CN107001497A - Colored curable resin composition - Google Patents

Colored curable resin composition Download PDF

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Publication number
CN107001497A
CN107001497A CN201580068513.9A CN201580068513A CN107001497A CN 107001497 A CN107001497 A CN 107001497A CN 201580068513 A CN201580068513 A CN 201580068513A CN 107001497 A CN107001497 A CN 107001497A
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China
Prior art keywords
mass
compound
resin composition
colored curable
curable resin
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CN201580068513.9A
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Inventor
稻田胜彦
代田协
代田协一
井樋昭人
高泽史博
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Kao Corp
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Kao 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C08K5/3465—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B17/00—Azine dyes
    • C09B17/02—Azine dyes of the benzene series
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

It is an object of the invention to provide the excellent colored curable resin composition of a kind of light-proofness and patternability, possess colour filter and dispersion using black matrix formed by the colored curable resin composition.[1] a kind of colored curable resin composition, it contains compound (A1), nigrosine (A2), dispersant (B), organic solvent (C) and the curability compound (D) represented by following formula (1), and compound (A1) is more than 0.10 and less than 0.50 relative to total mass ratio, the i.e. A1/ (A1+A2) of compound (A1) and nigrosine (A2)；[2] a kind of colour filter, it possesses using black matrix formed by the colored curable resin composition of [1] as described above；[3] a kind of dispersion, it contains compound (A1), nigrosine (A2), dispersant (B) and the organic solvent (C) represented by following formula (1), and compound (A1) is more than 0.10 and less than 0.50 relative to total mass ratio, the i.e. A1/ (A1+A2) of compound (A1) and nigrosine (A2).

Description

Colored curable resin composition
Technical field
The present invention relates to a kind of chromatic liquid crystal display equipment and to manufacture the filter used in colour pick-up tube component etc. The colored curable resin composition of color device, possess colour filter and dispersion using black matrix formed by it.
Prior art
Generally for contrast is improved, there is shading in the gap portion formation of the filter segments of the red, green, blue of colour filter Property be referred to as black matrix (hereinafter also referred to as " BM ") clathrate black pattern.
In order that the picture quality of liquid crystal display is excellent, and light-proofness is excellent to be required to BM.Wherein, in recent years, in order to More fine, more high brightness are tackled, industry is to the method according to such as existing formation BM on filter substrate in film Transistor (TFT) mode chromatic liquid crystal display equipment is thought to form BM BOA (Black Matrix on driving substrate Array) mode is studied.In the BOA modes, without the bonding process before this to be aligned with component, pixel Relative aperture (aperture opening ratio) can significantly increase, and can shorten manufacturing process, therefore can improve display quality, cut down cost, therefore, Advantage is more than the existing method that BM is formed on filter substrate.
However, when being intended to form BM situation in multiple substrate side, because BM can be contacted directly with liquid crystal in itself, therefore During the relatively low situation of BM insulating properties itself, the display of liquid crystal display can be caused bad.
Further, since the light shield alignment carried out when forming BM is carried out using infrared camera, therefore it is also required to one Determine the light transmission rate of the near infrared region of grade.Accordingly, with respect to the carbon black for being previously mainly used as BM materials, not only show higher Dielectric constant, the light transmission rate lacked in insulating properties, and near infrared region is relatively low, therefore, it is difficult to be aligned, and difficult For the liquid crystal panel of BOA modes.
As the method for solving such a problem, the method with light-proofness using specific organic pigment is disclosed (with reference to patent document 1).
[prior art literature]
[patent document]
Patent document 1：Japanese Unexamined Patent Application Publication 2012-515233 publications
The content of the invention
The present invention relates to following [1] to [3].
[1] a kind of colored curable resin composition, it contains compound (A1) represented by formula (1), nigrosine (aniline black) (A2), dispersant (B), organic solvent (C) and curability compound (D), and compound (A1) relative to Total mass ratio, the i.e. A1/ (A1+A2) of compound (A1) and nigrosine (A2) is more than 0.10 and less than 0.50.
[chemical formula 1]
[in formula (1), X represents double bond, is separately E bodies or Z bodies, R as geometric isomer1Independently earth's surface Show hydrogen atom, methyl, nitro, methoxyl group, bromine atoms, chlorine atom, fluorine atom, carboxyl or sulfonic group, R2Separately represent Hydrogen atom, methyl or phenyl, R3Separately represent hydrogen atom, methyl or chlorine atom]
[2] a kind of colour filter, it possesses using black as formed by colored curable resin composition described in [1] Matrix.
[3] a kind of dispersion, it contains compound (A1) represented by formula (1), nigrosine (A2), dispersant (B) and had Machine solvent (C), and compound (A1) is relative to compound (A1) and total mass ratio, the i.e. A1/ (A1+A2) of nigrosine (A2) For more than 0.10 and less than 0.50.
Embodiment
The BM of usual colour filter is to be formed at by photolithography on substrate, but the combination shown in above-mentioned patent document 1 It is insufficient in terms of patternability of the thing in light lithography process.It is therefore contemplated that providing a kind of light-proofness and patternability is excellent BM colored curable resin composition.
The problem of the present invention be to provide a kind of light-proofness and the excellent colored curable resin composition of patternability, Possess the colour filter and dispersion using black matrix formed by it.
The present inventor etc. has found, is made by the compound (A1) and nigrosine (A2) that contain formula (1) with specific mass ratio For black color material, light-proofness and the excellent colored curable resin composition of patternability can be obtained.
I.e. the present invention relates to following [1] to [3].
[1] a kind of colored curable resin composition, its contain compound (A1) represented by formula (1), nigrosine (A2), Dispersant (B), organic solvent (C) and curability compound (D), and compound (A1) is relative to compound (A1) and nigrosine (A2) total mass ratio, i.e. A1/ (A1+A2) is more than 0.10 and less than 0.50.
[chemical formula 2]
[in formula (1), X represents double bond, is separately E bodies or Z bodies, R as geometric isomer1Independently earth's surface Show hydrogen atom, methyl, nitro, methoxyl group, bromine atoms, chlorine atom, fluorine atom, carboxyl or sulfonic group, R2Separately represent Hydrogen atom, methyl or phenyl, R3Separately represent hydrogen atom, methyl or chlorine atom]
[2] a kind of colour filter, it possesses using black as formed by colored curable resin composition described in [1] Matrix.
[3] a kind of dispersion, it contains compound (A1) represented by formula (1), nigrosine (A2), dispersant (B) and had Machine solvent (C), and compound (A1) is relative to compound (A1) and total mass ratio, the i.e. A1/ (A1+A2) of nigrosine (A2) For more than 0.10 and less than 0.50.
According to the present invention, it is possible to provide the excellent colored curable resin composition of a kind of light-proofness and patternability, tool Standby colour filter and dispersion using black matrix formed by it.
The colored curable resin composition (following, also referred to as " resin combination ") of the present invention contains formula (1) institute table Compound (A1) (hereinafter also referred to " compound (A1) "), nigrosine (A2), dispersant (B), organic solvent (C) and the solidification shown Property compound (D).
On the resin combination of the present invention, for the viewpoint of light-proofness and patternability, compound (A1) is relative In total mass ratio, the i.e. A1/ (A1+A2) of compound (A1) and nigrosine (A2) be more than 0.10 and less than 0.50.
According to the present invention, used by the way that compound (A1) and nigrosine (A2) are combined, cooperative effect can have been given play to, and Obtain light-proofness and the excellent resin combination of patternability.
[colored curable resin composition]
[black color material]
＜ compounds (A1) ＞
The resin combination of the present invention contains the change represented by formula (1) for the viewpoint of light-proofness and patternability Compound (A1) and nigrosine (A2) are used as black color material.
[chemical formula 3]
In formula (1), X represents double bond, is separately E bodies or Z bodies, R as geometric isomer1Separately represent Hydrogen atom, methyl, nitro, methoxyl group, bromine atoms, chlorine atom, fluorine atom, carboxyl or sulfonic group, R2Separately represent hydrogen Atom, methyl or phenyl, R3Separately represent hydrogen atom, methyl or chlorine atom.
Compound represented by formula (1) may be used alone or in combination two or more and use.
For the viewpoint of the ease of manufacturing of compound (A1), R1It is preferred that being bonded to 6 of dihydroindolone ring, R3It is excellent Choosing is bonded to 4 of dihydroindolone ring.For same viewpoint, R1、R2And R3It is preferred that hydrogen atom.
Compound (A1) has EE bodies, ZZ bodies, EZ bodies as geometric isomer, and the compound used in the present invention can be Any number of single compound in them, or these geometric isomers mixture.
Above-claimed cpd (A1) can for example pass through International Publication publication WO2000/24736, International Publication publication WO2010/ Described method in 081624 and manufacture.As commercially available compound (A1), BASF AG's manufacture can be enumerated " Irgaphor Black S0100CF " etc..
＜ nigrosines (A2) ＞
So-called nigrosine, is the pigment for the black powder for manufacturing aniline oxidative condensation, is the oxygen of anil etc. Change condensation mixture.According to the reaction condition of oxidative condensation, and as the mixture with several intermediates or accessory substance.
On the average grain diameter of the nigrosine (A2) in the present invention, for the viewpoint of light-proofness, preferably more than 0.1 μm, More preferably more than 0.2 μm, and then preferably more than 0.24 μm, and then preferably more than 0.27 μm, and then preferably more than 0.30 μm, and then It is preferred that more than 0.35 μm, for the viewpoint of patternability, preferably less than 1.5 μm, more preferably less than 1.0 μm, and then preferably Less than 0.7 μm, and then preferably less than 0.5 μm.The assay method of the average grain diameter of nigrosine is according to side described in embodiment Method.
On the BET specific surface area of the nigrosine (A2) in the present invention, for the viewpoint of light-proofness, preferably 34m2/ g with Under, more preferably 17m2/ below g, and then preferably 14m2/ below g, and then preferably 12m2/ below g, and then preferably 11m2/ below g, For the viewpoint of patternability, preferably 2.2m2/ more than g, more preferably 3.3m2/ more than g, and then preferably 4.7m2/ more than g, And then preferably 6.6m2/ more than g.The assay method of the BET specific surface area of nigrosine is according to method described in embodiment.
For the viewpoint of security, nigrosine (A2) the preferably Chrome-free in the present invention.The nigrosine of Chrome-free can for example lead to Cross method described in International Publication publication WO2012/099203, International Publication publication WO2012/099204 and manufacture.
As commercially available nigrosine, it can enumerate：The manufacture of Tokyo Se Cai Industries, Incs " Toshiki 5030conc ", " No.2Super Black ", " No.2Aniline Black ", " No.25Aniline Black ", family field industry " NAB1101 " of limited company's manufacture, it is wild between chemical limited company's manufacture " Diamond Black S ", big east Be melted into limited company manufacture " Diamond Black S ", ICI companies manufacture " Monolite Black " series " B ", " BX ", " XBE-HD ", BASF AG manufacture " Diamond Black#300 ", " Cegnarlite Black SNT ", " Termosolid Supra Black SNT ", " Pigment black A ", " " D0080 " of Paliotol Black " series, " K0080 ", " L0080 " etc..
The resin combination of the present invention in the range of the effect of the present invention is not hindered, can containing above-claimed cpd (A1) and Black color material beyond nigrosine (A2).As other black color materials, it can enumerate：Carbon black, titanium are black etc..In this manual, Compound (A1), nigrosine (A2) and other black color materials are referred to as " black color material (A) ".
In the resin combination of the present invention, the conjunction on compound (A1) relative to compound (A1) and nigrosine (A2) The mass ratio of meter, i.e. A1/ (A1+A2), are more than 0.10, preferably more than 0.15, more preferably 0.20 for the viewpoint of light-proofness More than, and then preferably more than 0.24, and then preferably more than 0.28, it is less than 0.50 for the viewpoint of patternability, preferably Less than 0.40, more preferably less than 0.35, and then preferably less than 0.32.
On compound (A1) relative to compound (A1) and the total mass ratio, i.e. A1/ (A1+ of nigrosine (A2) A2), for obtaining the viewpoint of significant patternability, preferably less than 0.28, more preferably less than 0.26, and then preferably 0.25 Below.
In the resin combination of the present invention in contained black color material (A), compound (A1) and the conjunction of nigrosine (A2) Preferably more than 80 mass %, more preferably more than 90 mass % are measured, and for below 100 mass %, and then preferably 100 mass %.
Just improve for the compatibility of black color material and organic solvent, the viewpoint for improving dispersiveness and storage stability, make For black color material, it is possible to use advance with derivative of resin or macromolecule, above-claimed cpd (A1) or nigrosine (A2) etc. The black color material of surface treatment was implemented to the surface of compound (A1) or nigrosine (A2).
[dispersant (B)]
As dispersant, for example, it can enumerate：Main chain is used as with poly- (methyl) acrylate, polylactone, polyalkylene oxide etc. Or the polyurethanes system dispersant of side chain, polyamide-based dispersant, polyimides system dispersant, poly- (methyl) acrylic acid, The polycarboxylic-acid dispersants such as poly (acid anhydride), polyamine system dispersant and the scattered of quaternary ammonium salt etc. is imported with into one part Agent.These dispersants can be used alone or mix two or more and use.
Dispersant preferably make nitrogen-atoms numbers more than 1 and less than 5 polyamino compound, with average addition molal quantity 1 with The dispersant (B1) that upper and less than 100 lactone chain or the level Four agent of oxyalkylene chain are reacted and obtained.
As commercially available dispersant, it can enumerate：" Disperbyk " of BYK-Chemie Japan limited companies manufacture " 161 ", " 166 ", " 167 " of series, " Solsperse " series of Lubrizol limited companies of Japan manufacture The polyurethanes system such as " 55000 ", " 76500 " dispersant；The manufacture of BYK-Chemie Japan limited companies " 106 ", " 110 ", " 111 ", " Solsperse " of the manufacture of Lubrizol limited companies of Japan of " Disperbyk " series Polycarboxylic-acids such as " 36000 ", " 41000 ", " EFKA-5060 " of the manufacture of BASF Japan limited companies of series disperses Agent；" 116 ", " 130 ", Japan of " Disperbyk " series of BYK-Chemie Japan limited companies manufacture " 24000 ", " 32000 ", " 33000 ", " J200 " of " Solsperse " series of Lubrizol limited companies manufacture, " EFKA-4046 ", the manufacture of Ajinomoto Fine-Techno limited companies of BASF Japan limited companies manufacture " polyamine system dispersant such as " 821 ", " 822 ", " 824 ", " 881 " of Ajisper PB " series.Among them, with regard to dispersiveness For viewpoint, preferred polyamine system dispersant, be more preferably selected from " EFKA-4046 " and " it is at least one kind of in Solsperse J200 ", And then preferably " Solsperse J200 ".
＜ dispersants (B1) ＞
Dispersant (B1) preferably make nitrogen-atoms numbers more than 1 and less than 5 polyamino compound, with average addition molal quantity The dispersant that more than 1 and less than 100 lactone chain or the level Four agent of oxyalkylene chain are reacted and obtained, is, for example, to be used as nitrogen Atomicity more than 1 and less than 5 polyamino compound, with the oxyalkylene chain with average addition molal quantity more than 1 and less than 100 The dispersant of the reactant of level Four agent.
Equivalent proportion [level Four agent equivalent/polyamine equivalent] preferably 0.3 of the equivalent of level Four agent relative to polyamino compound More than, more preferably more than 0.6, with regard to the present invention dispersant ease of manufacturing viewpoint for for less than 1.0, preferably 0.9 with Under.
On the nitrogen-atoms numbers of polyamino compound, the storage stability of dispersed viewpoint and raising dispersion with regard to improving For viewpoint, preferably more than 1, more preferably more than 2, and preferably less than 4, more preferably less than 3, and preferably 2.
Compound represented by the preferred following formula of polyamino compound (B1a).
[chemical formula 4]
[in formula, R1、R2、R4May be the same or different, represent hydrogen atom the carbon number more than 1 that can replace through hydroxyl of a part and Less than 10 alkyl, R5Represent carbon number more than 1 and less than 18 alkane diyl is (wherein, with R1Adjacent R5Represent singly-bound), n1 is represented Average structure unit number, n1 is more than 1 and less than 5]
R1、R2It is preferred that carbon number more than 1 and less than 10 alkyl or carbon number more than 2 and less than 6 hydroxyalkyl, more preferably carbon number 1 Above and less than 5 alkyl or carbon number more than 3 and less than 6 hydroxyalkyl, and then preferably carbon number more than 1 and less than 3 alkyl or Carbon number more than 4 and less than 6 hydroxyalkyl.
R4Carbon number preferably less than 10, more preferably less than 8, and then preferably less than 6, and then preferably 1.R4It is preferred that without hydroxyl Substituted alkyl.Specifically, R4It can such as enumerate selected from methyl, ethyl, butyl, hexyl, methylol, hydroxyl butyl and hydroxyl hexyl In it is at least one kind of, be preferably selected from least one kind of in methyl and ethyl, more preferably methyl.
On R5Alkane diyl carbon number, with regard to improve pigment-dispersing viewpoint for be more than 1, preferably more than 2, just carry For the viewpoint of high pigment-dispersing, more preferably more than 3, it is less than 18, preferably 14 for improving the viewpoint of pigment-dispersing Hereinafter, more preferably less than 12, and then preferably less than 10, and then more preferably less than 6.
It is used as R5Alkane diyl, can for example enumerate selected from methylene, ethylidene, various glyceryl, various dihexyls, various It is at least one kind of in pungent diyl and various nonyl diyls, with regard to improve pigment-dispersing viewpoint for, be preferably selected from 1,3- glyceryl, It is at least one kind of in 1,6- dihexyl and 1,9- nonyl diyl, for improving the viewpoint of pigment-dispersing, it is more preferably selected from 1,3- third It is at least one kind of in diyl and 1,6- dihexyl, and then preferably 1,6- dihexyls.
As polyamino compound, it can enumerate：N, N, N', N'- 4-methyl hexamethylene diamine, N, N, N', N'- 4-methyl-diaminopropanes, Polyamine glycol of nitrogen-atoms numbers 2~4 etc..
Polyamino compound for example can be by making alkane glycol and primary amine or the side of secondary amine reaction in the presence of Cu-Ni catalyst Method is obtained the method for Alkylenediamine reductive alkylation using aldehyde.
In addition, as commercially available product, N, N, N' can be used, (Kao Corporation manufactures N'- 4-methyl hexamethylene diamines " KAOLIZER No.1 "), N, N, N', N'- 4-methyl-diaminopropanes (Kao Corporation manufacture " KAOLIZER No.2 "), polyamine glycol (Kao Corporation manufacture " KAOLIZER P200 ") etc..
As level Four agent, lactone chain or oxyalkylene chain with average addition molal quantity more than 1 and less than 100 can be enumerated Haloalkyl ester compounds.
The ring-opening polymerization polymer of for example preferred lactone of lactone chain.As lactone, it can enumerate：α-second lactone, beta-propiolactone, γ- Butyrolactone and δ-valerolactone, 6-caprolactone etc..They can be used alone or be used in the form of two or more combinations.Again Person, in the situation using a variety of lactones, it, which is arranged, to be any number of of random or block.
Among these lactones, preferred 6-caprolactone.
On the average addition molal quantity of polyester chain, just improve the dispersiveness of dispersion and the viewpoint of storage stability, It is more than 2, preferably more than 10, more preferably more than 15 for the developability of colour cell compound and the viewpoint of raising heat resistance, it is just same Viewpoint for be less than 100, preferably less than 70, more preferably less than 50.
The carbon number of oxyalkylene units preferably more than 2, and preferably less than 4, more preferably less than 3.
For improving the viewpoint of pigment-dispersing, the construction unit represented by the preferred following formula of oxyalkylene chain (B1b).
[chemical formula 5]
[in formula (B1b), PO represents the unit from expoxy propane, and EO represents the unit from oxirane, and b, c are represented Average addition molal quantity, b is that 0~100, c is that 0~100, b+c is 1~100.* bonding position is represented]
Above-mentioned formula (B1b) preferably construction unit be block polymer, and preferably above-mentioned formula (B1b) (PO) end side with Alkoxy is bonded, and (EO) end side is bonded to alkyl halide base ester.
On average addition molal quantity b, for improving fixed viewpoint of pigment-dispersing and exposure portion, preferably 10 More than, more preferably more than 21, and then preferably more than 25, the ease of manufacturing of dissolubility and dispersant (B1) with regard to non-exposed portion For viewpoint, preferably less than 60, more preferably less than 50, and then preferably less than 35.
On average addition molal quantity c, for improving the deliquescent viewpoint of pigment-dispersing and non-exposed portion, preferably More than 1, more preferably more than 5, and then preferably more than 10, for fixed viewpoint of exposure portion, preferably less than 95, more preferably Less than 70, and then preferably less than 50, and then more preferably less than 30, and then more preferably less than 20.
On above-mentioned b and c total (b+c), for improving the viewpoint of pigment-dispersing, preferably more than 15, more preferably More than 21, and then preferably more than 30, and then more preferably more than 40, and preferably less than 95, more preferably less than 70, and then preferably 50 with Under.
Total ratio (b/ (b+c)) on b relative to above-mentioned b and c, just improves consolidating for pigment-dispersing and exposure portion Qualitatively for viewpoint, preferably more than 0.2, more preferably more than 0.4, and then preferably more than 0.5, dissolubility with regard to non-exposed portion and For the viewpoint of the ease of manufacturing of dispersant (B1), preferably less than 0.97, more preferably less than 0.86, and then preferably less than 0.8.
The preferred alkoxy oxyalkylene group of oxyalkylene chain.
It is more than 1, preferably more than 6 for improving the viewpoint of pigment-dispersing, more preferably on the carbon number of the alkoxy More than 10, and preferably less than 18, more preferably less than 16, and then preferably less than 14, and then preferably less than 12.
As alkoxy, can enumerate selected from methyl, decyl, lauryl, oil base, stearyl, to octyl phenyl and to nonyl It is at least one kind of in phenyl.On alkoxy, for improving the viewpoint of pigment-dispersing, preferred aliphat alkyl is more preferably selected From at least one kind of in methyl, decyl and lauryl, and then preferably lauryl.
It is used as level Four agent, the preferably compound represented by following formula (B1c-1) or formula (B1c-2).
[chemical formula 6]
[in formula, R6Represent carbon number more than 1 and less than 4 alkane diyl, R71Carbon number more than 2 and less than 12 alkane diyl are represented, A represents average addition molal quantity, is more than 1 and less than 100, R8O represents alkoxy, Y1Represent to depart from base]
[chemical formula 7]
[in formula, R6Represent carbon number more than 1 and less than 4 alkane diyl, R72O represents carbon number more than 2 and less than 4 alkylene oxide Base, a represents average addition molal quantity, is more than 1 and less than 100, R8O represents alkoxy, Y1Represent to depart from base]
On Y1, the dispersiveness and the viewpoint of storage stability of ease of manufacturing and raising dispersion with regard to dispersant For, it is preferably selected from a kind in halogen atom, alkyl sulfide acidic group, benzene sulfonamide acyl group and alkylcarbonic acid ester group, more preferably halogen Atom, so be preferably selected from it is at least one kind of in chlorine atom, bromine atoms and iodine atom, and then preferably chlorine atom.
On R71Carbon number, with regard to improve dispersion dispersiveness and storage stability viewpoint for be more than 2, preferably 3 More than, more preferably more than 4, and then preferably more than 5, for same viewpoint for less than 12, preferably less than 10, more preferably 7 with Under, and then preferably less than 6, and then preferably less than 5.
It is used as R71, can for example enumerate selected from ethylidene, various glyceryl, various fourth diyls, various penta diyls, it is various oneself two It is at least one kind of in base and various diyls in heptan, for improving the dispersiveness of dispersion and the viewpoint of storage stability, preferably 1,5- Penta diyl.
On R72Carbon number, with regard to dispersiveness and storage stability viewpoint for, preferably less than 4, more preferably less than 3, it is excellent Select more than 2.It is used as R72, it is preferable to enumerate at least one kind of in ethylidene and propylidene.
It is more than 2, preferably more than 10 for improving the dispersiveness of dispersion and the viewpoint of storage stability, more on a It is preferred that more than 15, it is less than 100, preferably less than 70, more preferably less than 50 for same viewpoint.
On R6Carbon number, with regard to the present invention dispersant ease of manufacturing viewpoint for be less than 4, preferably less than 3, More preferably less than 2, and preferably more than 1, and then preferably 1.It is used as R6, preferred methylene.
On R8Carbon number, with regard to improve dispersion dispersiveness and storage stability viewpoint for be more than 1, preferably 6 More than, more preferably more than 10, it is less than 18, preferably less than 16, more preferably less than 14 for same viewpoint.On R8, just Improve for the dispersiveness of dispersion and the viewpoint of storage stability, be preferably selected from aliphatic alkyl and the alkyl with aromatic rings In at least one kind of, more preferably aliphatic alkyl, and then be preferably selected from least one kind of in alkyl and alkenyl, and then preferably alkyl.
It is used as R8, can for example enumerate selected from methyl, ethyl, octyl group, decyl, lauryl, myristyl, cetyl, oil base, Stearyl, phenyl, to octyl phenyl and at least one kind of in nonyl phenyl, just improve the dispersiveness of dispersion and preserve stable For the viewpoint of property, preferred lauryl.
In dispersant (B1), there can be the Component units from level Four agent other than the above.
As other level Four agents, it can enumerate with the carbon number more than 1 and less than 10 hydrocarbon compound for departing from base.On hydrocarbon The carbon number of compound, is less than 10, preferably less than 7 for improving the dispersiveness of dispersion and the viewpoint of storage stability, more It is preferred that less than 4, and then preferably less than 2, and be more than 1.
As with the hydrocarbon compound for departing from base, it can enumerate selected from dialkyl sulfate, alkyl halide, p-methyl benzenesulfonic acid alkyl It is at least one kind of in ester, specifically, it can enumerate：Dimethyl suflfate, dithyl sulfate, dipropyl sulfate, bromomethane, bromo Ethane, bromo propane, iodomethane, iodic ether, iodopropane etc..
Neutralized in addition, acid can also be used in dispersant (B1).
It is excellent for the viewpoint of dispersiveness, storage stability and redispersibility on dispersant (B1) weight average molecular weight 2, more than 000, more preferably 3, more than 000, and then preferably 3, more than 500 are selected, furthermore it is preferred that less than 35,000, more preferably 20, Less than 000, and then preferably 10, less than 000.The assay method of weight average molecular weight is according to method described in embodiment.
The manufacture method ＞ of ＜ dispersants (B1)
Dispersant (B1) can be obtained by making the polyamino compound of nitrogen-atoms numbers more than 1 and less than 5 be reacted with level Four agent .The inert gas atmospheres such as the preferred nitrogen atmosphere of reaction atmosphere, argon gas in the reaction of acquisition dispersant (B1).In the process Preferably more than 50 DEG C of the temperature of reaction, preferably more preferably more than 80 DEG C, less than 100 DEG C.
[organic solvent (C)]
As organic solvent, for example, it can enumerate：The monohydric alcohols such as ethanol, isopropanol；Acetone, methyl ethyl ketone, cyclohexanone etc. Ketone；The aromatic hydrocarbons such as toluene, dimethylbenzene；The aliphatic hydrocarbons such as hexamethylene；The polyalcohols such as propane diols；Ethers such as ethylene glycol diethyl ether etc.； In addition compound represented by ethyl acetate, silicone, grease etc. and following formula (SL1) etc..
[chemical formula 8]
In formula (SL1), R4And R5Separately represent what hydrogen can be replaced with carbon number more than 1 and less than 3 alkoxy The alkyl of carbon number more than 1 and less than 4 straight or branched, R6Represent hydrogen atom or methyl, n represent more than 0 and less than 3 it is whole Number.
In formula (SL1), R is used as4And R5, can enumerate：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, 3- methoxyl groups Butyl, isobutyl group, sec-butyl and the tert-butyl group, are preferably selected from least one kind of in methyl and ethyl.
N preferably 1 or 2.
As organic solvent, for the viewpoint of the dispersiveness, the dissolubility of dispersant or dispersiveness of colored materials, preferably Selected from ethylene glycol monoethylether acetate, propylene glycol methyl ether acetate (hereinafter also referred to as " PGMEA "), diethylene glycol monobutyl ether It is at least one kind of in acetic acid esters, acetic acid -3- methoxybutyls and propylene glycol monoethyl ether acetate, more preferably PGMEA.
Above-mentioned organic solvent may be used alone or in combination two or more and use.
[curability compound (D)]
As curability compound, for example, it can enumerate multifunctional polymerizable compound.
The multi-functional polymerizable compound ＞ of ＜
Multifunctional polymerizable compound has more than 2 ethene unsaturated bonds.
As the position with ethene unsaturated bond, it can enumerate：(methyl) is acrylate-based, vinyl etc..
It is used as multifunctional polymerizable compound, it is preferable to use multifunctional (methyl) acrylate based compound.
On the quantity of ethene unsaturated bond contained in multifunctional polymerizable compound, with regard to the viewpoint of patternability For, preferably more than 3, more preferably more than 4, and then preferably more than 5, and preferably less than 8, more preferably less than 7, enter And it is preferred that less than 6.
As multifunctional (methyl) the acrylate based compound, it can enumerate：Ethylene glycol two (methyl) acrylate, diethyl Glycol two (methyl) acrylate, tetraethylene glycol two (methyl) acrylate, propane diols two (methyl) acrylate, polypropylene glycol Two (methyl) acrylate, butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, glycerine two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol Double (4- (methyl) the acryloxy diethoxybenzenes of six (methyl) acrylate, pentaerythrite two (methyl) acrylate, 2,2- Base) propane, 2,2- double (4- (methyl) acryloxypolyethoxyphenyl) propane, (methyl) acrylic acid 2- hydroxyl -3- (first Base) acryloxy propyl ester, ethylene glycol diglycidylether two (methyl) acrylate, diethylene glycol diglycidyl glycerin ether two It is (methyl) acrylate, o-phthalic acid diglycidyl ester two (methyl) acrylate, glycerine three (methyl) acrylate, sweet The reactant ((first of oily poly- (methyl) acrylate of polyglycidyl ether, PIC and (methyl) acrylic acid hydroxy alkyl ester Base) propenoic methyl carbamate), di-2-ethylhexylphosphine oxide (methyl) acrylamide, dimethylene ether double (methyl) acrylamide, polyalcohols With the condensation product, triacryl formal of N- methylols (methyl) acrylamide etc..These multifunctional (methyl) acrylate Based compound may be used alone or in combination two or more and use.
Among them, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylic acid are preferably selected from Ester, pentaerythrite four (methyl) acrylate, (methyl) acrylate of dipentaerythritol five and dipentaerythritol six (methyl) third It is at least one kind of in olefin(e) acid ester, more preferably dipentaerythritol acrylate (hereinafter also referred to as " DPHA ").
In this manual, " (methyl) acrylate " refers at least 1 in acrylate and methacrylate Kind.Also, " (methyl) acrylamide " refers at least one kind of in acrylamide and Methacrylamide.
As curability compound, for example, it can also contain (methyl) acrylic acid, the alkyl with carbon number more than 1 and less than 18 The simple function polymerizable compound such as (methyl) acrylate, vinyl acetate.
The resin combination of the present invention can draw containing alkali soluble resin (E), mercaptan compound, fluorine compounds, photopolymerization Send out agent and light-initiated auxiliary agent etc..
[alkali soluble resin (E)]
When manufacturing colour filter by photolithography, alkali soluble resin is to make unexposed portion be dissolved in developer solution. As alkali soluble resin, the commonly used material of negative resist can be used, as long as can to have in alkaline aqueous solution Dissolubility wherein, i.e., in the 0.05 mass % tetramethyl ammonium hydroxide aqueous solution in 20 DEG C dissolve more than 1 mass %.
It is used as the alkali soluble resin used in the present invention, it is preferable to use (methyl) acrylate and (methyl) third The copolymer of olefin(e) acid.
As (methyl) acrylate, it can enumerate and be selected from (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) N-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid tributyl and (first Base) it is at least one kind of in benzyl acrylate, it is preferably selected from least 1 in (methyl) benzyl acrylate and (methyl) methyl acrylate Kind.That is, as the copolymer of (methyl) acrylate and (methyl) acrylic acid, be more preferably selected from (methyl) benzyl acrylate with The copolymer and (methyl) methyl acrylate of (methyl) acrylic acid with it is at least one kind of in the copolymer of (methyl) acrylic acid.
Formed (methyl) acrylate of above-mentioned copolymer and (methyl) acrylic acid mol ratio ((methyl) acrylate/ (methyl) acrylic acid) preferably more than 50/50, more preferably more than 70/30, and preferably less than 90/10, more preferably less than 80/20.
The weight average molecular weight of alkali soluble resin preferably 5, more than 000, more preferably 7, more than 000, and preferably 50,000 with Under, more preferably 30, less than 000.
In this manual, " (methyl) acrylic acid " refers at least one kind of in acrylic acid and methacrylic acid.
[mercaptan compound]
The METHYLPYRROLIDONE of polyimides predecessor is dissolved when BM is due to being submerged in form polyimide film In (hereinafter also referred to as " NMP ") equal solvent, therefore solvent resistance is required to BM.It is of the invention for the viewpoint of solvent resistance Resin combination can contain mercaptan compound.The preferred multi-thiol compound of mercaptan compound.
For the viewpoint of solvent resistance, mercaptan compound preferably has more than 3 sulfydryls.Think, by with 3 with Upper sulfydryl, crosslink density increases, therefore can further suppress as the swollen of the resin combination after the solidification caused by NMP equal solvents Profit, dissolution of black color material etc..
The quantity for the sulfydryl having on mercaptan compound, for the viewpoint of solvent resistance, preferably more than 3, more It is preferred that more than 4, for obtaining the viewpoint of easiness, preferably less than 9, more preferably less than 8, and then preferably less than 7, And then more preferably less than 6.
Mercaptan compound can enumerate analiphatic sulphur alcoholic compound, the mercaptan chemical combination with the cyclic structure such as heterocycle or aromatic rings Thing, for the viewpoint of solvent resistance, preferred aliphat mercaptan compound.
For the viewpoint of solvent resistance, mercaptan compound preferably has the structure from mercaptan carboxylic acid.
As analiphatic sulphur alcoholic compound, it can enumerate：1,2,3- tri- (sulfydryl methyl mercapto) propane, (the 2- sulfydryls of 1,2,3- tri- Ethylmercapto group) propane, 1,2,3- tri- (3- sulfydryl rosickyite base) propane, trimethylolpropane tris (2- mercaptoacetates), (2- of glycerine three Mercaptoacetate), pentaerythrite four (2- mercaptoacetates), dipentaerythritol five (2- mercaptoacetates), dipentaerythritol six (2- mercaptoacetates), trimethylolpropane tris (3-thiopropionate), pentaerythrite four (3-thiopropionate), two seasons penta 4 Alcohol six (3-thiopropionate), trimethylolpropane tris (3- mercaptobutylates), pentaerythrite four (3- mercaptobutylates), two seasons Penta tetrol six (3- mercaptobutylates) etc..
As the mercaptan compound with heterocycle, it can enumerate：Isocyanuric acid three [(3- mercaptopropionyls epoxide)-ethyl] ester, Isocyanuric acid three [(3- sulfydryls butyryl acyloxy)-ethyl] ester, (1,3,5- tri- (3- sulfydryl butyryl acyloxies ethyl) -1,3,5- triazines - 2,4,6 (1H, 3H, 5H)-triketones), isocyanuric acid three [(3- mercaptopropionyls epoxide)-methyl] ester etc..
As the mercaptan compound with aromatic rings, it can enumerate：1,2,3- tri-thiols benzene, 1,2,4- tri-thiols benzene, 1,3, 5- tri-thiols benzene, 1,2,3- tri- (thiopurine methyltransferase) benzene, 1,2,4- tri- (thiopurine methyltransferase) benzene, 1,3,5- tri- (thiopurine methyltransferase) benzene, 1,2,3- tri- (mercapto ethyl) benzene, 1,3,5- tri- (mercapto ethyl) benzene, 1,2,4- tri- (mercapto ethyl) benzene, the sulfydryl benzene of 1,2,3,4- tetra- etc..
Among above-mentioned mercaptan compound, pentaerythrite four (3-thiopropionate), three (3- mercaptopropionic acids) three are preferably selected from Hydroxymethyl-propane, 1,3,5- tri- (3- sulfydryl butyryl acyloxies ethyl) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone, two seasons It is at least one kind of in penta tetrol six (3-thiopropionate) and isocyanuric acid three-[(3- mercaptopropionyls epoxide)-ethyl] ester, it is more excellent At least one kind of, Jin Eryou of the choosing in pentaerythrite four (3-thiopropionate) and dipentaerythritol six (3-thiopropionate) Select pentaerythrite four (3-thiopropionate).
[fluorine compounds]
For the viewpoint of solvent resistance, resin combination of the invention can also contain fluorine compounds.As fluorine compounds, It can enumerate selected from the surfactant of fluorocarbon chain, fluorine system oligomer and with fluorocarbon chain and ethene unsaturated bond It is at least one kind of in compound etc..
As the surfactant with fluorocarbon chain, as commercially available product, it can enumerate：Sumitomo 3M limited companies Manufacture " Fluorinert FC " series " 430 ", " 431 ", DIC limited companies manufacture " MEGAFAC " series “F142D”、“F171”、“F172”、“F173”、“F177”、“F183”、“F554”、“R30”、Mitsubishi Materials The manufacture of Electronic Chemicals limited companies " " 301 ", " 303 ", " 351 " of Eftop EF " series, " S-381 ", " S-382 ", " SC- of " Surflon " series of " 352 ", AGC Seimi Chemical limited companies manufacture 101 ", " SC-105 ", " E5844 " of the manufacture of limited company of great Jin precision chemicals research institute etc..
As fluorine system oligomer, as commercially available product, it can enumerate：The manufacture of AGC Seimi Chemical limited companies " Surflon S-611 ", " Surflon S-651 " etc..
As the compound with fluorocarbon chain and ethene unsaturated bond, it can enumerate：The manufacture of DIC limited companies " MEGAFAC RS-72-K ", " MEGAFAC RS-75 ", " MEGAFAC RS-76-E " etc..
As fluorine compounds, for the viewpoint of solvent resistance, be preferably selected from fluorine system oligomer and with fluorocarbon chain and It is at least one kind of in the compound of ethene unsaturated bond, the compound more preferably with fluorocarbon chain and ethene unsaturated bond.Fluorine Be oligomer because molecular weight is higher, solubility of the fluorine compounds in solvent is relatively low, it is taken as that excellent solvent resistance.Have Can be with curability compound (D) combined polymerization, it is taken as that solid when the compound of fluorocarbon chain and ethene unsaturated bond is due to solidification The solvent resistance for changing film is more excellent.
Among fluorine system oligomer, preferably " Surflon S-611 ", " Surflon S-651 ".With fluorocarbon chain and ethene Among the compound of unsaturated bond, preferably " MEGAFAC RS-72-K ", " MEGAFAC RS-75 ", " MEGAFAC RS-76-E ".
Fluorine compounds used in the present invention can be one kind, or two or more mixtures.
[Photoepolymerizationinitiater initiater]
As Photoepolymerizationinitiater initiater, known polymerization initiator can be used, for example, it is preferable to 2- methyl isophthalic acids-(4- methylthiophenes Base) -2- morpholinopropane -1- ketone, 2,2- dimethoxy -1,2- diphenylethane -1- ketone, 1- [4- (2- hydroxyl-oxethyls)-benzene Base] -2- hydroxy-2-methyl -1- propane -1- ketone, 1- hydroxy-cyclohexyl-phenyls -one, 2- hydroxy-2-methyl -1- phenyl-the third Alkane -1- ketone, iodine, (4- aminomethyl phenyls) [4- (2- methyl-propyls) phenyl]-hexafluorophosphoric acid ester, 2- [2- oxo -2- phenylacetyls Epoxide ethyoxyl] ethyl ester and 2- (2- hydroxyl-oxethyls) ethyl ester mixture, ethanol acid phenenyl ester, benzophenone etc..As commercially available Photoepolymerizationinitiater initiater, for example preferably enumerate：" IRGACURE " series of BASF Japan limited companies manufacture “OXE02”、“369”、“907”、“651”、“2959”、“184”、“250”、“754”；" MBF ", " BP " of " DAROCUR " series, “1173”.These Photoepolymerizationinitiater initiaters may be used alone or in combination two or more and use.
(light-initiated auxiliary agent)
Light-initiated auxiliary agent also can be combined in the Photoepolymerizationinitiater initiater.
As light-initiated auxiliary agent, for example, it can enumerate：Triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethyl amines Yl benzoic acid methyl esters, 4- dimethyl amidos ethyl benzoate, 4- dimethyl amidos isoamyl benzoate, 4- dimethyl amido benzene first Sour 2- ethylhexyls, benzoic acid 2- dimethyl amidos ethyl ester, N, double (dimethyl amidos) two of N- dimethyl-p-toluidines, 4,4'- Benzophenone, 4,4'- double (diethyl amido) benzophenone, 9,10- dimethoxys anthracene, 2- ethyl -9,10- dimethoxys anthracene, 9, 10- diethoxies anthracene, 2- ethyl -9,10- diethoxy anthracenes etc..These light-initiated auxiliary agents may be used alone or in combination two or more And use.
[each component amount]
On the compound (A1) and total content of nigrosine (A2) in resin combination, with regard to light-proofness and productive For viewpoint, preferably more than 3 mass %, more preferably more than 5 mass %, and then preferably more than 10 mass %, it is just dispersed and resistance to For the viewpoint of solvent borne, preferably below 40 mass %, more preferably below 30 mass %, and then preferably below 25 mass %, enter And it is preferred that below 20 mass %, and then preferably below 15 mass %.
On the content of the compound (A1) in resin combination, for the viewpoint of light-proofness, preferably 0.3 mass % with On, more preferably more than 1.0 mass %, and then preferably more than 2.0 mass %, and then preferably more than 2.5 mass %, and then preferably More than 3.0 mass %, and then preferably more than 4.0 mass %.On the content of the compound (A1) in resin combination, with regard to pattern For the viewpoint of formative and solvent resistance, preferably below 20 mass %, more preferably below 15 mass %, and then preferably 10 matter Measure below %, and then preferably below 7.5 mass %, and then preferably below 3.5 mass %, and then preferably below 2.8 mass %.
On the content of the nigrosine (A2) in resin combination, for the viewpoint of patternability and solvent resistance, It is preferred that more than 1.5 mass %, more preferably more than 5.0 mass %, and then preferably more than 7.0 mass %, and then preferably 7.8 mass % More than.On the content of the nigrosine (A2) in resin combination, for the viewpoint of light-proofness, preferably below 36 mass %, More preferably below 27 mass %, and then preferably below 18 mass %, and then preferably below 10 mass %, and then preferably 9.0 matter Measure below %, and then preferably below 8.0 mass %, and then preferably below 7.5 mass %, and then preferably below 5.5 mass %.
On the content of the dispersant (B) in resin combination, for the viewpoint of dispersiveness, preferably 0.1 mass % with On, more preferably more than 0.5 mass %, and then preferably more than 1 mass %, for the viewpoint of light-proofness and solvent resistance, preferably Below 10 mass %, more preferably below 5 mass %, and then preferably below 3 mass %.
On the dispersant (B) in resin combination relative to compound (A1) and total 100 mass of nigrosine (A2) The content of part, for the viewpoint of dispersiveness, it is more than preferably 3 mass parts, it is more than more preferably 5 mass parts, and then preferably 10 mass More than part, and then more than more preferably 15 mass parts, for the viewpoint of light-proofness and solvent resistance, below preferably 50 mass parts, Below more preferably 40 mass parts, and then below preferably 30 mass parts, and then below preferably 25 mass parts.
On the content of the organic solvent (C) in resin combination, for the viewpoint of workability and dispersiveness, preferably 60 More than quality %, more preferably more than 70 mass %, and then preferably more than 75 mass %, for productive viewpoint, preferably 95 Below quality %, more preferably below 90 mass %, and then preferably below 85 mass %.
On the content of the curability compound (D) in resin combination, solvent resistance and good film-strength are just obtained Viewpoint for, preferably more than 0.3 mass %, more preferably more than 0.5 mass %, and then preferably more than 0.6 mass %, with regard to shading For the viewpoint of property and developability, preferably below 10 mass %, more preferably below 5 mass %, and then preferably below 2 mass %.
It is total relative to compound (A1) and nigrosine (A2) on the curability compound (D) in resin combination The content of 100 mass parts, for obtaining the viewpoint of solvent resistance and good film-strength, more than preferably 3 mass parts, more preferably More than 5 mass parts, and then more than preferably 6 mass parts, for the viewpoint of light-proofness and developability, below preferably 100 mass parts, Below more preferably 50 mass parts, and then below preferably 20 mass parts.
On the content of the alkali soluble resin (E) in resin combination, for the viewpoint of patternability, preferably 1 More than quality %, more preferably more than 2 mass %, and then preferably more than 3 mass %, just obtain solvent resistance and good film-strength Viewpoint for, preferably below 10 mass %, more preferably below 8 mass %, more preferably below 6 mass %.
It is total relative to compound (A1) and nigrosine (A2) on the alkali soluble resin (E) in resin combination The content of 100 mass parts, for the viewpoint of patternability, more than preferably 10 mass parts, more than more preferably 20 mass parts, enters And it is preferred that more than 30 mass parts, for obtaining the viewpoint of solvent resistance and good film-strength, below preferably 100 mass parts, Below more preferably 80 mass parts, and then below preferably 60 mass parts.
When the resin combination of the present invention contains the situation of mercaptan compound, on the mercaptan chemical combination in resin combination The content of thing, for the viewpoint of solvent resistance, preferably more than 0.1 mass %, more preferably more than 0.2 mass %, and then preferably More than 0.3 mass %, and then more preferably more than 0.4 mass %, for the viewpoint of dispersion stabilization, preferably 10 mass % with Under, more preferably below 5 mass %, and then preferably below 1 mass %.
When the resin combination of the present invention contains the situation of fluorine compounds, on the fluorine compounds in resin combination Content, for the viewpoint of insulating properties and solvent resistance, preferably more than 0.1 mass %, more preferably more than 0.2 mass %, and then It is preferred that more than 0.3 mass %, and then more preferably more than 0.35 mass %, for the viewpoint of the physical property of film, preferably 2 mass % Hereinafter, more preferably below 1 mass %, and then preferably below 0.5 mass %.
Content on the Photoepolymerizationinitiater initiater in resin combination relative to the mass parts of curability compound (D) 100, just For the viewpoint for obtaining good film hardness, it is more than preferably 1 mass parts, it is more than more preferably 50 mass parts, and then preferably 100 mass More than part, and then more than more preferably 120 mass parts, and below preferably 300 mass parts, below more preferably 250 mass parts, Jin Eryou Select below 200 mass parts.By being set to above range, sufficient heat resistance, chemical-resistant can be obtained, in addition, painting can be improved Film Forming ability, suppresses solidification bad.
Content on the light-initiated auxiliary agent in resin combination relative to the mass parts of curability compound (D) 100, is just obtained For the viewpoint of good film hardness, it is more than preferably 1 mass parts, it is more than more preferably 3 mass parts, and then preferably 5 mass parts with On, and below preferably 30 mass parts, below more preferably 20 mass parts, and then below preferably 15 mass parts.By being set to above-mentioned model Enclose, sufficient heat resistance, chemical-resistant can be obtained, in addition, carry can high film Forming ability, suppress solidification it is bad.
[manufacture method]
The manufacture method of the resin combination of the present invention preferably has following processes.
Process 1：Obtain inclusion compound (A1), nigrosine (A2), dispersant (B) and organic solvent (C), alkali optionally The process of the dispersion of soluble resin (E) and mercaptan compound
Process 2：By the dispersion obtained in above-mentioned operation, curability compound (D), alkali soluble resin optionally (E), the process of fluorine compounds, Photoepolymerizationinitiater initiater and light-initiated auxiliary agent mixing
[process 1]
The process 1 of above-mentioned manufacture method has following process 1a or process 1b-1 to 1b-3.
Process 1a：Make compound (A1), nigrosine (A2), dispersant (B) and organic solvent (C), alkali optionally solvable Property resin (E) and mercaptan compound it is scattered, and the process for obtaining dispersion
Process 1b-1：Make compound (A1), dispersant (B) and organic solvent (C), alkali soluble resin (E) optionally And mercaptan compound is scattered, and the process for obtaining dispersion b1
Process 1b-2：Make nigrosine (A2), dispersant (B) and organic solvent (C), alkali soluble resin (E) optionally And mercaptan compound is scattered, and the process for obtaining dispersion b2
Process 1b-3：Dispersion b1 and b2 are mixed, and the process for obtaining dispersion
In the resin combination of the present invention, at least black color is used as using two kinds of compound (A1) and nigrosine (A2) Material.These compounds (A1), nigrosine (A2) can together disperse (above-mentioned operation 1a), can also distinguish each self-dispersing (process 1b-1 ~1b-3).Among them, for the viewpoint of light-proofness and patternability, preferably make compound (A1) and nigrosine (A2) Together disperse (process 1a).
Process 1 it is scattered used in mixing dispersion machine known various dispersion machines can be used.It can such as enumerate：Homogeneous The high voltage types such as muller, the high pressure homogenizers such as the high speed such as mixer mixing stirring device, roller mill, kneader, extruder disperse Medium-type dispersion machine such as machine, paint shaker, ball mill etc..These devices can also use multiple combinations.
Among them, for making the viewpoint that black color material is equably mixed in organic solvent, preferred homogeneous mixer Etc. the medium-type dispersion machine such as high speed mixing stirring device, paint shaker or ball mill., can as commercially available medium-type dispersion machine Enumerate：Longevity Industries, Inc manufacture " Ultra Apex Mill ", Qian Tian ironworker limited company manufacture " PICO MILL " etc..
In the situation using medium-type dispersion machine, as the material of the medium used in dispersion step, preferably aoxidize The ceramics such as zirconium, titanium oxide, polyethylene, nylon Polymer material, metal etc., for the viewpoint of abrasivity, preferred zirconium oxide. As the diameter of medium, for the viewpoint of the aggregated particle in crushing black color material, preferably more than 0.003mm, more preferably More than 0.01mm, and preferably below 0.5mm, more preferably below 0.4mm.
It is preferably more than 0.3 hour, more excellent with regard to making black color material fully for the viewpoint of miniaturization on jitter time Select more than 1 hour, manufacture efficiency with regard to dispersion, using the excessively scattered viewpoint for suppressing to re-unite for, preferably 50 hours with Under, more preferably less than 10 hours.
The dispersion of the present invention contains compound (A1), nigrosine (A2), dispersant (B) and organic solvent (C).Furthermore, The dispersion of the present invention is compound (A1) and dispersion, the i.e. black color material dispersion of nigrosine (A2).
On the compound (A1) and total content of nigrosine (A2) in dispersion, with regard to light-proofness and productive viewpoint For, preferably more than 6 mass %, more preferably more than 10 mass %, and then preferably more than 16 mass %, with regard to dispersiveness and solvent resistant For the viewpoint of property, preferably below 60 mass %, more preferably below 40 mass %, and then preferably below 30 mass %.
On the content of the compound (A1) in dispersion, for the viewpoint of light-proofness, preferably more than 0.6 mass %, More preferably more than 2.0 mass %, and then preferably more than 4.0 mass %, and then preferably more than 5.0 mass %, and then preferably 6.0 matter Measure more than %, and then preferably more than 8.0 mass %.On the content of the compound (A1) in dispersion, with regard to patternability and For the viewpoint of solvent resistance, preferably below 30 mass %, more preferably below 20 mass %, and then preferably below 15 mass %, And then preferably below 7.0 mass %, and then preferably below 5.5 mass %.
On the content of the nigrosine (A2) in dispersion, for the viewpoint of patternability and solvent resistance, preferably More than 3.0 mass %, more preferably more than 10 mass %, and then preferably more than 14 mass %, and then preferably more than 16 mass %.Close The content of nigrosine (A2) in dispersion, for the viewpoint of light-proofness, preferably below 54 mass %, more preferably 36 matter Below %, and then preferably below 20 mass %, and then preferably below 18 mass %, and then preferably below 16 mass % are measured, and then It is preferred that below 15 mass %, and then preferably below 11 mass %.
On the content of the dispersant (B) in dispersion, for the viewpoint of dispersiveness, preferably more than 0.2 mass %, more It is preferred that more than 1 mass %, and then preferably more than 2 mass %, for the viewpoint of light-proofness and solvent resistance, preferably 20 mass % Hereinafter, more preferably below 10 mass %, and then preferably below 6 mass %.
Dispersant (B) in dispersion is relative to compound (A1) and the content of total 100 mass parts of nigrosine (A2) Preferred scope it is identical with the preferred scope of the content in above-mentioned resin combination.
On the content of the organic solvent (C) in dispersion, for the viewpoint of workability and dispersiveness, preferably 40 matter Measure more than %, more preferably more than 60 mass %, and then preferably more than 70 mass %, with regard to productivity and resin combination allotment from For the viewpoint spent, preferably below 95 mass %, more preferably below 90 mass %, and then preferably below 80 mass %.
The dispersion of the present invention can for example be obtained by above-mentioned operation 1a or process 1b-1~1b-3.
[process 2]
In process 2, by alkali soluble resin (E), mercaptan compound, fluorine compounds, Photoepolymerizationinitiater initiater optionally And the mixing of any condition such as light-initiated auxiliary agent.
There is no particular restriction for the mixed method of process 2, for example, can enumerate being stirred using roll-type mixer.Mixing time It is preferred that more than 5 minutes, more preferably more than 15 minutes, for the viewpoint of manufacture efficiency, preferably less than 10 hours, more preferably 1 is small When below.
[colour filter]
The resin combination of the present invention is preferably to manufacture colour filter, the more preferably black matrix to form colour filter.
Possess preferably is had such as using the manufacture method of the colour filter of black matrix formed by the resin combination of the present invention Lower process：Process (a), the resin combination of the present invention is coated on substrate by it, and be dried, photocuring, development, and obtain Obtain film；Process (b), the film obtained in above-mentioned operation (a) is heated to 200~300 DEG C and formed comprising cured film by it Black matrix；And process (c), the organic solvent solution of resin is coated in above-mentioned cured film and forms resin film by it.
Organic solvent is dried after the coating of process (a), for the flatness or productive viewpoint of film, preferably Heated or depressurized.
On above-mentioned photocuring, such as, to film irradiation ultraviolet radiation, the polyfunctional monomer in resin combination is crosslinked Reaction, and make curing of coating.Photocuring system is carried out to leave pattern by lasting being developed on glass substrate, is preferable over The part mounting removed by developing prevents the light shield of ultraviolet and is allowed to not solidify.
Cured coating film after photocuring is for example impregnated in alkaline aqueous solution by above-mentioned development, and then is rinsed and gone using water Except uncured portion.
Process (b) is post-bake process, by carrying out this process, can form the excellent cured film of hardness.
The resin of process (c) is, for example, polyimides.The organic solvent of process (c) is, for example, NMP.
On above-mentioned embodiment, it is of the invention so that disclose following resin combination, colour filter, dispersion and they Manufacture method etc..
[1] a kind of colored curable resin composition, it contains compound (A1) represented by following formula (1), nigrosine (A2), dispersant (B), organic solvent (C) and curability compound (D), and compound (A1) is relative to compound (A1) and benzene Total mass ratio, the i.e. A1/ (A1+A2) of amido black (A2) is more than 0.10 and less than 0.50.
[chemical formula 9]
[in above-mentioned formula (1), X represents double bond, is separately E bodies or Z bodies, R as geometric isomer1Independently Ground represents hydrogen atom, methyl, nitro, methoxyl group, bromine atoms, chlorine atom, fluorine atom, carboxyl or sulfonic group, R2Separately Represent hydrogen atom, methyl or phenyl, R3Separately represent hydrogen atom, methyl or chlorine atom]
[2] such as colored curable resin composition described in [1], wherein R1It is preferred that being bonded to dihydroindolone ring 6.
[3] such as colored curable resin composition described in [1] or [2], wherein R3It is preferred that being bonded to indoline 4 of ketone ring.
[4] colored curable resin composition as described in any one of [1] to [3], wherein R1、R2And R3It is preferred that hydrogen Atom.
[5] colored curable resin composition as described in any one of [1] to [4], wherein nigrosine (A2) it is flat Equal preferably more than 0.1 μm of particle diameter, enters by more preferably more than 0.2 μm, and then preferably more than 0.24 μm, and then preferably more than 0.27 μm And it is preferred that more than 0.30 μm, and then preferably more than 0.35 μm, and preferably less than 1.5 μm, more preferably less than 1.0 μm, and then preferably Less than 0.7 μm, and then preferably less than 0.5 μm.
[6] BET of the colored curable resin composition as described in any one of [1] to [5], wherein nigrosine (A2) The preferred 34m of specific surface area2/ below g, more preferably 17m2/ below g, and then preferably 14m2/ below g, and then preferably 12m2/ below g, And then preferably 11m2/ below g, and preferably 2.2m2/ more than g, more preferably 3.3m2/ more than g, and then preferably 4.7m2/ more than g, enters And it is preferred that 6.6m2/ more than g.
[7] colored curable resin composition as described in any one of [1] to [6], wherein compound (A1) are relative In compound (A1) and nigrosine (A2) total mass ratio, i.e. A1/ (A1+A2) preferably more than 0.15, more preferably 0.20 with On, and then preferably more than 0.24, and then preferably more than 0.28, and preferably less than 0.40, more preferably less than 0.35, and then preferably Less than 0.32.
[8] colored curable resin composition as described in any one of [1] to [7], wherein compound (A1) are relative In compound (A1) and nigrosine (A2) total mass ratio, i.e. A1/ (A1+A2) preferably less than 0.28, more preferably 0.26 with Under, and then preferably less than 0.25.
[9] colored curable resin composition as described in any one of [1] to [8], wherein dispersant (B) is to be selected from Polyurethanes system dispersant, polyamide-based dispersant, polyimides system dispersant, polycarboxylic-acid dispersant, polyamine system point Powder and it is imported with into one part at least one kind of in the dispersant of quaternary ammonium salt etc..
[10] colored curable resin composition as described in any one of [1] to [9], wherein dispersant (B) are preferably Make nitrogen-atoms numbers more than 1 and less than 5 polyamino compound, the lactone chain with having average addition molal quantity more than 1 and less than 100 Or the dispersant (B1) that the level Four agent of oxyalkylene chain is reacted and obtained.
[11] colored curable resin composition as described in any one of [1] to [10], wherein level Four agent work as Measure relative to polyamino compound equivalent proportion [level Four agent equivalent/polyamine equivalent] preferably more than 0.3, more preferably more than 0.6, and For less than 1.0, preferably less than 0.9.
[12] colored curable resin composition as described in any one of [1] to [11], wherein organic solvent (C) are excellent Choosing is selected from ethylene glycol monoethylether acetate, propylene glycol methyl ether acetate, butyl carbitol acetate, acetic acid -3- methoxies It is at least one kind of in base butyl ester and propylene glycol monoethyl ether acetate, more preferably propylene glycol methyl ether acetate.
[13] colored curable resin composition as described into [12] such as [1], wherein curability compound (D) are preferably Multifunctional polymerizable compound.
[14] such as colored curable resin composition described in [13], wherein multifunctional polymerizable compound is preferably more Function (methyl) acrylate based compound.
[15] such as colored curable resin composition described in [13] or [14], wherein multifunctional polymerizable compound In contained ethene unsaturated bond quantity preferably more than 3, more preferably more than 4, and then preferably more than 5, and preferably 8 It is individual following, more preferably less than 7, and then preferably less than 6.
[16] colored curable resin composition as described in any one of [13] to [15], wherein multifunctional polymerism Compound is preferably selected from trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite In four (methyl) acrylate, (methyl) acrylate of dipentaerythritol five and dipentaerythritol six (methyl) acrylate extremely Lack a kind, more preferably dipentaerythritol acrylate.
[17] colored curable resin composition as described in any one of [1] to [16], it is preferred and then contains alkali Soluble resin (E).
[18] colored curable resin composition as described in [17], wherein alkali soluble resin (E) preferably (first Base) acrylate and (methyl) acrylic acid copolymer.
[19] colored curable resin composition as described in any one of [1] to [18], itself so that containing preferred sulphur Alcoholic compound, more preferably multi-thiol compound.
[20] such as colored curable resin composition described in [19], the sulfydryl that wherein mercaptan compound has Quantity preferably more than 3, more preferably more than 4, and preferably less than 9, more preferably less than 8, and then preferably less than 7, enter And more preferably less than 6.
[21] such as colored curable resin composition described in [19] or [20], wherein mercaptan compound preferred fat Race's mercaptan compound, the mercaptan compound with the cyclic structure such as heterocycle or aromatic rings, more preferably analiphatic sulphur alcoholic compound.
[22] colored curable resin composition as described in any one of [19] to [21], wherein mercaptan compound is excellent Choosing is selected from pentaerythrite four (3-thiopropionate), three (3- mercaptopropionic acids) trimethylolpropanes, (the 3- sulfydryl butyryl of 1,3,5- tri- Epoxide ethyl) -1,3,5- triazines -2,4,6 (1H, 3H, 5H)-triketone, dipentaerythritol six (3-thiopropionate) and isocyanide urine It is at least one kind of in sour three-[(3- mercaptopropionyls epoxide)-ethyl] esters, it is more preferably selected from pentaerythrite four (3-thiopropionate) And it is at least one kind of in dipentaerythritol six (3-thiopropionate), and then preferably pentaerythrite four (3-thiopropionate).
[23] colored curable resin composition as described in any one of [1] to [22], it preferably comprises fluorination and closed Thing.
[24] such as colored curable resin composition described in [23], wherein fluorine compounds are preferably selected from fluorine carbon At least 1 in surfactant, fluorine system oligomer and compound with fluorocarbon chain and ethene unsaturated bond of chain etc. Kind.
[25] such as colored curable resin composition described in [23] or [24], wherein fluorine compounds are preferably selected from fluorine Be at least one kind of in oligomer and compound with fluorocarbon chain and ethene unsaturated bond, more preferably with fluorocarbon chain and The compound of ethene unsaturated bond.
[26] colored curable resin composition as described in any one of [1] to [25], it is preferred and then contains light Polymerization initiator.
[27] such as colored curable resin composition described in [26], it is preferred and then contains light-initiated auxiliary agent.
[28] colored curable resin composition as described in any one of [1] to [27], wherein in resin combination Compound (A1) and nigrosine (A2) total content preferably more than 3 mass %, more preferably more than 5 mass %, and then preferably More than 10 mass %, and preferably below 40 mass %, more preferably below 30 mass %, and then preferably below 25 mass %, and then It is preferred that below 20 mass %, and then preferably below 15 mass %.
[29] colored curable resin composition as described in any one of [1] to [28], wherein in resin combination Compound (A1) content preferably more than 0.3 mass %, more preferably more than 1.0 mass %, and then preferably 2.0 mass % with On, and then preferably more than 2.5 mass %, and then preferably more than 3.0 mass %, and then preferably more than 4.0 mass %.
[30] colored curable resin composition as described in any one of [1] to [29], wherein in resin combination Compound (A1) content preferably below 20 mass %, more preferably below 15 mass %, and then preferably below 10 mass %, enter And it is preferred that below 7.5 mass %, and then preferably below 3.5 mass %, and then preferably below 2.8 mass %.
[31] colored curable resin composition as described in any one of [1] to [30], wherein in resin combination Nigrosine (A2) content preferably more than 1.5 mass %, more preferably more than 5.0 mass %, and then preferably 7.0 mass % with On, and then preferably more than 7.8 mass %.
[32] colored curable resin composition as described in any one of [1] to [31], wherein in resin combination Nigrosine (A2) content preferably below 36 mass %, more preferably below 27 mass %, and then preferably below 18 mass %, enter And it is preferred that below 10 mass %, and then preferably below 9.0 mass %, and then preferably below 8.0 mass %, and then preferably 7.5 matter Measure below %, and then preferably below 5.5 mass %.
[33] colored curable resin composition as described in any one of [1] to [32], wherein in resin combination Dispersant (B) content preferably more than 0.1 mass %, more preferably more than 0.5 mass %, and then preferably more than 1 mass %, and It is preferred that below 10 mass %, more preferably below 5 mass %, and then preferably below 3 mass %.
[34] colored curable resin composition as described in any one of [1] to [33], wherein in resin combination Content preferably 3 mass parts of the dispersant (B) relative to total 100 mass parts of compound (A1) and nigrosine (A2) more than, More than more preferably 5 mass parts, and then more than preferably 10 mass parts, and then more than more preferably 15 mass parts, and preferably 50 mass parts Hereinafter, more preferably below 40 mass parts, and then below preferably 30 mass parts, and then below preferably 25 mass parts.
[35] colored curable resin composition as described in any one of [1] to [34], wherein in resin combination Organic solvent (C) content preferably more than 60 mass %, more preferably more than 70 mass %, and then preferably more than 75 mass %, And preferably below 95 mass %, more preferably below 90 mass %, and then preferably below 85 mass %.
[36] colored curable resin composition as described in any one of [1] to [35], wherein in resin combination Curability compound (D) content preferably more than 0.3 mass %, more preferably more than 0.5 mass %, and then preferably 0.6 matter Measure more than %, and preferably below 10 mass %, more preferably below 5 mass %, and then preferably below 2 mass %.
[37] colored curable resin composition as described in any one of [1] to [36], wherein in resin combination Content preferably 3 mass parts of the curability compound (D) relative to total 100 mass parts of compound (A1) and nigrosine (A2) More than, more than more preferably 5 mass parts, and then more than preferably 6 mass parts, and below preferably 100 mass parts, more preferably 50 mass parts Hereinafter, and then below preferably 20 mass parts.
[38] such as colored curable resin composition described in [17] or [18], wherein the alkali in resin combination can The content of soluble resin (E) is relative to preferably more than the 1 mass % of the solid constituent amount in resin combination, more preferably 2 mass % More than, and then preferably more than 3 mass %, and preferably below 10 mass %, more preferably below 8 mass %, more preferably 6 mass % with Under.
[39] colored curable resin composition as described in any one of [17], [18] and [38], wherein resin group Alkali soluble resin (E) in compound is preferred relative to the content of compound (A1) and total 100 mass parts of nigrosine (A2) It is more than 10 mass parts, more excellent more than more preferably 20 mass parts, and then more than preferably 30 mass parts, and below preferably 100 mass parts Select below 80 mass parts, and then below preferably 60 mass parts.
[40] colored curable resin composition as described in any one of [19] to [22], wherein in resin combination Mercaptan compound content preferably more than 0.1 mass %, more preferably more than 0.2 mass %, and then preferably 0.3 mass % with On, and then more preferably more than 0.4 mass %, and preferably below 10 mass %, more preferably below 5 mass %, and then preferably 1 matter Measure below %.
[41] colored curable resin composition as described in any one of [23] to [25], wherein in resin combination Fluorine compounds content preferably more than 0.1 mass %, more preferably more than 0.2 mass %, and then preferably more than 0.3 mass %, And then more preferably more than 0.35 mass %, and preferably below 2 mass %, more preferably below 1 mass %, and then preferably 0.5 matter Measure below %.
[42] such as colored curable resin composition described in [26] or [27], the wherein light in resin combination gathers Close initiator relative to content preferably 1 mass parts of the mass parts of curability compound (D) 100 more than, more preferably 50 mass parts with On, and then more than preferably 100 mass parts, and then more than more preferably 120 mass parts, and below preferably 300 mass parts, more preferably Below 250 mass parts, and then below preferably 200 mass parts.
[43] such as colored curable resin composition described in [27], the wherein light-initiated auxiliary agent in resin combination More than content preferably 1 mass parts of the mass parts of curability compound (D) 100, it is more than more preferably 3 mass parts, Jin Eryou Select more than 5 mass parts, and below preferably 30 mass parts, below more preferably 20 mass parts, and then below preferably 15 mass parts.
[44] a kind of manufacture method of colored curable resin composition, it has following processes.
Process 1：Obtain the dispersion of inclusion compound (A1), nigrosine (A2), dispersant (B) and organic solvent (C) Process
Process 2：By the dispersion obtained in above-mentioned operation and curability compound (D), alkali-soluble tree optionally Fat (E) and the process of fluorine compounds mixing
[45] such as the manufacture method of colored curable resin composition described in [44], wherein in z processes 1, preferably Also include alkali soluble resin (E).
[46] such as the manufacture method of colored curable resin composition described in [44] or [45], wherein in process 1 In, preferably also include mercaptan compound.
[47] manufacture method of the colored curable resin composition as described in any one of [44] to [46], wherein In process 2, preferably so that mix alkali soluble resin (E).
[48] manufacture method of the colored curable resin composition as described in any one of [44] to [47], wherein In process 2, preferably and then mixed fluoride compound.
[49] manufacture method of the colored curable resin composition as described in any one of [44] to [48], wherein In process 2, preferably so that mix Photoepolymerizationinitiater initiater.
[50] manufacture method of the colored curable resin composition as described in any one of [44] to [49], wherein In process 2, preferably so that mix light-initiated auxiliary agent.
[51] manufacture method of the colored curable resin composition as described in any one of [44] to [50], wherein work Sequence 1 preferably has following process 1a or process 1b-1 to 1b-3.
Process 1a：Compound (A1), nigrosine (A2), dispersant (B) and organic solvent (C), alkali optionally is solvable Property resin (E) and mercaptan compound it is scattered, and the process for obtaining dispersion
Process 1b-1：By compound (A1), dispersant (B) and organic solvent (C), alkali soluble resin (E) optionally And mercaptan compound is scattered, and the process for obtaining dispersion b1
Process 1b-2：By nigrosine (A2), dispersant (B) and organic solvent (C), alkali soluble resin (E) optionally And mercaptan compound is scattered, and the process for obtaining dispersion b2
Process 1b-3：The process that dispersion b1 and b2 are mixed and dispersion is obtained
[52] such as the manufacture method of colored curable resin composition described in [51], wherein process 1 is preferably above-mentioned Process 1a.
[53] a kind of dispersion, it contains compound (A1) represented by following formula (1), nigrosine (A2), dispersant (B) And organic solvent (C), and compound (A1) is relative to compound (A1) and the total mass ratio, i.e. A1/ (A1 of nigrosine (A2) + A2) it is more than 0.10 and less than 0.50.
[chemical formula 10]
[in above-mentioned formula (1), X represents double bond, is separately E bodies or Z bodies, R as geometric isomer1Independently Ground represents hydrogen atom, methyl, nitro, methoxyl group, bromine atoms, chlorine atom, fluorine atom, carboxyl or sulfonic group, R2Separately Represent hydrogen atom, methyl or phenyl, R3Separately represent hydrogen atom, methyl or chlorine atom]
[54] such as described dispersion in [53], compound (A1) and nigrosine (A2) wherein in dispersion it is total Content preferably more than 8 mass %, more preferably more than 10 mass %, and then preferably more than 16 mass %, and preferably 60 mass % with Under, more preferably below 40 mass %, and then preferably below 30 mass %.
[55] such as dispersion described in [53] or [54], the content of the compound (A1) wherein in dispersion is preferred More than 0.6 mass %, more preferably more than 2.0 mass %, and then preferably more than 4.0 mass %, so preferably 5.0 mass % with On, and then preferably more than 6.0 mass %, and then preferably more than 8.0 mass %.
[56] dispersion as described in any one of [53] to [55], the content of the compound (A1) wherein in dispersion It is preferred that below 30 mass %, more preferably below 20 mass %, and then preferably below 15 mass %, so preferably 7.0 mass % with Under, and then preferably below 5.5 mass %.
[57] dispersion as described in any one of [53] to [56], the content of the nigrosine (A2) wherein in dispersion It is preferred that more than 3.0 mass %, more preferably more than 10 mass %, and then preferably more than 14 mass %, so preferably 16 mass % with On.
[58] dispersion as described in any one of [53] to [57], the content of the nigrosine (A2) wherein in dispersion It is preferred that below 54 mass %, more preferably below 36 mass %, and then preferably below 20 mass %, so preferably 18 mass % with Under, and then preferably below 16 mass %, and then preferably below 15 mass %, and then preferably below 11 mass %.
[59] dispersion as described in any one of [53] to [58], the content of the dispersant (B) wherein in dispersion It is preferred that more than 0.2 mass %, more preferably more than 1 mass %, and then preferably more than 2 mass %, and preferably below 20 mass %, more It is preferred that below 10 mass %, and then preferably below 6 mass %.
[60] dispersion as described in any one of [53] to [59], wherein dispersant (B) is relative to compound (A1) And more than content preferably 3 mass parts of total 100 mass parts of nigrosine (A2), it is more than more preferably 5 mass parts, and then preferably 10 It is more excellent below more preferably 40 mass parts more than mass parts, and then more than more preferably 15 mass parts, and below preferably 50 mass parts Select below 30 mass parts, and then below preferably 25 mass parts.
[61] dispersion as described in any one of [53] to [60], organic solvent (C's) wherein in dispersion contains Measure preferably more than 40 mass %, more preferably more than 60 mass %, and then preferably more than 70 mass %, and preferably 95 mass % with Under, more preferably below 90 mass %, and then preferably below 80 mass %.
[62] dispersion as described in any one of [53] to [61], it preferably has as described in [2] into [18] Restriction item.
[63] purposes of a kind of colored curable resin composition as described in any one of [1] to [43], it is used to Manufacture colour filter.
[64] a kind of colored curable resin composition as described in any one of [1] to [43] is for forming colour filter Purposes in the black matrix of device.
[65] a kind of colour filter, it possesses using the colored curable resin group as described in any one of [1] to [43] Black matrix formed by compound.
[66] a kind of manufacture method of colour filter, it has following process：Process (a), its will as [1] into [43] it is any Colored curable resin composition described in is coated on substrate, and be dried, photocuring, development, and obtain film； Process (b), the film obtained in above-mentioned operation (a) is heated to 200~300 DEG C and forms the black matrix for including cured film by it； And process (c), it forms resin film in the organic solvent solution of application of resin in above-mentioned cured film.
[embodiment]
The evaluation of light-proofness and patternability, weight average molecular weight, the BET specific surface area of solid constituent and nigrosine with it is flat The measure of equal particle diameter is carried out by following method.
(1) evaluation of light-proofness
In on 10cm × 10cm glass substrate, the spin coater (" ACT- of Active limited companies manufacture is utilized 220DII ") coating resin composition.By substrate in standing 5 minutes on horizontal stand, and in 10 points of standing in 120 DEG C of heating plate Clock, and then handled in carrying out 20 minutes in 230 DEG C of dustless baking oven, and obtaining one side has the substrate of film.Make above-mentioned film Thickness turn into 1~2 μm.Using table above formula penetrating concentration meter, (X-Rite companies manufacture, and " model 361T " determines wavelength 550nm), the suction brightness of substrate is determined, and measured value is set to ODR.Manufactured using Tokyo Seimitsu Co., Ltd. " SURFCOM 1500DX " are measured to the thickness T (μm) for determining the film at the position for inhaling brightness.By every 1 μ m-thick of film The optical density (OD) of degree is set to " OD ", and is calculated by following formula.
OD=ODR/T(μm)
The OD is bigger, and light-proofness is better.
(2) evaluation of patternability
In on 10cm × 10cm glass substrate, the spin coater (" ACT- that Active limited companies manufacture is used 220DII ") coating resin composition, by substrate in standing 2 minutes in 100 DEG C of heating plate, and obtaining one side has film Substrate.Making the thickness of above-mentioned film turns into 1 μm.In the face for being coated with resin combination of substrate, it is separated by 0.5mm away from substrate and sets Put light shield.Above-mentioned light shield has the slit of width (unit μm) 10,20,30,40,50,60,70,80,90 and 100.Use The ultraviolet fiber optic point irradiation unit " MUV-202U " of Moritex limited companies manufacture, is situated between every above-mentioned light shield, substrate is shone Penetrate 100mJ/cm2Ultraviolet.Light shield is removed, substrate is impregnated 2 minutes in the 0.04 mass %KOH aqueous solution, pure water is utilized Rinse, and in 230 DEG C of dustless baking oven be heat-treated within 20 minutes.Using light microscope, observation is developed through above-mentioned light shield Substrate on fine rule, the fine rule of the most thin line width remained on substrate is set to remaining fine rule wide.Remaining fine rule is wide smaller, Patternability is more excellent.
(3) measure of weight average molecular weight
The ＞ of ＜ conditions 1
Use hydrogel permeation layer analyzer (hereinafter also referred to as " GPC ").Use phosphoric acid concentration 60mmol/L, bromo lithium concentration 50mmol/L DMF (hereinafter also referred to as " DMF ") solution is used as eluat.Sample is diluted using DMF, and The mass % of solid constituent 0.3 solution is made, GPC [devices are utilized：" the HLC- of Tosoh limited companies manufacture 8120GPC ", post：" TSK-GEL, α-M " × 2, flow velocity of Tosoh limited companies manufacture：1mL/min] to solution 0.1mL is measured.
The ＞ of ＜ conditions 2
Make the dimethyl dodecylamine (" Farmin of Kao Corporation's manufacture in the way of as 1mmol/L DM20 ") it is dissolved in chloroform, using the solution of gained as eluat, and pass through gel chromatography (GPC method, device：Tosoh strands " HLC-8320GPC " of part Co., Ltd manufacture, detector：It is attached to the Differential refractometer of device, post：Showa electrician's share has " K-804L " × 2 of limit company manufacture, flow velocity：1.0mL/min, column temperature：40 DEG C) it is measured.It is poly- using following single dispersings Styrene is used as standard substance.
Polystyrene standard that condition 1 and condition 2 are manufactured using Tosoh limited companies " A-500 (Mw=5.0 × 102) ", " A-2500 (Mw=2.63 × 103) ", " F-1 (Mw=1.02 × 104) ", " F-10 (Mw=9.64 × 104) " it is used as mark Quasi- material.
(4) measure of solid constituent
Glass bar and drying anhydrous sodium sulfate 10g are put into culture dish, sample 2g is measured and puts to wherein, utilize glass bar Mixed, and dried 2 hours using 105 DEG C of pressure Reduction Dryer (pressure 8kPa).Dried quality is weighed, will be under The value that formula is obtained is set to the solid constituent of sample.
Solid constituent (quality %)=[[dried quality-(quality of culture dish+glass bar+anhydrous sodium sulfate)]/ The quality of sample] × 100
(5) measure of the BET specific surface area of nigrosine and average grain diameter
Using specific area measuring device (limited company of Shimadzu Seisakusho Ltd. manufacture " Flowsorb III2310 "), Using nitrogen as gas is determined, to BET specific surface area Sm(unit：m2/ g) it is measured.
The value of obtained BET specific surface area is used, the R (units that will be obtained according to following formula：Nm) it is set to average grain diameter.
R=6000/ (d × Sm)
d：Real density (g/cm3)Sm：Specific surface area (m2/g)
Synthesis example 1 [compound A1-1 synthesis]
Burnt in be provided with the 5L that agitating device, thermometer, nitrogen are blown into pipe, Dean-Stark pipe and Dai Shi pipes four mouthfuls In bottle, by 2,5- dihydroxy benzenes-Isosorbide-5-Nitrae-oxalic acid (and Wako Pure Chemical Industries limited company manufactures) 115g, isatin (Isatin) (manufacture of Tokyo chemical conversion industry limited company) 150g, p-methyl benzenesulfonic acid monohydrate 35g and toluene 3750g mixed liquor adds Heat is stirred 7 hours to 110 DEG C when being dehydrated, and then in stirring 14 hours at 110 DEG C.The mixed liquor is cooled to room temperature, The suspension of black is filtered using No.2 filter paper (Advantec Toyo limited companies).The filtering is cleaned using methanol 5L Residue, and be dried under 60 DEG C/104Pa, and obtain compound A1-1 (the black things of 236g following formula (A1-1) Matter).
The atrament is dissolved in DMF, ESI/MS measure is carried out by liquid chromatography mass spectrography, confirms that molecular weight is 448.07。
[chemical formula 11]
Synthesis example 2 [synthesis of alkali soluble resin (copolymer of benzyl methacrylate and methacrylic acid)]
To being provided with the detachable flask of mixer, reflux condenser, nitrogen ingress pipe and thermometer, methyl is added Acrylic acid (hereinafter also referred to as " MAA ") 3.6g, benzyl methacrylate (hereinafter also referred to as " BzMA ") 36.4g, 3- sulfydryl third Sour 0.56g and PGMEA 40g, nitrogen displacement is carried out when stirring.
One is stirred one side in flask is warming up to 78 DEG C, by MAA 14.4g, BzMA 145.6g, 3- mercaptopropionic acids 2.2g, PGMEA 160g and 2,2'- azos double (2,4- methyl pentane nitriles) (and the manufacture of Wako Pure Chemical Industries limited company " V-65 " (hereinafter also referred to as " V-65 ")) 2.0g mixing and obtain solution, last 3 hours and the solution be added dropwise.After completion of dropwise addition, V-65 2.0g and PGMEA 10.0g mixed solution is added, and in stirring 1 hour at 78 DEG C.And then, addition V-65 1.0g with PGMEA 10.0g mixed solution, and in stirring 1 hour at 78 DEG C.PGMEA 100g are added, are cooled down when stirring, and Obtain the PGMEA solution of BzMA and MAA copolymer (hereinafter also referred to as " copolymer 1 ").Solid constituent is 40 mass %, altogether The weight average molecular weight of polymers 1 is 10900 (measured values according to the ＞ of ＜ conditions 1).
(preparation of transparent resist liquid)
By solution 42.2g, DPHA 6.64g, the light of the mass % of solid constituent 40.0 obtained in synthesis example 2 copolymer 1 Polymerization initiator (BASF Japan limited companies manufacture " IRGACURE OXE02 ") 11.07g, PGMEA 80g and ring Hexanone 60g is equably mixed, and obtains transparent resist liquid.
Synthesis example 3-a1 [polyester a1：The synthesis of bay epoxide poly- (6-caprolactone) (21)]
It is blown into agitating device, thermometer and nitrogen is provided with the 10L of pipe flask, addition laruyl alcohol (flower king's share Co., Ltd manufacture " Kalcol 2098 ") 350g (1.89 moles), 6-caprolactone (Tokyo chemical conversion industry limited company Manufacture) 4,500g (39.4 moles), tetrabutyl titanate 0.0606g, and start stirring.To carrying out nitrogen displacement in flask, in React 2 hours, and then reacted in 5 hours at 170 DEG C at 150 DEG C.Thereafter, be cooled to room temperature, and obtain bay epoxide it is poly- (ε-oneself Lactone) (21) (polyester a1).
Synthesis example 3-b1 [chloracetate b1：The synthesis of bay epoxide poly- (6-caprolactone) (21) monochloro acetic acid ester]
It is blown into agitating device, thermometer, nitrogen is provided with the 10L of pipe and condenser pipe flask, addition synthesis example 3- The polyester a1 4 obtained in a1,790g, monochloro acetic acid (and Wako Pure Chemical Industries limited company manufacture, special grade chemical) 199g, P-methyl benzenesulfonic acid-monohydrate (manufacture of bank field chemistry limited company, special grade chemical) 17.5g, and start stirring.To flask Interior carry out nitrogen displacement, under 140 DEG C, atmospheric pressure react 2 hours, and then, when being blown into nitrogen in 140 DEG C ,- It is allowed to react 21 hours under 0.1MPaG (gauge pressure) reduced pressure.Thereafter, recovered using nitrogen to atmospheric pressure, be cooled to 80 DEG C, Addition hydrotalcite (manufacture of consonance chemical industry limited company " Kyoword 500SH ") 131.8g, and stirred at 80 DEG C Mix 3 hours.The solution obtained is remained 80 DEG C, (Advantec Toyo limited companies manufacture using filter paper " No.5A ") filtered, and obtain bay epoxide poly- (6-caprolactone) (21) monochloro acetic acid ester (chloracetate b1).
[the dispersant B -2 of synthesis example 3：Chlorination N, N, N', N'- tetramethyl-N, N'- are double, and [bay epoxide is poly- (6-caprolactone) (21) carbonyl methylene]-propane-diammonium synthesis]
To the detachable flask for the 500mL for being provided with reflux condenser, thermometer, nitrogen ingress pipe and agitating device In, chloracetate b1 200g, the N obtained in synthesis example 3-b1 is added, N, N', N'- 4-methyl-diaminopropanes (spend king's share limited Company's manufacture " KAOLIZER No.2 ") 5.04g, and start stirring.To carrying out nitrogen displacement in flask, in making it at 80 DEG C Reaction 20 hours.Propylene glycol methyl ether acetate (PGMEA) 300g is added, after being stirred 1 hour at 80 DEG C, room temperature is cooled to, And obtain dispersant B -2：Double [bay epoxide poly- (6-caprolactone) (21) the carbonyl methylenes of chlorination N, N, N', N'- tetramethyl-N, N'- Base]-propane-diammonium PGMEA solution.The solid constituent of the solution is 39.8 mass %, and weight average molecular weight is 9,800 (according to ＜ bars The ＞ of part 2 measured value).
Embodiment 1 (manufacture of dispersion 1)
By the compound A1-1 15.0g obtained in synthesis example 1, nigrosine A2-1 (Tokyo Se Cai Industries, Incs Manufacture " Toshiki 5030conc ", BET specific surface area：10.9m2/ g, real density：1.42g/cm3, average grain diameter：388nm) 15.0g, as the Japanese Lubrizol limited companies of dispersant manufacture " Solsperse J-200 " 5.3g, as having PGMEA109.1g the and φ 0.3mm of machine solvent zirconium oxide bead (Nikkato manufacture " YTZ Ball ") 300g is added to appearance In the polyethylene container for measuring 500mL, " the Paint Shaker ", in 640rpm manufactured using Qian Tian ironworker limited company Lower stirring 3 hours.The copolymer 1 obtained in zirconium oxide bead, addition synthesis example 2 is removed by filtering from the dispersion liquid obtained PGMEA solution 5.6g and mixed, and obtain dispersion 1.
(preparation of resin combination 1)
The 11.2g of dispersion 1 and transparent resist liquid 10.1g is added into capacity 30mL glass container and bolt is tight. Using roll-type mixer (AS ONE limited companies manufacture " Mix Rotor Variable VMR-5R "), under 50rpm Mixing 20 minutes, and obtain resin combination 1.
Embodiment 2~12,51~52
(manufacture of dispersion 2~12,51~52)
Be changed in table 1 described component, in addition, by method same as Example 1 obtain dispersion 2~ 12nd, 51~52.Furthermore, the raw material used in manufacture is as described below.
(preparation of resin combination 2~12,51~52)
Component described in table 2 is changed to, in addition, resin combination is obtained by method same as Example 1 Thing 2~12,51~52.
A1-1：Compound A1-1 (synthesis example 1)
A2-1：Nigrosine (manufacture of Tokyo Se Cai Industries, Incs " Toshiki 5030conc ", BET compare table Area：10.9m2/ g, real density：1.42g/cm3, average grain diameter：388nm)
A2-2：Nigrosine (A2-1 particle type, BET specific surface area：13.6m2/ g, real density：1.47g/cm3, average grain Footpath：300nm)
A2-3：Nigrosine (A2-1 particle type, BET specific surface area：15.7m2/ g, real density：1.51g/cm3, average grain Footpath：253nm)
B-1：" the Solsperse J200 " of Japanese Lubrizol limited companies manufacture
B-2：Dispersant B -2 (synthesis example 3)
C-1：PGMEA
[table 1]
Table 1
* 40 mass %PGMEA solution of the copolymer 1 obtained in 1 synthesis example 2
[table 2]
Table 2
The numbering of dispersion used in the manufacture of * 1 resin combination
Obtained resin combination is used to carry out various evaluate.Show the result in table 3.
[table 3]
Table 3
* 1 adds up to the mass parts of 100 mass parts relative to pigment
*2 DPHA
The solid constituent of * 3 copolymer 1s
It can be seen from embodiment 1~12, using the resin combination of the present invention, light-proofness can be obtained and patternability is excellent Different colored curable resin composition.
Industrial applicability
According to the resin combination of the present invention, because light-proofness and patternability are excellent, therefore it can provide and possess performance The colour filter of excellent black matrix.

Claims (13)

1. a kind of colored curable resin composition, its contain compound (A1) represented by following formula (1), nigrosine (A2), Dispersant (B), organic solvent (C) and curability compound (D), and compound (A1) is relative to compound (A1) and nigrosine (A2) total mass ratio, i.e. A1/ (A1+A2) is more than 0.10 and less than 0.50,
In above-mentioned formula (1), X represents double bond, is separately E bodies or Z bodies, R as geometric isomer1Separately represent Hydrogen atom, methyl, nitro, methoxyl group, bromine atoms, chlorine atom, fluorine atom, carboxyl or sulfonic group, R2Separately represent hydrogen Atom, methyl or phenyl, R3Separately represent hydrogen atom, methyl or chlorine atom.
2. colored curable resin composition as claimed in claim 1, wherein, compound (A1) relative to compound (A1) with Total mass ratio, the i.e. A1/ (A1+A2) of nigrosine (A2) is more than 0.20 and less than 0.40.
3. colored curable resin composition as claimed in claim 1 or 2, wherein, compound (A1) and nigrosine (A2) Total content is more than 3 mass % and below 40 mass % in resin combination.
4. colored curable resin composition as claimed any one in claims 1 to 3, wherein, the content of dispersant (B) exists It is more than 0.1 mass % and below 10 mass % in resin combination.
5. the colored curable resin composition as any one of Claims 1-4, wherein, the content of organic solvent (C) It is more than 60 mass % and below 95 mass % in resin combination.
6. the colored curable resin composition as any one of claim 1 to 5, wherein, curability compound (D) Content is more than 0.3 mass % and below 10 mass % in resin combination.
7. the colored curable resin composition as any one of claim 1 to 6, wherein, compound (A1) and aniline Total content of black (A2) is more than 3 mass % and below 40 mass % in resin combination, and the content of dispersant (B) is in tree It is more than 0.1 mass % and below 10 mass % in oil/fat composition, the content of organic solvent (C) is 60 matter in resin combination More than % and below 95 mass % are measured, the content of curability compound (D) is more than 0.3 mass % and 10 in resin combination Below quality %.
8. the colored curable resin composition as any one of claim 1 to 7, it also includes alkali soluble resin (E)。
9. the colored curable resin composition as any one of claim 1 to 8, wherein, nigrosine (A2's) is averaged Particle diameter is more than 0.24 μm and less than 0.7 μm.
10. colored curable resin composition as claimed in any one of claims 1-9 wherein, it is used to form the black of colour filter Matrix.
11. the colored curable resin composition any one of claim 1 to 9 is in the black matrix for forming colour filter In purposes.
12. a kind of colour filter, it possess the colored curable resin composition any one of usage right requirement 1 to 10 and The black matrix of formation.
13. a kind of dispersion, it contains compound (A1) represented by following formula (1), nigrosine (A2), dispersant (B) and had Machine solvent (C), and compound (A1) is relative to compound (A1) and total mass ratio, the i.e. A1/ (A1+A2) of nigrosine (A2) For more than 0.10 and less than 0.50,
In above-mentioned formula (1), X represents double bond, is separately E bodies or Z bodies, R as geometric isomer1Separately represent Hydrogen atom, methyl, nitro, methoxyl group, bromine atoms, chlorine atom, fluorine atom, carboxyl or sulfonic group, R2Separately represent hydrogen Atom, methyl or phenyl, R3Separately represent hydrogen atom, methyl or chlorine atom.
CN201580068513.9A 2014-12-18 2015-12-16 Colored curable resin composition Pending CN107001497A (en)

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CN107962885A (en) * 2017-11-02 2018-04-27 苏州太平洋印务有限公司 A kind of double-colored nested typography of glass panel

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CN102282216A (en) * 2009-01-19 2011-12-14 巴斯夫欧洲公司 Black pigment dispersion
JP2013164445A (en) * 2012-02-09 2013-08-22 Dic Corp Color display device
TW201432323A (en) * 2012-12-27 2014-08-16 Fujifilm Corp Composition for color filter, infrared ray transmitting filter and fabricating method thereof, and infrared ray sensor

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CN102282216A (en) * 2009-01-19 2011-12-14 巴斯夫欧洲公司 Black pigment dispersion
JP2013164445A (en) * 2012-02-09 2013-08-22 Dic Corp Color display device
TW201432323A (en) * 2012-12-27 2014-08-16 Fujifilm Corp Composition for color filter, infrared ray transmitting filter and fabricating method thereof, and infrared ray sensor

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CN107962885A (en) * 2017-11-02 2018-04-27 苏州太平洋印务有限公司 A kind of double-colored nested typography of glass panel

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