CN101542393B - Colored resin composition, color filter, liquid crystal display device, and organic el display - Google Patents

Colored resin composition, color filter, liquid crystal display device, and organic el display Download PDF

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Publication number
CN101542393B
CN101542393B CN200880000397.7A CN200880000397A CN101542393B CN 101542393 B CN101542393 B CN 101542393B CN 200880000397 A CN200880000397 A CN 200880000397A CN 101542393 B CN101542393 B CN 101542393B
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resin composition
colored resin
general formula
anhydride
acid
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CN101542393A (en
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田中俊行
水上润二
土谷达格
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Mitsubishi Chemical Corp
Mitsubishi Rayon Co Ltd
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Mitsubishi Kasei Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133502—Antiglare, refractive index matching layers
    • 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

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)
  • Liquid Crystal (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

This invention provides a colored resin composition having excellent image forming properties even when the content of a colorant is high, and a color filter using the colored resin composition, a liquid crystal display device, and an organic EL display. The colored resin composition comprises at least (A) a colorant and (B) an organic binder, and is characterized in that the organic binder (B) contains an alkali soluble unsaturated resin having an acid value of not less than 10 mg-KOH/g and produced by reacting a reaction product, produced by reacting an epoxy compound (a) represented by general formula (1) with an unsaturated group-containing carboxylic acid (b), with a polybasic acid anhydride (d), (1) wherein X represents a specific linking group, provided that one or more adamantane structures are included in the molecular structure; and l is an integer of 2 or 3.

Description

Colored resin composition, color filter, liquid crystal indicator and organic EL display panel
Technical field
The present invention relates to colored resin composition, color filter, liquid crystal indicator and organic EL (electroluminescence) display screen.At length say; The present invention relates to provide the photosensitive color resin combination and color filter that uses this photosensitive color resin combination and liquid crystal indicator and the organic el panel that uses this color filter that are suitable for making color filter; The liquid stability of said photosensitive color resin combination, excellent heat resistance; Scum silica frost during development is few, and good with adaptation, the edge shape of pixel, the cone shape of substrate.
Background technology
In the past, as the autofrettage of the color filter that has used pigment, known had decoration method, electro-deposition method, ink-jet method, a pigment dispersing method etc.
When utilizing pigment dispersing manufactured color filter, usually in the colored resin composition that utilizes spreading agent etc. that pigment dispersing is formed, add resin glue, Photoepolymerizationinitiater initiater, photopolymerization monomer etc., this photosensitive color resin combination through sensitized is coated on the glass substrate; After carrying out drying, use mask to make public, and develop; Form colored pattern thus; Then it is heated, thereby pattern is fixed, form pixel.Repeat these operations according to each color, thereby form color filter.
The photosensitive color resin combination that is used for the imaging of such color filter requires to have sufficient resolution, with characteristics such as good adaptation, the development residue of substrate is few.In addition, in recent years, people require at the bottom of the high resin black of the high pixel of colour saturation and optical concentration always.Therefore, require the photosensitive color resin combination when containing colorants such as a large amount of pigment and carbon black, to have excellent above-mentioned characteristic.
General because photosensitive polymer combination is supplied in the photo-mask process through coating, drying, exposure, developing procedure, so in these operations, often require: the part of removing in developing procedure does not produce residue or scum silica frost; Remove part and have sufficient dissolubility; Improve pixels such as sharpening degree formation property of pattern edge.But, use the high photosensitive color resin combination of content of the colorant as above-mentioned form pixel and black matrix (below, sometimes pixel and black matrix are closed and are called " pattern ".) situation under, very easily produce following problem: produce residue, scum silica frost in the developing procedure on unexposed the substrate; Unexposed can not obtain fine solubility; The sharpening degree of pattern edge is relatively poor; The photocuring of exposure portion is not enough, so surface smoothing property is relatively poor; Or the like.
Particularly, owing to comprise black pigment at the bottom of the resin black, have light-proofness in the wavelength region may of broad, therefore produce more serious problem, for example (1) is difficult to make the cross-linking density in exposed portion and the unexposed portion to create a difference; (2) even the part after exposure also produces the poor of cross-linking density on film thickness direction, that is, even the photoirradiated surface side is fully solidified, the basal surface side also is difficult to solidify; (3) contain the black pigment that is insoluble to developer solution in a large number, therefore be difficult to obtain high development property; Or the like.
So,, have document to propose to use and have the photosensitive color resin combination (referring to patent documentation 1) of the phenolic aldehyde Epocryl of carboxyl as resin glue in order to solve such problem.But the research according to the inventor can be known; Even when using this resin glue; Also can produce following problem: for example; Because the balance of dissolubility and sensitivity is insufficient, therefore the infiltration of developer solution to exposure portion take place in unexposed dissolving, the rectilinearity of pattern edge part is lower; The adaptation of pattern and substrate is insufficient; Or the like.
In addition, there is document to propose to use and has the photosensitive polymer combination (referring to patent documentation 2) of the reaction product of the acryl resin of carboxyl and the unsaturated compound that ester ring type contains epoxy radicals as resin glue.But, can know that according to the inventor's research even when using this resin glue, sensitivity is also insufficient, so the adaptation of pattern and substrate is relatively poor, is difficult to form high fine pattern.
Have document to propose a kind of resin combination (referring to patent documentation 3) that contains the carboxylic acid compound of unsaturated group as resin glue, this carboxylic acid compound that contains unsaturated group reacts fluorenes type epoxy resin and (methyl) acrylic acid reaction product and polybasic carboxylic acid or its acid anhydrides and obtains.But, can know that according to the inventor's research this resin combination has high sensitivity and high resolution, but have in the tendency that on unexposed substrate, produces residue after the development.And, have strong skin irritation as the bisphenol fluorene and the fluorenes type epoxy resin of raw material, therefore there is report to think, can cause diseases such as macula during processing.
Patent documentation 1: japanese kokai publication hei 11-84126 communique
Patent documentation 2: japanese kokai publication hei 1-289820 communique
Patent documentation 3: japanese kokai publication hei 4-355450 communique
The object of the present invention is to provide the excellent colored resin composition of imaging and the color filter and liquid crystal indicator and the organic el panel that use this colored resin composition.
Summary of the invention
The inventor furthers investigate, and the result finds, through using the alkali solubility unsaturated polyester that is obtained by the specific epoxy compound with adamantane structure as organic bond, can address the above problem.
That is, main points of the present invention are following.
[1] a kind of colored resin composition; It is for contain (A) colorant and (B) colored resin composition of organic bond at least; It is characterized in that, the reaction product that said (B) organic bond contains epoxy compound (a) that makes following general formula (1) expression and the carboxylic acid (b) that contains unsaturated group react with multi-anhydride (d) obtain, acid number is the alkali solubility unsaturated polyester more than the 10mg-KOH/g.
[in said general formula (1), X representes following general formula (2a) or the linking group of (2b) representing.Wherein, in molecular structure, comprise more than one adamantane structure.The integer of 1 expression 2 or 3.
(at said general formula (2a) with (2b), R 1～R 4, R 13～R 15It is 1～12 alkyl that expression independently of one another has or do not have substituent adamantyl, hydrogen atom, has or do not have substituent carbon number, or have or do not have substituent phenyl.
At said general formula (2a) with (2b), * represent with general formula (1) in the position of glycidoxy bonding.)]
[2] a kind of colored resin composition; It is for contain (A) colorant and (B) colored resin composition of organic bond at least; It is characterized in that, said (B) organic bond contain with the reaction product of the epoxy compound of the epoxy compound (a) of following general formula (1) expression and/or following general formula (1A) expression (a ') and the carboxylic acid that contains unsaturated group (b) with they and multi-anhydride (d) are reacted after polyvalent alcohol (c) mixes to obtain, acid number is the alkali solubility unsaturated polyester more than the 10mg-KOH/g.
Figure G2008800003977D00041
[in said general formula (1), X representes following general formula (2a) or the linking group of (2b) representing.Wherein, in molecular structure, comprise more than one adamantane structure.The integer of 1 expression 2 or 3.
(at said general formula (2a) with (2b), R 1～R 4, R 13～R 15It is 1～12 alkyl that expression independently of one another has or do not have substituent adamantyl, hydrogen atom, has or do not have substituent carbon number, or have or do not have substituent phenyl.
At said general formula (2a) with (2b), * represent with general formula (1) in the position of glycidoxy bonding.)]
[in said general formula (1A), X ' representes the linking group of following general formula (3) expression.Wherein, in molecular structure, comprise more than one adamantane structure.The integer of 1 expression 2 or 3.
Figure G2008800003977D00051
(in above-mentioned general formula (3), R 5～R 12Represent hydrogen atom independently of one another, have or do not have substituent carbon number and be 1～12 alkyl, or have or do not have substituent phenyl.Y representes to have or do not have the substituent divalent linking group that comprises adamantane structure.
In above-mentioned general formula (3), * represent with general formula (1A) in the position of glycidoxy bonding.)]
Like [2] described colored resin composition, it is characterized in that [3] multi-anhydride (d) contains quaternary acid anhydrides and/or dibasic acid anhydride and contains tricarboxylic anhydride.
[4] a kind of colored resin composition; It is for contain (A) colorant and (B) colored resin composition of organic bond at least; It is characterized in that; The epoxy compound (a ') that said (B) organic bond contains the epoxy compound (a) that makes following general formula (1) expression and/or following general formula (1A) expression reacts with the reaction product and the multi-anhydride (d) of the carboxylic acid (b) that contains unsaturated group and obtains, acid number is the alkali solubility unsaturated polyester more than the 10mg-KOH/g, and multi-anhydride (d) contains quaternary acid anhydrides and/or dibasic acid anhydride and contains tricarboxylic anhydride.
Figure G2008800003977D00052
[in above-mentioned general formula (1), X representes following general formula (2a) or the linking group of (2b) representing.Wherein, in molecular structure, comprise more than one adamantane structure.The integer of 1 expression 2 or 3.
Figure G2008800003977D00053
(at above-mentioned general formula (2a) with (2b), R 1～R 4, R 13～R 15It is 1～12 alkyl that expression independently of one another has or do not have substituent adamantyl, hydrogen atom, has or do not have substituent carbon number, or have or do not have substituent phenyl.
At above-mentioned general formula (2a) with (2b), * represent with general formula (1) in the position of glycidoxy bonding.)]
Figure G2008800003977D00061
[in above-mentioned general formula (1A), X ' representes the linking group of following general formula (3) expression.Wherein, in molecular structure, comprise more than one adamantane structure.The integer of 1 expression 2 or 3.)
Figure G2008800003977D00062
(in above-mentioned general formula (3), R 5～R 12Represent hydrogen atom independently of one another, have or do not have substituent carbon number and be 1～12 alkyl, or have or do not have substituent phenyl.Y representes to have or do not have the substituent divalent linking group that comprises adamantane structure.
In above-mentioned general formula (3), * represent with general formula (1A) in the position of glycidoxy bonding.)]
Like each described colored resin composition of [2]～[4], it is characterized in that [5] Y in the said general formula (3) is the linking group with following formula (4) or (5) expression.
Figure G2008800003977D00063
(formula (4), (5) have or do not have substituting group, * represent with general formula (3) in the position of phenyl ring bonding.)
Like each described colored resin composition of [1]～[5], it is characterized in that [6] said general formula (2a) or the X that (2b) representes have 2～4 adamantane structures.
Like each described colored resin composition of [1]～[6], it is characterized in that [7] epoxy compound (a) of said general formula (1) expression is shown in following general formula (7).
Figure G2008800003977D00071
[in general formula (7), R 24, R 25It is 1～12 alkyl that expression independently of one another has or do not have substituent adamantyl, hydrogen atom, has or do not have substituent carbon number, or have or do not have substituent phenyl.
Adamantyl shown in the general formula (7) has or does not have substituting group.]
[8] like each described colored resin composition of [2]～[7], it is characterized in that, with the epoxy compound of said general formula (1A) expression (a ') shown in following general formula (6).
Figure G2008800003977D00072
[in general formula (6), R 16～R 23Represent hydrogen atom independently of one another, have or do not have substituent carbon number and be 1～12 alkyl, or have or do not have substituent phenyl.
Adamantyl shown in the general formula (6) has or does not have substituting group.]
Like each described colored resin composition of [1]～[8], it is characterized in that [9] molecular weight of the X in the said general formula (1) is 200～1000.
Like each described colored resin composition of [2]～[9], it is characterized in that [10] molecular weight of the X ' in the said general formula (1A) is 200～1000.
Like each described colored resin composition of [1]～[10], it is characterized in that [11] epoxide equivalent of the epoxy compound (a) of said general formula (1) expression is 210～450.
Like each described colored resin composition of [2]～[11], it is characterized in that [12] epoxide equivalent of the epoxy compound of said general formula (1A) expression (a ') is 210～450.
[13] like [2], [3], each described colored resin composition of [5]～[12]; It is characterized in that; Said polyvalent alcohol (c) is for being selected from by trimethylolpropane, two (trihydroxy methyl) propane, pentaerythrite, dipentaerythritol, trimethylolethane and 1; 2, the polyvalent alcohol of one or more in the group that 3-propane triol is formed.
[14] like each described colored resin composition of [3]～[13], wherein, said tricarboxylic anhydride is trimellitic anhydride and/or hexahydro trimellitic anhydride.
Like each described colored resin composition of [1]～[14], it is characterized in that [15] weight-average molecular weight of said alkali solubility unsaturated polyester is 2,000～20,000.
Like each described colored resin composition of [1]～[15], it is characterized in that [16] said colored resin composition also contains (C) spreading agent.
Like each described colored resin composition of [1]～[16], it is characterized in that [17] said colored resin composition also contains (E) monomer.
Like each described colored resin composition of [1]～[17], it is characterized in that [18] said colored resin composition also contains (D) Photoepolymerizationinitiater initiater.
Like each described colored resin composition of [1]～[18], it is characterized in that [19] in all solids composition of colored resin composition, the content of said (A) colorant is 30～70 weight %.
Like each described colored resin composition of [1]～[19], it is characterized in that [20] said (A) colorant contains black pigment.
[21] a kind of color filter is characterized in that, said color filter has pixel or the black matrix that each described colored resin composition of use [1]～[20] forms on transparency carrier.
[22] a kind of liquid crystal indicator, this liquid crystal indicator are to use [21] described color filter to make.
[23] a kind of organic el panel, this organic el panel are to use [21] described color filter to make.
According to the present invention; A kind of colored resin composition is provided; Even when this colored resin composition contains colorants such as pigment and carbon black with high concentration; Sensitivity and deliquescent balance are also excellent, and the sharpening degree of resulting edge of image shape and cone shape, the adaptation with substrate, surface smoothing property, prevent scum silica frost property, excellent heat resistance.In addition,, high-quality color filter can be provided, and then high-quality liquid crystal indicator or organic el panel can also be provided through using such colored resin composition.
Description of drawings
Fig. 1 is the schematic cross-section that shows an example of the organic EL that is equipped with color filter of the present invention.
Embodiment
Below, embodiment of the present invention is specified, but the present invention is not limited to following embodiment, can in the scope of its main points, carry out various distortion and implement.
In addition; In the present invention; " (methyl) acrylic acid " is meant " acrylic acid and/or methacrylic acid ", and " (methyl) acrylic ester ", " (methyl) acryloyl " also are meant " acrylic ester and/or methacrylate ", " acryloyl and/or methacryl " respectively.And " (many) hydroxyls " is meant " hydroxyl and/or polyhydroxy ".
In the present invention, " all solids composition " be meant, in the colored resin composition or after contained in the printing ink stated desolventize beyond all the components.
In the present invention, weight-average molecular weight is meant the weight-average molecular weight (Mw) that is gone out by polystyrene conversion of utilizing that GPC (gel permeation chromatography) obtains.
In addition, in the present invention, only otherwise special declaration, " amine value " expression is converted into the amine value of effective solid constituent, and the amine value is to use the value of representing with the weight of the KOH of the alkali number a great deal of of every 1g solid constituent of spreading agent.In addition, assay method is of the back.
[colored resin composition]
At first, colored resin composition of the present invention is described.
Colored resin composition of the present invention contains (A) colorant and (B) organic bond at least, it is characterized in that, this colored resin composition contains specific resin as (B) organic bond.
(blending constituent)
(A) colorant
The colorant that is used for colored resin composition of the present invention is meant the composition that colored resin composition is painted.
As colorant, can use dyestuff, pigment, but consider preferred pigments from aspects such as thermotolerance, photostability.As pigment, can use versicolor pigment such as blue pigment, viridine green, red pigment, yellow uitramarine, violet pigment, orange pigment, brown, black pigment.And as its structure, azo system, phthalocyanine system, quinacridone, benzimidazolone system, isoindolinone are that the 、 dioxazine is except that utilizing, indanthrene system, perylene system etc. are the organic pigment, can also utilize various inorganic pigments etc.Below, with the concrete example of the spendable pigment of pigment numbering expression.Terms such as " the C.I. paratoneres 2 " below enumerated is meant Colour index number (C.I.).
As red pigment, can enumerate C.I. paratonere 1,2,3,4,5,6,7,8,9,12,14,15,16,17,21,22,23,31,32,37,38,41,47,48,48:1,48:2,48:3,48:4,49,49:1,49:2,50:1,52:1,52:2,53,53:1,53:2,53:3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276.Wherein, C.I. pigment red 4 8:1,122,168,177,202,206,207,209,224,242,254 can be preferably enumerated, C.I. paratonere 177,209,224,254 can be more preferably enumerated.
As blue pigment, can enumerate C.I. pigment blue 1,1:2,9,14,15,15:1,15:2,15:3,15:4,15:6,16,17,19,25,27,28,29,33,35,36,56,56:1,60,61,61:1,62,63,66,67,68,71,72,73,74,75,76,78,79.Wherein, C.I. pigment blue 15,15:1,15:2,15:3,15:4,15:6 can be preferably enumerated, the C.I. pigment blue 15 can be more preferably enumerated: 6.
As viridine green, can enumerate C.I. naphthol green 1,2,4,7,8,10,13,14,15,17,18,19,26,36,45,48,50,51,54,55.Wherein, can preferably enumerate C.I. pigment Green 7,36.
As yellow uitramarine, can enumerate C.I. pigment yellow 1,1:1,2,3,4,5,6,9,10,12,13,14,16,17,24,31,32,34,35,35:1,36,36:1,37,37:1,40,41,42,43,48,53,55,61,62,62:1,63,65,73,74,75,81,83,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196,197,198,199,200,202,203,204,205,206,207,208.Wherein, C.I. pigment yellow 83,117,129,138,139,150,154,155,180,185 can be preferably enumerated, C.I. pigment yellow 83,138,139,150,180 can be more preferably enumerated.
As orange pigment, can enumerate C.I. pigment orange 1,2,5,13,16,17,19,20,21,22,23,24,34,36,38,39,43,46,48,49,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78,79.Wherein, can preferably enumerate C.I. pigment orange 38,71.
As violet pigment, can enumerate C.I. pigment violet 1,1:1,2,2:2,3,3:1,3:3,5,5:1,14,15,16,19,23,25,27,29,31,32,37,39,42,44,47,49,50.Wherein, C.I. pigment violet 19,23 can be preferably enumerated, the C.I. pigment Violet 23 can be more preferably enumerated.
As black pigment, can use independent black pigment, perhaps use the black pigment that colorants such as redness, green, blueness are mixed.These black pigments can be among inorganic or organic pigment, the dyestuff suitable the selection, can use a kind of separately or mix two or more the use.
As independent black pigment, can enumerate carbon black, acetylene black, dim, bone black, graphite, iron oxide black, nigrosine, cyanine is black, titanium is black etc.From the aspect of shading rate, picture characteristics, preferred especially carbon black, titanium are deceived among these.As the instance of the commercially available article of carbon black, can enumerate following trade name.
Mitsubishi Chemical society makes: MA7, MA8, MA11, MA100, MA220, MA230, #52, #50, #47, #45, #2700, #2650, #2200, #1000, #990, #900 etc.
Degussa society makes: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, SpecialBlack550, Special Black350, Special Black250, Special Black100 etc.
Cabot society makes: Monarch460, Monarch430, Monarch280, Monarch120, Monarch800, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACKPEARLS480, PEARLS130 etc.
Columbian Carbon society makes: RAVEN11, RAVEN15, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040 etc.
As the black manufacturing approach of titanium; Have the method (japanese kokai publication sho 57-205322 communique) of in reduction atmosphere gas, the amalgam heating of titania and Titanium being reduced with the method (japanese kokai publication sho 49-5432 communique) of reducing, the ultra rme titanium dioxide that in hydrogeneous reduction atmosphere gas, will obtain through the pyrohydrolysis of titanium tetrachloride, in the presence of the ammonia with the method (japanese kokai publication sho 60-65069 communique, japanese kokai publication sho 61-201610 communique) of titania or titanium hydroxide high temperature reduction, make vfanadium compound be attached to titania or titanium hydroxide and in the presence of ammonia, carry out the method (japanese kokai publication sho 61-201610 communique) etc. of high temperature reduction, but be not limited to these methods.
As the example of the black commercially available article of titanium, can enumerate the titanium of Mitsubishi Materials society manufacturing and deceive 10S, 12S, 13R, 13M, 13M-C etc.
Below, the black pigment that the coloring material for mixing of two or more colors is formed describes.
As a basic pigment mix Specific examples include Victoria Pure Blue (Victoria? PureBlue) (42595), Auramine O (41000), magnetic card Long bright yellow (cathilon? Brilliant? Yellow) (Alkaline 13) Rhodamine 6GCP (45160), Rhodamine B (45170), saffron OK70: 100 (50240), poppy red X (42080), No.120 / Roe Noel (Lionol) yellow (21090), Roe Noel yellow GRO (21090), the Secretary for Farm La (symuler) Fast Yellow 8GF (21105), benzidine Yellow 4T-564D (21095), Secretary Tim La Fast Red 4015 (12355), Roe Noel red 7B4401 (15850), Fastogen ? Blue? TGR-L (74160), Roe Noel Blue SM (26150), Roe Noel Blue ES (pigment Blue 15:6), Justin Noel red GD (pigment Red 168), Justin Noel green 2YS (pigment green 36), etc. (in addition, the figures in brackets refer to Colour Index (CI)).
In addition, to can further mixing other pigment of use,, can enumerate for example C.I. yellow uitramarine 20,24,86,93,109,110,117,125 with the expression of C.I. numbering; 137,138,147,148,153,154,166, the C.I. orange pigment 36,43,51,55,59; 61, the C.I. red pigment 9,97, and 122,123,149,168,177,180,192,215,216; 217,220,223,224,226,227,228,240, C.I. violet pigment 19,23,29,30; 37,40,50, C.I. blue pigment 15,15:1,15:4,22,60,64, C.I. viridine green 7, C.I. brown 23,25,26 etc.
In addition, above-mentioned carbon black also can share with other black or coloured inorganic, organic pigment.But the light-proofness or the picture characteristics of other pigment are lower than carbon black, are being used for the situation of black matrix, and blending ratio is restricted naturally.
Aforesaid colorant can use a kind of separately, also can share two or more.
In addition, when colored resin composition of the present invention contains black pigment, and during the black matrix of the color filter of stating after being used to form, significantly embody its excellent imaging, therefore preferred especially.
(B) organic bond
The organic bond that is used for colored resin composition of the present invention comprises any one alkali solubility unsaturated polyester of following (B-1)～(B-3).
(B-1) alkali solubility unsaturated polyester; The epoxy compound (a) that this alkali solubility unsaturated polyester makes following general formula (1) expression reacts with the reaction product of the carboxylic acid (b) that contains unsaturated group and multi-anhydride (d) and obtains, and the acid number of this alkali solubility unsaturated polyester is more than the 10mg-KOH/g.
(B-2) alkali solubility unsaturated polyester; This alkali solubility unsaturated polyester is with after polyvalent alcohol (c) mixes with reaction product (this reaction product is the epoxy compound (a) of following general formula (1) expression and/or the epoxy compound of following general formula (1A) expression (a ') and the reaction product of the carboxylic acid that contains unsaturated group (b)); They and multi-anhydride (d) are reacted obtain, the acid number of this alkali solubility unsaturated polyester is more than the 10mg-KOH/g.
(B-3) alkali solubility unsaturated polyester; This alkali solubility unsaturated polyester is to make reaction product (epoxy compound of the epoxy compound (a) of the following general formula of this reaction product (1) expression and/or following general formula (1A) expression (a ') and the reaction product that contains the carboxylic acid (b) of unsaturated group) reacting obtains with multi-anhydride (d) (this multi-anhydride (d) contains quaternary acid anhydrides and/or dibasic acid anhydride and contains tricarboxylic anhydride), and the acid number of this alkali solubility unsaturated polyester is more than the 10mg-KOH/g.
[in above-mentioned general formula (1), X represent following general formula (2a) or (2b) shown in linking group.Wherein, comprise more than one adamantane structure in the molecular structure.The integer of 1 expression 2 or 3.
Figure G2008800003977D00142
(at above-mentioned general formula (2a) with (2b), R 1～R 4, R 13～R 15It is 1～12 alkyl that expression independently of one another has or do not have substituent adamantyl, hydrogen atom, has or do not have substituent carbon number, or have or do not have substituent phenyl.
At above-mentioned general formula (2a) with (2b), * represent with general formula (1) in the position of glycidoxy bonding.)]
Figure G2008800003977D00143
[in above-mentioned general formula (1A), X ' representes the linking group of following general formula (3) expression.Wherein, comprise more than one adamantane structure in the molecular structure.The integer of 1 expression 2 or 3.
Figure G2008800003977D00151
(in above-mentioned general formula (3), R 5～R 12Represent hydrogen atom independently of one another, have or do not have substituent carbon number and be 1～12 alkyl, or have or do not have substituent phenyl.Y representes to have or do not have the substituent divalent linking group that comprises adamantane structure.
In above-mentioned general formula (3), * represent with general formula (1A) in the position of glycidoxy bonding.)]
Epoxy compound (a), (a ') >
In above-mentioned general formula (3), preferred Y is the linking group of following general formula (4) or (5) expression.
Figure G2008800003977D00152
[group of formula (4), (5) expression has or does not have substituting group, * represent with general formula (3) in the position of phenyl ring bonding.]
In addition, the X with above-mentioned general formula (2a), (2b) expression has 2～4 adamantane structures.If adamantane structure is 1, then there is anti-development fluidity to reduce the tendency of resolving power deterioration.
Particularly, preferably as following general formula (7) shown in, the epoxy compound of representing with above-mentioned general formula (1A) (a ') is preferably shown in following general formula (6) with the epoxy compound (a) of above-mentioned general formula (1) expression.
Figure G2008800003977D00161
[in general formula (6), R 16～R 23Represent hydrogen atom independently of one another, have or do not have substituent carbon number and be 1～12 alkyl, or have or do not have substituent phenyl.
In the general formula (7), R 24, R 25It is 1～12 alkyl that expression independently of one another has or do not have substituent adamantyl, hydrogen atom, has or do not have substituent carbon number, or have or do not have substituent phenyl.
Adamantyl shown in general formula (6), (7) has or does not have substituting group.]
As the R in above-mentioned general formula (2a), (2b), (3), (6), (7) 1～R 25Carbon number be 1～12 alkyl, can preferably enumerate carbon number and be 1～10 alkyl.
In addition, these alkyl also can have substituting group, and can enumerate halogen atom, hydroxyl, carbon number as this substituting group is that 1～10 alkoxy, carbon number are 2～10 alkenyl, phenyl, carboxyl, sulfenyl, phosphino-, amino, nitro etc.
In addition, as the R in above-mentioned general formula (2a), (2b), (3), (6), (7) 1～R 25The phenyl substituting group that also can have, can enumerate halogen atom, hydroxyl, carbon number and be 1～10 alkoxy, carbon number and be 2～10 alkenyl, phenyl, carboxyl, sulfenyl, phosphino-, amino, nitro etc.
In addition, as the R among above-mentioned general formula (2a), (2b) 1～R 4, R 13～R 15The diamantane ring that Y contained, the diamantane ring in the general formula (6), the adamantyl in the general formula (7), the R in the general formula (7) of adamantyl, general formula (3) 24, R 25The diamantane ring of adamantyl, formula (4), (5) substituting group that also can have, can enumerate halogen atom, hydroxyl, carbon number and be 1～10 alkoxy, carbon number and be 2～10 alkenyl, phenyl, carboxyl, sulfenyl, phosphino-, amino, nitro etc.
In the above-mentioned general formula (6), R 16～R 23Be preferably alkyl, halogen atom, alkoxy, alkenyl or phenyl especially.
In addition, in the above-mentioned general formula (7), R 24, R 25Be preferably alkyl, halogen atom, alkoxy, alkenyl or phenyl especially.
The molecular weight of X ' shown in X shown in the general formula (1) and the general formula (1A) is preferably 200～1000.If the molecular weight of X and X ', then has the relatively poor tendency of chemical proofing less than 200, when the molecular weight of X and X ' greater than 1000, then sensitivity might reduce.
In addition, be preferably more than 210 with the epoxy compound (a) of general formula (1) expression with the epoxide equivalent of the epoxy compound of general formula (1A) expression (a '), more preferably more than 230.And this epoxide equivalent is preferably below 450, more preferably below 400.The epoxide equivalent of epoxy compound (a) and epoxy compound (a ') is less than under 210 the situation; Sometimes alkali resistance can be not enough; The epoxide equivalent of epoxy compound (a) and epoxy compound (a ') is greater than under 450 the situation, and the sensitivity of the organic bond of generation has the tendency of reduction.
Epoxy compound (a) can use a kind of separately, also can make up two or more uses.And epoxy compound (a ') can use a kind of separately, also can make up two or more uses.Also can one or more epoxy compound (a) be share with one or more epoxy compound (a ').
Epoxy compound (a) and epoxy compound (a ') can use commercially available article, also can utilize the synthetic back of known method to use by following oxybenzene compound.
[the R in above-mentioned general formula (9a), (9b), (10) 1～R 15Definition respectively with general formula (2a), (2b), (3) in definition identical.]
For example; Make their reactions 1～10 hour with general formula (9a) or (9b) adding the temperature of alkali metal hydroxide (such as NaOH, potassium hydroxide etc.) in the dissolving mixt of compound and the excessive epihalohydrin (such as chloropropylene oxide, epibromohydrin etc.) of expression in advance in 20～120 ℃; Perhaps the temperature in 20～120 ℃ makes their reactions 1～10 hour when adding alkali metal hydroxide, can access X in the general formula (1) thus for the above-mentioned general formula (2a) or (2b) epoxy compound (a) of the linking group of expression.
In addition; When in dissolving mixt, adding alkali metal hydroxide (NaOH, potassium hydroxide etc.) in advance or add with the compound of general formula (10) expression and excessive epihalohydrin (such as chloropropylene oxide, epibromohydrin etc.); Make their reactions 1～10 hour 20～120 ℃ temperature, can access X ' in the general formula (1A) thus for the epoxy compound of the linking group of above-mentioned general formula (3) expression (a ').
In the reaction that obtains this epoxy compound (a) and epoxy compound (a '),, can use its WS as alkali metal hydroxide.In this case, can use following method: the WS of this alkali metal hydroxide is added continuously in the reaction system, meanwhile; Under reduced pressure or water and epihalohydrin continuous still are come out; Carry out separatory again, water is removed, epihalohydrin turns back in the reaction system continuously.
In addition; Also can produce with the epoxy compound (a) of general formula (1) expression or with the epoxy compound of general formula (1A) expression (a ') with following method: perhaps add quaternary ammonium salts such as tetramethyl ammonium chloride, tetramethylammonium bromide, Variquat B 200 as catalyzer in the dissolving mixt of compound and the epihalohydrin of (10) expression at above-mentioned general formula (9a), (9b); Make their reactions 1～5 hour at 50～150 ℃; Thereby obtain the perhaps halohydrin etherate of the compound of (10) expression of general formula (9a), (9b); The solid or the WS that in resulting halohydrin etherate, add alkali metal hydroxide; Make their reactions 1～10 hour in 20～120 ℃ temperature once more, so that said etherate dehydrohalogenation (closed loop), thereby said epoxy compound obtained.
With respect to 1 equivalent hydroxyl of the compound of representing with general formula (9a), (9b) or (10), the amount of the epihalohydrin that in such reaction, uses is generally 1～20 mole, is preferably 2～10 moles.And with respect to 1 equivalent hydroxyl of the compound of general formula (9a), (9b) or (10) expression, the consumption of alkali metal hydroxide is generally 0.8～15 mole, is preferably 0.9～11 mole.
In above-mentioned reaction, and then can add alcohols such as methyl alcohol, ethanol, can add aprotic polar solvents such as dimethyl sulfone, dimethyl sulfoxide etc. in addition, so that reaction is carried out smoothly.When using pure time-like, the consumption of alcohols is 2～20 weight % with respect to the amount of epihalohydrin, is preferably 4～15 weight %.In addition, when using the aprotic polar solvent, the consumption of aprotic polar solvent is 5～100 weight % with respect to the amount of epihalohydrin, is preferably 10～90 weight %.
< carboxylic acid (b) that contains unsaturated group >
As the carboxylic acid that contains unsaturated group (b); Can enumerate unsaturated carboxylic acid with ethylenic unsaturated group; As concrete example, can enumerate (methyl) acrylic acid, butenoic acid, adjacent vinyl benzoic acid, a vinyl benzoic acid, vinyl benzoic acid, cinnamic acid, alpha-position had monocarboxylic acids such as alkylhalide group, alkoxy, halogen atom, nitro or cyanic acid substituent (methyl) acrylic acid; 2-(methyl) acrylyl oxy-ethyl succinic acid; 2-(methyl) acrylyl oxy-ethyl hexane diacid; 2-(methyl) acrylyl oxy-ethyl phthalic acid; 2-(methyl) acrylyl oxy-ethyl hexahydro-phthalic acid; 2-(methyl) acrylyl oxy-ethyl maleic acid; 2-(methyl) acryloyl-oxy propyl group succinic acid; 2-(methyl) acryloyl-oxy propyl group hexane diacid; 2-(methyl) acryloyl-oxy propyl group tetrahydrophthalic acid; 2-(methyl) acryloyl-oxy propyl group phthalic acid; 2-(methyl) acryloyl-oxy propyl group maleic acid; 2-(methyl) acryloyl-oxy butyl succinic acid; 2-(methyl) acryloyl-oxy butyl hexane diacid; 2-(methyl) acryloyl-oxy butyl hydrogenation phthalic acid; 2-(methyl) acryloxy butyl phthalic acid; (methyl) acryloyloxyalkyl of dibasic acid such as 2-(methyl) acryloxy butyl maleic acid; On (methyl) acrylic acid addition lactone such as α-caprolactone, beta-propiolactone, gamma-butyrolacton, δ-Wu Neizhi and the monomer that obtains; (methyl) acrylic acid dimer etc.
And; As the carboxylic acid that contains unsaturated group (b), can also enumerate acid anhydrides such as addition succinic anhydride, maleic anhydride, tetrabydrophthalic anhydride, phthalic anhydride on the such unsaturated compound that contains hydroxyl of methacrylic acid addition products such as acrylic acid addition product at pentaerythrite three (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, trimethylolpropane diacrylate, methyl propenoic acid glycidyl base ester, methyl propenoic acid glycidyl base ester and the compound that obtains.
The carboxylic acid (b) that especially preferably contains unsaturated group is (methyl) acrylic acid.
These unsaturated carboxylic acids can use a kind of separately, also can mix two or more the use.
As the method that makes epoxy radicals and carboxylic acid (b) reaction that contains unsaturated group in epoxy compound (a) and/or the epoxy compound (a '), can use known method.For example; With tertiary amine (such as triethylamine, benzyl methyl amine etc.), quaternary ammonium salt (chlorination dodecyl trimethyl ammonium, tetramethyl ammonium chloride, etamon chloride, benzyltriethylammonium chloride etc.), pyridine, triphenylphosphine etc. is catalyzer; In organic solvent; Make above-mentioned epoxy compound (a) and/or epoxy compound (a ') and carboxylic acid (b) stoichiometric number that contains unsaturated group hour～tens of hours 50～150 ℃ of temperature of reaction, thus can be on epoxy compound the addition carboxylic acid.
With respect to reacting material mixture (epoxy compound (a) and/or epoxy compound (a ') and the total that contains the carboxylic acid (b) of unsaturated group), this catalyst consumption is preferably 0.01～10 weight %, is preferably 0.3～5 weight % especially.And; For the polymerization in preventing to react; The preferred polymerization inhibitor (for example MEHQ, quinhydrones, methylnaphthohydroquinone, p methoxy phenol, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol, phenothiazine etc.) that uses; The consumption of polymerization inhibitor is preferably 0.01～10 weight % with respect to reacting material mixture, is preferably 0.03～5 weight % especially.
Addition contain epoxy compound (a) and/or the epoxy compound (a ') of the carboxylic acid (b) of unsaturated group the ratio of epoxy radicals be generally 90～100 moles of %.Remaining epoxy radicals can produce harmful effect to storage stability; Therefore with respect to 1 equivalent epoxy radicals of epoxy compound (a) and/or epoxy compound (a '), the carboxylic acid (b) that preferably contains unsaturated group reacts with the ratio that is generally 0.8～1.5 equivalent, is in particular 0.9～1.1 equivalent.
< polyvalent alcohol (c) >
As polyvalent alcohol (c), be preferably selected from trimethylolpropane, two (trihydroxy methyl) propane, pentaerythrite, dipentaerythritol, trimethylolethane, 1,2, the polyvalent alcohol of one or more among the 3-propane triol.
Through using polyvalent alcohol (c), the molecular weight of (B) organic bond can be increased, and side chain can be in molecule, imported, realize the balance of molecular weight and viscosity.And, can increase the importing rate of acid groups in molecule, can be accomplished the organic bond of balance of sensitivity and adaptation etc.If the consumption of polyvalent alcohol (c) is very few; Then effect is relatively poor; If the consumption of polyvalent alcohol (c) is too much; Exist viscosity to increase or the possibility of gelation, therefore with respect to epoxy compound (a) and/or epoxy compound (a ') and the reaction product that contains the carboxylic acid (b) of unsaturated group, the consumption of polyvalent alcohol (c) is generally about 0.01 times of weight～0.5 times of weight, is preferably about 0.02 times of weight～0.2 times of weight.
< multi-anhydride (d) >
As multi-anhydride, can use dibasic acid anhydride, tricarboxylic anhydride, quaternary acid anhydrides etc.
As quaternary acid anhydrides (tetracarboxylic dianhydride), can use known quaternary acid anhydrides, can enumerate for example tetracarboxylic dianhydrides such as pyromellitic acid dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride etc.These quaternary acid anhydrides can use a kind of separately, also can make up two or more uses.
As the quaternary acid anhydrides, among above-mentioned exemplary compounds, preferred especially biphenyltetracarboxyacid acid acid anhydride.
The reaction product that makes epoxy compound (a) and/or epoxy compound (a ') and contain the carboxylic acid (b) of unsaturated group reacts with quaternary acid anhydrides as multi-anhydride, through cross-linking reaction molecular weight is increased thus.Therefore, have the effects such as adaptation, adjusting dissolubility, raising sensitivity and alkali resistance that improve with substrate, so be preferred.
As dibasic acid anhydride (dicarboxylic anhydride), can enumerate for example maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrabydrophthalic anhydride, hexahydro phthalic anhydride, the interior methylene tetrabydrophthalic anhydride of methyl, chlorendic anhydride, methyl tetrahydrophthalic anhydride etc.Wherein, preferred tetrabydrophthalic anhydride, succinic anhydride.These dibasic acid anhydrides can use a kind of separately, also can make up two or more uses.
The reaction product that makes epoxy compound (a) and/or epoxy compound (a ') and contain the carboxylic acid (b) of unsaturated group reacts with dibasic acid anhydride as multi-anhydride, regulates dissolubility thus easily, and has improved the adaptation with substrate, so be preferred.
As tricarboxylic anhydride (tricarboxylic acid anhydride), can enumerate trimellitic anhydride, hexahydro trimellitic anhydride etc., preferred especially trimellitic anhydride, hexahydro trimellitic anhydride.These tricarboxylic anhydrides can use a kind of separately, also can make up two or more uses.
Through using tricarboxylic anhydride, the molecular weight of (B) organic bond can be increased, and side chain can be in molecule, imported, realize the balance of molecular weight and viscosity.And, can increase the import volume of acid groups in molecule, can be accomplished the organic bond of balance of sensitivity and adaptation etc.
As multi-anhydride (d); Especially preferably use the quaternary acid anhydrides; In this case, the hydroxyl that generates when going up the carboxylic acid (b) that addition contains unsaturated group at epoxy compound (a) and/or epoxy compound (a '), the markup percentage of quaternary acid anhydrides is generally 10～100 moles of %; Be preferably 20～100 moles of %, more preferably 30～100 moles of %.If the markup percentage of quaternary acid anhydrides (d) is very few, the dissolubility of alkali solubility unsaturated polyester is not enough sometimes, and perhaps the adaptation with substrate is not enough sometimes.
In addition, consider that from the aspect that viscosity is regulated or dissolubility is regulated of colored resin composition preferably the part with above-mentioned quaternary acid anhydrides replaces to dibasic acid anhydride.
When share quaternary acid anhydrides and dibasic acid anhydride, its mol ratio is preferably dibasic acid anhydride: quaternary acid anhydrides=99:1～20:80, more preferably 80:20～30:70.When the quaternary acid anhydrides was very few with respect to this scope, resulting film rerum natura of filming might reduce, and when dibasic acid anhydride was very few, the viscosity of resulting resin solution can increase sometimes, handled to become difficult.
In addition; When quaternary acid anhydrides and/or dibasic acid anhydride and tricarboxylic anhydride are share, if the consumption of tricarboxylic anhydride is very few, DeGrain then; Alkali resistance might reduce; Therefore the hydroxyl that generates when going up the carboxylic acid (b) that addition contains unsaturated group at epoxy compound (a) and/or epoxy compound (a '), the consumption of tricarboxylic anhydride is generally 5～70 moles of %, is preferably about 10～40 moles of %.
As multi-anhydride; When using quaternary acid anhydrides and/or dibasic acid anhydride; Maybe when using quaternary acid anhydrides and/or dibasic acid anhydride and tricarboxylic anhydride, the hydroxyl that also generates when going up the carboxylic acid (b) that addition contains unsaturated group at epoxy compound (a) and/or epoxy compound (a '), total markup percentage of multi-anhydride (d) is generally 10～100 moles of %; Be preferably 20～100 moles of %, more preferably 30～100 moles of %.If the markup percentage of multi-anhydride (d) is very few, the dissolubility of alkali solubility unsaturated polyester is not enough sometimes, and perhaps the adaptation with substrate is not enough sometimes.
Make after above-mentioned epoxy compound (a) and/or epoxy compound (a ') and carboxylic acid (b) addition that contains unsaturated group or make above-mentioned epoxy compound (a) and/or epoxy compound (a ') and carboxylic acid (b) addition that contains unsaturated group and behind polyols blend (c) wherein; The multi-anhydride (d) that multi-anhydride (d) that addition quaternary acid anhydrides and/or dibasic acid anhydride are such or addition quaternary acid anhydrides and/or dibasic acid anhydride and tricarboxylic anhydride are such; As its addition method, can use known method.
Its temperature of reaction is generally 80～130 ℃, is preferably 90～125 ℃.If temperature of reaction is greater than 130 ℃, then polymerization can take place in the part unsaturated group, might cause the rapid increase of molecular weight, if temperature of reaction less than 80 ℃, is then reacted and can't be carried out smoothly, possible remaining multi-anhydride (d).
The acid number of the alkali solubility unsaturated polyester that obtains like this is generally more than the 10mg-KOH/g, is preferably more than the 50mg-KOH/g.If the acid number of this alkali solubility unsaturated polyester is less than 10mg-KOH/g, development property can be not enough sometimes.And if the acid number of alkali solubility unsaturated polyester is too high, the alkali resistance aspect goes wrong, and (that is, alkaline-based developer causes the asperitiesization of patterned surfaces sometimes or causes film thickness to reduce.), so acid number is preferably below the 200mg-KOH/g, more preferably below the 150mg-KOH/g.
The weight-average molecular weight of alkali solubility unsaturated polyester of the present invention is preferably more than 1,500, more preferably more than 2,000.And, be preferably below 20,000, more preferably below 10,000.If weight-average molecular weight is too small, then might have problems aspect sensitivity, coating strength, the alkali resistance, if weight-average molecular weight is excessive, then sometimes in development property or have problems aspect the dissolubility again.
In the scope of not damaging effect of the present invention, (B) of the present invention organic bond can contain the resin (hereinafter being called " other organic bonds ") beyond the above-mentioned alkali solubility unsaturated polyester.
As other organic bonds, not special restriction still, can be enumerated the resin glue of for example middle record such as TOHKEMY 2007-271727 communique, TOHKEMY 2007-316620 communique, TOHKEMY 2007-334290 communique etc.These resins can use a kind of separately, also can make up two or more uses.
(C) spreading agent
Because it is important making the fine dispersion of (A) colorant and making its disperse state stabilization, therefore preferably in colored resin composition of the present invention, mix (C) spreading agent.
(C) spreading agent is the material that all has compatibility with (A) colorant and (B) organic bond, can enumerate the surfactant, macromolecule dispersing agent of nonionic for example, cationic, anionic etc. etc.Wherein, preferred macromolecule dispersing agent especially preferably has the macromolecule dispersing agent of following basic functionality: primary amino radical, secondary amino group or uncle group amino or that derived by nitrogen heterocyclic rings such as pyridine, pyrimidine, pyrazines etc. for example.
As macromolecule dispersing agent with basic functionality; If concrete example illustrates preferred chemical constitution, then can enumerate and for example make the compound that has 1 or 2 hydroxyl in polyisocyanate compound, the molecule and with having in a part that the amino compound of reactive hydrogen and uncle reacts and the carbamate that obtains is a macromolecule dispersing agent.
Example as above-mentioned polyisocyanate compound; Can enumerate phenylene vulcabond, 2; 4-toluene diisocyanate, 2; 6-toluene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, naphthalene-1, aromatic diisocyanates such as 5-diisocyanate, tolidine diisocyanate; Hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4, aliphatic diisocyanates such as 4-trimethyl-hexamethylene diisocyanate, dimer acid diisocyanate; IPDI, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), ω, ω '-alicyclic diisocyanates such as diisocyanate based dimethyl cyclohexane; XDI, α, α, α ', α '-tetramethylxylylene diisocyanate etc. has the aliphatic diisocyanate of aromatic rings; Lysine ester triisocyanate, 1; 6; 11-undecane triisocyanate, 1; 8-is diisocyanate based-4-NCO methyloctane, 1,3, and triisocyanate and their tripolymer, water addition product and their polyvalent alcohol addition products etc. such as 6-hexa-methylene triisocyanate, bicycloheptane triisocyanate, three (NCO phenyl) methane, three (NCO phenyl) thiophosphate.
As polyisocyanates, the preferably tripolymer of diisocyanate, the most preferably tripolymer of toluene diisocyanate and Trimerization of Isophorone Diisocyanate body.These tripolymers can use separately, also can share.
Trimerical manufacturing approach as isocyanates; Can enumerate following method: use suitable catalyst for trimerization (for example tertiary amines, phosphine class, pure salt, metal oxide, metal carboxylate) etc.; Above-mentioned diisocyanates is carried out the part trimerizing of NCO; Through after adding catalytic poison trimerizing being stopped, utilizing solvent extraction, thin-film distillation to remove unreacted diisocyanate, thereby obtain the polyisocyanates that contains the isocyanuric acid ester group as target.
As with the compound that has 1 or 2 hydroxyl in a part, a terminal hydroxyl can enumerating PTMEG, polyester-diol, PCDL, polyolefin diols etc. and these compounds is that 1～25 alkyl has carried out compound and the potpourri of two or more these compounds after the alkoxylate by carbon number.
As PTMEG, can enumerate PTMEG, polyether ester glycol and the two or more potpourri among these.
As PTMEG; Can enumerate the PTMEG that makes alkylene oxide homopolymerization or copolymerization and obtain, for example polyglycol, polypropylene glycol, polyglycol-propylene glycol, polyoxy tetramethylene glycol, polyoxy hexa-methylene hexanediol, polyoxy eight methylene glycols and their potpourri.
As the polyether ester glycol; Can enumerate material through making the glycol (perhaps containing the glycol of ether and the potpourri of other glycol) that contains ether and dicarboxylic acid or its acid anhydrides react and obtain; The material that perhaps obtains through polyester-diol and alkylene oxide are reacted for example gathers (PolyTHF) hexanedioic acid ester etc.
As PTMEG, most preferably to use carbon number be 1～25 alkyl carries out the compound that alkoxylate obtains with a terminal hydroxyl of polyglycol, polypropylene glycol, polyoxy tetramethylene glycol or these compounds.
As polyester-diol, can enumerate and make dicarboxylic acid (succinic acid, glutaric acid, hexane diacid, decanedioic acid, fumaric acid, maleic acid, phthalic acid etc.) or their acid anhydrides and glycol (monoethylene glycol, diglycol, triethylene glycol, propylene glycol, DPG, tripropylene glycol, 1,2-butylene glycol, 1,3 butylene glycol, 1; 4-butylene glycol, 2,3-butylene glycol, 3-methyl isophthalic acid, 5-pentanediol, neopentyl glycol, 2-methyl isophthalic acid, ammediol, 2-methyl-2-propyl group-1; Ammediol, 2-butyl-2-ethyl-1, ammediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2; 4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1; 3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1; 8-ethohexadiol, 2-methyl isophthalic acid, 8-ethohexadiol, 1, aliphatic diols such as 9-nonanediol; Alicyclic diols such as hydroxymethyl-cyclohexane; Aromatic diols such as xylyleneglycol, two hydroxyl-oxethyl benzene; N-alkyl dioxane hydramine such as N methyldiethanol amine etc.) polycondensation and the polyester-diol that obtains (for example polyethyleneglycol adipate, polytetramethylene glycol adipate, gather the hexanediol adipate, gather (ethylene glycol and 1,2-propylene glycol) adipate etc.); Or the polylactone glycol that to use said glycols or carbon number be 1～25 monohydroxy alcohol obtains as initial substance or polylactone monohydroxy alcohol (for example polycaprolactone glycol, gather methylpent lactone (polymethylvalerolactone)), and the two or more potpourri of these polymkeric substance.
As polyester-diol, polycaprolactone glycol or be the polycaprolactone that 1～25 alcohol obtains as initial substance with carbon number most preferably.
As PCDL, can enumerate and gather (1, the 6-hexanediol) carbonic ester, gather (3-methyl isophthalic acid, 5-pentanediol) carbonic ester etc., as polyolefin diols, can enumerate polybutadiene diol, hydrogenated butadiene polymer glycol, hydrogenated polyisoprene glycol etc.
Number-average molecular weight with the compound that has 1 or 2 hydroxyl in a part is generally 300～10, and 000, be preferably 500～6,000, further be preferably 1,000～4,000.
Describe being used for the compound that in a part, has reactive hydrogen and uncle's amino of the present invention.As reactive hydrogen (that is) with the hydrogen atom of oxygen atom, nitrogen-atoms or sulphur atom Direct Bonding, can enumerate the hydrogen atom in the functional groups such as hydroxyl, amino, thiol, wherein, preferred amino hydrogen atom, the hydrogen atom of preferred especially primary amino radical.To amino not special qualification of uncle.And, amino as uncle, can enumerate and have the amino or heterocycle structure that carbon number is 1～4 alkyl, more particularly, can enumerate imidazole ring or triazole ring.
If illustration goes out to have in so same a part reactive hydrogen and the amino compound of uncle, then can enumerate N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1; 3-propanediamine, N, N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N; N-dimethyl-ethylenediamine, N, N-diethyl ethylenediamine, N, N-dipropyl ethylenediamine, N, N-dibutyl ethylenediamine, N; N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N; N-dipropyl-1 ,-4-butanediamine, N, N-dibutyl-1,4-butanediamine etc.
In addition; When uncle's amino is nitrogen heterocyclic ring, can enumerate such as nitrogenous five-ring heterocycles such as pyrazoles ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, diazosulfide rings; Such as nitrogenous hexa-member heterocycles such as pyridine ring, pyridazine, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline rings.As these nitrogen heterocyclic rings, preferably imidazole ring or triazole ring.
Have imidazole ring and amino compound if concrete example illustrates these, then can enumerate 1-(3-aminopropyl) imidazoles, histidine, 2-aminooimidazole, 1-(2-amino-ethyl) imidazoles etc.And, if illustrating, concrete example has triazole ring and amino compound, then can enumerate 3-amino-1,2; 4-triazole, 5-(2-amino-5-chlorphenyl)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2; 4-triazole-3,5-glycol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1; 4-diphenyl-1,2,3-triazoles, 3-amino-1-benzyl-1H-2,4-triazole etc.
Wherein, preferred N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1-(3-aminopropyl) imidazoles, 3-amino-1,2,4-triazole.
Blending ratio about the spreading agent raw material; With respect to 100 weight portion polyisocyanate compounds, the number-average molecular weight that in a part, has 1 or 2 hydroxyl is that 300～10,000 compound is generally 10～200 weight portions; Be preferably 20～190 weight portions; Further be preferably 30～180 weight portions, be generally 0.2～25 weight portion, be preferably 0.3～24 weight portion with having the amino compound of reactive hydrogen and uncle in a part.
The weight-average molecular weight (Mw) that is obtained by polystyrene conversion that gel permeation chromatography (GPC) measures of passing through with macromolecule dispersing agent of basic functionality is generally 1,000～200,000, is preferably 2,000～100,000, and more preferably 3,000～50,000.If the molecular weight of macromolecule dispersing agent with basic functionality is less than 1; 000; Sometimes dispersedly understand deterioration, if the molecular weight of macromolecule dispersing agent with basic functionality is greater than 200,000 with dispersion stabilization; Then might dissolubility reduce and dispersed deterioration, might be difficult to the control reaction simultaneously.
Carbamate is that macromolecule dispersing agent can be according to the manufacturing approach manufacturing of known urethane resin.
Solvent when being macromolecule dispersing agent as the manufacturing carbamate can use ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone usually; Ester classes such as ethyl acetate, butyl acetate, cellosolve acetate; Hydro carbons such as benzene,toluene,xylene, hexane; Part alcohols such as diacetone alcohol, isopropyl alcohol, 2-butanols, the tert-butyl alcohol; Chloride such as methylene chloride, methenyl choloride; Ethers such as tetrahydrofuran, ether; Aprotic polar solvents such as dimethyl formamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) etc.
And; As catalyzer, can use general urethane catalysts, specifically; Can enumerate in the following catalyzer one or more: for example, tin such as dibutyl tin laurate, two lauric acid dioctyl tins, two sad dibutyl tins, stannous octoate system; Iron such as acetyl acetone iron, iron chloride system; Tertiary amine such as triethylamine, triethylenediamine system etc.
In the amine value of resulting macromolecule dispersing agent, will be controlled in the scope of 1～100mg-KOH/g with the consumption that has the amino compound of reactive hydrogen and uncle in a part.This amine value is the scope of 5～95mg-KOH/g more preferably.
In addition, the amine value of spreading agent with the spreading agent sample in the KOH weight of alkali number a great deal of of per 1 gram solid constituent (having removed solvent) represent that the amine value of spreading agent is measured through following method.
Accurate weighing 0.5～1.5g spreading agent sample dissolves with 50mL acetate in the beaker of 100mL.The automatic titration device of pH electrode is equipped with in use, uses 0.1mol/L HClO 4Acetum carries out acid-base titration to this solution.With titration pH point of inflexion on a curve is titration end-point, obtains the amine value by following formula.
Amine value [mg-KOH/g]=(561 * V)/(W * S)
(wherein, W representes the spreading agent sample amount of weighing [g], and V is shown in the titer [mL] of titration end-point, and S representes the solid component concentration [wt%] of spreading agent sample.)
If the tendency that the amine value during less than above-mentioned scope, then has dispersibility to reduce, and if the amine value greater than above-mentioned scope, then the development property of colored resin composition is prone to reduce.
In addition, when the carbamate that obtains through above reaction is remaining when NCO is arranged in the macromolecule dispersing agent molecule, make the reaction of this NCO and alcohol or amino-compound, the ageing stability of spreading agent improves thus, so be preferred.
(D) Photoepolymerizationinitiater initiater
Colored resin composition of the present invention provides except that mentioned component the photosensitive color resin combination that also contains (D) Photoepolymerizationinitiater initiater.
Usually with the form use Photoepolymerizationinitiater initiater (D) of the accelerator and the potpourri (Photoepolymerizationinitiater initiater system) of the adjuvants such as sensitizing coloring matter that add as required.Photoepolymerizationinitiater initiater system is direct absorbing light or under photosensitization, causes decomposition reaction or hydrogen abstraction reaction and produce the composition of polymerization activity free radical.
As Photoepolymerizationinitiater initiater, can enumerate the metallocene compound that comprises the cyclopentadiene titanium compound that for example japanese kokai publication sho 59-152396 communique, japanese kokai publication sho 61-151197 number each communique are put down in writing; The Hexaarylbiimidazole derivant that TOHKEMY 2000-56118 communique is put down in writing; The halogen Jia Jiization oxadiazole derivant of japanese kokai publication hei 10-39503 communique record; The halomethyl Striazine derivative, such as N-such as N-phenylglycine aryl-alpha-amido acids, such as N-aryl-a-amino acid salt, N-aryl-free radical activity agent, alpha-aminoalkyl benzophenone based compounds such as α-An Jisuanzhi class; The oxime ester based compound that TOHKEMY 2000-80068 communique, TOHKEMY 2006-36750 communique etc. are put down in writing etc.
Specifically, for example,, can enumerate dichloride dicyclopentadienyltitanium, diphenyl dicyclopentadienyltitanium, two (2 as the cyclopentadienyltitanium derivatives class; 3,4,5,6-phenyl-pentafluoride-1-yl) dicyclopentadienyltitanium, two (2; 3,5,6-phenyl tetrafluoride-1-yl) dicyclopentadienyltitanium, two (2,4; 6-trifluoro-benzene-1-yl) dicyclopentadienyltitanium, two (2,6-two fluorobenzene-1-yl) dicyclopentadienyltitanium, two (2,4-two fluorobenzene-1-yl) dicyclopentadienyltitanium, two (2; 3,4,5; 6-phenyl-pentafluoride-1-yl) two (methyl cyclopentadiene) titanium, two (2,6-two fluorobenzene-1-yl), two (methyl cyclopentadienyl) titanium, (2,6-two fluoro-3-(pyrroles-1-yl)-benzene-1-yl) dicyclopentadienyltitanium etc.
In addition; As the bisglyoxaline derivatives class, can enumerate 2-(2 '-chlorphenyl)-4,5-diphenyl-imidazole dimer, 2-(2 '-chlorphenyl)-4; Two (3 '-methoxyphenyl) imidazoles dimers of 5-, 2-(2 '-fluorophenyl)-4; 5-diphenyl-imidazole dimer, 2-(2 '-methoxyphenyl)-4,5-diphenyl-imidazole dimer, (4 '-methoxyphenyl)-4,5-diphenyl-imidazole dimer etc.
In addition, as halogen Jia Jiization oxadiazole derivatives class, can enumerate 2-trichloromethyl-5-(2 '-benzofuranyl)-1; 3,4-oxadiazole, 2-trichloromethyl-5-(β-(2 '-benzofuranyl) vinyl)-1,3; 4-oxadiazole, 2-trichloromethyl-5-[β-(2 '-(6 "-benzofuranyl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1; 3,4-oxadiazole etc.
In addition; As halomethyl Striazine derivative class; Can enumerate 2-(4-methoxyphenyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(4-methoxyl naphthyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(4-ethoxy naphthyl)-4; Two (trichloromethyl) s-triazine of 6-, 2-(4-carbethoxyl group naphthyl)-4, two (trichloromethyl) s-triazine of 6-etc.
In addition; As alpha-aminoalkyl benzophenone derivatives class; Can enumerate 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4-lignocaine acetophenone, 4-dimethylamino propiophenone, 4-dimethylaminobenzoic acid-2-ethylhexyl (2-エ チ Le ヘ キ シ Le-1; 4-ジ メ チ Le ア ミ ノ Block Application ゾ エ-ト), 2, two (the 4-lignocaine benzylidene) cyclohexanone of 5-, 7-lignocaine-3-(4-lignocaine benzoyl) cumarin, 4-(lignocaine) chalcone etc.
In addition, be derivatives class as the oxime ester, can enumerate for example following compound etc.
Figure G2008800003977D00301
Figure G2008800003977D00311
Figure G2008800003977D00321
Figure G2008800003977D00331
In addition, also can enumerate benzoin alkylether classes such as benzoin methylether, benzoin phenylate, benzoin isobutyl ether, benzoin iso-propylether; Anthraquinone derivative classes such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; Benzophenone derivates classes such as benzophenone, Michler's keton (Michler ' s ketone), 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorobenzophenone, 4-bromine benzophenone, 2-carboxyl benzophenone; 2; 2-dimethoxy-2-phenyl acetophenone, 2; 2-diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-aminomethyl phenyl acetone, 1-hydroxyl-1-Methylethyl-(p-isopropyl phenyl) ketone, 1-hydroxyl-1-(to dodecylphenyl) ketone, 2-methyl-(4 '-methyl mercapto phenyl)-2-morpholino-1-acetone, 1; 1,1-trichloromethyl-acetophenone derivative classes such as (to butyl phenyl) ketone; Thioxanthones, 2-ethyl thioxanthones, 2-isopropyl thioxanthone, 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2, thioxanthone derivates classes such as 4-diisopropyl thioxanthones; (dimethylamino)-ethyl benzoate, to benzoate derivatives classes such as lignocaine ethyl benzoates; Acridine derivatives classes such as 9-phenylacridine, 9-(p-methoxyphenyl) acridine; 9, azophenlyene derivatives class such as 10-dimethylbiphenyl azophenlyene; Anthracyclinone derivatives classes such as benzanthrone etc.
Consider that from the aspect of sensitivity among these Photoepolymerizationinitiater initiaters, preferred especially oxime ester is a derivatives class.
Accelerator as constituting the Photoepolymerizationinitiater initiater set member can use for example N, N such as N-dimethylaminobenzoic acid ethyl ester, N-dialkyl amido benzoic acid alkyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole etc. have the sulfhydryl compound of heterocycle; Or the multifunctional sulfhydryl compound of aliphatics etc.
These Photoepolymerizationinitiater initiaters and accelerator can use separately separately, also can share.
As concrete Photoepolymerizationinitiater initiater set member; For example can enumerate " FineChemicals " (1991; March 1; Vol.20, the dialkyl group acetyl benzene series of record, benzoin, thioxanthone derivates etc. in No.4) the 16th～26 page, can also enumerate in addition records such as japanese kokai publication sho 58-403023 communique, the special public clear 45-37377 communique of Japan, Hexaarylbiimidazole system, trihalomethyl s-triazine system; But in japanese kokai publication hei 4-221958 communique, the japanese kokai publication hei 4-219756 communique etc. record with cyclopentadienyltitanium and xanthene pigment, have the system that the compound of the ethylenic unsaturated double-bond that contains addition polymerization of amino or carbamate groups combines; Or the like.
The sensitizing coloring matter that can in the Photoepolymerizationinitiater initiater set member, mix the wavelength that is fit to the image exposure light source as required is to improve induction sensitivity.As said sensitizing coloring matter, can enumerate the xanthene pigment that japanese kokai publication hei 4-221958 number, japanese kokai publication hei 4-219756 communique are put down in writing; The cumarin pigment that japanese kokai publication hei 3-239703 number, japanese kokai publication hei 5-289335 communique are put down in writing with heterocycle; The 3-ketone group coumarin compound (3-ketocoumarins) of japanese kokai publication hei 3-239703 number, japanese kokai publication hei 5-289335 number record; Pyrroles's methine pigment that japanese kokai publication hei 6-19240 communique is put down in writing can be enumerated the pigment with dialkyl amido benzene skeleton that japanese kokai publication sho 47-2528 number, japanese kokai publication sho 54-155292 number, special public clear 45-37377 number of Japan, japanese kokai publication sho 48-84183 number, japanese kokai publication sho 52-112681 number, japanese kokai publication sho 58-15503 number, japanese kokai publication sho 60-88005 number, japanese kokai publication sho 59-56403 number, japanese kokai publication hei 2-69 number, japanese kokai publication sho 57-168088 number, japanese kokai publication hei 5-107761 number, japanese kokai publication hei 5-210240 number, japanese kokai publication hei 4-288818 communique put down in writing etc. in addition.
Among these sensitizing coloring matters, preferably contain amino sensitizing coloring matter, more preferably in a part, have the compound of amino and phenyl.Particularly preferably be, for example 4,4 '-dimethylamino benzophenone, 4; 4 '-lignocaine benzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4; 4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, 3, benzophenone based compounds such as 4-diaminobenzophenone; 2-(to dimethylamino phenyl) benzoxazole, 2-(to the lignocaine phenyl) benzoxazole, 2-(to dimethylamino phenyl) benzo [4; 5] benzoxazoles, 2-(to dimethylamino phenyl) benzo [6; 7] benzoxazoles, 2; Two (to the lignocaine phenyl)-1 of 5-; 3,4-oxazole, 2-(to dimethylamino phenyl) benzothiazole, 2-(to the lignocaine phenyl) benzothiazole, 2-(to dimethylamino phenyl) benzimidazole, 2-(to the lignocaine phenyl) benzimidazole, 2, two (to the lignocaine phenyl)-1 of 5-; 3,4-thiadiazoles, (to dimethylamino phenyl) pyridine, (to the lignocaine phenyl) pyridine, (to dimethylamino phenyl) quinoline, (to the lignocaine phenyl) quinoline, (to dimethylamino phenyl) pyrimidine, (to the lignocaine phenyl) pyrimidine etc. contain compound of dialkyl amido phenyl etc.
Among these most preferably 4,4 '-dialkyl amido benzophenone.
In addition, sensitizing coloring matter can use a kind of separately, also can mix two or more the use.
(E) monomer
In colored resin composition of the present invention, monomer is not a neccessary composition, but the preferred monomer that uses.
As the monomer that uses among the present invention, use compound with an above ethylenic unsaturated group (below be called ethylenic compound).Specifically, can enumerate the ester of aliphatics (many) hydroxyl compound and unsaturated carboxylic acid; The ester of aromatic series (many) hydroxyl compound and unsaturated carboxylic acid; The ester that obtains by unsaturated carboxylic acid, polybasic carboxylic acid and aliphatic polyhydroxy compound; The esterification reaction product of the ethylene oxide of aromatic polyhydroxy compounds or propylene oxide adduct and unsaturated carboxylic acid; The esterification reaction product of the ethylene oxide of aliphatic polyhydroxy compound or propylene oxide adduct and unsaturated carboxylic acid; The ester of caprolactone modification polyvalent alcohol and unsaturated carboxylic acid; The reaction product of polyvalent alcohol, polyisocyanates and unsaturated carboxylic acid; The terminal compound of styryl; The phosphoric acid unsaturated compound; The addition product of polyepoxides and unsaturated carboxylic acid; Or the like.
Among these; Ester as aliphatics (many) hydroxyl compound and unsaturated carboxylic acid; Specifically; Can enumerate acrylic ester such as glycol diacrylate, triethylene glycol diacrylate, neopentylglycol diacrylate, hexanediyl ester, trimethylolpropane triacrylate, trimethylolethane trimethacrylate acrylic ester, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate, glycerine acrylic ester, the acrylic ester of these exemplary compounds is replaced with methacrylate and the methacrylate that obtains, likewise acrylic ester replaced with itaconate and the itaconate of these exemplary compounds of obtaining, replace with butenoate and the butenoate that obtains or replace with maleate and the maleate that obtains etc.
As the ester of aromatic series (many) hydroxyl compound and unsaturated carboxylic acid, can enumerate quinhydrones diacrylate, quinhydrones dimethylacrylate, resorcinol diacrylate, resorcinol dimethylacrylate, 1,2,3,-thrihydroxy-benzene triacrylate etc.
As the ester that the esterification of unsaturated carboxylic acid and polybasic carboxylic acid and polyol obtains, might not be one matter, as representational concrete example, can enumerate the condensation product of (methyl) acrylic acid, phthalic acid and monoethylene glycol; The condensation product of (methyl) acrylic acid, maleic acid and diglycol; The condensation product of (methyl) acrylic acid, terephthalic acid (TPA) and pentaerythrite; The condensation product of (methyl) acrylic acid, hexane diacid, butylene glycol and glycerine etc.
In addition, as the example that is used for ethylenic compound of the present invention, acrylic amides such as ethylenebis acrylic amide; Allyl ester classes such as diallyl phthalate; It also is useful that phthalic acid divinyl ester etc. contains compound of vinyl etc.
Among the above ethylenic compound of enumerating, preferably have the ethylenic compound of (methyl) acryloyl group, more preferably have the ethylenic compound of acryloyl group.As preferred especially compound, can enumerate trimethylolpropane triacrylate, trimethylolethane trimethacrylate acrylic ester, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate etc.
These (E) monomers can use a kind of separately, also can share two or more.
(F) solvent
For colored resin composition of the present invention, usually with (A) colorant, (B) organic bond, (C) spreading agent and (D) Photoepolymerizationinitiater initiater that mixes as required, (E) monomer, after (G) other compositions dissolvings of stating or the state that is dispersed in the solvent use.
As (F) solvent, be the solvent of 100～300 ℃ scope preferably from making each the composition dissolving that constitutes colored resin composition or selecting boiling point the solvent that disperses.The solvent that more preferably has 120～280 ℃ boiling point.
As such solvent, for example can enumerate following solvent.
Glycol monoalkyl ethers as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list n-butyl ether, glycol tertiary butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diglycol monotertiary n-butyl ether, methoxy amylalcohol, DPG list ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, three sweet 2-ethoxyethanols, tripropylene glycol methyl ether;
Glycol dialkyl ether as glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethyl carbitol, diglycol dipropyl ether, diethylene glycol dibutyl ether, DPG dimethyl ether;
Ethylene glycol monomethyl ether acetate; Ethylene glycol monoethyl ether acetate; The ethylene glycol mono-n-butyl ether acetic acid esters; Propylene glycol methyl ether acetate; Propylene glycol monoethyl ether acetate; The propylene glycol monopropyl ether acetic acid esters; The propylene glycol monobutyl ether acetic acid esters; Methoxyl butylacetic acid ester; 3-methoxyl butylacetic acid ester; Methoxyl amyl group acetic acid esters; The diethylene glycol monomethyl ether acetic acid esters; The diethylene glycol monoethyl ether acetic acid esters; Diglycol monotertiary n-butyl ether acetic acid esters; The dipropylene glycol monomethyl ether acetic acid esters; The triethylene glycol monomethyl ether acetic acid esters; The triethylene glycol monoethyl ether acetate; 3-methyl-such glycol alkyl ether the acetate esters of 3-methoxyl butylacetic acid ester;
Ethylene acetate, 1,3 butylene glycol diacetate esters, 1, glycol diacetate classes such as 6-hexanediol diacetate esters;
Alkyl acetate classes such as adnoral acetate;
Amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl oxide, diamyl ether, ethyl isobutyl ether, the such ethers of two hexyl ethers;
Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl Ketone, methyl isoamyl ketone, diisopropyl ketone, DIBK, methyl isobutyl ketone, cyclohexanone, ethyl pentyl group ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, the such ketone of methoxy pentanone;
Ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, monoethylene glycol, propylene glycol, butylene glycol, diglycol, DPG, triethylene glycol, methoxy amylalcohol, glycerine, such monohydroxy alcohol or the polyalcohols of phenmethylol;
N-pentane, normal octane, diisobutylene, normal hexane, hexene, isoprene, cinene, the such aliphatic hydrocarbon of dodecane;
Cyclohexane, methylcyclohexane, methylcyclohexene, the such ester ring type hydro carbons of dicyclo hexane;
Such aromatic hydrocarbon based of benzene,toluene,xylene, cumene;
Amyl formate; Ethyl formate; Ethyl acetate; Butyl acetate; Propyl acetate; Pentyl acetate; Methyl isobutyrate; The ethylene glycol ethyl ethers acid esters; Ethyl propionate; Propyl propionate; Butyl butyrate; Isobutyl isobutyrate (IBIB); Methyl isobutyrate; Ethyl caprilate; Butyl stearate; Ethyl benzoate; 3-ethoxy-propionic acid methyl esters; The 3-ethoxyl ethyl propionate; 3-methoxypropionic acid methyl esters; 3-methoxy propyl acetoacetic ester; 3-methoxy propyl propyl propionate; 3-methoxy propyl acid butyl ester; Chain ester that gamma-butyrolacton is such or cyclic ester class;
3-methoxypropionic acid, the such alkoxy carboxylic acids of 3-ethoxy-propionic acid;
Chlorobutane, the such halogenated hydrocarbon of chloropentane;
The ether ketone that the methoxy pentanone is such;
Nitrile that acetonitrile, benzonitrile are such etc.
As with above-mentioned suitable commercially available solvent; Can enumerate Mineral Spirit (a kind of solvent oil, about 150-200 ℃ cut), valsol (バ Le ソ Le) #2, Apco (ア プ コ) #18Solvent, Apco thinning agent, Socal solvent No.1 and No.2, SOLVESO#150, Shell TS28 Solvent, carbitol, ethyl carbitol, BC, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methylcellosolve acetate, diethylene glycol dimethyl ether (more than be trade name) etc.
These solvents can use separately, also can share two or more.
(solvent when forming pixel or the black matrix of color filter) with photoetching process
When utilizing photoetching process to form pixel or the black matrix of color filter, as solvent, preferably select boiling point be 100～200 ℃ (under pressure 1013.25 [hPa] condition.Hereinafter, relevant with boiling point pressure condition is all like this) the solvent of scope.More preferably boiling point is 120～170 ℃ a solvent.
The solubleness of the constituent from the balance of coating, surface tension etc. the good and composition is considered preferred diol alkyl ether acetate esters in the above-mentioned solvent than higher aspect.
In addition, the glycol alkyl ether acetate esters can use separately, but also can share other solvents.As the solvent that share, particularly preferably be the glycol monoalkyl ethers.Wherein, the deliquescent angle of the constituent from composition, preferred especially propylene glycol monomethyl ether.In addition; The polarity of glycol monoalkyl ethers is high; If addition is too much, then pigment is prone to aggegation, the tendency that the storage stabilities such as viscosity rising of the colored resin composition that obtains after existing reduce; Therefore the ratio of the glycol monoalkyl ethers in the solvent is preferably 5 weight %～30 weight %, more preferably 5 weight %～20 weight %.
In addition, also preferably share solvent and (hereinafter be sometimes referred to as " high boiling solvent " with boiling point more than 150 ℃.)。Through share such high boiling solvent, colored resin composition is difficult for doing, and has the effect that the homogeneously dispersed state that prevents pigment in the composition is destroyed by rapid draing.That is, have and for example prevent the effect of separating out, solidifying the foreign matter defective that causes that occurs colorant etc. at slit spray nozzle front end.Consider from the aspect that such effect is high, among above-mentioned all kinds of solvents, preferred especially diglycol monotertiary n-butyl ether, diglycol monotertiary n-butyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters.
High boiling solvent in the solvent contain the proportional 3 weight %～50 weight % that are preferably, more preferably 5 weight %～40 weight % are preferably 5 weight %～30 weight % especially.If the amount of high boiling solvent is very few; Then for example colorant etc. might separate out, solidify and cause the foreign matter defective at slit spray nozzle front end; And if the amount of high boiling solvent is too much; Then the rate of drying of composition is slack-off, after in the color filter manufacturing process that states, might cause the such problem of beat pin hole not good or prebake that drying under reduced pressure is handled.
In addition, the high boiling solvent of boiling point more than 150 ℃ can be the glycol alkyl ether acetate esters, and can be the glycol alkyl ether class, in this case, can not contain the high boiling solvent of boiling point more than 150 ℃ in addition.
As preferred high boiling solvent; Among for example above-mentioned all kinds of solvents; Can enumerate diglycol monotertiary n-butyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol methyl ether acetic acid esters, 1,3 butylene glycol diacetate esters, 1,6-hexanediol diacetate esters, glycerol triacetate etc.
(solvent when utilizing ink-jet method to form the pixel of color filter)
When utilizing ink-jet method to form the pixel of color filter, the solvent that as solvent, boiling point is generally 130 ℃～300 ℃, be preferably 150 ℃～280 ℃ is suitable.If the boiling point of solvent is low excessively, then there is the bad tendency of resulting homogeneity of filming.On the contrary; If the boiling point of solvent is too high, then as the back was said, it is better that the drying of colored resin composition suppresses effect; But also there is a large amount of residual solvents in after heat is fired, filming sometimes; Produce the problem on the quality, prolong the drying time that has perhaps produced vacuum drying etc., increased the problems such as time of productive temp.
And,, use that vapor pressure is generally below the 10mmHg, is preferably below the 5mmHg, the solvent below the 1mmHg more preferably from resulting inhomogeneity viewpoint of filming.
In addition, in the color filter that utilizes ink-jet method was made, the printing ink that is sprayed by nozzle was very fine, at number skin liter～tens of skin liters, and before being splashed in jet hole periphery or the pixel storehouse (picture element バ Application Network), solvent evaporation, concentrated, dried solid tendency that printing ink has.For fear of this tendency, the boiling point of the solvent that preferred colored resin composition is contained is higher, and specifically, it is the solvent more than 180 ℃ that colored resin composition preferably contains boiling point.It is the solvent more than 200 ℃ that colored resin composition more preferably contains boiling point, and especially preferably containing boiling point is the solvent more than 220 ℃.And, after the printing ink stated and/or color filter with whole solvents that colored resin composition contained in, boiling point is that the high boiling solvent more than 180 ℃ is preferably more than the 50 weight %, more preferably more than the 70 weight %, most preferably is more than the 90 weight %.At whole solvent mid-boiling points is under the situation of ratio less than 50 weight % of the high boiling solvent more than 180 ℃, can't give full play to preventing the effect of solvent by droplet evaporation sometimes.
Preferred solvent as the high boiling solvent of boiling point more than 180 ℃; For example among above-mentioned all kinds of solvents; Can enumerate diglycol monotertiary n-butyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol methyl ether acetic acid esters, 1; 3-butylene glycol diacetate esters, 1,6-hexanediol diacetate esters, glycerol triacetate etc.
And then for the solubleness of the viscosity of stating printing ink, colored resin composition after adjusting and adjustment solid constituent, it also is resultful containing the solvent that some boiling point is lower than 180 ℃.As such solvent, preferred viscosities is low and dissolubility is high, the low such solvent of surface tension, preferred ethers, ester class or ketone etc.Wherein, preferred especially cyclohexanone, DPG dimethyl ether, adnoral acetate etc.
On the other hand, if solvent contains alcohols, the deterioration sometimes of the ejection stability in the ink-jet method then.Therefore, preferably alcohols is set at below the 20 weight % that account for whole solvents, more preferably below the 10 weight %, below the preferred especially 5 weight %.
(G) other composition
Colored resin composition of the present invention can also be added with adaptation improving agent, coating improving agent, development modifying agent etc. as required except that being added with (A) colorant, (B) organic bond, (C) spreading agent and (D) Photoepolymerizationinitiater initiater that mixes as required, (E) monomer, (F) the solvent.
{ blending ratio }
In colored resin composition of the present invention, in all solids composition of colored resin composition, (A) combined amount of colorant is generally 30～70 weight %, is preferably 35～65 weight %.
If (A) combined amount of colorant is less than above-mentioned scope, then coloring (when (A) colorant has light-proofness during for black) might reduce.Particularly, be difficult to form at the bottom of the resin black with enough optical concentrations containing black pigment as in the situation of black matrix with colored resin composition of (A) colorant.On the contrary,, then there are inadequate situation such as sensitivity, resolution, development property, might be difficult to imaging if (A) combined amount of colorant is greater than above-mentioned scope.
In colored resin composition of the present invention, (B) combined amount of organic bond is generally 5～80 weight % in all solids composition of colored resin composition, is preferably 10～50 weight %.
If (B) combined amount of organic bond is lower than above-mentioned scope, the not enough tendency of development property is arranged, if (B) combined amount of organic bond is higher than above-mentioned scope, the tendency or the not enough possibility of colour saturation of sensitivity deterioration arranged then.
In colored resin composition of the present invention, (C) usage ratio of spreading agent is preferably 0.1～30 weight % with respect to (A) colorant, is preferably 0.5～25 weight % especially.
If (C) combined amount of spreading agent is lower than above-mentioned scope, then dispersion stabilization can be not enough sometimes, if (C) combined amount of spreading agent is higher than above-mentioned scope, then optical concentration, sensitivity or development property can be not enough sometimes.
In colored resin composition of the present invention, with respect to 100 weight portions (B) organic bond, (D) combined amount of Photoepolymerizationinitiater initiater is generally 0.1～50 weight portion, is preferably 1～45 weight portion.If (D) combined amount of Photoepolymerizationinitiater initiater is less than above-mentioned scope, then sensitivity meeting sometimes is not enough, and if (D) combined amount of Photoepolymerizationinitiater initiater surpass above-mentioned scope, then have the tendency that the film forming that makes colored resin composition reduces.
With respect to 100 weight portions (B) organic bond, (E) monomer of use is generally 0～200 weight portion, is preferably 3～180 weight portions.If (E) usage ratio of monomer is less than above-mentioned scope, then cross-linking density is not enough sometimes, and the permanance of resulting pattern, thermotolerance etc. go wrong.And if the usage ratio of monomer surpasses above-mentioned scope, then development property can reduce sometimes.
And with respect to 100 weight portions (B) organic bond, the combined amount of above-mentioned sensitizing coloring matter is generally 0.1～30 weight portion, is preferably 0.1～10 weight portion.If the combined amount of sensitizing coloring matter surpasses above-mentioned scope, then the shape of resulting pattern might worsen.
In addition, colored resin composition of the present invention uses above-mentioned (F) solvent to adjust, so that its solid component concentration is generally 5～50 weight %, is preferably the scope of 10～30 weight %.
{ manufacturing approach }
Below, colored resin composition of the present invention (hereinafter is sometimes referred to as " resist ".) manufacturing approach describe.
When making colored resin composition of the present invention, (A) colorant preferably uses paint regulator (Paint Conditioner), sand mill, bowl mill, edge runner, burrstone mill, airslide disintegrating mill, homogenizer etc. to carry out dispersion treatment in advance usually.Through dispersion treatment, because (A) colorant is by micronize, so the coating characteristics of resist is improved.And, when using black pigment, help to improve light shielding ability as (A) colorant.
Preferably with share (A) colorant, (C) disperse material and (F) a part of or whole system of solvent and (B) organic bond in case of necessity carry out dispersion treatment.(below, the composition that will be used for the potpourri of dispersion treatment sometimes and utilize this processing to obtain is called " printing ink ".) when particularly using macromolecule dispersing agent as (C) spreading agent, the viscosity that can suppress resulting printing ink and resist increases (dispersion stabilization is excellent) in time, and is therefore preferred.In addition, when the liquid that contains all the components that is mixed in colored resin composition was carried out dispersion treatment, the heat release that produces during owing to dispersion treatment was so the character of the composition of high response might change.Thereby, preferably carry out dispersion treatment with the system that contains above-mentioned composition.
When utilizing sand mill that colorant is disperseed, preferably use the beaded glass or the zirconium oxide bead of the particle diameter about 0.1mm～8mm.About the dispersion treatment condition, temperature is generally 0 ℃～100 ℃, is preferably the scope of room temperature～80 ℃.Because the composition of liquid and dispersion treatment device size etc. is different, and makes suitable jitter time different, therefore to the jitter time adjusting that suits.The standard of disperseing is: the gloss of control printing ink, so that 20 degree mirror surface lusters (JIS Z8741) of resist are 100～200 scope.When the glossiness of resist was hanged down, dispersion treatment was insufficient, and thick pigment (colorant) particle is residual in a large number, and development property, adaptation, resolution etc. might be not enough.In addition, if dispersion treatment is proceeded to gloss number greater than above-mentioned scope, then pigment is damaged, produces a large amount of ultra microns, has the tendency of infringement dispersion stabilization on the contrary.
Next, above-mentioned other compositions that contained in the printing ink that will be obtained by above-mentioned dispersion treatment and the resist mix, and process uniform solution.Therefore in the manufacturing process of resist, fine impurity is often sneaked in the liquid, preferably utilizes filtrator etc. that resulting resist is carried out filtration treatment.
[color filter]
Next, the color filter that uses colored resin composition of the present invention is described according to its manufacturing approach.
In order to make color filter of the present invention; At first on transparency carrier, be coated with photosensitive color resin combination of the present invention and carry out drying; On this sample, place photomask then, carry out image exposure across this photomask, and develop; Carry out heat curing or photocuring as required, thereby form pattern.Utilize this method, at first produce usually at the bottom of the resin black, next form 3 color pixels of red (R), green (G), blue (B), form color filter thus.
(transparency carrier)
To the not special restriction of the material of transparency carrier, for example can enumerate polyester such as polyethylene terephthalate; Polyolefin such as polypropylene, tygon etc.; Thermoplastics sheets such as polycarbonate, polymethylmethacrylate, polysulfones; Epoxy resin, vibrin, gather thermosetting plastics sheets such as (methyl) acryl resin; Or various glass plates etc.Particularly consider, preferably use glass plate, heat-resistant plastic sheet from stable on heating aspect.
For the rerum naturas such as cohesiveness to the transparency carrier surface improve, also can carry out the film of various polymkeric substance such as Corona discharge Treatment, ozone treatment, silane coupling agent or urethane polymer etc. in advance to transparency carrier.
(coating of colored resin composition and drying)
The method of coating colored resin composition has no particular limits on transparency carrier, yet uses spinner usually, coiling rod, curtain coater, mould be coated with apparatus for coating such as machine, roll coater, sprayer and be coated with.
Drying after the coating can be used heating plate, IR bake, convection oven etc., and preferred drying condition is 40～150 ℃, and be 10 seconds～60 minutes scope drying time.
With will be coated with, thickness at the bottom of the dried resin black is set in common 0.1～2 μ m, preferred 0.1～1.5 μ m, further preferred 0.1～1 mu m range is advisable.In addition, consider that from the aspect of light-proofness the optical concentration of per 1 μ m thickness is more than 3.0 at the bottom of the resin black in the preferred color filter of the present invention.And as the index of the disperse state of (A) colorant, 20 degree mirror surface lusters (JIS Z8741) of preferred black matrix are 100～200.
(exposure and development)
About the light source that uses in the exposure, for example can enumerate LASER Light Sources such as lamp source such as xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp or Argon ion laser, YAG laser instrument, excimer laser, nitrogen laser etc.When only using specific irradiation light wavelength, also can utilize light filter.
The developer solution that uses in the development treatment does not receive special restriction, as long as it is the liquid with ability of the resist film dissolving that makes unexposed.Can use for example organic solvents such as acetone, methylene chloride, triclene, cyclohexanone, but the most contaminated environment of organic solvent, harmful, have a fire risk etc., the therefore preferred alkaline-based developer that does not have such danger that uses.
As such alkaline-based developer, for example can enumerate and contain such as inorganic alkaline agent such as sodium carbonate, sal tartari, sodium silicate, potassium silicate, NaOH, potassium hydroxide or such as the WS of organic basic agent such as diethanolamine, triethanolamine, tetraalkylammonium hydroxide salt.
Can also contain surfactant, water miscible organic solvent in the alkaline-based developer in case of necessity, have the low molecular compound of hydroxyl or carboxyl etc.Particularly, surfactant has improved effect to development property, resolution, scum silica frost etc. mostly, the therefore preferred surfactant that adds.
For example; As the surfactant that uses in the developer solution, can enumerate have the sodium naphthalene sulfonate group, the anionic surfactant of benzene sulfonic acid sodium salt group, have the polyalkylene oxide base nonionic surfactant, have the cationic surfactant of tetraalkyl ammonium etc.
To the not special restriction of developing method, but be generally 10～50 ℃, be preferably under 15～45 ℃ the development temperature and utilize the method for immersion development, spray development, brush development, ultrasound wave development etc. to carry out development treatment.
Utilize coating, drying, exposure and the developing procedure of above-mentioned colored resin composition, produce at the bottom of the resin black and the pixel of RGB3 look, obtain color filter thus.At this moment, colored resin composition of the present invention can either be used to form black matrix, also can be used in the pixel that forms RGB.
In addition, when using colored resin composition of the present invention to form the pixel of color filter,, make public, develop, the formation image so barrier to oxygen such as polyvinyl alcohol (PVA) can be set because sensitivity is very high with resolving power.
[liquid crystal indicator (panel)]
Use above-mentioned color filter, can make liquid crystal indicator of the present invention as follows.
At first, on color filter, form alignment films, after disposing chock insulator matter (SPACER) on this alignment films, form liquid crystal cell with the subtend baseplate-laminating.Next, liquid crystal is injected the liquid crystal cell that forms, be connected with counter electrode with lead, thereby accomplish liquid crystal indicator of the present invention.
Resin moldings such as the preferred polyimide of alignment films.Usually adopt woodburytype or aniline printing method for forming alignment films, the thickness of alignment films is set to 10～100nm usually.After utilizing heat to fire alignment films is cured processing, through ultraviolet irradiation or utilize the processing of friction cloth to carry out surface treatment, be processed into the surface state of the degree of tilt that can regulate liquid crystal.
Chock insulator matter uses size to be fit to the chock insulator matter with the space (gap) of subtend substrate, and the chock insulator matter that is generally 2～8 μ m is fit to.On filter substrate, form the light chock insulator matter (PS) of transparent resin film with photoetching process, also can utilize this light chock insulator matter (PS) to replace chock insulator matter.As the subtend substrate, use array base palte usually, TFT (thin film transistor (TFT)) substrate is specially suitable.
With different and different according to the purposes of liquid crystal indicator of the space of the applying of subtend substrate, but select in the scope that is being generally 2～8 μ m.Behind the subtend baseplate-laminating, the part except that liquid crystal injecting port seals with encapsulants such as epoxy resin.Through UV irradiation and/or heating encapsulant is solidified, and with the sealing of liquid crystal cell periphery.
After the liquid crystal cell that periphery is sealed cuts into panel unit, in vacuum chamber, reduce pressure, above-mentioned liquid crystal injecting port impregnated in liquid crystal after, through liquid crystal being injected in the liquid crystal cell to indoor seepage.Decompression degree in the liquid crystal cell is generally 1 * 10 -2～1 * 10 -7Pa is preferably 1 * 10 -3～1 * 10 -6Pa.And, preferably when decompression, heating liquid crystal cell, heating-up temperature is generally 30～100 ℃, is preferably 50～90 ℃.Keep the time of heating to be generally 10～60 minutes during decompression, impregnated in the liquid crystal thereafter.For the liquid crystal cell that has injected liquid crystal,,, thereby accomplished liquid crystal indicator (panel) with the liquid crystal injecting port sealing through the curing of UV cured resin.
The kind of liquid crystal is restriction especially not, for existing known liquid crystal such as fragrant family, fatty family, polycyclic compound, both can be lyotropic liquid crystal, also can be thermotropic liquid crystal etc.Thermotropic liquid crystal is known to have nematic crystal, smectic crystal, cholesteryl liquid crystal etc., and liquid crystal of the present invention can be any one in them.
[organic el panel]
When using color filter of the present invention to make organic el panel; For example as shown in Figure 1; At first be produced on the transparent support substrate 10 and form figuratum color filter, this pattern by colored resin composition form (that is, pixel 20 and be arranged on the resin black between the adjacent pixels 20 at the bottom of (not shown)); On this color filter,, can produce organic EL 100 thus across organic protection layer 30 and inorganic oxide film 40 lamination organic luminorphors 500.In addition, at least one among at the bottom of pixel 20 and resin black is to use colored resin composition of the present invention to produce.As the lamination method of organic luminorphor 500, can enumerate: the method that on color filter, forms transparent anode 50, hole injection layer 51, hole transmission layer 52, luminescent layer 53, electron injecting layer 54 and negative electrode 55 successively; To be fitted in method on the inorganic oxide film 40 etc. at the organic luminorphor that forms on other substrates 500.Use the organic EL 100 produce like this, for example can utilize method that " organic el panel " (オ-system society, distribution on August 20th, 2004, former quiet scholar, Anda thousand wave vectors, village Tian Yingxing work) put down in writing etc. to produce organic el panel.
In addition, color filter of the present invention can either be applied to organic el panel of passive type of drive, also can be applied to organic el panel of active drive mode.
Embodiment
Below enumerate synthetic example, embodiment and comparative example the present invention is explained more specifically, but the present invention only otherwise exceed its main points, is not limited to the record of following examples.
[synthetic example]
< preparation of macromolecule dispersing agent solution >
Synthetic example 1
Tripolymer (Mitsubishi Chemical society makes " マ イ テ ッ Network GP750A ", the resin solid composition is 50 weight %, butyl acetate solution) and 0.02g with the 32g toluene diisocyanate dissolves as the dibutyl tin laurate dilution of catalyzer with 47g propylene glycol methyl ether acetate (PGMEA).Under agitation to number-average molecular weight 1 that wherein to splash into end of 14.4g be methoxyl; 000 polyglycol (Japanese grease society's manufacturing " Uniox M-1000 ") and 9.6g number-average molecular weight 1; The potpourri of 000 polypropylene glycol (Sanyo changes into " the SANNIX PP-1000 " that industrial society makes) reacted 3 hours in 70 ℃ then again.Next, add the N of 1g, N-dimethylamino-1, the 3-propanediamine was reacted 1 hour in 40 ℃ again.Obtain the amine value of the solution that contains alkaline macromolecule dispersing agent that obtains like this through acid-base titration, the amine value is 14mg-KOH/g as a result.And utilize drying (the De ラ イ ア ッ プ) method (on heating plate, removed in 30 minutes in 150 ℃ of heating and desolvate, calculate resin concentration by the weight change amount) of weighing to obtain resin content, resin content is 40 weight % as a result.
< synthesizing of organic bond >
Synthetic example 2
Figure G2008800003977D00471
Acetate 3-methoxyl butyl ester, 0.936g triphenylphosphine and the 0.032g p methoxy phenol of the epoxy compound (epoxide equivalent 264) of input 50g said structure, 13.65g acrylic acid, 60.5g in the flask that thermometer, stirring machine, condenser pipe are installed; Under agitation in 90 ℃ make their the reaction, be below the 5mg-KOH/g up to acid number.Reaction needed 12 hours obtains epoxy acrylic ester solution (2-0).
In the flask that thermometer, stirring machine, condenser pipe are housed, drop into resulting epoxy acrylic ester solution (2-0) and trimethylolpropane (TMP), biphenyl tetracarboxylic dianhydride (BPDA), tetrabydrophthalic anhydride (THPA) and trimellitic anhydride (TMA) with the weight ratio shown in the table 1; Under agitation slowly be warmed up to 105 ℃; Make their reactions (wherein, not use TMP in resin glue solution (2-2) and the preparation (2-3).)。Resin solution becomes when transparent, dilutes with methoxy butyl acetate, and adjusting to solid constituent is 50 weight %, thus the epoxy acrylate reactant liquor (resin glue solution) that obtains the solid constituent acid number shown in the table 1 (2-1), (2-2) and (2-3).
Synthetic example 3
In the flask that thermometer, stirring machine, condenser pipe are installed, drop into epoxy compound (epoxide equivalent 264), 13.65g acrylic acid, 60.5g methoxy butyl acetate, 0.936g triphenylphosphine and the 0.032g p methoxy phenol of 50g said structure; Under agitation in 90 ℃ make their the reaction, be below the 5mg-KOH/g up to acid number.Reaction needed 12 hours obtains epoxy acrylic ester solution (3-0).
Make resulting epoxy acrylic ester solution (3-0) and trimethylolpropane (TMP), biphenyl tetracarboxylic dianhydride (BPDA) and tetrabydrophthalic anhydride (THPA) (wherein, not use TMP in the preparation of resin glue solution (3-2) with the weight ratio shown in the table 1 with the reaction likewise of synthetic example 2.), the epoxy acrylate reactant liquor (resin glue solution) that obtains the solid constituent acid number shown in the table 1 (3-1) with (3-2).
Synthetic example 4
Figure G2008800003977D00491
In the flask that thermometer, stirring machine, condenser pipe are installed, drop into epoxy compound (epoxide equivalent 231), 12.7g acrylic acid, 47.8g methoxy butyl acetate, 1.00g triphenylphosphine and the 0.025g p methoxy phenol of 40g said structure; Under agitation in 90 ℃ make their the reaction, be below the 5mg-KOH/g up to acid number.Reaction needed 15 hours obtains epoxy acrylic ester solution (4-0).
Make resulting epoxy acrylic ester solution (4-0) and trimethylolpropane (TMP), biphenyl tetracarboxylic dianhydride (BPDA) and tetrabydrophthalic anhydride (THPA) (wherein, not use TMP in the preparation of resin glue solution (4-2) with the weight ratio shown in the table 1 with the reaction likewise of synthetic example 2.), the epoxy acrylate reactant liquor (resin glue solution) that obtains the solid constituent acid number shown in the table 1 is (4-1) or (4-2).
Synthetic example 5
Figure G2008800003977D00492
In the flask that thermometer, stirring machine, condenser pipe are installed, drop into epoxy compound (epoxide equivalent 252), 11.6g acrylic acid, 46.5g methoxy butyl acetate, 1.00g triphenylphosphine and the 0.025g p methoxy phenol of 40g said structure; Under agitation in 95 ℃ make their the reaction, be below the 5mg-KOH/g up to acid number.Reaction needed 15 hours obtains epoxy acrylic ester solution (5-0).
Make resulting epoxy acrylic ester solution (5-0) and biphenyl tetracarboxylic dianhydride (BPDA) and tetrabydrophthalic anhydride (THPA) and the reaction likewise of synthetic example 2 with the weight ratio shown in the table 1, the epoxy acrylate reactant liquor (resin glue solution) that obtains the solid constituent acid number shown in the table 1 (5-1).
[table 1]
Figure G2008800003977D00501
< preparation of printing ink >
Synthetic example 6
In the twin-screw kneader that 100g is colored with carbon black (" MA-8 " of Mitsubishi Chemical society manufacturing, mean grain size 24 μ m, DBP oil absorption 58ml/100g) with the 500ml ultrapure water mixing 20 minutes, through removing by filter ultrapure water.Add ultrapure water in the carbon black after filtration once more, carry out mixingly, carry out 4 times repeatedly and filter.The carbon black that last filtration is obtained carries out drying, thereby obtains the carbon black through cleaning.To be that the solution that contains alkaline macromolecule dispersing agent of preparation in 50 weight portions, the synthetic example 1 is counted the ratio of 10 weight portions and reached the mode of 30 weight % with solid component concentration with solid constituent through the carbon black that cleans, add carbon black, the solution that contains alkaline macromolecule dispersing agent and PGMEA.The general assembly (TW) of dispersion liquid is 50g.With stirring machine said dispersion liquid is fully stirred to carry out premixed.
Next, utilize the coating wobbler to carry out 6 hours dispersion treatment 25～45 ℃ scope.The zirconium oxide bead that bead uses
Figure G2008800003977D0050111228QIETU
adds the zirconium oxide bead with the dispersion liquid identical weight.Disperse to finish back (degree of 20 among JIS Z8741 mirror surface luster is 170), through filtrator bead is separated with dispersion liquid, thereby prepare carbon black dispersion printing ink.
[embodiment 1～5 and comparative example 1～3]
(1) preparation of resist
Use the carbon black dispersion printing ink of preparation in the synthetic example 6, add each composition, utilize stirrer to stir, make their dissolvings, thereby prepare black resist with following blending ratio.
<blending ratio >
The printing ink of preparation in the synthetic example 6: as solid constituent is 50g
The resin glue solution of preparation in the synthetic example 2～5: as solid constituent is 30g
Photopolymerization monomer (ethylenic compound: dipentaerythritol acrylate): 10g
The solution that contains alkaline macromolecule dispersing agent of preparation in the synthetic example 1: as solid constituent is 5g
Photoepolymerizationinitiater initiater (Ciba Specialty Chemicals CGI242; Compound shown in the following structural formula): 5g
Organic solvent (PGMEA): 300g
Surfactant (" FC-430 " fluorine class surfactant that 3M society in Sumitomo makes): the concentration in the resist reaches the amount of 100ppm
(2) evaluation of resist
Utilize the black resist-coated that obtains in the preparation of spinner with (1) resist on glass substrate (" 7059 " that Corning society makes), with heating plate in 80 ℃ of dryings 1 minute.With the thickness of the dried resist of contact pin type film thickness gauge (" α-STEP " that Tencor society makes) mensuration, thickness is 1 μ m as a result.Next, utilizing high-pressure sodium lamp to change exposure through mask makes public to this sample., in the aqueous sodium carbonate of temperature 25 ℃ working concentration 0.8 weight %s, under pressure 0.15MPa carry out spray development, obtain the resist pattern thus thereafter.To the sensitivity of formed resist pattern evaluation, resolving power and light-proofness, the result lists in table 2 with following benchmark.
1. sensitivity
Can form the correct exposure amount (mj/cm of the mask pattern that is of a size of 20 μ m with accurate dimension 2) expression sensitivity.That is, the resist that exposure is few can form images with low exposure, so the few resist of exposure is represented highly sensitive.
2. resolving power
With 200 times multiples under the exposure of the mask pattern that can faithful reappearance be of a size of 20 μ m, distinguishable minimum pattern size carries out microscopic examination, estimate with following benchmark.
Minimum pattern is of a size of below the 10 μ m: ◎
The minimum pattern size is greater than 10 μ m and be below the 15 μ m: zero
The minimum pattern size is greater than 15 μ m: *
3. light-proofness
Measure the optical concentration (OD) of image with Macbeth reflection of the concentration (" TR927 " that コ Le モ Le グ Application society makes).In addition, the numerical value of OD value representation light shielding ability, numerical value is big more, and the expression light-proofness is strong more.
4. residue
At first, to each resist that utilizes the above embodiments and comparative example to obtain obtain according to after state " time is used in unexposed dissolving " that method is confirmed.In this " time is used in unexposed dissolving ", the part (unexposed portion) of having removed resist to developing fully examines, and estimates with following benchmark.
Do not find film fully: zero
Can see more shallow tunica albuginea: *
< time is used in unexposed dissolving >
With with above-mentioned " evaluation of (2) resist " identical mode; The black resist of coating on glass substrate; And it is dry; The aqueous sodium carbonate of working concentration 0.8 weight % carries out spray development to resulting drying coating film and (says exactly and make the drying coating film dissolving under the condition of 25 ℃ of developer temperaturs, pressure 0.15MPa.)。Colored resin composition on the substrate is dissolved in the developer solution fully, and the time that substrate is exposed is decided to be " time is used in unexposed dissolving " of this colored resin composition.
[table 2]
The kind of organic bond (resin glue solution) Sensitivity (nJ) Resolving power Light-proofness (OD value) Residue
Embodiment 1 2-1 30 ◎ 3.8 ○
Embodiment 2 2-2 30 ○ 3.8 ○
On the spot the example 3 2-3 30 ◎ 3.8 ○
Embodiment 4 3-1 30 ◎ 3.8 ○
Embodiment 5 3-2 30 ○ 3.8 ○
Comparative example 1 4-1 40 ◎ 3.8 ×
Comparative example 2 4-2 30 × 3.8 ○
Comparative example 3 5-1 30 ○ 3.8 ×
Can know that by table 2 through using specific resin as (B) organic bond, thereby colored resin composition of the present invention is excellent aspect sensitivity, resolving power, light-proofness, and does not produce residue, is excellent colored resin composition.
Use ad hoc fashion that the present invention is specified, but those skilled in the art understand under the condition that does not break away from the intent of the present invention and scope and can carry out various distortion.
In addition, the Japanese patent application that the application proposed based on April 20th, 2007 (Japan special hope 2007-111990) is quoted its full content by reference.

Claims (14)

1. colored resin composition; It is for contain (A) colorant and (B) colored resin composition of organic bond at least; It is characterized in that; Reaction product and the multi-anhydride (d) that said (B) organic bond contains epoxy compound (a) that makes following general formula (7) expression and the carboxylic acid (b) that contains unsaturated group react obtain, alkali solubility unsaturated polyester that acid number is 50mg-KOH/g～200mg-KOH/g
Figure FDA00001634281100011
In general formula (7), R 24, R 25Represent that independently of one another adamantyl, hydrogen atom, carbon number are 1～12 alkyl or phenyl,
Said multi-anhydride (d) contains quaternary acid anhydrides and dibasic acid anhydride or contains tricarboxylic anhydride and contain quaternary acid anhydrides and/or dibasic acid anhydride.
2. colored resin composition, it is characterized in that for containing (A) colorant and (B) colored resin composition of organic bond at least,
(B) organic bond contains the reaction product of the epoxy compound (a) of following general formula (7) expression and/or the epoxy compound of following general formula (6) expression (a ') and the carboxylic acid that contains unsaturated group (b) and the alkali solubility unsaturated polyester that they and multi-anhydride (d) is reacted after polyvalent alcohol (c) mixes to obtain, acid number is 50mg-KOH/g～200mg-KOH/g
Figure FDA00001634281100021
In general formula (7), R 24, R 25Represent that independently of one another adamantyl, hydrogen atom, carbon number are 1～12 alkyl or phenyl,
Figure FDA00001634281100022
In general formula (6), R 16～R 23Represent that independently of one another hydrogen atom, carbon number are 1～12 alkyl or phenyl,
Said polyvalent alcohol (c) is for being selected from by trimethylolpropane, two (trihydroxy methyl) propane, pentaerythrite, dipentaerythritol, trimethylolethane and 1,2, the polyvalent alcohol of one or more in the group that 3-propane triol is formed,
Said multi-anhydride (d) contains quaternary acid anhydrides and dibasic acid anhydride or contains tricarboxylic anhydride and contain quaternary acid anhydrides and/or dibasic acid anhydride.
3. according to claim 1 or claim 2 colored resin composition is characterized in that, the epoxide equivalent of the epoxy compound (a) of said general formula (7) expression is 210～450.
4. colored resin composition as claimed in claim 2 is characterized in that, is 210～450 with the epoxide equivalent of the epoxy compound of said general formula (6) expression (a ').
5. according to claim 1 or claim 2 colored resin composition, wherein, said tricarboxylic anhydride is trimellitic anhydride and/or hexahydro trimellitic anhydride.
6. according to claim 1 or claim 2 pigmentary resin constituent is characterized in that the weight-average molecular weight of said alkali solubility unsaturated polyester is 2,000～20,000.
7. according to claim 1 or claim 2 colored resin composition is characterized in that said colored resin composition also contains (C) spreading agent.
8. according to claim 1 or claim 2 colored resin composition is characterized in that said colored resin composition also contains (E) monomer.
9. according to claim 1 or claim 2 colored resin composition is characterized in that said colored resin composition also contains (D) Photoepolymerizationinitiater initiater.
10. according to claim 1 or claim 2 colored resin composition is characterized in that in all solids composition of said colored resin composition, the content of said (A) colorant is 30 weight %～70 weight %.
11. colored resin composition according to claim 1 or claim 2 is characterized in that, said (A) colorant contains black pigment.
12. a color filter is characterized in that, said color filter has pixel or the black matrix of using each described colored resin composition of claim 1～11 to form on transparency carrier.
13. a liquid crystal indicator, this liquid crystal indicator are to use the described color filter of claim 12 to make.
14. an organic EL display panel, this organic EL display panel are to use the described color filter of claim 12 to make.
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