CN107108769A - Resin combination, colored filter, its manufacture method and image-displaying member - Google Patents

Resin combination, colored filter, its manufacture method and image-displaying member Download PDF

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Publication number
CN107108769A
CN107108769A CN201580070146.6A CN201580070146A CN107108769A CN 107108769 A CN107108769 A CN 107108769A CN 201580070146 A CN201580070146 A CN 201580070146A CN 107108769 A CN107108769 A CN 107108769A
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China
Prior art keywords
resin combination
resin
methyl
epoxy radicals
acidic group
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CN201580070146.6A
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CN107108769B (en
Inventor
柳正义
川口恭章
木下健宏
坂本淳
仓本拓树
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Lishennoco Co ltd
Resonac Holdings Corp
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Showa Denko KK
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Liquid Crystal (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The present invention provides a kind of resin combination, and the resin combination contains：The polynary acid monoester (B) and solvent (C) of multifunctional (methyl) acrylate of resin (A), hydroxyl containing epoxy radicals and acidic group, wherein, relative to 1 mole of acidic group in the resin (A) containing epoxy radicals and acidic group, epoxy radicals is 0.5~3.0 mole.

Description

Resin combination, colored filter, its manufacture method and image-displaying member
Technical field
The present invention relates to a kind of resin combination, colored filter, its manufacture method and image-displaying member.
Background technology
Colored filter is generally by the transparency carriers such as glass substrate, red (R), green (G) that is formed on the transparent substrate and indigo plant (B) pixel, the stain matrix formed in pixel boundary and the diaphragm composition formed in pixel and stain matrix.Tool There is the colored filter of the structure, generally made by sequentially forming stain matrix, pixel and diaphragm on the transparent substrate Make.As pixel and the forming method of stain matrix (being below referred to as pixel and stain matrix " colored pattern "), it has been proposed that Various methods, but main flow is pigment/dye dispersion method now, and this method is used to be used as the photosensitive resin composition of resist The photoetching process (photolithography) that coating, exposure, development and the baking of thing repeat.
The photosensitive polymer combination for being commonly used for photoetching process contains alkali soluble resin, reactive diluent, light Polymerization initiator, colouring agent and solvent.In pigment/dye dispersion method, the excellent in te pins of durability of light resistance and heat resistance etc. can Form the few colored pattern of defect such as pin hole, but on the contrary, pattern and diaphragm due to being repeatedly formed stain matrix, R, G, B, Therefore it is required that the high solvent resistance of cured coating film.
It is thus proposed that for example, using having epoxy radicals or oxetanylmethoxy (oxetanyl) and carboxyl or phenol hydroxyl The copolymer of base, to improve the method (patent document 1 and 2) of solvent resistance；Or, using containing with the Evil of containing trihalomethyl The material of the molecule of diazole structure or triazine structure is as polymerization initiator, to improve the method (patent document 3) of solvent resistance.
In addition, in order to improve color reproduction (color reproduction) characteristic of colored filter, it is necessary to increase institute The content of the colouring agent of addition thickens thickness etc., but at the same time there are problems that producing sensitivity decrease, developability Tendency, it is desirable to further improve performance (patent document 4).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2012-22048 publications
Patent document 2：Japanese Unexamined Patent Publication 2013-25203 publications
Patent document 3：Japanese Unexamined Patent Publication 2003-330184 publications
Patent document 4：Japanese Unexamined Patent Publication 2014-164021 publications
The content of the invention
The technical problem to be solved in the present invention
However, conventional photosensitive polymer combination has that sensitivity, developability are insufficient or can not obtain resistance to The situation of the excellent cured coating film of solvent borne.
Therefore, the present invention completes for solution above-mentioned technical problem, its object is to there is provided a kind of resin combination, its While sensitivity, developability are good, the cured coating film of excellent solvent resistance can be formed.In addition, the purpose of the present invention exists In there is provided a kind of colored filter, it has the colored pattern formed by the cured coating film of excellent solvent resistance.
Solve the technological means of technical problem
That is, the present invention is as shown in following [1]~[14].
[1] a kind of resin combination, it contains the resin (A) containing epoxy radicals and acidic group, multifunctional (methyl) of hydroxyl The polynary acid monoester (B) and solvent (C) of acrylate, it is characterised in that relative to the resin containing epoxy radicals and acidic group (A) 1 mole of acidic group in, epoxy radicals is 0.5~3.0 mole.
[2] resin combination according to [1], it, which contains, have olefinic carbon-to-carbon double bond and ring in a comfortable molecule The monomeric unit of the monomer (a-1) of epoxide, is used as the structures alone unit of the resin (A) containing epoxy radicals and acidic group.
[3] resin combination according to [1] or [2], it contains the monomeric unit from unsaturated carboxylic acid (a-2), It is used as the structures alone unit of the resin (A) containing epoxy radicals and acidic group.
[4] resin combination according to [3], wherein, the resin (A) containing epoxy radicals and acidic group contains：Coming From a part for the carboxyl of the unsaturated carboxylic acid (a-2), addition has the functional group having in a molecule with carboxyl reaction With structures alone unit monomer (a-3), with olefinic carbon-to-carbon double bond of olefinic carbon-to-carbon double bond.
[5] resin combination according to [2], wherein, it is described that there is olefinic carbon-to-carbon double bond and epoxy in a molecule The monomer (a-1) of base is (methyl) acrylate containing epoxy radicals.
[6] resin combination according to [4], wherein, the functional group having in a molecule with carboxyl reaction With the monomer (a-3) of olefinic carbon-to-carbon double bond, for selected from (methyl) acrylate containing epoxy radicals and the (first containing NCO Base) it is one kind or two or more in acrylate.
[7] resin combination according to any one of [1]~[6], wherein, multifunctional (methyl) of the hydroxyl The polynary acid monoester (B) of acrylate, for selected from the polynary acid monoester by the two of pentaerythrite or three (methyl) acrylate, two It is one kind or two or more in the group that the polynary acid monoester of two, three, four or five (methyl) acrylate of pentaerythrite is constituted.
[8] resin combination according to any one of [1]~[7], wherein, the resin containing epoxy radicals and acidic group (A) acid number is 10~350mgKOH/g.
[9] resin combination according to any one of [1]~[8], it further contains Photoepolymerizationinitiater initiater (D).
[10] resin combination according to any one of [1]~[9], it further contains colouring agent (E).
[11] resin combination according to [10], wherein, the colouring agent (E) is selected from by dyestuff and pigment institute group Into group in it is at least one kind of.
[12] a kind of colored filter, it has what is formed as the cured coating film of the resin combination described in [10] or [11] Colored pattern.
[13] a kind of image-displaying member, it possesses the colored filter described in [12].
[14] a kind of manufacture method of colored filter, it includes following process：To [10] or [11] Suo Shu on substrate The resin combination process that is coated, exposes and is developed by alkaline aqueous solution；Temperature strip below 215 DEG C Toasted under part, the process for forming colored pattern.
Invention effect
In accordance with the invention it is possible to provide a kind of resin combination, its sensitivity, developability are good, while can be formed resistance to The excellent cured coating film of solvent borne.In addition, the solidification of the state after the exposure formed by the resin combination of the present invention, before baking Film has developability, therefore the value in various resist fields is high, the solidification of the state after particularly toasting The excellent solvent resistance of film, therefore be useful on the colored pattern for forming colored filter.
Brief description of the drawings
Fig. 1 is the profile of the colored filter of an embodiment of the invention.
Embodiment
The resin combination of the present invention contains the resin (A) containing epoxy radicals and acidic group, multifunctional (methyl) third of hydroxyl The polynary acid monoester (B) and solvent (C) of olefin(e) acid ester, it is characterised in that relative to 1 in the resin (A) containing epoxy radicals and acidic group Mole acidic group, epoxy radicals is 0.5~3.0 mole.
In the present invention, " (methyl) acrylate " refers at least one kind of in methacrylate and acrylate.It is right It is also identical in " (methyl) acrylic acid ".
The resin (A) containing epoxy radicals and acidic group used in the present invention, as long as there is epoxy radicals and acidic group in resin, And relative to 1 mole of acidic group in resin, epoxy radicals exists with 0.5~3.0 mole, is not particularly limited.Acidic group does not have It is particularly limited to, but can generally enumerates：Carboxyl (- COOH), phosphate (- PO (OH)2), sulfonic group (- SO3H) etc..From the present invention's From the viewpoint of the curability of resin combination, preferred carboxyl.Easiness, the resin containing epoxy radicals and acidic group are obtained from raw material (A) from the viewpoint of ease of manufacturing and solvent resistance when improving the resin combination of the solidification present invention, preferably contain Have has the monomeric unit of olefinic carbon-to-carbon double bond and the monomer (a-1) of epoxy radicals as structures alone unit in a molecule Resin；From the viewpoint of developability, more preferably further contain the monomeric unit conduct from unsaturated carboxylic acid (a-2) The resin of structures alone unit.In addition, in the case of the species of structures alone is known with mol ratio, relative to containing epoxy radicals And the 1 mole of acidic group of resin (A), the molal quantity of epoxy radicals of acidic group, it can be calculated by the addition ratio of structures alone.By closing When the resin (A) containing epoxy radicals and acidic group after calculates the molal quantity relative to the epoxy radicals of 1 mole of acidic group, by with JIS The value of acid number of the epoxide equivalent determined on the basis of K 7236 with being determined on the basis of JIS K 0070 and calculate.
From the viewpoint of the ease of manufacturing of the resin (A) containing epoxy radicals and acidic group, (methyl) preferably containing epoxy radicals Acrylate is used as monomer (a-1).As monomer (a-1) concrete example, it can include：(methyl) glycidyl acrylate, 3,4- epoxycyclohexyls (methyl) methyl acrylate and its lactone addition product (such as Daicel with ester ring type epoxy radicals Corporation manufacture CYM (registration mark) A200, M100), 3,4- epoxycyclohexyl-methyls -3', 4'- 7-oxa-bicyclo[4.1.0 List (methyl) acrylate of carboxylate, the epoxides of dicyclopentenyl (methyl) acrylate, dicyclopentenyl epoxide second Epoxides of base (methyl) acrylate etc..Wherein, particularly from the viewpoint of easy degree, reactivity is obtained, preferably (methyl) glycidyl acrylate.
As unsaturated carboxylic acid (a-2) concrete example, it can enumerate：(methyl) acrylic acid, crotonic acid, cinnamic acid, itaconic acid, The adjacent benzene two of maleic acid, fumaric acid, vinyl sulfonic acid, 2- (methyl) acryloyl-oxyethyls butanedioic acid, 2- acryloyl-oxyethyls Formic acid, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid etc..From the viewpoint of raw material is obtained, preferred (methyl) third Olefin(e) acid and crotonic acid, more preferably (methyl) acrylic acid.
The resin (A) containing epoxy radicals and acidic group that the present invention is used, can contain from demonomerization (a-1) and unsaturated carboxylic The monomeric unit of the monomer of free redical polymerization beyond sour (a-2), is used as structures alone unit.As demonomerization (a-1) and The concrete example of the monomer of free redical polymerization beyond unsaturated carboxylic acid (a-2), can be enumerated：2- (methyl) acryloyl-oxyethyl The dienes such as acid phosphoric acid ester, butadiene；(methyl) methyl acrylate, (methyl) isopropyl acrylate, (methyl) acrylic acid penta Ester, (methyl) benzyl acrylate, (methyl) isoamyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid ten Diester, (methyl) cyclohexyl acrylate, 1,4 cyclohexane dimethanol list (methyl) acrylate, (methyl) acrylic acid rosin ester, (methyl) acrylic acid norborneol ester, (methyl) allyl acrylate, (methyl) tetrahydrofurfuryl acrylate, 1,1,1- trifluoroethyls (methyl) acrylate, (methyl) perfluoroethyl ethyl ester, (methyl) acrylic acid triphenylmethyl, (methyl) acrylic acid cumyl Ester, 3- (N, N- dimethylamino) propyl group (methyl) acrylate, glycerine list (methyl) acrylate, penta triol list (methyl) Acrylate, the ring pentyl ester of (methyl) acrylic acid two, (methyl) isobornyl acrylate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (first Base) (methyl) esters of acrylic acid such as acrylic acid naphthalene ester；ENB (bicyclic [2.2.1] hept-2-ene"), 5- methyl bicycles Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5- ethyls, Fourth Ring [4.4.0.12,5.17,10] 12-3- alkene, two rings penta Diene, three ring [5.2.1.02,6] decyl- 8- alkene, Fourth Ring [4.4.0.12,5.17,10.01,6] 12-3- alkene, five rings [6.5.1.13, 6.02,7.09,13] 15-4- alkene, 5- ENB-2- carboxylic acids, 5- ENB-2,3- dicarboxylic anhydrides；(methyl) acrylic acid acyl Amine, (methyl) acrylic acid N, N- diacetayl amide, (methyl) acrylic acid anthryl acid amides, (methyl) acrylic acid morpholine, diacetone (first Base) (methyl) acrylic acid amides such as acrylamide；(methyl) acrylic acid anilid, (methyl) propylene acyl cyanide, methacrylaldehyde, chloroethene The second such as alkene, vinylidene chloride, PVF, vinylidene, N- vinylpyrrolidones, vinylpyridine, vinyl acetate, vinyl toluene Ene compound；Styrene, styrene α-, it is o-, m-, to alkyl, nitro, cyano group, amide derivatives；Citraconic acid diethylester, horse Carry out the unsaturated dicarboxylic diester such as diethyl phthalate；The list maleimide such as N-phenylmaleimide, N- N-cyclohexylmaleimides Amine；The unsaturation multi-anhydride such as maleic anhydride, itaconic anhydride.These materials may be used alone or in combination two or more and use.This Outside, wherein, from the viewpoint of heat resistance and the transparency, preferably (methyl) benzyl acrylate, the ring pentyl ester of (methyl) acrylic acid two, Styrene, vinyltoluene, (methyl) isobornyl acrylate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, ENB, N- isopropyls (methyl) acrylamide, (methyl) acrylic acid morpholine and diacetone (methyl) acrylamide, more preferably (methyl) acrylic acid benzyl Ester, the ring pentyl ester of (methyl) acrylic acid two, styrene, vinyltoluene, (methyl) isobornyl acrylate, (methyl) acrylic acid gold Firm alkyl ester and ENB.
For monomer (a-1) adding proportion, as long as relative to 1 equimolar acid in the resin (A) containing epoxy radicals and acidic group Base, epoxy radicals is not particularly limited with 0.5~3.0 mole of presence, but relative to the resin (A) containing epoxy radicals and acidic group The total amount of structures alone, preferably 40~90 moles %, more preferably 50~90 moles %, more preferably 60~80 rub You are %.If the adding proportion of monomer (a-1) is 40~90 moles of %, developability is good, while can obtain sufficient solvent resistant Property.
For unsaturated carboxylic acid (a-2) adding proportion, as long as relative to 1 in the resin (A) containing epoxy radicals and acidic group Mole acidic group, epoxy radicals is not particularly limited with 0.5~3.0 mole of presence, but relative to the resin containing epoxy radicals and acidic group (A) total amount of structures alone, preferably 10~60 moles %, more preferably 10~50 moles %, more preferably 20~ 40 moles of %.By making the adding proportion of unsaturated carboxylic acid (a-2) be 10~60 moles of %, developability is good, can obtain simultaneously Sufficient solvent resistance.
In the monomer of the free redical polymerization beyond using demonomerization (a-1) and unsaturated carboxylic acid (a-2), it adds ratio Example is not particularly limited, but the total amount of the structures alone relative to the resin (A) containing epoxy radicals and acidic group, and preferably greater than 0 rubs Your % and be 50 moles of below %, more preferably higher than 0 mole % and be 40 moles of below %.
Relative to the total amount of the structures alone unit of the resin (A) containing epoxy radicals and acidic group, further preferably 40~90 rub Your % monomeric unit from monomer (a-1) and 10~60 moles of % monomeric unit from unsaturated carboxylic acid (a-2), Further preferably 60~80 moles % monomeric unit from monomer (a-1) and 20~40 moles of %'s comes from insatiable hunger With the monomeric unit of carboxylic acid (a-2).
Copolyreaction for manufacturing the resin (A) containing epoxy radicals and acidic group, can according to it is well known in the art from Carried out by base polymerization.For example, by demonomerization (a-1), unsaturated carboxylic acid (a-2) and monomer (a-1) and unsaturated carboxylic acid (a-2) monomer (any condition) of the free redical polymerization beyond is dissolved in after solvent, and polymerization initiator is added into the solution, It is set to react at 50~130 DEG C 1~20 hour.By the copolyreaction, it can obtain with the addition ratio with monomer The random copolymer of the of substantially equal monomeric unit ratio of example.
As the solvent available for the copolyreaction, for example, it can include：Glycol monoethyl ether, triethylene glycol monomethyl ether, Poly glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol list isopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monohexyl ether, second two Alcohol single 2-ethyl hexyl ether, ethylene glycol monoallyl ether, ethylene glycol list phenyl ether, diethylene glycol single-benzyl ether, ethylene glycol monoethyl ether second Acid esters, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol methyl ether acetate, glycol dimethyl ether, diethylene glycol methyl ethyl Ether and dimethyl ether etc..These solvents may be used alone or in combination two or more and use.
The moisture content of solvent is not particularly limited, but preferably below 1 mass %.If moisture content is below 1 mass %, The resin (A) containing epoxy radicals and acidic group with better solvent resistance can be obtained.In addition, the moisture content of solvent can pass through Karl_Fischer method (Karl Fischer), is measured with following conditions.
Device：The KF moisture meters MKA-520 of KYOTO ELECTRONICS MANUFACTURING CO., LTD. manufactures
Injection rate：1mL
Titrating solution：AQUAMICRON (registration mark) titrant SS 3mg (API Corporation manufactures)
Electrode solution：AQUAMICRON (registration mark) dehydrated solvents PP (API Corporation manufactures)
The addition of solvent when manufacturing resin (A) containing epoxy radicals and acidic group is not particularly limited, but will contain epoxy When the total amount of the structures alone of the resin (A) of base and acidic group is set to 100 mass parts, it is preferably 30~1000 mass parts, more excellent Elect 50~800 mass parts as.Particularly, by the way that the addition of solvent is set to below 1000 mass parts, chain tra nsfer can be passed through Effect suppresses the reduction of the molecular weight of the resin (A) containing epoxy radicals and acidic group, and can be by the resin (A) containing epoxy radicals and acidic group Viscosity control in optimum range.In addition, by the way that the addition of solvent is set to more than 30 mass parts, exception can be being prevented While polymerisation, stable progress polymerisation, the coloring and gelation of the resin (A) containing epoxy radicals and acidic group are prevented.
As the polymerization initiator available for resin (A) of the manufacture containing epoxy radicals and acidic group, it is not particularly limited, for example may be used Enumerate：Azodiisobutyronitrile, AMBN, benzoyl peroxide, t-butyl peroxy -2 ethyl hexanoic acid ester etc..These gather Conjunction initiator may be used alone or in combination two or more and use.
When the total amount of the structures alone of the resin (A) containing epoxy radicals and acidic group is set into 100 mass parts, polymerization initiator Addition be preferably 0.5~20 mass parts, more preferably 1.0~10 mass parts.
In addition it is also possible to without using organic solvent, and use monomer (a-1), unsaturated carboxylic acid (a-2), as it is any into The monomer and polymerization initiator of free redical polymerization beyond the demonomerization (a-1) and unsaturated carboxylic acid (a-2) that divide, are carried out Polymerisation in bulk.
In the resin (A) containing epoxy radicals and acidic group obtained in above-mentioned copolyreaction, olefinic carbon-to-carbon can be further imported Double bond.Thus sensitivity and the developability of resin combination are improved.
For example, it is also possible in the carboxyl from the unsaturated carboxylic acid (a-2) for constituting the resin (A) containing epoxy radicals and acidic group Contain in a part, in the molecule of addition one with the functional group with carboxyl-reactive and the monomer (a-3) of olefinic carbon-to-carbon double bond, So as to import olefinic carbon-to-carbon double bond.Thus, the resin (A) containing epoxy radicals and acidic group contains：From unsaturated carboxylic acid (a-2) Carboxyl a part on, addition, which has, has functional group with carboxyl reaction and the monomer (a- of olefinic carbon-to-carbon double bond in a molecule 3), construction unit with olefinic carbon-to-carbon double bond.As the functional group with carboxyl reaction, NCO, epoxy can be enumerated Base, vinyl ether group etc..Wherein, from the viewpoint of reactivity during addition reaction, preferred isocyanate base.As with epoxy The monomer (a-3) of base, can be used the monomer identical monomer with being illustrated as monomer (a-1).In addition, as with isocyanic acid The monomer (a-3) of ester group, is not particularly limited, and is preferably (methyl) acrylate containing NCO, specifically, can arrange Lift 2- (methyl) acryloyloxyethyl isocyanate, 1,1- (double (methyl) acryloyloxymethyls) ethyl isocyanate, 2- (different Cyanic acid ester group ethyl epoxide) ethyl (methyl) acrylate etc..Wherein, there is NCO and olefinic preferably in a molecule The monomer of carbon-to-carbon double bond.More preferably 2- (methyl) acryloyloxyethyl isocyanate.It is used as the monomer with vinyl ether group (a-3), it is not particularly limited, preferably vinyl ethers (methyl) acrylate, specifically, (methyl) acrylic acid 2- can be enumerated (2- vinyloxyethoxies) ethyl ester etc..
Further, can also be in the molecule of addition one in the case where the resin (A) containing epoxy radicals and acidic group contains anhydride group With the functional group reacted with anhydride group and the monomer of olefinic carbon-to-carbon double bond, so as to import olefinic carbon-to-carbon double bond.As with acid The functional group of anhydride group reaction, can enumerate hydroxyl.
Addition contains with reactivity on carboxyl, epoxy radicals or anhydride group in the resin (A) containing epoxy radicals and acidic group Functional group monomer and import the reaction of carbon-to-carbon double bond, as long as addition addition is in the list of the resin (A) containing epoxy radicals and acidic group Body, polymerization inhibitor and catalyst, preferably 50~150 DEG C, more preferably reacted at 80~130 DEG C.In addition, adding at this Into in reaction, even if containing the solvent used in above-mentioned copolyreaction, also in the absence of special problem, therefore, in copolyreaction After end, solvent can not be removed and carry out addition reaction.
Here, in order to prevent the gelation caused by the polymerization of the resin (A) containing epoxy radicals and acidic group, can also add Polymerization inhibitor.As polymerization inhibitor, it is not particularly limited, for example, can enumerates hydroquinones, methyl hydroquinone, hydroquinone monomethyl ether Deng.In addition, as catalyst, being not particularly limited, for example, it can enumerate：Such as tertiary amine, such as triethyl benzyl ammonia chloride of triethylamine Quaternary ammonium salt, the phosphide of such as triphenylphosphine, the chelate of chromium.
Acid number (the JIS K 6901 of the resin (A) containing epoxy radicals and acidic group used in the present invention：2008 5.3.2) do not have It is restricted, but when for colored filter purposes, preferably 10~350mgKOH/g, more preferably 30~200mgKOH/g, More preferably 50~180mgKOH/g, particularly preferably 70~150mgKOH/g.If the acid number more than 10mgKOH/g, Sufficient developability can then be obtained.On the other hand, if the acid number is below 350mgKOH/g, exposed portion (photo-cured portion) Alkaline-based developer is not dissolved in, sufficient developability is obtained.
In addition, the molecular weight of the resin (A) containing epoxy radicals and acidic group (is surveyed using gel permeation chromatography described later (GPC) The fixed weight average molecular weight for being converted into polystyrene) it is preferably 1000~50000, more preferably 3000~40000.If the molecule Measure as more than 1000, then do not produce the defect of colored pattern after development, good sensitivity can be obtained.On the other hand, if should Molecular weight is less than 50000, then developing time is very short, there is practicality.
In addition, when the resin (A) containing epoxy radicals and acidic group has unsaturated group, the equivalent of the unsaturated group does not have Limitation, more preferably preferably 100~4000g/mol, 200~3000g/mol.If the equivalent of the unsaturated group is 100g/ More than mol, then be effective in terms of resistance to pyrolytic and heat-resisting xanthochromia is further improved.On the other hand, if the unsaturation The equivalent of group is below 4000g/mol, then is effective in terms of sensitivity is further improved.
The resin combination of the present invention contains the polynary acid monoester (B) of multifunctional (methyl) acrylate of hydroxyl.Make For the polynary acid monoester (B) of multifunctional (methyl) acrylate of hydroxyl, for example, it can enumerate：Two or three (first of pentaerythrite Base) acrylate polynary acid monoester, the polynary acid monoester of two, three, four or five (methyl) acrylate of dipentaerythritol, tool Body can be enumerated：The succinate modified thing of Dipentaerythritol Pentaacrylate, the succinate modified thing of pentaerythritol triacrylate, two seasons The orthophthalic modified thing of the acrylate of penta tetrol five, the orthophthalic modified thing of pentaerythritol triacrylate etc., containing Addition has the modified by polyacid thing of acid anhydrides on the hydroxyl of multifunctional (methyl) acrylate of hydroxyl.These materials can be used alone Or combine two or more and use.Wherein, from the viewpoint of solvent resistance, preferred multifunctional (methyl) acrylate of hydroxyl Succinate modified thing.
Relative to the summation of (A) composition and (B) composition, the polynary acid monoester of multifunctional (methyl) acrylate of hydroxyl (B) addition is preferably 10~90 mass %, more preferably 20~80 mass %, more preferably 25~70 mass %. If the addition of the scope, then the resin combination with suitable viscosity is formed, by adding Photoepolymerizationinitiater initiater described later (D), with suitable photo-curable.
The resin combination of the present invention contains solvent (C).As solvent (C), as long as dissolving is containing epoxy radicals and acidic group The polynary acid monoester (B) and the inertia do not reacted with them of multifunctional (methyl) acrylate of resin (A) and hydroxyl Solvent, is not particularly limited.
As solvent (C), used in the usable copolyreaction with when manufacturing resin (A) containing epoxy radicals and acidic group Solvent identical solvent, contained solvent can also be directly used in after copolyreaction.The tree of the present invention can also prepared Further added during oil/fat composition.Or, it is aftermentioned addition other compositions when, also can be used directly with these compositions coexist it is molten Agent.As solvent (C) concrete example, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether second can be enumerated Acid esters, ethyl acetate, butyl acetate, isopropyl acetate, dipropylene glycol monomethyl ether, Tripropylene glycol monomethyl Ether, glycol monoethyl ether, Diethylene glycol monomethyl ether, MEK, methylisobutylketone, cyclohexanone, ethylene glycol monoethylether acetate, diethylene glycol monoethyl ether acetic acid Ester etc..These solvents may be used alone or in combination two or more and use.In addition, wherein, preferably in manufacture containing epoxy radicals and acidic group The glycol ethers solvents such as propylene glycol monomethyl ether, the propylene glycol methyl ether acetate used in copolyreaction during resin (A).
If the summation of the composition of the solvent (C) in the resin combination for removing the present invention is set into 100 mass parts, solvent (C) addition is preferably 30~1000 mass parts, more preferably 50~800 mass parts, more preferably 100~700 matter Measure part.If the addition of the scope, then the resin combination with suitable viscosity is formed.
When being used to be formed the colored pattern of colored filter by the resin combination of the present invention, photopolymerization is further added Initiator (D) and colouring agent (E) and use.
As Photoepolymerizationinitiater initiater (D), it is not particularly limited, for example, can enumerates：The styraxes such as styrax, benzoin methyl ether And its alkyl ether；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 1,1- dichloroacetophenones, 4- (1- tert-butyl groups dioxy - 1- Methylethyls) acetophenones such as acetophenone；1- hydroxycyclohexyl phenyl ketones, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone etc. Alkylbenzene ketone；The Anthraquinones such as 2-methylanthraquinone, 2- amyl anthraquinones, 2- tert-butyl groups anthraquinone, 1- chloroanthraquinones；2,4- dimethyl thiophenes The thioxanthene ketone class such as ton ketone, 2,4- diisopropylthioxanthones, CTX；Acetophenone dimethyl ketal, benzyl dimethyl ketal Deng ketal class；Benzophenone, 4- (epoxide -1- Methylethyls of the 1- tert-butyl groups two) benzophenone, the 3,3', (tert-butyl groups two of 4,4'- tetra- Oxygen carbonyl) benzophenone such as benzophenone；1,2- acetyl caproyls, 1- [4- (phenyl)-, 2- (O- benzoyls oxime)], ethyl ketone (ethanone), 1- [9- ethyls -6- (2- methyl benzoyls) -9H- carbazole -3- bases] -, the oxime esters such as 1- (0- acetyl oxime)； 2- methyl isophthalic acids-[4- (methyl thio) phenyl] -2- morpholinoes-propane -1- ketone；2- benzyl -2- dimethylaminos -1- (4- morpholines For phenyl) -1- butanone；2,4,6- trimethylbenzoyls diphenyl phosphine oxide, the oxidation of double (2,4,6- trimethylbenzoyls) phenyl The acylphosphine oxide class such as phosphine；And xanthone class etc..These Photoepolymerizationinitiater initiaters may be used alone or in combination two or more and use.
If the summation of (A) composition and (B) composition is set into 100 mass parts, the addition of Photoepolymerizationinitiater initiater (D) is preferred For 0.1~30 mass parts, more preferably more preferably 0.5~20 mass parts, 1~15 mass parts.If the scope adds Dosage, then form the resin combination with suitable photo-curable.
Colouring agent (E) is not particularly limited as long as being dissolved or dispersed in the resin combination of the present invention, for example, can arranged Lift dyestuff or pigment etc..
Particularly in the resin combination of the present invention, due to as it is explained in detail hereinafter, even in lower temperature (less than 215 DEG C) It is lower to be toasted, sufficient solvent resistance can be also obtained, therefore be not likely to produce the dye deterioration caused by heat.Cause This, in the resin combination of the present invention, can freely use a greater variety of dyestuffs, obtain colored pattern.
As dyestuff, dissolubility or dispersiveness from the resin combination to the present invention, with other in resin combination into Divided by the viewpoint such as interaction, heat resistance, preferably use the acid dyes with acidic-groups such as carboxyls, acid dyes with The salt of nitride, sulfanilamide (SN) body of acid dyes etc..As the example of this dyestuff, it can enumerate：Acid alizarine purple (acid alizarin violet)N；Acid black (acid black) 1,2,24,48；Acid blue (acid blue) 1,7,9,25,29, 40、45、62、70、74、80、83、90、92、112、113、120、129、147；Sour chrome violet (acid chrome violet) K；Acid Property pinkish red (acid Fuchsin)；Acid green (acid green) 1,3,5,25,27,50；Acid orange (acid orange) 6,7, 8、10、12、50、51、52、56、63、74、95；Acid red (acid Red) 1,4,8,14,17,18,26,27,29,31,34, 35、37、42、44、50、51、52、57、69、73、80、87、88、91、92、94、97、103、111、114、129、133、134、 138、143、145、150、151、158、176、183、198、211、215、216、217、249、252、257、260、266、274； Acid violet (acid violet) 6B, 7,9,17,19；Indian yellow (acid yellow) 1,3,9,11,17,23,25,29,34, 36、42、54、72、73、76、79、98、99、111、112、114、116；Food Huang (food yellow) 3；VALIFAST Blue 2620 and their derivative etc..Wherein, the preferred acid dyes of azo, oxa anthracenes, Anthraquinones or phthalocyanines.These things Matter can be used alone or in combination of two or more kinds according to the pixel color as purpose.
As the example of pigment, can enumerate C.I. pigment yellows (Pigment Yellow) 1,3,12,13,14,15,16,17, 20、24、31、53、83、86、93、94、109、110、117、125、128、137、138、139、147、148、150、153、154、 166th, the yellow uitramarine such as 173,194,214；C.I. pigment orange (Pigment Orange) 13,31,36,38,40,42,43,51, 55th, the orange pigment such as 59,61,64,65,71,73；C.I. paratonere (Pigment Red) 9,97,105,122,123,144, 149th, the red pigment such as 166,168,176,177,180,192,209,215,216,224,242,254,255,264,265； C.I. alizarol saphirol (Pigment Blue) 15,15：3、15：4、15：6th, the blue pigment such as 60；C.I. pigment violet (Pigment Violet) 1,19,23,29,32,36,38 etc. violet pigment；C.I. the green of naphthol green (Pigment Green) 7,36,58 etc. Pigment；C.I. the brown of pigment brown (Pigment Brown) 23,25 etc.；C.I. pigment black (Pigment Black) 1,7, charcoal Black pigments such as black, titanium is black, acidifying iron etc..These pigment can be used alone or combine 2 according to the pixel color as purpose Plant used above.
In addition, above-mentioned dyestuff and pigment combination can also be used according to the pixel color as purpose.
When adding colouring agent (E), relative to the solvent (C) in the resin combination of the removing present invention of 100 mass parts Composition summation, the addition is preferably 5~80 mass parts, more preferably 5~70 mass parts, more preferably 10~60 Mass parts.
, can also be in resin group from the viewpoint of the dispersiveness for improving pigment when using pigment as colouring agent (E) Known dispersant is added in compound.As dispersant, preferably use through when scattered excellent in stability macromolecule dispersing agent.Make For the example of macromolecule dispersing agent, it can enumerate：Urethane class dispersant, polyethyleneimine amine dispersant, polyoxyethylene alkyl ether class Dispersant, the esters dispersant of polyoxyethylene glycol two, polyoxyethylensorbitan fatty race esters dispersant, aliphatic modified esters dispersant Deng.As such macromolecule dispersing agent, it can be used with EFKA (registration mark, エ フ カ ー ケ ミ カ Le ズ ビ ー Block イ (BASF) society manufactures), Disperbyk (registration mark, BYK Japan K.K. manufacture), DISPARLON (registration mark, Kusumoto Chemicals, Ltd. manufacture), SOLSPERSE (registration mark, The Lubrizol Corporation manufactures) The dispersant commercially sold etc. trade name.
The addition of dispersant, suitably sets according to the species of the pigment used etc..
When being used to be formed the colored pattern of colored filter by the resin combination of the present invention, containing epoxy radicals and acidic group Resin (A), the polynary acid monoester (B) of multifunctional (methyl) acrylate of hydroxyl, solvent (C), Photoepolymerizationinitiater initiater (D) and The addition of colouring agent (E), is preferably the summation relative to (A) composition and (B) composition, the resin (A) containing epoxy radicals and acidic group For 90~10 mass %, the polynary acid monoester (B) of multifunctional (methyl) acrylate of hydroxyl is 10~90 mass %；If will The summation for removing the composition of the solvent (C) in resin combination is set to 100 mass parts, then solvent (C) is 30~1000 mass parts； If the summation of (A) composition and (B) composition is set into 100 mass parts, Photoepolymerizationinitiater initiater (D) is 0.1~30 mass parts；If will The summation for removing the composition of the solvent (C) in resin combination is set to 100 mass parts, then colouring agent (E) is 5~80 mass parts； More preferably relative to the summation of (A) composition and (B) composition, the resin (A) containing epoxy radicals and acidic group is 80~20 mass %, contained The polynary acid monoester (B) of multifunctional (methyl) acrylate of hydroxyl is 20~80 mass %；If will remove in resin combination The summation of composition of solvent (C) be set to 100 mass parts, then solvent (C) is 50~800 mass parts；If by (A) composition and (B) The summation of composition is set to 100 mass parts, then Photoepolymerizationinitiater initiater (D) is 0.5~20 mass parts；If will remove in resin combination The summation of composition of solvent (C) be set to 100 mass parts, then colouring agent (E) is 5~70 mass parts；It is more preferably relative In the summation of (A) composition and (B) composition, the resin (A) containing epoxy radicals and acidic group is 75~30 mass %, hydroxyl it is multifunctional The polynary acid monoester (B) of (methyl) acrylate is 25~70 mass %；If by remove resin combination in solvent (C) into The summation divided is set to 100 mass parts, then solvent (C) is 100~700 mass parts；If the summation of (A) composition and (B) composition is set For 100 mass parts, then Photoepolymerizationinitiater initiater (D) is 1~15 mass parts；If by remove resin combination in solvent (C) into The summation divided is set to 100 mass parts, then colouring agent (E) is 10~60 mass parts.
When the resin combination of the present invention is free of colouring agent (E), the resin (A) containing epoxy radicals and acidic group, containing hydroxyl The addition of the polynary acid monoester (B) of multifunctional (methyl) acrylate of base, solvent (C) and Photoepolymerizationinitiater initiater (D) also may be used It is applicable above-mentioned numerical value.
Similarly, when the resin combination of the present invention is free of Photoepolymerizationinitiater initiater (D) and colouring agent (E), containing ring The resin (A) of epoxide and acidic group, the polynary acid monoester (B) of multifunctional (methyl) acrylate of hydroxyl and adding for solvent (C) Dosage also applicable above-mentioned numerical value.
In order to assign defined characteristic, in addition to the above-mentioned components, resin combination of the invention can also add public affairs Additive known to coupling agent, levelling agent, thermal polymerization inhibitor for knowing etc..If in the range of effect of the present invention is not hindered, The addition of the additive is not particularly limited.
Known mixing arrangement can be used in the resin combination of the present invention, is manufactured by mixing mentioned component.
In addition, the resin combination of the present invention also can be prepared formerly containing resin (A), hydroxyl containing epoxy radicals and acidic group The polynary acid monoester (B) of multifunctional (methyl) acrylate and the resin combination of solvent (C) after, mixing photopolymerization trigger Agent (D) and arbitrary colouring agent (E) and manufacture.In addition, the resin combination of the present invention, except available for forming colored filter Outside colored pattern, it can also be used to other purposes.
The resin combination of the invention obtained as described above has alkali development, therefore can be by using alkaline water Solution is developed.Particularly the sensitivity of resin combination of the invention and developability are excellent, and can form solvent resistant The excellent cured coating film of property.Therefore, resin combination of the invention can be suitable as various resists, pacify especially for being formed Loaded on organic el display, liquid crystal display device, the colored pattern of the colored filter of solid-state imager and use it is against corrosion Agent.In addition, the resin combination of the present invention can form the cured coating film of the excellents such as solvent resistance, therefore it can be additionally used in each Plant smears, bonding agent, adhesive for printing ink etc..
Then, the colored filter that the resin combination using the present invention is manufactured is illustrated.The colored filter of the present invention Mating plate has the colored pattern obtained by above-mentioned resin combination.
Accompanying drawing used below, is illustrated to the colored filter of one embodiment of the present invention.
Fig. 1 is the profile of the colored filter of an embodiment of the invention.In Fig. 1, colored filter is by substrate 1st, formed the pixel 2 of RGB on substrate 1 and formed the border of pixel 2 stain matrix 3 and formed in pixel 2 and black Diaphragm 4 on dot matrix 3 is constituted.In the structure shown here, except at least one of pixel 2 and stain matrix 3 (colored pattern) make Formed with above-mentioned resin combination, other structures can be using known structure.In addition, the colored filter shown in Fig. 1 For an example, the structure is not limited to.
Then, the manufacture method to the colored filter of one embodiment of the present invention is illustrated.
First, colored pattern is formed on substrate 1.Specifically, stain matrix 3 and pixel are sequentially formed on substrate 1 2.Here, as substrate 1, be not particularly limited, can be used glass substrate, silicone substrate, polycarbonate substrate, polyester substrate, Polyamide substrate, polyamideimide-based plate, polyimide substrate, aluminium base, printed circuit board, array base palte etc..
Colored pattern can be formed by using photoetching process.Specifically, above-mentioned resin combination is coated on substrate 1 On, formed after coated film, coated film is exposed across the photomask of predetermined pattern, makes exposed portion photocuring.Then, make After being developed with alkaline aqueous solution to unexposed portion, by baking, defined pattern can be formed.
As the coating method of resin combination, it is not particularly limited, screen printing process, rolling method, curtain can be used to apply Cloth method, spraying process, spin-coating method etc..In addition, also can be as needed, after coating resin composition, circulating baking oven, infrared be used The firing equipments such as line heater, electric furnace are heated, and the volatile ingredients such as solvent (C) is volatilized.Heating condition, without special Limit, can be appropriately configured according to the species of the resin combination used.Generally heated 30 seconds with 50 DEG C~120 DEG C of temperature ~30 minutes.
As the light source used in exposure, be not particularly limited, can be used low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, Xenon lamp, metal halide lamp etc..In addition, light exposure is also not particularly limited, as long as according to the kind of the resin combination used Class suitably adjust.
As the alkaline aqueous solution used in development, be not particularly limited, can be used sodium carbonate, potassium carbonate, calcium carbonate, The aqueous solution such as sodium hydroxide, potassium hydroxide；The aqueous solution of the aminated compounds such as ethamine, diethylamine, dimethylethanolamine；3- first Base -4- amino-N, N- diethylaniline, 3- methyl -4- amino-N- ethyl-N- beta-hydroxies MEA, 3- methyl -4- amino - N- ethyls-N- β-first sulfanilamide (SN) MEA, 3- methyl -4- amino-N- ethyls-N- 'beta '-methoxies MEA and these materials Aqueous solution of the P- pHENYLENE dI AMINE class compound such as sulfate, hydrochloride or tosilate etc..Wherein, preferably use to Asia The aqueous solution of phenylenediamine class compound.In addition, in these aqueous solution, defoamer or surface-active can be added as needed on Agent.Furthermore it is preferred that after being developed using above-mentioned alkaline aqueous solution, being washed and drying it.
The condition of baking, is not particularly limited, as long as being heated i.e. according to the species of the resin combination used Can, by using the resin combination of the present invention, it can be toasted with lower temperature than ever, preferably below 215 DEG C, Heated 10~60 minutes more preferably at 130~215 DEG C.Due to also can under baking temperature lower than ever Sufficient solvent resistance is obtained, therefore for the non-serviceable dyestuff due to deterioration problem caused by heat, also can be with more kinds of Class is used.
By using the resin combination for stain matrix 3 and the resin combination for pixel 2, it is repeated in Coating, exposure, development and the baking stated, can form desired colored pattern.
In addition, in above-mentioned, the method that colored pattern is formed by photocuring is illustrated, still, if using Resin combination added with curing accelerator and known epoxy resin replaces Photoepolymerizationinitiater initiater (D), can also make After being coated with ink-jet method, desired colored pattern is formed by heating.
Then, diaphragm 4 is formed on colored pattern (pixel 2 and stain matrix 3).As diaphragm 4, do not limit especially It is fixed, as long as using known material formation.
The colored filter manufactured through the above way, due to excellent and can be formed using sensitivity and developability The resin combination of the cured coating film of excellent solvent resistance and manufacture, therefore with excellent solvent resistance colored pattern.
Embodiment
Referring to embodiment, the present invention is described in detail, but the present invention is not limited to these examples.In addition, In this embodiment, part and percentage unless otherwise specified, with quality criteria.In addition, acid number is according to JIS K6901：The acid number for the resin (A) containing epoxy radicals and acidic group that 2008 5.3.2 are determined, refers to that neutralizing 1g contains epoxy radicals and acidic group Resin (A) in potassium hydroxide needed for contained acid ingredient mg numbers.In addition, weight average molecular weight, refers to ooze using gel Saturating chromatography (GPC), the weight average molecular weight for being converted into polystyrene standard determined by following conditions.
Post：Shodex (registration mark) LF-804+LF-804 (SHOWA DENKO K.K. manufactures)
Column temperature：40℃
Sample：0.2% tetrahydrofuran solution of resin
Eluent：Tetrahydrofuran
Detector：Differential refractometer (Shodex (registration mark) RI-71S) (SHOWA DENKO K.K. manufactures)
Flow velocity：1mL/min
The ＞ of ＜ synthesis examples 1
Into the flask with agitating device, dropping funel, capacitor, thermometer and gas introduction tube, 324 mass are added The propylene glycol methyl ether acetate of part, carries out nitrogen displacement while stirring, is warming up to 80 DEG C.Then, will be to by 86 mass The methacrylic acid of part (1 mole) and the monomer mixing of the GMA formation of 71 mass parts (0.5 mole) Double (2,4- methyl pentane nitriles) (polymerization initiator, Wako Pure Chemical of 2,2- azos of 17 mass parts are with the addition of in thing Industries, Ltd. manufacture V-65) material, with 2 hours from dropping funel is added dropwise to flask.After the completion of titration, Further stirring 2 hours, progress copolyreaction, obtains No.1 resinous liquid (solid constituent acid number 320mgKOH/ at 80 DEG C G, weight average molecular weight 10000).In addition, relative to 1 mole of acidic group of the resin in obtained resinous liquid, mole of epoxy radicals Number is 0.5.
The ＞ of ＜ synthesis examples 2~5
Except according to shown in table 1, changing propylene glycol methyl ether acetate (PGMEA), methacrylic acid (MAa) and methyl Beyond the usage amount of glycidyl acrylate (GMA), with the identical mode of synthesis example 1, obtain the resinous of No.2~5 Liquid.
[table 1]
PGMEA：Propylene glycol methyl ether acetate
MAa：Methacrylic acid
GMA：GMA
The ＞ of ＜ synthesis examples 6
Into the flask with agitating device, dropping funel, capacitor, thermometer and gas introduction tube, 470 mass are added The propylene glycol methyl ether acetate of part, carries out nitrogen displacement while stirring, is warming up to 80 DEG C.Then, will be to by 86 mass The methacrylic acid of part (1 mole) and the monomer mixture of the GMA formation of 142 mass parts (1 mole) In with the addition of double (2,4- methyl pentane nitriles) (polymerization initiator, Wako Pure Chemical of 2,2- azos of 25 mass parts Industries, Ltd. manufacture V-65) material, with 2 hours from dropping funel is added dropwise to flask.After the completion of titration, Further stirred 2 hours at 80 DEG C, carry out copolyreaction.
Then, two fourth tin dilaurate ester (catalyst, Wako Pure of 0.1 mass parts are added into flask at 60 DEG C Chemical Industries, Ltd. manufacture) and 78 mass parts (0.5 mole) isocyanatoethyl (SHOWA DENKO K.K. are manufactured), carry out after stirring in 1 hour, put into the propylene glycol methyl ether acetate of 160 mass parts, obtain No.6's Resinous liquid (solid constituent acid number 85mgKOH/g, weight average molecular weight 13000).In addition, relative in obtained resinous liquid 1 mole of acidic group of resin, the molal quantity of epoxy radicals is 2.
The ＞ of ＜ synthesis examples 7
Into the flask with agitating device, dropping funel, capacitor, thermometer and gas introduction tube, 977 mass are added The propylene glycol methyl ether acetate of part, carries out nitrogen displacement while stirring, is warming up to 80 DEG C.Then, will be to by 86 mass The methacrylic acid of the methacrylic acid of part (1 mole), the styrene of 104 mass parts (1 mole) and 284 mass parts (2 moles) The 2,2- azos double (2,4- methyl pentane nitriles) of 52 mass parts are with the addition of in the monomer mixture of ethylene oxidic ester formation, and (polymerization is drawn Send out agent, Wako Pure Chemical Industries, Ltd. manufactures V-65) material, with 2 hours from dropping funel It is added dropwise in flask.After the completion of titration, further stirring 2 hours, progress copolyreaction, obtains the resinous of No.7 at 80 DEG C Liquid (solid constituent acid number 120mgKOH/g, weight average molecular weight 8000).In addition, relative to the resin in obtained resinous liquid 1 mole of acidic group, the molal quantity of epoxy radicals is 2.
The preparation ＞ of ＜ resin combinations
Using the mixed proportion shown in table 2 as basic addition, change resin contains liquid and polymerism as shown in table 3 and 4 The species of monomer, prepares the resin combination of embodiment 1~10 and comparative example 1~7.
[table 2]
[table 3]
PETA-SA：Succinate modified thing (degree of modification 50~60%, KYOEISHA of pentaerythritol triacrylate CHEMICAL Co., LTD manufacture)
DPEPA-SA：Succinate modified thing (degree of modification 35~60%, KYOEISHA of Dipentaerythritol Pentaacrylate CHEMICAL Co., LTD manufacture)
[table 4]
Used resinous liquid Used polymerizable monomer
Comparative example 1 No.2 EODPHA
Comparative example 2 No.2 DPHA
Comparative example 3 No.4 PETA-SA
Comparative example 4 No.5 PETA-SA
Comparative example 5 No.4 DPEPA-SA
Comparative example 6 No.5 DPEPA-SA
Comparative example 7 No.5 DPHA
EODPHA：Ethylene-oxide-modified dipentaerythritol acrylate
DPHA：Dipentaerythritol acrylate (KYOEISHA CHEMICAL Co., LTD manufacture)
PETA-SA：Succinate modified thing (degree of modification 50~60%, KYOEISHA of pentaerythritol triacrylate CHEMICAL Co., LTD manufacture)
DPEPA-SA：Succinate modified thing (degree of modification 35~60%, KYOEISHA of Dipentaerythritol Pentaacrylate CHEMICAL Co., LTD manufacture)
The evaluation ＞ of ＜ solvent resistances
To the METHYLPYRROLIDONE as usually used solvent in the diaphragm formation process of colored filter (NMP) evaluation of solvent resistance is carried out.
On the glass substrate (alkali-free glass substrate) of 5cm square, so that the thickness after being toasted at 210 DEG C is 2.5 μm Mode, the resin combination of preparation is carried out after spin coating, is heated 3 minutes at 90 DEG C, solvent is volatilized.Then, using ripple Long 365nm light is exposed (light exposure 300mJ/cm to coated film2), after making exposed portion photocuring, in baking temperature Placed 20 minutes in 210 DEG C of drier, make cured coating film.Use spectrophotometer UV-1650PC (Shimadzu Corporation is manufactured), determine transmissivity of the test film with cured coating film at wavelength 675nm.Then, to training with cover Support and the METHYLPYRROLIDONEs (NMP) of 55 mass parts added in ware, by the test film dipping with cured coating film wherein it Afterwards, the transmissivity after 30 minutes is determined at 60 DEG C.As a result it is as shown in table 5.The rising of transmissivity, it is meant that colouring agent to METHYLPYRROLIDONE (NMP) dissolution, it may be said that initial stage, transmissivity after METHYLPYRROLIDONE (NMP) impregnation with transmiting A poor small side for rate, solvent resistance is high.
The evaluation ＞ of ＜ alkali developments
, will to make the thickness after exposure in the way of 2.5 μm on the glass substrate (alkali-free glass substrate) of 5cm square The resin combination of preparation is carried out after spin coating, is heated 3 minutes at 90 DEG C, solvent is volatilized.Then, at 100 μm away from coated film Distance configure predetermined pattern photomask, (light exposure 150mJ/cm is exposed to coated film across the photomask2), make exposure Light part photocuring.Then, the aqueous solution containing 0.1 mass % sodium carbonate is sprayed with 23 DEG C of temperature and 0.3MPa pressure Mist, after dissolving unexposed portion and being developed, by being toasted 30 minutes at 210 DEG C, forms predetermined pattern, confirms that alkalescence is aobvious The residue of movie queen.The electron microscope S- manufactured by using Hitachi High-Technologies Corporation Pattern after 3400 observation alkaline developments, to confirm the residue after alkaline development.The metewand is as described below.As a result such as table 5 It is shown.
○：Without residue
×：There is residue
The evaluation ＞ of ＜ sensitivity
The alkaline development of above-mentioned use spraying in 30 seconds is carried out, passes through contact pin type segment difference meter ET4000M (Kosaka Laboratory Ltd. are manufactured) decrement of pattern thickness before and after alkaline development is measured, thus judge the excellent of sensitivity It is bad.It may be said that the decrement of the pattern thickness is smaller, then sensitivity is better, therefore the metewand is as described below.As a result such as table 5 It is shown.
○：Less than 0.20 μm
×：More than 0.20 μm
[table 5]
As shown in Table 5, if using the resin combination of embodiment 1~10, developability and sensitivity are good, energy The cured coating film of excellent solvent resistance is enough formed, on the other hand, if using the resin combination of comparative example 1~7, solvent resistant Property is insufficient.
Industrial applicibility
It was found from result above, according to the present invention, it is possible to provide a kind of sensitivity and developability are good and can be formed and have The resin combination of the cured coating film of abundant solvent resistance.Therefore, resin combination of the invention is suitable for colored filter use Resist.Further, by using the resin combination of the present invention, the colored pattern with excellent solvent resistance can be obtained , the colored filter that reliability is high.
Description of reference numerals
1：Substrate；2：Pixel；3：Stain matrix；4：Diaphragm.

Claims (14)

1. a kind of resin combination, it contains：Multifunctional (methyl) propylene of resin (A), hydroxyl containing epoxy radicals and acidic group The polynary acid monoester (B) and solvent (C) of acid esters, it is characterised in that relative in the resin (A) containing epoxy radicals and acidic group 1 mole of acidic group, epoxy radicals be 0.5~3.0 mole.
2. resin combination according to claim 1, it, which contains, have olefinic carbon-to-carbon double bond and ring in a comfortable molecule The monomeric unit of the monomer (a-1) of epoxide, is used as the structures alone unit of the resin (A) containing epoxy radicals and acidic group.
3. resin combination according to claim 1 or 2, it contains the monomeric unit from unsaturated carboxylic acid (a-2), makees For the structures alone unit of the resin (A) containing epoxy radicals and acidic group.
4. resin combination according to claim 3, wherein, the resin (A) containing epoxy radicals and acidic group contains：Coming From a part for the carboxyl of the unsaturated carboxylic acid (a-2), addition has the functional group having in a molecule with carboxyl reaction With structures alone unit monomer (a-3), with olefinic carbon-to-carbon double bond of olefinic carbon-to-carbon double bond.
5. resin combination according to claim 2, wherein, it is described that there is olefinic carbon-to-carbon double bond and ring in a molecule The monomer (a-1) of epoxide is (methyl) acrylate containing epoxy radicals.
6. resin combination according to claim 4, wherein, the functional group having in a molecule with carboxyl reaction With the monomer (a-3) of olefinic carbon-to-carbon double bond, for selected from (methyl) acrylate containing epoxy radicals and the (first containing NCO Base) it is one kind or two or more in acrylate.
7. according to resin combination according to any one of claims 1 to 6, wherein, multifunctional (methyl) of the hydroxyl The polynary acid monoester (B) of acrylate, for selected from the polynary acid monoester by the two of pentaerythrite or three (methyl) acrylate, two It is one kind or two or more in the group that the polynary acid monoester of two, three, four or five (methyl) acrylate of pentaerythrite is constituted.
8. according to resin combination according to any one of claims 1 to 7, wherein, the resin containing epoxy radicals and acidic group (A) acid number is 10~350mgKOH/g.
9. according to resin combination according to any one of claims 1 to 8, it further contains Photoepolymerizationinitiater initiater (D).
10. according to resin combination according to any one of claims 1 to 9, it further contains colouring agent (E).
11. resin combination according to claim 10, wherein, the colouring agent (E) is selected from by dyestuff and pigment institute It is at least one kind of in the group of composition.
12. a kind of colored filter, it has what is formed as the cured coating film of the resin combination described in claim 10 or 11 Colored pattern.
13. a kind of image-displaying member, it possesses the colored filter described in claim 12.
14. a kind of manufacture method of colored filter, it includes following process：
The resin combination described in claim 10 or 11 is coated on substrate, expose and entered by alkaline aqueous solution The process of row development；And
Toasted under temperature conditionss below 215 DEG C, the process for forming colored pattern.
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