CN106574125B - Color material dispersion liquid, colored filter colored resin composition, colored filter and display device - Google Patents

Color material dispersion liquid, colored filter colored resin composition, colored filter and display device Download PDF

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Publication number
CN106574125B
CN106574125B CN201580043192.7A CN201580043192A CN106574125B CN 106574125 B CN106574125 B CN 106574125B CN 201580043192 A CN201580043192 A CN 201580043192A CN 106574125 B CN106574125 B CN 106574125B
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color material
mentioned
acid
formula
group
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CN106574125A (en
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石原星儿
大岛裕史
小野充史
市川裕司
前野义人
竹内义浩
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DNP Fine Chemicals Co Ltd
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DNP Fine Chemicals Co Ltd
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    • 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
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0066—Aqueous dispersions of pigments containing only dispersing agents
    • 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
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—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

Abstract

This case invention provides a kind of color material dispersion liquid for the film that ageing stability is excellent, can form heat resistance is promoted.Color material dispersion liquid of the invention contains color material, dispersing agent, organic acid compound and solvent shown in the following general formula (I), above-mentioned dispersing agent is at least to have Component units (a) shown in the following general formula (II) and amine value for 70mgKOH/g or more and 160mgKOH/g block copolymer below, above-mentioned solvent is that the solubility of the above-mentioned color material at 23 DEG C is 0.1 (g/10ml solvent) solvent below, the color material dispersion liquid meets following formula (1) and formula (2), when X is the range less than 1, further satisfaction following formula (3).The formula of X≤1.5 (1) formula of A × X >=40 (2) A × (1-X)≤42 formula (3)

Description

Color material dispersion liquid, colored filter colored resin composition, colored filter and aobvious Showing device
Technical field
The present invention relates to color material dispersion liquid, colored filter colored resin composition, colored filter and display devices.
Background technique
Flat type image display device, i.e. so-called flat-panel monitor with display etc. for representative, compared with cathode-ray tube Escope is thinner and does not take up space and is characterized in longitudinal direction, and lists in large quantities.Its market price is with production skill The evolution of art and price tends to rationally year by year, and then expanded demand, output also increase year by year.Especially colored liquid crystal television is several Become the mainstream of TV.In addition, recently, such as passing through the organic light emission of the visual higher organic el display of self-luminous etc Display device is also attracted attention as next-generation image display device.For the performance of these image display devices, the strong phase It hopes the further higher image quality such as raising of contrast or color reproduction or consumes the reduction of electric power.
In these liquid crystal display devices or organic light-emitting display device, colored filter is used.For example, in color liquid crystal In the case where display, using backlight as light source, light quantity is controlled by electrically-driven liquid crystal, the light is by colored filter, thus It is existing to carry out color table.Therefore, for the color table of LCD TV is existing, colored filter is indispensable, and is responsible for left and right display The key player of energy.In addition, in organic light-emitting display device, sometimes using colored filter carry out pixel color adjustment or this, Sometimes color image is identically formed with liquid crystal display device using colored filter to white luminous organic illuminating element.
As trend in recent years, it is desirable that the electric power saving of image display device, and in order to improve the utilization efficiency of backlight, Specially require the high brightness of colored filter.Especially in Leading format device (mobile phone, smart phone, tablet PC) As larger project.
Though due to technological progress, battery capacity becomes larger, and mobile charge capacity is still limited, on the other hand, have with Screen size expands and consumes the increased tendency of electric power.Due to being directly related to up time or the charging frequency of mobile terminal Degree, therefore include that the image display device of colored filter will move left and right the design or performance of terminal.
Here, colored filter usually includes transparent substrate；It is formed on transparent substrate and includes Red Green Blue Colored pattern coloring layer；The light shielding part on transparent substrate is formed in a manner of dividing each colored pattern.
In the forming method of such coloring layer, use the pigment of heat resistance or excellent in light-resistance as the pigment of color material point Arching pushing is widely used.However, becoming difficult to reach wanting for current more high brightness using the colored filter of previous pigment It asks.
As a kind of means to reach high brightness, colored filter using dyestuff is had studied with photonasty tree Oil/fat composition.Compared to pigment, the usual transmitance of dyestuff is higher, can manufacture the colored filter of high brightness, but have heat resistance or The problem of light resistance is poor, and colorations are easily varied when high-temperature heating in colored filter manufacturing process etc..In addition, using dyestuff Photosensitive polymer combination have in drying process be easy be precipitated foreign matter the problem of.If foreign matter is precipitated in film, contrast It is obvious to deteriorate, and be difficult to be used as coloring layer.
Patent document 1 discloses a kind of specific photosensitive composition, contains containing particular dye and pigment Color material and specific solvent.It can get heat resistance height by the photosensitive composition according to patent document 1, apply The few film of cloth unevenness.
In addition, patent document 2 discloses a kind of specific blue-sensitive resin combination, having containing specific structure Solvent soluble dye and organic pigment are as color material.According to patent document 2, by using the coloring phototonus resin group Closing object can get the colored filter of high brightness.
Above-mentioned particular dye in patent document 1 and 2 is dissolved in solvent and uses, and heat resistance or light resistance are poor, and because containing Have for make dyestuff dissolve polar solvent and stability is poor.
Patent document 3 discloses a kind of colored filter colored resin composition, contains specific color material, the color material Containing it is more than the divalent for being crosslinked multiple dyestuff skeletons by crosslinking group cation, with anion more than divalent.Its disclosure: Being formed by coloring layer with colored resin composition using the colored filter containing above-mentioned color material is high contrast, solvent resistance And electricity is excellent in reliability.
Citation
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2010-211198 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2010-32999 bulletin
Patent document 3: No. 2012/144521 pamphlet of International Publication No.
Summary of the invention
Problem to be solved by the invention
The colored resin composition containing special color material recorded in patent document 3, there are be difficult to ensure viscosity stabilization The project of property.In addition, the further heat resistance of coloring layer is also required to be promoted.
The present invention is complete winner in view of above-mentioned actual conditions, it is intended that providing: ageing stability is excellent, can shape At the color material dispersion liquid for the film that heat resistance is promoted；Ageing stability is excellent, can form the coloured silk for the coloring layer that heat resistance improves Colo(u)r filter colored resin composition；The colored filter of the high brightness of the colored resin composition is used；And have The display device of the colored filter.
The means used to solve the problem
Color material dispersion liquid of the invention, which is characterized in that contain color material, dispersing agent, organic acid shown in the following general formula (I) Compound and solvent,
Above-mentioned dispersing agent be at least have Component units (a) and amine value shown in the following general formula (II) be 70mgKOH/g with Upper and 160mgKOH/g block copolymer below,
Above-mentioned solvent is that the solubility of the above-mentioned color material at 23 DEG C is 0.1 (g/10ml solvent) solvent below,
The above-mentioned amine value of above-mentioned dispersing agent is being set as A (mgKOH/g), is being had above-mentioned contained in above-mentioned color material dispersion liquid The amount X of the substance of machine acid compoundA(mol) with the above-mentioned composition list that constitutes above-mentioned dispersing agent contained in above-mentioned color material dispersion liquid The amount X of the substance of first (a)BThe ratio between (mol) it is set as X (=XA/XB) when, meet following formula (1) and formula (2), is the range less than 1 in X When, further satisfaction following formula (3).
The formula of X≤1.5 (1)
The formula of A × X >=40 (2)
A × (1-X)≤42 formula (3)
[changing 1]
Logical formula (I)
(in logical formula (I), A is the organic group for a valence for not having pi bond with the carbon atom of N Direct Bonding, the organic group It indicates at least in the aliphatic alkyl with the end of N Direct Bonding with saturated aliphatic hydrocarbons or with the aliphatic alkyl Aromatic group, can also contain O, S, N in carbochain.BC-Indicate at least c valence polybasic acid anion containing tungsten.Ri~RvRespectively It is independent to indicate hydrogen atom, have the alkyl of substituent group or can have the aryl of substituent group, RiiWith Riii、RivWith RvBonding shape At ring structure.Ar1Indicate the divalent aromatic group that there can be substituent group.Multiple Ri~RvAnd Ar1Difference can be identical or different.
A and c indicates that 2 or more integer, b and d indicate 1 or more integer.E is 0 or 1, and key is not present when e is 0.It is multiple E can be identical or different.)
[changing 2]
Logical formula (II)
(in logical formula (II), R1For hydrogen atom or methyl, Q is Direct Bonding key or divalent concatenating group, R2For the Asia of carbon number 1~8 Alkyl ,-[CH (R5)-CH(R6)-O]x-CH(R5)-CH(R6)-or-[(CH2)y-O]z-(CH2)yShown in divalent organic group, R3 And R4Independently indicating can substituted chain or cricoid alkyl or R3And R4It bonds together and forms cyclic structure.R5And R6It is each independently hydrogen atom or methyl.
X indicates that 1~18 integer, y indicate that 1~5 integer, z indicate 1~18 integer.)
In color material dispersion liquid of the invention, from the viewpoint of dispersion stabilization, preferably above-mentioned organic acid compound is 1 kind or more selected from the group as composed by the following general formula (IV) and the following general formula (V).
[changing 3]
(in formula (IV) and formula (V), RaAnd Ra'Be each independently hydrogen atom, hydroxyl, the alkyl of carbon number 1~18, carbon number 2~ 18 alkenyl, aralkyl, aryl ,-[CH (Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-ReOr-O-Ra”Shown in 1 valence base Group, RaAnd Ra'Any one contain carbon atom.Ra”For the alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, aralkyl, aryl ,- [CH(Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-ReShown in 1 valence group.
RbFor the alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, aralkyl, aryl ,-[CH (Rc)-CH(Rd)-O]s- Re、-[(CH2)t-O]u-ReOr-O-Rb'Shown in 1 valence group.Rb'For the alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, virtue Alkyl, aryl ,-[CH (Rc)-CH(Rd)-O]s-ReOr-[(CH2)t-O]u-ReShown in 1 valence group.
RcAnd RdIt is each independently hydrogen atom or methyl, ReFor the alkyl of hydrogen atom or carbon number 1~18, carbon number 2~18 Alkenyl, aralkyl, aryl ,-CHO ,-CH2CHO ,-CO-CH=CH2、-CO-C(CH3)=CH2Or-CH2COORfShown in 1 valence base Group, RfFor hydrogen atom or the alkyl of carbon number 1~5.
Ra、Ra'And RbIn, alkyl, alkenyl, aralkyl, aryl can have substituent group respectively.
S indicates that 1~18 integer, t indicate that 1~5 integer, u indicate 1~18 integer.)
In color material dispersion liquid of the invention, Cong Secai dispersion stabilization is excellent, furthermore when colored resin composition is made Inhibit the generation of development residue and have high development adhesion, solvent be redissolved property it is excellent from the perspective of, preferably above-mentioned dispersion The acid value of agent is 1mgKOH/g or more and 18mgKOH/g hereinafter, the glass transition temperature of the dispersing agent is 30 DEG C or more.
Color material dispersion liquid of the invention, from the viewpoint of it can be adjusted to required tone, preferably also containing selected from two 1 kind or more of oxazines system color material and xanthene system color material.
Color material dispersion liquid of the invention, from the viewpoint of heat resistance, the metallochrome of preferably above-mentioned xanthene system color material xanthene Shallow lake color material.
Colored filter colored resin composition of the invention, which is characterized in that the color material containing aforementioned present invention point Dispersion liquid, alkali soluble resin, polyfunctional monomer and initiator.
Colored filter colored resin composition of the invention goes out from the viewpoint for the heat resistance for promoting gained coloring layer Hair, the acid value of preferably above-mentioned alkali soluble resin are 80mgKOH/g or more and 300mgKOH/g or less.
Colored filter colored resin composition of the invention, it is excellent from alkali-developable, the resulting coloring layer of promotion From the perspective of heat resistance, preferably above-mentioned polyfunctional monomer has carboxyl.
Colored filter colored resin composition of the invention, it is excellent from the adhesion to substrate, development patience it is also excellent From the perspective of different, preferably above-mentioned alkali soluble resin is the resin with olefinic double bond.
Colored filter colored resin composition of the invention, it is excellent from the viewpoint of dispersion stabilization and heat resistance Being selected as above-mentioned alkali soluble resin is the resin with hydrocarbon ring.
In colored filter colored resin composition of the invention, promoted from the curability by promoting coloring layer resistance to From the perspective of the residual film ratio of solvent borne, improvement water infiltration dye (water dye body) and coloring layer is got higher, preferably above-mentioned alkali-soluble tree Hydrocarbon ring possessed by rouge is selected from by cyclopenta, cyclohexyl, bornyl, isobornyl, bicyclopentyl, dicyclopentenyl, Buddha's warrior attendant 1 kind or more of group composed by substituent group shown in alkyl and following chemical formula (A).
[changing 4]
In colored filter colored resin composition of the invention, promoted from the curability by promoting coloring layer resistance to From the perspective of the residual film ratio of solvent borne, improvement water infiltration dye and coloring layer is got higher, preferably above-mentioned alkali soluble resin is following General formula (B) compound represented.
[changing 5]
(here, X indicates that group shown in the following general formula (D), Y independently indicate polybasic carboxylic acid in above-mentioned general formula (B) Or the residue of its acid anhydrides, RiIndicate the following general formula (C) shown in group, j be 0~4 integer, k be 0~3 integer, n be 1 with On integer.)
[changing 6]
(here, in above-mentioned general formula (C), RiiFor hydrogen atom or methyl, RiiiIndependently indicate hydrogen atom or methyl.)
[changing 7]
(here, in above-mentioned general formula (D), RivIndependently indicate that hydrogen atom, the alkyl of carbon number 1~5, phenyl or halogen are former Son, RvExpression-O- or-OCH2CH2O-。)
It is excellent from inhibiting water to seep dye, solvent resistance and sensitivity in colored filter colored resin composition of the invention From the perspective of different, preferably above-mentioned initiator is oxime ester system Photoepolymerizationinitiater initiater.
Colored filter colored resin composition of the invention, from colored resin composition to the warp of the adhesion of substrate When excellent in stability from the perspective of, preferably the content ratio of silane coupling agent is relative to total solid in colored resin composition Body ingredient is 1 mass % or less.
Colored filter of the invention, which is characterized in that at least have transparent substrate and be set on the transparent substrate Coloring layer, the coloring layer at least one be with make aforementioned present invention colored filter colored resin composition solidify and The coloring layer of formation.
Display device of the invention, which is characterized in that the colored filter with aforementioned present invention.
The effect of invention
According to the present invention, it is possible to provide: the color material dispersion for the film that ageing stability is excellent, is capable of forming heat resistance is promoted Liquid；The colored filter colored resin composition for the coloring layer that ageing stability is excellent, is capable of forming heat resistance is promoted；It uses The colored filter of the high brightness of the colored resin composition；And the display device with the colored filter.
Detailed description of the invention
Fig. 1 is the summary section for indicating an example of colored filter of the invention.
Fig. 2 is the summary section for indicating an example of display device of the invention.
Fig. 3 is another summary section for indicating display device of the invention.
Fig. 4 is the schematic diagram for indicating the molecular association state of color material shown in logical formula (I).
Fig. 5 is the X-A plane of the relationship between the A and X for indicating the color material dispersion liquid of embodiment 1~19 and comparative example 1~16 Figure.
Specific embodiment
Hereinafter, successively illustrating color material dispersion liquid of the invention, colored filter colored resin composition, colored filter And display device.
It should be noted that in the present invention, it further includes putting that light, which includes the electromagnetic wave of the wavelength in visible and non-visible region, Ray, radioactive ray include such as microwave, electron beam.Specifically, referring to 5 μm of wavelength electromagnetic waves and electron beam below.
In the present invention, (methyl) acrylic acid indicates one of acrylic acid and methacrylic acid；(methyl) acrylate table Show one of acrylate and methacrylate.
In the present invention, organic group refers to the group with 1 or more carbon atom.
In addition, solid component refers to all the components other than the solvent for constituting colored resin composition in the present invention, even if It is that liquid monomer also includes in the solid component.
1. color material dispersion liquid
Color material dispersion liquid of the invention, which is characterized in that contain color material, dispersing agent, organic acid shown in the following general formula (I) Compound and solvent,
Above-mentioned dispersing agent be at least have Component units (a) and amine value shown in the following general formula (II) be 70mgKOH/g with Upper and 160mgKOH/g block copolymer below,
Above-mentioned solvent is that the solubility of the above-mentioned color material at 23 DEG C is 0.1 (g/10ml solvent) solvent below,
The above-mentioned amine value of above-mentioned dispersing agent is being set as A (mgKOH/g), is being had above-mentioned contained in above-mentioned color material dispersion liquid The amount X of the substance of machine acid compoundA(mol) with the above-mentioned composition list that constitutes above-mentioned dispersing agent contained in above-mentioned color material dispersion liquid The amount X of the substance of first (a)BThe ratio between (mol) it is set as X (=XA/XB) when, meet following formula (1) and formula (2), is the range less than 1 in X When, further satisfaction following formula (3).
The formula of X≤1.5 (1)
The formula of A × X >=40 (2)
A × (1-X)≤42 formula (3)
[changing 8]
Logical formula (I)
(in logical formula (I), A is the organic group for a valence for not having pi bond with the carbon atom of N Direct Bonding, the organic group It indicates at least in the aliphatic alkyl with the end of N Direct Bonding with saturated aliphatic hydrocarbons or with the aliphatic alkyl Aromatic group, can also contain O, S, N in carbochain.BC-Indicate at least c valence polybasic acid anion containing tungsten.Ri~RvRespectively It is independent to indicate hydrogen atom, have the alkyl of substituent group or can have the aryl of substituent group, RiiWith Riii、RivWith RvBonding shape At ring structure.Ar1Indicate the divalent aromatic group that there can be substituent group.Multiple Ri~RvAnd Ar1Difference can be identical or different.
A and c indicates that 2 or more integer, b and d indicate 1 or more integer.E is 0 or 1, and key is not present when e is 0.It is multiple E can be identical or different.)
[changing 9]
Logical formula (II)
(in logical formula (II), R1For hydrogen atom or methyl, Q is Direct Bonding key or divalent concatenating group, R2For the Asia of carbon number 1~8 Alkyl ,-[CH (R5)-CH(R6)-O]x-CH(R5)-CH(R6)-or-[(CH2)y-O]z-(CH2)yShown in divalent organic group, R3 And R4Independently indicating can substituted chain or cricoid alkyl or R3And R4It bonds together and forms cyclic structure.R5And R6It is each independently hydrogen atom or methyl.
X indicates that 1~18 integer, y indicate that 1~5 integer, z indicate 1~18 integer.)
The color material dispersion liquid of aforementioned present invention is due to above-mentioned specific color material, above-mentioned specific dispersing agent, organic acid Compound, specific solvent, therefore the ageing stability of the color material dispersion liquid is excellent, can get the film that heat resistance is promoted.
For playing the effect of effect as above by above-mentioned specific combination, though still there is unclear portion Point, but can push away sentence it is as follows.
Color material shown in logical formula (I) is as shown in figure 4, contain anion 202 more than divalent and cation more than divalent 201, therefore in the agglutination body of the color material, anion and cation not merely carry out ionic bond to 1 molecule with 1 molecule It closes, pushes away the molecular association body 210 for sentencing by ionic bond 203 and being formed multiple molecular associations.Therefore, lead to color material shown in formula (I) Apparent molecular weight substantially increase compared to the molecular weight of previous color lake color material.Infer the shape due to such molecular association body At therefore the cohesive force under solid state more improves, and reduces warm-up movement, can inhibit dissociation or the cation portion of ion pair Separation promotes heat resistance.
Color material dispersion liquid of the invention is that color material shown in such logical formula (I) in specific solvent, is used organic acidification Close object, as dispersing agent have side chain tool amino Component units (a) and amine value be 70mgKOH/g or more and 160mgKOH/g block copolymer below is dispersed.About the dispersing agent, amino pair possessed by Component units (a) Color material shown in logical formula (I) is affinity, therefore is adsorbed in color material shown in above-mentioned logical formula (I), push away sentence can make the color material with The state of molecular association is dispersed.It is 70mgKOH/g or more and 160mgKOH/g block copolymerization below by using amine value The ratio at object, the compatibility position hence for color material and the compatibility position for solvent becomes appropriate and dispersed excellent. In addition, by using the compatibility position to above-mentioned such color material in the form of block existing for block copolymer, can be effective It is adsorbed in rate the above-mentioned color material with molecular association state, dispersion stabilization is excellent.
It pushes away and sentences amino possessed by above-mentioned dispersing agent in the state further with above-mentioned organic acid compound forming salt When, the compatibility of above-mentioned special color material is further promoted.Therefore, if pushing away the amino after sentencing forming salt is adsorbed in above-mentioned lead to Color material shown in formula (I), then make molecular association in stable conditionization of the color material, and dispersion stabilization is promoted.As a result, inhibiting viscosity Ongoing change.In addition, since molecular association in stable conditionization of above-mentioned color material still maintains in resulting coloring layer Molecular association state, and become excellent heat resistance person, even if can still keep high brightness after heating process.
The inventors of the present invention are through concentrating on studies as a result, obtaining following opinions: the above-mentioned amine value of above-mentioned dispersing agent is being set as A (mgKOH/g), by the amount X of the substance of above-mentioned organic acid compound contained in above-mentioned color material dispersion liquidA(mol) above-mentioned with composition The amount X of the substance of the above-mentioned Component units (a) of above-mentioned dispersing agent contained in color material dispersion liquidBThe ratio between (mol) it is set as X (=XA/ XB) when,
Above-mentioned dispersing agent is selected in a manner of the relationship for meeting A × X >=40, and there is above-mentioned organic acid compound, thus Value suitable for dispersion is become to the compatibility of color material, therefore dispersion stabilization is especially promoted, through when viscosity change be inhibited.
In addition, obtaining following opinions: when X is less than 1, being selected in a manner of meeting A × (1-X)≤42 relationship above-mentioned Dispersing agent, and cooperate above-mentioned organic acid compound, the amount for thus not carrying out the amino of salt formation is reduced, therefore in dispersion step In, the molecular association state of color material can be stably kept, the especially excellent film of heat resistance can be formed.
It is carried out in the state of not carrying out salt shape mostly with the Component units (a) of dispersing agent it should be noted that pushing away and sentencing In the case where dispersion step, when the color material shown in the logical formula (I) for making to be formed above-mentioned molecular association state is dispersed, dispersing In process and sintering process, the amino of dispersing agent carries out salt with the cation in color material shown in logical formula (I) and exchanges, point of color material Sub- associated state is by partial destruction, as a result, heat resistance deterioration sometimes.
In addition, X be more than 1 range, i.e. organic acid compound relative to Component units (a) with excess quantity there are the case where Under, direction is formed since balance is more biased towards salt, therefore the amino for not carrying out salt formation is more reduced, the molecular association state of color material is difficult to It is destroyed.Therefore, even if in resulting coloring layer, molecular association state is still maintained, therefore becomes excellent heat resistance person.
If X is 1.5 or less, the i.e. above-mentioned organic acid compound relative to Component units (a) possessed by above-mentioned dispersing agent For 1.5 molar equivalents hereinafter, not carrying out salt formation then and existing organic acid compound facilitates the stabilization of molecular association state Change, therefore dispersion stabilization is excellent, and since its ratio is less thus organic acid compound is not precipitated.Sentence it should be noted that pushing away Relative to 1 amino possessed by dispersing agent, 1 organic acid compound carries out salt and is formed, no matter the organic acidification of the relationship of A and X Close object valence mumber and be identical.
In this way, in the relationship and A × (1-X)≤42 relationship of color material dispersion liquid of the invention to meet A × X >=40 The mode of any one, selection use above-mentioned specific dispersing agent and organic acid compound, therefore the color material dispersion liquid through when it is steady It is qualitative excellent, it can get the film that heat resistance is promoted.
Color material dispersion liquid of the invention at least contains color material, organic acid compound and solvent shown in logical formula (I), not Under the premise of damaging effect of the present invention, it optionally also can further contain other compositions.
Hereinafter, each ingredient of such color material dispersion liquid of the invention is successively described in detail.
[color material shown in logical formula (I)]
Color material dispersion liquid of the invention contains color material shown in the following general formula (I).
[changing 10]
Logical formula (I)
(in logical formula (I), A is the organic group for a valence for not having pi bond with the carbon atom of N Direct Bonding, the organic group It indicates at least in the aliphatic alkyl with the end of N Direct Bonding with saturated aliphatic hydrocarbons or with the aliphatic alkyl Aromatic group, can also contain O, S, N in carbochain.BC-Indicate the polybasic acid anion of at least c valence containing tungsten；Ri~RvPoint It is not independent to indicate hydrogen atom, have the alkyl of substituent group or can have the aryl of substituent group, RiiWith Riii、RivWith RvIt is bonding Form ring structure；Ar1Indicate the aromatic group that there can be the divalent of substituent group.Multiple Ri~RvAnd Ar1Respectively can it is identical or It is different.
A and c indicates that 2 or more integer, b and d indicate 1 or more integer.E is 0 or 1, and key is not present when e is 0.It is multiple E can be identical or different.)
It is not particularly limited as color material shown in logical formula (I), it can be by such as No. 2012/144520 brochure of International Publication No. Suitably selection uses in the logical formula (I) compound represented that son is recorded, and can be used alone and a kind or combines two or more use.
It should be noted that color material shown in logical formula (I) is also included in aftermentioned color lake color material, but as long as meeting general formula (I) color material shown in is regarded as meeting color material shown in logical formula (I) then in the present invention.
The manufacturing method of color material shown in logical formula (I) is not particularly limited.It can be for example, by International Publication No. 2012/ No. 144520 pamphlets record manufacturing method and obtain.
Its allochromatic colour material of < >
Color material dispersion liquid of the invention within the scope of the effect of the invention, for the purpose of tone control, also may be used Further contain its allochromatic colour material.As its allochromatic colour material, well known pigment and dyestuff can be enumerated, can be used one kind or two or more.
From the viewpoint of obtaining required tone, preferably further containing selected from dioxazines system color material and xanthene system color 1 kind or more of material is used as its allochromatic colour material.As the concrete example of preferred dioxazines pigment, pigment Violet 23 etc. can be enumerated.In addition, making For the concrete example of preferred xanthene system color material, can enumerate: CI 45430,52,87,92,94,289,388；C.I. acid violet 9, 30,102；Sulforhodamine G, Sulforhodamine B, Sulforhodamine 101, Sulforhodamine 640 etc.；Japanese Unexamined Patent Publication 2010- The xanthene dye of the records such as No. 4492760 No. 32999 bulletins, Japanese Unexamined Patent Publication 2010-211198 bulletin, Japanese Patent No. bulletins Deng furthermore also being aftermentioned xanthene system color lake color material.In the present invention, from the viewpoint of having both brightness and heat resistance, preferably To use xanthene system color lake color material.
In the present invention, so-called color lake color material, refer to the color material and counter ion counterionsl gegenions soluble to solvent tool carry out salt formation and Thawless color material.Color lake color material usually can by by aftermentioned color material, mixed in a solvent with aftermentioned color lake agent and obtain.Make Has soluble color material to solvent to be above-mentioned, from the viewpoint of the high brightness of colored filter, it is preferable to use transmitance High dyestuff.The dyestuff visually needed for tone and suitably select, can be azo based dye, anthraquinone based dye, triarylmethane system Dyestuff, xanthene based dye, cyanine based dye, indigo based dye etc. have the dyestuff at any basic framework (color development position).Separately Outside, above-mentioned dyestuff also can be the acid dyes with anionic substituent, basic dye with cationic substituent group etc. It is classified as any dyestuff.
As acid dyes, it can be mentioned, for example: C.I. acid violet 29,31,33,34,36,36:1,39,41,42,43,47, 51,63,76,103,118,126, C.I. acid blue 2,8,14,25,27,35,37,40,41,41:1,41:2,43,45,46, 47,49,50,51,51,53,54,55,56,57,58,62,62:1,63,64,65,68,69,70,78,79,80,81,96, 111,124,127,127:1,129,137,138,143,145,150,175,176,183,198,203,204,205,208, 215、220、221、225、226、227、230、231、232、233、235、239、245、247、253、257、258、260、261、 264,266,270,271,272,273,274,277,277:1,278,280,281,282,286,287,288,289,290, 291、292、293、294、295、298、301、302、304、305、306、307、313、316、318、322、324、327、331、 333,336,339,340,343,344,350, C.I. acid green 10,17,25,25:1,27,36,37,38,40,41,42,44, 54,59,69,71,81,84,95,101,110,117 etc. anthraquinone system acid dyes；C.I. acid violet 15,16,17,19,21, 23,24,25,38,49,72, C.I. Blue VRS, 3,5,7,9,19,22,83,90,93,100,103,104,109, C.I. acidity The triarylmethane system acid dyes of green 3,5,6,7,8,9,11,13,14,15,16,18,22,50,50:1 etc.；C.I. acid red 50,51,52,87,92,94,289,388, C.I. acid violet 9,30,102, Sulforhodamine G, Sulforhodamine B, sulfo group Luo Dan Bright 101, the xanthenes system such as Sulforhodamine 640 acid dyes etc..In xanthene system acid dyes, preferably C.I. acid red 50, C.I. the rhodamine system of acid red 52, C.I. acid red 289, C.I. acid violet 9, C.I. acid violet 30, C.I. Blue VRS 9 etc. Acid dyes.
In addition, as commercially available basic dye, it can be mentioned, for example C.I. alkaline purple 1,3,14, C.I. alkali blue 1,5,7,8, 11,26, the triarylmethane system basic dye of C.I. Viride Nitens 1,4 etc.；C.I. the flower cyanines of basic yellow 13, C.I. alkali red 1:1 4 etc. It is basic dye；C.I. alkaline red 29 equal azo system basic dye；C.I. the xanthene system basic dye etc. of alkali violet 11:1 etc..This A little dyestuffs, which can be used alone, or combines two or more use by a kind.
In the present invention, from the viewpoint of being easy to get required tone as coloring layer, wherein it is preferable to use selected from upper State one or more of xanthene system acid dyes and above-mentioned xanthene system basic dye dyestuff.
In the color material of color lake, counter ion counterionsl gegenions are different according to above-mentioned dyes, and the counter ion counterionsl gegenions of acid dyes are cation, alkali Property dyestuff counter ion counterionsl gegenions be anion.Therefore, above-mentioned color lake agent suitably selects to use according to above-mentioned dyestuff.That is, will Above-mentioned acid dyes carries out using the compound for the counter cation for generating the dyestuff as color lake in thawless situation Agent；Will under above-mentioned basic dye carries out thawless situation, use the compound for the counter anion for generating the dyestuff as Color lake agent.
As the counter cation of acid dyes, other than ammonium cation, metal cation or inorganic polymeric can be enumerated Object etc..
It is suitable for that it can be mentioned, for example primary amino-compound, secondary amine compound, tertiary amines by person as the color lake agent for generating ammonium cation Compound etc., wherein, it is preferable to use secondary amine compound or tertiary amine compound from the viewpoint of heat resistance and excellent in light-resistance.
In addition, as the color lake agent for generating metal cation, it can be appropriate from the metal salt with required metal ion Selection.
The counter cation of acid dyes, which can be used alone, or combines two or more use by a kind.
On the other hand, as inorganic anion, it can be mentioned, for example the anion of oxyacid (phosphate ion, sulfate ion, chromium Acid ion, wolframic acid ion (WO4 2-), molybdic acid ion (MoO4 2-) etc.), multiple oxyacid be condensed obtained by polybasic acid anion etc. Or mixtures thereof inorganic anion.
In the present invention, color lake color material is from the viewpoint of heat resistance and light resistance, wherein preferably comprising basic dye with The color lake color material of inorganic anion more preferably includes the color lake color material of basic dye and polybasic acid anion.
In the present invention, the metallic lakes color material of xanthene based dye is particularly preferably combined as its allochromatic colour material, wherein preferably The metallic lakes color material of xanthene system acid dyes.
As the xanthene system acid dyes in the color lake color material, wherein compound shown in preferred the following general formula (VI), that is, With rhodamine system acid dyes person.
[changing 11]
Logical formula (VI)
(in logical formula (VI), R10~R13Independently indicate hydrogen atom, alkyl, aryl or heteroaryl, R10With R12、R11With R13Also bonding formation ring structure.R14Indicate that acidic groups, X indicate halogen atom.M indicates 0~5 integer.Logical formula (VI) has 1 A above acidic groups, the integer that n is 0 or more.)
R10~R13In alkyl be not particularly limited.It can be mentioned, for example the straight chain for the carbon number 1~20 that can have substituent group or Branched-chain alkyl etc., wherein the preferably straight chain or branch of the alkyl of the linear chain or branched chain of carbon number 1~8, more preferably carbon number 1~5 The alkyl of chain.It as the substituent group that alkyl can have, is not particularly limited, it can be mentioned, for example aryl, halogen atom, hydroxyls etc., make For the alkyl being substituted, benzyl etc. can be enumerated, furthermore also can have halogen atom, acidic groups as substituent group.
R10~R13In aryl be not particularly limited.It can be mentioned, for example the aryl with substituent group of carbon number 6~20, Wherein, preferably phenyl, naphthalene etc..R10~R13In heteroaryl, the heteroaryl with substituent group of carbon number 5~20 can be enumerated Base preferably comprises nitrogen-atoms, oxygen atom, sulphur atom as hetero atom.
As the substituent group that aryl or heteroaryl can have, it can be mentioned, for example the alkyl of carbon number 1~5, halogen atom, acidity Base, hydroxyl, alkoxy, carbamoyl, carboxylate etc..
It should be noted that R10~R13It can be identical or different.
As acidic groups or the concrete example of its salt, carboxyl (- COOH), carboxylic acid foundation (- COO can be enumerated-), carboxylate group (- COOM, this M indicate metallic atom), sulfonic acid foundation (- SO3 -), sulfonic group (- SO3H), sulfonate group (- SO3M is indicated in this M Metallic atom) etc.；Wherein, preferably there is sulfonic acid foundation (- SO3 -), sulfonic group (- SO3) or sulfonate group (- SO H3M in) extremely It is a kind few.It should be noted that sodium atom, potassium atom etc. can be enumerated as metallic atom M.
As compound shown in logical formula (VI), from the viewpoint of high brightness, wherein preferably acid red 50, acidity Red 52, acid red 289, acid violet 9, acid violet 30, Blue VRS 9 etc..
In addition, leading in formula (VI), the change with betaine structure of preferably m=1 and n=0 from the viewpoint of heat resistance Close object.
The metallic lakes color material of above-mentioned xanthene system acid dyes uses the color material that contains metallic atom as color lake agent. By using the color lake agent containing metallic atom, the heat resistance of color material is got higher.As such color lake agent, preferably comprise as 2 The color lake agent of the metallic atom of the above metal cation of valence.
In the case where combining its allochromatic colour material use in above-mentioned color lake color material, the mixing ratio of color material is to obtain required tone Mode give appropriate adjustment.From the viewpoint of heat resistance and excellent in light-resistance, wherein relative to incorporating color lake color 100 mass parts of color material total amount of material and its allochromatic colour material, above-mentioned color lake color material be preferably 30~100 mass parts, more preferably 60~ 99 mass parts, further preferably 70~98 mass parts.
[dispersing agent]
Color material dispersion liquid of the invention, using at least having Component units (a) and the amine value shown in the following general formula (II) to be 70mgKOH/g or more and 160mgKOH/g block copolymer below is as dispersing agent.
[changing 12]
Logical formula (II)
(in logical formula (II), R1For hydrogen atom or methyl, Q is divalent concatenating group, R2Alkylidene ,-[CH for carbon number 1~8 (R5)-CH(R6)-O]x-CH(R5)-CH(R6)-or-[(CH2)y-O]z-(CH2)yShown in divalent organic group, R3And R4Respectively Independent expression can substituted chain or cricoid alkyl or R3And R4It bonds together and forms cyclic structure.R5And R6It is only respectively It is on the spot hydrogen atom or methyl.
X indicates that 1~18 integer, y indicate that 1~5 integer, z indicate 1~18 integer.)
Amino possessed by Component units (a) shown in above-mentioned logical formula (II) has color material shown in above-mentioned logical formula (I) Compatibility can be such that the color material is dispersed with molecular association state by being adsorbed in the color material.It should be noted that of the invention Formula of (II) though shown in Component units (a) in dispersion liquid, with aftermentioned organic acid compound carry out salt formation feelings Under condition, it is regarded as including the Component units shown in above-mentioned logical formula (II).
As the divalent concatenating group Q of above-mentioned logical formula (II), it can be mentioned, for example the alkylidene of carbon number 1~10, arlydene ,- CONH- base ,-COO- base, the ether (- R'-OR "-: R' and R " is separately alkylidene) of carbon number 1~10 and their group Close etc..Wherein, from the heat resistance of resulting polymer, to the propylene glycol monomethyl ether acetate (PGMEA) for being suitable as solvent Dissolubility and belong to from the perspective of relatively cheap material, Q be preferably-COO- base.
The divalent organic group R of above-mentioned logical formula (II)2Alkylidene ,-[CH (R for carbon number 1~85)-CH(R6)-O]x-CH (R5)-CH(R6)-or-[(CH2)y-O]z-(CH2)y.The alkylidene of above-mentioned carbon number 1~8 can be appointing in straight-chain, branched It is one kind, for example, methylene, ethylidene, trimethylene, propylidene, various butylidenes, various pentylidene, various hexylidenes, each Kind octamethylene etc..
R5And R6It is separately hydrogen atom or methyl.
As above-mentioned R2, from the viewpoint of dispersibility, the preferably alkylidene of carbon number 1~8, wherein R2It is more preferably sub- Methyl, ethylidene, propylidene, butylidene, further preferably methylene and ethylidene.
R as above-mentioned logical formula (II)3、R4The cyclic structure for bonding together and being formed, it can be mentioned, for example containing for 5~7 Yuans rings Azacyclo- monocycle or they with 2 condensation made of condensed ring.The nitrogen-containing heterocycle does not preferably have armaticity, is more preferably saturated Ring.
It as Component units (a) shown in above-mentioned logical formula (II), can enumerate: by (methyl) acryloxypropyl dimethyl Amine, (methyl) acryloyl-oxyethyl dimethyl amine, (methyl) acryloxypropyl diethylamide, (methyl) acryloxy Component units derived from ethyl diethylamide etc. etc., but do not schedule this.
In above-mentioned dispersing agent, Component units (a) shown in logical formula (II) are preferably by forming color material parent containing 3 or more With the block portion of property.From dispersibility and dispersion stabilization it is excellent, inhibit through when viscosity change, excellent heat resistance viewpoint go out Hair, the block portion of the color material compatibility preferably comprises Component units (a) 3~50 shown in above-mentioned logical formula (II), more preferably contains There are 6~40, further preferably 10~30.
Component units (a) shown in logical formula (II) may include a kind, can also contain Component units of more than two kinds.
Other Component units of < >
Above-mentioned block copolymer preferably includes from the viewpoint of dispersibility and has composition shown in above-mentioned logical formula (II) The color material compatibility block portion (hereinafter sometimes referred to as A block) of unit；Do not have and constitutes list shown in above-mentioned logical formula (II) First (a) and there is the solvent compatibility block portion for the Component units that can be copolymerized with above-mentioned logical formula (II) (to record sometimes below For B block).In the present invention, the configuration of each block of block copolymer is not particularly limited, and can be set as such as AB block copolymerization Object, ABA block copolymer, BAB block copolymer etc..Wherein, from the viewpoint of dispersibility is excellent, preferably AB block copolymerization Object or ABA block copolymer.
As the Component units that can be copolymerized with above-mentioned logical formula (II), from point for promoting color material shown in logical formula (I) From the perspective of dissipating property and dispersion stabilization, promoting heat resistance simultaneously, preferably constituted shown in the following general formula (III) single Member.
[changing 13]
Logical formula (III)
(in logical formula (III), R7Indicate hydrogen atom or methyl；A indicates Direct Bonding key or divalent concatenating group；R8For carbon number 1~ Alkenyl, aralkyl, aryl, the-[CH (R of 18 alkyl, carbon number 2~189)-CH(R10)-O]x-R11Or-[(CH2)y-O]z-R11 Shown in 1 valence group.R9And R10It is separately hydrogen atom or methyl, R11For the alkyl of hydrogen atom or carbon number 1~18, carbon Alkenyl, aralkyl, the aryl ,-CHO ,-CH of number 2~182CHO or-CH2COOR12Shown in 1 valence group, R12For hydrogen atom or Straight-chain, branched or the cricoid alkyl of carbon number 1~5.X indicates that 1~18 integer, y indicate that 1~5 integer, z indicate 1 ~18 integer.M indicates that 3~200 integer, n indicate 10~200 integer.)
The concatenating group A of divalent as above-mentioned logical formula (III) can be set as person identical as the Q in above-mentioned logical formula (II), from institute Polymer heat resistance or to the dissolubility of the propylene glycol monomethyl ether acetate (PGMEA) for being suitable as solvent or belong to From the perspective of relatively cheap material, A is preferably-COO- base.
R8In, the alkyl of above-mentioned carbon number 1~18 can be any one of straight-chain, branched, ring-type, and it can be mentioned, for example first Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, various amyls, various hexyls, various octyls, Various decyls, various dodecyls, various tetradecyls, various palmityls, various octadecyls, cyclopenta, cyclohexyl, cyclooctyl, ring Dodecyl, bornyl, isobornyl, bicyclopentyl, adamantyl, low alkyl group replace adamantyl etc..
The alkenyl of above-mentioned carbon number 2~18 can be any one of straight-chain, branched, ring-type.As such alkenyl, can arrange Citing such as vinyl, allyl, acrylic, various cyclobutenyls, various hexenyls, various octenyls, various decene bases, various ten Dialkylene, various tetradecene bases, various hexadecylene bases, various octadecylene bases, cyclopentenyl, cyclohexenyl group, cyclo-octene base etc..
Wherein, from the viewpoint of dispersibility, substrate adhesion, R8Preferably methyl, various butyl, various hexyls, benzyl Base, cyclohexyl, ethoxy.
As the aryl that there can be substituent group, phenyl, xenyl, naphthalene, tolyl, xylyl etc. can be enumerated.Aryl Carbon number be preferably 6~24, more preferably 6~12.
As the aralkyl that there can be substituent group, benzyl, phenethyl, menaphthyl, diphenylmethyl etc. can be enumerated.Aralkyl Carbon number be preferably 7~20, more preferably 7~14.
The substituent group of aromatic rings as aryl, aralkyl etc., in addition to the straight-chain of carbon number 1~4, branched alkyl it Outside, alkenyl, nitro, halogen atom etc. can be enumerated.
In addition, above-mentioned R11For hydrogen atom or can have substituent group, carbon number 1~18 alkyl, carbon number 2~18 alkenyl, Aralkyl, aryl ,-CHO ,-CH2CHO or-CH2COOR12Shown in 1 valence group, R12For hydrogen atom or the straight chain of carbon number 1~5 Shape, branched or cricoid alkyl.
Above-mentioned R11Shown in 1 valence group, as the substituent group that can have, it can be mentioned, for example the straight-chain of carbon number 1~4, Branched or the halogen atoms such as cricoid alkyl, F, Cl, Br etc..
Above-mentioned R11In carbon number 1~18 alkyl and carbon number 2~18 alkenyl, aralkyl, aryl, such as above-mentioned R8It is shown.
Above-mentioned R8In, the R in x, y and z and above-mentioned logical formula (II)2It is identical.
In the present invention, the glass transition temperature (Tg) in the block portion of the solvent compatibility of above-mentioned block copolymer is suitably selected It selects.From the viewpoint of heat resistance, wherein the glass transition temperature (Tg) in the block portion of solvent compatibility is preferably 80 DEG C or more, more preferably 100 DEG C or more.
The glass transition temperature (Tg) in the block portion of the solvent compatibility in the present invention can be calculate by the following formula, and same Ground can also calculate the glass transition temperature of color material compatibility block portion and block copolymer.
1/Tg=Σ (Xi/Tgi)
Here, n monomer component until solvent compatibility block portion is set as from i=1 to n is copolymerized.Xi is i-th The weight rate (Σ Xi=1) of monomer, Tgi are the glass transition temperature (absolute temperature) of the homopolymer of i-th of monomer.Its In, Σ is derived from the sum of i=1 to n.It should be noted that the value (Tgi) of the homopolymer glass transition temperature of each monomer can be used Polymer Handbook (3rd Edition) (J.Brandrup, E.H.Immergut work (Wiley-Interscience, 1989) value).
The quantity of the Component units in the block portion of solvent compatibility is constituted, so that the amine value of dispersing agent becomes 70mgKOH/g Above and 160mgKOH/g range appropriate adjustment below.Wherein, from solvent compatibility position and color material compatibility position From the perspective of effectively acting on, promoting color material dispersibility, the quantity for constituting the Component units in the block portion of solvent compatibility is excellent It is selected as 10~200, more preferably 10~100, further preferably 10~70.
As long as the block portion of solvent compatibility is selected in a manner of playing function as solvent compatibility position, constitute The repetitive unit in the block portion of solvent compatibility can be constituted by a kind, can also contain repetitive unit of more than two kinds.
Be used as inventive dispersant block copolymer in, as Component units shown in logical formula (II) unit number m, With the ratio m/n for the unit number n for constituting solvent compatibility block portion, in the range of preferably 0.01~1, the dispersion of Cong Secai From the perspective of property, dispersion stabilization, in the range of more preferably 0.05~0.7.
In the present invention, dispersing agent selects using amine value to be 70mgKOH/g or more and 160mgKOH/g or less person.By making amine Value is the then ageing stability, excellent heat resistance of viscosity in above range, while to be redissolved property also excellent for alkali-developable, solvent. In the present invention, from the viewpoint of dispersibility and dispersion stabilization, the amine value of dispersing agent is preferably 80mgKOH/g or more, more excellent It is selected as 90mgKOH/g or more.On the other hand, from the viewpoint of solvent redissolution property, the amine value of dispersing agent is preferably 120mgKOH/g or less, more preferably 105mgKOH/g or less.
Amine value refers to the potassium hydroxide with perchloric acid needed for contained amine component in neutralization sample 1g quite (Japanese: equivalent) Mg number, can be measured by method defined in JIS-K7237.When being measured by this method, in dispersing agent Organic acid compound carry out in the amino of salt formation, the usual organic acid compound dissociates, therefore can measure to be used as and disperse The amine value of the block copolymer of agent itself.
The acid value of dispersing agent used in the present invention, from the viewpoint of the inhibitory effect of performance development residue, lower limit is excellent It is selected as 1mgKOH/g or more.Wherein, from the viewpoint of the inhibitory effect of development residue is more excellent, the acid value of dispersing agent is more preferable For 2mgKOH/g or more.In addition, the acid value of dispersing agent used in the present invention, from the deterioration or solvent that can prevent development adhesion From the perspective of the deterioration of redissolution property, the upper limit is preferably 18mgKOH/g or less.Wherein, molten again from development adhesion and dissolution Solution property it is good from the perspective of, the acid value of dispersing agent be more preferably 16mgKOH/g or less, further preferably 14mgKOH/g with Under.
In addition, in the present invention, the glass transition temperature of dispersing agent, from the viewpoint of being promoted and developing adhesion, preferably It is 30 DEG C or more.If the glass transition temperature of dispersing agent is lower, especially close to developer temperatur (usually 23 DEG C or so), There is the anxiety of development adhesion reduction.Its reason can be pushed away and is judged to: if the glass transition temperature close to developer temperatur, when developing The movement of dispersing agent becomes larger, as a result, development adhesion deteriorates.By making 30 DEG C of glass transition temperature or more, can inhibit The molecular motion of dispersing agent when development, therefore push away the reduction sentenced and can inhibit development adhesion.
The glass transition temperature of dispersing agent, from the viewpoint of adhesion of developing, wherein preferably 32 DEG C or more, it is more excellent It is selected as 35 DEG C or more.From the perspective of operability when on the other hand, by being easy the uses such as smart scale, preferably 200 DEG C or less.
The glass transition temperature of dispersing agent of the invention can be measured according to JIS K7121, by Differential Scanning Calorimeter (DSC) it is measured and acquires.
In addition, in the present invention, Cong Secai dispersion stabilization is excellent, inhibits development residue when as colored resin composition Occur and solvent be redissolved property is excellent, furthermore there is high development adhesion from the perspective of, the acid value of above-mentioned dispersing agent is preferably 1mgKOH/g or more and 18mgKOH/g are hereinafter, glass transition temperature is 30 DEG C or more.
If improving color material concentration, increasing dispersant, reduced since amount of binder is opposite, therefore colored resin layer is aobvious It is easy to be removed by basal substrate when shadow.By making dispersing agent contain the B block comprising the Component units from carboxyl group-containing monomer, and With above-mentioned specific acid value and glass transition temperature, thus adhesion promotion of developing.However, sentencing when acid value is excessively high though pushing away Right developability is excellent, but polarity is excessively high and be easy to happen removing in development.
As above-mentioned carboxyl group-containing monomer, can be used can be total to having the monomer of Component units shown in logical formula (II) The poly- and monomer containing unsaturated double-bond and carboxyl.As such monomer, it can be mentioned, for example (methyl) acrylic acid, vinyl benzene Formic acid, maleic acid, maleic acid mono alkyl ester, fumaric acid, itaconic acid, crotonaldehyde, cinnamic acid, acrylic acid dimer etc..In addition, It is available: the monomer and maleic anhydride, phthalic anhydride, hexamethylene two with hydroxyl of (methyl) acrylic acid 2- hydroxyl ethyl ester etc. Addition reaction, ω-carboxyl-polycaprolactone list (methyl) acrylate of the cyclic acid anhydride of carboxylic acid anhydrides etc etc..In addition, can also Use the monomer containing anhydride group of maleic anhydride, itaconic anhydride, citraconic anhydride etc. as carboxyl precursor.Wherein, from copolymerization, cost, From the perspective of dissolubility, glass transition temperature etc., particularly preferably (methyl) acrylic acid.
In above-mentioned block copolymer, the content ratio of the Component units from carboxyl group-containing monomer, with the acid of block copolymer The mode that value becomes in above-mentioned specific acid value is suitably set, and is not particularly limited, relative to the total of block copolymer Total quality of Component units, preferably 0.05~4.5 mass %, more preferably 0.07~3.7 mass %.
More than the above-mentioned lower limit value of content ratio by making the Component units from carboxyl group-containing monomer, it is residual to can express development The inhibitory effect of slag, by for above-mentioned upper limit value hereinafter, the development deterioration of adhesion, solvent can be prevented to be redissolved the deterioration of property.
As long as it should be noted that the Component units from carboxyl group-containing monomer be above-mentioned specific acid value, can be by a kind It constitutes, Component units of more than two kinds can also be contained.
In addition, the glass transition temperature of dispersing agent used in the present invention is set as particular value or more, develop from being promoted From the perspective of adhesion, the monomer that the value (Tgi) of the glass transition temperature of the homopolymer of monomer is 10 DEG C or more preferably with Add up to meter and is set as 75 mass % or more, more preferably 85 mass % or more in B block.
In above-mentioned block copolymer, the unit number m of the Component units as above-mentioned A block and the composition list of above-mentioned B block The ratio m/n of the unit number n of member, in the range of preferably 0.05~1.5, dispersibility, the viewpoint of dispersion stabilization of Cong Secai It sets out, in the range of more preferably 0.1~1.0.
The weight average molecular weight Mw of above-mentioned block copolymer is not particularly limited, and from making, color material is dispersed and dispersion stabilization is good From the perspective of good, preferably 1000~20000, more preferably 2000~15000, further preferably 3000~12000.
Here, weight average molecular weight (Mw) is gel permeation chromatography (GPC) in the form of standard polystyren scaled value It acquires.
The manufacturing method of above-mentioned block copolymer is not particularly limited.Block copolymer can be manufactured by known method, In, preferably manufactured with living polymerization.The reason for this is that being difficult to happen, chain is mobile, inactivates, and can manufacture molecular weight uniform Copolymer can promote dispersibility etc..As living polymerization, living radical polymerization, group transfer polymerization method etc. can be enumerated Active anionic polymerization method, living cationic polymerization etc..It polymerize monomer successively using these methods, thus can manufactures copolymerization Object.For example, first manufacturing A block, it polymerize the Component units for constituting B block with A block, thus can manufactures block copolymerization Object.In addition, can also make A block opposite with the polymerization sequence of B block in above-mentioned manufacturing method.In addition, can also manufacture A respectively Block and B block are coupled A block with B block thereafter.
In color material dispersion liquid of the invention, at least using the polymer with Component units shown in above-mentioned logical formula (II) A kind of to be used as dispersing agent, content regards used color material type and aftermentioned colored filter photosensitive color resin Solid component concentration in composition etc. and it is suitably selected.
The content of dispersing agent, from the viewpoint of dispersibility and dispersion stabilization, relative to total solid in color material dispersion liquid 100 mass parts of body ingredient are preferably cooperated with 3~45 mass parts, more preferably with the ratio of 5~35 mass parts.
Especially when forming the highly concentrated film of color material or coloring layer, the content of dispersing agent is relative in color material dispersion liquid 100 mass parts of total solid content, preferably cooperated with 3~25 mass parts, more preferably with the ratios of 5~20 mass parts.
It should be noted that solid component is the whole components other than above-mentioned solvent, also molten including being dissolved in the present invention Monomer etc. in agent.
[organic acid compound]
Color material dispersion liquid of the invention contains organic acid compound.As long as in the present invention organic acid compound be can with it is above-mentioned The organic acid compound of amino forming salt person possessed by block copolymer as dispersing agent can suitably select to use. In the present invention, by using above-mentioned organic acid compound, so that the dispersibility of color material and dispersion stabilization are excellent, it can be obtained heat-resisting Property excellent film, additionally due to aqueous alkali when salt forming part is to alkali development has high-affinity, therefore it is aobvious to can be made into alkali The excellent color material dispersion liquid of shadow.
Organic acid compound is with amino forming salt possessed by Component units (a) shown in above-mentioned logical formula (II) the case where Under, become structure shown in general formula (II').
[changing 14]
General formula (II')
(in general formula (II'), A?For the anion from organic acid compound, other symbols and above-mentioned logical formula (II) phase Together.)
In the present invention, if organic acid compound be with 1 or more carbon atom and the compound of acidic groups, and It is not particularly limited.As acidic groups possessed by organic acid compound, carboxyl, sulfonic group, phosphate etc. can be enumerated, from dispersion From the perspective of property, dispersion stabilization, heat resistance and alkali-developable, preferably sulfonic group or phosphate.In addition, from alkali-developable From the perspective of, it is however preferred to have phosphate.
The quantity of acidic groups contained in 1 molecule of organic acid compound is not particularly limited, from dispersibility, stably dispersing Property, from the perspective of heat resistance and alkali-developable, the acidic groups in 1 molecule is preferably 1~3, more preferably 1~2.Separately Outside, the valence mumber of acidic groups is not particularly limited, from the viewpoint of dispersion stabilization, heat resistance and developability, preferably 1~3 The acid of the acid of valence, more preferably 1~divalent.
In the present invention, organic acid compound, from the viewpoint of being easy to carry out salt formation with amino possessed by dispersing agent, Molecular weight is preferably 5000 or less, more preferably 100 or more and 1000 or less, further preferably 150 or more and 500 or less.
In the present invention, from the viewpoint of dispersibility, dispersion stabilization, heat resistance and alkali-developable it is excellent, organic acidification Close a kind or more that object is preferably selected from the group as composed by the following general formula (IV) and the following general formula (V).
[changing 15]
(in formula (IV) and formula (V), RaAnd Ra'Be each independently hydrogen atom, hydroxyl, the alkyl of carbon number 1~18, carbon number 2~ 18 alkenyl, aralkyl, aryl ,-[CH (Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-ReOr-O-Ra”Shown in 1 valence base Group, RaAnd Ra'Any one contain carbon atom.Ra”For the alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, aralkyl, aryl ,- [CH(Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-ReShown in 1 valence group.
RbFor the alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, aralkyl, aryl ,-[CH (Rc)-CH(Rd)-O]s- Re、-[(CH2)t-O]u-ReOr-O-Rb'Shown in 1 valence group.Rb'For the alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, virtue Alkyl, aryl ,-[CH (Rc)-CH(Rd)-O]s-ReOr-[(CH2)t-O]u-ReShown in 1 valence group.
RcAnd RdIt is separately hydrogen atom or methyl, ReFor the alkyl of hydrogen atom or carbon number 1~18, carbon number 2~18 Alkenyl, aralkyl, aryl ,-CHO ,-CH2CHO ,-CO-CH=CH2、-CO-C(CH3)=CH2Or-CH2COORfShown in 1 valence Group, RfFor hydrogen atom or the alkyl of carbon number 1~5.
Ra、Ra'And RbIn, alkyl, alkenyl, aralkyl, aryl can have substituent group respectively.
S indicates that 1~18 integer, t indicate that 1~5 integer, u indicate 1~18 integer.)
In above-mentioned logical formula (IV), in RaAnd Ra'In the case where aromatic rings, there can be substitution appropriate on the aromatic rings Base, such as straight-chain, the alkyl of branched of carbon number 1~4 etc..
Alkyl, aralkyl, the aryl of above-mentioned carbon number 1~18 can be set as and the R in above-mentioned dispersing agent8Identical person.
In RaAnd/or Ra'For-O-Ra”When, become acid phosphoric acid ester.
It should be noted that in Ra”In the case where aromatic rings, can also have substituent group appropriate, example on the aromatic rings The alkyl of the straight-chain, branched of such as carbon number 1~4.
In above-mentioned ReIn 1 represented valence group, as the substituent group that can have, it can be mentioned, for example the straight chains of carbon number 1~4 Shape, branched or the halogen atoms such as cricoid alkyl, F, Cl, Br etc..
Above-mentioned ReIn carbon number 1~18 for example above-mentioned R of alkyl8It is shown, for example above-mentioned R of the alkenyl of carbon number 2~18aAnd Ra'It is shown.
In Ra、Ra'And Ra”In, the integer that s is 1~18, the integer that t is 1~5, the integer that u is 1~18.S is preferably 1~4 Integer, more preferably 1~2 integer；T be preferably 1~4 integer, more preferably 2 or 3.U is preferably 1~4 integer, more Preferably 1~2 integer.
In above-mentioned logical formula (V), in RbIn the case where aromatic rings, can have substituent group appropriate, example on the aromatic rings The alkyl of the straight-chain, branched of such as carbon number 1~4.
In RbFor-O-Rb'When, become acid sulfate.Above-mentioned Rb'For the alkyl of carbon number 1~18, carbon number 2~18 alkenyl, Aralkyl, aryl ,-[CH (Rc)-CH(Rd)-O]s-ReOr-[(CH2)t-O]u-ReShown in 1 valence group.
For example above-mentioned R of alkyl, aralkyl, aryl of above-mentioned carbon number 1~188It is shown；For example above-mentioned R of the alkenyl of carbon number 2~18aAnd Ra'It is shown.It should be noted that in Rb'In the case where aromatic rings, there can be substituent group appropriate on the aromatic rings, such as Straight-chain, alkyl of branched of carbon number 1~4 etc..
Above-mentioned Rc、RdAnd ReIt is same as described above.
In above-mentioned RbAnd Rb'In, the integer that s is 1~18, the integer that t is 1~5, the integer that u is 1~18.Preferred s, t, U and above-mentioned Ra、Ra'And Ra”It is identical.
As organic acid compound shown in above-mentioned logical formula (IV), from the dispersibility and coloring obtained for promoting color material From the perspective of contrast is higher and excellent heat resistance of layer, preferably are as follows: the R in above-mentioned logical formula (IV)aAnd Ra'Separately For hydrogen atom, hydroxyl, methyl, ethyl, the aryl or aralkyl that can have substituent group, vinyl, allyl ,-[CH (Rc)-CH (Rd)-O]s-ReOr-[(CH2)t-O]u-ReOr-O-Ra”Shown in 1 valence group, RaAnd Ra”Any one include carbon atom, and Ra”For methyl, ethyl, the aryl or aralkyl that can have substituent group, vinyl, allyl ,-[CH (Rc)-CH(Rd)-O]s-Re、 Or-[(CH2)t-O]u-Re, RcAnd RdIt is separately hydrogen atom or methyl；More preferably: RaFor hydroxyl, and Ra'For that can have The aryl of substituent group.
In addition, as organic acid compound shown in logical formula (V), from the dispersibility and coloring obtained for promoting color material From the perspective of contrast is higher and excellent heat resistance of layer, preferably are as follows: the R in general formula (V)bFor methyl, ethyl, can have Aryl or aralkyl, vinyl, allyl, the-[CH (R of substituent groupc)-CH(Rd)-O]s-ReOr-[(CH2)t-O]u-ReOr Person-O-Rb'Shown in 1 valence group, Rb'For methyl, ethyl, the aryl or aralkyl that can have substituent group, vinyl, allyl Base ,-[CH (Rc)-CH(Rd)-O]s-ReOr-[(CH2)t-O]u-Re, RcAnd RdIt is separately hydrogen atom or methyl；It is more excellent It is selected as: RbFor that can have the aryl of substituent group.
Wherein, organic acid compound shown in above-mentioned logical formula (IV) and logical formula (V), from the dispersibility and institute for promoting color material From the perspective of the contrast of the coloring layer of acquisition is higher and excellent heat resistance, preferably are as follows: as Ra、Ra'And/or Ra”And/ Or RbAnd/or Rb', and there is aromatic rings.From the viewpoint of color material dispersibility, preferably Ra、Ra'And Ra”In at least one or Person RbOr Rb'For that can have the aryl or aralkyl of substituent group, more specifically benzyl, phenyl, tolyl, naphthalene, biphenyl Base.In above-mentioned logical formula (IV), in RaAnd Ra'One of have aromatic rings when, RaAnd Ra'Another one be suitable for using hydrogen atom or Hydroxyl.
In addition, from the viewpoint of heat resistance or drug resistance, especially alkali resistance, as above-mentioned logical formula (IV) and general formula (V) organic acid compound shown in, preferably carbon atom are bonded directly to the compound of phosphorus (P), sulphur (S), preferably RaAnd Ra'Point It independently is not hydrogen atom, hydroxyl, the alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, aralkyl, aryl ,-[CH (Rc)-CH (Rd)-O]s-Re、-[(CH2)t-O]u-ReShown in 1 valence group, RaAnd Ra'Any one include carbon atom.Additionally, it is preferred that RbFor The alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, aralkyl, aryl ,-[CH (Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-Re Shown in 1 valence group.
In the present invention, from dispersibility, heat resistance aspect, organic acid compound be preferably benzene sulfonic acid, p-methyl benzenesulfonic acid, Monobutyl phosphoric acid, dibutylphosphoric acid, methyl acid phosphate, dibenzyl phosphoric acid, diphenylphosphoric acid, phenyl-phosphonic acid etc., wherein more preferably P-methyl benzenesulfonic acid, phenyl-phosphonic acid.It should be noted that organic acid compound can be used such as p-methyl benzenesulfonic acid monohydrate etc Hydrate.
In the present invention, organic acid compound, which can be used alone, or combines two or more use by a kind.
In the present invention, total content of dispersing agent and organic acid compound is not particularly limited, steady from dispersibility and dispersion From the perspective of qualitative, relative to 100 mass parts of color material, total content of dispersing agent and organic acid compound is preferably 10~ 120 mass parts, more preferably 20~100 mass parts, further preferably 30~80 mass parts.
[dispersing agent, the relationship with organic acid compound]
Color material dispersion liquid of the invention, by the way that dispersing agent and organic acid compound are applied in combination in the following manner, and makes color The color material dispersibility and dispersion stabilization of material dispersion liquid are excellent, the film of excellent heat resistance can be obtained, additionally due to salt forming portion Aqueous alkali when position is to alkali development has highly dissoluble, therefore can form the excellent person of alkali-developable, wherein the mode are as follows: The above-mentioned amine value of above-mentioned dispersing agent is set as A (mgKOH/g), by above-mentioned organic acid compound contained in above-mentioned color material dispersion liquid Substance amount XA(mol) with the object for the above-mentioned Component units (a) for constituting above-mentioned dispersing agent contained in above-mentioned color material dispersion liquid The amount X of matterBThe ratio between (mol) it is set as X (=XA/XB) when, meet following formula (1) and formula (2)；In the range of X is less than 1, further Meet following formula (3).
The formula of X≤1.5 (1)
The formula of A × X >=40 (2)
A × (1-X)≤42 formula (3)
Above formula (1) indicates that, relative to amino possessed by above-mentioned dispersing agent, above-mentioned organic acid compound is 1.5 molar equivalents Below.If organic acid compound be 1.5 molar equivalents hereinafter, if do not carry out the ratio of salt formation and existing organic acid compound Few, the dispersion stabilization of color material is excellent, and organic acid compound is not precipitated.It should be noted that not carrying out salt formation and existing Organic acid compound has the effect of promoting the heat resistance and alkali-developable of film.In the present invention, preferably X≤1.3, more preferably For 0.7≤X≤1.2.
Above formula (2) indicates that the amino of the organic acid added by being assumed to be and dispersing agent is formed with 1:1 100% salt of progress When, in the amino possessed by dispersing agent, it is equivalent to the amine value of the part formed for salt.It should be noted that being more than 1 in X Range when, push away and sentence superfluous organic acid compound and make the color lake structure stabilization of compound (I), therefore heat resistance further mentions It rises.Meet the color material dispersion liquid of above formula (2) compatibility of color material is suitable for dispersing, therefore dispersion stabilization is excellent.
In addition, recently as the High precision of colored filter, and the coloring layer of colored filter is required to be thinned.In order to Coloring layer is thinned, it is necessary to improve pigment concentration to the solid component in colored resin composition, the developability of dispersing agent is also made At larger impact.
Even if, in order to realize sufficient developability, preferably salt is formed in the high colored resin composition of pigment concentration Portion is more, i.e. more A × X >=60 of organic acid, more preferably A × X >=80.
From the viewpoint of the redissolution to solvent, preferably salt forming portion is less, i.e. the less A × X of organic acid≤ 130, A × X≤110 are more preferably.
In addition, above formula (2) is indicated assuming that the amino of added organic acid and dispersing agent carries out 100% salt shape with 1:1 Cheng Shi, in the amino possessed by dispersing agent, with the comparable amine value in part for not carrying out salt formation.Meet the color material of above formula (2) Dispersion liquid is since the amino for not carrying out salt formation is less, therefore the molecular association state of color material is difficult to be destroyed.Therefore, using satisfaction The viscosity stability of colored resin composition made by the color material dispersion liquid of above formula (2) is excellent, even if utilizing the coloured tree Oil/fat composition is formed by coloring layer, due to still maintain molecular association state, therefore excellent heat resistance.In addition, X be 1 with On range when, it is heat-resisting since the amino for not carrying out salt formation is few, therefore in the same manner as the case where X is less than 1 and meets above formula (2) Property is excellent.
It should be noted that in the present invention, XAFor the amount of the substance of organic acid compound, it is set as not including color lake color material Contained counter anion or alkali soluble resin.
[solvent]
It the use of solubility of the color material shown in above-mentioned logical formula (I) at 23 DEG C is 0.1 (g/ as solvent in the present invention 10ml solvent) solvent below.This substantially solvent of undissolved solvent or slightly solubility is used relative to color material, by This, color material dispersion liquid of the invention can be such that color material shown in above-mentioned logical formula (I) makes in a solvent with the dispersion of molecular association state With.Solvent used in the present invention, from the viewpoint of it dispersibility, excellent heat resistance, the film of high brightness can be obtained, preferably Solubility for color material shown in the above-mentioned logical formula (I) at 23 DEG C is 0.05 (g/10ml solvent) solvent below.
It should be noted that in the present invention, the solubility of above-mentioned color material and above-mentioned xanthene based dye at 23 DEG C is 0.1 (g/10ml solvent) solvent below, can simply be determined by following evaluation method.
Firstly, can determine whether substantially dissolve color material shown in above-mentioned logical formula (I) by following methods Solvent.
In 20mL sample phial, investment is intended to judge deliquescent color material 0.1g, is put into using 10ml whole pipette molten Agent S, with ultrasonication 3 minutes after further covering.Gained liquid stands keeping 60 minutes in 23 DEG C of water-baths.By its supernatant 5ml is filtered with PTFE5 μm of membrane filter, then is filtered with 0.25 μm of membrane filter, and insoluble matter is removed.With ultraviolet Visible spectrophotometer (such as Shimadzu Seisakusho Ltd. corporation UV-2500PC) measures the extinction spectrum of gained filtrate using 1cm slot. Acquire the absorbance (abs) of the maximum absorption wavelength of each color material.At this point, if absorbance (abs) is less than the 40% of determination of the upper limit value (in the case where Shimadzu Seisakusho Ltd. corporation UV-2500PC, absorbance (abs) is less than 2), then the solvent can be evaluated as substantially not Dissolve the solvent of above-mentioned color material.At this point, further passing through lower commentary when absorbance (abs) is 40% or more of determination of the upper limit value Valence method acquires solubility.
Firstly, replace above-mentioned solvent S, using being intended to judge the good solvent (such as alcohol of methanol etc.) of deliquescent color material, together Filtrate is made to sample, makes color material solution, is suitably diluted to 10000 times~100000 times degree thereafter, similarly measures color material Maximum absorption wavelength absorbance.By the absorbance and dilution of the color material solution of the color material solution and good solvent of above-mentioned solvent S Multiplying power calculates color material to the solubility of above-mentioned solvent S.
As a result, the solubility of above-mentioned color material is 0.1 (g/10ml solvent) solvent below, being judged as in the present invention can make , solvent that color material is slightly solubility.
The solubility of above-mentioned color material is 0.1 (g/10ml solvent) solvent below, steady from the dispersion for promoting color material dispersion liquid From the perspective of qualitative, 95 mass % or more are contained preferably in the total solvent of color material dispersion liquid, more preferably contain 98 matter It measures % or more, be most preferably to contain 100 mass %.
In color material dispersion liquid of the invention, from the viewpoint of dispersing stability, wherein preferably by appropriate in ester series solvent Selection uses.
As ester series solvent, it can be mentioned, for example: ethyl acetate, butyl acetate, methoxy methyl propionate, ethoxy-propionic acid second Ester, ethyl lactate, methoxy ethyl acetate, propylene glycol monomethyl ether acetate, 3- methoxyl group-3- methyl-1-butylacetic acid Ester, 3- methoxybutyl acetate, methoxybutyl acetate, ethoxyethyl group acetate, ethyl cellosolve acetate, dipropyl Glycol ether acetate, propylene glycol diacetate, 1,3 butylene glycol diacetate, cyclohexanol acetic ester, 1,6-HD two Acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate etc..
Wherein, low from the risk to human body, near room temperature volatility it is low but the good viewpoint of heat drying goes out Hair is, it is preferable to use propylene glycol monomethyl ether acetate (PGMEA).In the case, though also have with used it is previous Not the advantages of special washing procedure is not needed when the switching of the colored resin composition of PGMEA yet.
As solvent used in the present invention, preferably propylene glycol monomethyl ether acetate contains 50 matter in total solvent % or more is measured, more preferably contains 70 mass % or more, further preferably contain 90 mass % or more.
These solvents can use alone or in combination of two kinds or more.
Color material dispersion liquid of the invention, relative to the total amount of the color material dispersion liquid containing the solvent, usually with 50~95 matter Measure %, the ratio of preferably 60~85 mass % is prepared using solvent as above.If solvent is very few, viscosity rises, disperses Property is easily reduced.In addition, color material concentration reduces if solvent is very few, has and preparing colored filter colored resin composition It is difficult to the case where reaching the chromaticity coordinate of target afterwards.
(other compositions)
In color material dispersion liquid of the invention, under the premise of not damaging effect of the present invention, optionally also can further it cooperate Disperse assisted resin, other compositions.
As dispersion assisted resin, illustrated by aftermentioned colored filter colored resin composition Alkali soluble resin.Make color material be difficult to contact each other by the steric hindrance of alkali soluble resin, has dispersion stability, because of this point It dissipates stabilization effect and reduces the effect of dispersing agent.As alkali soluble resin, wherein from the sight of dispersion stabilization and heat resistance Point sets out, it is preferable to use the resin with hydrocarbon ring, molecular association in stable conditionization of Cong Secai, the viewpoint for promoting heat resistance go out Hair is, it is preferable to use the high resin of acid value.
In addition, it can be mentioned, for example the surfactants, defoaming agent, anti-shrinkage for promoting wettability as other compositions Agent, antioxidant, anti-agglutinant, ultraviolet absorbing agent etc..
Color material dispersion liquid of the invention is used as being used to prepare the preparation of aftermentioned colored filter colored resin composition Prepared product.That is, so-called color material dispersion liquid refers to, in the last stage for preparing aftermentioned colored resin composition, preparation preparation (the color material ingredient in composition)/(solid component other than color material ingredient in composition) color material more higher than (mass ratio) point Dispersion liquid.Specifically, (the color material ingredient in composition)/(solid component other than color material ingredient in composition) is than (quality Than) it is usually 1.0 or more.For example, dispersion can be prepared by mixing color material dispersion liquid at least photonasty adhesive ingredients etc. The excellent colored resin composition of property.
[manufacturing method of color material dispersion liquid]
In the present invention, as long as the manufacturing method of color material dispersion liquid is that color material shown in above-mentioned logical formula (I) is utilized dispersing agent And the method for obtaining being scattered in color material dispersion liquid in solvent, then be not particularly limited, such as: (1) in advance by dispersant, stir It mixes in solvent, prepares dispersant solution, then mixed organic acid compound, make amino possessed by dispersing agent and organic acidification Object progress salt is closed to be formed.It is mixed with color material shown in logical formula (I) with other compositions optionally, using known blender or The method that dispersion machine is dispersed；(2) dispersant, stirring are prepared dispersant solution, then mixes general formula in solvent (I) color material and organic acid compound shown in and other compositions optionally, are dispersed using known blender or dispersion machine Method；(3) dispersant, stirring are prepared into dispersant solution in solvent, then mixes color material shown in logical formula (I) And other compositions optionally, using known blender or dispersal mechanism at dispersion liquid after, the method for adding organic acid compound Deng.
In the present invention, from the perspective of the dispersion stabilization of Cong Secai, the method that is preferably set to above-mentioned (1).
As the dispersion machine for carrying out decentralized processing, roller mills, ball mill, the vibratory millings such as double roller, three rollers can be enumerated The ball mills such as the ball mills such as machine, coating reconciliation device, continuous dish-type ball mill, continuous ring-like ball mill.As the preferred of ball mill Dispersion condition, used pearl diameter is preferably 0.03~2.00mm, more preferably 0.10~1.0mm.
Specifically, can enumerate: preparing dispersion by being carried out with the biggish 2mm zirconium oxide bead of pearl diameter, then smaller with pearl diameter 0.1mm zirconium oxide bead carry out main dispersion.In addition, being preferably filtered by 0.5~0.1 μm of membrane filter after dispersion.
2. colored filter colored resin composition
Colored filter colored resin composition of the invention is characterized in that the color material containing aforementioned present invention disperses Liquid, alkali soluble resin, polyfunctional monomer and initiator.
Colored filter colored resin composition of the invention contains the color material dispersion liquid of aforementioned present invention, thus through when it is steady Qualitative coloring layer that is excellent, can forming heat resistance promotion, alkali-developable are also excellent.
Colored filter colored resin composition of the invention at least contains color material shown in logical formula (I), dispersing agent, has Machine acid compound, alkali soluble resin, polyfunctional monomer, initiator and solvent, under the premise of not damaging effect of the present invention, It optionally also can further contain other compositions.
Hereinafter, each ingredient of such colored filter colored resin composition of the invention is successively described in detail, but close In color material, dispersing agent, organic acid compound and solvent, since the same person of color material dispersion phase with aforementioned present invention can be set as, therefore In this, the description thereof will be omitted.
[alkali soluble resin]
Alkali soluble resin in the present invention usually has carboxyl, if it plays a role as adhesive resin, and To used developer solution when forming pattern, be particularly preferably solubility to alkaline developer, then can suitably select to use.It needs Bright, alkali soluble resin can also include in organic acid compound, but in the present invention alkali soluble resin be considered as with it is organic Acid compound is not jljl.
The acid value of alkali soluble resin is not particularly limited in the present invention.From promotion dispersion stabilization etc. through Shi Wending Property, promote the heat resistance of the coloring layer obtained using the resin combination from the perspective of, as alkali soluble resin, preferably make It is 80mgKOH/g or more and 300mgKOH/g resin below with acid value.Push away and sentence: acid value is the resin of 80mgKOH/g or more The quantity of acidic groups is relatively more, makes possessed by the molecular association body and above-mentioned dispersing agent of color material shown in above-mentioned logical formula (I) Interaction between amino stabilizes, and promotes the ageing stability of dispersion stabilization etc., and promotion is obtained using the resin combination Coloring layer heat resistance.
It should be noted that acid value indicates the quality for neutralizing KOH required for solid component 1g in the present invention (mg), refer to according to JIS K 0070, by the obtained value of potential difference titration.
The alkali soluble resin that acid value is 80mgKOH/g or more due to for the resin with relatively large number of acidic groups, therefore It is easy and alkalinity base phase possessed by anion existing near the molecular association body surface face of color material shown in above-mentioned logical formula (I) Interaction is easily adsorbed at above-mentioned molecular association body surface face as a result, pushing away and sentencing alkali soluble resin.Due to the alkali soluble resin Acid value it is relatively high, therefore once adsorb, even if being then also difficult to dissociate at high temperature heat, can more inhibit the decomposition of color material Deng, push away sentence can inhibit brightness reduction, significant increase heat resistance.In addition, solvable by using the alkali that acid value is 80mgKOH/g or more Property resin, so that the acidic groups facilitates the adhesion between substrate, even if being not used previous close between substrate for improving Connecing property and the silane coupling agent used, are still promoted with the adhesion of substrate.
Preferred alkali soluble resin in the present invention, specifically, can enumerate the acrylic acid series copolymer with carboxyl, Epoxy (methyl) acrylate with carboxyl etc..Among these, particularly preferably there is carboxyl in side chain and also in side Chain has the alkali soluble resin of the optical polymerism functional group of olefinic unsaturated group etc..The reason is that by containing photopolymerization Property functional group, be formed by cured film film-strength improve.In addition, these acrylic acid series copolymers and epoxy acrylate tree Rouge can mix two or more use.
The acrylic acid series copolymer for having the Component units with carboxyl is, for example, that carboxylic olefinic is unsaturated single Body and copolymerizable other monomers optionally carry out the (co) polymer that (co) polymerization obtains by well known method.
As carboxylic ethylenically unsaturated monomer, it can be mentioned, for example (methyl) acrylic acid, vinyl benzoic acid, Malaysia Acid, maleic acid mono alkyl ester, fumaric acid, itaconic acid, crotonaldehyde, cinnamic acid, acrylic acid dimer etc..In addition, also using (first Base) acrylic acid 2- hydroxyl ethyl ester etc. the monomer and maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic acid acid anhydride etc with hydroxyl Addition reaction, ω-carboxyl-polycaprolactone list (methyl) acrylate of cyclic acid anhydride etc..In addition, maleic acid also can be used The precursor containing anhydride monomers as carboxyl of acid anhydride, itaconic anhydride, citraconic anhydride etc..Wherein, from copolymerizable, cost, dissolubility, glass From the perspective of glass transition temperature etc., particularly preferably (methyl) acrylic acid.
Alkali soluble resin preferably also has hydrocarbon ring from the viewpoint of the adhesion of coloring layer is excellent.By can in alkali There is the hydrocarbon ring for belonging to bulky group in soluble resin, can inhibit contraction when solidification, mitigate the removing between substrate, promoted Substrate adhesion.In addition, the inventors of the present invention have found, by using the alkali soluble resin with hydrocarbon ring, gained coloring can inhibit The solvent resistance of layer, especially can inhibit the swelling of coloring layer.It is not yet clear about its effect, but push away and sentence: by coloring layer The interior hydrocarbon ring containing large volume, and the molecule in coloring layer is inhibited to act, as a result coating strength is made to get higher and solvent is inhibited to be made At swelling.
It as such hydrocarbon ring, can enumerate: can have the annular aliphatic hydrocarbon ring of substituent group, can have the aromatic series of substituent group Ring and their combination, hydrocarbon ring can have the substituent group of carbonyl, carboxyl, oxygen carbonyl, acylamino- etc..Wherein, containing aliphatic When ring, the heat resistance or adhesion of coloring layer can be promoted, while the brightness of gained coloring layer can be promoted.
It as the concrete example of hydrocarbon ring, can enumerate: cyclopropane, cyclobutane, pentamethylene, hexamethylene, norbornane, tricyclic The aliphatic hydrocarbon ring of [5.2.1.0 (2,6)] decane (bicyclopentane), adamantane etc.；The aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, fluorenes；Connection The chain of benzene, terphenyl, diphenyl methane, triphenyl methane, talan etc. is polycyclic, cardo shown in following chemical formula (A) Structure etc..
[changing 16]
As hydrocarbon ring, when containing aliphatic ring, from promoting the heat resistance of coloring layer, adhesion, promote gained simultaneously From the perspective of the brightness of chromatograph particularly preferably.
In addition, containing cardo structure shown in above-mentioned chemical formula (A), from promoting the curability of coloring layer, mention It is particularly preferred from the perspective of liter solvent resistance (NMP swelling inhibits).
In alkali soluble resin used in the present invention, from be easily adjusted each Component units amount, increase it is above-mentioned have hydrocarbon The Component units amount of ring and be easy to be promoted possessed by this composition unit from the perspective of function, it is preferable to use in addition to carboxyl Component units except, be provided additionally with the acrylic acid series copolymer of the Component units with above-mentioned hydrocarbon ring.
Have the Component units with carboxyl, the acrylic acid series copolymer with above-mentioned hydrocarbon ring, it can be by using with hydrocarbon ring Ethylenically unsaturated monomer prepared as above-mentioned " copolymerizable other monomers ".
As the ethylenically unsaturated monomer with hydrocarbon ring, it can be mentioned, for example (methyl) cyclohexyl acrylates, (methyl) propylene Sour two ring pentyl esters, (methyl) isobornyl acrylate, (methyl) benzyl acrylate, (methyl) phenoxyethyl acrylate etc..
Alkali soluble resin of the invention promotes development patience from the film-strength for promoting cured film and inhibits cured film Thermal contraction and from the perspective of keeping the adhesion between substrate excellent, preferably there is olefinic double bond.With olefinic double bond In the case of, in the curing process of the resin combination in colored filter manufacture, the alkali soluble resin is each other or the alkali can Soluble resin and polyfunctional monomer etc. can form cross-bond.As a result, pushing away the film-strength for sentencing the cured film that can promote coloring layer, press down The thermal contraction of cured film processed and the adhesion between substrate is excellent.By selecting using the alkali-soluble tree with olefinic double bond Rouge, so that coloring layer is formed by with colored resin composition using colored filter of the invention, even if relative to coloring In the case that aftermentioned silane coupling agent is set as 1 below the mass by the total solid content of resin combination, substrate adhesion is still excellent It is different.
The method that olefinic double bond is imported in alkali soluble resin, as long as suitably being selected from known method. It can be mentioned, for example: to carboxyl possessed by alkali soluble resin, chemical combination of the addition intramolecular with epoxy group and olefinic double bond Object, such as (methyl) glycidyl acrylate etc., and the method for importing olefinic double bond in side chain；In advance by the structure with hydroxyl It is directed into copolymer at unit, intramolecular is made to have the compound addition of isocyanate group and olefinic double bond, and is imported in side chain The method etc. of olefinic double bond.
Alkali soluble resin of the invention can further contain the tool such as (methyl) methyl acrylate, (methyl) ethyl acrylate There are other Component units of Component units of ester group etc..Component units with ester group serve not only as that colored filter is inhibited to use The ingredient of the alkali-soluble of chromoresin composition and play a role, also as improve it is molten again to the dissolubility of solvent, even solvent Solution property ingredient and play a role.
Alkali soluble resin in the present invention preferably has the Component units with carboxyl and the composition list with hydrocarbon ring The acrylic acid series copolymer of member more preferably has the Component units with carboxyl, the Component units with hydrocarbon ring and has alkene Belong to the acrylic acid series copolymer of the Component units of double bond.
As alkali soluble resin of the invention, the above-mentioned epoxy with carboxyl containing cardo structure is preferably used (methyl) acrylate (hereinafter referred to as cardo resin).
Epoxy (methyl) acrylate (hereinafter referred to as cardo resin) with carboxyl containing above-mentioned cardo structure Correct mechanism it is not yet clear, but since fluorene skeleton contains pi-conjugated system, therefore be believed that free radical in high sensitivity.Pass through By aftermentioned oxime ester system's Photoepolymerizationinitiater initiater and cardo resin combination, solvent tolerance can be further promoted, water seeps dye, sensitivity etc. Requirement performance.
As cardo resin, preferably it can be mentioned, for example the following general formula that Japanese Unexamined Patent Publication 2007-119720 bulletin is recorded (B) epoxy (methyl) with fluorene skeleton that polymerizable compound shown in and Japanese Unexamined Patent Publication 2006-308698 bulletin are recorded Acrylate and the reactant (condensation polymer) of polyacid etc..
[changing 17]
(wherein, in above-mentioned general formula (B), X indicates that group shown in the following general formula (D), Y independently indicate polybasic carboxylic acid Or the residue of its acid anhydrides, RiIndicate the following general formula (C) shown in group, j be 0~4 integer, k be 0~3 integer, n be 1 with On integer.)
[changing 18]
(wherein, in above-mentioned general formula (C), RiiIndicate hydrogen atom or methyl, RiiiIndependently indicate hydrogen atom or methyl.)
[changing 19]
(wherein, in above-mentioned general formula (D), RivIndependently indicate that hydrogen atom, the alkyl of carbon number 1~5, phenyl or halogen are former Son, RvExpression-O- or-OCH2CH2O-。)
Cardo resin used in the present invention, such as fluorenes pair can be made and fluorenes bisphenol compound is carried out epoxidation The epoxide of phenolic compounds reacts it with (methyl) acrylic acid and epoxy (methyl) acrylate is made, makes the epoxy (methyl) acrylate is obtained with polybasic carboxylic acid or its anhydride reaction.
As fluorenes bisphenol compound, can preferably enumerate in above-mentioned general formula (D), RvFor-O- and this-O- becomes-OH person.
As fluorenes bisphenol compound, bis- (4- hydroxyphenyl) fluorenes of 9,9-, 9,9- bis- (4- hydroxy-3-methyl phenyl) can be enumerated Bis- (4- hydroxyl -3,5- 3,5-dimethylphenyl) fluorenes of bis- (the 4- hydroxy 3-methoxybenzene base) fluorenes of fluorenes, 9,9-, 9,9-, bis- (the 4- hydroxyls of 9,9- Base -3- fluorophenyl) fluorenes, bis- (4- hydroxyl -3- chlorphenyl) fluorenes of 9,9-, 9,9- bis- (4- hydroxyl -3- bromophenyl) fluorenes, the bis- (4- of 9,9- Hydroxyl -3,5- dichlorophenyl) bisphenol compounds and their mixing such as fluorenes, bis- (4- hydroxyl -3,5- dibromo phenyl) fluorenes of 9,9- Object.
Polybasic carboxylic acid used in reaction as above-mentioned epoxy (methyl) acrylate with fluorene skeleton and Its acid anhydrides can be enumerated: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, Methyl tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic tetrahydrophthalic acid, chlorendic acid, methyl tetrahydrophthalic acid, penta 2 The dicarboxylic acids of acid etc. or their acid anhydrides；Xenyl tetrabasic carboxylic acid, benzophenone tetrabasic carboxylic acid, Biphenyl Ether tetrabasic carboxylic acid, biphenyl sulfone tetracarboxylic acid The tetrabasic carboxylic acid of acid, 4- (bis- carboxyethyl of 1,2-) -1,2,3,4- naphthane -1,2- dicarboxylic acids, butane tetracarboxylic acid, pyromellitic acid etc. or Their acid dianhydride；Tricarboxylic acids or their acid anhydrides of trimellitic acid or its acid anhydrides etc. etc..These can be used alone, also can be simultaneously Use two or more.
It as cardo resin used in the present invention, can preferably enumerate: belong to fluorenes ring oxygen (methyl) acrylate derivative With epoxy (methyl) acrylate addition product with fluorene skeleton of dicarboxylic anhydride and/or the addition product of tetracarboxylic dianhydride.
The trade name of commercially available object as cardo resin workable for the present invention, can enumerate INR-16M (Nagase ChemteX (strain) system), trade name V259ME (Nippon Steel live aurification (strain) make) etc..
Epoxy (methyl) acrylate with carboxyl can use individually a kind, can also be used in combination of two or more.
Alkali soluble resin used in colored filter colored resin composition can be used alone a kind, also can group Two or more use is closed, there is no particular restriction for content, and the solid component relative to colored filter colored resin composition is total Amount, alkali soluble resin are preferably 5~60 mass %, are more preferably in the range of 10~40 mass %.If alkali soluble resin Content be less than above-mentioned lower limit value, then the case where being unable to get sufficient alkali-developable, in addition, if alkali soluble resin contains Amount is more than above-mentioned upper limit value, then coarse, pattern defect that there is a situation where films when having a development.It should be noted that in the present invention, Gu Body ingredient refers to all the components other than above-mentioned solvent, also includes the polyfunctional monomer etc. of liquid.
Alkali soluble resin can be by the amount of fill of each Component units of appropriate adjustment, and the alkali with required performance is made can Soluble resin.
The amount of fill of carboxylic ethylenically unsaturated monomer, it is preferably 5~50 mass %, more excellent relative to monomer total amount It is selected as 10~40 mass %.
When the ratio of carboxylic ethylenically unsaturated monomer is less than 5 mass %, then film obtained is to alkaline developer Dissolubility reduces, and pattern formation becomes difficult.In addition, if the ratio of carboxylic ethylenically unsaturated monomer is more than 50 mass %, Then have when being developed using alkaline developer, be easy to cause be formed by pattern self-reference substrate fall off, the film of patterned surfaces it is thick Rough tendency.
In addition, be preferably used as alkali soluble resin, have Component units with carboxyl and with the composition of hydrocarbon ring In the acrylic acid series copolymer of unit, the amount of fill of carboxylic ethylenically unsaturated monomer relative to monomer total amount, preferably 5~ 50 mass %, more preferably 10~40 mass %.In addition, the olefinic containing hydrocarbon cyclic base is unsaturated in the acrylic acid series copolymer The amount of fill of monomer is relative to monomer total amount, preferably 30~80 mass %, more preferably 40~75 mass %.
In addition, more preferably as alkali soluble resin, have Component units with carboxyl, with the composition of hydrocarbon ring In the acrylic acid series copolymer of unit and the Component units with olefinic double bond, to carboxylic ethylenically unsaturated monomer addition Intramolecular has the compound of epoxy group and olefinic double bond concurrently, and in the case where importing olefinic double bond, carboxylic olefinic is unsaturated The amount of fill of monomer is relative to monomer total amount, preferably 5~50 mass %, more preferably 10~40 mass %.In the acrylic acid In based copolymer, the amount of fill of the ethylenically unsaturated monomer containing hydrocarbon cyclic base relative to monomer total amount, preferably 30~80 mass %, More preferably 40~75 mass %.In addition, having compound phase of the epoxy group with olefinic double bond concurrently in the acrylic acid series copolymer For the amount of fill of carboxylic ethylenically unsaturated monomer, preferably 10~95 mass %, more preferably 15~90 mass %.
When acrylic acid series copolymer has the Component units with carboxyl and hydrocarbon ring, this composition unit, which is considered as, to be contained in respectively Component units with carboxyl, in the Component units with hydrocarbon ring.
In alkali soluble resin of the invention, the Component units with carboxyl, the Component units with hydrocarbon ring and have alkene Belong to other Component units contained other than the Component units of double bond, is preferably 0~30 mass % in total Component units, more preferable For 0~20 mass %.
Above-mentioned alkali soluble resin, from the viewpoint of the developability (dissolubility) to aqueous alkali used in developer solution, with And from the perspective of promoting the heat resistance of coloring layer, select using acid value to be 80mgKOH/g or more and 300mgKOH/g or less person. Wherein, preferably 90mgKOH/g or more and 280mgKOH/g or less, more preferably 100mgKOH/g or more and 250mgKOH/g with Under.Acid value is the alkali soluble resin of 100mgKOH/g or more, is from the viewpoint of promoting brightness and heat resistance and adhesion It is preferred that.In addition, when the metallic lakes color material of color material shown in logical formula (I) and acid dyes to be applied in combination, it is heat-resisting from being promoted Property from the perspective of, it is preferable to use acid value be 90mgKOH/g or more alkali soluble resin.
Acid value is the alkali soluble resin of above-mentioned lower limit value or more, is easy and is present in color material shown in above-mentioned logical formula (I) Molecular association body surface face near anion possessed by basic group interaction, as a result, push away sentence alkali soluble resin appearance Easily it is adsorbed in above-mentioned molecular association body surface face.It pushes away and sentences: since the acid value of the alkali soluble resin is relatively high, therefore once adsorbing, It then is difficult to dissociate at high temperature heat, can more inhibit the decomposition etc. of color material, can inhibit brightness reduction, be substantially improved resistance to It is hot.
In the case where the side chain of alkali soluble resin has ethylenically unsaturated group, ethylenic unsaturated bond equivalent is preferably 100~2000 range, the range for being particularly preferably 140~1500.The ethylenic unsaturated bond equivalent is if 2000 hereinafter, then showing Shadow patience, adhesion are excellent.In addition, if 100 or more, since the above-mentioned Component units with carboxyl can be made, with hydrocarbon ring The ratio relative increase of other Component units of Component units etc., therefore developability, excellent heat resistance.
Here, so-called ethylenic unsaturated bond equivalent, refers to every 1 mole of ethylenic unsaturated bond in above-mentioned alkali soluble resin Weight average molecular weight, by following numerical expressions (4) indicate.
[number 1]
Numerical expression (4)
(in numerical expression (4), W indicates the quality (g) of alkali soluble resin, and M indicates alkene contained in alkali soluble resin W (g) Belong to the molal quantity (mol) of double bond.)
Above-mentioned ethylenic unsaturated bond equivalent, for example, can according to JIS K 0070:1992 record iodine value test method and It calculates.
In addition, the W in numerical expression (1) also can be by being set as constituting alkali soluble resin by above-mentioned ethylenic unsaturated bond equivalent M is set as the olefinic in the alkali soluble resin calculated by following numerical expressions (5) by total quality (g) of monomer and compound The molal quantity (mol) of double bond, and use level when by the synthesis of alkali soluble resin simply calculates.
(other resins)
In colored resin composition of the invention, within the scope of the effect of the invention, also can further it contain Other resins.As the concrete example of other resins, it can be mentioned, for example: polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrole Alkanone resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, Corvic, melamine resin, phenolic aldehyde tree Rouge, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, polyamide, polyimide resin Deng, wherein from the viewpoint of heat resistance, preferably polyamide or polyimide resin more preferably have cyclic annular knot The polyamide of structure or polyimide resin with cyclic structure.These resins also can be able to be for alkali-soluble person Without alkali-soluble person.In addition, these resins can combine it is one kind or two or more.
The weight average molecular weight of alkali soluble resin is not particularly limited.Wherein, preferably 1,000~500,000 range, More preferably 3,000~200,000.When less than 1,000, the binder performance after solidification is substantially reduced；If more than 500,000, When then being developed by alkaline developer, there is the case where pattern formation becomes difficult.
Alkali soluble resin used in colored filter colored resin composition of the invention, can be used alone 1 Kind, it can also combine two or more use, content is relative to 100 mass parts of color material contained by colored resin composition, and usually 10 In the range of~1000 mass parts, in the range of preferably 20~500 mass parts.If the content of alkali soluble resin is very few, The case where being unable to get sufficient alkali-developable, in addition, the ratio of color material is opposite if the content of alkali soluble resin is excessive Be lower, be unable to get adequately colour saturation the case where.
[polyfunctional monomer]
Polyfunctional monomer used in colored filter colored resin composition of the invention, as long as after for that can pass through It states initiator and carries out polymerization person, be not particularly limited, usually using the chemical combination of the ethylenical unsaturated double bonds with 2 or more Object, particularly preferably with 2 or more acryloyl groups or the multifunctional (methyl) acrylate of methylacryloyl, more preferably For multifunctional (methyl) acrylate more than trifunctional.
In multifunctional (methyl) acrylate, as multifunctional (methyl) acrylate more than trifunctional, example can be enumerated Such as: trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, glycerol three (methyl) propylene Acid esters, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, alkyl-modified dipentaerythritol three (methyl) acrylate, succinic anhydride modified pentaerythrite four (methyl) acrylate, tricresyl phosphate (methyl) acrylate, three (acryloyl-oxyethyl) chlorinated isocyanurates, three (methacryloxyethyl) chlorinated isocyanurates, pentaerythrite four (methyl) Acrylate, dipentaerythritol four (methyl) acrylate, two (trimethylolpropane) tetraacrylates, alkyl-modified two season penta Tetrol four (methyl) acrylate, dipentaerythritol monohydroxy five (methyl) acrylate, dipentaerythritol six (methyl) propylene Acid esters, dipentaerythritol five (methyl) acrylate, alkyl-modified dipentaerythritol five (methyl) acrylate, carboxyl acid modified two Pentaerythrite five (methyl) acrylate, succinic anhydride modified dipentaerythritol five (methyl) acrylate, carbamate three (methyl) acrylate, ester three (methyl) acrylate, carbamate six (methyl) acrylate, ester six (methyl) acrylic acid Ester etc..
In the present invention, from the viewpoint of promoting photo-curable (high sensitivity), polyfunctional monomer preferably has 3 (three It is more than function) more than polymerizable double bond, can suitably enumerate poly- (methyl) esters of acrylic acid of such as 3 yuan or more of polyalcohol. In addition, from the viewpoint of promoting alkali-developable, polyfunctional monomer preferably has carboxyl in the present invention.As with carboxyl Polyfunctional monomer, it can be mentioned, for example the carboxyl acid modified objects etc. of poly- (methyl) esters of acrylic acid of above-mentioned polyalcohol.
The concrete example of poly- (methyl) esters of acrylic acid as polyalcohol, can enumerate: trimethylolpropane tris (methyl) third Olefin(e) acid ester, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol four (methyl) third Olefin(e) acid ester, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..
In addition, the carboxyl acid modified object of poly- (methyl) esters of acrylic acid as polyalcohol, can enumerate three (first of pentaerythrite Base) the succinate modified object of acrylate, the succinate modified object of dipentaerythritol five (methyl) acrylate etc..
These polyfunctional monomers can be used alone a kind, can also combine two or more use.For example, also can will be with carboxyl Polyfunctional monomer is applied in combination with the polyfunctional monomer for not having carboxyl.It is excellent from the viewpoint of promoting heat resistance and adhesion It is selected as the succinate modified object with the pentaerythrite three (methyl) acrylate of carboxyl, dipentaerythritol five (methyl) acrylic acid The succinate modified object of ester.
Commercially available object also can be suitably used in such polyfunctional monomer, such as is used as and contains dipentaerythritol five (methyl) acrylic acid The commercially available object of the succinate modified object of ester can enumerate trade name M-520D, TO-2371 (East Asia synthesizes (strain) society system) etc..
The content of above-mentioned polyfunctional monomer used in colored filter of the invention colored resin composition has no Especially limitation, relative to the solid component total amount of colored resin composition, the content of polyfunctional monomer is preferably 5~60 matter Measure %, more preferably 10~40 mass %.If the content of polyfunctional monomer be less than above range, photocuring be unable to fully into Row, exposed portion dissolves out sometimes, in addition, having the anxiety of alkali-developable reduction if the content of polyfunctional monomer is more than above range.
[initiator]
As initiator used in colored filter colored resin composition of the invention, there is no particular restriction, It can be by combining one kind or two or more use in known various initiators.
It as initiator, can enumerate: aromatic ketones, benzoin ethers, halogenated methyl oxadiazole compound, alpha-amido Ketone, bisglyoxaline class, N, N- dimethylamino benzophenone, halogenated methyl-S- triazine based compound, thioxanthones etc..As initiation The concrete example of agent can be enumerated: the bis- diethylamino benzophenone of benzophenone, 4,4'-, 4- methoxyl group -4'- dimethylamino two Benzoin, 2- (the adjacent chlorine of benzoin ethers, the ethyl benzoin of aromatic ketones, the benzoin methyl ether of Benzophenone etc. etc. etc. Phenyl) the bisglyoxaline class of -4,5- phenylimidazole dimer etc., 2- trichloromethyl -5- (to methoxyl-styrene) -1,3,4- dislike The halogenated methyl oxadiazole compound of diazole etc., 2- (4- butoxy-naphthalene -1- base) -4,6- be double-trichloromethyl-S- triazine etc. Halogenated methyl-S- triazine based compound, 2,2- dimethoxy-1,2- diphenylethane-1- ketone, 2- methyl-1-[4- (methyl mercapto) Phenyl] -2- morpholinopropanone, 1,2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butanone -1,1- hydroxy-cyclohexan Base-phenyl ketone, benzyl, benzoyl benzoic acid, benzoyl methyl benzoate, 4- benzoyl -4'- methyldiphenyl base sulphur Ether, benzylmethylketal, dimethyl aminobenzoate, ESCAROL 507 isopentyl ester, 2- n-butoxyethyl -4- Dimethyl aminobenzoate, 2-chlorothioxanthone, 2,4- diethyl thioxanthone, 2,4- dimethyl thioxanthone, isopropyl thioxanthone, 4- Benzovl-methvl diphenylsulfide, 1- hydroxy-cyclohexyl-phenyl ketone, 2- benzyl -2- (dimethylamino) -1- [4- (4- Morpholinyl) phenyl] -1- butanone, 2- (dimethylamino) -2- [(4- aminomethyl phenyl) methyl] -1- [4- (4- morpholinyl) phenyl] - Bis- (2,4,6- trimethylbenzoyl) phosphine oxides of 1- butanone, alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone, phenyl, 2- methyl-1- [4- (methyl mercapto) phenyl] -2- (4- morpholinyl) -1- acetone etc..
Wherein, it is preferable to use 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino propane-1- ketone, 2- benzyl-2- (dimethylamino) -1- (4- morphlinophenyl) -1- butanone, bis- (diethylamino) benzophenone of 4,4'-, diethyl thioxanthene Ketone.From the viewpoint of adjustment sensitivity, water being inhibited to seep dye, promote development patience, 2- methyl-1-[4- (first sulphur is more preferably combined Base) phenyl] the alpha-aminoacetophenone series initiators of -2- morpholino propane -1- ketone etc and the thioxanthene of diethyl thioxanthone etc Ketone series initiators.
The content of alpha-aminoacetophenone series initiators and thioxanthones series initiators, the solid relative to colored resin composition Ingredient total amount, preferably 5~15 mass %.If amount of initiator be 15 mass % hereinafter, if sublimate in manufacturing process lower, Therefore it is preferred that.If initiator is 5 mass % or more, water seeps the development patience such as dye and is promoted.
In the present invention, about initiator, wherein from the viewpoint of water seeps dye inhibitory effect height, preferably comprise oxime ester system Photoinitiator.It should be noted that so-called water seeps dye, after referring to alkali development, after being eluted with pure water, occur as water seeps dye The phenomenon that trace.Such water seeps dye and disappears after rear baking, pretends for product and no problem, but after development in patterning face When visual examination, the problem of being detected to be uneven abnormal, and cannot be distinguished from normal product and abnormal article.Therefore, if The inspection sensitivity of check device is reduced when visual examination, then result causes under the yield rates of final colorized optical filtering sheet articles Drop, and throw into question.
As the oxime ester system photoinitiator, the colored filter colored resin composition caused by lower because of decomposition product From the perspective of pollution, device pollution, wherein preferably with the initiator of aromatic rings, more preferably have containing aromatic rings The initiator of condensed ring, further preferably with the initiator of the condensed ring containing phenyl ring and heterocycle.
As oxime ester system photoinitiator, can by 1,2- octadione- 1- [4- (thiophenyl)-, 2- (o-benzoyl base oxime)], 1- (adjacent acetyl group oxime) 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base]-ethyl ketone, Japanese Unexamined Patent Publication 2000- No. 80068 bulletins, Japanese Unexamined Patent Publication 2001-233842 bulletin, Japanese Unexamined Patent Application Publication 2010-527339, Japanese Unexamined Patent Application Publication 2010- 527338, it is suitably selected in the oxime ester system photoinitiator of the records such as Japanese Unexamined Patent Publication 2013-041153.As commercially available object, can also make With IRGACURE OXE-01, IRGACURE OXE-02, IRGACURE OXE-03 (the above are BASF AG's systems), ADEKA OPT-N-1919, ADEKA ARKLS NCI-930, ADEKA ARKLS NCI-831 (the above are ADEKA corporations), TR-PBG- 304, TR-PBG-326, TR-PBG-345, TR-PBG-3057 (the above are Changzhou electronic strong new material corporations) etc..
As the oxime ester system photoinitiator used in the present invention, occur from solvent resistance, development patience, pattern defect From the perspective of inhibitory effect and the raw inhibitory effect of water infiltration hair dyeing are excellent, wherein it is preferable to use generation aryl radical, especially It is the oxime ester system photoinitiator of generation phenyl radical, more preferably generates methyl certainly using generation alkyl diradical, especially By the oxime ester system photoinitiator of base.Push away and sentence: compared to aryl radical, the free radical of alkyl diradical is mobile to be easy activation. As the oxime ester system photoinitiator for generating alkyl diradical, can enumerate: 1- (adjacent acetyl group oxime) 1- [9- ethyl -6- (2- methylbenzene Formoxyl) -9H- carbazole -3- base]-ethyl ketone (trade name: IRGACURE OXE-02, BASF system), (2,4,6- trimethylphenyl) [8- [[(acetyl group oxygroup] imino group] [2- (2,2,3,3- tetrafluoro propoxyl group) phenyl] methyl] -11- (2- ethylhexyl) - 11H- benzo [a] carbazole -5- base]-ketone (trade name: IRGACURE OXE-03, BASF system), 1- (adjacent acetyl group oxime) 1- [9- Ethyl -6- (1,3- dioxolanes, 4- (2- methoxyphenoxy) -9H- carbazole -3- base]-ethyl ketone (trade name: ADEKA OPT- N-1919, ADEKA corporation), adjacent acetyl group oxime (9- ethyl -6- nitro -9H- carbazole -3- base) [4- (2- methoxyl group -1- methyl Ethyoxyl -2- aminomethyl phenyl)]-ketone (trade name: ADEKA ARKLS NCI-831, ADEKA corporation), 1- (adjacent acetyl group Oxime) 3- cyclopenta -1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -1- acetone (trade name: TR-PBG- 304, Changzhou electronic strong new material corporation), 1- (adjacent acetyl group oxime) 3- cyclopenta -1- [2- (2- pyrimidine-based sulfur-base) -9H- Carbazole -3- base] -1- propane (trade name: TR-PBG-314, Changzhou electronic strong new material corporation), 1- (adjacent acetyl group oxime) 2- cyclohexyl -1- [2- (2- pyrimidine radicals oxygroup) -9H- carbazole -3- base]-ethyl ketone (trade name: TR-PBG-326, Changzhou strength electricity Sub- new material corporation), 1- (adjacent acetyl group oxime) 2- cyclohexyl -1- [2- (2- pyrimidine-based sulfur-base) -9H- carbazole -3- base]-ethyl ketone (trade name: TR-PBG-331, Changzhou electronic strong new material corporation), 1- (adjacent acetyl group oxime) 1- [4- [3- [1- [(acetyl Base oxygroup) imino group] ethyl] -6- [4- [(4,6- dimethyl -2- pyrimidine radicals) sulfenyl] -2- methyl benzoyl] -9H- carbazole - 9- yl] phenyl] -1- octanone (trade name: EXTA-9, UNION CHEMICAL system) etc..
In addition, combination has tertiary amine structure preferably in oxime ester system photoinitiator from the viewpoint of promoting sensitivity Photoinitiator uses.The reason is that the photoinitiator with tertiary amine structure, belongs to oxygenquencher due to having in the molecule Tertiary amine structure, therefore the free radical as caused by initiator is difficult to inactivate because of oxygen, and sensitivity can be improved.It is above-mentioned that there is tertiary amine structure Photoinitiator commercially available object, it can be mentioned, for example 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholino propane-1- ketone (such as IRGACURE 907, BASF AG's system), 2- benzyl -2- (dimethylamino) -1- (4- morphlinophenyl) -1- butanone (such as IRGACURE 369, BASF AG's system), bis- (diethylamino) benzophenone of 4,4'- (such as HICURE ABP, Kawaguchi's drug System) etc..
In the present invention, it is preferable to use oxime ester system photoinitiators for initiator, wherein further preferably alkyl diradical system oxime ester Compound.
In the case where being combined with alkyl diradical system oxime ester compound and alpha-aminoalkyl benzophenone series initiators, can obtain The excellent film of dye inhibitory effect is seeped to water, the adjusting of sensitivity also becomes easy.
In addition, the case where combining alkyl diradical system oxime ester compound and aryl radical system oxime ester compound uses Under, solvent resistance can be obtained with less amount of initiator and water seeps the film that dye inhibits especially excellent, and adjustment of sensitivity also becomes It is easy.
The amount of alkyl diradical system oxime ester compound, relative to the solid component total amount of colored resin composition, preferably 2 ~7 mass %.If amount of initiator is less than 7 mass %, since film will not be excessively thick with respect in mask open, therefore it is preferred that.If Amount of initiator is 2 mass % or more, then solvent resistance becomes good.
The content of initiator used in colored resin composition of the invention, there is no particular restriction, relative to coloring The solid component total amount of resin combination, preferably 1~40 mass %, more preferably 2~30 mass %, particularly preferably 3~ 20 mass %.If its content is less than above range, sufficient polymerization reaction can not be generated, therefore whether there is or not methods, and the hard of coloring layer is made The case where spending abundant person, on the other hand, if being more than above range, color material in the solid component of colored resin composition etc. Content is opposite to tail off, be unable to get adequately in the case where colour saturation.
Any adding ingredient > of <
In colored resin composition of the invention, within the scope without prejudice to the object of the present invention, optionally can also it contain Various additives.As additive, it can be mentioned, for example antioxidant, short-stopper, chain-transferring agent, levelling agent, plasticizer, tables Face activating agent, defoaming agent, silane coupling agent, ultraviolet absorbing agent, contiguity promotor etc..
(silane coupling agent)
In the present invention, in order to promote the adhesion with substrate, silane coupling agent can be used.In the present invention, silane coupling agent It is to indicate the compound with 1 or more the group selected from silanol group and alkoxysilyl.
Silane coupling agent, from the viewpoint of adhesion, usually relative to the total solid content of colored resin composition Use 2 mass % or more.In this regard, the inventors of the present invention find, by silane coupling agent, with above-mentioned logical formula (I) shown in color material group It closes in use, ongoing change occurs for the silane coupling agent.Therefore, even if after being taken care of during length still not to the adhesion of substrate Reduce and inhibit change of sensitivity and from the perspective of the available pattern-like coloring layer as designed, preferably with respect to coloring Silane coupling agent is set as 1 mass % hereinafter, more preferably relative to colored resin composition by the solid component of resin combination Total solid content, be set as 0.5 mass % hereinafter, further preferably contain substantially no.
It as the concrete example of silane coupling agent, can enumerate: vinyl three ('beta '-methoxy ethyoxyl) silane, vinyl ethoxy The vinyl silanes class of base silane, vinyltrimethoxysilane etc.；γ-methacryloxypropyl trimethoxy silane, (methyl) acrylsilanes class of 3- methacryloxypropyl trimethoxy silane etc.；β-(3,4- expoxycyclohexyl) second Base trimethoxy silane, β-(3,4- expoxycyclohexyl) methyltrimethoxysilane, β-(3,4- expoxycyclohexyl) ethyl Triethoxysilane, β-(3,4- expoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyl group trimethoxy silicon The epoxy silane class of alkane, γ-epoxy propoxy propyl triethoxysilane etc.；N- β (amino-ethyl) gamma-amino propyl trimethoxy Base silane, N- β (amino-ethyl) γ aminopropyltriethoxy silane, N- β (amino-ethyl) gamma-amino hydroxypropyl methyl diethyl Oxysilane, γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, N- phenyl-gamma-amino propyl three The amino silicone alkanes of methoxy silane, N- phenyl-γ aminopropyltriethoxy silane etc.；γ-mercaptopropyi trimethoxy silicon The silane coupling agent of the sulfenyl silanes of alkane, γ-Mercaptopropyltriethoxysilane etc. etc., wherein from the contiguity between substrate From the perspective of property, preferably 3- methacryloxypropyl trimethoxy silane, 3- methacryloyloxypropyl methyl Dimethoxysilane, 3- methacryloxypropyl methyl diethoxysilane, three ethoxy of 3- methacryloxypropyl Base silane.
(antioxidant)
Colored resin composition of the invention preferably comprises antioxidant from the viewpoint of heat resistance and light resistance.It is anti- Oxidant can be by suitably selecting in previous known person.As the concrete example of antioxidant, it is anti-oxidant that it can be mentioned, for example hindered phenolics Agent, amine antioxidant, phosphorous antioxidant, sulfur antioxidant, hydrazine system antioxidant etc., from heat resistance and sunproof sight Point sets out, it is preferable to use hindered phenolic antioxidant.
As hindered phenolic antioxidant, it can be mentioned, for example: [the 3- (3,5- di-t-butyl -4- hydroxyphenyl) of pentaerythrite four Propionic ester] (trade name: IRGANOX 1010, BASF AG's system), 1,3,5- tri- (3,5- di-t-butyl -4- acrinyl) isocyanide ureas Acid esters (trade name: IRGANOX 3114, BASF AG's system), 2,4,6- tri- (4- hydroxyl -3,5- di-t-butyl benzyls) 1,3,5- Mesitylene (trade name: IRGANOX 1330, BASF AG's system), 2,2'- di-2-ethylhexylphosphine oxide (6- tert-butyl -4- sylvan) (quotient The name of an article: Sumilizer MDP-S, Sumitomo Chemical system), bis- (2- tert-butyl -4- the sylvan) (trade names: IRGANOX of 6,6'- sulphur 1081, BASF AG's system), 3,5- di-t-butyl -4- acrinyl sulfonic acid diethylester (trade name: IRGAMOD 195, BASF AG System) etc..Wherein, from the viewpoint of heat resistance and light resistance, preferably [3- (3,5- di-t-butyl -4- oxybenzenes of pentaerythrite four Base) propionic ester] (trade name: IRGANOX 1010, BASF AG's system).
When using antioxidant, as long as use level is not damage the range of effect of the present invention, it is not particularly limited.Make For the use level of antioxidant, relative to 100 mass parts of total solid content in colored resin composition, antioxidant is preferably 0.1~5.0 mass parts, more preferably 0.5~4.0 mass parts.More than above-mentioned lower limit value, then heat resistance and light resistance are excellent It is different.On the other hand, if above-mentioned upper limit value hereinafter, colored resin composition of the invention can then be made to become the photosensitive of high sensitivity Property resin combination.
In addition, as above-mentioned surfactant, it can be mentioned, for example: polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, Polyoxyethylene oleyl ether, NONIN HS 240, ethylene nonyl phenyl ether, polyethylene glycol dilaurate, poly- second Glycol distearate, sorbitan fatty acid esters class, fatty acid modified polyesters, tertiary-amine modified polyurethanes etc..Separately Outside, fluorine system surfactant also can be used in other.
In addition, as plasticizer, it can be mentioned, for example: dibutyl phthalate, dioctyl phthalate, front three phenyl ester (ト リ Network レ ジ Le) etc..As defoaming agent, levelling agent, it can be mentioned, for example silicon systems, fluorine system, compounds of acrylic acid series etc..
(chain-transferring agent)
As chain-transferring agent, preferably such as simple function mercaptan compound, multi-functional thiol's compound, wherein being more preferably Multi-functional thiol's compound.
It as simple function mercaptan compound, can enumerate: 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2- sulfydryl benzo Oxazole, 2 mercaptomethyl benzimidazole, 2- mercapto methyl benzoxazoles, 2- mercapto methyl benzothiazole etc..Wherein, by gathering light From the perspective of closing the movement of the progress chain of free radical caused by initiator, promoting curability, simple function mercaptan compound is preferably 2- mercapto methyl benzothiazole.
It as multi-functional thiol's compound, is not particularly limited, various compounds can be used.Multi-functional thiol's compound can It enumerates for example: pungent two mercaptan of 1,2- dithioglycol, 1,3- dimercaptopropane, 1,4- succinimide mercaptans, 1,6- ethanthiol, 1,8-, 1, 2- cyclohexandithiol, two mercaptan of the last of the ten Heavenly stems, glycol dimercaptosuccinate, ethylene glycol bis- (3-thiopropionates), dimercapto acetic acid second Diol ester, dimercapto acetic acid 1,4- butanediol ester, 1,4- butanediol bis- (3-thiopropionates), trimethylolpropane tris sulfydryl second Acid esters, trimethylolpropane tris (3-thiopropionate), tetra hydrosulfuryl pentaerythritol tetraacetate, (the 3- mercaptopropionic acid of pentaerythrite four Ester), dipentaerythritol six (3-thiopropionate) and various polyalcohols and thioacetic acid, mercaptopropionic acid etc. contain mercapto The ester of carboxylic acid.
In addition, tri-thiol propionic acid three (2- ethoxy) isocyanuric acid ester, Isosorbide-5-Nitrae-can be enumerated as multi-functional thiol's compound Dimethyl sulfydryl benzene, 2,4,6- tri-thiol-s- triazine, 2- (N, N- dibutylamino) -4,6- dimercapto-s- triazine etc..In addition, Multi-functional thiol's compound can be enumerated: bis- (1- mercaptoethyl) benzene of 2,5- ethanthiol, two mercaptan of the 2,9- last of the ten Heavenly stems, 1,4-, adjacent benzene two Formic acid two (1- mercapto ethyl ester), phthalic acid two (2- sulfydryl propyl ester), phthalic acid two (3- sulfydryl butyl ester), O-phthalic Sour two (3- mercaptoisobutanoic esters) etc. have the multifunctional sulphur of substituent group in α and/or β carbon atoms relative to mercapto Alcoholic compound；Ethylene glycol bis- (3- mercaptobutylates), propylene glycol bis- (3- mercaptobutylates), bis- (the 3- mercaptobutyric acids of diethylene glycol Ester), butanediol bis- (3- mercaptobutylates), ethohexadiol bis- (3- mercaptobutylates), trimethylolpropane tris (3- mercaptobutyric acid Ester), pentaerythrite four (3- mercaptobutylate), dipentaerythritol six (3- mercaptobutylate), the bis- (2 mercaptopropionic acids of ethylene glycol Ester), it is propylene glycol bis- (2 mercaptopropionic acid esters), diethylene glycol bis- (2 mercaptopropionic acid esters), butanediol bis- (2 mercaptopropionic acid esters), pungent Glycol bis- (2 mercaptopropionic acid esters), trimethylolpropane tris (2 mercaptopropionic acid ester), pentaerythrite four (2 mercaptopropionic acid ester), two Pentaerythrite six (2 mercaptopropionic acid ester), ethylene glycol bis- (3- mercaptoisobutanoic acid esters), propylene glycol bis- (3- mercaptoisobutanoic acid esters), two Ethylene glycol bis- (3- mercaptoisobutanoic acid esters), butanediol bis- (3- mercaptoisobutanoic acid esters), ethohexadiol bis- (3- mercaptoisobutanoic acid esters), three Hydroxymethyl-propane three (3- mercaptoisobutanoic acid esters), pentaerythrite four (3- mercaptoisobutanoic acid esters), (3- sulfydryl is different for dipentaerythritol six Butyrate), bis- (2- sulfydryl is different for ethylene glycol bis- (2- mercaptoisobutanoic acid esters), propylene glycol bis- (2- mercaptoisobutanoic acid esters), diethylene glycol Butyrate), butanediol bis- (2- mercaptoisobutanoic acid esters), ethohexadiol bis- (2- mercaptoisobutanoic acid esters), trimethylolpropane tris (2- mercapto Base isobutyrate), pentaerythrite four (2- mercaptoisobutanoic acid esters), dipentaerythritol six (2- mercaptoisobutanoic acid esters), ethylene glycol it is double (4- mercaptopentanoic acid ester), propylene glycol bis- (4- sulfydryl isovalerates), diethylene glycol bis- (4- mercaptopentanoic acid esters), the bis- (4- of butanediol Mercaptopentanoic acid ester), ethohexadiol bis- (4- mercaptopentanoic acid esters), trimethylolpropane tris (4- mercaptopentanoic acid ester), four (4- of pentaerythrite Mercaptopentanoic acid ester), dipentaerythritol six (4- mercaptopentanoic acid ester), ethylene glycol bis- (3- mercaptopentanoic acid esters), bis- (the 3- sulfydryls of propylene glycol Valerate), diethylene glycol bis- (3- mercaptopentanoic acid esters), propylene glycol bis- (3- mercaptopentanoic acid esters), bis- (the 3- mercaptopentanoic acids of ethohexadiol Ester), trimethylolpropane tris (3- mercaptopentanoic acid ester), pentaerythrite four (3- mercaptopentanoic acid ester), (the 3- sulfydryl of dipentaerythritol six Valerate) etc..
In the present invention, wherein in above-mentioned multi-functional thiol's compound preferably pentaerythrite four (3- mercaptobutylate).
As product, pentaerythrite four (3- mercaptobutylate) (PTMP can be enumerated；Showa electrician corporation " Karenz MT (trade mark) PE1 ").
The mixing ratio > of each ingredient in < colored resin composition
Total content of color material shown in logical formula (I) and its allochromatic colour material, the solid component relative to colored resin composition Total amount is preferably cooperated with 3~65 mass %, more preferably with the ratio of 4~55 mass %.If above-mentioned lower limit value with On, then the coloring layer when colored resin composition is coated into regulation film thickness (usually 1.0~5.0 μm) has abundant color dense Degree.In addition, and can obtain that there is abundant hardness and base hereinafter, then dispersibility and dispersion stability are excellent if above-mentioned upper limit value The coloring layer of the adhesion of plate.It should be noted that in the present invention, solid component be other than above-mentioned solvent it is all at Point, it also include the polyfunctional monomer etc. of liquid.
In addition, the content as dispersing agent, as long as the content that color material shown in logical formula (I) can be made to be uniformly dispersed, It is not particularly limited, such as relative to the solid component total amount of colored resin composition, 3~40 mass % can be used.In addition, phase For the solid component total amount of colored resin composition, preferably 5~35 mass %, particularly preferably 5~25 mass %.If More than above-mentioned lower limit value, then the dispersibility and dispersion stability of color material shown in logical formula (I) are excellent, viscosity ageing stability is excellent It is different.In addition, if above-mentioned upper limit value hereinafter, then the brightness of coloring layer become good.
Total content of alkali soluble resin and polyfunctional monomer and initiator, relative to consolidating for colored resin composition Body ingredient total amount is preferably cooperated with 10~92 mass %, more preferably with the ratio of 15~87 mass %.If above-mentioned More than lower limit value, then it can obtain the coloring layer for the adhesion for having between abundant hardness and substrate.In addition, if above-mentioned upper limit value Hereinafter, then because the generation of the small wrinkle caused by being heat-shrinked also is suppressed.
In addition, the content of solvent can be suitably set in the range of precisely can form coloring layer.Relative to comprising The total amount of the above-mentioned colored resin composition of the solvent, generally, it is preferred in the range of 55~95 mass %, wherein more preferably In the range of 65~88 mass %.In content above range by making above-mentioned solvent, the excellent person of coating can be made into.
The manufacturing method > of < colored filter colored resin composition
The manufacturing method of colored filter colored resin composition of the invention, as long as being the color containing aforementioned present invention Material dispersion liquid and alkali soluble resin, polyfunctional monomer, initiator, solvent and the various adding ingredients used depending on needed for, can So that color material is dispersed in the method in solvent using dispersing agent, can be mixed by using well known mixed media and Preparation.
As the preparation method of the resin combination, it can be mentioned, for example: (1) in the color material dispersion liquid of aforementioned present invention, The method of mixing alkali soluble resin, polyfunctional monomer, initiator and the various adding ingredients used depending on needed for；(2) molten In agent, while putting into color material, dispersing agent, alkali soluble resin, polyfunctional monomer, initiator and various adding with what is used depending on needed for Addition point, and mixed method；(3) in a solvent, dispersing agent, alkali soluble resin, polyfunctional monomer, initiator are added With the various adding ingredients that use and after being mixed depending on needed for, the method that color material is added and is dispersed；(4) in solvent In, it adds color material, dispersing agent and alkali soluble resin and prepares dispersion liquid, in the dispersion liquid, further addition, mixed base can Soluble resin, polyfunctional monomer, initiator and the method for various adding ingredients used depending on needed for etc..
In these methods, from the viewpoint of effectivelying prevent the agglutination of color material, keeping its evenly dispersed, preferably above-mentioned (4) Method.
3. colored filter
Colored filter of the invention at least has transparent substrate and the coloring layer on the transparent substrate, the coloring At least one of layer has the coloring layer for being solidified to form the colored resin composition of aforementioned present invention.
For such colored filter of the invention, it is described with reference to the accompanying drawings.Fig. 1 is to indicate colorized optical filtering of the invention The summary section of an example of piece.According to Fig. 1, colored filter 10 of the invention has transparent substrate 1, light shielding part 2 and coloring Layer 3.
(coloring layer)
Coloring layer used in colored filter of the invention, at least one is the colored filter for making aforementioned present invention The coloring layer being solidified to form with colored resin composition.
Coloring layer is generally formed in the opening portion of the light shielding part on aftermentioned transparent substrate, usually by color-patch maps more than 3 colors Case is constituted.
In addition, the arrangement as the coloring layer, is not particularly limited, such as stripe, Mosaic style, triangle can be set as Type, 4 pixel configuration types etc. generally arrange.In addition, the width of coloring layer, area etc. can arbitrarily be set.
The thickness of the coloring layer can be by adjusting coating method, the solid component concentration of colored resin composition or viscosity etc. And suitable control, it is often preferred that 1~5 μm of range.
For example, the coloring layer can pass through following methods shape when colored resin composition is photosensitive polymer combination At.
Firstly, using the coating means such as spray coating method, dip coating, stick coating method, rolling method, spin-coating method, die coating method by above-mentioned The colored filter of invention is coated on aftermentioned transparent substrate with colored resin composition, forms wet coating.
Then, it after keeping the wet coating dry using heating plate or baking oven etc., is carried out on it by the exposure mask of predetermined pattern Exposure makes alkali soluble resin and polyfunctional monomer etc. carry out photopolymerization reaction, photosensitive film is made.Made as exposure Light source, it can be mentioned, for example: ultraviolet light, electron beam of Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, metal halide lamp etc. etc..It exposes Light quantity appropriate adjustment according to thickness of used light source or film etc..
In addition, after exposure, in order to promote polymerization reaction, can also be heated.Heating condition is according to used in Thickness of the mixing ratio of each ingredient in colored resin composition or film etc. and suitably select.
Then, development treatment is carried out using developer solution, dissolution removes unexposed portion, is thus formed and is applied with required pattern Film.As developer solution, being generally used in water or water-soluble solvent makes the solution of alkali soluble solution.In the alkaline solution, can also it fit Amount addition surfactant etc..In addition, conventional method can be used in developing method.
After development treatment, the drying of the cleaning of developer solution, the cured coating film of colored resin composition is usually carried out, is formed Chromatograph.It should be noted that, in order to solidify film sufficiently, can also be heated after development treatment.Heating condition has no It is particularly limited to, can suitably be selected according to the purposes of film.
(light shielding part)
Light shielding part in colored filter of the invention is the light shielding part for being formed as pattern-like on aftermentioned transparent substrate, It can be set as light shielding part identical with the person that is used as light shielding part in general colored filter.
The pattern form of the light shielding part, is not particularly limited, and it can be mentioned, for example the shapes of striated, rectangular etc..As The light shielding part, it can be mentioned, for example be dispersed or dissolved in black pigment in adhesive resin and the gold of winner or chromium, chromium oxide etc. Belong to film etc..The metallic film can be CrOx2 layer stackups of film (x be arbitrary number) and Cr film and winner, in addition, also can for into The CrO of one step reduction reflectivityxFilm (x is arbitrary number), CrNy3 layer stackups of film (y be arbitrary number) and Cr film and winner.
The light shielding part be dispersed or dissolved in black color material in adhesive resin and when winner, as the light shielding part Forming method, as long as being not particularly limited, it can be mentioned, for example use shading for patterned method can be carried out to light shielding part Photoetching process, print process, ink-jet method of portion's colored resin composition etc..
The light shielding part of pattern-like for example can method identical with the formation of above-mentioned coloring layer formed.
The film thickness of light shielding part is set as 0.2~0.4 μm or so in the case where metallic film, for make black color material disperse Or be dissolved in adhesive resin and when winner, it is set as 0.5~2 μm or so.
The coloration of the coloring layer of colored filter, can according to light source etc. appropriate adjustment, be not particularly limited, such as in indigo plant In the case where chromatic colorant layer, in the coloration (x, y) under illuminant-C, preferably x is 0.12~0.27, y is 0.04~0.18 range It is interior.
(transparent substrate)
As the transparent substrate in colored filter of the invention, if it is the substrate transparent to visible light, and It is not particularly limited, transparent substrate used in general colored filter can be used.Specifically, quartz glass, nothing can be enumerated Alkali glass, synthetic quartz plate etc. are without flexible transparent rigid material or transparent resin film, optical resin plate, flexible glass Deng the transparent soft material with pliability.
The thickness of the transparent substrate is not particularly limited, the purposes of colored filter according to the present invention, such as can be used The transparent substrate of 100 μm~1mm or so.
It should be noted that colored filter of the invention is other than above-mentioned transparent substrate, light shielding part and coloring layer, example Such as also can be form protective layer, transparent electrode layer and alignment films, directed projection, column spacer colored filter.
4. display device
Display device of the invention is characterized in that thering is the colored filter of aforementioned present invention.In the present invention, display dress The composition set is not particularly limited, can by suitably being selected in known display device, it can be mentioned, for example liquid crystal display device, Or organic light-emitting display device etc..
[liquid crystal display device]
The feature of liquid crystal display device is the colored filter with aforementioned present invention, opposite substrate and is formed in above-mentioned Liquid crystal layer between colored filter and above-mentioned opposite substrate.
For such liquid crystal display device of the invention, it is described with reference to the accompanying drawings.Fig. 2 is to indicate liquid crystal display device The skeleton diagram of an example.As shown in Fig. 2, liquid crystal display device 40 has colored filter 10, the opposite direction with tft array substrate etc. Substrate 20 and the liquid crystal layer 30 being formed between above-mentioned colored filter 10 and above-mentioned opposite substrate 20.
It should be noted that liquid crystal display device of the invention is not limited to the composition shown in Fig. 2, may generally form The known composition as the liquid crystal display device for using colored filter.
It as the driving method of liquid crystal display device of the invention, is not particularly limited, general liquid crystal display dress can be used Set used driving method.As such driving method, it can be mentioned, for example: TN mode, IPS mode, OCB mode and the side MVA Formula etc..In the present invention, any way in them can be suitably used.
In addition, as opposite substrate, can liquid crystal display device according to the present invention driving method etc. and suitably select to make With.
In addition, as the liquid crystal for constituting liquid crystal layer, the driving method etc. of liquid crystal display device according to the present invention be can be used Dielectric anisotropy different various liquid crystal and their mixture.
As the forming method of liquid crystal layer, the method for being typically used as the production method of liquid crystal cells can be used, example can be enumerated Such as vacuum injection mode or liquid crystal drop under type.
[organic light-emitting display device]
Organic light-emitting display device is characterized in that thering is the colored filter and organic luminorphor of aforementioned present invention.
For such organic light-emitting display device, it is described with reference to the accompanying drawings.Fig. 3 is to indicate organic light-emitting display device The summary section of an example.As shown in figure 3, organic light-emitting display device 100 of the invention has colored filter 10 and organic Illuminator 80.Can also have organic protection layer 50, inorganic oxide film 60 between colored filter 10 and organic luminorphor 80.
As the laminating method of organic luminorphor 80, it can be mentioned, for example: transparent sun is gradually formed above to colored filter Pole 71, hole injection layer 72, hole transmission layer 73, luminescent layer 74, electron injecting layer 75 and cathode 76 method；Or it will be formed The method etc. on inorganic oxide film 60 is fitted in the organic luminorphor 80 on another substrate.Transparent sun in organic luminorphor 80 Pole 71, hole injection layer 72, hole transmission layer 73, luminescent layer 74, electron injecting layer 75 and cathode 76, other compositions, can fit As the known person of use.So made organic light-emitting display device 100 is equally applicable for the organic of such as passive drive mode In the organic el display of EL display or active matrix driving mode.
It should be noted that organic light-emitting display device of the invention is not limited to the composition shown in Fig. 3, usually may be used It is formed as the organic light-emitting display device using colored filter and known composition.
[embodiment]
Below for the present invention, illustrative embodiments are specifically described.The present invention is not limited to these records.
It should be noted that the weight average molecular weight Mw of neutral and alkali copolymer of the present invention, is by GPC (gel permeation chromatography Method) it is acquired in the form of standard polystyren scaled value.The HLC-8120GPC that measurement is made using Tosoh (strain), to be added to The N-Methyl pyrrolidone of the lithium bromide of 0.01 mol/L is set as eluent, by calibration curve with polystyrene standard (the above are Polymer for Mw377400,210500,96000,50400,20650,10850,5460,2930,1300,580 Laboratories corporation Easi PS-2 series) and Mw1090000 (Tosoh (strain) system), with TSK-GEL ALPHA-M × bis- Root (Tosoh (strain) system) is carried out as measuring column.It should be noted that for the macromolecular for the raw material for becoming base copolymer Monomer or graft copolymer are also carried out with above-mentioned condition.
In addition, acid value (mgKOH/g) is to pass through the obtained value of potential difference titration according to JIS K 0070.
(synthesis example 1: the synthesis of intermediate 1)
Make and the pure medicine of light (strain) 1- iodine naphthalene 15.2g (60mmol) processed, Mitsui Chemicals (strain) norbornane diamines processed (NBDA) (CAS No.56602-77-8) 4.63g (30mmol), sodium tert-butoxide 8.07g (84mmol), Aldrich 2- dicyclohexylphosphontetrafluoroborate Base -2', 6'- dimethoxy-biphenyl 0.09g (0.2mmol), He Guangchun medicine (strain) palladium acetate 0.021g (0.1mmol) processed are scattered in Dimethylbenzene 30mL is reacted 48 hours with 130-135 DEG C.After reaction, it is cooled to room temperature plus water is extracted.Then with sulfuric acid Magnesium is dry, is concentrated, thus obtains intermediate 1 shown in 8.5g (yield 70%) following chemical formula (1).
Resulting compound is confirmed as target compound by following analysis result.
MS (ESI) (m/z): 407 (M+H)
Elemental analysis value: CHN measured value (85.47%, 8.02%, 6.72%)；Theoretical value (85.26%, 8.11%, 6.63%)
[changing 20]
Chemical formula (1)
(synthesis example 2: the synthesis of intermediate 2)
It is packed into bis- (dimethylamino) the hexichol first of intermediate 1, Tokyo chemical conversion industry 4,4'- of 8.46g (20.8mmol) Ketone 13.5g (41.6mmol), toluene 60mL, are stirred with 45-50 DEG C.It drips and Wako Pure Chemical Industries phosphoryl chloride phosphorus oxychloride 6.38g (51.5mmol) flows back 2 hours and cooling.After reaction, toluene is decanted.Chloroform 40mL, water are added to resin-like precipitate 40mL, concentrated hydrochloric acid are dissolved, and liquid separation goes out chloroform layer.By chloroform layer with water washing, it is dried, is concentrated with magnesium sulfate.To dense Contracting object is added ethyl acetate 65mL and flows back.Cooled and filtered precipitate obtains 15.9g (yield 70%) following chemical formula (2) Shown in intermediate 2 (BB7-Nb-dimer).
Resulting compound is confirmed as target compound by following analysis result.
MS (ESI) (m/z): 511 (+), divalent
Elemental analysis value: CHN measured value (78.13%, 7.48%, 7.78%)；Theoretical value (78.06%, 7.75%, 7.69%)
[changing 21]
Chemical formula (2)
(synthesis example 3: the synthesis of color material A)
The intermediate 2 of 5.00g (4.58mmol) is added into water 300ml, makes it dissolve that intermediate 2 is made is molten with 90 DEG C Liquid.Then by Japanese inorganic chemistry industry phosphotungstic acid n hydrate H3[PW12O40]·nH2O (n=30) 10.44g (3.05mmol) is added in water 100mL, is stirred with 90 DEG C, is prepared phosphotungstic acid aqueous solution.Previous in 2 solution of intermediate with 90 DEG C of mixing phosphotungstic acid aqueous solutions, the sediment that leaching generates, with water washing.By resulting filtration cakes torrefaction, obtains 13.25g and (produce Rate 98%) color material A shown in following chemical formula (3).
Resulting compound is confirmed as target compound by following analysis result.(molar ratio W/Mo=100/0)
MS (ESI) (m/z): 510 (+), divalent
Elemental analysis value: CHN measured value (41.55%, 5.34%, 4.32%)；Theoretical value (41.66%, 5.17%, 4.11%)
In addition, passing through31The polyacid structure that P-NMR confirms phosphotungstic acid still remains after becoming color material A.
[changing 22]
Chemical formula (3)
(synthesis example 4: the synthesis of block copolymer I)
After four mouthfuls of removable flasks of 500ml are dried under reduced pressure, it is replaced into Ar (argon).Under Ar air-flow, dehydration is added THF100g, methyl trimethoxy base silicyl dimethyl ketene acetal 1.6g, tetrabutylammonium -3- chlorobenzoic acid ester (TBACB) 1M acetonitrile solution 0.15ml, mesitylene 0.2g.Using the funnel that drips, 45 minutes methyl methacrylates that drip are lasted thereto 40g.Due to fever when reaction carries out, therefore temperature is maintained below 40 DEG C by ice-cold.After 1 hour, lasts 15 minutes and drip Dimethylaminoethyl methacrylate 10g.After reaction 1 hour, methanol 5g, which is added, stops reaction.Solvent under reduced pressure is removed, Obtain block copolymer I.Measuring (NMP LiBr10mM) obtained weight average molecular weight Mw by GPC is 7,600, and amine value is 70mgKOH/g。
Resulting block copolymer I is dissolved in PGMEA, makes 60wt% solution.
(synthesis example 5: the synthesis of block copolymer II)
In synthesis example 4, in addition to be changed to methyl methacrylate 37g, dimethylaminoethyl methacrylate 13g with Outside, remaining mode same as synthesis example 4 carries out, and obtains block copolymer II.Weight average molecular weight Mw is 7,600, and amine value is 90mgKOH/g。
(synthesis example 6: the synthesis of block copolymer III)
In synthesis example 4, in addition to be changed to methyl methacrylate 35g, dimethylaminoethyl methacrylate 15g with Outside, remaining mode same as synthesis example 4 carries out, and obtains block copolymer III.Weight average molecular weight Mw is 7,600, and amine value is 105mgKOH/g。
(synthesis example 7: the synthesis of block copolymer IV)
In synthesis example 4, in addition to be changed to methyl methacrylate 33g, dimethylaminoethyl methacrylate 17g with Outside, remaining mode same as synthesis example 4 carries out, and obtains block copolymer IV.Weight average molecular weight Mw is 7,600, and amine value is 120mgKOH/g。
(synthesis example 8: the synthesis of block copolymer V)
In synthesis example 4, in addition to be changed to methyl methacrylate 30g, dimethylaminoethyl methacrylate 20g with Outside, remaining mode same as synthesis example 4 carries out, and obtains block copolymer V.Weight average molecular weight Mw is 7,600, and amine value is 140mgKOH/g。
(synthesis example 9: the synthesis of block copolymer VI)
In synthesis example 4, in addition to being changed to methyl methacrylate 27.5g, dimethylaminoethyl methacrylate Other than 22.5g, remaining mode same as synthesis example 4 is carried out, and obtains block copolymer VI.Weight average molecular weight Mw is 7,600, amine Value is 160mgKOH/g.
(comparing synthesis example 1: the synthesis of block copolymer VII)
In synthesis example 4, in addition to being changed to methyl methacrylate 41.5g, dimethylaminoethyl methacrylate Other than 8.5g, remaining mode same as synthesis example 4 is carried out, and obtains block copolymer VII.Weight average molecular weight Mw is 7,600, amine Value is 60mgKOH/g.
(comparing synthesis example 2: the synthesis of block copolymer VIII)
In synthesis example 4, in addition to be changed to methyl methacrylate 26g, dimethylaminoethyl methacrylate 24g with Outside, remaining mode same as synthesis example 4 carries out, and obtains block copolymer VIII.Weight average molecular weight Mw is 7,600, and amine value is 170mgKOH/g。
Resulting block copolymer VIII is dissolved in PGMEA, makes 60wt% solution.
(comparing synthesis example 3: the synthesis of graft copolymer I)
(1) synthesis of macromonomer-I
In the reactor for having cooling tube, addition funnel, nitrogen air inlet, machine mixer, numerical digit thermometer Methyl proxitol acetate (abbreviation PGMEA) 80.0 mass parts are added, is stirred, is heated up on one side under nitrogen flowing on one side 90 DEG C of temperature.Last 1.5 hours and drip 50.0 mass parts of methyl methacrylate, 30.0 mass parts of n-BMA, 20.0 mass parts of benzyl methacrylate, 4.0 mass parts of mercaptoethanol, 30 mass parts of PGMEA, α, α '-azodiisobutyronitrile The mixed solution of (abbreviation AIBN) 1.0 mass parts further reacts 3 hours.Then, stop nitrogen stream, the reaction solution is cold But to 80 DEG C, be added Karenz MOI (manufacture of Showa electrician (strain) society) 8.74 mass parts, dibutyl tin dilaurate 0.125g, 0.125 mass parts of p methoxy phenol and 10 mass parts of PGMEA simultaneously stir 3 hours, thus to obtain macromonomer I's 49.5% solution.The GPC measurement result of gained macromonomer I is that weight average molecular weight (Mw) is 4010, number-average molecular weight (Mn) It is 1910, molecular weight distribution (Mw/Mn) is 2.10.
(2) synthesis of graft copolymer I
In the reactor for having cooling tube, addition funnel, nitrogen air inlet, machine mixer, numerical digit thermometer 80.0 mass parts of PGMEA are added, is stirred under nitrogen flowing on one side, is heated up to 85 DEG C of temperature on one side.It lasts 1.5 hours and drips Under 75.76 mass parts of macromonomer I solution (effective 49.5 mass parts of solid component) of above-mentioned (1), dimethylaminoethyl acrylate methyl 12.5 mass parts of base amino ethyl ester (abbreviation DMMA), 1.24 mass parts of N- n-dodecane mercaptan, 20.0 mass parts of PGMEA, AIBN The mixed solution of 0.5 mass parts after heating stirring 3 hours, lasts 10 minutes and drips 0.10 mass parts of AIBN, PGMEA 10.0 The mixed liquor of mass parts further carries out curing for 1 hour at the same temperature, and 25.4% thus to obtain graft copolymer I is molten Liquid.The GPC measurement of resulting graft copolymer I as a result, weight average molecular weight (Mw) is 11480, number-average molecular weight (Mn) is 4650, molecular weight distribution (Mw/Mn) is 2.47.It should be noted that amine value is 89mgKOH/g.
(Production Example 1: the synthesis of alkali soluble resin A)
150 mass parts of PGMEA are put into polymerization tank, after being warming up to 100 DEG C under nitrogen atmosphere, by methacrylic acid (MAA) 22 mass parts, 64 mass parts of cyclohexyl methacrylate (CHMA) and PERBUTYL O (Japan Oil Co's system) 6 mass Part, chain-transferring agent (N- n-dodecane mercaptan) 2 mass parts last 1.5 hours and continuously drip.Thereafter, 100 DEG C of sustained responses are kept, End is dripped after 2 hours in above-mentioned main chain formation mixture, adds 0.1 mass parts of p methoxy phenol as polymerization inhibitor And stop polymerization.
Then, it is blown into air on one side, adds glycidyl methacrylate (GMA) 14 mass parts on one side and is used as containing epoxy Based compound, after being warming up to 110 DEG C, add 0.8 mass parts of triethylamine and with 110 DEG C progress addition reaction 15 hours, obtain Alkali soluble resin solution A (weight average molecular weight (Mw) 9,000, acid value 90mgKOH/g, 40 mass % of solid component).
It should be noted that above-mentioned weight average molecular weight, using THF as eluent, is led to using polystyrene as standard substance Shodex GPC System-21H is crossed to be measured.In addition, the measuring method system of acid value is measured according to JIS K 0070.With Under, alkali soluble resin B~E also in kind measures weight average molecular weight, acid value.
(Production Example 2: the synthesis of alkali soluble resin B)
In Production Example 1, in addition to methacrylic acid (MAA) is set as 26.5 mass parts, cyclohexyl methacrylate (CHMA) it is set as other than 59.5 mass parts, remaining mode same as Production Example 1 carries out, and obtains the PGMEA of alkali soluble resin B Solution (40 mass % of solid component).The weight average molecular weight of alkali soluble resin B is 9,000, acid value 120mgKOH/g.
(Production Example 3: the synthesis of alkali soluble resin C)
In Production Example 1, in addition to methacrylic acid (MAA) is set as 29.5 mass parts, cyclohexyl methacrylate (CHMA) it is set as other than 56.5 mass parts, remaining mode same as Production Example 1 carries out, and obtains the PGMEA of alkali soluble resin C Solution (40 mass % of solid component).The weight average molecular weight of alkali soluble resin C is 9,000, acid value 140mgKOH/g.
(Production Example 4: the synthesis of alkali soluble resin D)
In Production Example 1, in addition to methacrylic acid (MAA) is set as 18.5 mass parts, cyclohexyl methacrylate (CHMA) it is set as other than 67.5 mass parts, remaining mode same as Production Example 1 carries out, and obtains the PGMEA of alkali soluble resin D Solution (40 mass % of solid component).The weight average molecular weight of alkali soluble resin D is 9,000, acid value 70mgKOH/g.
(Production Example 5: the synthesis of alkali soluble resin E)
129 mass parts of PGMEA are put into polymerization tank, after being warming up to 100 DEG C under nitrogen atmosphere, by methacrylic acid (MAA) 5.8 mass parts, 20.4 mass parts of methyl methacrylate (MMA), 59.8 matter of glycidyl methacrylate (BzMA) Amount part and PERBUTYL O (Japan Oil Co's system) 6 mass parts, chain-transferring agent (N- n-dodecane mercaptan) 2 mass parts last It continuously drips within 1.5 hours.Thereafter, 100 DEG C of sustained responses are kept, it is small through 2 in the end of dripping of above-mentioned main chain formation mixture Shi Hou, addition 0.1 mass parts of p methoxy phenol stop polymerizeing as polymerization inhibitor, and obtaining alkali soluble resin E solution, (weight is equal Molecular weight (Mw) 9,000, acid value 70mgKOH/g, 40 mass % of solid component).
(preparation example 1: the preparation of photonasty adhesive ingredients CR-1)
To the resulting alkali soluble resin solution A of Production Example 1 (40 mass % of solid component) 31.4 mass parts, conduct is added Dipentaerythritol hexaacrylate (DPHA) (ARONIX M402 (East Asia synthesis system)) 18.8 mass parts of polyfunctional monomer are made For IRGACURE 907 (BASF system) 5.9 mass parts of initiator, KAYACURE-DETX-S (Japanese chemical drug system) 2.0 mass parts, Antioxidant IRGANOX 1010 (BASF system) 0.8 mass parts, 41.2 mass parts of PGMEA, obtain photonasty adhesive ingredients CR-1。
(preparation example 2~3: the preparation of photonasty adhesive ingredients CR-2~CR-3)
In preparation example 1, in addition to replacing alkali soluble resin solution A (40 mass % of solid component), and respectively using system It makes other than alkali soluble resin B~C solution (40 mass % of solid component) of example 2~3, remaining mode same as preparation example 1 It carries out, obtains photonasty adhesive ingredients CR-2~CR-3.
(preparation example 4: the preparation of photonasty adhesive ingredients CR-4)
To the resulting alkali soluble resin B solution of Production Example 2 (40 mass % of solid component) 31.4 mass parts, conduct is added The modified by polyacid acrylic acid oligomer (ARONIX M520 (East Asia synthesis system) of polyfunctional monomer) 18.8 mass parts, as drawing Send out IRGACURE 907 (BASF system) 5.9 mass parts, KAYACURE-DETX-S (Japanese chemical drug system) 2.0 mass parts, antioxygen of agent Agent IRGANOX 1010 (BASF system) 0.8 mass parts, 41.2 mass parts of PGMEA, obtain photonasty adhesive ingredients CR-4.
(preparation example 5: the preparation of photonasty adhesive ingredients CR-5)
In preparation example 1, in addition to replacing alkali soluble resin solution A (40 mass % of solid component), and Production Example 4 is used Alkali soluble resin solution D (40 mass % of solid component) other than, remaining mode same as preparation example 1 carries out, and is felt Photosensitiveness adhesive ingredients CR-5.
(embodiment 1: the preparation of color material dispersion liquid A-1)
In 225mL mayonnaise bottle (ズ bottles of マ ヨ ネ ー), it is molten that 65.1 mass parts of PGMEA, alkali soluble resin E is added Liquid (40 mass % of solid component) 14.6 mass parts, block copolymer (60 mass % of solid component) 6.8 mass parts of synthesis example 4 And it stirs.In wherein addition phenyl-phosphonic acid (trade name: PPA, Nissan Chemical corporation) 0.48 mass parts (relative to block copolymerization The tertiary amino of object is 0.6 molar equivalent), it is stirred at room temperature 30 minutes.
13.0 mass parts of color material A, 100 mass parts of partial size 2.0mm zirconium oxide bead of synthesis example 3 are packed into, are vibrated by coating Device (shallow field ironworker company system), which vibrates, is used as preparation solution broken for 1 hour, is then changed to 200 parts of partial size 0.1mm zirconium oxide bead and passes through Paint shaker progress dispersion in 4 hours is broken as formally solving, and obtains color material dispersion liquid A-1.
(embodiment 2~19: color material dispersion liquid A-2~A-3, B-1~B-6, C-1~C-2, D-1~D-4, E-1~E-2, The preparation of F-1~F-2)
In embodiment 1, in addition to being set as total mass parts of the solid component of block copolymer and organic acid compound It is fixed, the type of block copolymer is changed such as table 1, with other than the compounding ratio of phenyl-phosphonic acid, remaining is similarly to Example 1 Mode carries out, and obtains color material dispersion liquid A-2~A-3, B-1~B-6, C-1~C-2, D-1~D-4, E-1~E-2, F-1~F-2.
(comparative example 1~15: color material dispersion liquid A-4, B-7~B-8, C-3~C-4, D-5~D-7, E-3~E-4, F-3~ The preparation of F-5, G, H)
In embodiment 1, in addition to being set as total mass parts of the solid component of block copolymer and organic acid compound It is fixed, the type of block copolymer is changed such as table 1, with other than the compounding ratio of phenyl-phosphonic acid, remaining is similarly to Example 1 Mode carries out, and obtains color material dispersion liquid A-4, B-7~B-8, C-3~C-4, D-5~D-7, E-3~E-4, F-3~F-5, G, H.
(comparative example 16: the preparation of color material dispersion liquid I)
In 225mL mayonnaise bottle, 65.3 mass parts of PGMEA, alkali soluble resin E solution (40 matter of solid component are added Measure %) 14.6 mass parts, Disperbyk LPN6919 (BYK Chemie corporation, acrylic acid dispersant, 60 matter of solid component Amount %) it (amine value 120mgKOH/g, 60 mass % of solid component) 6.3 mass parts and stirs.In wherein addition phenyl-phosphonic acid (commodity Name: PPA, Nissan Chemical corporation) 0.77 mass parts (tertiary amino relative to LPN6919 is 0.6 molar equivalent), it is stirred in room temperature It mixes 30 minutes.
13.0 mass parts of color material A, 100 mass parts of partial size 2.0mm zirconium oxide bead of synthesis example 3 are packed into, are vibrated by coating Device (shallow field ironworker company system), which vibrates, is used as preparation solution broken for 1 hour, is then changed to 200 parts of partial size 0.1mm zirconium oxide bead and passes through Paint shaker progress dispersion in 4 hours is broken as formally solving, and obtains color material dispersion liquid I.
(comparative example 17: the preparation of color material dispersion liquid J)
In 225mL mayonnaise bottle, 57.6 mass parts of PGMEA, alkali soluble resin E solution (40 matter of solid component are added Amount %) 14.6 mass parts, compare the graft copolymer I (amine value 89mgKOH/g, 25.4 mass % of solid component) of synthesis example 4 13.7 mass parts simultaneously stir.In wherein addition phosphoric acid dimethacrylate oxygroup ethyl ester (trade name: P-2M, common prosperity society chemistry system) 1.07 mass parts (tertiary amino relative to graft copolymer I is 0.6 molar equivalent), are stirred at room temperature 30 minutes.
13.0 mass parts of color material A, 100 mass parts of partial size 2.0mm zirconium oxide bead of synthesis example 3 are packed into, are vibrated by coating Device (shallow field ironworker company system), which vibrates, is used as preparation solution broken for 1 hour, is then changed to 200 parts of partial size 0.1mm zirconium oxide bead and passes through Paint shaker progress dispersion in 4 hours is broken as formally solving, and obtains color material dispersion liquid J.
The dispersion stabilization of < color material dispersion liquid evaluates >
By the color material dispersion liquid of Examples and Comparative Examples respectively in (25 DEG C) of room temperature keepings, 1 is being prepared after 1 day and taken care of After a month, viscosity is measured respectively.Viscosity system uses vibrating type viscometer (SEKONIC VM-200T2), at 25.0 ± 1.0 DEG C It is measured, the value after being started 30 seconds using measurement.
Viscosity change is that person is set as A within 10% by the viscosity after more dispersed 1 day and the viscosity after preservation 1 month, It is more than 10% to be set as B by viscosity change.Show the result in table 1.If viscosity change is within 10%, dispersion stabilization is excellent It is different, it is evaluated as usage range.
[table 1]
(embodiment 20: the preparation of colored resin composition)
The photonasty adhesive ingredients CR-1 of 30.5 mass parts of color material dispersion liquid A-1 of mix embodiment 1, preparation example 1 26.9 mass parts, surfactant MEGAFAC R08MH (DIC system) 0.01 mass parts, 42.5 mass parts of PGMEA, are implemented The colored resin composition of example 20.
(embodiment 21~38: the preparation of colored resin composition)
In embodiment 20, in addition to replace color material dispersion liquid A-1 and be changed to respectively the following table 2 record color material dispersion liquid with Outside, remaining mode similarly to Example 20 carries out, and obtains the colored resin composition of embodiment 21~38.
(embodiment 39~42: the preparation of colored resin composition)
In embodiment 20, color material dispersion liquid D-1 is used in addition to replacing color material dispersion liquid A-1, replaces photonasty bonding Agent ingredient CR-1 and respectively using other than photonasty adhesive ingredients CR-2~CR-5, remaining mode similarly to Example 20 into Row, obtains the colored resin composition of embodiment 39~42.
(comparative example 18~34: the preparation of colored resin composition)
Combination in embodiment 20, in addition to color material dispersion liquid and photonasty adhesive ingredients to be changed to the following table 2 respectively In addition, remaining mode similarly to Example 20 carries out, and obtains the colored resin composition of comparative example 18~34.
The viscosity stability of < colored resin composition evaluates >
To the colored resin composition of Examples and Comparative Examples, using identical as the dispersion stabilization evaluation of color material dispersion liquid Method be measured.
Viscosity change is that person is set as A within 3% by the viscosity after comparing preparation 1 day and the viscosity after preservation 1 month, will Viscosity change be more than within 3% and 5% person be set as B, will be more than 5% to be set as C.Show the result in table 2.If viscosity change is Within 5%, then excellent in stability, is evaluated as usage range.
< Evaluation of Heat Tolerance >
The colored resin composition of Examples and Comparative Examples is coated on using spinner to the glass substrate of thick 0.7mm respectively On (NH TECHNO GLASS (strain) system, " NA35 ").Thereafter, in being thermally dried 3 minutes in 80 DEG C of heating plates.Not across Photomask and use extra-high-pressure mercury vapour lamp irradiate 60mJ/cm2Ultraviolet light, thus obtain cured film (blue-colored film).This is solid Change the film thickness (T of film；μm) adjusted in such a way that the coloration after toasting after aftermentioned becomes y=0.090.Measure the coloration of this coloring film (L0、a0、b0), thereafter, toasts 25 minutes after the glass plate for foring coloring film is carried out with 230 DEG C of Non-dust furnace, measure again Coloration (the L of gained coloring film1、a1、b1)。
It should be noted that the coloration of coloring film uses Olympus (strain) society system " micro-spectral measurement device OSP- SP200 " is measured.
By following formula, the coloration variation of the coloring film of baking front and back after evaluation.Show the result in table 2.
Δ Eab={ (L1- L0)2+(a1- a0)2+(b1- b0)2}1/2
It is that 3 or less persons are set as A by Δ Eab, is more than that 3 and 5 or less persons are set as B by Δ Eab, is more than 5 and 6 or less by Δ Eab Person is set as C, is more than 6 to be set as D by Δ Eab.If Δ Eab be 5 hereinafter, if excellent heat resistance, be evaluated as usage range.
The evaluation > of < developing time
Embodiment and comparative example medium viscosity estimation of stability are used respectively for the colored resin composition of the comparative example of B Spinner is coated on the glass substrate (NH TECHNO GLASS (strain) system, " NA35 ") of thick 0.7mm.Film thickness is adjusted to 2.5 μ m.Thereafter, it after being thermally dried 3 minutes in 80 DEG C of heating plates, is irradiated across photomask pattern using extra-high-pressure mercury vapour lamp 60mJ/cm2Ultraviolet light.Thereafter, to the glass plate for foring coloring layer, use 0.05 mass % potassium hydroxide aqueous solution as Alkaline developer carries out spray development, measures the time until photomask pattern occurs completely.Show the result in table 2.
The evaluation > of < solvent redissolution property
The glass bar for only preparing the quantity of evaluated colored resin composition, front end is immersed in respectively embodiment and Comparative example medium viscosity estimation of stability makes its attachment for 3cm in the colored resin composition of the comparative example of B or so, Yu Wendu 23 DEG C, it is 30 minutes dry in the environment of humidity 70%.Thereafter, the front end for being attached to the glass bar of colored resin composition is impregnated in In PGMEA, stir 15 seconds.The colored resin composition whole dissolution person that glass bar is attached in after stirring 1 minute is set as A, Whole does not dissolve and remaining stripping film person is set as B.Show the result in table 2.
[table 2]
[result integration]
It is found that there is color material, dispersing agent, organic acid compound shown in logical formula (I), and dispersing agent and organic acid compound Meet the color material dispersion liquid of above-mentioned formula (1)~formula (3) embodiment 1~19, even if viscosity change is still after keeping 1 month Within 10%, dispersion stabilization is excellent.
In addition, it is found that the pigmentary resin of embodiment 20~42 prepared by color material dispersion liquid using the embodiment 1~19 Composition, dispersion stabilization is excellent, can form the film of heat resistance promotion.
In addition, it is found that the pigmentary resin group for the embodiment 21,22,25~28,30,32~34,36 and 38 that X is 0.9 or more Close object；The embodiment 39 and 40 for the alkali soluble resin for having used acid value high；And the polyfunctional monomer with carboxyl is used Embodiment 41 colored resin composition, have especially excellent heat resistance.
Illustrate the result of Examples and Comparative Examples referring to Fig. 5.Fig. 5 is the color for indicating embodiment 1~19 and comparative example 1~16 The X-A plan view of the relationship of the A and X of material dispersion liquid.In addition, in Fig. 5, indicate A × X=40, A × (1-X)=42, A=160, The chart of A=70, X=1.5.In Fig. 5, the area of A × X >=40, A × (1-X)≤42, A≤160, A >=70, X≤1.5 will be met Domain is set as region I；The region for meeting A × X >=40, A × (1-X) > 42 and A≤160 is set as region II；A × X < will be met 40, the region of A × (1-X)≤42 and A >=70 is set as region III；To meet A × X < 40, A × (1-X) > 42, A≤160, The part of A >=70 is set as region IV.
In the I of region, the color material dispersion liquid including 1~embodiment of embodiment 19.Include in the II of region comparative example 3,5,7,8, 10,12 and 13 color material dispersion liquid.It include the color material dispersion liquid of comparative example 1 in the III of region.In addition, including comparing in the IV of region The color material dispersion liquid of example 2,4,6,9 and 11.
Shown in the result of table 1 as above, the color material dispersion liquid of Examples and Comparative Examples included by region I and II, dispersion is surely It is qualitative excellent.Especially by embodiment 1, the color material dispersion liquid of comparative example 3,5,7,10 and 12 and Comparative Examples 1 and 2,4,6,9 and 11 Color material dispersion liquid comparison it is found that in the case where A × X=40 becomes boundary line, meets A × X >=40 (formula 2), color material point The dispersion stabilization of dispersion liquid is excellent.
On the other hand, as shown in the result of table 2, it is known that, use color material dispersion liquid included by inclusion region I and III The colored resin composition of embodiment 20~42 and comparative example 18 is formed by coloring film, and Evaluation of Heat Tolerance is A or B, heat resistance It is excellent.Especially by used the embodiment 4,10,12,16 and 18 of the point on A × (1-X)=42 embodiment 23,29, 31,35 and 37 result it is found that A × (1-X)=42 become boundary line, meet A × (1-X)≤42 (formula 3) in the case where, The excellent heat resistance of coloring film.
(embodiment 43~61: the preparation of color material dispersion liquid)
In embodiment 1~19, in addition to replacing PPA respectively using the p-methyl benzenesulfonic acid monohydrate of equimolar amounts (east Capital chemical conversion industry Co. Ltd. system) other than, remaining mode same as embodiment 1~19 carries out, and obtains embodiment 43~61 Color material dispersion liquid (is followed successively by K-1~K-3, L-1~L-6, M-1~M-2, N-1~N-4, O-1~O-2, P-1~P-2).
(comparative example 35~47: the preparation of color material dispersion liquid)
In comparative example 1~13, in addition to replacing PPA respectively using the p-methyl benzenesulfonic acid monohydrate of equimolar amounts (east Capital chemical conversion industry Co. Ltd. system) other than, remaining mode same as comparative example 1~13 carries out, and obtains comparative example 35~47 Color material dispersion liquid (is followed successively by K-4, L-7~L-8, M-3~M-4, N-5~N-7, O-3~O-4, P-3~P-4).
To the color material dispersion liquid of embodiment 43~61 and comparative example 35~47, with the stably dispersing with above-mentioned color material dispersion liquid Property the identical method of evaluation, evaluate the dispersion stabilization of color material dispersion liquid.Show the result in table 3.
[table 3]
(embodiment 62~80: the preparation of colored resin composition)
In embodiment 20, other than color material dispersion liquid and photonasty adhesive ingredients are changed to the combination of the following table 4, Remaining mode similarly to Example 20 carries out, and obtains the colored resin composition of embodiment 62~80.
(comparative example 48~60: the preparation of colored resin composition)
In embodiment 20, other than color material dispersion liquid and photonasty adhesive ingredients are changed to the combination of the following table 4, Remaining mode similarly to Example 20 carries out, and obtains the colored resin composition of comparative example 48~60.
To the colored resin composition of embodiment 62~80 and comparative example 48~60, respectively to be combined with above-mentioned pigmentary resin The identical method of evaluation of viscosity stability evaluation, Evaluation of Heat Tolerance, the evaluation of developing time and solvent the redissolution property of object, It is evaluated.Show the result in table 4.
[table 4]
[result integration]
It is found that having color material, dispersing agent, organic acid compound and dispersing agent and organic acid compound shown in logical formula (I) Meet the color material dispersion liquid of above-mentioned formula (1)~formula (3) embodiment 43~61, even if viscosity change is still after keeping 1 month Within 10%, dispersion stabilization is excellent.
In addition, it is found that the coloured tree of embodiment 62~80 prepared by color material dispersion liquid using the embodiment 43~61 Oil/fat composition, dispersion stabilization is excellent, can form the film of heat resistance promotion.
According to table 2 compared with table 4, used belong to the phenyl-phosphonic acid of divalent organic acid compound embodiment 20~42, And the colored resin composition of comparative example 18~30, and other than having used the p-methyl benzenesulfonic acid of 1 valence organic acid compound, its The colored resin composition of the remaining embodiment 62~80 for corresponding respectively to above-mentioned colored resin composition and comparative example 48~60, The evaluation of viscosity stability evaluation, Evaluation of Heat Tolerance, the evaluation of developing time and solvent the redissolution property of colored resin composition Obtain result same as corresponding colored resin composition.No matter it follows that the valence mumber of organic acid compound, formula (1)~formula (3) is still set up.Its results presumption is the reason is that, block copolymer has Component units shown in logical formula (II) No matter (a) and the valence mumber of organic acid compound organic acid compound and formed with 1 pair of 1 progress salt.
(synthesis example 10: the synthesis of block copolymer IX)
In synthesis example 4, in addition to being changed to methyl methacrylate 36.5g, dimethylaminoethyl methacrylate Other than 13.5g, remaining mode same as synthesis example 4 is carried out, and obtains block copolymer IX.Weight average molecular weight Mw is 7,600, amine Value is 95mgKOH/g.
(synthesis example 11: the synthesis of block copolymer X)
In the 500mL round bottom for having cooling tube, addition funnel, nitrogen air inlet, machine mixer, digital thermometer THF250 mass parts, 0.6 mass parts of lithium chloride are added in four mouthfuls of removable flasks, sufficiently carry out nitrogen displacement.Reaction flask is cold But to after -60 DEG C, injection tube is used to inject 4.9 mass parts of butyl lithium (15 mass % hexane solution), 1.1 mass of diisopropylamine Part, 1.0 mass parts of methyl isobutyrate.By 2.2 mass parts of methacrylic acid 1- ethoxy ethyl ester (EEMA) of B block monomer, Methacrylic acid 2- (trimethylsiloxy group) ethyl ester (TMSMA) 29.1 mass parts, 2-Ethylhexyl Methacrylate (EHMA) 12.8 mass parts, 13.7 mass parts of n-BMA (BMA), 9.5 mass parts of benzyl methacrylate (BzMA), methyl 17.5 mass parts of methyl acrylate (MMA), last 60 minutes with funnel using addition and drip.After 30 minutes, it will be used as A block 26.7 mass parts of dimethylaminoethyl methacrylate (DMMA) of monomer last 20 minutes and drip.After reaction 30 minutes, add Entering 1.5 mass parts of methanol stops reaction.Resulting precursor block copolymer THF solution carries out reprecipitation in hexane, passes through Filtering, vacuum drying are refined, and 30 mass % solution of solid component is made with PGMEA dilution.32.5 mass parts of water are added, rise Temperature to 100 DEG C react 7 hours, the Component units from EEMA are deprotected and are made from methacrylic acid (MAA) Component units from TMSMA are deprotected and are made from 2-Hydroxyethyl methacrylate (HEMA) by Component units Component units.Make resulting block copolymer PGMEA solution reprecipitation in hexane, refined by filtering, being dried in vacuo, Obtain block copolymer X (acid value 8mgKOH/g, Tg38 DEG C).So resulting block is confirmed with GPC (gel permeation chromatography) Copolymer X, as a result weight average molecular weight Mw is 7730.In addition amine value is 95mgKOH/g.
(synthesis example 12~15: the synthesis of block copolymer XI~XIV)
In synthesis example 11, other than changing output-input ratio in a manner of shown in monomer ratio becomes table 5, remaining and conjunction It is carried out at the same mode of example 11, obtains block copolymer XI~XIV.
[table 5]
Abbreviation in table is as shown below.
PME-200: methoxy poly (ethylene glycol) monomethacrylates (trade name: PME-200, Japan Oil Co's system, BLEMMER-PME-200, ethyleneoxy repeat number=4)
(preparation example 6: the preparation of photonasty adhesive ingredients CR-6)
To the resulting alkali soluble resin solution A of Production Example 1 (40 mass % of solid component) 36.9 mass parts, conduct is added Dipentaerythritol hexaacrylate (DPHA) (ARONIX M402 (East Asia synthesis system)) 22.1 mass parts of polyfunctional monomer are made For IRGACURE 907 (BASF system) 1.8 mass parts of initiator, KAYACURE-DETX-S (Japanese chemical drug system) 0.6 mass parts, Antioxidant IRGANOX 1010 (BASF system) 0.8 mass parts, 37.9 mass parts of PGMEA, obtain photonasty adhesive ingredients CR-6。
(preparation example 7~12: the preparation of photonasty adhesive ingredients CR-7~12)
In preparation example 6, the column note of the embodiment 96~101 in addition to the type of initiator and use level to be changed to table 8 Other than the combination of load, remaining mode same as preparation example 6 is carried out, and obtains photonasty adhesive ingredients CR-7~12.
It should be noted that the abbreviation of the initiator in table 8 is as follows.
IRG907:IRGACURE 907 (BASF system)
DETX:KAYACURE-DETX-S (Japanese chemical drug system)
OXE01:IRGACURE OXE01 (BASF system)
OXE02:IRGACURE OXE02 (BASF system)
NCI930:ADEKA ARKLS NCI-930 (ADEKA system, oxime ester system photoinitiator)
PBG304:TR-PBG-304 (Changzhou electronic strong new material corporation, oxime ester system photoinitiator)
(preparation example 13~19: the preparation of photonasty adhesive ingredients CR-13~19)
In addition to replacing alkali soluble resin solution A (40 mass % of solid component), it is changed to alkali soluble resin F solution (epoxy (methyl) acrylate with carboxyl containing cardo structure, model INR-16M Nagase ChemteX (strain) system, solid component 54.5%), and by solid component become identical mass parts in a manner of adjust other than usage amount, remaining with The same mode of preparation example 6~12 carries out, and obtains photonasty adhesive ingredients CR-13~19.
(preparation example 20~26: the preparation of photonasty adhesive ingredients CR-20~26)
In addition to replacing alkali soluble resin solution A (40 mass % of solid component), it is changed to alkali soluble resin G solution (the propylene glycol monomethyl ether acetate solution of the acid anhydrides condensation polymer of the epoxy acrylate with fluorene skeleton, trade name V259ME, Aurification (strain) system, 55.8 mass % of solid component live in Nippon Steel), and adjusted in such a way that solid component becomes identical mass parts Other than usage amount, remaining mode same as preparation example 6~12 is carried out, and obtains photonasty adhesive ingredients CR-20~26.
(preparation example 27: the preparation of photonasty adhesive ingredients CR-27)
To alkali soluble resin G solution (55.8 mass % of solid component) 26.4 mass parts, addition is used as polyfunctional monomer Pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA) (ARONIX M305 (East Asia synthesis system)) 22.1 matter Measure part, IRGACURE OXE01 (BASF system) 1.2 mass parts as initiator, IRGACURE OXE02 (BASF system) 1.2 matter Part, antioxidant IRGANOX 1010 (BASF system) 0.8 mass parts, 37.9 mass parts of PGMEA are measured, photonasty adhesive is obtained Ingredient CR-27.
(preparation example 28: the preparation of photonasty adhesive ingredients CR-28)
To alkali soluble resin G solution (55.8 mass % of solid component) 26.4 mass parts, addition is used as polyfunctional monomer Modified by polyacid acrylic acid oligomer (ARONIX M520 (East Asia synthesis system)) 22.1 mass parts, as initiator IRGACURE OXE01 (BASF system) 1.2 mass parts, IRGACURE OXE02 (BASF system) 1.2 mass parts, antioxidant IRGANOX 1010 (BASF system) 0.8 mass parts, 37.9 mass parts of PGMEA, obtain photonasty adhesive ingredients CR-28.
(embodiment 81: the preparation of color material dispersion liquid Q)
In 225mL mayonnaise bottle, 63.3 mass parts of PGMEA, alkali soluble resin E solution (40 matter of solid component are added Measure %) 13.0 mass parts, synthesis example 10 block copolymer IX solution (amine value 95mgKOH/g, 45 mass % of solid component) 10.0 mass parts simultaneously stir.It is (opposite in phenyl-phosphonic acid (trade name: PPA, Nissan Chemical corporation) 0.72 mass parts are wherein added In block copolymer tertiary amino be 0.6 molar equivalent), be stirred at room temperature 30 minutes.
13.0 mass parts of color material A, 100 mass parts of partial size 2.0mm zirconium oxide bead of synthesis example 3 are packed into, are vibrated by coating Device (shallow field ironworker company system), which vibrates, is used as preparation solution broken for 1 hour, is then changed to 200 parts of partial size 0.1mm zirconium oxide bead and passes through Paint shaker progress dispersion in 4 hours is broken as formally solving, and obtains color material dispersion liquid Q.
(embodiment 82~87: the preparation of color material dispersion liquid)
In embodiment 81, in addition to replacing block copolymer IX solution, the block for being changed to synthesis example 11~15 respectively is total Other than polymers X~XIV solution, remaining mode same as embodiment 81 is carried out, and obtains the color material dispersion liquid R of embodiment 82~87 ~W.
To the color material dispersion liquid in embodiment 81~87, with same as the evaluation of the dispersion stabilization of above-mentioned color material dispersion liquid Method evaluates the dispersion stabilization of color material dispersion liquid.Show the result in table 6.
[table 6]
(embodiment 88: the preparation of colored resin composition)
The photonasty adhesive ingredients CR-1 of 27.4 mass parts of color material dispersion liquid Q of mix embodiment 81, preparation example 1 23.5 mass parts, pentaerythrite four (3- mercaptobutylate) (PTMP；Showa electrician corporation " Karenz MT (trade mark) PE1 ") 0.47 mass parts, surfactant MEGAFAC R08MH (DIC system) 0.01 mass parts, 48.6 mass parts of PGMEA, are implemented The colored resin composition of example 88.
(embodiment 89~94: the preparation of colored resin composition)
In embodiment 88, in addition to replace color material dispersion liquid Q, be changed to other than color material dispersion liquid R~W respectively, remaining with The same mode of embodiment 88 carries out, and obtains the colored resin composition of embodiment 89~94.
To the colored resin composition of embodiment 88~94, respectively with the viscosity stability with above-mentioned colored resin composition The identical method of evaluation of evaluation, Evaluation of Heat Tolerance, the evaluation of developing time and solvent redissolution property, is evaluated.By result It is shown in table 7.
[table 7]
(embodiment 95~117: the preparation of colored resin composition)
In embodiment 88, in addition to replacing photonasty adhesive ingredients CR-1, it is changed to photonasty adhesive ingredients respectively Other than CR-6~28, remaining mode same as embodiment 88 is carried out, and obtains the colored resin composition of embodiment 95~117.
(embodiment 118: the preparation of colored resin composition)
The photonasty adhesive ingredients CR-6 of 27.4 mass parts of color material dispersion liquid R of mix embodiment 82, preparation example 6 23.5 mass parts, pentaerythrite four (3- mercaptobutylate) (PTMP；Showa electrician corporation " Karenz MT (trade mark) PE1 ") 0.47 mass parts, surfactant MEGAFAC R08MH (DIC system) 0.01 mass parts, 48.6 mass parts of PGMEA, are implemented The colored resin composition of example 118.
(embodiment 119~140: the preparation of colored resin composition)
In embodiment 118, in addition to replacing photonasty adhesive ingredients CR-6, it is changed to photonasty adhesive ingredients respectively Other than CR-7~26, remaining mode same as embodiment 118 is carried out, and obtains the pigmentary resin combination of embodiment 119~140 Object.
(embodiment 141~150: the preparation of colored resin composition)
In embodiment 118, in addition to it is as shown in the table change color material dispersion liquid and photonasty adhesive ingredients other than, remaining with The same mode of embodiment 118 carries out, and obtains the colored resin composition of embodiment 141~150.
< solvent resistance: NMP swell test >
Film thickness use spinner to toast respectively the colored resin composition of embodiment later after is as 2.5 μm or so Mode is coated on thick 0.7mm, 100mm × 100mm glass substrate (NH TECHNO GLASS (strain) system, " NA35 ").Its Afterwards, in being thermally dried 3 minutes in 80 DEG C of heating plates.Extra-high-pressure mercury vapour lamp is not used to irradiate 40mJ/cm across photomask2 Ultraviolet light, toasted 30 minutes after being carried out with 220 DEG C of Non-dust furnace, thus obtain cured film (blue-colored film).
Measure the film thickness of gained cured film and as T1.Thereafter, by this film immersion 60 in 25 DEG C of N-Methyl pyrrolidones Minute, measure the film thickness after just taking out and as T2.It calculating T2/T1 × 100 (%), will be less than 103% the case where, is set as AA, 103% more than and less than 105% the case where be set as A, 105% more than and less than 110% the case where be set as B, 110% or more and small C is set as in 115% the case where, 115% or more situation is set as D.Show the result in table 8~10.If above-mentioned evaluation criteria be AA, A, B or C, then be available for it is practical, if but evaluation result is B, even A, effect is more excellent.
< development residue evaluates >
The colored resin composition of embodiment is coated on thick 0.7mm, 100mm × 100mm glass using spinner respectively After on glass substrate (NH TECHNO GLASS (strain) system, " NA35 "), 3 minutes are dried in 80 DEG C using heating plate, thus shape At thick 3.0 μm of coloring layer.By the above-mentioned glass plate for foring coloring layer, use 0.05 mass % potassium hydroxide aqueous solution as Alkaline developer carries out spray development 60 seconds.Visually to observe the unexposed portion (50mm of the glass substrate after above-mentioned coloring layer is formed × 50mm) after, it is sufficiently wiped by the lens cleaning cloth (Toray system, trade name TORAYSEE MK cleaning cloth) containing ethyl alcohol It wipes, visually to observe the coloring degree of its lens cleaning cloth.Show the result in table 8~10.
(development residue evaluation criteria)
A: not confirm development residue, the complete non-coloring of lens cleaning cloth visually.
B: not confirm development residue visually, the slightly coloring of lens cleaning cloth is confirmed.
C: with visual confirmation to development residue slightly, and the coloring of lens cleaning cloth is confirmed.
D: with visual confirmation to development residue, and the coloring of lens cleaning cloth is confirmed.
If above-mentioned evaluation criteria A, B or C, then it is available for practical；But if evaluation result is B, even A, effect is more It is excellent.Show the result in table 8~10.
< water seeps dye evaluation >
The colored resin composition of embodiment is coated on thick 0.7mm, 100mm × 100mm glass using spinner respectively After on glass substrate (NH TECHNO GLASS (strain) system, " NA35 "), 3 minutes are dried in 80 DEG C using heating plate, thus shape At thick 3.0 μm of coloring layer.Thereafter, 40mJ/cm is not irradiated comprehensively using extra-high-pressure mercury vapour lamp across photomask2It is ultraviolet Line.Then, rotation development is carried out using 0.05wt% potassium hydroxide (KOH) as developer solution, after so that it is connect liquid 60 seconds with developer solution Development treatment is carried out with pure water, the substrate after washing is rotated 10 seconds after going water removal with centrifugation, the survey as following at once Determine the contact angle of pure water, evaluation water seeps dye.
The measurement of the contact angle of pure water, the coloring layer surface after water is eliminated to above-mentioned rigid centrifugation, drips 1.0 μ L's of pure water Drop measures the static contact angle after dripping 10 seconds with the method for θ/2.Measurement device uses the contact angle of consonance interface science corporation Meter DM 500 is measured.Show the result in table 8~10.
(evaluation criteria)
A: 80 degree of contact angle or more
B: 65 degree of contact angle more than and less than 80 degree
C: 50 degree of contact angle more than and less than 65 degree
D: contact angle is less than 50 degree
If water seeps dye, evaluation criteria is A or B, is available for practical；But if evaluation result is A, effect is more excellent.
< development adhesion evaluates >
The resulting colored filter of Examples and Comparative Examples is used into spinner with photosensitive color resin combination respectively After being coated on thick 0.7mm, 100mm × 100mm glass substrate (NH TECHNO GLASS (strain) system, " NA35 "), using adding Hot plate is dried 3 minutes in 60 DEG C, and thick 2.5 μm of coloring layer is consequently formed.To this coloring layer across with 2~80 μm of exposure masks The photomask of opening width and use extra-high-pressure mercury vapour lamp to irradiate 60mJ/cm2Ultraviolet light.To the above-mentioned glass for foring coloring layer Glass plate uses 0.05 mass % potassium hydroxide aqueous solution to carry out spray development 60 seconds as alkaline developer.It is seen with optical microscopy Substrate after examining development, whether there is or not the coloring layers relative to mask open line width for observation.Show the result in table 8~10.
(development adhesion evaluation criteria)
A: in partially observable coloring layer of the mask open line width less than 10 μm.
B: in 10 μm of the mask open line width partially observable coloring layers more than and less than 20 μm.
C: in 20 μm of the mask open line width partially observable coloring layers more than and less than 50 μm.
D: in 50 μm of the mask open line width partially observable coloring layers more than and less than 80 μm.
E: coloring layer is not observed in 80 μm of parts below of mask open line width.
If above-mentioned evaluation criteria is A, B or C, it is available for practical；If but evaluation result is B, even A, colorized optical filtering Piece is with photosensitive color resin combination more suitable for High precision.
[table 8]
[table 9]
[table 10]
[result integration]
It is found that having used, acid value is 1mgKOH/g or more and 18mgKOH/g or less, glass transition temperature are 30 DEG C or more Dispersing agent colored resin composition, development residue, substrate adhesion, development adhesion it is especially excellent.
It is found that having used the colored resin composition of alkali soluble resin shown in general formula (B), NMP institute is more inhibited Caused by be swollen, excellent solvent resistance.
In addition, it is found that having used the solvent resistance (NMP swelling inhibits) of the embodiment of oxime ester series initiators excellent, more Water is inhibited to seep the generation of dye.
Symbol description
1 transparent substrate
2 light shielding parts
3 coloring layers
10 colored filters
20 opposite substrates
30 liquid crystal layers
40 liquid crystal display devices
50 organic protection layers
60 inorganic oxide films
71 transparent anodes
72 hole injection layers
73 hole transmission layers
74 luminescent layers
75 electron injecting layers
76 cathodes
80 organic luminorphors
100 organic light-emitting display devices
Cations more than 201 divalents
Anion more than 202 divalents
203 ionic bonds
210 molecular association bodies

Claims (16)

1. a kind of color material dispersion liquid, containing color material, dispersing agent, organic acid compound and solvent shown in the following general formula (I),
The dispersing agent be at least have the following general formula (II) shown in Component units a, amine value be 70mgKOH/g or more and 160mgKOH/g block copolymer below,
The solvent is that the solubility of the color material at 23 DEG C is calculated as 0.1 solvent below with g/10ml solvent,
The amine value of the dispersing agent is being set as AmgKOH/g, by organic acidification contained in the color material dispersion liquid Close the amount X of the substance of objectAThe object of mol and the Component units a for constituting the dispersing agent contained in the color material dispersion liquid The amount X of matterBThe ratio between mol is set as X i.e. XA/XBWhen, meet following formula (1) and formula (2), when X is the range less than 1, further satisfaction Following formula (3),
The formula of X≤1.5 (1)
The formula of A × X >=40 (2)
A × (1-X)≤42 formula (3)
Logical formula (I)
In logical formula (I), A is the organic group for a valence for not having pi bond with the carbon atom of N Direct Bonding, the organic group indicate to Less in the aliphatic alkyl with the end of N Direct Bonding with saturated aliphatic hydrocarbons or with the fragrance of the aliphatic alkyl Race's group can also contain O, S, N in carbochain；Bc-Indicate at least c valence polybasic acid anion containing tungsten；Ri~RvIndependently table Show hydrogen atom, there can be the alkyl of substituent group or can have the aryl of substituent group, RiiWith Riii、RivWith RvBonding formation ring knot Structure；Ar1Indicate the divalent aromatic group that there can be substituent group；Multiple Ri~RvAnd Ar1Difference can be identical or different,
A and c indicates that 2 or more integer, b and d indicate 1 or more integer；E is 0 or 1, and key is not present when e is 0；Multiple e can With identical or different,
Logical formula (II)
In logical formula (II), R1For hydrogen atom or methyl, Q is Direct Bonding key or divalent concatenating group, R2For the alkylene of carbon number 1~8 Base ,-[CH (R5)-CH(R6)-O]x-CH(R5)-CH(R6)-or-[(CH2)y-O]z-(CH2)yShown in divalent organic group, R3And R4Independently indicating can substituted chain or cricoid alkyl or R3And R4It bonds together and forms cyclic structure；The divalent Concatenating group Q is alkylidene, arlydene ,-CONH- base ,-COO- base, the ether of carbon number 1~10 and their group of carbon number 1~10 It closes；R5And R6It is each independently hydrogen atom or methyl,
X indicates that 1~18 integer, y indicate that 1~5 integer, z indicate 1~18 integer.
2. color material dispersion liquid as described in claim 1, wherein the organic acid compound be selected from by the following general formula (IV), And a kind or more of group composed by the following general formula (V),
In formula (IV) and formula (V), RaAnd Ra′It is each independently the alkene of hydrogen atom, hydroxyl, the alkyl of carbon number 1~18, carbon number 2~18 Base, aralkyl, aryl ,-[CH (Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-ReOr-O-Ra″Shown in 1 valence group, RaAnd Ra′Any one contain carbon atom；Ra″For the alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, aralkyl, aryl ,-[CH (Rc)-CH(Rd)-O]s-Re、-[(CH2)t-O]u-ReShown in 1 valence group,
RbFor the alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, aralkyl, aryl ,-[CH (Rc)-CH(Rd)-O]s-Re、- [(CH2)t-O]u-ReOr-O-Rb′Shown in 1 valence group；Rb′For the alkyl of carbon number 1~18, the alkenyl of carbon number 2~18, aralkyl, Aryl ,-[CH (Rc)-CH(Rd)-O]s-ReOr-[(CH2)t-O]u-ReShown in 1 valence group,
RcAnd RdIt is each independently hydrogen atom or methyl, ReFor the alkyl of hydrogen atom or carbon number 1~18, carbon number 2~18 alkenyl, Aralkyl, aryl ,-CHO ,-CH2CHO ,-CO-CH=CH2、-CO-C(CH3)=CH2Or-CH2COORfShown in 1 valence group, Rf For hydrogen atom or the alkyl of carbon number 1~5,
Ra、Ra′And RbIn, the carbon number of the aryl is 6~24, and the carbon number of the aralkyl is 7~20, in addition, aryl and aralkyl The substituent group that the aromatic rings of base can have be the straight-chain of carbon number 1~4, the alkyl of branched, alkenyl, nitro, halogen atom,
S indicates that 1~18 integer, t indicate that 1~5 integer, u indicate 1~18 integer.
3. color material dispersion liquid as described in claim 1, wherein the acid value of the dispersing agent be 1mgKOH/g or more and 18mgKOH/g is hereinafter, the glass transition temperature of the dispersing agent is 30 DEG C or more.
4. color material dispersion liquid as described in claim 1, wherein also containing 1 selected from dioxazines system color material and xanthene system color material Kind or more.
5. color material dispersion liquid as claimed in claim 4, wherein the xanthene system color material is the metallic lakes color of xanthene based dye Material.
6. a kind of colored filter colored resin composition disperses containing color material described in any one of claims 1 to 5 Liquid, alkali soluble resin, polyfunctional monomer and initiator.
7. colored filter colored resin composition as claimed in claim 6, wherein the acid value of the alkali soluble resin For 80mgKOH/g or more and 300mgKOH/g or less.
8. colored filter colored resin composition as claimed in claim 6, wherein the polyfunctional monomer has carboxylic Base.
9. colored filter colored resin composition as claimed in claim 6, wherein the alkali soluble resin be with The resin of olefinic double bond.
10. the colored filter colored resin composition as described in any one of claim 6 to 9, wherein the alkali is solvable Property resin be the resin with hydrocarbon ring.
11. colored filter colored resin composition as claimed in claim 10, wherein the alkali soluble resin is had Some hydrocarbon rings be selected from by cyclopenta, cyclohexyl, bornyl, isobornyl, bicyclopentyl, dicyclopentenyl, adamantyl and 1 kind or more of group composed by substituent group shown in following chemical formula (A),
12. colored filter colored resin composition as claimed in claim 6, wherein under the alkali soluble resin is General formula (B) compound represented is stated,
Here, X indicates that group shown in the following general formula (D), Y independently indicate polybasic carboxylic acid or its acid in the general formula (B) The residue of acid anhydride, RiIndicate the following general formula (C) shown in group, j be 0~4 integer, k be 0~3 integer, n be 1 or more it is whole Number,
Here, in the general formula (C), RiiFor hydrogen atom or methyl, RiiiIndependently indicate hydrogen atom or methyl,
Here, in the general formula (D), RivIndependently indicate hydrogen atom, the alkyl of carbon number 1~5, phenyl or halogen atom, RvTable Show-O- or-OCH2CH2O-。
13. colored filter colored resin composition as claimed in claim 6, wherein the initiator is oxime ester system light Polymerization initiator.
14. colored filter colored resin composition as claimed in claim 6, wherein the colored resin composition is appointed Choosing contains silane coupling agent, and the content ratio of silane coupling agent is 1 relative to the total solid content in colored resin composition Quality % or less.
15. a kind of colored filter, which is characterized in that the coloring layer at least having transparent substrate and being set on the transparent substrate,
At least one of the coloring layer, which has, solidifies colored filter colored resin composition as claimed in claim 6 and shape At coloring layer.
16. a kind of display device, which is characterized in that the colored filter with claim 15.
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