CN103454858B - Color filter photosensitive coloring composition and color filter - Google Patents

Color filter photosensitive coloring composition and color filter Download PDF

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Publication number
CN103454858B
CN103454858B CN201310308253.0A CN201310308253A CN103454858B CN 103454858 B CN103454858 B CN 103454858B CN 201310308253 A CN201310308253 A CN 201310308253A CN 103454858 B CN103454858 B CN 103454858B
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component units
methyl
precursor
weight
general formula
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CN103454858A (en
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二井洋文
宫川章乃
村木修一
北野原光子
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Artience Co Ltd
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Toyo Ink SC Holdings Co Ltd
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Priority claimed from JP2008131769A external-priority patent/JP5124341B2/en
Priority claimed from JP2008131768A external-priority patent/JP5047057B2/en
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    • 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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Abstract

The invention provides a kind of color filter photosensitive coloring composition and color filter.Described color filter photosensitive coloring composition contains resin, colorant, Photoepolymerizationinitiater initiater, polymerizable monomer and solvent.Described resin is the Component units (a) represented by following general formula (1), the Component units (b) with carboxyl and the vinyl polymers formed except the Component units (c) except Component units (a) and Component units (b), in general formula (1), R 1for hydrogen atom or methyl, R 2the alkylidene of to be carbon number be 2 or 3, R 3for hydrogen atom, the carbon number maybe can with phenyl ring are the alkyl of 1 ~ 20, l is the integer of 1 ~ 15.General formula (1):

Description

Color filter photosensitive coloring composition and color filter
The Chinese application number that the application is the applying date is on May 20th, 2009, denomination of invention is " color filter photosensitive coloring composition and color filter " is the divisional application of 200910141090.5.
Technical field
The present invention relates to the photosensitive coloring composition used in the manufacture of color filter and this color filter used in color liquid crystal display arrangement, colour pick-up tube element etc.
Background technology
In recent years, liquid crystal indicator is applied in television monitor purposes, PC monitor purposes, mobile office purposes etc., as wherein used color filter, widely uses pigment-dispersing type color filter.When making paints decentralized color filter, widely use following photoetching process: use spreading agent, solvent etc. to make pigment disperse in resin (acryl resin etc.) and obtain coloured composition, photopolymerization monomer and polymerization initiator is added to carry out photonasty in this coloured composition, gained photosensitive coloring composition is coated on the transparent supporting bodies such as glass substrate, form the painted film such as dyed layer and light shield layer, thus carry out Butut.Through the film of Butut in order to give the patience in operation below, toast after carrying out under the high temperature more than 200 DEG C.
In addition, along with the widespread use of liquid crystal indicator product, expect declining to a great extent of product price.Accompany therewith, the cost degradation of color filter becomes problem in recent years.Recently, as one of the effective and easy means of cost degradation, carry out following trial: by being carried out renovating to recycle (being designated as below " reprocessing ") by the glass substrate with the painted film after creating bad rear baking, thus the waste of the glass substrate that proportion is maximum in the fee of material of color filter is reduced (" can reprocess efficiently " being designated as " re-workability is good " below).
As the means of reprocessing, have following method: using as color filter through Butut and after the painted film rework solution of baking strip down from glass substrate, thus again become and be coated with the state before photosensitive coloring composition on the glass substrate.Film on glass substrate after rear baking has high thermotolerance and solvent resistance, as the rework solution for reprocessing, generally must use the strong alkali solution of high temperature, high concentration.When reprocessing, not only the painted film of the color filter after baking after Butut to be stripped down from glass substrate, and in order to prevent the rework solution blocking filter recycled via the filter trapping stripping film, need stripping film to become fine.
Patent Document 1 discloses a kind of containing there is carboxyl and not there is the photosensitive coloring composition of the resin of hydroxyl.By using this resin, above-mentioned re-workability becomes good.But the pigment dispersion stability of the photosensitive coloring composition containing this resin is low, and long-term storing stability is insufficient.
Patent Document 2 discloses a kind of photosensitive coloring composition, wherein, in order to improve the long-term storing stability of photosensitive coloring composition, employing the resin at side chain or end with the alkylidene that instead of phenyl ring.Said composition, by the π electron effect of phenyl ring, becomes good to the absorption of surface of pigments, orientation, demonstrates excellent pigment-dispersing.But, when photosensitive coloring composition containing this resin toasts after after Butut, due to the impact of heat curing reaction, how the film of the color filter after Butut after baking is peeled off to get off yet, even if or peel off, also be that stripping film is present in rework solution with larger bulk, therefore can cause the blocking of filter, generation reprocessing is bad.
Even by above-mentioned re-workability good but the dispersion stabilization of the resin of the dispersion stabilization difference of pigment and pigment good but the resin of re-workability difference carries out the photosensitive coloring composition be obtained by mixing when, re-workability is also insufficient.
Patent documentation 1: Japanese Unexamined Patent Publication 10-171119 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2004-101728 publication
Summary of the invention
The object of the present invention is to provide and have excellent re-workability and long-term storing stability concurrently and the photosensitive coloring composition of the key propertys such as developability can not be damaged and possess the color filter of filter section and/or the black matrix" using this photosensitive coloring composition to be formed.
Above-mentioned purpose is achieved by following photosensitive coloring composition, this photosensitive coloring composition contains resin, colorant, Photoepolymerizationinitiater initiater, polymerizable monomer and solvent, it is characterized in that, described resin is the Component units (a) represented by following general formula (1), the Component units (b) with carboxyl and the vinyl polymers formed except the Component units (c) except above-mentioned Component units (a) and Component units (b).
General formula (1):
(in general formula (1), R 1for hydrogen atom or methyl, R 2the alkylidene of to be carbon number be 2 or 3, R 3for hydrogen atom, the carbon number maybe can with phenyl ring are the alkyl of 1 ~ 20, l is the integer of 1 ~ 15.）
In addition, in optimal way of the present invention, the Component units (b1) that above-mentioned Component units (b) represents for following general formula (2) and/or following Component units (b2), described Component units (b2) is Component units (d) addition that unsaturated monoacid and following general formula (5) are represented and the Component units making multi-anhydride and the hydroxyl addition generated and obtain.
General formula (2):
(in general formula (2), R 4for hydrogen atom or methyl, X 1for the group that following general formula (3) represents, Y 1for the group that following general formula (4) represents.）
General formula (3):
(in general formula (3), R 5to be carbon number be 2 ~ 12 alkylidene, m is the integer of 1 or 2.）
General formula (4):
(in general formula (4), R 6for main chain has 2 ~ 20 carbon atoms alkylidene, there is the cycloalkylidene of 6 ~ 8 ring carbon atoms or there is the arlydene of 6 ~ 14 ring carbon atoms, n is the integer of 0 or 1.）
General formula (5):
(in general formula (5), R 7for hydrogen atom or methyl, R 8for glycidyl, methylglycidyl, 3,2-glycidoxypropyl ethyls, 3,4-epoxycyclohexyls, 3,4-epoxybutyl or 4,5-epoxypentyl.）
In addition, in optimal way of the present invention, above-mentioned Component units (c) is the Component units without hydroxyl.
In addition, in optimal way of the present invention, above-mentioned resin is the vinyl based copolymer precursor of the Component units (a) of 1 ~ 35 % by weight (a '), the precursor (b ') of Component units (b) of 10 ~ 90 % by weight and the precursor (c ') of the Component units (c) of 1 ~ 75 % by weight being carried out copolymerization.
In addition, in optimal way of the present invention, above-mentioned resin makes unsaturated monoacid and the addition of vinyl based copolymer, then makes multi-anhydride and the hydroxyl addition generated and the resin that obtains, and described vinyl based copolymer is that the precursor of the Component units (a) of 1 ~ 35 % by weight (a '), the precursor (d ') of Component units (d) of 4 ~ 75 % by weight and the precursor (c ') of the Component units (c) of 1 ~ 75 % by weight are carried out copolymerization.
In addition, in optimal way of the present invention, the oxirane of the precursor of above-mentioned Component units (a) (a ') containing p-cumylphenol and/or epoxy pronane modification (methyl) acrylate.
In addition, in optimal way of the present invention, and the precursor of above-mentioned Component units (c) (c ') containing (methyl) alkyl acrylate.
In addition, in optimal way of the present invention, the precursor of above-mentioned Component units (c) (c ') is containing (methyl) benzyl acrylate and/or (methyl) acrylic acid bicyclopentyl ester and/or (methyl) acrylic acid dicyclopentenyl ester and/or (methyl) acrylic acid cyclopentyloxy ethyl ester.
In addition, the invention provides a kind of color filter, it is characterized in that, it possesses the filter section and/or black matrix" that are formed by photosensitive coloring composition of the present invention.
The photosensitive coloring composition of the re-workability excellence of the application of the invention, can make the waste of glass substrate in color filter manufacture be reduced, and can obtain color filter at a low price.
Embodiment
Photosensitive coloring composition of the present invention contains resin, colorant, Photoepolymerizationinitiater initiater, polymerizable monomer and solvent.Below each composition is described in detail.In addition, in the present specification and claims, term " (methyl) acrylic acid ", " (methyl) acrylate " and " (methyl) acryloxy " refer to " acrylic acid and/or methacrylic acid ", " acrylate and/or methacrylate " and " acryloxy and/or methacryloxy " respectively.Similarly, term " (methyl) acrylamide " refers to " acrylamide and/or Methacrylamide ".
< resin >
Resin contained in photosensitive coloring composition of the present invention is the Component units (a) represented by following general formula (1), the Component units (b) with carboxyl and the vinyl polymers formed with the Component units (c) except (b) except Component units (a).Component units (a) plays function as solvent compatibility position, Component units (b) plays function as pigment adsorption position and alkali-soluble position, and Component units (c) is for obtaining the physical property as painted film and required Component units that only cannot realize by Component units (a) and Component units (b).
General formula (1):
In general formula (1), R 1for hydrogen atom or methyl, R 2the alkylidene of to be carbon number be 2 or 3, R 3for hydrogen atom, the carbon number maybe can with phenyl ring are the alkyl of 1 ~ 20, l is the integer of 1 ~ 15.
Use the resin meeting following characteristic in the present invention.
(1) dispersed
The aggegation of the pigment as colorant in coloured composition can be prevented, and can maintain the state of pigment fine dispersion for a long time.
(2) developability
Unexposed portion can be only removed with (alkalescence) developer solution when developing.
(3) re-workability
Can with the painted film after baking after the removing of (strong basicity) rework solution, and the stripping film of painted film can not be made to become thick.
In order to meet all above-mentioned characteristics, it is important for carrying out resin design as follows, namely, make Component units (a), Component units (b) and Component units (c) balance coexist well, be maintained as the dispersion stabilization of the pigment of colorant, and, when developing, (alkalescence) developer solution only soaks into unexposed portion, only make unexposed portion swelling, react with the carboxyl in unexposed portion, thus a part becomes solvable and removes, when reprocessing, (strong basicity) rework solution soaks into exposure portion, make exposure portion swelling, react with carboxyl, thus a part becomes solvable and removes.
In addition, consider that the balance of Component units (a), Component units (b) and Component units (c) designs in the film the removed mode flowed out in developer solution and rework solution as far as possible more carefully, this is also important from production efficiency aspect.
Component units (a) shown in mutual-through type (1) is described below.
The alkylene moiety with the pi-electron of side-chain benzene ring in Component units (a) with the side chain of moderate length plays a role effectively as solvent compatibility position.Side-chain benzene ring orientation in as the pigment of colorant, therefore also has and promotes the resin adsorption in pigment and the effect suppressing pigment aggegation.Thus, high storage stability can be maintained by the dispersion that the resin with Component units (a) has carried out surface-treated pigment.
In addition, if Component units (a) plays a role as surface of pigments adsorption site when pigment disperses, the Component units (b) with carboxyl when developing or reprocessing time and alkali react and become alkali-soluble position, then correspondingly, Component units (a) plays function as the position of non-alkali-soluble, therefore want the water wettability of part that removes and hydrophobic balance good, and easily become fine platy.
In general formula (1), R 3the carbon number of alkyl be 1 ~ 20, be more preferably 1 ~ 10.Alkyl not only comprises straight-chain alkyl, and comprises branched-chain alkyl and have the alkyl of phenyl ring alternatively base.R 3the carbon number of alkyl when being 1 ~ 10, it is close with what suppress between resin that alkyl becomes steric hindrance, thus promote the absorption/orientation to pigment, if carbon number is more than 10, then the sterically hindered effect of alkyl improves, and demonstrates and also hampers the tendency of phenyl ring to the absorption/orientation of pigment.This tendency is along with R 3alkyl carbon chain lengths increase and become remarkable, if carbon number is more than 20, then absorption/the orientation of phenyl ring becomes extremely low.As R 3the shown alkyl with phenyl ring, can list benzyl, 2-phenyl (different) propyl group etc.By increasing a side-chain benzene ring, solvent compatibility and pigment orientation improve further, and the dispersiveness not only as the pigment of colorant improves, and developability and re-workability also improve.
As the precursor (a ') of Component units (a), oxirane (EO) modification (methyl) acrylate of phenol, the EO of p-cumylphenol or epoxypropane (PO) modification (methyl) acrylate, EO modification (methyl) acrylate of nonyl phenol, PO modification (methyl) acrylate etc. of nonyl phenol can be listed.Precursor (a ') is not limited to above-mentioned example, and can be used alone or two or more is also used.In precursor (a '), EO or PO modification (methyl) acrylate of most preferably p-cumylphenol, because the π electron effect of above-mentioned phenyl ring wherein adds its stereoeffect, can form better absorption/oriented surface to pigment.
Below, Component units (b) is described.
The Component units (b) with carboxyl plays a role as pigment adsorption group when the pigment dispersion as colorant, alkali-soluble group when developing as unexposed portion plays a role, and the highly basic soluble groups when reprocessing as exposed portion plays a role.
As the precursor (b ') of Component units (b) with carboxyl, unsaturated dicarboxylic acid or its acid anhydrides etc. such as (methyl) acrylic acid, crotonic acid, α-chloro-acrylicacid, maleic acid, maleic anhydride, fumaric acid can be listed containing carboxyl and there is the compound etc. of ethylenic unsaturated double-bond.
As the Component units (b) with carboxyl, the particularly preferably Component units (b1) that represents of following general formula (2) and/or following Component units (b2), described Component units (b2) is Component units (d) addition that unsaturated monoacid and following general formula (5) are represented and the Component units making multi-anhydride and the hydroxyl addition generated and obtain.Component units (b1) is by carrying out copolymerization by its precursor (b1 ') and other precursor and obtaining, and Component units (d) is by carrying out copolymerization by its precursor (d ') and other precursor and obtain.
General formula (2):
(in general formula (2), R 4for hydrogen atom or methyl, X 1for the group that following general formula (3) represents, Y 1for the group that following general formula (4) represents.）
General formula (3):
(in general formula (3), R 5to be carbon number be 2 ~ 12 alkylidene, m is the integer of 1 or 2.）
General formula (4):
(in general formula (4), R 6for main chain has 2 ~ 20 carbon atoms alkylidene, there is the cycloalkylidene of 6 ~ 8 ring carbon atoms or there is the arlydene of 6 ~ 14 ring carbon atoms, n is the integer of 0 or 1.）
General formula (5):
(in general formula (5), R 7for hydrogen atom or methyl, R 8for glycidyl, methylglycidyl, 3,2-glycidoxypropyl ethyls, 3,4-epoxycyclohexyls, 3,4-epoxybutyl or 4,5-epoxypentyl.）
In general formula (3), as R 5the carbon number represented is the concrete example of the alkylidene of 2 ~ 12, such as, can list-CH 2-CH 2-,-CH 2-CH (CH 3)-,-CH (CH 3)-CH 2-,-(CH 2) 5-,-CH 2-CH 2-CH 2-,-CH 2-CH 2-CH (CH 3)-,-CH 2-CH 2-C (CH 3) 2-,-CH (CH 3)-CH 2-CH 2-,-CH (CH 2cH 3)-CH 2-CH 2-,-CH (CH 2cH 3cH 3)-CH 2-CH 2-,-CH (CH 3)-CH 2-CH 2-CH 2-,-CH (CH 2cH 3)-CH 2-CH 2-CH 2-,-CH (CH 2cH 2cH 3)-CH 2-CH 2-CH 2-,-CH [(CH 2) 5cH 3]-(CH 2) 10-etc.
In general formula (4), R 6it is alkylidene main chain (the straight line position by the carbonylic carbon atom bonding in the carbonylic carbon atom in formula (4) and formula (2)) with 2 ~ 20 carbon atoms, or there is the cycloalkylidene of 6 ~ 8 ring carbon atoms, or there is the arlydene of 6 ~ 14 ring carbon atoms.Wherein, for alkylidene main chain with 2 ~ 20 carbon atoms, as side chain substituents, alkyl, alkenyl, naphthenic base, cycloalkenyl group, dialkyl group, alkynyl, alkynyl phenyl, alkynyl allyl, aromatic substituents, nitro, halogen etc. can be had; For there is the cycloalkylidene of 6 ~ 8 ring carbon atoms and there is the arlydene of 6 ~ 14 ring carbon atoms, alternatively base, can have alkyl, alkenyl, naphthenic base, cycloalkenyl group, dialkyl group, alkynyl, alkynyl phenyl, alkynyl allyl, aromatic substituents, nitro, halogen etc.
As alkylidene main chain with 2 ~ 20 carbon atoms, such as ,-CH can be listed 2-CH 2-,-CH 2-CH 2-CH 2-,-CH 2-CH (CH 3)-,-CH 2-CH 2-CH 2-CH 2-,-CH 2-CH 2-CH (CH 3)-,-CH 2-CH [(CH 2) 3cH 3[]-,-CH 2-CH [(CH 2) 7cH 3]-,-CH 2-CH [(CH 2) 9cH 3]-,-CH 2-CH [(CH 2) 11cH 3]-,-CH 2-CH [(CH 2) 13cH 3]-,-CH 2-CH [(CH 2) 15cH 3]-,-CH 2-CH [(CH 2) 17cH 3]-etc.Alkylidene main chain with 2 ~ 20 carbon atoms preferably adds up to and has 2 ~ 20 carbon atoms.
As the cycloalkylidene with 6 ~ 8 ring carbon atoms, such as can list the cycloalkylidene shown in following formula (6) ~ (9), the ring subunit shown in these formulas (6) ~ (9) can have the alternatively base such as abovementioned alkyl, alkenyl, naphthenic base, cycloalkenyl group, dialkyl group, alkynyl, alkynyl phenyl, alkynyl allyl, aromatic substituents, nitro, halogen respectively.
As the arlydene with 6 ~ 14 ring carbon atoms, such as can list the arlydene shown in following formula (10) ~ (13), the arlydene shown in these formulas (10) ~ (13) can have the alternatively base such as abovementioned alkyl, alkenyl, naphthenic base, cycloalkenyl group, dialkyl group, alkynyl, alkynyl phenyl, alkynyl allyl, aromatic substituents, nitro, halogen respectively.
Formula (6):
Formula (7):
Formula (8):
Formula (9):
Formula (10):
Formula (11):
Formula (12):
Formula (13):
From the view point of the balance of developability and re-workability, as the precursor (b1 ') of Component units (b1) with carboxyl, preferred compound can list acrylic acid dimer [R 5:-CH 2-CH 2-], β-carboxy ethyl (methyl) acrylate [R 5:-CH 2-CH 2-], 2-(methyl) acryloyloxyethyl succinate [R 5:-CH 2-CH 2-, R 6:-CH 2-CH 2-], 2-(methyl) acryloyl-oxyethyl phthalic ester [R 5:-CH 2-CH 2-, R 6: phenylene], 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid ester [R 5:-CH 2-CH 2-, R 6: cyclohexylidene], 2-(methyl) acryloxypropyl succinate [R 5:-CH 2-CH (CH 3)-, R 6:-CH 2-CH 2-), 2-(methyl) acryloxypropyl phthalic ester [R 5:-CH 2-CH (CH 3)-, R 6: phenylene], 2-(methyl) acryloxypropyl hexahydrophthalic acid ester [R 5:-CH 2-CH (CH 3)-, R 6: cyclohexylidene], polyethylene oxide modified succinic acid (methyl) acrylate [R 5:-CH 2-CH 2-, R 6:-CH 2-CH 2-], ω-carboxyl-Polycaprolactone modified list (methyl) acrylate [R 5:-(CH 2) 5-], polyethylene oxide modified phthalic acid (methyl) acrylate [R 5:-CH 2-CH 2-, R 6: phenylene] etc.Precursor (b ') is not limited to above-mentioned example, and can be used alone or two or more is also used.
Component units (b2) can by by making unsaturated monoacid and precursor (d ') addition, then make multi-anhydride and the hydroxyl addition that generates and the precursor (b ') that obtains carries out copolymerization to obtain, also, after can forming Component units (d) by being carried out being polymerized by precursor (d '), making unsaturated monoacid and its addition, then multi-anhydride and the hydroxyl addition that generates being obtained.More specifically, and precursor (d ') there is epoxy radicals, this epoxy radicals and unsaturated monacid carboxyl react and generate ester, and generate a hydroxyl, a carboxyl of this hydroxyl and multi-anhydride reacts and generates ester simultaneously.
As the precursor (d ') of the Component units (d) shown in general formula (5), (methyl) glycidyl acrylate, (methyl) acrylic acid methylglycidyl esters, (methyl) acrylic acid 2-glycidoxypropyl ethyl ester, (methyl) acrylic acid 3 can be listed, 4 epoxybutyl esters and (methyl) acrylic acid 3,4 epoxycyclohexyl esters, they may be used alone, two or more kinds can also be used.From ensuing operation with unsaturated monacid reactive viewpoint, be preferably (methyl) glycidyl acrylate.
As the unsaturated monoacid with Component units (d) addition, the monocarboxylic acids etc. such as (methyl) acrylic acid, crotonic acid, o-, m-or p-vinyl benzoic acid, (methyl) acrylic acid α position haloalkyl, alkoxy, halogen, nitro, cyano group substituent can be listed, in addition, as the multi-anhydride that the hydroxyl with its addition reaction reacts, tetrabydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride etc. can be listed, they may be used alone, two or more kinds can also be used.
In order to increase the number etc. of the carboxyl in Component units (b '), as required, the tetracarboxylic dianhydrides such as tricarboxylic acid anhydride or pyromellitic acid dianhydride such as trimellitic anhydride also can be used to be hydrolyzed by remaining acid anhydride base.
The carboxyl of Component units (b1) and/or Component units (b2) is compared with the carboxyl of the Component units such as obtained by the precursor polymeric of (methyl) acrylic acid etc., further from the main chain of multipolymer (resin), sterically hindered little.Therefore, rework solution (strong alkali aqueous solution) is fast to soaking into of the film that the cross-linking density by exposure improves, compatibility might as well, thus swelling, reaction and dissolving successfully is carried out.
In addition, the functional group with carboxyl reaction is there is in photosensitive coloring composition of the present invention, even if a part for the carboxyl of its functional group and Component units (b1) and/or Component units (b2) is reacted and is cross-linked when rear baking, but because main chain and crosslinking points separate, therefore can not hinder rework solution soaking into film, successfully can carry out the removing of film.
As the precursor (c ') of Component units (c), only otherwise the functional group had with carboxyl reaction before developing procedure, be not particularly limited, can list:
(methyl) alkyl-acrylates of the straight-chain such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) stearyl acrylate ester and (methyl) lauryl acrylate or branched;
(methyl) acrylate base ester classes such as (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate and (methyl) acrylic acid bicyclopentyl ester;
(methyl) benzyl acrylate and (methyl) phenyl acrylate etc. have (methyl) alkyl-acrylates of aromatic ring;
(methyl) acrylic acid tetrahydro furfuryl ester etc. has (methyl) esters of acrylic acid of heterocycle;
Alkoxy (gathering) aklylene glycol (methyl) esters of acrylic acids such as methoxyl (gathering) propylene glycol (methyl) acrylate and ethoxy (gathering) ethylene glycol (methyl) acrylate;
(methyl) acrylamide, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N-isopropyl (methyl) acrylamide, diacetone (methyl) acrylamide and acryloyl morpholine etc. (methyl) acrylic amide;
The phenylethylene such as styrene and α-methyl styrene;
The vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether and IVE;
The fatty acid vinyl ester classes such as vinyl-acetic ester and vinyl propionate base ester;
The ethene base system monomer class with carboxyl except precursor (b ') such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid;
(methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2(or 3)-hydroxy propyl ester, (methyl) acrylic acid 2(or 3 or 4) alkyl-Alpha-hydroxy alkyl acrylate such as (methyl) hydroxyalkyl acrylates such as-hydroxybutyl and cyclohexanedimethanol list (methyl) acrylate and ethyl-Alpha-hydroxy methacrylate etc. has (methyl) alkyl-acrylates of hydroxyl;
(gathering) aklylene glycol (methyl) esters of acrylic acids such as (gathering) propylene glycol (methyl) acrylate and (gathering) ethylene glycol (methyl) acrylate;
N-(2-hydroxyethyl) (methyl) acrylamide, N-(2-hydroxypropyl) (methyl) acrylamide, N-(2-hydroxybutyl) and the N-(hydroxy alkyl such as (methyl) acrylamide) (methyl) acrylamide, there is (methyl) acrylic amide of hydroxyl;
2-hydroxyethyl vinyl ether, 2-(or 3-) hydroxypropyl vinyl ether and 2-(or 3-or 4-) hydroxybutyl vinyl ether etc. has the vinyl ether system class of hydroxyl;
2-hydroxyethyl allyl ether, 2-(or 3-) hydroxypropyl allyl ether and 2-(or 3-or 4-) the hydroxy alkyl allyl ether etc. such as hydroxybutyl allyl ether has the allyl ether series of hydroxyl;
Glycerine list (methyl) acrylate etc. has (methyl) esters of acrylic acid of 2 hydroxyls;
N, N-dimethyl aminoethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylate, N, N-diethyl amino propyl (methyl) acrylate etc. has N, alkyl (methyl) esters of acrylic acid of N-dialkyl amido; And,
N, N-dimethyl aminoethyl (methyl) acrylamide, N, N-diethylamino ethyl (methyl) acrylamide, N, N-dimethylaminopropyl (methyl) acrylamide, N, N-diethyl amino propyl (methyl) acrylamide etc. has N, (methyl) acrylic amide etc. of N-dialkyl amido, and these compounds can be used alone, also can two or more be used in combination, but these compounds might not be defined in.
Component units (c) is for obtaining the physical property as painted film and required Component units that only cannot realize by Component units (a) and Component units (b).Component units (c) does not preferably have hydroxyl.This is because if Component units (c) has hydroxyl, then cause the dehydration condensation with the carboxyl of Component units (b) due to the heating of film, the cross-linking density of result ester bond improves, and re-workability is deteriorated.From the view point of making film, the precursor of Component units (c) (c ') be preferably (methyl) alkyl acrylate, wherein, from the view point of pigment-dispersing, stability and film patience, be more preferably (methyl) benzyl acrylate and/or (methyl) acrylic acid bicyclopentyl ester.
In order to obtain in photosensitive coloring composition of the present invention contained resin precursor (a '), precursor (b ') and precursor (c ') are carried out copolymerization time, relative to whole precursor, the polymerization ratio of above-mentioned precursor (a ') is preferably 1 ~ 50 % by weight, is more preferably 1 ~ 35 % by weight.When the polymerization ratio of precursor (a ') is less than 1 % by weight, the dispersion effect as the pigment of colorant reduces, and cannot obtain sufficient dispersion effect.In addition, if more than 50 % by weight, then hydrophobicity increases, and significantly reduces with the compatibility of other constituent in photosensitive coloring composition, cause the reduction of the developability of photosensitive coloring composition or the generation of residue sometimes, and then also can cause the precipitation of monomer or Photoepolymerizationinitiater initiater.For having the precursor of 1 ~ 35 % by weight (a ') copolymerization and the resin of the Component units (a) obtained, the balance of the ratio of its Component units (a) and Component units (b) and Component units (c) is good, can play excellent developability and re-workability.
In order to obtain in photosensitive coloring composition of the present invention contained resin precursor (a '), precursor (b ') and precursor (c ') are carried out copolymerization time, relative to whole precursor, the polymerization ratio of above-mentioned precursor (b ') is preferably 5 ~ 91 % by weight, is more preferably 10 ~ 90 % by weight.When the ratio of precursor (b ') is less than 5 % by weight, the sufficient reactivity with developer solution or rework solution cannot be obtained.In addition, if more than 91 % by weight, then the amount of the carboxyl in photosensitive composite increases, and because hydrogen bond causes producing structural viscosity, the dispersion stabilization sometimes as the pigment of colorant can reduce.For having the precursor of 10 ~ 90 % by weight (b ') copolymerization and the resin of the Component units (b) obtained, the balance of the ratio of its Component units (b) and Component units (a) and Component units (c) is good, can play excellent developability and re-workability.
In order to obtain in photosensitive coloring composition of the present invention contained resin precursor (a '), precursor (b ') and precursor (c ') are carried out copolymerization time, relative to whole precursor, the polymerization ratio of above-mentioned precursor (c ') is preferably 1 ~ 80 % by weight, is more preferably 1 ~ 75 % by weight.When the ratio of precursor (c ') is less than 1 % by weight, sufficient film physical property cannot be obtained.In addition, if more than 80 % by weight, then Component units (a) and Component units (b) tail off, and cannot obtain the sufficient dispersiveness of the pigment as colorant, developability and re-workability.For the resin with the Component units (c) that Component units (c) copolymerization of 1 ~ 75 % by weight is obtained, the balance of the ratio of its Component units (c) and Component units (a) and Component units (b) is good, can play excellent developability and re-workability.
In order to obtain in photosensitive coloring composition of the present invention contained resin precursor (a '), precursor (d ') and precursor (c ') are carried out copolymerization time, relative to whole precursor, the polymerization ratio of precursor (a ') is preferably 1 ~ 50 % by weight, is more preferably 1 ~ 35 % by weight.When the polymerization ratio of precursor (a ') is less than 1 % by weight, the dispersion effect as the pigment of colorant reduces, and cannot obtain sufficient dispersion effect.In addition, if more than 50 % by weight, then hydrophobicity increases, and significantly reduces with the compatibility of other constituent in photosensitive coloring composition, cause the reduction of the developability of photosensitive coloring composition or the generation of residue sometimes, and then also can cause the precipitation of monomer or Photoepolymerizationinitiater initiater.Make unsaturated monoacid and multi-anhydride and have the precursor of 1 ~ 35 % by weight (a ') copolymerization and resin (precursor resin) addition of the Component units (a) obtained, the balance of the ratio of the Component units (a) of the resin obtained and Component units (b2) and Component units (c) is good, can play excellent developability and re-workability.
In order to obtain in photosensitive coloring composition of the present invention contained resin precursor (a '), precursor (d ') and precursor (c ') are carried out copolymerization time, relative to whole precursor, the polymerization ratio of precursor (d ') is preferably 2 ~ 80 % by weight, is more preferably 4 ~ 75 % by weight.When the ratio of precursor (d ') is less than 2 % by weight, for making unsaturated monoacid and gained multipolymer (precursor resin) addition, then makes multi-anhydride and the hydroxyl addition generated and the resin of the present invention that obtains, the abundant effect of reprocessing cannot be obtained.In addition, if more than 80 % by weight, then the amount of the carboxyl in photosensitive composite increases, and because hydrogen bond causes producing structural viscosity, the dispersion stabilization sometimes as the pigment of colorant also can reduce.Make unsaturated monoacid and multi-anhydride and have the precursor of 4 ~ 75 % by weight (d ') copolymerization and resin (precursor resin) addition of the Component units (d) obtained and obtain Component units (b2), ratio and the Component units (a) with the Component units (b2) of the resin of Component units (b2) are good with the balance of Component units (c), can play excellent developability and re-workability.
In order to obtain in photosensitive coloring composition of the present invention contained resin precursor (a '), precursor (d ') and precursor (c ') are carried out copolymerization time, relative to whole precursor, the polymerization ratio of precursor (c ') is preferably 1 ~ 80 % by weight, is more preferably 1 ~ 75 % by weight.When the ratio of precursor (c ') is less than 1 % by weight, sufficient film physical property cannot be obtained.In addition, if more than 80 % by weight, then Component units (a) and Component units (b2) tail off, and cannot obtain the sufficient dispersiveness of the pigment as colorant, developability and re-workability.Make unsaturated monoacid and multi-anhydride and have the precursor of 1 ~ 75 % by weight (c ') copolymerization and resin (precursor resin) addition of the Component units (c) obtained, the balance of the ratio of the Component units (c) of gained resin and Component units (a) and Component units (b2) is good, can play excellent developability and re-workability.
From the view point of the dispersiveness of the pigment as colorant, stability and film patience, for the precursor (c ') as Component units (c), the part by weight of preferred (methyl) benzyl acrylate and/or (methyl) acrylic acid bicyclopentyl ester and/or (methyl) acrylic acid dicyclopentenyl ester and/or (methyl) acrylic acid cyclopentyloxy ethyl ester, (comprises unsaturated monoacid and multi-anhydride) and is preferably 1 ~ 80 % by weight in whole precursor when being formed by Component units (d).If be less than 1 % by weight, then Physical properties of coating film is insufficient, if more than 80 % by weight, then Component units (a) and Component units (b) less, therefore, poor as the dispersiveness of the pigment of colorant, developability and re-workability.
From the view point of the dispersiveness of the pigment as colorant, stability and film patience, for the precursor (c ') as Component units (c), the polymerization ratio of preferred (methyl) benzyl acrylate and/or (methyl) acrylic acid bicyclopentyl ester, (comprises unsaturated monoacid and multi-anhydride) and is preferably 1 ~ 65 % by weight in whole precursor when being formed by Component units (d).If be less than 1 % by weight, then Physical properties of coating film is insufficient, if more than 65 % by weight, then Component units (a) and Component units (b) less, therefore poor as the dispersiveness of the pigment of colorant, developability and re-workability.
Resin contained in photosensitive coloring composition of the present invention can obtain as follows: make precursor (a '), precursor (b '), precursor (c ') carry out free radical polymerization with 2 ~ 10 hours under the existence of radical polymerization initiator, under the air-flow of inertness gas, at 50 ~ 150 DEG C.Or, resin contained in photosensitive coloring composition of the present invention can obtain as follows: make precursor (a '), precursor (d '), precursor (c ') carry out free radical polymerization with 2 ~ 10 hours under the existence of radical polymerization initiator, under the air-flow of inertness gas, at 50 ~ 150 DEG C, then reaction atmosphere is replaced into air, add quinhydrones, unsaturated monoacid was reacted with 2 ~ 10 hours at 50 ~ 150 DEG C, then add triethylamine, multi-anhydride was reacted with 2 ~ 10 hours at 50 ~ 150 DEG C.Polyreaction can be carried out as required in the presence of the solvent.
As radical polymerization initiator, the organic peroxides, 2 such as benzoyl peroxide, cumene hydrogen peroxide, t-butylhydroperoxide, diisopropyl peroxycarbonates, di-tert-butyl peroxide, tert butyl peroxy benzoate can be listed, the azo-compounds etc. such as 2'-azoisobutyronitrile, but be not limited to these, and can be used alone or two or more is also used.Relative to whole precursors 100 weight portion of resin, the usage ratio of radical polymerization initiator is preferably 1 ~ 20 weight portion.
As the solvent that can use when above-mentioned Raolical polymerizable, water and/or water miscibility organic solvent or the acetate esters such as ethyl cellosolve acetate, propylene glycol monomethyl ether can be used; The ketone such as cyclohexanone, methyl isobutyl ketone; Dimethylbenzene, ethylbenzene etc.As water miscibility organic solvent, the list or dialkyl ether etc. of alcohol series solvent, ethylene glycol or the diethylene glycols such as ethanol, isopropyl alcohol, n-propanol can be listed, but be not limited to these, and to can be used alone or two or more is also used.
The weight-average molecular weight (Mw) of resin contained in photosensitive coloring composition of the present invention is preferably 5000 ~ 100000, from the view point of the dispersiveness of the pigment as colorant, developability, re-workability and patience, is more preferably 7000 ~ 50000.When weight-average molecular weight is less than 5000, pigment-dispersing and film patience are deteriorated, if be greater than 100000, then not only developability and re-workability are deteriorated, and the viscosity of photosensitive coloring composition is too high, and operability and coating are also deteriorated.
Resin used in photosensitive coloring composition of the present invention plays excellent dispersion effect in nearly all pigment, when therefore using the filter section of the photosensitive coloring composition formation color filter of the present invention of the pigment utilizing this resin to disperse as colorant, the filter section that pigment agglutinator is few can be obtained.
Relative to colorant (pigment) 100 weight portion, resin used in photosensitive coloring composition of the present invention can use with the ratio of 30 ~ 800 weight portions.If be less than 30 weight portions, then sufficient dispersion stabilization cannot be obtained, if more than 800 weight portions, then concentration and the thickness of the colorant (pigment) required by color filter cannot be taken into account.
< colorant >
As colorant used in photosensitive coloring composition of the present invention, the pigment of organic or inorganic can be used alone or two or more is used in combination.High and the pigment that thermotolerance is high of the preferred colour rendering of pigment, the pigment that particularly preferably resistance to pyrolytic is high, uses organic pigment usually.
The object lesson of the organic pigment that can use in photosensitive coloring composition of the present invention is shown with color index (C.I.) number below.
In the red colored composition saved for the formation of red filter, as red pigment, such as can use C.I. paratonere 7,9,14,41,48:1,48:2,48:3,48:4,81:1,81:2,81:3,97,122,123,146,149,168,177,178,180,184,185,187,192,200,202,208,210,215,216,217,220,223,224,226,227,228,240,242,246,254,255,264 and 272 etc.Can also with yellow uitramarine, orange pigment in red colored composition.
As the yellow uitramarine added in red colored composition, such as C.I. pigment yellow 1 can be used, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194 and 199 etc.Wherein preferred C.I. pigment yellow 13 8,139,150 and 185.
As the orange pigment added in red colored composition, such as C.I. pigment orange 36,43,51,55,59,61 and 71 etc. can be used.
In the green coloring composition saved for the formation of green filter, as viridine green, such as C.I. pigment Green 7,10,36,37 and 58 etc. can be used.Yellow uitramarine can be used in green coloring composition.
As the yellow uitramarine added in green coloring composition, such as C.I. pigment yellow 1 can be used, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194 and 199 etc.Wherein preferred C.I. pigment yellow 13 8,139,150 and 185.
In the blue colored composition saved for the formation of blue electric-wave filter, as blue pigment, such as C.I. pigment blue 15,15:1,15:2,15:3,15:4,15:6,16,22,60 and 64 etc. can be used.Can in blue colored composition and with C.I. pigment violet 1,19,23,27,29,30,32,37,40, the violet pigments such as 42 and 50.
In the yellow coloring composition saved for the formation of yellow filter, such as C.I. pigment yellow 1 can be used, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, the yellow uitramarines such as 194 and 199.
For the formation of in the orange coloured composition of orange filter section, can use such as C.I. pigment orange 36,43,51,55,59, the orange pigments such as 61 and 71.
In the cyan coloured composition saved for the formation of cyan filter, such as C.I. pigment blue 15 can be used: 1,15:2,15:4,15:3,15:6, the blue pigments such as 16 and 81.
For the formation of in the magenta coloured composition of magenta filter section, such as C.I. pigment violet 1 and the red pigments such as violet pigment and C.I. paratonere 144,146,177,169 and 81 such as 19 can be used.Can in magenta coloured composition and with the yellow uitramarine same with the yellow coloring composition saved for the formation of yellow filter.
In addition, in order to obtain the balance of chroma and brightness and guarantee good coating, sensitivity and developability etc., also inorganic pigment and above-mentioned organic pigment can be combinationally used.As inorganic pigment, lead and yellow-collation, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine, dark blue, metal oxide powder, metal sulfide powder, the metal powder etc. such as chrome oxide green, cobalt green can be listed.In addition, in order to mix colours, dyestuff can be included in the scope not making thermotolerance reduce.In addition, photosensitive coloring composition of the present invention can manufacture as follows: use the various dispersion means such as triple-roller mill, two roller mill, sand milling, kneader, Ultrafine Grinding, pigment conditioner (PaintConditioner), be dispersed in imperceptibly in photosensitive coloring composition by colorant.
Below, as the black pigment of light shield layer, the carbon black #2400 of Mitsubishi Chemical Ind can be listed, #2350, #2300, #2200, #1000, #980, #970, #960, #950, #900, #850, MCF88, #650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, #4000, #4010, #55, #52, #50, #47, #45, #44, #40, #33, #32, #30, #20, #10, #5, CF9, #3050, #3150, #3250, #3750, #3950, ダ イ ヤ Block ラ ッ Network A, ダ イ ヤ Block ラ ッ Network N220M, ダ イ ヤ Block ラ ッ Network N234, ダ イ ヤ Block ラ ッ Network I, ダ イ ヤ Block ラ ッ Network LI, ダ イ ヤ Block ラ ッ Network II, ダ イ ヤ Block ラ ッ Network N339, ダ イ ヤ Block ラ ッ Network SH, ダ イ ヤ Block ラ ッ Network SHA, ダ イ ヤ Block ラ ッ Network LH, ダ イ ヤ Block ラ ッ Network H, ダ イ ヤ Block ラ ッ Network HA, ダ イ ヤ Block ラ ッ Network SF, ダ イ ヤ Block ラ ッ Network N550M, ダ イ ヤ Block ラ ッ Network E, ダ イ ヤ プ ラ ッ Network G, ダ イ ヤ Block ラ ッ Network R, ダ イ ヤ Block ラ ッ Network N760M, ダ イ ヤ Block ラ ッ Network LR, the carbon black サ ー マ ッ Network ス N990 of キ ャ ン カ ー Block Inc., N991, N907, N908, N990, N991, N908, the carbon black rising sun #80 of Xu カ ー ボ Application Inc., rising sun #70, rising sun #70L, rising sun F-200, rising sun #66, rising sun #66HN, rising sun #60H, rising sun #60U, rising sun #60, rising sun #55, rising sun #50H, rising sun #51, rising sun #50U, rising sun #50, rising sun #35, rising sun #15, ア サ ヒ サ ー マ Le, the carbon black ColorBlackFw200 of デ グ サ Inc., ColorBlackFw2, ColorB1ackFw2V, ColorBlackFw1, ColorBlackFw18, ColorBlackS170, ColorBlackS160, Specia1Black6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, SpecialBlack350, PrintexU, PrintexV, Printex140U, Printex140V(is trade name) etc.
Can containing the spreading agent for disperseing the pigment as colorant in photosensitive coloring composition of the present invention.The pigment-dispersing of spreading agent is excellent, prevents the effect of the aggegation again of the pigment after disperseing large, therefore uses the spreading agent composition be dispersed in by pigment in photosensitive coloring composition can obtain the excellent color filter of the transparency.As spreading agent, resin-bonded pigment spreading agent, pigment derivative, surfactant etc. can be used.The addition of spreading agent is not particularly limited, but from the view point of dispersed and color characteristics, and relative to colorant (pigment) 100 weight portion, spreading agent is preferably with 0.1 ~ 40 weight portion, more preferably use with the amount of 0.1 ~ 30 weight portion.
Resin-bonded pigment spreading agent contains the pigment compatibility position with the character being adsorbed in pigment and has the position of compatibility with resin, and it has and is adsorbed in pigment with the effect of the stably dispersing making pigment in photosensitive coloring composition.As resin-bonded pigment spreading agent, the acid amides that the reaction can use the modifier of the polycarboxylate such as polyurethane, polyacrylate, unsaturated polyester acid amides, poly carboxylic acid, poly carboxylic acid (part) amine salt, poly carboxylic acid ammonium salt, poly carboxylic acid alkylamine salt, polysiloxane, long-chain polyaminoamide phosphate, hydroxyl polycarboxylate, these compounds, passing through the polyester gathering (low-grade alkylidene imines) and have free carboxy is formed or its salt etc.In addition, water soluble resin or water-soluble high-molecular compound, Polyester, modified polyacrylate, the ethylene oxide/propylene oxide addition products etc. such as (methyl) acrylic-styrene copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol (PVA), polyvinyl pyrrolidone can also be used.They can be used alone or two or more is used in combination.
As commercially available resin-bonded pigment spreading agent, the Disperbyk-101 of BYK Inc. can be listed, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS or Bykumen etc., the SOLSPERSE-3000 of Japan ル ー Block リ ゾ ー Le Inc., 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32600, 34750, 36600,38500, 41000, 41090, 53095 etc., the EFKA-46 of エ Off カ ケ ミ カ Le ズ Inc., 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503 etc.
Pigment derivative is in organic pigment, introduce substituent compound.Also the flaxen aromatic series polycyclic compund such as naphthalene system, anthraquinone system not generally being called as pigment is comprised in organic pigment.As pigment derivative, can use the pigment derivative recorded in JP 63-305173 publication, examined patent publication 57-15620 publication, examined patent publication 59-40172 publication, examined patent publication 63-17102 publication, JP 5-9469 publication etc., they can be used alone or two or more is used in combination.
< Photoepolymerizationinitiater initiater >
Containing Photoepolymerizationinitiater initiater in photosensitive coloring composition of the present invention.
As Photoepolymerizationinitiater initiater, can use:
4-phenoxydichloroacetophenone, the 4-tert-butyl group-dichloroacetophenone, diethoxy acetophenone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-hydroxycyclohexylphenylketone and 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) the acetophenone system Photoepolymerizationinitiater initiater such as-butane-1-ketone;
The benzoin system Photoepolymerizationinitiater initiaters such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzyl dimethyl ketal;
Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenyl benzophenone, dihydroxy benaophenonel, acrylated benzophenone and 4-benzoyl-4 ' the benzophenone series Photoepolymerizationinitiater initiater such as-methyldiphenyl sulfide;
The thioxanthones system Photoepolymerizationinitiater initiaters such as thioxanthones, CTX, 2-methyl thioxanthones, isopropyl thioxanthone and 2,4-diisopropylthioxanthone;
2, 4, 6-trichloto-s-triazine, 2-phenyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(p-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(p-methylphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-piperonyl-4, two (the trichloromethyl)-s-triazine of 6-, 2, two (the trichloromethyl)-6-styryl-s-triazine of 4-, 2-(naphtho--1-base)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-methoxyl-naphtho--1-base)-4, two (the trichloromethyl)-s-triazine of 6-, 2, 4-trichloromethyl-(piperonyl)-6-triazine, and 2, the triazine system Photoepolymerizationinitiater initiaters such as 4-trichloromethyl (4 '-methoxyl-styrene)-6-triazine,
Borate-based Photoepolymerizationinitiater initiater;
Carbazole system Photoepolymerizationinitiater initiater; And,
Imidazoles system Photoepolymerizationinitiater initiater etc.
Photoepolymerizationinitiater initiater, relative to colorant (pigment) 100 weight portion in photosensitive coloring composition, with 5 ~ 200 weight portions, preferably uses with the amount of 10 ~ 150 weight portions.
Above-mentioned Photoepolymerizationinitiater initiater can be used alone or two or more is used in combination.Also can be used together alpha-acyloxy ester, acylphosphine oxide, glyoxalic acid aminomethyl phenyl ester, benzil, 9; 10-phenanthrenequione, camphorquinone, EAQ, 4; 4 '-diethyl isophthalic diformyl-benzenes, 3; 3; 4; the compounds such as 4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone and 4,4'-diethylamino benzophenone are as sensitizer.Sensitizer can use with the amount of 0.1 ~ 60 weight portion relative to Photoepolymerizationinitiater initiater 100 weight portion in photosensitive coloring composition.
< polymerizable monomer >
Polymerizable monomer is added with in photosensitive coloring composition of the present invention.
As polymerizable monomer, can list:
The monofunctional monomers such as (methyl) acrylic acid, styrene, vinyl-acetic ester, (methyl) acrylamide, vinyl cyanide, (methyl) cyclohexyl acrylate and (methyl) acrylic acid three ring decyl ester;
1, 4-butylene glycol two (methyl) acrylate, diethylene glycol two (methyl) acrylate, 1, 6-ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyglycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, two (methyl) acrylate of other poly alkylene glycol, two (methyl) acrylate of various polyester-diol, two (methyl) acrylate of various polyurethane diol, two (methyl) acrylate of EO modified bisphenol A, and two functional monomers such as two (methyl) acrylate of various two functional epoxide compound, and,
Trimethylolpropane tris (methyl) acrylate, two (trimethylolpropane) four (methyl) acrylate, three (methyl) acrylate of various isocyanuric acid ester, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, (methyl) acrylate of various polyfunctional epoxy resin, and the polyfunctional monomer such as caprolactone modification dipentaerythritol acrylate, but be not limited to these, and can be used alone or two or more is also used.
Polymerizable monomer can use with the ratio of 20 ~ 200 weight portions relative to colorant (pigment) 100 weight portion.
< solvent >
As organic solvent contained in photosensitive coloring composition of the present invention, 1,2,3-trichloropropane can be listed, 1,3-BDO, 1,3-BDO, 1,3-BDO diacetate esters, Isosorbide-5-Nitrae-diox, 2-HEPTANONE, 2-methyl isophthalic acid, ammediol, Isophorone, 3,3,5-trimethylcyclohexanone, 3-ethoxyl ethyl propionate, 3-methyl isophthalic acid, 3-butylene glycol, MMB, 3-methoxyl-3-Methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetic acid esters, 4-heptanone, m-xylene, between diethylbenzene, between dichlorobenzene, DMA, DMF, normal butyl alcohol, n-butylbenzene, n-propyl acetate, 1-METHYLPYRROLIDONE, o-xylene, o-chloro-toluene, adjacent diethylbenzene, adjacent dichlorobenzene, to chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl benzene, gamma-butyrolacton, isobutyl alcohol, isophorone, ethylene glycol bisthioglycolate ethylether, ethylene glycol bisthioglycolate butyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol mono-tert-butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol list propyl ether, ethylene glycol mono hexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetic acid ester, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, TC acetic acid esters, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetic acid esters, diethylene glycol monomethyl ether, cyclohexanol, ring alcohol, acetic acid ester, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetic acid esters, dihydroxypropane single-ethyl ether, dipropylene glycol mono butyl base ether, dipropylene glycol list propyl ether, DPGME, diacetone alcohol, glyceryl triacetate, tripropylene glycol monobutyl base ether, tripropylene glycol monomethyl ether, propylene-glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl, propylene glycol monoethyl acetic acid esters, glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether propionic ester, benzylalcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid ester etc., but be not limited to these, and can be used alone or two or more is used in combination.Organic solvent relative to colorant (pigment) 100 weight portion in photosensitive coloring composition with 800 ~ 4000 weight portions, preferably use with the amount of 1000 ~ 2500 weight portions.
In photosensitive coloring composition of the present invention can containing for make composition through time viscosity stabilization storage-stable agent.
As storage-stable agent, such as, can list:
The ammonium chlorides such as benzyltrimethylammonium chloride, diethylhydroxylamine hydrochloride;
The organic acid such as lactic acid and oxalic acid;
Above-mentioned organic acid methyl esters;
The catechol such as tert-butyl catechol and catechol;
The organic phosphines such as tetraethyl phosphine and tetraphenyl phosphine; And,
Phosphite etc.
Storage-stable agent can use with the amount of 0.1 ~ 10 weight portion relative to colorant 100 weight portion in photosensitive coloring composition.
In addition, in order to improve the adaptation with transparency carrier, also can containing closely sealed improving agents such as silane coupling agents.
As silane coupling agent, can list:
The vinyl silanes classes such as vinyl three ('beta '-methoxy ethoxy) silane, vinylethoxysilane and vinyltrimethoxy silane;
(methyl) acryosilane classes such as γ-methacryloxypropyl trimethoxy silane;
β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3,4-epoxycyclohexyl) methyltrimethoxy silane, β-(3,4-epoxycyclohexyl) the epoxy silane class such as ethyl triethoxysilane, β-(3,4-epoxycyclohexyl) methyl triethoxysilane, γ-glycidoxypropyltrimewasxysilane and γ-glycidoxypropyl triethoxysilane;
The amino silicone alkanes such as N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane, N-β (amino-ethyl) γ aminopropyltriethoxy silane, N-β (amino-ethyl) gamma-amino hydroxypropyl methyl diethoxy silane, γ aminopropyltriethoxy silane, gamma-amino propyl trimethoxy silicane, N-phenyl-gamma-amino propyl trimethoxy silicane and N-phenyl-γ aminopropyltriethoxy silane; And,
The Thiosilicane classes etc. such as γ mercaptopropyitrimethoxy silane and γ-Mercaptopropyltriethoxysilane.
Silane coupling agent can relative to colorant (pigment) 100 weight portion in photosensitive coloring composition with 0.01 ~ 10 weight portion, preferably use with the amount of 0.05 ~ 5 weight portion.
Photosensitive coloring composition of the present invention can be modulated into intaglio printing printing-ink, anhydrous offset printing ink, silk screenink, solvent developable or the painted anticorrosive additive material of alkali developable.Solvent developable or the painted anticorrosive additive material of the alkali developable toner that is scattered here and there in the composition containing resin, Photoepolymerizationinitiater initiater, polymerizable monomer and organic solvent obtains.
Photosensitive coloring composition of the present invention removes the oversize grain of more than 5 μm, the preferred dust removing the oversize grain of more than 1 μm, the oversize grain of more preferably removing more than 0.5 μm and be mixed into preferably by centrifuging, means such as sintering filter, membrane filter etc.
< color filter >
Below, color filter of the present invention is described.
Color filter of the present invention is the color filter with the filter section using photosensitive coloring composition of the present invention to be formed.Color filter has: the additive color mixing type possessing at least one red filter joint, at least one green filter joint and at least one blue electric-wave filter joint; Or possess the substractive color mixing type of at least one magenta filter section, at least one cyan filter joint and at least one yellow filter joint.
Color filter of the present invention by utilizing photoetching process, can use photosensitive coloring composition of the present invention to form assorted filter section on the transparent substrate and manufacturing.
As transparency carrier, the resin plates such as glass plate, polycarbonate, polymethylmethacrylate, polyethylene terephthalate can be used.
The formation of photolithographic assorted filter section is utilized to be undertaken by following method.That is, by coating processes such as spraying, spin coating, slot coated, roller coat, by being modulated into the photosensitive coloring composition coating of above-mentioned solvent developable or the painted anticorrosive additive material of alkali developable on the transparent substrate, dry film thickness is made to reach 0.2 ~ 5 μm.To film dry as required, by carrying out ultraviolet exposure with the mask with predetermined pattern contacted with this film or non-contacting state is arranged.Then, be immersed in solvent or alkaline developer, or by ejection developer solutions such as sprayings, thus remove uncured portion, the pattern needed for formation, afterwards same operation is repeated to other color, thus can color filter be manufactured.In addition, in order to promote the polymerization of painted anticorrosive additive material, heating also can be implemented as required.According to photoetching process, color filter more high-precision than print process can be made.
When developing, as alkaline developer, the aqueous solution of sodium carbonate, NaOH, potassium hydroxide etc. can be used, also can use the organic base such as dimethyl benzyl amine, triethanolamine.In addition, also defoamer or surfactant can be added in developer solution.
In addition, in order to improve the photonasty of ultraviolet exposure, also can after above-mentioned painted anticorrosive additive material coating drying, be coated with water-soluble or also drying such as alkali soluble resin, such as pva coating or water soluble acrylic resin etc., thus form anti-block and cause being polymerized the film hindered, and then carry out ultraviolet exposure.
Color filter of the present invention, except photoetching process, can also be manufactured by electrodeposition process, transfer printing etc.Electrodeposition process is following method: utilize the nesa coating that transparency carrier is formed, and by the electrophoresis of colloidal particle, forms assorted filter section, manufacture color filter thus at nesa coating substrates.In addition, transfer printing is following method: on the surface of the transfer printing substrate of fissility, be pre-formed color-filter layer, be then transferred on desired transparency carrier by this color-filter layer.
For color filter of the present invention, if find unfavorable condition in its production process, the stripper of the strong alkali solution containing high concentration (being designated as below " rework solution ") can be used, peel off from substrate surface, by base material recycling (reprocessing).
The benchmark of cycling processability is: the solubleness of film in the rework solution 100g of 65 DEG C of burning till the photosensitive coloring composition after 60 minutes at 230 DEG C is 30 ~ 120mg.If be less than 30mg, then can not peel off, or stripping film is comparatively large, cause the blocking of the rework solution recycled, efficiency is poor.If be greater than 120mg, then weak caustic solution also can be peeled off, and therefore develops too fast, cannot form the color filter of fine.By the synergy of the Component units (a) of resin of the present invention, Component units (b) and Component units (c), if above-mentioned solubleness is 30 ~ 120mg, then stripping film is fine, can reprocess efficiently.
The pH of rework solution used is here high (pH is more than 11), and containing KOH and/or NaOH, organic base, hydrophilic solvent, surfactant and water.PK-CFR310, the PK-CFR320 of PARKERCORPORATION Inc. can be listed particularly, PK-CFR370, the セ ミ Network リ ー Application DF-7 of Yokohama Oils & Fats Industry Co., Ltd., EP-10, the pure medicine of Co., Ltd. ミ Star ワ カ study made ア Application ラ ス ト Network リ ー Na ー 22 etc.
[embodiment]
Illustrate in greater detail the present invention by the following examples, but following embodiment there is not any restriction to interest field of the present invention.In addition, " part " and " % " in embodiment refers to " weight portion " and " % by weight " respectively.
First, the preparation of the acrylic resin soln used in embodiment and comparative example is described.The molecular weight of the acryl resin in acrylic resin soln is the weight-average molecular weight of the polystyrene conversion measured by gel permeation chromatography (GPC).
The preparation > of < acrylic resin soln 1
In reaction vessel, add propylene glycol monomethyl ether 370 parts, while be heated to 80 DEG C to nitrogen injection limit in container, dripped the potpourri of following monomer and thermal polymerization at the same temperature with 1 hour, carry out polyreaction.
The ethylene-oxide-modified acrylate of p-cumylphenol
(East Asia Synesis Company system " ア ロ ニ ッ Network ス M110 ") 10.0 parts
2-methacryloxyethyl phthalic ester
(chemical company of Xin Zhong village system " NKESTERCB-1 ") 50.0 parts
Benzyl methacrylate 40.0 parts
Azoisobutyronitrile 3.5 parts
React at 100 DEG C after 3 hours after dropping, interpolation cyclohexanone 50 parts dissolves azoisobutyronitrile 1.0 parts of solution obtained, then at 100 DEG C, continue reaction 1 hour, obtains the solution of acryl resin again.The weight-average molecular weight of this acryl resin is about 15000.
After being cooled to room temperature, sample tree lipoprotein solution is about 2g, heat drying 20 minutes at 180 DEG C, measure nonvolatile component, according to this measured value, in the resin solution of previously synthesis, add cyclohexanone reach 30% to make nonvolatile component, thus prepared acrylic resin soln 1.
The preparation > of < acrylic resin soln 2
In reaction vessel, add propylene glycol monomethyl ether 370 parts, while be heated to 80 DEG C to nitrogen injection limit in container, dripped the potpourri of following monomer and thermal polymerization at the same temperature with 1 hour, carry out polyreaction.
The ethylene-oxide-modified acrylate of p-cumylphenol 20.0 parts
Glycidyl methacrylate 24.5 parts
Benzyl methacrylate 16.8 parts
Azoisobutyronitrile 2.1 parts
React at 100 DEG C after 3 hours after dropping, interpolation cyclohexanone 50 parts dissolves azoisobutyronitrile 1.0 parts of solution obtained, then at 100 DEG C, continue reaction 1 hour again.Then, atmosphere in container is replaced into air, 12.4 parts, acrylic acid (100mol% of glycidyl), three (dimethylamino) phenol 0.3 part and quinhydrones 0.1 part is added in said vesse, reaction is continued 6 hours at 120 DEG C, until terminate reaction when solid constituent acid number reaches 0.5mgKOH/g, obtain the solution of acryl resin.Then add tetrabydrophthalic anhydride 26.3 parts (100mo1% of the hydroxyl of generation), triethylamine 0.3 part, react 3.5 hours at 120 DEG C, thus obtain the solution of acryl resin.The weight-average molecular weight of this acryl resin is about 15000.
After being cooled to room temperature, sample tree lipoprotein solution is about 2g, heat drying 20 minutes at 180 DEG C, measure nonvolatile component, according to this measured value, in the resin solution of previously synthesis, add propylene glycol monomethyl ether reach 30% to make nonvolatile component, thus prepared acrylic resin soln 2.
The preparation > of < acrylic resin soln 3
Except the benzyl methacrylate in the preparation of acrylic resin soln 2 being replaced by methacrylic acid bicyclopentyl ester (Hitachi changes into Inc. " Off ァ Application Network リ Le FA-513M "), synthesize by the method same with acrylic resin soln 2, prepared the acrylic resin soln 3 that solid constituent is 30%.The weight-average molecular weight of this acryl resin is about 15000.
The preparation > of < acrylic resin soln 4
In reaction vessel, add propylene glycol monomethyl ether 370 parts, while be heated to 80 DEG C to nitrogen injection limit in container, dripped the potpourri of following monomer and thermal polymerization at the same temperature with 1 hour, carry out polyreaction.
The ethylene-oxide-modified acrylate of p-cumylphenol 6.0 parts
Glycidyl methacrylate 34.1 parts
Benzyl methacrylate 6.0 parts
Azoisobutyronitrile 1.5 parts
React at 100 DEG C after 3 hours after dropping, interpolation cyclohexanone 50 parts dissolves azoisobutyronitrile 1.0 parts of solution obtained, then at 100 DEG C, continue reaction 1 hour again.Then, atmosphere in container is replaced into air, 17.3 parts, acrylic acid (100mol% of glycidyl), three (dimethylamino) phenol 0.5 part and quinhydrones 0.1 part is added in said vesse, reaction is continued 6 hours at 120 DEG C, until terminate reaction when solid constituent acid number reaches 0.5mgKOH/g, obtain the solution of acryl resin.Then add tetrabydrophthalic anhydride 36.5 parts (100mo1% of the hydroxyl of generation), triethylamine 0.5 part, react 3.5 hours at 120 DEG C, thus obtain the solution of acryl resin.The weight-average molecular weight of this acryl resin is about 15000.
After being cooled to room temperature, sample tree lipoprotein solution is about 2g, heat drying 20 minutes at 180 DEG C, measure nonvolatile component, according to this measured value, in the resin solution of previously synthesis, add propylene glycol monomethyl ether reach 30% to make nonvolatile component, thus prepared acrylic resin soln 4.
The preparation > of < acrylic resin soln 5
In reaction vessel, add propylene glycol monomethyl ether 370 parts, while be heated to 80 DEG C to nitrogen injection limit in container, dripped the potpourri of following monomer and thermal polymerization at the same temperature with 1 hour, carry out polyreaction.
The ethylene-oxide-modified acrylate of p-cumylphenol 3.0 parts
Glycidyl methacrylate 36.9 parts
Benzyl methacrylate 2.0 parts
Azoisobutyronitrile 1.5 parts
React at 100 DEG C after 3 hours after dropping, interpolation cyclohexanone 50 parts dissolves azoisobutyronitrile 1.0 parts of solution obtained, then at 100 DEG C, continue reaction 1 hour again.Then, atmosphere in container is replaced into air, 18.7 parts, acrylic acid (100mol% of glycidyl), three (dimethylamino) phenol 0.5 part and quinhydrones 0.1 part is added in said vesse, reaction is continued 6 hours at 120 DEG C, until terminate reaction when solid constituent acid number reaches 0.5mgKOH/g, obtain the solution of acryl resin.Then add tetrabydrophthalic anhydride 39.4 parts (100mo1% of the hydroxyl of generation), triethylamine 0.5 part, react 3.5 hours at 120 DEG C, thus obtain the solution of acryl resin.The weight-average molecular weight of this acryl resin is about 15000.
After being cooled to room temperature, sample tree lipoprotein solution is about 2g, heat drying 20 minutes at 180 DEG C, measure nonvolatile component, according to this measured value, in the resin solution of previously synthesis, add propylene glycol monomethyl ether reach 30% to make nonvolatile component, thus prepared acrylic resin soln 5.
The preparation > of < acrylic resin soln 6
In reaction vessel, add propylene glycol monomethyl ether 370 parts, while be heated to 80 DEG C to nitrogen injection limit in container, dripped the potpourri of following monomer and thermal polymerization at the same temperature with 1 hour, carry out polyreaction.
The ethylene-oxide-modified acrylate of p-cumylphenol 50.0 parts
Glycidyl methacrylate 0.8 part
Benzyl methacrylate 48.0 parts
Azoisobutyronitrile 3.5 parts
React at 100 DEG C after 3 hours after dropping, interpolation cyclohexanone 50 parts dissolves azoisobutyronitrile 1.0 parts of solution obtained, then at 100 DEG C, continue reaction 1 hour again.Then, atmosphere in container is replaced into air, 0.4 part, acrylic acid (100mol% of glycidyl), three (dimethylamino) phenol 0.1 part and quinhydrones 0.1 part is added in said vesse, reaction is continued 6 hours at 120 DEG C, until terminate reaction when solid constituent acid number reaches 0.5mgKOH/g, obtain the solution of acryl resin.Then add tetrabydrophthalic anhydride 0.8 part (100mo1% of the hydroxyl of generation), triethylamine 0.1 part, react 3.5 hours at 120 DEG C, thus obtain the solution of acryl resin.The weight-average molecular weight of this acryl resin is about 15000.
After being cooled to room temperature, sample tree lipoprotein solution is about 2g, heat drying 20 minutes at 180 DEG C, measure nonvolatile component, according to this measured value, in the resin solution of previously synthesis, add propylene glycol monomethyl ether reach 30% to make nonvolatile component, thus prepared acrylic resin soln 6.
The preparation > of < acrylic resin soln 7
In reaction vessel, add propylene glycol monomethyl ether 370 parts, while be heated to 80 DEG C to nitrogen injection limit in container, dripped the potpourri of following monomer and thermal polymerization at the same temperature with 1 hour, carry out polyreaction.
The ethylene-oxide-modified acrylate of p-cumylphenol 20.0 parts
Methacrylic acid 15.0 parts
Benzyl methacrylate 65.0 parts
Azoisobutyronitrile 3.5 parts
React at 100 DEG C after 3 hours after dropping, interpolation cyclohexanone 50 parts dissolves azoisobutyronitrile 1.0 parts of solution obtained, then at 100 DEG C, continue reaction 1 hour, thus obtains the solution of acryl resin again.The weight-average molecular weight of this acryl resin is about 15000.
After being cooled to room temperature, sample tree lipoprotein solution is about 2g, heat drying 20 minutes at 180 DEG C, measure nonvolatile component, according to this measured value, in the resin solution of previously synthesis, add cyclohexanone reach 30% to make nonvolatile component, thus prepared acrylic resin soln 7.
The preparation > of < acrylic resin soln 8
Except the benzyl methacrylate in the preparation of acrylic resin soln 7 is replaced by except methacrylic acid bicyclopentyl ester, synthesize by the method same with acrylic resin soln 7, thus prepared the acrylic resin soln 8 that solid constituent is 30%.The weight-average molecular weight of this acryl resin is about 15000.
The preparation > of < acrylic resin soln 9
Except the benzyl methacrylate in the preparation of acrylic resin soln 2 is replaced by except methyl methacrylate, synthesize by the method same with acrylic resin soln 2, thus prepared the acrylic resin soln 9 that solid constituent is 30%.The weight-average molecular weight of this acryl resin is about 15000.
The preparation > of < acrylic resin soln 10
Except ethylene-oxide-modified for the p-cumylphenol in the preparation of acrylic resin soln 2 acrylate being replaced by phenolethylene oxide modification acrylate (Osaka organic chemistry Inc. " PVC ス コ ー ト #192 "), synthesize by the method same with acrylic resin soln 2, thus prepared the acrylic resin soln 10 that solid constituent is 30%.The weight-average molecular weight of this acryl resin is about 15000.
The preparation > of < acrylic resin soln 11
Except ethylene-oxide-modified for the p-cumylphenol in the preparation of acrylic resin soln 7 acrylate and benzyl methacrylate are replaced by except methyl methacrylate, synthesize by the method same with acrylic resin soln 7, thus prepared the acrylic resin soln 11 that solid constituent is 30%.The weight-average molecular weight of this acryl resin is about 15000.
The preparation > of < acrylic resin soln 12
Except ethylene-oxide-modified for the p-cumylphenol in the preparation of acrylic resin soln 7 acrylate is replaced by phenolethylene oxide modification acrylate, is replaced by except 2-hydroxyethyl methacrylate by benzyl methacrylate, synthesize by the method same with acrylic resin soln 7, thus prepared the acrylic resin soln 12 that solid constituent is 30%.The weight average molecular weight of this acryl resin is about 15000.
The preparation > of < acrylic resin soln 13
Except ethylene-oxide-modified for the p-cumylphenol in the preparation of acrylic resin soln 7 acrylate being replaced by phenolethylene oxide modification acrylate, methacrylic acid being replaced by except methacrylic acid bicyclopentyl ester, synthesize by the method same with acrylic resin soln 7, thus prepared the acrylic resin soln 13 that solid constituent is 30%.The weight-average molecular weight of this acryl resin is about 15000.
The preparation > of < acrylic resin soln 14
Except ethylene-oxide-modified for the p-cumylphenol in the preparation of acrylic resin soln 2 acrylate is replaced by except methacrylic acid bicyclopentyl ester, synthesize by the method same with acrylic resin soln 2, thus prepared the acrylic resin soln 14 that solid constituent is 30%.The weight-average molecular weight of this acryl resin is about 15000.
The preparation > of < acrylic resin soln 15
In reaction vessel, add propylene glycol monomethyl ether 370 parts, while be heated to 80 DEG C to nitrogen injection limit in container, dripped the potpourri of following monomer and thermal polymerization at the same temperature with 1 hour, carry out polyreaction.
The ethylene-oxide-modified acrylate of p-cumylphenol
(East Asia Synesis Company system " ア ロ ニ ッ Network ス M110 ") 30.0 parts
2-methacryloxyethyl phthalic ester
(chemical company of Xin Zhong village system " NKESTERCB-1 ") 20.0 parts
Benzyl methacrylate 50.0 parts
Azoisobutyronitrile 3.5 parts
React at 100 DEG C after 3 hours after dropping, interpolation cyclohexanone 50 parts dissolves azoisobutyronitrile 1.0 parts of solution obtained, then at 100 DEG C, continue reaction 1 hour, thus obtains the solution of acryl resin again.The weight-average molecular weight of this acryl resin is about 15000.
After being cooled to room temperature, sample tree lipoprotein solution is about 2g, heat drying 20 minutes at 180 DEG C, measure nonvolatile component, according to this measured value, in the resin solution of previously synthesis, add cyclohexanone reach 30% to make nonvolatile component, thus prepared acrylic resin soln 15.
The preparation > of < acrylic resin soln 16
In reaction vessel, add propylene glycol monomethyl ether 370 parts, while be heated to 80 DEG C to nitrogen injection limit in container, dripped the potpourri of following monomer and thermal polymerization at the same temperature with 1 hour, carry out polyreaction.
The ethylene-oxide-modified acrylate of p-cumylphenol
(East Asia Synesis Company system " ア ロ ニ ッ Network ス M110 ") 30.0 parts
2-methacryloxyethyl phthalic ester
(chemical company of Xin Zhong village system " NKESTERCB-1 ") 20.0 parts
Benzyl methacrylate 35.0 parts
2-hydroxyethyl methacrylate 15.0 parts
Azoisobutyronitrile 3.5 parts
React at 100 DEG C after 3 hours after dropping, interpolation cyclohexanone 50 parts dissolves azoisobutyronitrile 1.0 parts of solution obtained, then at 100 DEG C, continue reaction 1 hour, thus obtains the solution of acryl resin again.The weight-average molecular weight of this acryl resin is about 15000.
After being cooled to room temperature, sample tree lipoprotein solution is about 2g, heat drying 20 minutes at 180 DEG C, measure nonvolatile component, according to this measured value, in the resin solution of previously synthesis, add cyclohexanone reach 30% to make nonvolatile component, thus prepared acrylic resin soln 16.
The preparation > of < acrylic resin soln 17
In reaction vessel, add propylene glycol monomethyl ether 370 parts, while be heated to 80 DEG C to nitrogen injection limit in container, dripped the potpourri of following monomer and thermal polymerization at the same temperature with 1 hour, carry out polyreaction.
The ethylene-oxide-modified acrylate of p-cumylphenol
(Osaka Organic Chemical Industry Inc. " V#315 ") 17.5 parts
Glycidyl methacrylate 28.0 parts
Benzyl methacrylate 10.5 parts
Azoisobutyronitrile 2.0 parts
React at 100 DEG C after 3 hours after dropping, interpolation cyclohexanone 50 parts dissolves azoisobutyronitrile 1.0 parts of solution obtained, then at 100 DEG C, continue reaction 1 hour again.Then, atmosphere in container is replaced into air, 14.2 parts, acrylic acid (100% of glycidyl), three (dimethylamino) phenol 0.5 part and quinhydrones 0.1 part is added in said vesse, reaction is continued 6 hours at 120 DEG C, until terminate reaction when solid constituent acid number reaches 0.5mgKOH/g, obtain the solution of acryl resin.Then add the tetrabydrophthalic anhydride 29.9 parts hydroxyl of the generation (100%), triethylamine 0.5 part, react 3.5 hours at 120 DEG C, thus obtain the solution of acryl resin.The weight-average molecular weight of this acryl resin is about 15000.
After being cooled to room temperature, sample tree lipoprotein solution is about 2g, heat drying 20 minutes at 180 DEG C, measure nonvolatile component, according to this measured value, in the resin solution of previously synthesis, add propylene glycol monomethyl ether reach 30% to make nonvolatile component, thus prepared acrylic resin soln 17.
The preparation > of < acrylic resin soln 18
In reaction vessel, add propylene glycol monomethyl ether 370 parts, while be heated to 80 DEG C to nitrogen injection limit in container, dripped the potpourri of following monomer and thermal polymerization at the same temperature with 1 hour, carry out polyreaction.
The ethylene-oxide-modified acrylate of p-cumylphenol
(Osaka Organic Chemical Industry Inc. " V#315 ") 18.3 parts
Glycidyl methacrylate 29.3 parts
Benzyl methacrylate 11.0 parts
Azoisobutyronitrile 2.0 parts
React at 100 DEG C after 3 hours after dropping, interpolation cyclohexanone 50 parts dissolves azoisobutyronitrile 1.0 parts of solution obtained, then at 100 DEG C, continue reaction 1 hour again.Then, atmosphere in container is replaced into air, 14.8 parts, acrylic acid (100% of glycidyl), three (dimethylamino) phenol 0.1 part and quinhydrones 0.1 part is added in said vesse, reaction is continued 6 hours at 120 DEG C, until terminate reaction when solid constituent acid number reaches 0.5, obtain the solution of acryl resin.Then add the tetrabydrophthalic anhydride 26.6 parts hydroxyl of the generation (85%), triethylamine 0.1 part, react 3.5 hours at 120 DEG C, thus obtain the solution of acryl resin.The weight-average molecular weight of this acryl resin is about 15000.
After being cooled to room temperature, sample tree lipoprotein solution is about 2g, heat drying 20 minutes at 180 DEG C, measure nonvolatile component, according to this measured value, in the resin solution of previously synthesis, add propylene glycol monomethyl ether reach 30% to make nonvolatile component, thus prepared acrylic resin soln 18.
The preparation > of < acrylic resin soln 19
In reaction vessel, add propylene glycol monomethyl ether 370 parts, while be heated to 80 DEG C to nitrogen injection limit in container, dripped the potpourri of following monomer and thermal polymerization at the same temperature with 1 hour, carry out polyreaction.
The ethylene-oxide-modified acrylate of p-cumylphenol
(Osaka Organic Chemical Industry Inc. " V#315 ") 5.3 parts
Glycidyl methacrylate 37.0 parts
Benzyl methacrylate 5.3 parts
Azoisobutyronitrile 1.7 parts
React at 100 DEG C after 3 hours after dropping, interpolation cyclohexanone 50 parts dissolves azoisobutyronitrile 1.0 parts of solution obtained, then at 100 DEG C, continue reaction 1 hour again.Then, atmosphere in container is replaced into air, 18.8 parts, acrylic acid (100% of glycidyl), three (dimethylamino) phenol 0.5 part and quinhydrones 0.1 part is added in said vesse, reaction is continued 6 hours at 120 DEG C, until terminate reaction when solid constituent acid number reaches 0.5, obtain the solution of acryl resin.Then add the tetrabydrophthalic anhydride 33.7 parts hydroxyl of the generation (85%), triethylamine 0.5 part, react 3.5 hours at 120 DEG C, thus obtain the solution of acryl resin.The weight-average molecular weight of this acryl resin is about 15000.
After being cooled to room temperature, sample tree lipoprotein solution is about 2g, heat drying 20 minutes at 180 DEG C, measure nonvolatile component, according to this measured value, in the resin solution of previously synthesis, add propylene glycol monomethyl ether reach 30% to make nonvolatile component, thus prepared acrylic resin soln 19.
The preparation > of < acrylic resin soln 20
In reaction vessel, add propylene glycol monomethyl ether 370 parts, while be heated to 80 DEG C to nitrogen injection limit in container, dripped the potpourri of following monomer and thermal polymerization at the same temperature with 1 hour, carry out polyreaction.
The ethylene-oxide-modified acrylate of p-cumylphenol
(Osaka Organic Chemical Industry Inc. " V#315 ") 50.0 parts
Glycidyl methacrylate 3.3 parts
Benzyl methacrylate 42.1 parts
Azoisobutyronitrile 3.3 parts
React at 100 DEG C after 3 hours after dropping, interpolation cyclohexanone 50 parts dissolves azoisobutyronitrile 1.0 parts of solution obtained, then at 100 DEG C, continue reaction 1 hour again.Then, atmosphere in container is replaced into air, 1.7 parts, acrylic acid (100% of glycidyl), three (dimethylamino) phenol 0.1 part and quinhydrones 0.1 part is added in said vesse, reaction is continued 6 hours at 120 DEG C, until terminate reaction when solid constituent acid number reaches 0.5, obtain the solution of acryl resin.Then add the tetrabydrophthalic anhydride 3.0 parts hydroxyl of the generation (85%), triethylamine 0.1 part, react 3.5 hours at 120 DEG C, thus obtain the solution of acryl resin.The weight-average molecular weight of this acryl resin is about 15000.
After being cooled to room temperature, sample tree lipoprotein solution is about 2g, heat drying 20 minutes at 180 DEG C, measure nonvolatile component, according to this measured value, in the resin solution of previously synthesis, add propylene glycol monomethyl ether reach 30% to make nonvolatile component, thus prepared acrylic resin soln 20.
The preparation > of < acrylic resin soln 21
Except the benzyl methacrylate in the preparation of acrylic resin soln 17 being replaced by methacrylic acid bicyclopentyl ester (Hitachi changes into Inc. " Off ァ Application Network リ Le FA-513M "), synthesize by the method same with acrylic resin soln 17, thus prepared the acrylic resin soln 21 that solid constituent is 30%.The weight-average molecular weight of this acryl resin is about 15000.
The preparation > of < acrylic resin soln 22
Except ethylene-oxide-modified for the p-cumylphenol in the preparation of acrylic resin soln 17 acrylate being replaced by phenol EO modification acrylate (East Asia Synesis Company system " ア ロ ニ ッ Network ス M102 "), synthesize by the method same with acrylic resin soln 17, thus prepared the acrylic resin soln 22 that solid constituent is 30%.The weight-average molecular weight of this acryl resin is about 15000.
The preparation > of < acrylic resin soln 23
Except ethylene-oxide-modified for the p-cumylphenol in the preparation of acrylic resin soln 20 acrylate is replaced by except methacrylic acid bicyclopentyl ester, synthesize by the method same with acrylic resin soln 20, thus prepared the acrylic resin soln 23 that solid constituent is 30%.The weight-average molecular weight of this acryl resin is about 15000.
The preparation > of < acrylic resin soln 24
Except ethylene-oxide-modified for the p-cumylphenol in the preparation of acrylic resin soln 16 acrylate being replaced by phenol EO modification acrylate, 2-methacryloxyethyl phthalic ester being replaced by except methacrylic acid, synthesize by the method same with acrylic resin soln 16, thus prepared the acrylic resin soln 24 that solid constituent is 30%.The weight-average molecular weight of this acryl resin is about 15000.
The preparation > of < acrylic resin soln 25
Except ethylene-oxide-modified for the p-cumylphenol in the preparation of acrylic resin soln 15 acrylate being replaced by phenol EO modification acrylate, 2-methacryloxyethyl phthalic ester being replaced by except methacrylic acid bicyclopentyl ester, synthesize by the method same with acrylic resin soln 15, thus prepared the acrylic resin soln 25 that solid constituent is 30%.The weight-average molecular weight of this acryl resin is about 15000.
The preparation > of < photosensitive coloring composition
First, by pigment, spreading agent, acrylic resin soln and the solvent planet-shaped ball milling shown in table 1A ~ 1E, use zirconia bead to carry out mixing pigment is disperseed, thus prepare pigment dispersion (R-1 ~ R-19, G-1 ~ G-19, B-1 ~ B-19, CR-1 ~ CR-7, CG-1 ~ CG-7 and CB-1 ~ CB-7).In addition, in Table 1, the use level of each composition is the ratio (% by weight) in following coloured composition.
Then, shown in table 2A ~ table 2E, acrylic resin soln, polymerizable monomer, Photoepolymerizationinitiater initiater and solvent is uniformly mixed in pigment dispersion (R-1 ~ R-19, G-1 ~ G-19, B-1 ~ B-19, CR-1 ~ CR-7, CG-1 ~ CG-7 and CB-1 ~ CB-7), then use the frit of 1 μm, thus prepare photosensitive coloring composition (R01 ~ R19, G01 ~ G19, B01 ~ B19, CR01 ~ CR07, CG01 ~ CG07 and CB01 ~ CB07).
Composition in table 1A ~ 1E is as follows.
< pigment >
P.R.254:C.I. paratonere 254
CibaSpecialtyChemicals Inc. IRGACUREREDBCF
P.R.177:C.I. paratonere 177
CibaSpecialtyChemicals Inc. CROMOPHTALREDA2B
P.Y.150:C.I. pigment yellow 150
LANXESS Inc. E4GN
P.G.36:C.I. pigment green 36
Toyo Ink manufacturing company Lionolgreen6YK
P.B.15:6:C.I. pigment blue 15: 6
Toyo Ink manufacturing company LionolblueES
P.V.23:C.I. pigment Violet 23
Toyo Ink manufacturing company リ オ ノ ゲ Application バ イ オ レ ッ ト RL
< spreading agent >
Japan ル ー Block リ ゾ ー Le Inc. " ソ Le ス パ ー ス 20000 "
< resin solution >
The acrylic resin soln of aforementioned preparation
< solvent >
Propylene glycol monomethyl ether
< polymerizable monomer >
Dipentaerythritol acrylate
< Photoepolymerizationinitiater initiater >
2-(dimethylamino) and-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone
< sensitizer >
2,4-diethyl thioxanthone
To the photosensitive coloring composition obtained in above-described embodiment and comparative example, by following method, dispersion stabilization, developability and re-workability are evaluated.Result is shown in table 3.
< dispersion stabilization evaluates >
Use E type viscosity Meter (TOKISANGYO Inc. TUE-20L type), under rotating speed 20rpm, the viscosity of photosensitive coloring composition at 25 DEG C is measured.Measure the viscosity on preparation same day of photosensitive coloring composition as initial stage viscosity (η 0:mPas), and measure photosensitive coloring composition is preserved the viscosity (η 7:mPas) after 7 days in the constant temperature enclosure of 40 DEG C, calculate viscosity ratio (η 7/ η 0).Then, by following benchmark evaluation dispersion stabilization.
Zero: η 7/ η 0 is less than 1.20, and the rising of viscosity does not occur substantially, and dispersion stabilization is good
△: η 7/ η 0 is more than or equal to 1.20 but is less than 1.50, and observe the slightly rising of viscosity, dispersion stabilization is slightly poor
×: η 7/ η 0 is more than or equal to 1.50, and the rising of viscosity is obvious, and dispersion stabilization is poor.
< developability evaluates >
Spin coating photosensitive coloring composition on the transparent glass substrate of 10 × 10cm, carries out the prebake conditions of 20 minutes at 70 DEG C, forms the film that dry film thickness is about 2.0 μm, measures its thickness (T1).Then, carry out ultraviolet exposure with exposure 50mJ, developed for 50 seconds with alkaline developer, measure the thickness (T2) after development, calculate Film Thickness Ratio (T2/T1).
Metewand is as follows.
Zero: Film Thickness Ratio (T2/Tl) is more than 0.95
×: Film Thickness Ratio (T2/T1) is less than 0.95
< re-workability evaluates >
The film being used for the evaluation of above-mentioned developability is formed substrate rear baking at 230 DEG C and, after 90 minutes, cut out the size that 1.5cm is square, as sample.
The rework solution 2mL(horizontal creek oil prodution industry セ ミ ク リ ー Application DF-7 being heated to 65 DEG C is added in ware), sample to be immersed in rework solution 5 minutes.After 5 minutes, rework solution is transferred to round-bottomed flask from ware together with sample, again by the Filter paper filtering of the 5 μm of apertures of the rework solution containing the film stripped down, diameter 3cm, the size of the stripping film using the light microscope determining with dimension measurement function to launch on filter paper.
Condition determination is: with optical microscope, with the multiplying power of 500 times, equally spaced 4 on the concentric circles of the center of filter paper and distance filter paper center 1cm amount to 5 places, sequentially determining 10 point from the length of the most long portion of stripping film is maximum, obtain the mean value of its most long portion.
Metewand is as follows.
◎: dissolve (not having the stripping film that available optical microscope confirms)
Zero: the most long portion of stripping film is on average less than 300 μm
△: the most long portion of stripping film is on average more than or equal to 300 μm but is less than 500 μm
×: the most long portion of stripping film is on average more than or equal to 500 μm but is less than 1000 μm
××: the most long portion of stripping film is on average more than or equal to 1000 μm
Table 3A:
Table 3B:
Known, long-term storing stability and the developability of the photosensitive coloring composition of comparative example 1 ~ 21 are good, but re-workability is poor, on the other hand, the photosensitive coloring composition of embodiments of the invention 1 ~ 57 also has excellent re-workability when maintaining long-term storing stability and developability.

Claims (8)

1. a photosensitive coloring composition, it contains resin, colorant, Photoepolymerizationinitiater initiater, polymerizable monomer and solvent, it is characterized in that, described resin is the Component units (a) represented by following general formula (1), the Component units (b) with carboxyl and the vinyl polymers formed except the Component units (c) except described Component units (a) and Component units (b)
General formula (1):
In general formula (1), R 1for hydrogen atom or methyl, R 2the alkylidene of to be carbon number be 2 or 3, R 3for hydrogen atom, the carbon number maybe can with phenyl ring are the alkyl of 1 ~ 20, l is the integer of 1 ~ 15;
The Component units (b1) that described Component units (b) represents for following general formula (2) and/or following Component units (b2), described Component units (b2) is Component units (d) addition that unsaturated monoacid and following general formula (5) are represented and the Component units making multi-anhydride and the hydroxyl addition generated and obtain
General formula (2):
In general formula (2), R 4for hydrogen atom or methyl, X 1for the group that following general formula (3) represents, Y 1for the group that following general formula (4) represents,
General formula (3):
In general formula (3), R 5to be carbon number be 2 ~ 12 alkylidene, m is the integer of 1 or 2;
General formula (4):
In general formula (4), R 6for main chain has 2 ~ 20 carbon atoms alkylidene, there is the cycloalkylidene of 6 ~ 8 ring carbon atoms or there is the arlydene of 6 ~ 14 ring carbon atoms, n is the integer of 0 or 1;
General formula (5):
In general formula (5), R 7for hydrogen atom or methyl, R 8for glycidyl, methylglycidyl, 3,2-glycidoxypropyl ethyls, 3,4-epoxycyclohexyls, 3,4-epoxybutyl or 4,5-epoxypentyl,
Described resin is the vinyl based copolymer precursor of the described Component units (a) of 1 ~ 50 % by weight (a '), the precursor (b ') of described Component units (b) of 5 ~ 91 % by weight and the precursor (c ') of the described Component units (c) of 1 ~ 80 % by weight being carried out copolymerization, or
Described resin makes unsaturated monoacid and the addition of vinyl based copolymer, then makes multi-anhydride and the hydroxyl addition generated and the resin that obtains, and described vinyl based copolymer is that the precursor of the described Component units (a) of 1 ~ 50 % by weight (a '), the precursor (d ') of described Component units (d) of 2 ~ 80 % by weight and the precursor (c ') of the described Component units (c) of 1 ~ 80 % by weight are carried out copolymerization.
2. photosensitive coloring composition according to claim 1, it is characterized in that, described resin is the vinyl based copolymer precursor of the Component units (a) of 1 ~ 35 % by weight (a '), the precursor (b ') of Component units (b) of 10 ~ 90 % by weight and the precursor (c ') of the Component units (c) of 1 ~ 75 % by weight being carried out copolymerization.
3. photosensitive coloring composition according to claim 1, it is characterized in that, described resin makes unsaturated monoacid and the addition of vinyl based copolymer, then makes multi-anhydride and the hydroxyl addition generated and the resin that obtains, and described vinyl based copolymer is that the precursor of the Component units (a) of 1 ~ 35 % by weight (a '), the precursor (d ') of Component units (d) of 4 ~ 75 % by weight and the precursor (c ') of the Component units (c) of 1 ~ 75 % by weight are carried out copolymerization.
4. photosensitive coloring composition according to claim 1, is characterized in that, the oxirane of the precursor of described Component units (a) (a ') containing p-cumylphenol and/or epoxy pronane modification (methyl) acrylate.
5. photosensitive coloring composition according to claim 1, is characterized in that, and the precursor of described Component units (c) (c ') containing (methyl) alkyl acrylate.
6. photosensitive coloring composition according to claim 1, it is characterized in that, the precursor of described Component units (c) (c ') is containing (methyl) benzyl acrylate and/or (methyl) acrylic acid bicyclopentyl ester and/or (methyl) acrylic acid dicyclopentenyl ester and/or (methyl) acrylic acid cyclopentyloxy ethyl ester.
7. photosensitive coloring composition according to claim 1, it is characterized in that, the precursor of described Component units (b) (b ') for being selected from acrylic acid dimer, β-carboxy ethyl (methyl) acrylate, 2-(methyl) acryloyloxyethyl succinate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid ester, 2-(methyl) acryloxypropyl succinate, 2-(methyl) acryloxypropyl phthalic ester, 2-(methyl) acryloxypropyl hexahydrophthalic acid ester, polyethylene oxide modified succinic acid (methyl) acrylate, more than any one in ω-carboxyl-Polycaprolactone modified list (methyl) acrylate and polyethylene oxide modified phthalic acid (methyl) acrylate.
8. a color filter, is characterized in that, it possesses the filter section and/or black matrix" that are formed by the photosensitive coloring composition described in any one of claim 1 ~ 7.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1252136A (en) * 1997-02-13 2000-05-03 Dsm有限公司 Photocurable resin composition
US6114092A (en) * 1997-09-29 2000-09-05 Kansai Paint Co., Ltd. Photosensitive resin compositions for photoresist
JP2004101728A (en) * 2002-09-06 2004-04-02 Toyo Ink Mfg Co Ltd Photosensitive colored composition
CN1507580A (en) * 2001-07-24 2004-06-23 Jsr株式会社 Positive type radiosensitive composition and method for forming pattern
CN1975471A (en) * 2005-11-30 2007-06-06 东洋油墨制造株式会社 Black composition and its production method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4561101B2 (en) 2003-03-06 2010-10-13 Ｊｓｒ株式会社 Radiation sensitive composition for color filter and color filter
JP4802746B2 (en) * 2006-02-08 2011-10-26 凸版印刷株式会社 Photosensitive coloring composition and color filter
JP2008070647A (en) 2006-09-14 2008-03-27 Toppan Printing Co Ltd Photosensitive colored composition, color filter using the same and liquid crystal display
JP4923894B2 (en) * 2006-09-15 2012-04-25 東洋インキＳｃホールディングス株式会社 Coloring composition for color filter and color filter using the same
JP5298653B2 (en) 2007-07-06 2013-09-25 Ｊｓｒ株式会社 Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1252136A (en) * 1997-02-13 2000-05-03 Dsm有限公司 Photocurable resin composition
US6114092A (en) * 1997-09-29 2000-09-05 Kansai Paint Co., Ltd. Photosensitive resin compositions for photoresist
CN1507580A (en) * 2001-07-24 2004-06-23 Jsr株式会社 Positive type radiosensitive composition and method for forming pattern
JP2004101728A (en) * 2002-09-06 2004-04-02 Toyo Ink Mfg Co Ltd Photosensitive colored composition
CN1975471A (en) * 2005-11-30 2007-06-06 东洋油墨制造株式会社 Black composition and its production method

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