Figure JPOXMLDOC01-appb-C000083
（ＴＡＭ００５Ｐの合成）
　ＴＡＭ００４Ｐの合成と同様の手法でＴＡＭ００５Ｐを合成した。 (Synthesis of TAM005P)
TAM005P was synthesized in the same manner as TAM004P.
Figure JPOXMLDOC01-appb-C000084
Figure JPOXMLDOC01-appb-C000084
（ＴＡＭ００６Ｐの合成）
　ＴＡＭ００４Ｐの合成と同様の手法でＴＡＭ００６Ｐを合成した。 (Synthesis of TAM006P)
TAM006P was synthesize | combined by the method similar to the synthesis | combination of TAM004P.
Figure JPOXMLDOC01-appb-C000085
Figure JPOXMLDOC01-appb-C000085
（Ｄｙｅ００１（キサンテン染料）の合成）
　本発明で用いるＤｙｅ００１の中間体およびＤｙｅ００１は、特許２０１３－１４４７２４号公報の段落０１５９、特許２０１３－１１６９５５号公報の段落００６２～００６４に記載の合成法を用いて合成することができる。下記キサンテン染料Ａに対し、水素化ナトリウム存在下、臭化プロピルを用いてプロピル基を導入することでキサンテン染料１－３２を得た。Ｄｙｅ００１のメタノール中でのモル吸光係数は６８，０００であり、最大吸収波長は５６７ｎｍであった。 (Synthesis of Dye001 (xanthene dye))
The intermediate of Dye001 and Dye001 used in the present invention can be synthesized using the synthesis method described in paragraph 0159 of JP2013-144724A and paragraphs 0062 to 0064 of JP2013-116955A. The xanthene dye 1-32 was obtained by introducing a propyl group into the following xanthene dye A using propyl bromide in the presence of sodium hydride. The molar extinction coefficient of Dye001 in methanol was 68,000, and the maximum absorption wavelength was 567 nm.
Figure JPOXMLDOC01-appb-C000086
Figure JPOXMLDOC01-appb-C000086
（Ｄｙｅ００２（ジピロメテン系金属錯体化合物）の合成）
　Ｄｙｅ００２は、特開２００８－２９２９７０号公報の段落番号０１３１～０１５７に記載のジピロメテン系金属錯体化合物の合成方法によって合成できる。 (Synthesis of Dye002 (dipyrromethene metal complex compound))
Dye002 can be synthesized by a method for synthesizing a dipyrromethene metal complex compound described in paragraphs 0131 to 0157 of JP-A-2008-292970.
Figure JPOXMLDOC01-appb-C000087
Figure JPOXMLDOC01-appb-C000087
（ＴＡＭ０１２の合成）
　ＴＡＭ０１２は以下のルートにしたがって合成した。 (Synthesis of TAM012)
TAM012 was synthesized according to the following route.
Figure JPOXMLDOC01-appb-C000088
Figure JPOXMLDOC01-appb-C000088
（合成中間体（化合物３）の合成）
　化合物１（１－ナフチルアミン）１７．０ｇ（１１８．８ｍｍｏｌ）と１，２－エポキシシクロヘキサン１１．６５ｇ（１１８．７ｍｍｏｌ）をヘキサフルオロイソプロパノール５０ｍＬに溶解させた後、５時間加熱還流した。反応終了を確認後、酢酸エチル５０ｍＬおよび水、食塩水により目的物を有機層に抽出および洗浄後、濃縮させた。この粗生成物をヘキサンで溶解、再結晶させた後、ろ過することで化合物３を１９．２ｇ得た（収率６７％）。 (Synthesis of Synthetic Intermediate (Compound 3))
17.0 g (118.8 mmol) of Compound 1 (1-naphthylamine) and 11.65 g (118.7 mmol) of 1,2-epoxycyclohexane were dissolved in 50 mL of hexafluoroisopropanol, and then heated to reflux for 5 hours. After confirming the completion of the reaction, the target compound was extracted into an organic layer with 50 mL of ethyl acetate, water and brine, and then concentrated. This crude product was dissolved in hexane, recrystallized, and then filtered to obtain 19.2 g of Compound 3 (yield 67%).
（合成中間体（化合物４）の合成）
　化合物３（２．４ｇ（１０ｍｍｏｌ））、およびトリエチルアミン１．５ｇ（１５ｍｍｏｌ）をＴＨＦ１０ｍＬに溶解させた。この溶液を０℃に冷却後メタクリル酸クロライド１．１５ｇ（１１ｍｏｌ）を滴下した。反応完了を確認後酢酸エチル２０ｍＬおよび水、食塩水により目的物を有機層に抽出および洗浄後濃縮した。この粗生成物をカラムクロマトグラフィーにより精製することで化合物４を１．８ｇ得た（収率５８％）。 (Synthesis of Synthetic Intermediate (Compound 4))
Compound 3 (2.4 g (10 mmol)) and 1.5 g (15 mmol) of triethylamine were dissolved in 10 mL of THF. After the solution was cooled to 0 ° C., 1.15 g (11 mol) of methacrylic acid chloride was added dropwise. After confirming the completion of the reaction, the target product was extracted into an organic layer with 20 mL of ethyl acetate, water and brine, concentrated after washing. This crude product was purified by column chromatography to obtain 1.8 g of Compound 4 (yield 58%).
（ＴＡＭ１１２の合成）
　化合物４（１．９ｇ（５．８ｍｍｏｌ））、化合物５（１．８ｇ（５．８ｍｍｏｌ））、オキシ塩化リン１．０ｇ（６．４ｍｍｏｌ）をトルエン６ｍＬに溶解し、９０℃に加温して１時間撹拌した。反応終了を確認後、この溶液に酢酸エチル１０ｍＬを加え目的物を上澄みとして取り出す操作を３回繰り返し、化合物６を酢酸エチル溶液として取り出した。この溶液に別途調製したビストリフルオロメタンスルホンイミドリチウム塩２．０ｇ（７．０ｍｍｏｌ）のメタノール２０ｍＬ溶液を添加した。塩交換反応が完了したことを確認後、水５０ｍＬを添加し、化合物を酢酸エチル層に抽出・濃縮後、カラムクロマトグラフィーにより精製することで目的化合物ＴＡＭ１１２を１．７ｇ（３３％）得た。
１Ｈ　ＮＭＲ（ＣＨＣｌ３）　：１．２５（ｍ，１６Ｈ）、１．８（ｓ，３Ｈ）、３．６（ｔ，８Ｈ）、３．７５（ｂｓ，１Ｈ）、５．２（ｄｔ，１Ｈ）、５．５５（ｓ，１Ｈ）、６．１（ｓ，１Ｈ）、６．２（ｄ，１Ｈ）、６．７５（ｄ，４Ｈ）、７．２－７．５（ｍ，９Ｈ）、７．８（ｄ，１Ｈ） (Synthesis of TAM112)
Compound 4 (1.9 g (5.8 mmol)), compound 5 (1.8 g (5.8 mmol)), and phosphorus oxychloride 1.0 g (6.4 mmol) were dissolved in 6 mL of toluene and heated to 90 ° C. And stirred for 1 hour. After confirming the completion of the reaction, the operation of adding 10 mL of ethyl acetate to this solution and taking out the target product as a supernatant was repeated three times, and compound 6 was taken out as an ethyl acetate solution. A separately prepared bistrifluoromethanesulfonimide lithium salt 2.0 g (7.0 mmol) in methanol 20 mL was added to this solution. After confirming that the salt exchange reaction was completed, 50 mL of water was added, the compound was extracted and concentrated in an ethyl acetate layer, and purified by column chromatography to obtain 1.7 g (33%) of the target compound TAM112.
1 H NMR (CHCl 3 ): 1.25 (m, 16H), 1.8 (s, 3H), 3.6 (t, 8H), 3.75 (bs, 1H), 5.2 (dt, 1H), 5.55 (s, 1H), 6.1 (s, 1H), 6.2 (d, 1H), 6.75 (d, 4H), 7.2-7.5 (m, 9H) ), 7.8 (d, 1H)
（ＴＡＭ０１３の合成）
ＴＡＭ０１２と同様の手法でＴＡＭ０１３を合成した。 (Synthesis of TAM013)
TAM013 was synthesized by the same method as TAM012.
Figure JPOXMLDOC01-appb-C000089
Figure JPOXMLDOC01-appb-C000089
（Ｄｙｅ９０１の合成）
　ＴＡＭ００１－Ａの合成において、２，４，６－トリメチルアニリンの代わりにアニリンを用いたこと以外は同様の方法でＴＡＭ０１６－Ａを合成した。 (Synthesis of Dye901)
TAM016-A was synthesized by the same method except that aniline was used instead of 2,4,6-trimethylaniline in the synthesis of TAM001-A.
Figure JPOXMLDOC01-appb-C000090
Figure JPOXMLDOC01-appb-C000090
　下記の手順に従いＤｙｅ９０１を合成した。 Dye901 was synthesized according to the following procedure.
Figure JPOXMLDOC01-appb-C000091
Figure JPOXMLDOC01-appb-C000091
（Ｄｙｅ９０２の合成）
　Ｃ．Ｉ．ベーシックブルー７を３．６ｇ、ビス（トリフルオロメタンスルホニル）イミドリチウム（東京化成工業株式会社製）５．８ｇ、メタノール３０ｍＬをフラスコに入れ、室温で撹拌し溶解させた。ここに、水１００ｍＬを滴下して析出させた。得られた結晶をシリカゲルカラムクロマトグラフィーで精製することで、Ｄｙｅ９０２の結晶を３．０ｇ得た。 (Synthesis of Dye902)
C. I. 3.6 g of Basic Blue 7, 5.8 g of bis (trifluoromethanesulfonyl) imidolithium (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 mL of methanol were placed in a flask and dissolved by stirring at room temperature. Here, 100 mL of water was dropped and precipitated. The obtained crystals were purified by silica gel column chromatography to obtain 3.0 g of Dye902 crystals.
Figure JPOXMLDOC01-appb-C000092
Figure JPOXMLDOC01-appb-C000092
（Ｄｙｅ９０３の合成）
　ＴＡＭ００１－Ｃ　１．２ｇ、４，４‘-ビス（ジエチルアミノ）ベンゾフェノン　２．２ｇ、塩化ホスホリル１．８４ｇ、トルエン２０ｍＬをフラスコに加えて９０℃で４時間加熱撹拌した。室温まで冷却し、ヘキサン２０ｍＬを加えて、ヘキサン相をデカンテーションで除去し、さらに同じ操作を２回行い、粘性オイルとしてＤｙｅ９０３－Ｃｌを得た。ここにメタノール２０ｍＬを加えて、さらにビス（トリフルオロメタンスルホニル）イミドリチウム３．０ｇを加えて溶解させた。撹拌しながら、ここに水６０ｍＬを滴下した。分離した水相を除去し、得られた粘性オイルをシリカゲルカラムクロマトグラフィーにて精製することで、Ｄｙｅ９０３を２．２ｇ得た。 (Synthesis of Dye903)
1.2 g of TAM001-C, 2.2 g of 4,4′-bis (diethylamino) benzophenone, 1.84 g of phosphoryl chloride and 20 mL of toluene were added to the flask and stirred with heating at 90 ° C. for 4 hours. After cooling to room temperature, 20 mL of hexane was added, the hexane phase was removed by decantation, and the same operation was further performed twice to obtain Dye903-Cl as a viscous oil. 20 mL of methanol was added thereto, and 3.0 g of bis (trifluoromethanesulfonyl) imide lithium was further added and dissolved. While stirring, 60 mL of water was added dropwise thereto. The separated aqueous phase was removed, and the resulting viscous oil was purified by silica gel column chromatography to obtain 2.2 g of Dye903.
Figure JPOXMLDOC01-appb-C000093
Figure JPOXMLDOC01-appb-C000093
（Ｄｙｅ９０４の合成）
　ＴＡＭ００１の合成と同様の方法でＴＡＭ００１－Ｄを４４ｇ得た。 (Synthesis of Dye904)
44 g of TAM001-D was obtained by a method similar to the synthesis of TAM001.
Figure JPOXMLDOC01-appb-C000094
Figure JPOXMLDOC01-appb-C000094
　下記化合物を用いて、Ｄｙｅ９０３と同様の手順でＤｙｅ９０４を合成した。 Dye904 was synthesized in the same procedure as Dye903 using the following compounds.
Figure JPOXMLDOC01-appb-C000095
Figure JPOXMLDOC01-appb-C000095
（Ｄｙｅ９０５の合成）
　国際公開ＷＯ２０１２／１２８３１８Ａ１号公報に記載の化合物Ｄの合成において、Ｎ－エチル－ｐ－トルイジンの代わりにエチルアニリンを用いたこと以外は同様の方法でＤｙｅ９０５－Ａを合成した。ＴＡＭ００１の合成と同様の方法でＴＡＭ００１－Ｄを４合成した。次いで、下記の手順に従いＤｙｅ９０５を合成した。 (Synthesis of Dye905)
In the synthesis of Compound D described in International Publication WO2012 / 128318A1, Dye905-A was synthesized in the same manner except that ethylaniline was used instead of N-ethyl-p-toluidine. Four TAM001-Ds were synthesized in the same manner as the synthesis of TAM001. Next, Dye905 was synthesized according to the following procedure.
Figure JPOXMLDOC01-appb-C000096
Figure JPOXMLDOC01-appb-C000096
（Ｄｙｅ９０６の合成）
　国際公開ＷＯ２０１２／１２８３１８Ａ１号公報に記載の方法を用いて、国際公開ＷＯ２０１２／１２８３１８Ａ１号公報に記載の化合物Ｄを合成した。ＴＡＭ００１の合成と同様の方法でＴＡＭ００１－Ｄを合成した。次いで、下記化合物を用いて、Ｄｙｅ９０３と同様の手順でＤｙｅ９０６を合成した。 (Synthesis of Dye906)
Compound D described in International Publication WO2012 / 128318A1 was synthesized using a method described in International Publication WO2012 / 128318A1. TAM001-D was synthesized by the same method as TAM001 synthesis. Subsequently, Dye906 was synthesize | combined in the same procedure as Dye903 using the following compound.
Figure JPOXMLDOC01-appb-C000097
Figure JPOXMLDOC01-appb-C000097
（Ｄｙｅ９０７の合成）
　下記化合物を用いて、Ｄｙｅ９０３と同様の手順でＤｙｅ９０７を合成した。 (Synthesis of Dye907)
Dye907 was synthesize | combined in the procedure similar to Dye903 using the following compound.
Figure JPOXMLDOC01-appb-C000098
Figure JPOXMLDOC01-appb-C000098
（Ｄｙｅ９０８の合成）
　ＴＡＭ００１－Ａの合成において、２，４，６－トリメチルアニリンの代わりにｐ－トルイジンを用いたこと以外は同様の方法でＤｙｅ００８－Ａを合成した。 (Synthesis of Dye908)
Dye008-A was synthesized by the same method except that p-toluidine was used instead of 2,4,6-trimethylaniline in the synthesis of TAM001-A.
Figure JPOXMLDOC01-appb-C000099
Figure JPOXMLDOC01-appb-C000099
　１－ブロモナフタレン（東京化成工業株式会社製）２９ｇ、ｐ－トルイジン２１ｇ、ｔｅｒｔ－ブトキシナトリウム７．２ｇ、トルエン３００ｍＬをフラスコに入れ、窒素雰囲気下、室温で撹拌した。ここに、酢酸パラジウム（和光純薬工業株式会社製）５６ｍｇ、トリ－ｔｅｒｔ－ブチルホスホニウムテトラフルオロボラート（和光純薬工業株式会社製）２６６ｍｇを加えた後、加熱還流条件下で１時間撹拌した。冷却後、酢酸エチル２００ｍＬと水２００ｍＬを加えて、抽出し、得られた有機相を硫酸ナトリウムで脱水した。濃縮後、シリカゲルカラムクロマトグラフィーで精製することで、Ｄｙｅ００８－Ｂの結晶３７ｇを得た。 1-Bromonaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) 29 g, p-toluidine 21 g, tert-butoxy sodium 7.2 g, and toluene 300 mL were placed in a flask and stirred at room temperature in a nitrogen atmosphere. To this, 56 mg of palladium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) and 266 mg of tri-tert-butylphosphonium tetrafluoroborate (manufactured by Wako Pure Chemical Industries, Ltd.) were added, followed by stirring for 1 hour under heating and refluxing conditions. . After cooling, 200 mL of ethyl acetate and 200 mL of water were added for extraction, and the resulting organic phase was dehydrated with sodium sulfate. After concentration, the residue was purified by silica gel column chromatography to obtain 37 g of Dye008-B crystals.
Figure JPOXMLDOC01-appb-C000100
Figure JPOXMLDOC01-appb-C000100
　下記化合物を用いて、Ｄｙｅ９０３と同様の手順でＤｙｅ９０８を合成した。 Dye908 was synthesized in the same procedure as Dye903 using the following compounds.
Figure JPOXMLDOC01-appb-C000101
Figure JPOXMLDOC01-appb-C000101
　（Ｄｙｅ９０９の合成）
　　国際公開ＷＯ２０１２／１２８３１８Ａ１号公報に記載の染料（４）を、国際公開ＷＯ２０１２／１２８３１８Ａ１号公報の記載に従って合成し、Ｄｙｅ９０９を得た。 (Synthesis of Dye909)
The dye (4) described in International Publication WO2012 / 128318A1 was synthesized according to the description of International Publication WO2012 / 128318A1 to obtain Dye909.
Figure JPOXMLDOC01-appb-C000102
Figure JPOXMLDOC01-appb-C000102
　（Ｄｙｅ９１０の合成）
　　下記化合物を用いて、Ｄｙｅ９０３と同様の手順でＤｙｅ９１０を合成した。 (Synthesis of Dye910)
Dye910 was synthesized in the same procedure as Dye903 using the following compound.
Figure JPOXMLDOC01-appb-C000103
Figure JPOXMLDOC01-appb-C000103
（顔料分散液１の調製）
　顔料分散液１を次のようにして調製した。下記に記載の組成となるように原料を混合し、ホモジナイザーを用いて回転数３，０００ｒ．ｐ．ｍ．で３時間撹拌して、混合溶液を調製した。さらに０．１ｍｍφジルコニアビーズを用いたビーズ分散機ウルトラアペックスミル（寿工業社製）にて８時間分散処理を行なった。ここで、Ｄｉｓｐｅｒｂｙｋ１１０の吸着基はリン酸塩（酸価５３ｍｇＫＯＨ／ｇ）である。
（組成）
・Ｃ．Ｉ．ピグメントブルー１５：６　　　　　　　　　９．７部
・Ｄｉｓｐｅｒｂｙｋ１１０　ビックケミー社製（不揮発分５２％）
　　　　　　　　　　　　　　　　　　　　　　　　　１３．３部
・プロピレングリコールメチルエーテルアセテート（以下、ＰＧＭＥＡと称する。）　　　　　　　　　　　　　　　　　　　　　７７．０部 (Preparation of pigment dispersion 1)
Pigment dispersion 1 was prepared as follows. The raw materials were mixed so that the composition described below was obtained, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. For 3 hours to prepare a mixed solution. Furthermore, the dispersion process was performed for 8 hours with a bead disperser Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) using 0.1 mmφ zirconia beads. Here, the adsorption group of Disperbyk110 is a phosphate (acid value 53 mgKOH / g).
(composition)
・ C. I. Pigment Blue 15: 6 9.7 parts Dispersbyk110 manufactured by Big Chemie (non-volatile content 52%)
13.3 parts propylene glycol methyl ether acetate (hereinafter referred to as PGMEA) 77.0 parts
（顔料分散液２の調製）
　分散剤をＤｉｓｐｅｒｂｙｋ１６２（ビックケミー社製、不揮発分３８％）に変更した以外は顔料分散液１と同様の方法で顔料分散液２を調製した。なお、顔料分散液中の分散剤不揮発分は顔料分散液１と等しくなるようにＰＧＭＥＡの添加量を調整した。ここで、Ｄｉｓｐｅｒｂｙｋ１６２の吸着基はアミン（アミン価１３ｍｇＫＯＨ／ｇ）である。 (Preparation of pigment dispersion 2)
Pigment dispersion 2 was prepared in the same manner as pigment dispersion 1, except that the dispersant was changed to Disperbyk 162 (Bic Chemie, nonvolatile content 38%). The amount of PGMEA added was adjusted so that the non-volatile content of the dispersant in the pigment dispersion was equal to that of the pigment dispersion 1. Here, the adsorption group of Disperbyk162 is an amine (amine value 13 mgKOH / g).
（顔料分散液３の調製）
　分散剤をＤｉｓｐｅｒｂｙｋ１９１（ビックケミー社製、不揮発分９８％）に変更した以外は顔料分散液１と同様の方法で顔料分散液３を調製した。なお、顔料分散液中の分散剤不揮発分は顔料分散液１と等しくなるようにＰＧＭＥＡの添加量を調整した。ここで、Ｄｉｓｐｅｒｂｙｋ１９１の吸着基はカルボン酸吸着基（酸価３０ｍｇＫＯＨ／ｇ）である。 (Preparation of pigment dispersion 3)
Pigment dispersion 3 was prepared in the same manner as pigment dispersion 1 except that the dispersant was changed to Disperbyk 191 (by Big Chemie, non-volatile content 98%). The amount of PGMEA added was adjusted so that the non-volatile content of the dispersant in the pigment dispersion was equal to that of the pigment dispersion 1. Here, the adsorption group of Disperbyk 191 is a carboxylic acid adsorption group (acid value 30 mgKOH / g).
（顔料分散液４の調製）
　顔料分散液４を次のようにして調製した。下記に記載の組成となるように原料を混合し、ホモジナイザーを用いて回転数３，０００ｒ．ｐ．ｍ．で３時間撹拌して、混合溶液を調製した。さらに０．１ｍｍφジルコニアビーズを用いたビーズ分散機ウルトラアペックスミル（寿工業社製）にて８時間分散処理を行なった。ここで、Ｄｉｓｐｅｒｂｙｋ２０００の吸着基は４級アンモニウム（アミン価４ｍｇＫＯＨ／ｇ）である。
（組成）
・Ｃ．Ｉ．ピグメントブルー１５：６　　　　　　　　　９．７部
・Ｄｉｓｐｅｒｂｙｋ２０００　ビックケミー社製（不揮発分４０％）
　　　　　　　　　　　　　　　　　　　　　　　　　１７．３部
・プロピレングリコールメチルエーテルアセテート（ＰＧＭＥＡ）
　　　　　　　　　　　　　　　　　　　　　　　　　７３．０部 (Preparation of pigment dispersion 4)
Pigment dispersion 4 was prepared as follows. The raw materials were mixed so that the composition described below was obtained, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. For 3 hours to prepare a mixed solution. Furthermore, the dispersion process was performed for 8 hours with a bead disperser Ultra Apex Mill (manufactured by Kotobuki Industries Co., Ltd.) using 0.1 mmφ zirconia beads. Here, the adsorption group of Disperbyk2000 is quaternary ammonium (amine value 4 mgKOH / g).
(composition)
・ C. I. Pigment Blue 15: 6 9.7 parts ・ Disperbyk2000 manufactured by Big Chemie (nonvolatile content 40%)
17.3 parts propylene glycol methyl ether acetate (PGMEA)
73.0 parts
（顔料分散液５の調製）
　分散剤をＤｉｓｐｅｒｂｙｋ１４０（ビックケミー社製、不揮発分５２％）に変更した以外は顔料分散液４と同様の方法で顔料分散液５を調製した。なお、顔料分散液中の分散剤不揮発分は顔料分散液４と等しくなるようにＰＧＭＥＡの添加量を調整した。ここで、Ｄｉｓｐｅｒｂｙｋ１４０の吸着基はアルキルアンモニウム塩吸着基（酸価７３ｍｇＫＯＨ／ｇ、アミン価７６ｍｇＫＯＨ／ｇ）である。 (Preparation of pigment dispersion 5)
A pigment dispersion 5 was prepared in the same manner as the pigment dispersion 4 except that the dispersant was changed to Disperbyk 140 (Bic Chemie, non-volatile content 52%). The amount of PGMEA added was adjusted so that the non-volatile content of the dispersant in the pigment dispersion was equal to that of the pigment dispersion 4. Here, the adsorption group of Disperbyk140 is an alkylammonium salt adsorption group (acid value 73 mgKOH / g, amine value 76 mgKOH / g).
（顔料分散液６の調製）
　分散剤をＤｉｓｐｅｒｂｙｋ１４２（ビックケミー社製、不揮発分６０％）に変更した以外は顔料分散液４と同様の方法で顔料分散液５を調製した。なお、顔料分散液中の分散剤不揮発分は顔料分散液４と等しくなるようにＰＧＭＥＡの添加量を調整した。ここで、Ｄｉｓｐｅｒｂｙｋ１４２の吸着基はリン酸塩吸着基（酸価４６ｍｇＫＯＨ／ｇ、アミン価４３ｍｇＫＯＨ／ｇ）である。 (Preparation of pigment dispersion 6)
A pigment dispersion 5 was prepared in the same manner as the pigment dispersion 4 except that the dispersant was changed to Disperbyk 142 (by Big Chemie, nonvolatile content 60%). The amount of PGMEA added was adjusted so that the non-volatile content of the dispersant in the pigment dispersion was equal to that of the pigment dispersion 4. Here, the adsorption group of Disperbyk142 is a phosphate adsorption group (acid value 46 mgKOH / g, amine value 43 mgKOH / g).
（実施例１）
（着色硬化性組成物の調製）
　下記の組成１となるように着色硬化性組成物を調製した。染料化合物にはＴＡＭ００１を用い、ＴＡＭ００１の含有量は３．２質量部とした。 (Example 1)
(Preparation of colored curable composition)
A colored curable composition was prepared so as to have the following composition 1. TAM001 was used as the dye compound, and the content of TAM001 was 3.2 parts by mass.
＜組成１＞
・染料化合物　　　　　　　　　         Ｘ質量部（後述の表に記載）
・（Ｔ－１）重合性化合物　　　                   　６．０質量部
・（Ｕ－２）アルカリ可溶性樹脂　                 　４．２質量部
・（Ｖ－４）光重合開始剤　　　                   ０．３１質量部
・（Ｖ－５）架橋剤　　　                         ０．２３質量部
・（Ｖ－６）架橋剤　　　　                       ０．４０質量部
・（Ａ－１）酸化防止剤　　　                     ０．３２質量部
・（Ｘ－１）溶剤　　　　                         ６２．０質量部
・（Ｘ－３）溶剤　　　　                         １２．６質量部
・（Ｚ－１）界面活性剤　　　                     ０．０１質量部 <Composition 1>
-Dye compound X parts by mass (described in the table below)
(T-1) polymerizable compound 6.0 parts by mass (U-2) alkali-soluble resin 4.2 parts by mass (V-4) photopolymerization initiator 0.31 parts by mass (V-5) crosslinking Agent 0.23 parts by mass. (V-6) Cross-linking agent 0.40 parts by mass. (A-1) Antioxidant 0.32 parts by mass. (X-1) Solvent 62.0 parts by mass. (X-3. ) 12.6 parts by mass of solvent / 0.01 parts by mass of (Z-1) surfactant
　組成１の各成分の詳細は下記の通りである。
　・重合性化合物（Ｔ－１）：ＫＡＹＡＲＡＤ　ＤＰＨＡ（日本化薬（株）製、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートとの混合物）
　・アルカリ可溶性樹脂（Ｕ－２）：メタクリル酸アリル／メタクリル酸（７７／２３「質量比」共重合体、重量平均分子量３７，０００、酸価１３７ｍｇＫＯＨ／ｇ）
　・光重合開始剤（Ｖ－４）：ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２（ＢＡＳＦジャパン）
　・架橋剤（Ｖ－５）：カレンズＭＴＢＤ－１（昭和電工株式会社）
・架橋剤（Ｖ－６）：セロキサイド２０２１Ｐ　（ダイセル化学株式会社）
・酸化防止剤（Ａ－１）：ＡＯ－６０：アデカスタブＡＯ－６０（ＡＤＥＫＡ製）
・溶剤（Ｘ－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
・溶剤（Ｘ－３）：メチルエチルジグリコール（ＭＥＧＤ）（日本乳化剤株式会社製）
・界面活性剤（Ｚ－１）：メガファックＦ５５４　（ＤＩＣ（株）製） Details of each component of composition 1 are as follows.
Polymerizable compound (T-1): KAYARAD DPHA (Nippon Kayaku Co., Ltd., mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
Alkali-soluble resin (U-2): allyl methacrylate / methacrylic acid (77/23 “mass ratio” copolymer, weight average molecular weight 37,000, acid value 137 mg KOH / g)
-Photopolymerization initiator (V-4): IRGACURE OXE-02 (BASF Japan)
・ Crosslinking agent (V-5): Karenz MTBD-1 (Showa Denko KK)
・ Crosslinking agent (V-6): Celoxide 2021P (Daicel Chemical Co., Ltd.)
Antioxidant (A-1): AO-60: ADK STAB AO-60 (manufactured by ADEKA)
Solvent (X-1): Propylene glycol monomethyl ether acetate Solvent (X-3): Methyl ethyl diglycol (MEGD) (Nippon Emulsifier Co., Ltd.)
・ Surfactant (Z-1): MegaFuck F554 (manufactured by DIC Corporation)
（実施例２～１４）
　染料化合物を下記表１に記載した化合物とした以外は、実施例１と同様に着色硬化性組成物を調製した。 (Examples 2 to 14)
A colored curable composition was prepared in the same manner as in Example 1 except that the dye compound was a compound described in Table 1 below.
（実施例１５）
　下記の組成２となるように着色硬化性組成物を調製した。染料化合物にはＴＡＭ００１を用い、ＴＡＭ００１の含有量は３．２質量部とした。顔料分散液には、上述した顔料分散液１を用いた。 (Example 15)
A colored curable composition was prepared so as to have the following composition 2. TAM001 was used as the dye compound, and the content of TAM001 was 3.2 parts by mass. The pigment dispersion liquid 1 described above was used as the pigment dispersion liquid.
＜組成２＞
・染料化合物　　　　　　　　　          Ｘ質量部（後述の表に記載）
・顔料分散液（分散液種類は後述の表に記載）　　　１１．０６質量部
・（Ｔ－１）重合性化合物　　　                      ６．０質量部
・（Ｕ－２）アルカリ可溶性樹脂　                 　 ３．７質量部
・（Ｖ－４）光重合開始剤　　　                    ０．３１質量部
・（Ｖ－５）架橋剤　　　　                        ０．２３質量部
・（Ｖ－６）架橋剤　　　　                        ０．４０質量部
・（Ａ－１）酸化防止剤　　　                      ０．３２質量部
・（Ｘ－１）溶剤　　　　                          ６２．０質量部
・（Ｘ－３）溶剤　　　　                          １２．６質量部
・（Ｚ－１）界面活性剤　　                        ０．０１質量部 <Composition 2>
-Dye compound X parts by mass (described in the table below)
Pigment dispersion (dispersion type is described in the table below) 11.06 parts by mass (T-1) polymerizable compound 6.0 parts by mass (U-2) alkali-soluble resin 3.7 parts by mass V-4) Photopolymerization initiator 0.31 parts by mass. (V-5) Crosslinker 0.23 parts by mass. (V-6) Crosslinker 0.40 parts by mass. (A-1) Antioxidant 0. 32 parts by mass, (X-1) solvent 62.0 parts by mass, (X-3) solvent 12.6 parts by mass, (Z-1) surfactant 0.01 part by mass
（実施例１６～７４）
　染料化合物を下記表２または３に記載した化合物とし、顔料分散液を下記表２または３に記載した顔料分散液とした以外は、実施例１５と同様に着色硬化性組成物を調製した。 (Examples 16 to 74)
A colored curable composition was prepared in the same manner as in Example 15 except that the dye compound was a compound described in Table 2 or 3 below and the pigment dispersion was a pigment dispersion described in Table 2 or 3 below.
（実施例７５～１０１）
　染料化合物を下記表４に記載した化合物の組み合わせとし、顔料分散液を下記表４に記載した顔料分散液とした以外は、実施例１５と同様に着色硬化性組成物を調製した。 (Examples 75 to 101)
A colored curable composition was prepared in the same manner as in Example 15 except that the dye compound was a combination of the compounds described in Table 4 below and the pigment dispersion was a pigment dispersion described in Table 4 below.
（比較例１～１２）
　染料化合物を下記表５に記載した化合物とした以外は、実施例１と同様に着色硬化性組成物を調製した。 (Comparative Examples 1 to 12)
A colored curable composition was prepared in the same manner as in Example 1 except that the dye compound was a compound described in Table 5 below.
（比較例１３～５４）
　染料化合物を下記表６または７に記載した化合物とし、顔料分散液を下記表６または７に記載した顔料分散液とした以外は、実施例１５と同様に着色硬化性組成物を調製した。 (Comparative Examples 13 to 54)
A colored curable composition was prepared in the same manner as in Example 15 except that the dye compound was a compound described in Table 6 or 7 below and the pigment dispersion was a pigment dispersion described in Table 6 or 7 below.
（評価）
（トリアリールメタン染料の電導度）
　トリアリールメタン染料１０ｍｇをメタノール／水溶媒３ｍｌに対して混合し、２０分撹拌後の電導度を電導度計（堀場製作所（株）製、ＬＡＱＵＡｔｗｉｎ）にて測定した。メタノール／水溶媒は、メタノール／水の体積比が２／１となるように混合した溶媒とした。また、電導度測定時のトリアリールメタン染料の溶解液の温度は２３℃とした。電導度は１０μｓ／ｃｍ未満が良好であり、電導度が１０μｓ／ｃｍ以上２０μｓ／ｃｍ未満は概ね良好である。 (Evaluation)
(Conductivity of triarylmethane dye)
10 mg of triarylmethane dye was mixed with 3 ml of a methanol / water solvent, and the electric conductivity after stirring for 20 minutes was measured with an electric conductivity meter (LAQUATwin, manufactured by Horiba, Ltd.). The methanol / water solvent was a solvent mixed so that the volume ratio of methanol / water was 2/1. Moreover, the temperature of the solution of triarylmethane dye at the time of measuring conductivity was set to 23 ° C. The conductivity is good when it is less than 10 μs / cm, and the conductivity is generally good when it is 10 μs / cm or more and less than 20 μs / cm.
（着色硬化性組成物の評価方法）
（着色層Ａ（着色硬化膜Ａ）の作製）
　ガラス（コーニング社製、商品名：１７３７）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、着色層を得た。この着色層にフォトマスクを介さない全面露光の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質量％）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、スプレーで乾燥した。乾燥後の膜をクリーンオーブンで２３０℃、２０分焼成し、青色の着色層Ａを得た。 (Evaluation method of colored curable composition)
(Preparation of colored layer A (colored cured film A))
After applying the colored curable composition prepared above on a glass (Corning Corporation, trade name: 1737) substrate by spin coating, the volatile components are volatilized by drying at room temperature for 30 minutes, and the colored layer is formed. Obtained. This colored layer was irradiated with i-rays (wavelength 365 nm) exposed on the entire surface without using a photomask 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 of 2.4% by mass) at 26 ° C. for 45 seconds, and then rinsed with running water for 20 seconds. After that, it was dried with a spray. The dried film was baked at 230 ° C. for 20 minutes in a clean oven to obtain a blue colored layer A.
（レジスト相溶性）
　着色層Ａの面状を観察し、レジスト相溶性を評価した。面状の観察には、光学顕微鏡（オリンパス（株）製、ＭＸ５０）を用い、倍率を２００倍として観察した。レジスト相溶性については、下記の評価基準で評価をした。
　ここで、色ムラは、染料と夾雑物（例えば、開始剤、モノマー、樹脂成分）の相溶性が悪い場合、緩やかな相分離を起こすため塗布面の染料分布が不均一となることで発生する。色ムラは光学顕微鏡にて観察をした場合に認知される。なお、相分離が著しい場合には同一成分のみが高濃度に寄り集まることで凝集体として認知されるが、下記の表か基準においては、このような凝集体についても色ムラと定義した。
Ａ：着色層Ａの面状に色ムラが観察されずレジスト相溶性は良好。
Ｂ：着色層Ａの周辺部にやや薄い色ムラが観察される。レジスト相溶性は概ね良好。
Ｃ：着色層Ａの面状に色ムラが観察される。レジスト相溶性に問題あり。 (Resist compatibility)
The surface state of the colored layer A was observed and the resist compatibility was evaluated. For planar observation, an optical microscope (manufactured by Olympus Corporation, MX50) was used, and the magnification was 200 times. The resist compatibility was evaluated according to the following evaluation criteria.
Here, color unevenness occurs when the dye distribution on the coated surface becomes non-uniform due to the gradual phase separation when the compatibility between the dye and impurities (for example, initiator, monomer, resin component) is poor. . Color unevenness is recognized when observed with an optical microscope. When the phase separation is significant, only the same components are gathered at a high concentration and recognized as an aggregate. However, in the following table or standard, such an aggregate is also defined as color unevenness.
A: Color unevenness is not observed on the surface of the colored layer A, and the resist compatibility is good.
B: Slightly uneven color unevenness is observed in the periphery of the colored layer A. Resist compatibility is generally good.
C: Color unevenness is observed on the surface of the colored layer A. There is a problem with resist compatibility.
（耐熱性）
　着色層Ａの透過スペクトルと、着色層Ａをさらに２３０℃、６０分焼成したときの透過スペクトルの色差ΔＥａｂを算出した。ΔＥａｂ値は、ＣＩＥ１９７６（Ｌ＊，ａ＊，ｂ＊）空間表色系による以下の色差公式から求められる値である（日本色彩学会編　新編色彩科学ハンドブック（昭和６０年）ｐ．２６６）。透過スペクトルの測定には、色度計（大塚電子（株）製、ＭＣＰＤ３７００）を用いた。
ΔＥａｂ＝｛（ΔＬ＊）２＋（Δａ＊）２＋（Δｂ＊）２｝１／２
　耐熱性は、ΔＥａｂが３．０未満で良好であり、３．０以上５．０未満で概ね良好である。 (Heat-resistant)
A color difference ΔEab between the transmission spectrum of the colored layer A and the transmission spectrum when the colored layer A was further baked at 230 ° C. for 60 minutes was calculated. The ΔEab value is a value obtained from the following color difference formula according to the CIE 1976 (L *, a *, b *) space color system (Japanese Color Society edited by New Color Science Handbook (Showa 60) p.266). A chromaticity meter (manufactured by Otsuka Electronics Co., Ltd., MCPD3700) was used for measurement of the transmission spectrum.
ΔEab = {(ΔL *) 2 + (Δa *) 2 + (Δb *) 2 } 1/2
The heat resistance is good when ΔEab is less than 3.0, and generally good when it is 3.0 or more and less than 5.0.
（電圧保持率）
　ＩＴＯ電極つきのガラス基板（コーニング社製、商品名：１７３７）上に、着色硬化性組成物を乾燥後の膜厚が２．０μｍとなるように塗布し、９０℃のオーブンで６０秒乾燥（プリベーク）した。その後、マスクを介さずに１００ｍＪ／ｃｍ２の露光（照度は２０ｍＷ／ｃｍ２）をし、アルカリ現像液（富士フィルムエレクトロニクスマテリアルズ（株）製、商品名：ＣＤＫ－１）の１％水溶液を用いて２５℃で現像し、水洗、乾燥した。乾燥後の塗布膜を２３０℃のオーブンで３０分間加熱処理（ポストベーク）し、着色硬化膜を形成した。次いで、この着色硬化膜を形成したガラス基板とＩＴＯ電極を所定形状に蒸着しただけのガラス基板とを、５μｍのガラスビーズを混合したシール剤で貼り合わせたのち、基板間に液晶（メルク社製、商品名：ＭＪ９７１１８９）を注入して、液晶セルを作製した。
　次いで、液晶セルを７０℃の恒温層に４８時間入れた後、液晶セルの電圧保持率を、液晶電圧保持率測定システム（東陽テクニカ社製、商品名：ＶＨＲ－１Ａ型）を用いて下記の測定条件により測定し、下記基準により評価した。
（測定条件）
・電極間距離　：５～１５μｍ
・印加電圧パルス振幅　：５Ｖ
・印加電圧パルス周波数：６０Ｈｚ
・印加電圧パルス幅　：１６．６７ｍｓｅｃ
＊電圧保持率：１６．７ミリ秒後の液晶セル電位差／０ｍｓｅｃで印加した電圧の値
　評価Ｂ以上が実用レベルである。
（評価基準）
Ａ：９０％以上　　　　　　　
Ｂ：８０％以上９０％未満　　
Ｃ：８０％未満　　　　　　　 (Voltage holding ratio)
A colored curable composition was applied onto a glass substrate with ITO electrodes (Corning, product name: 1737) so that the film thickness after drying was 2.0 μm, and dried in an oven at 90 ° C. for 60 seconds (prebaked). )did. Then, exposure was performed at 100 mJ / cm 2 without using a mask (illuminance was 20 mW / cm 2 ), and a 1% aqueous solution of an alkaline developer (product name: CDK-1 manufactured by Fuji Film Electronics Materials Co., Ltd.) was used. It was developed at 25 ° C., washed with water and dried. The dried coating film was heat-treated (post-baked) for 30 minutes in an oven at 230 ° C. to form a colored cured film. Next, the glass substrate on which the colored cured film is formed and the glass substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealant mixed with 5 μm glass beads, and then a liquid crystal (manufactured by Merck & Co., Ltd.) is bonded between the substrates. , Product name: MJ971189) was injected to produce a liquid crystal cell.
Next, after putting the liquid crystal cell in a constant temperature layer at 70 ° C. for 48 hours, the voltage holding ratio of the liquid crystal cell was measured using a liquid crystal voltage holding ratio measuring system (trade name: VHR-1A type, manufactured by Toyo Technica Co., Ltd.) Measurement was performed under measurement conditions, and evaluation was performed according to the following criteria.
(Measurement condition)
・ Distance between electrodes: 5-15μm
・ Applied voltage pulse amplitude: 5V
・ Applied voltage pulse frequency: 60 Hz
・ Applied voltage pulse width: 16.67 msec
* Voltage holding ratio: liquid crystal cell potential difference after 16.7 milliseconds / value of voltage applied at 0 msec Evaluation B or higher is a practical level.
(Evaluation criteria)
A: 90% or more
B: 80% or more and less than 90%
C: less than 80%
Figure JPOXMLDOC01-appb-T000104
Figure JPOXMLDOC01-appb-T000104
Figure JPOXMLDOC01-appb-T000105
Figure JPOXMLDOC01-appb-T000105
Figure JPOXMLDOC01-appb-T000106
Figure JPOXMLDOC01-appb-T000106
Figure JPOXMLDOC01-appb-T000107
Figure JPOXMLDOC01-appb-T000107
Figure JPOXMLDOC01-appb-T000108
Figure JPOXMLDOC01-appb-T000108
Figure JPOXMLDOC01-appb-T000109
Figure JPOXMLDOC01-appb-T000109
Figure JPOXMLDOC01-appb-T000110
Figure JPOXMLDOC01-appb-T000110
　上記結果から、実施例の着色硬化性組成物を用いた着色層は、ΔＥａｂの値が小さく、耐熱性が優れていることがわかる。すなわち、本発明では、耐熱性に優れた着色硬化性組成物を提供できることがわかった。また、実施例の着色硬化性組成物を用いて形成されたカラーフィルタを含む素子においては、電圧保持率も優れていることがわかった。 From the above results, it can be seen that the colored layer using the colored curable composition of the example has a small ΔEab value and excellent heat resistance. That is, it turned out that in this invention, the colored curable composition excellent in heat resistance can be provided. Moreover, in the element containing the color filter formed using the colored curable composition of an Example, it turned out that the voltage retention is also excellent.
　さらに、実施例の着色硬化性組成物は、レジスト相溶性にも優れていることがわかった。カチオン染料の場合、対アニオンとのイオンペア性が弱いと、一部はカチオンとして存在するため、疎水性のポリマーやモノマー、溶剤との相溶性が悪化する傾向となる。一方、実施例のカチオン染料はイオンペア性が高く、疎水性のポリマーやモノマー、溶剤との相溶性が高い。このことは、染料溶液の電導度が低いことと概ね相関していることがわかった。 Furthermore, it turned out that the colored curable composition of an Example is excellent also in resist compatibility. In the case of a cationic dye, if the ion-pairing property with the counter-anion is weak, a part of the cationic dye is present as a cation, so that the compatibility with a hydrophobic polymer, monomer, or solvent tends to deteriorate. On the other hand, the cationic dyes of the examples have high ion-pair properties and high compatibility with hydrophobic polymers, monomers, and solvents. This was found to correlate generally with the low conductivity of the dye solution.

Claims (16)

  1. 　カチオンを含むトリアリールメタン構造と対アニオンとを有するトリアリールメタン染料と、重合性化合物と、を含み、
    　前記トリアリールメタン染料１０ｍｇを、メタノール／水の体積比が２／１の混合溶媒３ｍｌに溶解させた溶解液の２３℃における電導度が２０μｓ／ｃｍ未満である着色硬化性組成物。     A triarylmethane dye having a triarylmethane structure containing a cation and a counter anion, and a polymerizable compound,
    A colored curable composition having a conductivity at 23 ° C. of less than 20 μs / cm of a solution obtained by dissolving 10 mg of the triarylmethane dye in 3 ml of a mixed solvent having a volume ratio of methanol / water of 2/1.
  2. 　さらに顔料と分散剤とを含み、前記分散剤の吸着基は、酸性吸着基および塩基性吸着基の少なくとも一方を含む請求項１に記載の着色硬化性組成物。 The colored curable composition according to claim 1, further comprising a pigment and a dispersant, wherein the adsorption group of the dispersant contains at least one of an acidic adsorption group and a basic adsorption group.
  3. 　前記顔料は、銅フタロシアニン系青色顔料である請求項２に記載の着色硬化性組成物。 The colored curable composition according to claim 2, wherein the pigment is a copper phthalocyanine blue pigment.
  4. 　前記トリアリールメタン染料は、下記一般式（ＴＰ１）で表される化合物を含む請求項１～３のいずれか１項に記載の着色硬化性組成物；
    Figure JPOXMLDOC01-appb-C000001
     　一般式（ＴＰ１）中、Ｒｔｐ２１はそれぞれ独立して水素原子または炭素数１～６のアルキル基を表し、Ｒｔｐ２２は、それぞれ独立して炭素数６～１０のアリール基を表す；Ｒ１は、置換基を表す；Ｘはアニオンを示す。     The colored curable composition according to any one of claims 1 to 3, wherein the triarylmethane dye contains a compound represented by the following general formula (TP1);
    Figure JPOXMLDOC01-appb-C000001
     In the general formula (TP1), Rtp 21 each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Rtp 22 each independently represents an aryl group having 6 to 10 carbon atoms; R 1 is Represents a substituent; X represents an anion.
  5. 　前記トリアリールメタン染料は、下記一般式（ＴＰ２）で表される化合物を含む請求項１～４のいずれか１項に記載の着色硬化性組成物；
    Figure JPOXMLDOC01-appb-C000002
     　一般式（ＴＰ２）中、Ｒｔｐ２１はそれぞれ独立して水素原子または炭素数１～６のアルキル基を表し、Ｒｔｐ２２は、それぞれ独立して炭素数６～１０のアリール基を表す；Ｌ１は炭素数２～３０の２価の連結基を表し、Ｐ１は重合性基を表す；Ｘはアニオンを示す。     The colored curable composition according to any one of claims 1 to 4, wherein the triarylmethane dye comprises a compound represented by the following general formula (TP2);
    Figure JPOXMLDOC01-appb-C000002
     In the general formula (TP2), Rtp 21 each independently represents a hydrogen atom or an alkyl group having a carbon number of 1 ~ 6, Rtp 22 each independently represents an aryl group having 6 to 10 carbon atoms; L 1 is Represents a divalent linking group having 2 to 30 carbon atoms, P 1 represents a polymerizable group, and X represents an anion.
  6. 　前記トリアリールメタン染料は、下記一般式（ＴＰ３）で表される化合物を含む請求項１～５のいずれか１項に記載の着色硬化性組成物；
    Figure JPOXMLDOC01-appb-C000003
     　一般式（ＴＰ３）中、Ｒｔｐ２３およびＲｔｐ２４はそれぞれ独立して水素原子または炭素数１～４のアルキル基を表し、Ｒｔｐ２５は水素原子または炭素数１～３のアルキル基を表す；Ｌ１は炭素数２～３０の２価の連結基を表し、Ｐ１は重合性基を表す；Ｘはアニオンを示す。     The colored curable composition according to any one of claims 1 to 5, wherein the triarylmethane dye contains a compound represented by the following general formula (TP3);
    Figure JPOXMLDOC01-appb-C000003
     In general formula (TP3), Rtp 23 and Rtp 24 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Rtp 25 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; L 1 Represents a divalent linking group having 2 to 30 carbon atoms, P 1 represents a polymerizable group, and X represents an anion.
  7. 　前記一般式（ＴＰ３）において、Ｌ１は、炭素数６～１０のシクロアルキレン基を含む基である請求項６に記載の着色硬化性組成物。 The colored curable composition according to claim 6, wherein, in the general formula (TP3), L 1 is a group containing a cycloalkylene group having 6 to 10 carbon atoms.
  8. 　前記一般式（ＴＰ３）において、Ｐ１はアクリロイル基またはメタクリロイル基である請求項６または７に記載の着色硬化性組成物。 In the general formula (TP3), P 1 is colored curable composition according to claim 6 or 7 acryloyl group or a methacryloyl group.
  9. 　前記一般式（ＴＰ３）において、Ｘは、ビストリフルオロメタンスルホニルイミドアニオン、トリストリフルオロメタンスルホニルメチドアニオンまたはパーフルオロメタンスルホン酸アニオンを表す請求項６～８のいずれか１項に記載の着色硬化性組成物。 The colored curable property according to any one of claims 6 to 8, wherein in the general formula (TP3), X represents a bistrifluoromethanesulfonylimide anion, a tristrifluoromethanesulfonylmethide anion, or a perfluoromethanesulfonate anion. Composition.
  10. 　前記トリアリールメタン染料は、多量体構造を含む請求項１～９のいずれか１項に記載の着色硬化性組成物。 The colored curable composition according to any one of claims 1 to 9, wherein the triarylmethane dye includes a multimeric structure.
  11. 　カラーフィルタの着色層形成用である請求項１～１０のいずれか１項に記載の着色硬化性組成物。 The colored curable composition according to any one of claims 1 to 10, which is used for forming a colored layer of a color filter.
  12. 　請求項１～１１のいずれか１項に記載の着色硬化性組成物を硬化させてなる着色硬化膜。 A colored cured film obtained by curing the colored curable composition according to any one of claims 1 to 11.
  13. 　請求項１２に記載の着色硬化膜を有するカラーフィルタ。 A color filter having the colored cured film according to claim 12.
  14. 　請求項１～１１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適用して着色硬化性組成物層を形成する工程と、前記着色硬化性組成物層を硬化させて着色硬化膜を形成する工程と、を有し、さらに下記（ａ）工程または（ｂ）工程を有するカラーフィルタの製造方法；
    　（ａ）前記着色硬化膜上にフォトレジスト層を形成する工程と、露光および現像することにより前記フォトレジスト層をパターニングしてレジストパターンを得る工程とを含む工程；
    　（ｂ）前記着色硬化膜をドライエッチングしてレジストパターンを得る工程。     A step of applying a colored curable composition according to any one of claims 1 to 11 on a support to form a colored curable composition layer; and curing the colored curable composition layer to color A process for forming a cured film, and a method for producing a color filter further comprising the following step (a) or step (b):
    (A) including a step of forming a photoresist layer on the colored cured film and a step of patterning the photoresist layer by exposure and development to obtain a resist pattern;
    (B) A step of dry-etching the colored cured film to obtain a resist pattern.
  15. 　請求項１３に記載のカラーフィルタを有する固体撮像素子。 A solid-state imaging device having the color filter according to claim 13.
  16. 　請求項１３に記載のカラーフィルタを有する画像表示装置。 An image display device having the color filter according to claim 13.
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