Classifications

• • 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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