CN104145196A - Photosensitive resin composition for black matrix, and method for producing same - Google Patents

Photosensitive resin composition for black matrix, and method for producing same Download PDF

Info

Publication number
CN104145196A
CN104145196A CN201380011626.6A CN201380011626A CN104145196A CN 104145196 A CN104145196 A CN 104145196A CN 201380011626 A CN201380011626 A CN 201380011626A CN 104145196 A CN104145196 A CN 104145196A
Authority
CN
China
Prior art keywords
acid
photosensitive polymer
polymer combination
black matrix
carbon black
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201380011626.6A
Other languages
Chinese (zh)
Other versions
CN104145196B (en
Inventor
井户川浩幸
东学
中岛祥人
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Nippon Steel Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Steel Chemical Co Ltd filed Critical Nippon Steel Chemical Co Ltd
Publication of CN104145196A publication Critical patent/CN104145196A/en
Application granted granted Critical
Publication of CN104145196B publication Critical patent/CN104145196B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Optical Filters (AREA)
  • Materials For Photolithography (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The present invention pertains to a photosensitive resin composition for a color filter black matrix having outstanding storage stability, and which is used for forming thin line pattern black matrices with high light-shielding properties and high resistance. This photosensitive resin composition for black matrix and method for producing same is characterized by adding and mixing, in predetermined quantities, to a carbon black pigment dispersant containing dye-coated carbon black obtained by coating the surface of carbon black with a dye, a predetermined epoxy (meth)acrylate acid addition compound, a dispersant, and a solvent: an unsaturated group-containing alkali-soluble resin; a photopolymerisable monomer having an ethylenic unsaturated bond; a photoinitiator; and a solvent.

Description

Photosensitive polymer combination and manufacture method thereof for black matrix
Technical field
The present invention relates to a kind of black matrix that is suitable for forming high shading and high-resistance thread pattern, and storage stability also photosensitive polymer combination and the manufacture method thereof for black matrix of excellent color filter.
Background technology
In recent years, in all spectras such as liquid crystal TV set, LCD monitor, color liquid crystal mobile phone, bring into use color liquid crystal display arrangement.One of important parts that color filter is the identification of control color liquid crystal display arrangement, in order to obtain the raising of identification, i.e. distincter image, the black matrix of color filter must be realized further high shading, must be in photosensitive polymer combination the light screening materials such as pigment that add in large quantities compared with the past.
Yet, produce following problem: if increase the content of the light screening materials such as pigment, when color filter forms, in black photoresistance film, the light of ultraviolet range becomes and is difficult to arrive the deep of filming, and the pattern while producing the closely sealed bad of pattern or development because of curing bad in Photocurable composition peels off, the sharp keen property reduction of edge shape.
Therefore, even in the situation that the light screening materials such as pigment that contain high concentration do not produce yet solidify bad, use the acrylic monomers that highly sensitive Photoepolymerizationinitiater initiater or the degree of polymerization are high, but in current technology, about Photoepolymerizationinitiater initiater or acrylic monomers, present situation is that high-sensitivity reaches capacity, in the high concentration field of the light screening materials such as pigment, existence can not obtain for carry out sufficient sensitivity that good pattern forms or with the problem of the adaptation of glass substrate and the storage stability of photosensitive polymer combination.
Therefore, proposed before the inventor etc. as the alkali soluble resin using when the Pigments, utilize the acid adduct of specific epoxy (methyl) acrylate, use and have the photosensitive polymer combination for color filter (with reference to patent documentation 1) that they is divided into together with spreading agent to loose pigment dispersion.According to described photosensitive polymer combination, in the field of the light screening materials such as pigment that contain the high concentration that realizes high shading with black matrix, there is high sensitivity, the high adhesion energy to glass substrate, and can realize the storage stability of photosensitive polymer combination excellence.
But, in order to become brighter, distincter color filter, in the mode that the further graph thinning of black matrix, obscurity are also improved, require more and more High Level of characteristic, and, due to the display mode of liquid crystal, must make black matrix than in the past higher resistance.Become when realizing the addition of the light screening materials such as high-caliber so high shading, high-resistance pigment, cannot guarantee fully the development adaptation of the thread pattern below 10 μ m, while assembling color filter on liquid crystal panel, be also difficult to compared with highland, maintain the problem with the adaptation of glass substrate by sealant.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-9401 communique
Summary of the invention
Invent problem to be solved
As mentioned above, be difficult to obtain being used to form the black matrix photosensitive polymer combination of high shading and high-resistance thread pattern, for example, while adding carbon black in large quantities for shading, can not obtain fully the thread pattern below 10 μ m adaptation or with the adaptation of glass substrate, also be difficult to become high resistance, on the contrary, while making the adaptation of thread pattern or resistance become requirement level, do not increase the thickness of filming and just can not obtain sufficient light-proofness, in the design of color filter, can not be suitable for etc., strong request addresses the above problem.
The present invention puts and the invention that completes in view of the above problems, its object is, a kind of black matrix photosensitive polymer combination and manufacture method thereof are provided, described black matrix uses photosensitive polymer combination in above-mentioned photosensitive polymer combination, maintaining high shading, high-resistance while, in the situation that forming thread pattern, guarantee fully the adaptation of developing, also excellent with the adaptation of glass substrate, storage stability is also excellent.
In order to solve the means of problem
Above-mentioned purpose of the present invention realizes by following means.
(1) the present invention is the manufacture method of photosensitive polymer combination for the black matrix of a kind of color filter, it is characterized in that, after modulation has (A) pigment dispersion of following (A1)～(A4) composition in advance, following by containing (B)～(E) composition mixes with described (A) pigment dispersion as the gradation composition of neccessary composition
(A1) the coating dye carbon black that surface is formed by coating dye,
(A2) spreading agent,
(A3) there is the alkali soluble resin containing unsaturated group of the structure of following general formula (I),
(A4) solvent,
(B) contain the alkali soluble resin of unsaturated group,
(C) there is the photopolymerization monomer of ethylenic unsaturated bond,
(D) Photoepolymerizationinitiater initiater,
(E) solvent,
[general formula (I) is for making to have the epoxy compound of 2 glycidyl ethers that derived by bisphenols and (methyl) acrylic acid reactant, and the mode that with (a) dicarboxylic acid or tricarboxylic acids or any sour single acid anhydride and (b) tetrabasic carboxylic acid or its acid dianhydride become 1:10～10:1 with (a) and mol ratio (b) is reacted and the acid adduct of epoxy (methyl) acrylate that obtains.At this, in formula, R 1, R 2, R 3and R 4the alkyl, halogen atom or the phenyl that represent independently respectively hydrogen atom, carbon number 1～5, R 5represent hydrogen atom or methyl, represent-CO-of A ,-SO 2-,-C (CF 3) 2-,-Si (CH 3) 2-,-CH 2-,-C (CH 3) 2-,-O-, 9,9-fluorenyl or Direct Bonding, X represents the carboxylic acid residues of 4 yuan, Y 1and Y 2represent independently respectively hydrogen atom or-OC-Z-(COOH) m(wherein, Z represents 2 yuan or 3 yuan of carboxylic acid residues, and m represents 1～2 number), n represents 1～20 integer.]
(2) in addition, the present invention is the black matrix photosensitive polymer combination of a kind of color filter, it is characterized in that, following by having (A1)～(A4) composition and in advance (A) pigment dispersion of modulation with contain that following (B)～(E) composition mixes as the gradation composition of neccessary composition
(A1) the coating dye carbon black that surface is formed by coating dye,
(A2) spreading agent,
(A3) there is the alkali soluble resin containing unsaturated group of the structure of following general formula (I),
(A4) solvent,
(B) contain the alkali soluble resin of unsaturated group,
(C) there is the photopolymerization monomer of ethylenic unsaturated bond,
(D) Photoepolymerizationinitiater initiater,
(E) solvent,
[general formula (I) is for making to have the epoxy compound of 2 glycidyl ethers that derived by bisphenols and (methyl) acrylic acid reactant, and the mode that with (a) dicarboxylic acid or tricarboxylic acids or any sour single acid anhydride and (b) tetrabasic carboxylic acid or its acid dianhydride become 1:10～10:1 with (a) and mol ratio (b) is reacted and the acid adduct of epoxy (methyl) acrylate that obtains.At this, in formula, R 1, R 2, R 3and R 4the alkyl, halogen atom or the phenyl that represent independently respectively hydrogen atom, carbon number 1～5, R 5represent hydrogen atom or methyl, represent-CO-of A ,-SO 2-,-C (CF 3) 2-,-Si (CH 3) 2-,-CH 2-,-C (CH 3) 2-,-O-, 9,9-fluorenyl or Direct Bonding, X represents the carboxylic acid residues of 4 yuan, Y 1and Y 2represent independently respectively hydrogen atom or-OC-Z-(COOH) m(wherein, Z represents 2 yuan or 3 yuan of carboxylic acid residues, and m represents 1～2 number), n represents 1～20 integer.]
(3) in addition, the present invention is (2) described black matrix photosensitive polymer combination of color filter, and wherein the containing ratio of the described dyestuff of (A1) coating dye carbon black is 0.5～10 quality %.
(4) in addition, the present invention is (2) to (3) described black matrix photosensitive polymer combination of color filter, and the dyestuff of wherein said coating dye carbon black is the dyestuff of anionic property or nonionic.
(5) in addition, the present invention is the black matrix photosensitive polymer combination of color filter described in any one in (2) to (4), and the dyestuff of wherein said coating dye carbon black is the dyestuff of dark system.
(6) in addition, the present invention is the black matrix photosensitive polymer combination of color filter described in any one in (2) to (5), and the dyestuff of wherein said coating dye carbon black is by metal or slaine color lake.
(7) in addition, the present invention is (6) described black matrix photosensitive polymer combination of color filter, and wherein said metal or slaine are aluminium, magnesium, calcium, strontium, barium or manganese or their salt.
(8) in addition, the present invention is the black matrix photosensitive polymer combination of color filter described in any one in (2) to (7), and the carbon black that wherein said coating dye carbon black is used surface to have at least a kind of acidic functionality obtains.
(9) in addition; the present invention is the black matrix photosensitive polymer combination of color filter described in any one in (2) to (8), and wherein said acidic functionality is hydroxyl, oxo base, hydroperoxy, carbonyl, carboxyl, peroxycarboxylic acid base, aldehyde radical, ketone group, nitro, nitroso-, amide group, imide, sulfonic group, sulfinic acid base, sulfenic groups, thiocarboxylic acid base, sub-chlorine acyl group, chlorine acyl group, crosses chlorine acyl group, idous acyl group or iodoxy.
(10) in addition, the present invention is the black matrix photosensitive polymer combination of color filter described in any one in (2) to (9), and wherein (A3) is 2～20 quality % containing the use level of the alkali soluble resin of unsaturated group.
(11) in addition, the present invention is the black matrix photosensitive polymer combination of color filter described in any one in (2) to (10), and wherein the use level of (A1) coating dye carbon black in the solid constituent of photosensitive polymer combination is 45～60 quality %.
(12) in addition, the present invention is the color filter photosensitive polymer combination described in any one in (2) to (11), the alkali soluble resin containing unsaturated group that the general formula (I) that wherein at least a portion of (B) composition is served as reasons in (1) represents.
(13) in addition, the present invention is a kind of filming, and it is that the black matrix of color filter of (2) to (12) is solidified to form with photosensitive polymer combination.
(14) in addition, the present invention is a kind of black matrix, and it is by after photosensitive polymer combination coating for the black matrix (2) to (12) Suo Shu, masking, makes the position of selecting carry out photocuring, with alkaline developer, develops and obtains.
(15) in addition, the present invention is a kind of color filter, and it is that (14) described black matrix forms.
Invention effect
Black matrix of the present invention is fabricated to the black matrix photosensitive polymer combination of feature with the pigment dispersion that photosensitive polymer combination forms for the acid adduct that contains the surperficial coating dye carbon black being formed by coating dye and specific epoxy (methyl) acrylate with use, due to excellent storage stability, coating and the developability of filming is excellent, therefore, can form high shading and high resistance, with the thread pattern of the adaptation excellence of glass substrate, while being applied to color filter, can make high light-proofness and high resistance, black matrix that reliability is high.
Embodiment
Below, embodiments of the present invention are at length described.
First black matrix of the present invention modulates (A) pigment dispersion with photosensitive polymer combination, its constituent is: (A1) coating dye carbon black, (A2) spreading agent, (A3) have general formula (I) structure containing the alkali soluble resin of unsaturated group, and (A4) solvent.
The kind of the raw material carbon black utilizing in coating dye carbon black of the present invention is not particularly limited, and can utilize the known carbon blacks such as dim, acetylene black, thermal black, channel black, furnace black.
In addition, the average primary particle diameter of raw material carbon black is preferably 5～60nm, and more preferably 10～50nm, is particularly preferably 20～45nm.At this, average primary particle diameter refers to the arithmetic mean of the primary particle size of obtaining with 1500 of electron microscope observation carbon black primary particles.The average primary particle diameter of raw material carbon black, lower than above-mentioned in limited time lower, easily causes cohesion, the bad stability of grinding material, it is difficult that the dispersion of high concentration becomes, on the other hand, and when it surpasses above-mentioned in limited time upper, black matrix easily produces shape defect, and surfaceness is variation also, therefore all not preferred.
In addition, the DBP uptake of raw material carbon black is preferably below 100ml/100g.At this, DBP uptake refers to the capacity of the dibutyl phthalate (DBP) that carbon black 100g absorbs, and according to the method for recording in JISK6217-4, measures.The DBP uptake of raw material carbon black surpasses above-mentioned in limited time upper, and resistance value reduces, and viscosity raises, so coating variation, and degree of blackness reduces, therefore not preferred.
And then the pH value of raw material carbon black is preferably 2～10, more preferably 5～9, be particularly preferably 4～8.At this, pH value refers to measures the mixed liquor of carbon black and distilled water the value of gained with glass electrode pH meter, according to the method for JISK6221-1982, measure.The pH of raw material carbon black is lower than above-mentioned in limited time lower, and whole balance is collapsed, and dispersion stabilization variation is in limited time upper over above-mentioned when it, easily produces film to peel off, therefore all not preferred.
And then raw material carbon black utilizes that ash content is below 1.0%, specific surface area is 20～300m aptly 2the carbon black of/g.Ash content is measured according to the method for recording in JISK6218-2, and specific surface area is measured according to the C method of recording in JISK6217-2.Ash content surpasses above-mentioned in limited time upper, and resistance value reduces, so not preferred, and in addition, specific surface area, lower than above-mentioned in limited time lower, easily produces the shape defect of black matrix, when it surpasses above-mentioned upper prescribing a time limit, needs in large quantities spreading agent, resin, dyestuff etc., therefore all not preferred.
In addition, preferably in advance raw material carbon black implemented oxidation processes and on surface, had at least a kind of acidic functionality, more preferably implementing multiple oxidation processes and on surface, there is acidic functionality of more than two kinds.Do not implement in advance the raw material carbon black of oxidation processes owing to not thering is acidic functionality on surface, or the quantity of acidic functionality is insufficient, therefore in photosensitive polymer combination, can not make fully carbon black small dispersion equably, the resistance value of the black matrix obtaining reduces.Therefore, conducting between the transparency electrode on color filter and black matrix and between counter electrode and easily cause that image is bad, therefore not preferred.
As described oxidation processes, can enumerate the method for oxygenants such as using ozone gas, nitric acid, sodium hypochlorite, hydrogen peroxide, nitric oxide gas, nitrogen dioxide gas, anhydrous slufuric acid, fluorine gas, the concentrated sulphuric acid, nitric acid, various superoxide.In addition; as above-mentioned acidic functionality, can enumerate: hydroxyl, oxo base, hydroperoxy, carbonyl, carboxyl, peroxycarboxylic acid base, aldehyde radical, ketone group, nitro, nitroso-, amide group, imide, sulfonic group, sulfinic acid base, sulfenic groups, thiocarboxylic acid base, sub-chlorine acyl group, chlorine acyl group, mistake chlorine acyl group, idous acyl group, iodoxy etc.
As the dyestuff utilizing in coating dye carbon black of the present invention, so long as can be adsorbed in the surperficial dyestuff of carbon black, just be not particularly limited, can utilize known basic-dyeable fibre, acid dyes, direct dyes, chemically-reactive dyes etc., but from sulfo group or carboxyl interact with the functional group carbon black, aminoly react with alkali soluble resin, can be insoluble in aluminium sulphate etc. etc. aspect consideration, can more appropriately utilize the dyestuff of anionic property or nonionic.In addition, in order further to improve the light-proofness of the black matrix obtaining, use aptly the dyestuff close to the dark color system of the high black of light absorption.As the concrete example of this dyestuff, can enumerate: Food Black No.1, Food Black No.2, Food Red No.40, Food Blue No.1, the food coloring dyestuffs such as Food Yellow No.7, Bernacid Red 2BMN, Basacid Black X34 (BASF X-34) (BASF AG's system), Kayanol Red 3BL (Nippon Kayaku Company company system), Dermacarbon 2GT (Sandoz company system), Telon Fast Yellow 4GL-175, BASF Basacid Black SE 0228, Basacid Black X34 (BASF X-34) (BASF AG's system), Basacid Blue 750 (BASF AG's system), Bernacid Red (Bemcolors, Poughkeepsie, N.Y. company system), the acid dyess of all kinds such as BASF Basacid Black SE 0228 (BASF AG's system), Pontamine Brilliant Bond Blue A and other Pontamine Brilliant Bond Blue A and other Pontamine (registered trademark) dyestuff (Bayer Chemicals Corporation, Pittsburgh, PA company system), Cartasol Yellow GTF Presscake (Sandoz, Inc company system), Cartasol Yellow GTF Liquid Special 110 (Sandoz, Inc. company system), Yellow Shade 16948 (Tricon company system), Direct Brilliant Pink B (Crompton & Knowles company system), Carta Black 2GT (Sandoz, Inc. company system), Sirius Supra Yellow GD 167, Cartasol Brilliant Yellow 4GF (Sandoz company system), Pergasol Yellow CGP (Ciba-Geigy company system), Pyrazol Black BG (JCI company system), Diazol Black RN Quad (JCJ company system), Pontamine Brilliant Bond Blue, the direct dyess of all kinds such as Berncolor A.Y.34, Cibacron Brilliant Red 3B-A (Reactive Red 4) (Aldrich Chemical, Milwaukee, WI company system), Drimarene Brilliant Red X-2B (Reactive Red56) (Pylam Products, Inc.Tempe, AZ company system), Levafix Brilliant Red E-4B, Levafix Brilliant Red F-6BA and similarly Levafix (registered trademark) dyes Dystar L.P. (Charlotte, NC company system) dyestuff of system, the chemically-reactive dyess of all kinds such as Procion Red H8B (Reactive Red 31) (JCI America company system), Neozapon Red 492 (BASF AG's system), Orasol Red G (Ciba-Geigy company system), Aizen Spilon Red C-BH (Hodogaya Chemical Company company system), Spirit Fast Yellow 3G, Aizen Spilon Yellow C-GNH (Hodogaya Chemical Company company system), Orasol Black RL (Ciba-Geigy company system), Orasol Black RLP (Ciba-Geigy company system), Savinyl Black RLS (Sandoz company system), Orasol Blue GN (Ciba-Geigy company system), Luxol Blue MBSN (Morton-Thiokol company system), the oil-soluble dyes such as Morfast Black Concentrate A (Morton-Thiokol company system) etc.These materials both can utilize separately, or also can combine and utilize two or more.
In addition, the content of the dyestuff in the coating dye carbon black utilizing in the present invention is preferably 0.5～10 quality %, and more preferably 1～7 quality %, is particularly preferably 1～5 quality %.The content of dyestuff is lower than above-mentioned in limited time lower, coated insufficient, can not obtain high resistance value, and in limited time upper over above-mentioned when it, the remaining dyestuff not being wrapped by hinders dispersed, easily causes that tackify condenses, therefore all not preferred.
And then the coating dye carbon black utilizing in the present invention makes above-mentioned dyestuff color lake by metal or slaine aptly.By described color lake, dyestuff is fixed on via metal or slaine on the surface or above-mentioned acidic functionality of carbon black, and dyestuff is difficult to depart from from the surface of carbon black, and therefore, dyestuff is difficult to stripping, can maintain high covering property.As the metal utilizing in described color lake or slaine, can enumerate simple substance or their hydrochloride, the sulfate etc. of aluminium, magnesium, calcium, strontium, barium or manganese, these materials can be used singly or in combination to two or more.The metal utilizing in color lake or the addition of slaine are preferably more than 0.3 times mole with respect to dyestuff, more preferably more than 0.5 times mole, are particularly preferably more than 0.8 times mole.The addition of metal or slaine is when above-mentioned, and fixing of dye is insufficient, easily from carbon blacksurface, depart from, and the bad stability of grinding material, resistance value also reduces, therefore not preferred.
Then, the manufacture method of the coating dye carbon black utilizing in the present invention is described.First, the carbon black of raw material and water (in the fixing mode of conductivity degree, ion exchange water is suitably mixed and the water adjusted with tap water, below identical) mixed and make slurry, adding the thermal agitation stipulated time, carbon black is carried out to cleaning treatment, again wash after cooling.Then, in the carbon black obtaining, add water and make again slurry, adding above-mentioned oxygenant, under set point of temperature, stirring the stipulated time, oxidation processes is carried out in the surface of carbon black, washing.Change as required the kind of oxygenant and carry out repeatedly oxidation processes.Then, the carbon black through oxidation processes obtaining is mixed with water and also make again slurry, to become the mode of afore mentioned rules content with respect to target coating dye carbon black, add dyestuff, at 40～90 ℃, stir 1～5 hour, by sorption of dye in the surface of carbon black and make it coated.And then, add and the equimolar above-mentioned metal of dyestuff or the slaine that add, at 30～70 ℃, stir 1～5 hour, dyestuff is carried out to color lake with metal or slaine, make the fixing of dye on the surface of carbon black.And, wash after it is cooling, filtration drying, can obtain thus target coating dye carbon black.
The use level of the above-mentioned coating dye carbon black in (A) of the present invention pigment dispersion is 15～35 quality %, be preferably 20～30 quality %.The use level of coating dye carbon black is lower than above-mentioned in limited time lower, and it is insufficient that light-proofness becomes, and in order to obtain preferred contrast, must make thickness thicken, and is difficult to obtain the face flatness of black matrix.In addition, the use level of coating dye carbon black surpasses above-mentioned in limited time upper, and the dispersion stabilization of pigment dispersion reduces, and in addition, the content that becomes the photoresist of initial bonding agent also reduces, and therefore can not obtain good developing property, therefore all not preferred.
Be explained, (A) of the present invention pigment dispersion, except above-mentioned coating dye carbon black, also can contain the carbon black of the processing that implements common or regulation.Pigment or the light screening material etc. that also can contain in addition, other.As other pigment, can use and the black organic pigment that is selected from that example is as black in perylene, cyanine is black etc., pigment at least of more than two kinds in red, blue, green, purple, yellow, livid purple, pinkish red etc. are mixed and carry out simulating the colour mixture organic pigment of black.In addition, as other light screening material, can enumerate: chromium oxide, iron oxide, titanium are black, nigrosine, cyanine are black.Pigment or light screening material beyond coating dye carbon black also can suitably be selected two or more respectively and use, and also can mutually be used in combination.
(A2) of the present invention is as long as composition spreading agent has the effect that other the pigment etc. that makes (A1) composition coating dye carbon black or according to circumstances contain stably disperses as pigment dispersion, for example, can use the known spreading agents such as various macromolecule dispersing agents.As the concrete example of macromolecule dispersing agent, can enumerate especially the macromolecule dispersing agent of the basic functionalities such as nitrogen heterocyclic ring such as thering is primary, secondary or tertiary amino, pyridine, pyrimidine, pyrazine.About the use level of this (A2) composition, with respect to dyestuff, process CB, be 1～30 quality %, be preferably 2～25 quality %.
(A3) of the present invention composition is the acid adduct by epoxy (methyl) acrylate shown in following general formula (I) containing the alkali soluble resin of unsaturated group.
[in formula, R 1, R 2, R 3and R 4the alkyl, halogen atom or the phenyl that represent independently respectively hydrogen atom, carbon number 1～5, R 5represent hydrogen atom or methyl, represent-CO-of A ,-SO 2-,-C (CF 3) 2-,-Si (CH 3) 2-,-CH 2-,-C (CH 3) 2-,-O-, 9,9-fluorenyl or Direct Bonding, X represents the carboxylic acid residues of 4 yuan, Y 1and Y 2represent independently respectively hydrogen atom or-OC-Z-(COOH) m(wherein, Z represents 2 yuan or 3 yuan of carboxylic acid residues, and m represents 1～2 number), n represents 1～20 integer]
The acid adduct of epoxy (methyl) acrylate of the general formula utilizing in the present invention (I) is to make to have the epoxy compound of 2 glycidyl ethers that derived by bisphenols and (methyl) acrylic acid reactant, reacts and obtains with dicarboxylic acid or tricarboxylic acids or any sour single acid anhydride and tetrabasic carboxylic acid or its acid dianhydride.
Wherein, as the bisphenols of acid adduct that gives epoxy (methyl) acrylate of general formula of the present invention (I), can enumerate: two (4-hydroxy phenyl) ketone, two (4-hydroxyl-3,5-3,5-dimethylphenyl) ketone, two (4-hydroxyl-3,5-dichlorophenyl) ketone, two (4-hydroxy phenyl) sulfone, two (4-hydroxyl-3,5-3,5-dimethylphenyl) sulfone, two (4-hydroxyl-3,5-dichlorophenyl) sulfone, two (4-hydroxy phenyl) HFC-236fa, two (4-hydroxyl-3,5-3,5-dimethylphenyl) HFC-236fa, two (4-hydroxyl-3,5-dichlorophenyl) HFC-236fa, two (4-hydroxy phenyl) dimethylsilane, two (4-hydroxyl-3,5-3,5-dimethylphenyl) dimethylsilane, two (4-hydroxyl-3,5-dichlorophenyl) dimethylsilane, two (4-hydroxy phenyl) methane, two (4-hydroxyl-3,5-dichlorophenyl) methane, two (4-hydroxyl-3,5-dibromo phenyl) methane, two (4-hydroxy phenyl) propane of 2,2-, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) propane of 2,2-, two (4-hydroxyl-3, the 5-dichlorophenyl) propane of 2,2-, two (the 4-hydroxy-3-methyl phenyl) propane of 2,2-, two (4-hydroxyl-3-chlorphenyl) propane of 2,2-, two (4-hydroxy phenyl) ether, two (4-hydroxyl-3,5-3,5-dimethylphenyl) ether, two (4-hydroxyl-3,5-dichlorophenyl) ether, two (4-hydroxy phenyl) fluorenes of 9,9-, two (the 4-hydroxy-3-methyl phenyl) fluorenes of 9,9-, two (4-hydroxyl-3-chlorphenyl) fluorenes of 9,9-, two (4-hydroxyl-3-bromophenyl) fluorenes of 9,9-, two (4-hydroxyl-3-fluorophenyl) fluorenes of 9,9-, two (4-hydroxyl-3, the 5-3,5-dimethylphenyl) fluorenes of 9,9-, two (4-hydroxyl-3, the 5-dichlorophenyl) fluorenes of 9,9-, two (4-hydroxyl-3, the 5-dibromo phenyl) fluorenes of 9,9-, 4,4 '-bis-phenol, 3,3 '-bis-phenol etc. and their derivant.Wherein, particularly preferably utilize the material with 9,9-fluorenyl.
And, make the reaction of above-mentioned bisphenols and chloropropylene oxide and obtain having the epoxy compound of 2 glycidyl ethers.When this reacts, generally with the oligomeric materialization of 2-glycidyl ether compound, therefore obtain the compound of following general formula (II).R in the formula of general formula (II) 1, R 2, R 3, R 4, A is the meaning same with general formula (I).I is 0～10 integer.Preferred R 1, R 2, R 3, R 4for hydrogen atom, preferred A is 9,9-fluorenyl.In addition, because normally a plurality of values of I mix, therefore become mean value 0～10 (being not limited to integer), but the mean value of preferred I is 0～3.When the value of I surpasses higher limit, as the compound of general formula (I), while forming resin combination, the viscosity of composition becomes excessive, cannot successfully apply, or can not give fully alkali-soluble, the alkali-developable non-constant that becomes.
Then, both react with the compound of general formula (II) to make acrylic or methacrylic acid or they, make omega-dicarboxylic acids (or tricarboxylic acids) as polyprotonic acid and tetracarboxylic acid acids at least each a kind with the reactant reaction with hydroxyl obtaining, obtain the acid adduct (I) of epoxy (methyl) acrylate.Because the acid adduct (I) of this epoxy (methyl) acrylate has ethylenical unsaturated double bonds and carboxyl simultaneously, therefore give the photo-curable of alkali development-type photosensitive resin composition excellence, good developability, pattern Formation and characteristics, obtain good black matrix.
The omega-dicarboxylic acids utilizing in acid adduct as epoxy (methyl) acrylate of general formula of the present invention (I), is used chain type hydrocarbon dicarboxylic acid or its acid anhydrides or ester ring type dicarboxylic acid or its acid anhydrides, aromatic dicarboxylic acid or its acid anhydrides.At this; as chain type hydrocarbon dicarboxylic acid or its acid anhydrides; compounds such as succinic acid, acetyl group succinic acid, maleic acid, hexane diacid, itaconic acid, azelaic acid, citraconic acid, malonic acid, glutaric acid, citric acid, tartrate, ketoglutaric acid, heptandioic acid, decanedioic acid, suberic acid, diglycolic acid, and then can have substituent omega-dicarboxylic acids or its acid anhydrides arbitrarily for importing.In addition, as ester ring type dicarboxylic acid or its acid anhydrides, compounds such as hexahydro-phthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, and then can have substituent omega-dicarboxylic acids or its acid anhydrides arbitrarily for importing.And then, as aromatic dicarboxylic acid or its acid anhydrides, compounds such as phthalic acid, m-phthalic acid, and then can have substituent omega-dicarboxylic acids or its acid anhydrides arbitrarily for importing.In addition, replace omega-dicarboxylic acids, also can use tricarboxylic acids, can enumerate for example trihemellitic acid or its sour single acid anhydride.
In addition, the tetracarboxylic acid acids utilizing in acid adduct as epoxy (methyl) acrylate of general formula of the present invention (I), is used chain type hydrocarbon tetrabasic carboxylic acid or its acid dianhydride or ester ring type tetrabasic carboxylic acid or its acid dianhydride or aromatic polycarboxylic acid or its acid dianhydride.At this, as chain type hydrocarbon tetrabasic carboxylic acid or its acid dianhydride, such as BTCA, pentane tetrabasic carboxylic acid, hexane tetrabasic carboxylic acid etc., and then can have substituent tetracarboxylic acid acids or its acid dianhydride for importing.In addition, as ester ring type tetrabasic carboxylic acid or its acid dianhydride, such as cyclo-butane tetrabasic carboxylic acid, cyclopentane tetrabasic carboxylic acid, cyclohexane tetrabasic carboxylic acid, cycloheptane tetrabasic carboxylic acid, norbornane tetrabasic carboxylic acid etc., and then can have substituent tetracarboxylic acid acids or its acid dianhydride for importing.And then, as aromatic tetracarboxylic acid or its acid dianhydride, can enumerate for example pyromellitic acid, benzophenone tetrabasic carboxylic acid, biphenyltetracarboxyacid acid, Biphenyl Ether tetrabasic carboxylic acid or its acid dianhydride, and then can have substituent tetracarboxylic acid acids or its acid dianhydride for importing.
The usage ratio of (a) omega-dicarboxylic acids utilizing in the acid adduct of epoxy (methyl) acrylate of general formula of the present invention (I) and (b) tetracarboxylic acid acids is 1:10～10:1, is preferably the scope of 1:5～1:1 for (a) and mol ratio (b).When the omega-dicarboxylic acids in the acid adduct of epoxy (methyl) acrylate of general formula (I) and the usage ratio of tetracarboxylic acid acids depart from above-mentioned scope, can not obtain the suitableeest molecular weight, alkali-developable, transmitance, thermotolerance, solvent resistance, pattern form etc. are deteriorated, therefore not preferred.Be explained, exist the usage ratio of tetracarboxylic acid acids larger, the tendency that alkali dissolubility is larger, molecular weight is larger.
In addition, the suitable weight-average molecular weight (Mw) of the acid adduct of epoxy (methyl) acrylate of the general formula utilizing in the present invention (I), between 2000～10000, is particularly preferably between 3000～7000.Weight-average molecular weight (Mw), lower than 2000 o'clock, can not maintain the adaptation of the pattern while developing, and produces pattern and peels off, in addition, weight-average molecular weight (Mw) surpasses at 10000 o'clock, and the adaptation of glass substrate is become to too high, and the residual film of residue or drafting department becomes easily residual.And then preferred its acid number of acid adduct of epoxy (methyl) acrylate of general formula (I) is in the scope of 30～200KOHmg/g.When this value is less than 30KOHmg/g, alkali develops and cannot successfully carry out, or needs the special development conditions such as highly basic, when it surpasses 200KOHmg/g, alkaline developer soak into quickening, peel off development, so all not preferred.
The acid adduct of epoxy (methyl) acrylate of the general formula utilizing in the present invention (I) can utilize above-mentioned operation, by the method that known method is for example recorded in patent documentation 1, manufacture.First, the method of reacting with the monocarboxylic acid that contains unsaturated group as the epoxy compound that makes general formula (II), for example: in solvent, add with the epoxy radicals of epoxy compound with mole the monocarboxylic acid containing unsaturated group, at catalyzer (triethyl benzyl ammonia chloride, 2,6-diisobutyl phenol etc.) under existence, while being blown into air, adding thermal agitation at 90～120 ℃, make the method for its reaction.Then, as making resultant of reaction, it is the method for hydroxyl and the anhydride reaction of epoxy acrylic ester compounds, there is following method: the ormal weight that adds epoxy acrylic ester compounds and acid dianhydride and sour single acid anhydride in solvent, under the existence of catalyzer (tetraethylammonium bromide, triphenylphosphine etc.), at 90～130 ℃, add thermal agitation, make its reaction.
In addition, the use level of the acid adduct [(A3) composition] of above-mentioned epoxy (methyl) acrylate in (A) of the present invention pigment dispersion is 2～20 quality %, is preferably 5～15 quality %.The use level of the acid adduct of epoxy (methyl) acrylate is lower than above-mentioned lower prescribing a time limit, the bad stability of grinding material, resistance value reduction, therefore not preferred, when it surpasses above-mentioned upper prescribing a time limit, the viscosity of grinding material raises, coating variation, flatness reduces, therefore not preferred.
As (A4) of the present invention solvent, can enumerate: methyl alcohol, ethanol, n-propanol, isopropyl alcohol, ethylene glycol, the alcohols such as propylene glycol, α-or the terpenes such as β-terpilenol etc., acetone, methyl ethyl ketone, cyclohexanone, the ketones such as METHYLPYRROLIDONE, toluene, dimethylbenzene, tetramethylbenzenes etc. are aromatic hydrocarbon based, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol monomethyl ether, DPE, triethylene glycol monomethyl ether, the glycol ethers such as triethylene glycol list ether, ethyl acetate, butyl acetate, cellosolve acetic acid esters, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetic acid esters, ethyl carbitol acetic acid esters, acetate of butyl carbitol, propylene glycol methyl ether acetate, single or the mixed solvents such as acetate esters such as propylene glycol monoethyl ether acetate.
(A) of the present invention pigment dispersion by the solvent of optimal dose, add general formula (I) epoxy (methyl) acrylate acid adduct and other compositions that add as required and carry out after mixed dissolution, add coating dye carbon black, add after the media such as beaded glass, zirconium oxide bead, by paint regulator, sand mill, bowl mill, roller mill, burrstone mill, jet mill, homogenizer, ultrasound wave etc. separately or multiple combination carry out dispersion treatment and obtain.By this dispersion treatment, coating dye carbon black is by corpusculed and decentralized stabilization, therefore the raising of the coating characteristics of the photosensitive polymer combination that has this pigment dispersion is used in expection, the light shielding ability that is conducive to black matrix improve and use carbon black and so on there is the light screening material of electric conductivity time high resistance.
(A) the average aggregate particle size of the coating dye carbon black after the dispersion treatment of pigment dispersion is aptly becoming 50～200nm, preferably the mode of 80～150nm is modulated.Average aggregate particle size at this is the value of the use-case mean grain size that the granulometry device of laser-Doppler formula is obtained as is well known.In addition, when (A) viscosity of pigment dispersion is obtained by known cone-plate type viscosity meter, at 25 ℃ of the fluid temperatures of (A) pigment dispersion, be adjusted into aptly 3.0～100.0mPas, preferred 3.0～20.0mPas.
Then, as (B), containing the alkali soluble resin of unsaturated group, be more appropriately used as the acid adduct of epoxy (methyl) acrylate of the general formula (I) of (A3) composition.In addition, for example replace the epoxy compound being derived by bisphenols, can use phenol phenolic varnish type epoxy compound or cresols phenolic varnish type epoxy compound etc. to there is the compound of 2 above glycidyl ethers, use derivant to change into have as the unsaturated double-bond of photonasty group and bring the alkali soluble resin containing unsaturated group of compound of the acidic functionalities such as carboxyl of alkali-soluble.(B) alkali soluble resin containing unsaturated group can be used alone, but also also mix together two or more.For high shading and high-resistance photosensitive polymer combination, use aptly the composition same with the common dispersion resin (A3) of (A) pigment dispersion.
As the photopolymerization monomer with ethylenic unsaturated bond of (C) composition, for example can enumerate: (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) 2-EHA etc. has (methyl) esters of acrylic acid of hydroxyl, or two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid diglycol ester, two (methyl) acrylic acid triethyleneglycol ester, two (methyl) acrylic acid tetraethylene glycol ester, two (methyl) acrylic acid tetramethylene glycol ester, three (methyl) acrylic acid trihydroxymethylpropanyl ester, three (methyl) acrylic acid trimethylolethane ester, two (methyl) acrylic acid pentaerythritol ester, three (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid dipentaerythritol ester, (methyl) acrylic acid glyceride, five (methyl) acrylic acid sorbitol ester, five (methyl) acrylic acid dipentaerythritol ester, or six (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid sorbitol ester, oxyalkylene modification six (methyl) acrylate of phosphine nitrile, (methyl) esters of acrylic acids such as caprolactone modification six (methyl) acrylic acid dipentaerythritol ester, can be used the one kind or two or more of these materials.In addition, this photopolymerization monomer with ethylenic unsaturated bond is used the monomer that the molecule with the alkali soluble resin containing unsaturated group of 3 above optical polymerism groups can be cross-linked to each other aptly.Be explained, (C) photopolymerization monomer with ethylenic unsaturated bond of composition does not have free carboxyl.
In photosensitive polymer combination of the present invention, containing the mixing ratio (respectively becoming component is the amount of the solid constituent outside desolventizing) of unsaturated group resin ((A3)+(B)) composition and (C) composition with mass ratio ((A3)+(B)): (C) count 20:80～90:10, be preferably 40:60～80:20.When the mixing ratio of ((A3)+(B)) composition is few, solidfied material after photocuring becomes fragile, in addition, and because the acid number of filming in unexposed portion is low, therefore the dissolubility with respect to alkaline developer reduces, and produces the uneven and obtuse problem that becomes of pattern edge.On the contrary, when they are many, in resin, the ratio of shared photoreactivity functional group is few, the formation of crosslinked configuration is insufficient, and then the acid number in resinous principle is too high, with respect to the dissolubility of the alkaline developer in exposure portion, raise, so likely produce the pattern forming, to be compared to the line width of target thin, or damaged and so on the problem of pattern easily occurs.
As the Photoepolymerizationinitiater initiater of (D) composition, can use a kind of above initiating agent.Be explained, in the present invention, said Photoepolymerizationinitiater initiater is used not contain the meaning of sensitizer.
As operable Photoepolymerizationinitiater initiater, for example can enumerate: acetophenone, 2,2-diethoxy acetophenone, to dimethyl acetophenone, to dimethylaminophenyl ethyl ketone, dichloroacetophenone, trichloroacetophenone, the acetophenones such as p-tert.-butyl acetophenone, benzophenone, 2-chlorobenzophenone, p, p '-benzophenones such as bis-dimethylamino benzophenone, benzil, benzoin, benzoin methylether, benzoin iso-propylether, the benzoin ethers such as benzoin isobutyl ether, 2-(Chloro-O-Phenyl)-4,5-phenyl bisglyoxaline, 2-(Chloro-O-Phenyl)-4,5-bis-(m-methoxyphenyl) bisglyoxaline, 2-(adjacent fluorophenyl)-4,5-diphenyl bisglyoxaline, 2-(o-methoxyphenyl)-4,5-diphenyl bisglyoxaline, the bisglyoxaline based compound classes such as 2,4,5-triaryl bisglyoxaline, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(to cyano styrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(to methoxyl-styrene)-1,3, the halomethyl thiazolium compounds classes such as 4-oxadiazole, 2,4,6-tri-(trichloromethyl)-1,3,5-triazines, 2-methyl-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-phenyl-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-chlorphenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-methoxyl naphthyl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-methoxyl-styrene)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(3,4,5-trimethoxy styryl)-4, two (the trichloromethyl)-1,3,5-triazines of 6-, 2-(4-methyl thio phenyl vinyl)-4, two (trichloromethyl)-halomethyl-S-triazine based compound classes such as 1,3,5-triazines of 6-, 1,2-octane diketone, 1-[4-(phenyl sulfo-) phenyl]-, 2-(o-benzoyl oxime), 1-(4-phenyl sulfophenyl phenyl) butane-1,2-diketone-2-oxime-o-benzoate, 1-(4-methyl sulfophenyl phenyl) butane-1,2-diketone-2-oxime-adjacent acetal, 1-(4-methyl sulfophenyl phenyl) butane-1-ketoxime-adjacent acyl group oxime compound classes such as adjacent acetal, benzyl dimethyl ketal, thioxanthones, CTX, 2,4-diethyl thioxanthone, 2-methyl thioxanthones, the sulphur compounds such as ITX, 2-EAQ, prestox anthraquinone, 1,2-benzo anthraquinone, the Anthraquinones such as 2,3-diphenyl anthraquinone, azobis isobutyronitrile, benzoyl peroxide, the organic peroxides such as cumene hydroperoxide thing, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, the mercaptan compounds such as 2-mercaptobenzothiazole, triethanolamine, the tertiary amines such as triethylamine etc.
(D) use amount of composition Photoepolymerizationinitiater initiater take (A3) and (B) containing the alkali soluble resin of unsaturated group and (C) total 100 mass parts of each composition of photopolymerization monomer be benchmark, be 2～60 mass parts, be preferably 10～50 mass parts.(D) when the mixing ratio of composition is few, slack-off and the sensitivity of photopolymerisable speed, on the other hand, when it is too much, sensitivity is excessively strong, pattern lines width becomes thick state with respect to pattern mask, and likely producing cannot faithful reappearance line width for mask, or the uneven and obtuse problem that becomes of pattern edge.
As the solvent of (E) composition, so long as the illustrative solvent of (A4) composition, just can use aptly, can at least contain the solvent identical with (A4) composition.Be explained, also can use solvent of more than two kinds.
Above (A) pigment dispersion of photosensitive polymer combination for black matrix of the present invention, (B) containing the alkali soluble resin of unsaturated group, photopolymerization monomer that (C) has ethylenic unsaturated bond, (D) Photoepolymerizationinitiater initiater and (E) solvent be neccessary composition, but can coordinate as required curing accelerator, thermal polymerization inhibitor, plastifier, packing material, levelling agent, defoamer, spreading agent and the other adjuvants such as surfactant.As thermal polymerization inhibitor, can enumerate p-dihydroxy-benzene, hydroquinone monomethyl ether, 1,2,3,-thrihydroxy-benzene, tert-butyl catechol, phenothiazine etc., as plastifier, can enumerate dibutyl phthalate, dioctyl phthalate, phosphate trimethylbenzene etc., as packing material, can enumerate glass fibre, silicon dioxide, mica, aluminium oxide etc., in addition, as defoamer or levelling agent, can enumerate for example compound of silicon system, fluorine system, acrylic acid series.
Photosensitive polymer combination of the present invention contains above-mentioned (A)～(E) composition as major component, except after the solidifying of desolventizing, in also comprising the solid constituent that becomes the monomer of solid constituent etc., the one-tenth component outside the desolventizing of (A)～each composition (D) contain ideally account for add up to 70 quality % above, be preferably 80 quality %, more preferably more than 90 quality %.The amount of solvent changes according to the viscosity as target, is desirably the scope of 20～90 quality %.Solid constituent can remove desolventizing in 2 hours and measures by the solution of photosensitive polymer combination is heated at 160 ℃.
(A1) containing ratio of the coating dye carbon black of composition can coordinate in the mode becoming in the solid constituent of photosensitive polymer combination more than 40 quality %.Can be preferably 45～60 quality %, the scope of 50～55 quality % more preferably.(A1) when the containing ratio of composition is low, it is insufficient that light-proofness becomes, and in order to obtain desirable contrast, must make thickness thicken, and is difficult to obtain the face flatness of black matrix.On the contrary, (A1) when the containing ratio of composition is high, not only the pigment dispersion of (A) composition but also the dispersion stabilization of photosensitive polymer combination reduce, in addition, likely produce following undesirable problem: the content that becomes the photoresist of bonding agent also reduce, can not give fully development adaptation or with the adaptation of glass substrate, or alkali-soluble is not enough and cannot obtain good developing property.
Of the present invention filming such as by above-mentioned black photoresistance is gone up and is dried in substrate etc. by the solution coat of photosensitive polymer combination, irradiates light (comprising ultraviolet ray, radioactive ray etc.), makes it solidify and obtain.If light-struck part and non-irradiated part are set, only make light-struck partly solidifiedly, other parts are dissolved in aqueous slkali, obtain filming of desired pattern.
Then, to using, there is black photoresistance of the present invention to describe by the manufacture method of the color filter of photosensitive polymer combination.First, on the surface of substrate, black photoresistance is coated to substrate with photosensitive polymer combination, to distinguish the mode of the part that forms pixel, form light shield layer (black matrix).Then, the liquid photosensitive polymer combination (ink) that coating is dispersed with for example red pigment on this substrate afterwards, carries out prebake and makes solvent evaporation, and formation is filmed.Then, after this is filmed and is exposed via photomask, use alkaline-based developer to develop, the unexposed portion that makes to film dissolves and removes, and after carrying out thereafter, cures, and forms thus the pel array that has red pattern of pixels with regulation alignment arrangements.Thereafter, use is dispersed with the ink of the pigment of green or blueness, with above-mentioned red pixel array similarly, carry out the coating of each fluid composition, prebake, exposure, develop and after cure, on same substrate, form successively green pel array and blue pel array, thus by redness, green and blue trichromatic pixel array configuration is on substrate, and then thereon as diaphragm, the fluid composition of photoresist of colorant and similarly above-mentioned will do not contained, be coated with, prebake, exposure, develop and after cure, obtain being formed with the color filter of diaphragm.
When black photoresistance of the present invention is coated to substrate with the fluid composition of photosensitive polymer combination, except known solution dipping method, spray-on process, also can adopt any means such as roll coater, knife type coater, slit coater or spin coater, silk screen print method or ink jet printing method.By these methods, after desired thickness coating, except desolventizing (prebake), form thus tunicle.Prebake is by utilizing heating, vacuum drying or their combination of baking oven, electric hot plate etc. to carry out.Heating-up temperature in prebake and heat time are suitably selected according to the solvent using, for example, at the temperature of 80～120 ℃, carry out 1～10 minute.
When making color filter, as in order to make photosensitive polymer combination exposure, to solidify and the radioactive ray of use, can use such as luminous ray, ultraviolet ray, far ultraviolet, electron beam, X ray etc., optimal wavelength is at the radioactive ray of the scope of 250～450nm.Then, carry out alkali development, as the developer solution that is suitable for alkali development, can enumerate such as the aqueous solution of the carbonate of alkaline metal or earth alkali metal, the aqueous solution of alkali-metal oxyhydroxide etc., particularly can use the weak alkaline aqueous solution of carbonate 0.05～10 quality % such as containing sodium carbonate, sal tartari, lithium carbonate, at the temperature of 20～30 ℃, develop, can use commercially available developing machine or supersonic wave cleaning machine etc. critically to form fine image.Be explained, alkali is washed after developing conventionally.As development treatment method, can be suitable for spray development method, spray development method, immersion development method, oar formula (full liquid) development method etc.Under the preferred normal temperature of development conditions 10～120 seconds.
After developing like this, under the condition of the temperature of 180～250 ℃ and 20～100 minutes, heat-treat (curing afterwards).After this, cure with the objects such as adaptation for filming of improving that pattern forms and substrate and carry out.Itself and prebake similarly, are undertaken by utilizing baking oven, electric hot plate etc. to heat.Filming that pattern of the present invention forms forms through utilizing above photolithographic each operation.
As in formation, have pixel and black matrix color filter time the substrate that uses, can use such as the substrate etc. that is formed with the transparency electrodes such as ITO, gold at glass, the upper evaporation of hyaline membrane (such as polycarbonate, polyethylene terephthalate, polyethersulfone etc.) or pattern.In addition, to these substrates, according to desired, also can implement to utilize the suitable pre-treatment such as medicine processing, Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum evaporation of silane coupling agent etc.
Embodiment
Then, embodiment is shown, black matrix of the present invention is described in further detail by the manufacture method of photosensitive polymer combination and the characteristic of this photosensitive polymer combination, but the present invention is not limited to these embodiment.
[modulation example 1]
Modulation (1) > of < coating dye carbon black
Carbon black (TPX-1099:Cabot company system) 1000g is mixed with water and modulates slurry 10L, at 95 ℃, stir 1 hour, naturally cooling after, wash.It is modulated to slurry 10L with water hybrid processing again, add 70% nitric acid 42.9g, at 40 ℃, stir 4 hours.By it naturally cooling and wash after, then mix with water and modulate slurry 10L, add 13% aqueous sodium hypochlorite solution 769.2g, at 40 ℃, stir 6 hours.By it naturally cooling and wash after, then mix with water and modulate slurry 10L, add dyestuff (the Direct Deep BLACK) 38.1g of purity 38.4%, at 40 ℃, stir 1 hour,, further add aluminium sulphate 10.1g, at 40 ℃, stir 1 hour thereafter.After it is naturally cooling, wash and filtration drying, obtain coating dye carbon black.
The mensuration of carboxyl amount
According to the method for recording in TOHKEMY 2000-248197 communique, the following acidic functionality amount (carboxyl amount) of measuring the coating dye carbon black obtaining.
Weigh coating dye carbon black 10g, in the sodium bicarbonate aqueous solution 50ml of 0.1 equivalent, vibrate 1 hour and make and, after its reaction, filter, take the supernatant 20ml of filtrate, with the aqueous hydrochloric acid solution of 0.01 equivalent, carry out titration.Carboxyl amount, as the mM amount (mmol/g) in carbon black 1g, is obtained according to the following formula.
Carboxyl amount=(50/20 * 0.01 * (titer-empty titer))/carbon black sample mass
The carboxyl amount of the coating dye carbon black obtaining is 53.9mmol/g.
[modulation example 2]
< dyestuff is the modulation > of coated carbon black not
Except not implementing coating dye and processing with aluminium sulphate color lake, roughly similarly process with modulation example 1, obtain the not coated carbon black of dyestuff.
[modulation example 3]
The modulation > of < resin-coating carbon black
In Polyvinylchloride (daily output chemistry (strain) ニ ッ processed サ Application PVC ニ Le (Nissan Vinyl) E-430), add cyclohexanone, be heated to approximately 90 ℃ and make its dissolving, modulate the cyclohexanone solution that contains Polyvinylchloride 10 quality %.On the other hand, carbon black (furnace black, the #3050 processed of Mitsubishi Chemical's (strain)) is mixed to strong stirring, the uniform suspending liquid that modulation contains carbon black 6 quality % with water.Then, on one side by suspension agitation in above-mentioned cyclohexanone solution, add on one side, the carbon black of water is shifted as solvent phase.Then,, after removing the water separated with carbon black by decant, mixing approximately 5 minutes of the roller mill with 2 rollers with being heated to 80～120 ℃, obtains resin combination.Then, utilize warm-up mill that resin combination is cut into sheet, passed into the roller mill with 2 rollers of normal temperature, be crushed to after the size below about 30mm, move in water, with the speed stir about of about 3000rpm 3 minutes, the mode that becomes the shot-like particle of 0.1～3mm with average aggregate particle size was carried out crushing and pelletizing, obtains whole grain thing.This whole grain thing is dried at 80～150 ℃, obtains resin-coating carbon black.
[modulation example 4]
The modulation > of < (A)-1 pigment dispersion of the present invention
With ball mill, coating dye carbon black (A1 composition) 600g obtaining in example 1 will be modulated, BYK-167 (PVC ッ Network ゲ ミ ー ジ ャ パ Application (BYK chemistry Japan) company's system) 93.2g as the polyurethane series spreading agent of A2 composition, propylene glycol methyl ether acetate solution (resin solid constituent concentration=56.5 quality % as the acid adduct of the epoxy acrylate with fluorenes bone lattice of A3 composition, Zhu Jin chemical company of Nippon Steel system " V259ME ") 378g and disperseing as the solvent propylene glycol methyl ether acetate 1328.8g of A4 composition, obtain pigment dispersion of the present invention (A)-1.Average 2 particle diameters of the coating dye carbon black of the pigment dispersion obtaining (A)-1 are 110nm.
[modulation example 5]
< (A)-2 relatively uses the modulation > of pigment dispersion (the not coated carbon black of dyestuff is used)
Replace coating dye carbon black and use the not coated carbon black of the dyestuff obtaining in modulation example 2, in addition, roughly similarly process with modulation example 4, obtain relatively using pigment dispersion (A)-2.
[modulation example 6]
< (A)-3 relatively uses the modulation > of pigment dispersion (use of resin-coating carbon black)
Replace coating dye carbon black and use the resin-coating carbon black obtaining in modulation example 3, in addition, roughly similarly process with modulation example 4, obtain relatively using pigment dispersion (A)-3.
[reference example 7]
< (A)-4 relatively uses the modulation > of pigment dispersion (there is no dispersion resin)
Do not add the propylene glycol methyl ether acetate solution of the acid adduct of the epoxy acrylate with fluorenes bone lattice, making solvent propylene glycol methyl ether acetate is 1706.8g, in addition, roughly similarly process with modulation example 4, obtain relatively using pigment dispersion (A)-4.
[composition of (B) of use～(E) and adjuvant (F)～(G) composition]
< (B)-1 has the alkali soluble resin > containing unsaturated group of general formula (I) structure
The propylene glycol methyl ether acetate solution (resin solid constituent concentration=56.5 quality %, Zhu Jin chemical company of Nippon Steel system " V259ME ") of acid adduct with the epoxy acrylate of fluorenes bone lattice
The alkali soluble resin > containing unsaturated group beyond < (B)-2 general formula (I) structure
The propylene glycol methyl ether acetate solution of N-phenylmaleimide/acrylic acid/styrol copolymer (resin solid constituent concentration=35.5 quality %, N-phenylmaleimide: acrylic acid: styrene=19:22:59 % by mole, weight-average molecular weight 9000, acid number 80)
< (C) has the photopolymerization monomer > of ethylenic unsaturated bond
The potpourri of six acrylic acid dipentaerythritol ester and five acrylic acid dipentaerythritol ester (Japanese chemical drug company's system " KAYARAD-DPHA ")
< (D) Photoepolymerizationinitiater initiater >
Ethyl ketone, 1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl]-1-(0-acetyl group oxime) (BASF AG's system " イ Le ガ キ ュ ア (Irgacure) OXE02 ")
< (E)-1 solvent 1>
Propylene glycol methyl ether acetate
< (E)-2 solvent 2>
Cyclohexanone
< (F) silane coupling agent >
3-methacryloxypropyl trimethoxy silane (chemical company of SHIN-ETSU HANTOTAI system " KBM-503 ")
< (G) surfactant >
メ ガ Off ァ ッ Network (Megafac) F475 (DIC company system)
[embodiment 1]
The modulation > of photosensitive polymer combination for the black matrix of <
Pigment dispersion (A)-1565g, (the B)-143.7g, (C) 25g, (D) 15g and silane coupling agent (F) 2.5g that in modulation example 4, obtain, surfactant (G) 2.0g are mixed equably in solvent (E)-1537.9g, (E)-2752.0g, modulate black matrix photosensitive polymer combination.The gradation composition of this gradation composition and following comparative example is shown in table 1.
[comparative example 1]
Except replacing pigment dispersion (A)-1, use (A)-2, with roughly similarly operation of embodiment 1, modulation ratio is with black matrix photosensitive polymer combination.
[comparative example 2]
Except replacing pigment dispersion (A)-1, use (A)-3, with roughly similarly operation (wherein, gradation composition is as shown in table 1) of embodiment 1, modulation ratio is with black matrix photosensitive polymer combination.
[comparative example 3]
Except replacing using (B)-2 containing the alkali soluble resin (B)-1 of unsaturated group, with roughly similarly operation (wherein, gradation composition is as shown in table 1) of embodiment 1, modulation ratio is with black matrix photosensitive polymer combination.
[comparative example 4]
Except replacing pigment dispersion (A)-1, use (A)-4, roughly similarly operate (wherein, gradation composition is as shown in table 1), modulation ratio with black matrix photosensitive polymer combination with embodiment 1.
[table 1]
* the g number containing unsaturated group resin in the numeric representation pigment dispersion of 1 () and resin solution.
* 2 are set as the ratio containing unsaturated group resin (solid constituent)+monomer=100 o'clock in photosensitive polymer combination.(in (A)+(B) containing unsaturated group resin/(C)).
Shared mass ratio (%) in the solid constituent of light screening material (A1) in * 3 (A) pigment dispersion in photosensitive polymer combination
[evaluation]
The photosensitive polymer combination that uses embodiment 1 and comparative example 1～4, carries out the evaluation of the following stated.These evaluation results are shown in table 2.
The evaluation > of < developing property (pattern lines width pattern rectilinearity resolution)
Use rotary coating machine, by each photosensitive polymer combination obtained above so that after thickness after curing to be that the mode of 1.0 μ m is coated the glass substrate (Corning1737) of 125mm * 125mm upper, at 90 ℃, prebake is 1 minute.Thereafter, exposing clearance is adjusted into 100 μ m, on dry coating, cover the minus photomask of line/space=2 μ m/2 μ m, 4 μ m/4 μ m, 5 μ m/5 μ m, 6 μ m/6 μ m, 8 μ m/8 μ m, 10 μ m/10 μ m and 20 μ m/20 μ m, with i ray illumination 30mW/cm 2extra-high-pressure mercury vapour lamp irradiate 80mJ/cm 2ultraviolet ray, carry out the photocuring reaction of sensitization part.
Then, the coated plate that this is completed to exposure is in 25 ℃, 0.08% potassium hydroxide aqueous solution, with 1kgf/cm 2spray development pressure, from starting to occur the development time (break time=BT) of pattern, behind+10 seconds ,+development of 20 seconds, carry out 5kgf/cm 2the spraying washing of pressure, removes the unexposed portion of filming, and forms pattern of pixels on glass substrate, thereafter, use air drier, after within 230 ℃, 30 minutes, curing after heat, evaluate line width, pattern rectilinearity and resolution with respect to the mask width of 10 μ m lines.Be explained, each evaluation method is as described below.
Pattern lines width: use and survey the pattern lines width that long microscope (ニ コ Application (NIKON) company's system " XD-20 ") is measured mask width 10 μ m.
Pattern rectilinearity: with 10 μ m mask patterns after curing after microscopic examination, by do not see with respect to substrate peel off or the average evaluation of the sawtooth of pattern edge part is zero, by the average evaluation of seeing in a part, be △, by the average evaluation of seeing in integral body, be *.
Resolution: in 2 μ m, 4 μ m, 5 μ m, 6 μ m, 8 μ m, 10 μ m and 20 μ m mask patterns, minimum pattern size residual on substrate is made as to resolution.
[table 2]
The evaluation > of <OD
Use rotary coating machine, by each photosensitive polymer combination obtained above so that after thickness after curing to be that the mode of 1.0 μ m is coated the glass substrate (Corning1737) of 125mm * 125mm upper, at 90 ℃, prebake is 1 minute., exposing clearance be adjusted into 100 μ ms, on dry coating, cover the minus photomask with 15mm * 15mm opening, with i ray illumination 30mW/cm thereafter 2extra-high-pressure mercury vapour lamp irradiate 80mJ/cm 2ultraviolet ray, carry out the photocuring reaction of sensitization part.
Then, the coated plate that this is completed to exposure is in 25 ℃, 0.08% potassium hydroxide aqueous solution, with 1kgf/cm 2spray development pressure, from starting to occur the development time (break time=BT) of pattern, after the development of+20 seconds, carry out 5kgf/cm 2the spraying washing of pressure, removes the unexposed portion of filming, and forms pattern of pixels on glass substrate, thereafter, use air drier, after within 230 ℃, 30 minutes, curing after heat, the OD that uses Macbeth penetrating concentration meter to evaluate in the formed pixel of 15mm * 15mm peristome.
The evaluation > of < surface resistance
Use rotary coating machine, by each photosensitive polymer combination obtained above so that after thickness after curing to be that the mode of 1.0 μ m is coated the glass substrate (Corning1737) of 125mm * 125mm upper, at 90 ℃, prebake is 1 minute.Thereafter, with i ray illumination 30mW/cm 2extra-high-pressure mercury vapour lamp do not have photomask to irradiate 80mJ/cm 2ultraviolet ray, carry out photocuring reaction.Then, the coated plate that this is completed to exposure is in 25 ℃, 0.08% potassium hydroxide aqueous solution, with 1kgf/cm 2spray development pressure, from start to occur the development time (break time=BT) of pattern when covering photomask, after the development of+20 seconds, carry out 5kgf/cm 2the spraying washing of pressure, is used air drier, after within 230 ℃, 30 minutes and 180 minutes, curing after heat, measures surface resistance.
The evaluation > of the adaptation of < and glass substrate
Use rotary coating machine, by each photosensitive polymer combination obtained above so that after thickness after curing to be that the mode of 1.0 μ m is coated the glass substrate (Corning1737) of 125mm * 125mm upper, at 90 ℃, prebake is 1 minute., do not use minus photomask, with i ray illumination 30mW/cm thereafter 2extra-high-pressure mercury vapour lamp, with 80mJ/cm 2carry out blanket exposure, use air drier, at 230 ℃, 30 minutes, after heat, cure.And, to after obtained above, cure substrate, utilize according to the evaluation assessment of 3 closely sealed test methods of bending of JISK6856-1994 the dhering strength of following evaluation and glass substrate.
By curing substrate after above-mentioned and not having the glass substrate (Corning1737) of coating resin composition to cut into respectively the rectangle of 20mm * 63mm, prepare test film.The painting lamina membranacea curing after completing and the glass substrate that there is no photosensitive resin coating composition are bonding agent (ス ト ラ Network ト ボ Application De (Structbond) XN-21s (Mitsui Chemicals system)) and overlapping via a certain amount of sealant epoxy, fit both substrate (test film) of the mode that becomes 8mm with width.Sealant epoxy when this is overlapping is the circle that is shaped as of bonding agent, and diameter is about 5mm., by overlapping test film 90 ℃ at prebake 20 minute, then, 150 ℃ at respectively implement 2 hour after cure, make three point bending test sheet thereafter.And then the glass sheet that there is no coating of 20mm * 63mm also makes by method same as described above the sample that the comparison test of laminating is used each other.
In test film obtained above, mode centered by overlapping part becomes, by coated panel and subtend substrate (uncoated substrate), or the support body supports (length of the supporter of 2 is 3cm) of 2 for the glass substrate that the comparison test that there is no coating is used, from directly over overlapping portion under, use オ リ エ Application テ ッ Network (ORIENTEC) company's system " UCT-100 ", while applying loading with the speed of 1mm/ minute, read the observation of release surface and loading now, it divided by sealant epoxy, is the spreading area of bonding agent, the loading of per unit area is designated as to dhering strength.In addition, under the condition of 121 ℃, 100%RH, 2atm and 5 hours, implement after PCT (pressure cooker test), implement same dhering strength test, evaluate the dhering strength before and after PCT.The glass that there is no painting erosion resistant agent before and after using the dhering strength of each composition as PCT dhering strength is each other made as respectively the relative value of 100 o'clock and represents.To be more than 70 to be made as zero before and after the PCT, by it lower than 70 being made as *.
As shown in Table 2, the black matrix of embodiments of the invention 1 is compared with the photosensitive polymer combination of each comparative example with photosensitive polymer combination, in the developing property of pattern lines width, pattern rectilinearity and resolution, all bring into play excellent performance, simultaneously surface resistance and also excellent with the dhering strength of glass substrate.Particularly, while using the coated carbon black of dyestuff as comparative example 1, although the such developing property of pattern rectilinearity, resolution is no problem, surface resistance and with the adaptation of glass substrate in, can not obtain the characteristic of needs.While using resin-coating carbon black as comparative example 2, meet in the situation of condition of obscurity and surface resistance developing property and insufficient with the dhering strength of glass substrate.As comparative example 3 coordinate with pigment dispersion when using the resin of general formula (I) structure in addition in the alkali soluble resin of unsaturated group, find that developing property is insufficient, the surface resistance after heat treated reduces.As comparative example 4, use when modulation and use and have while the resin of general formula (I) (A3) not being divided into the photosensitive polymer combination of loose pigment dispersion, find that the surface resistance after heat treated reduces.
Industrial applicability
As mentioned above, when black matrix of the present invention is used photosensitive polymer combination with carbon black dispersion for black matrix, can form high resistance and developing property and with the thread pattern of the adaptation excellence of glass substrate, while being applicable to color filter, can make the black matrix that high light-proofness and high resistance and reliability are high.Therefore, be applied to the ink using in the various multicolor displaying bodies such as color liquid crystal display arrangement, colour facsimile, image sensor or optical device etc., and there is the situation of display etc. of color filter, televisor, video monitor or the computing machine of black matrix, be very useful.As using towards the middle-size and small-size fine display of smart mobile phone, be particularly useful.

Claims (15)

1. the manufacture method of photosensitive polymer combination for the black matrix of a color filter, it is characterized in that, after modulation has (A) pigment dispersion of following (A1)～(A4) composition in advance, following by containing (B)～(E) composition mixes with described (A) pigment dispersion as the gradation composition of neccessary composition
(A1) the coating dye carbon black that surface is formed by coating dye,
(A2) spreading agent,
(A3) there is the alkali soluble resin containing unsaturated group of the structure of following general formula (I),
(A4) solvent,
(B) contain the alkali soluble resin of unsaturated group,
(C) there is the photopolymerization monomer of ethylenic unsaturated bond,
(D) Photoepolymerizationinitiater initiater,
(E) solvent,
General formula (I) is for making to have the epoxy compound of 2 glycidyl ethers that derived by bisphenols and (methyl) acrylic acid reactant, and with (a) dicarboxylic acid or tricarboxylic acids or any sour single acid anhydride with (b), tetrabasic carboxylic acid or its acid dianhydride be take (a) and mol ratio (b) is 1:10～10:1 mode are reacted the acid adduct of epoxy (methyl) acrylate obtaining; At this, in formula, R 1, R 2, R 3and R 4the alkyl, halogen atom or the phenyl that represent independently respectively hydrogen atom, carbon number 1～5, R 5represent hydrogen atom or methyl, represent-CO-of A ,-SO 2-,-C (CF 3) 2-,-Si (CH 3) 2-,-CH 2-,-C (CH 3) 2-,-O-, 9,9-fluorenyl or Direct Bonding, X represents the carboxylic acid residues of 4 yuan, Y 1and Y 2represent independently respectively hydrogen atom or-OC-Z-(COOH) m, wherein Z represents 2 yuan or 3 yuan of carboxylic acid residues, and m represents 1～2 number, and n represents 1～20 integer.
2. the black matrix photosensitive polymer combination of color filter, it is characterized in that, following by having (A1)～(A4) composition and in advance (A) pigment dispersion of modulation with contain that following (B)～(E) composition mixes as the gradation composition of neccessary composition
(A1) the coating dye carbon black that surface is formed by coating dye,
(A2) spreading agent,
(A3) there is the alkali soluble resin containing unsaturated group of the structure of following general formula (I),
(A4) solvent,
(B) contain the alkali soluble resin of unsaturated group,
(C) there is the photopolymerization monomer of ethylenic unsaturated bond,
(D) Photoepolymerizationinitiater initiater,
(E) solvent,
General formula (I) is for making to have the epoxy compound of 2 glycidyl ethers that derived by bisphenols and (methyl) acrylic acid reactant, and with (a) dicarboxylic acid or tricarboxylic acids or any sour single acid anhydride with (b), tetrabasic carboxylic acid or its acid dianhydride be take (a) and mol ratio (b) is 1:10～10:1 mode are reacted the acid adduct of epoxy (methyl) acrylate obtaining; At this, in formula, R 1, R 2, R 3and R 4the alkyl, halogen atom or the phenyl that represent independently respectively hydrogen atom, carbon number 1～5, R 5represent hydrogen atom or methyl, represent-CO-of A ,-SO 2-,-C (CF 3) 2-,-Si (CH 3) 2-,-CH 2-,-C (CH 3) 2-,-O-, 9,9-fluorenyl or Direct Bonding, X represents the carboxylic acid residues of 4 yuan, Y 1and Y 2represent independently respectively hydrogen atom or-OC-Z-(COOH) m, wherein Z represents 2 yuan or 3 yuan of carboxylic acid residues, and m represents 1～2 number, and n represents 1～20 integer.
3. the black matrix photosensitive polymer combination of color filter according to claim 2, wherein the containing ratio of the dyestuff of (A1) coating dye carbon black is 0.5～10 quality %.
4. according to the black matrix photosensitive polymer combination of the color filter described in claim 2 or 3, the dyestuff of wherein said coating dye carbon black is the dyestuff of anionic property or nonionic.
5. according to the black matrix photosensitive polymer combination of the color filter described in any one in claim 2～4, the dyestuff of wherein said coating dye carbon black is the dyestuff of dark system.
6. according to the black matrix photosensitive polymer combination of the color filter described in any one in claim 2～5, the dyestuff of wherein said coating dye carbon black is by metal or slaine color lake.
7. the black matrix photosensitive polymer combination of color filter according to claim 6, wherein said metal or slaine are aluminium, magnesium, calcium, strontium, barium or manganese or their salt.
8. according to the black matrix photosensitive polymer combination of the color filter described in any one in claim 2～7, the carbon black that wherein said coating dye carbon black is used surface to have at least a kind of acidic functionality obtains.
9. according to the black matrix photosensitive polymer combination of the color filter described in any one in claim 2～8, wherein said acidic functionality is hydroxyl, oxo base, hydroperoxy, carbonyl, carboxyl, peroxycarboxylic acid base, aldehyde radical, ketone group, nitro, nitroso-, amide group, imide, sulfonic group, sulfinic acid base, sulfenic groups, thiocarboxylic acid base, sub-chlorine acyl group, chloryl, crosses chlorine acyl group, idous acyl group or iodoxy.
10. according to the black matrix photosensitive polymer combination of the color filter described in any one in claim 2～9, wherein (A3) is 2～20 quality % containing the use level of the alkali soluble resin of unsaturated group.
11. according to the black matrix photosensitive polymer combination of the color filter described in any one in claim 2～10, and wherein the use level of (A1) coating dye carbon black in the solid constituent of photosensitive polymer combination is 45～60 quality %.
12. according to the color filter photosensitive polymer combination described in any one in claim 2～11, wherein at least a portion of (B) composition basic resin containing unsaturated group that described general formula (I) represents of serving as reasons.
Film for 13. 1 kinds, it is to make to be solidified to form with photosensitive polymer combination according to the black matrix of the color filter described in claim 2～12.
14. 1 kinds of black matrixes, it is by according to after photosensitive polymer combination coating for the black matrix described in claim 2～12, masking, makes the position of selecting carry out photocuring, with alkaline developer, develops and obtains.
15. 1 kinds of color filters, it is that black matrix according to claim 14 forms.
CN201380011626.6A 2012-02-29 2013-02-26 Black matrix photosensitive polymer combination and its manufacture method Active CN104145196B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012044105 2012-02-29
JP2012-044105 2012-02-29
PCT/JP2013/054970 WO2013129403A1 (en) 2012-02-29 2013-02-26 Photosensitive resin composition for black matrix, and method for producing same

Publications (2)

Publication Number Publication Date
CN104145196A true CN104145196A (en) 2014-11-12
CN104145196B CN104145196B (en) 2017-06-09

Family

ID=49082600

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380011626.6A Active CN104145196B (en) 2012-02-29 2013-02-26 Black matrix photosensitive polymer combination and its manufacture method

Country Status (5)

Country Link
JP (1) JP6426469B2 (en)
KR (1) KR102001628B1 (en)
CN (1) CN104145196B (en)
TW (1) TWI585527B (en)
WO (1) WO2013129403A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105629660A (en) * 2014-11-25 2016-06-01 奇美实业股份有限公司 Photosensitive resin composition for black matrix and application thereof
CN105717742A (en) * 2014-12-19 2016-06-29 奇美实业股份有限公司 Photosensitive resin composition and application thereof
CN107121522A (en) * 2017-06-06 2017-09-01 深圳市华星光电技术有限公司 A kind of method for detecting photoresistance acid-base value
CN108445713A (en) * 2017-02-16 2018-08-24 三星Sdi株式会社 Photosensitive polymer combination defines layer and display device using its black picture element
CN108475012A (en) * 2015-12-24 2018-08-31 三菱化学株式会社 Photosensitive coloring composition, solidfied material, coloring spacer, image display device
CN114156329A (en) * 2021-11-30 2022-03-08 武汉华星光电半导体显示技术有限公司 Display panel, manufacturing method thereof and display device

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014002374A (en) * 2012-05-25 2014-01-09 Nippon Steel & Sumikin Chemical Co Ltd Photosensitive resin composition containing silica sol and cured product using the same
JP5991040B2 (en) * 2012-06-22 2016-09-14 凸版印刷株式会社 Black photosensitive resin composition, black matrix and color filter
JP6365118B2 (en) * 2013-09-20 2018-08-01 三菱ケミカル株式会社 Photosensitive resin composition, cured product obtained by curing it, black matrix, and image display device
JP6375236B2 (en) * 2014-02-04 2018-08-15 新日鉄住金化学株式会社 Photosensitive composition for light shielding film and cured product thereof
JP6708365B2 (en) * 2014-03-07 2020-06-10 日鉄ケミカル＆マテリアル株式会社 Black photosensitive resin composition for light-shielding film, cured product using the same, and color filter and touch panel using the cured product as a light-shielding film
CN103923498B (en) * 2014-04-10 2016-06-22 京东方科技集团股份有限公司 Form the compositions of black matrix, black matrix, display base plate and method of modifying
KR101735917B1 (en) * 2014-06-03 2017-05-15 주식회사 엘지화학 An ink composition for marking on release treatment surface and protective film having the same
JP6713746B2 (en) * 2015-10-08 2020-06-24 日鉄ケミカル＆マテリアル株式会社 Photosensitive resin composition for light-shielding film having spacer function, light-shielding film, liquid crystal display device, method for producing photosensitive resin composition for light-shielding film having spacer function, method for producing light-shielding film, and production of liquid crystal display device Method
JP6630222B2 (en) * 2016-04-08 2020-01-15 富士フイルム株式会社 Transfer film, decorative material, touch panel, and method of manufacturing decorative material
JP6838866B2 (en) * 2016-04-28 2021-03-03 東京応化工業株式会社 Photosensitive resin composition
US20200319549A1 (en) * 2017-09-29 2020-10-08 Toray Industries, Inc. Photosensitive resin composition, cured film, element having cured film, organic el display, and method for manufacturing organic el display
US10921709B2 (en) 2018-02-06 2021-02-16 Samsung Sdi Co., Ltd. Photosensitive resin composition, photosensitive resin layer using the same, and color filter
KR102154680B1 (en) 2018-07-02 2020-09-10 삼성에스디아이 주식회사 Curable composition including quantum dot, resin layer using the same and display device
CN109739068B (en) * 2018-12-27 2022-03-25 北京欣奕华材料科技有限公司 Carbon black dispersion, photosensitive resin composition, color filter, and display device
JP7368162B2 (en) * 2019-09-30 2023-10-24 日鉄ケミカル＆マテリアル株式会社 Polymerizable unsaturated group-containing alkali-soluble resin, method for producing the same, photosensitive resin composition, and cured film thereof.
CN112538157A (en) * 2019-09-20 2021-03-23 日铁化学材料株式会社 Epoxy acrylate resin, alkali-soluble resin and method for producing the same, curable and photosensitive resin composition and cured product thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004224950A (en) * 2003-01-24 2004-08-12 Toyo Ink Mfg Co Ltd Process for preparing composite carbon black
JP2006126387A (en) * 2004-10-28 2006-05-18 Toda Kogyo Corp Black coloring material for black matrix, black composition for black matrix, black matrix and color filter
CN1912755A (en) * 2005-08-01 2007-02-14 佳能株式会社 Toner
TW200804875A (en) * 2006-06-01 2008-01-16 Nippon Steel Chemical Co Resist composition for color filter, method for making such composition and color filter using such composition
JP2009181040A (en) * 2008-01-31 2009-08-13 Fuji Xerox Co Ltd Water-based light-shielding coating composition for display device, insulating light-shielding film for display device, and display device
CN102585546A (en) * 2011-12-30 2012-07-18 山东宇虹颜料有限公司 Preparation method for C.I. pigment red 53:1

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4871237A (en) * 1971-12-24 1973-09-27
JP3515841B2 (en) * 1995-05-11 2004-04-05 御国色素株式会社 Liquid crystal panel composition
AUPN728595A0 (en) * 1995-12-21 1996-01-18 Tonejet Corporation Pty Ltd Method of preparation of inks
JP3356932B2 (en) * 1996-07-24 2002-12-16 シャープ株式会社 Color filter, manufacturing method thereof and liquid crystal display device
JP3861508B2 (en) * 1999-04-28 2006-12-20 東洋インキ製造株式会社 Aqueous pigment dispersion and ink jet recording liquid
JP3781616B2 (en) * 1999-08-27 2006-05-31 三菱化学株式会社 High resistance carbon black and color filter
JP2004198717A (en) * 2002-12-18 2004-07-15 Showa Denko Kk Color filter black matrix resist composition and carbon black dispersed liquid composition used for same composition
JP4464081B2 (en) * 2003-06-27 2010-05-19 東海カーボン株式会社 Carbon black pigment for black matrix
JP2005222631A (en) * 2004-02-06 2005-08-18 Toyo Ink Mfg Co Ltd Coating material to form non-magnetic layer and coating material to form back layer on magnetic recording medium
US7090962B2 (en) * 2004-12-03 2006-08-15 Industrial Technology Research Institute Alkali-soluble resin with polyaromatic group and photosensitive composition comprising the resin
JP5255783B2 (en) * 2006-06-01 2013-08-07 新日鉄住金化学株式会社 Resist composition for color filter, method for producing the same, and color filter using the same
JP2008003299A (en) * 2006-06-22 2008-01-10 Tokyo Ohka Kogyo Co Ltd Colored photosensitive resin composition
CN102436142B (en) * 2010-09-29 2013-11-06 第一毛织株式会社 Black photosensitive resin composition and light blocking layer using the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004224950A (en) * 2003-01-24 2004-08-12 Toyo Ink Mfg Co Ltd Process for preparing composite carbon black
JP2006126387A (en) * 2004-10-28 2006-05-18 Toda Kogyo Corp Black coloring material for black matrix, black composition for black matrix, black matrix and color filter
CN1912755A (en) * 2005-08-01 2007-02-14 佳能株式会社 Toner
TW200804875A (en) * 2006-06-01 2008-01-16 Nippon Steel Chemical Co Resist composition for color filter, method for making such composition and color filter using such composition
JP2009181040A (en) * 2008-01-31 2009-08-13 Fuji Xerox Co Ltd Water-based light-shielding coating composition for display device, insulating light-shielding film for display device, and display device
CN102585546A (en) * 2011-12-30 2012-07-18 山东宇虹颜料有限公司 Preparation method for C.I. pigment red 53:1

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105629660A (en) * 2014-11-25 2016-06-01 奇美实业股份有限公司 Photosensitive resin composition for black matrix and application thereof
CN105717742A (en) * 2014-12-19 2016-06-29 奇美实业股份有限公司 Photosensitive resin composition and application thereof
CN108475012A (en) * 2015-12-24 2018-08-31 三菱化学株式会社 Photosensitive coloring composition, solidfied material, coloring spacer, image display device
CN108475012B (en) * 2015-12-24 2022-07-15 三菱化学株式会社 Photosensitive coloring composition, cured product, coloring spacer and image display device
CN108445713A (en) * 2017-02-16 2018-08-24 三星Sdi株式会社 Photosensitive polymer combination defines layer and display device using its black picture element
CN108445713B (en) * 2017-02-16 2021-10-15 三星Sdi株式会社 Photosensitive resin composition, black pixel defining layer using same, and display device
CN107121522A (en) * 2017-06-06 2017-09-01 深圳市华星光电技术有限公司 A kind of method for detecting photoresistance acid-base value
CN114156329A (en) * 2021-11-30 2022-03-08 武汉华星光电半导体显示技术有限公司 Display panel, manufacturing method thereof and display device

Also Published As

Publication number Publication date
TWI585527B (en) 2017-06-01
JPWO2013129403A1 (en) 2015-07-30
TW201346444A (en) 2013-11-16
WO2013129403A1 (en) 2013-09-06
KR102001628B1 (en) 2019-07-18
CN104145196B (en) 2017-06-09
JP6426469B2 (en) 2018-11-21
KR20140130216A (en) 2014-11-07

Similar Documents

Publication Publication Date Title
CN104145196A (en) Photosensitive resin composition for black matrix, and method for producing same
TWI719016B (en) Colored photosensitive resin composition, color filter, and image display apparatus comprising the same
KR101302508B1 (en) Negative photosensitive resin composition, liquid crystal display having that curing product, method of forming a pattern of liquid crystal display using the same
JP5647279B2 (en) Colorant dispersion, method for producing colorant dispersion, colored resin composition for color filter, color filter, liquid crystal display device, and organic light emitting display device
CN103376658B (en) Radioactivity-sensitive coloured composition, colored filter and display element
CN104254790B (en) Black matrix&#34; carbon black dispersion
JP6641468B2 (en) Fluorene-containing oxime esters photoinitiators, their synthesis, photosensitive resin compositions containing them and their use
TW201734144A (en) Colored photosensitive resin composition, color filter and method for manufacturing the same, and image display device which is composed of colorant, resin, photopolymerization compound, photopolymerization initiator, polyfunctional thiol compound or organic silicon compound and solvent
JP5895925B2 (en) Non-aqueous dispersant, color material dispersion for color filter, color filter, liquid crystal display device and organic light emitting display device
JP6725663B2 (en) Fluorene-type polyfunctional photoinitiator, production and use thereof, photosensitive resin composition containing fluorene-type photoinitiator and use thereof
CN102445847A (en) Colored photosensitive resin composition, color filter and liquid crystal display
CN103509151A (en) Alkali soluble resin and photosensitive resin composition containing the same
CN103221849B (en) The manufacture method of color filter, display element and color filter
CN101943863B (en) Photosensitive resin composition for black resist, and light shielding film of color filter
JP4255299B2 (en) Pigment dispersion composition, ionizing radiation curing resin composition, color filter and liquid crystal display device
CN103969949A (en) Colored Photosensitive Resin Composition
CN103019031A (en) A photosensitive resin composition, and a coating film and color filter using the composition
CN104678705A (en) Red photosensitive resin composition for color filter and application thereof
JP3938896B2 (en) Maleimide-based alkali-soluble copolymer, ionizing radiation curing resin composition, color filter, and liquid crystal display device
JP4050121B2 (en) Maleimide-based alkali-soluble copolymer, ionizing radiation curing resin composition, color filter, and liquid crystal display device
JP4210549B2 (en) Pigment dispersion composition, photosensitive coloring composition, color filter, and liquid crystal display device
JP4301716B2 (en) Color filter composition and color filter
JP2007233230A (en) Photosensitive black composition and color filter
JP3752925B2 (en) Color liquid crystal display
JP6091198B2 (en) Photosensitive resin composition, color filter, liquid crystal display device, and organic light emitting display device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20191212

Address after: No.13-1, No.1, No.1, No

Patentee after: Nippon Iron Chemical Materials Co., Ltd.

Address before: Tokyo, Japan

Patentee before: Nippon Steel Chemical Co.