CN107108769B - Resin combination, colored filter, its manufacturing method and image-displaying member - Google Patents

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

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Publication number
CN107108769B
CN107108769B CN201580070146.6A CN201580070146A CN107108769B CN 107108769 B CN107108769 B CN 107108769B CN 201580070146 A CN201580070146 A CN 201580070146A CN 107108769 B CN107108769 B CN 107108769B
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methyl
resin combination
resin
group
acrylate
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CN107108769A (en
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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
    • 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
    • C08F265/02—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
    • 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, the resin combination contains: the polynary acid monoester (B) and solvent (C) of the multifunctional (methyl) acrylate of resin (A), hydroxyl containing epoxy group and acidic group, wherein, relative to 1 mole of acidic group in the resin (A) containing epoxy group and acidic group, epoxy group is 0.5~3.0 mole.

Description

Resin combination, colored filter, its manufacturing method and image-displaying member
Technical field
The present invention relates to a kind of resin combination, colored filter, its manufacturing method and image-displaying members.
Background technique
Red (R), green (G) and the indigo plant that colored filter is usually formed by transparent substrates such as glass substrates, on the transparent substrate (B) pixel, the stain matrix formed in pixel boundary and the protective film formed in pixel and stain matrix are constituted.Tool There is the colored filter of the structure, is usually made and sequentially forming stain matrix, pixel and protective film on the transparent substrate It makes.As pixel and the forming method of stain matrix (pixel and stain matrix are known as " colored pattern " below), it has been proposed that Various methods, but mainstream is pigment/dye dispersion method now, and this method uses will be as the photosensitive resin composition of resist The photoetching process (photolithography) that coating, exposure, development and the baking of object repeat.
The photosensitive polymer combination for being commonly used for photoetching process contains alkali soluble resin, reactive diluent, light Polymerization initiator, colorant and solvent.In pigment/dye dispersion method, the excellent in te pins of durability of light resistance and heat resistance etc. can The few colored pattern of the defects of forming pin hole, but on the contrary, pattern and protective film 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 group or oxetanylmethoxy (oxetanyl) and carboxyl or phenol hydroxyl The copolymer of base, to improve the method (patent document 1 and 2) of solvent resistance；Alternatively, using containing with the evil containing trihalomethyl The substance 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, needing to increase institute to improve the color reproduction of colored filter (color reproduction) characteristic The content of the colorant of addition thickens film thickness etc., but exists generate sensitivity decrease at the same time, the problems such as developability reduces Tendency, it is desirable that further increase performance (patent document 4).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2012-22048 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2013-25203 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2003-330184 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2014-164021 bulletin
Summary of the invention
The technical problem to be solved in the present invention
However, previous photosensitive polymer combination has that sensitivity, developability are insufficient or can not obtain resistance to The case where solvent borne excellent cured coating film.
Therefore, the present invention completes to solve above-mentioned technical problem, it is intended that a kind of resin combination is provided, It is good meanwhile, it is capable to form the cured coating film of excellent solvent resistance in sensitivity, developability.In addition, the purpose of the present invention exists In providing a kind of colored filter, there is the colored pattern that is formed of cured coating film by excellent solvent resistance.
Solve the technological means of technical problem
That is, shown in the present invention [1] for example below~[14].
[1] a kind of resin combination contains multifunctional (methyl) of resin (A) containing epoxy group and acidic group, hydroxyl The polynary acid monoester (B) and solvent (C) of acrylate, which is characterized in that relative to the resin containing epoxy group and acidic group (A) 1 mole of acidic group in, epoxy group are 0.5~3.0 mole.
[2] resin combination according to [1], contain to come from has olefinic carbon-to-carbon double bond and ring in a molecule The monomeric unit of the monomer (a-1) of oxygroup, the structures alone unit as the resin (A) containing epoxy group and acidic group.
[3] resin combination according to [1] or [2], contains the monomeric unit from unsaturated carboxylic acid (a-2), Structures alone unit as the resin (A) containing epoxy group and acidic group.
[4] resin combination according to [3], wherein the resin (A) containing epoxy group and acidic group contains: coming From a part of the carboxyl of the unsaturated carboxylic acid (a-2), addition has and has the functional group reacted with carboxyl in a molecule With the monomer (a-3) of olefinic carbon-to-carbon double bond, structures alone unit with olefinic carbon-to-carbon double bond.
[5] resin combination according to [2], wherein 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 group.
[6] resin combination according to [4], wherein described that there is the functional group reacted with carboxyl in a molecule With the monomer (a-3) of olefinic carbon-to-carbon double bond, for selected from (methyl) acrylate containing epoxy group and containing the (first of isocyanate group 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 by the two of pentaerythrite or three (methyl) acrylate polynary acid monoester, two It is one kind or two or more in group composed by the polynary acid monoester of two, three, four or five (methyl) acrylate of pentaerythrite.
[8] resin combination according to any one of [1]~[7], wherein the resin containing epoxy group and acidic group (A) acid value is 10~350mgKOH/g.
[9] resin combination according to any one of [1]~[8], further contains Photoepolymerizationinitiater initiater (D).
[10] resin combination according to any one of [1]~[9], further contains colorant (E).
[11] resin combination according to [10], wherein the colorant (E) is selected from by dyestuff and pigment institute group At group in it is at least one kind of.
[12] a kind of colored filter, what the cured coating film with the resin combination as described in [10] or [11] was formed Colored pattern.
[13] a kind of image-displaying member has colored filter described in [12].
[14] a kind of manufacturing method of colored filter comprising following process: to described in [10] or [11] on substrate The resin combination process that is coated, exposes and is developed by alkaline aqueous solution；In 215 DEG C of temperature strips below It is 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, sensitivity, developability are good, while being capable of forming resistance to The excellent cured coating film of solvent borne.In addition, the solidification of the state after the exposure formed by resin combination of the invention, before baking Film has developability, therefore the utility value in various resist fields is high, the solidification of the state after especially toasting The excellent solvent resistance of film, therefore be useful on the colored pattern for forming colored filter.
Detailed description of the invention
Fig. 1 is the sectional view of the colored filter of an embodiment of the invention.
Specific embodiment
Resin combination of the invention contains multifunctional (methyl) third of resin (A) containing epoxy group and acidic group, hydroxyl The polynary acid monoester (B) and solvent (C) of olefin(e) acid ester, which is characterized in that relative to 1 in the resin (A) containing epoxy group and acidic group Mole acidic group, epoxy group are 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 ".
Resin (A) containing epoxy group and acidic group used in the present invention, as long as there is epoxy group and acidic group in resin, And relative to 1 mole of acidic group in resin, epoxy group exists with 0.5~3.0 mole, is not particularly limited.Acidic group does not have It is particularly limited to, but can usually enumerate: carboxyl (- COOH), phosphate (- PO (OH)2), sulfonic group (- SO3H) etc..From of the invention From the viewpoint of the curability of resin combination, preferred carboxyl.From raw material accessibility, the resin containing epoxy group and acidic group (A) ease of manufacturing and from the viewpoint of improving solvent resistance when solidifying resin combination of the invention, preferably contains There is the monomeric unit of the monomer (a-1) with olefinic carbon-to-carbon double bond and epoxy group in a molecule as structures alone unit 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, structures alone type and molar ratio be known situation under, relative to contain epoxy group And 1 mole of acidic group of the resin (A) of acidic group, epoxy group molal quantity, it can be calculated by the addition ratio of structures alone.By closing When the resin (A) containing epoxy group and acidic group after calculates the molal quantity relative to the epoxy group of 1 mole of acidic group, by with JIS The epoxide equivalent measured on the basis of K 7236 is calculated with the value by the acid value measured on the basis of JIS K 0070.
From the viewpoint of the ease of manufacturing of the resin (A) containing epoxy group and acidic group, preferably (methyl) containing epoxy group Acrylate is as monomer (a-1).As the concrete example of monomer (a-1), can enumerate: (methyl) glycidyl acrylate, 3,4- epoxycyclohexyl (methyl) methyl acrylate and its lactone addition product (such as Daicel with ester ring oxygroup Corporation manufacture CYM (registered trademark) A200, M100), 3,4- epoxycyclohexyl-methyl -3', 4'- 7-oxa-bicyclo[4.1.0 List (methyl) acrylate of carboxylate, the epoxides of dicyclopentenyl (methyl) acrylate, dicyclopentenyl oxygroup second The epoxides etc. of base (methyl) acrylate.Wherein, especially from the viewpoint of obtaining easy degree, reactivity, preferably (methyl) glycidyl acrylate.
As the concrete example of unsaturated carboxylic acid (a-2), can enumerate: (methyl) acrylic acid, crotonic acid, cinnamic acid, itaconic acid, Maleic acid, fumaric acid, vinyl sulfonic acid, 2- (methyl) acryloyl-oxyethyl succinic acid, 2- acryloyl-oxyethyl neighbour benzene two Formic acid, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid etc..From the viewpoint of obtaining from raw material, preferred (methyl) third Olefin(e) acid and crotonic acid, more preferable (methyl) acrylic acid.
The resin (A) containing epoxy group and acidic group that the present invention uses, can be containing from demonomerization (a-1) and unsaturated carboxylic The monomeric unit of the monomer of free redical polymerization other than sour (a-2), as structures alone unit.As demonomerization (a-1) and The concrete example of the monomer of free redical polymerization other than unsaturated carboxylic acid (a-2), can enumerate: 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 norbornyl ester, (methyl) allyl acrylate, (methyl) tetrahydrofurfuryl acrylate, 1,1,1- trifluoroethyl (methyl) acrylate, (methyl) perfluoroethyl ethyl ester, (methyl) acrylic acid triphenylmethyl, (methyl) acrylic acid cumyl Ester, 3- (N, N- dimethylamino) propyl (methyl) acrylate, glycerine list (methyl) acrylate, penta triol list (methyl) Acrylate, (methyl) dicyclopentanyl acrylate, (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；Norbornene (bicyclic [2.2.1] hept-2-ene"), 5- methyl bicycle Bicyclic [2.2.1] hept-2-ene" of [2.2.1] hept-2-ene", 5- ethyl, Fourth Ring [4.4.0.12,5.17,10] 12-3- alkene, two rings penta Diene, tricyclic [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- norbornene-2- carboxylic acid, 5- norbornene-2,3- dicarboxylic anhydride；(methyl) acrylic acid acyl Amine, (methyl) acrylic acid N, N- diacetayl amide, (methyl) acrylic acid anthryl amide, (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, vinyl fluoride, vinylidene, N- vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyl toluene Ene compound；Styrene, styrene α-, it is o-, m-, to alkyl, nitro, cyano, amide derivatives；Citraconic acid diethylester, horse Carry out the unsaturated dicarboxylics diester such as diethyl phthalate；The list maleimide such as N-phenylmaleimide, N- N-cyclohexylmaleimide Amine；The unsaturation multi-anhydride such as maleic anhydride, itaconic anhydride.These substances may be used alone or in combination two or more use.This Outside, wherein from the viewpoint of heat resistance and the transparency, preferably (methyl) benzyl acrylate, (methyl) dicyclopentanyl acrylate, Styrene, vinyltoluene, (methyl) isobornyl acrylate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, norbornene, N- isopropyl (methyl) acrylamide, (methyl) acrylic acid morpholine and diacetone (methyl) acrylamide, more preferable (methyl) acrylic acid benzyl Ester, (methyl) dicyclopentanyl acrylate, styrene, vinyltoluene, (methyl) isobornyl acrylate, (methyl) acrylic acid gold Rigid alkyl ester and norbornene.
For the adding proportion of monomer (a-1), as long as relative to 1 equimolar acid in the resin (A) containing epoxy group and acidic group Base, epoxy group exist with 0.5~3.0 mole, are not particularly limited, but relative to the resin (A) containing epoxy group and acidic group The total amount of structures alone, preferably 40~90 moles of %, more preferably 50~90 moles of %, further preferably 60~80 rub You are %.If the adding proportion of monomer (a-1) is 40~90 moles of %, developability is good, while sufficient solvent resistant can be obtained Property.
For the adding proportion of unsaturated carboxylic acid (a-2), as long as relative to 1 in the resin (A) containing epoxy group and acidic group Mole acidic group, epoxy group exist with 0.5~3.0 mole, are not particularly limited, but relative to the resin containing epoxy group and acidic group (A) total amount of structures alone, preferably 10~60 moles of %, more preferably 10~50 moles of %, further preferably 20~ 40 moles of %.By making 10~60 moles of % of adding proportion of unsaturated carboxylic acid (a-2), developability is good, can be obtained simultaneously Sufficient solvent resistance.
When using the monomer of the free redical polymerization other than demonomerization (a-1) and unsaturated carboxylic acid (a-2), ratio is added Example is not particularly limited, but the total amount of the structures alone relative to the resin (A) containing epoxy group and acidic group, and preferably greater than 0 rubs Your % and be 50 moles of % hereinafter, more preferably higher than 0 mole of % and be 40 moles of % or less.
The total amount of structures alone unit relative to the resin (A) containing epoxy group and acidic group, further preferably 40~90 rub The monomeric unit from unsaturated carboxylic acid (a-2) of the monomeric unit and 10~60 moles of % from monomer (a-1) of your %, The monomeric unit from monomer (a-1) of further preferably 60~80 moles of % and 20~40 moles of %'s comes from insatiable hunger With the monomeric unit of carboxylic acid (a-2).
For manufacturing the copolyreaction of the resin (A) containing epoxy group and acidic group, can according to it is well known in the art from It is 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) after the monomer (any ingredient) of the free redical polymerization other than is dissolved in solvent, polymerization initiator is added into the solution, React it 1~20 hour.By the copolyreaction, can obtain with the addition ratio with monomer The random copolymer of the of substantially equal monomeric unit ratio of example.
As the solvent that can be used for the copolyreaction, such as can enumerate: 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 use.
The moisture content of solvent is not particularly limited, but preferably 1 mass % or less.If moisture content be 1 mass % hereinafter, if It can obtain the resin (A) containing epoxy group and acidic group with more good solvent resistance.In addition, the moisture content of solvent can pass through Karl_Fischer method (Karl Fischer), is measured with following conditions.
Device: the KF moisture meter MKA-520 of KYOTO ELECTRONICS MANUFACTURING CO., LTD. manufacture
Injection rate: 1mL
Titrating solution: AQUAMICRON (registered trademark) titrant SS 3mg (API Corporation manufacture)
Electrode solution: AQUAMICRON (registered trademark) dehydrated solvent PP (API Corporation manufacture)
The additive amount of solvent when manufacturing resin (A) containing epoxy group and acidic group is not particularly limited, but will contain epoxy It is preferably 30~1000 mass parts when the total amount of the structures alone of the resin (A) of base and acidic group is set as 100 mass parts, it is more excellent It is selected as 50~800 mass parts.In particular, chain tra nsfer can be passed through by the way that the additive amount of solvent is set as 1000 below the mass Effect inhibits the reduction of the molecular weight of the resin (A) containing epoxy group and acidic group, and can be by the resin (A) containing epoxy group and acidic group Viscosity control in optimum range.In addition, by the way that the additive amount of solvent is set as 30 mass parts or more exception can be being prevented While polymerization reaction, stable progress polymerization reaction, the coloring and gelation of the resin (A) containing epoxy group and acidic group are prevented.
As the polymerization initiator for the resin (A) that can be used for manufacturing containing epoxy group and acidic group, it is not particularly limited, such as can It enumerates: azodiisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butyl peroxy -2 ethyl hexanoic acid ester etc..These are poly- Closing initiator may be used alone or in combination two or more use.
When the total amount for containing the structures alone of the resin (A) of epoxy group and acidic group is set as 100 mass parts, polymerization initiator Additive amount be preferably 0.5~20 mass parts, more preferably 1.0~10 mass parts.
In addition it is also possible to do not use organic solvent, and use monomer (a-1), unsaturated carboxylic acid (a-2), as it is any at The monomer and polymerization initiator of free redical polymerization other than the demonomerization (a-1) and unsaturated carboxylic acid (a-2) that divide carry out Bulk polymerization.
In the resin (A) containing epoxy group and acidic group obtained in above-mentioned copolyreaction, olefinic carbon-to-carbon can be further imported Double bond.Thus the sensitivity and 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 group and acidic group In a part, in one molecule of addition containing have with the functional group of carboxyl-reactive and the monomer (a-3) of olefinic carbon-to-carbon double bond, To import olefinic carbon-to-carbon double bond.Resin (A) as a result, containing epoxy group and acidic group contains: coming from unsaturated carboxylic acid (a-2) Carboxyl a part on, addition has and has the monomer (a- of functional group and olefinic carbon-to-carbon double bond reacted with carboxyl in a molecule 3), structural unit with olefinic carbon-to-carbon double bond.As the functional group reacted with carboxyl, isocyanate group, epoxy can be enumerated Base, vinyl ether group etc..Wherein, from the viewpoint of reactivity when addition reaction, preferred isocyanate base.As with epoxy Monomer identical with the monomer illustrated as monomer (a-1) can be used in the monomer (a-3) of base.In addition, as with isocyanic acid The monomer (a-3) of ester group, is not particularly limited, preferably (methyl) acrylate containing isocyanate group, specifically, can arrange It is (different to lift 2- (methyl) acryloyloxyethyl isocyanate, 1,1- (bis- (methyl) acryloyloxymethyls) ethyl isocyanate, 2- Cyanic acid ester group ethyl oxygroup) ethyl (methyl) acrylate etc..Wherein, there is isocyanate group and olefinic preferably in a molecule The monomer of carbon-to-carbon double bond.More preferable 2- (methyl) acryloyloxyethyl isocyanate.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- vinyloxyethoxy) ethyl ester etc..
It further, can also be in one molecule of addition in the case where the resin (A) containing epoxy group and acidic group contains anhydride group Monomer with the functional group and olefinic carbon-to-carbon double bond reacted with anhydride group, to import olefinic carbon-to-carbon double bond.As with acid The functional group of anhydride group reaction, can enumerate hydroxyl.
In the resin (A) containing epoxy group and acidic group carboxyl, addition contains in epoxy group or anhydride group has reactivity 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 group 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 At in reaction, even if containing the solvent used in above-mentioned copolyreaction, special problem is also not present, therefore, in copolyreaction After, solvent can not be removed and carry out addition reaction.
Here, can also be added by gelation caused by the polymerization of the resin (A) containing epoxy group and acidic group in order to prevent Polymerization inhibitor.It as polymerization inhibitor, is not particularly limited, such as hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether can be enumerated Deng.In addition, being not particularly limited as catalyst, such as it can enumerate: such as the tertiary amine of triethylamine, such as triethyl benzyl ammonia chloride Quaternary ammonium salt, the phosphide of such as triphenylphosphine, chromium chelate.
The acid value (JIS K 6901:2008 5.3.2) of resin (A) containing epoxy group and acidic group used in the present invention does not have It is restricted, but when being used for colored filter purposes, preferably 10~350mgKOH/g, more preferably 30~200mgKOH/g, Further preferably 50~180mgKOH/g, particularly preferably 70~150mgKOH/g.The acid value if 10mgKOH/g or more, It then can get sufficient developability.On the other hand, if the acid value be 350mgKOH/g hereinafter, if exposed portion (photo-cured portion) It is not dissolved in alkaline-based developer, obtains sufficient developability.
In addition, the molecular weight of the resin (A) containing epoxy group and acidic group (is surveyed using aftermentioned gel permeation chromatography (GPC) The fixed weight average molecular weight for being converted into polystyrene) it is preferably 1000~50000, more preferably 3000~40000.If the molecule Amount is 1000 or more, then does not generate the defect of colored pattern after development, can get good sensitivity.It on the other hand, if should Molecular weight is 50000 hereinafter, then developing time is very short, there is practicability.
In addition, the equivalent of the unsaturated group does not have when the resin (A) containing epoxy group and acidic group has unsaturated group Limitation, preferably 100~4000g/mol, more preferably 200~3000g/mol.If the equivalent of the unsaturated group is 100g/ Mol or more is then effective in terms of further increasing resistance to pyrolytic and heat-resisting xanthochromia.On the other hand, if the unsaturation The equivalent of group is 4000g/mol hereinafter, being then effective in terms of further increasing sensitivity.
Resin combination of the invention contains the polynary acid monoester (B) of the multifunctional (methyl) acrylate of hydroxyl.Make It for the polynary acid monoester (B) of the multifunctional (methyl) acrylate of hydroxyl, such as can enumerate: two or three (first of pentaerythrite Base) the polynary acid monoester of acrylate, dipentaerythritol two, three, four or five (methyl) acrylate polynary acid monoester, tool Body can be enumerated: the succinate modified object of Dipentaerythritol Pentaacrylate, the succinate modified object of pentaerythritol triacrylate, two seasons The orthophthalic modified object of penta tetrol, five acrylate, the orthophthalic modified object of pentaerythritol triacrylate etc., containing Addition has the modified by polyacid object of acid anhydrides on the hydroxyl of the multifunctional (methyl) acrylate of hydroxyl.These substances can be used alone Or combine two or more use.Wherein, from the viewpoint of solvent resistance, the preferred multifunctional (methyl) acrylate of hydroxyl Succinate modified object.
Relative to the summation of (A) ingredient and (B) ingredient, the polynary acid monoester of the multifunctional (methyl) acrylate of hydroxyl (B) additive amount is preferably 10~90 mass %, more preferably 20~80 mass %, further preferably 25~70 mass %. If the additive amount of the range, then the resin combination with suitable viscosity is formed, by adding aftermentioned Photoepolymerizationinitiater initiater (D), there is suitable photo-curable.
Resin combination of the invention contains solvent (C).As solvent (C), as long as dissolution is containing epoxy group and acidic group The multifunctional (methyl) acrylate of resin (A) and hydroxyl polynary acid monoester (B) and the inertia do not reacted with them Solvent is not particularly limited.
As solvent (C), used in the usable copolyreaction with when manufacturing resin (A) containing epoxy group and acidic group The identical solvent of solvent, contained solvent after copolyreaction can also be directly used in.Tree of the invention can also prepared It is further added when oil/fat composition.Alternatively, in aftermentioned addition other compositions, also can be used directly coexisted with these ingredients it is molten Agent.As the concrete example of solvent (C), 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, methyl ethyl ketone, 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 use.Furthermore, wherein preferably in manufacture containing epoxy group and acidic group The glycol ethers solvents such as propylene glycol monomethyl ether, propylene glycol methyl ether acetate used in copolyreaction when resin (A).
If the summation of the ingredient of the solvent (C) removed in resin combination of the invention is set as 100 mass parts, solvent (C) additive amount is preferably 30~1000 mass parts, more preferably 50~800 mass parts, further preferably 100~700 matter Measure part.If the additive amount of the range, then the resin combination with suitable viscosity is formed.
When resin combination of the invention to be used to form to the colored pattern of colored filter, photopolymerization is further added Initiator (D) and colorant (E) and use.
It as Photoepolymerizationinitiater initiater (D), is not particularly limited, such as can enumerate: the styraxes such as styrax, benzoin methyl ether And its alkyl ether；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, 1,1- dichloroacetophenone, 4- (1- tert-butyl dioxy - 1- Methylethyl) acetophenones such as acetophenone；1- hydroxycyclohexyl phenyl ketone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone etc. Alkylbenzene ketone；The Anthraquinones such as 2-methylanthraquinone, 2- amyl anthraquinone, 2- tert-butyl anthraquinone, 1- chloroanthraquinone；2,4- dimethyl thiophene The thioxanthene ketone class such as ton ketone, 2,4- diisopropylthioxanthone, 2-chlorothioxanthone；Acetophenone dimethyl ketal, benzyl dimethyl ketal Equal ketals class；Benzophenone, 4- (two oxygroup -1- Methylethyl of 1- tert-butyl) benzophenone, the 3,3', (tert-butyl two of 4,4'- tetra- Oxygen carbonyl) benzophenones such as benzophenone；1,2- acetyl caproyl, 1- [4- (phenyl)-, 2- (O- benzoyl oxime)], ethyl ketone (ethanone), 1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -, the oximes esters such as 1- (0- acetyl oxime)； 2- methyl-1-[4- (methyl thio) phenyl]-2- morpholino-propane-1- ketone；2- benzyl -2- dimethylamino -1- (4- morpholine For phenyl) -1- butanone；2,4,6- trimethylbenzoyl diphenyl phosphine oxide, the oxidation of bis- (2,4,6- trimethylbenzoyl) 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 use.
If the summation of (A) ingredient and (B) ingredient is set as 100 mass parts, the additive amount of Photoepolymerizationinitiater initiater (D) is preferred For 0.1~30 mass parts, more preferably 0.5~20 mass parts, further preferably 1~15 mass parts.If adding for the range Dosage then forms the resin combination with suitable photo-curable.
Colorant (E) is not particularly limited as long as being dissolved or dispersed in resin combination of the invention, such as can arrange Lift dyestuff or pigment etc..
Especially in resin combination of the invention, due to as it is explained in detail hereinafter, even if at lower temperature (215 DEG C or less) Under toasted, can also obtain sufficient solvent resistance, therefore caused by being not likely to produce because of heat the advantages of dye deterioration.Cause This can freely use a greater variety of dyestuffs in resin combination of the invention, obtain colored pattern.
As dyestuff, to resin combination of the invention dissolubility or dispersibility, with other in resin combination at Point the viewpoints such as interaction, heat resistance from the point of view of, it is preferable to use acid dyes, acid dyes with acidic-groups such as carboxyls with Salt, sulfanilamide (SN) body of acid dyes of nitride etc..It as the example of this dyestuff, 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； 6B, 7,9,17,19 acid violet (acid violet)；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 objects Matter can be used alone or in combination of two or more kinds according to pixel color as a purpose.
As the example of pigment, can enumerate C.I. pigment yellow (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、 166, the yellow uitramarines such as 173,194,214；C.I. pigment orange (Pigment Orange) 13,31,36,38,40,42,43,51, 55, the orange pigments such as 59,61,64,65,71,73；C.I. paratonere (Pigment Red) 9,97,105,122,123,144, 149, the red pigments such as 166,168,176,177,180,192,209,215,216,224,242,254,255,264,265； C.I. the blue pigments such as pigment blue (Pigment Blue) 15,15:3,15:4,15:6,60；C.I. pigment violet (Pigment Violet) 1,19,23,29,32,36,38 etc. violet pigment；C.I. naphthol green (Pigment Green) greens such as 7,36,58 Pigment；C.I. pigment brown (Pigment Brown) browns such as 23,25；C.I. pigment black (Pigment Black) 1,7, charcoal Black pigments such as black, titanium is black, acidification iron etc..These pigment can be used alone or combine 2 according to pixel color as a purpose Kind is used above.
In addition, above-mentioned dyestuff and pigment combination can also be used according to pixel color as a purpose.
Solvent (C) when adding colorant (E), in the resin combination of the invention relative to the removing of 100 mass parts Ingredient summation, which is preferably 5~80 mass parts, more preferably 5~70 mass parts, further preferably 10~60 Mass parts.
It, can also be in resin group from the viewpoint of the dispersibility for improving pigment when using pigment as colorant (E) It closes and adds well known dispersing agent in object.As dispersing agent, it is preferable to use through when disperse excellent in stability macromolecule dispersing agent.Make It for the example of macromolecule dispersing agent, can enumerate: urethane class dispersing agent, polyethyleneimine amine dispersing agent, polyoxyethylene alkyl ether class Dispersing agent, two esters dispersing agent of polyoxyethylene glycol, polyoxyethylensorbitan fatty race esters dispersing agent, aliphatic modified esters dispersing agent Deng.As such macromolecule dispersing agent, can be used with EFKA (registered trademark, エ フ カ ー ケ ミ カ Le ズ ビ ー Block イ (BASF) society manufactures), Disperbyk (registered trademark, BYK Japan K.K. manufacture), DISPARLON (registered trademark, Kusumoto Chemicals, Ltd. manufacture), SOLSPERSE (registered trademark, The Lubrizol Corporation manufacture) Etc. the dispersing agent sold on the market of trade names.
The additive amount of dispersing agent is suitably set according to the type of the pigment used etc..
When resin combination of the invention to be used to form to the colored pattern of colored filter, containing epoxy group and acidic group The polynary acid monoester (B) of the multifunctional (methyl) acrylate of resin (A), hydroxyl, solvent (C), Photoepolymerizationinitiater initiater (D) and The additive amount of colorant (E), the preferably summation relative to (A) ingredient and (B) ingredient, the resin (A) containing epoxy group and acidic group For 90~10 mass %, the polynary acid monoester (B) of the multifunctional (methyl) acrylate of hydroxyl is 10~90 mass %；If will The summation for removing the ingredient of the solvent (C) in resin combination is set as 100 mass parts, then solvent (C) is 30~1000 mass parts； If the summation of (A) ingredient and (B) ingredient is set as 100 mass parts, Photoepolymerizationinitiater initiater (D) is 0.1~30 mass parts；If will The summation for removing the ingredient of the solvent (C) in resin combination is set as 100 mass parts, then colorant (E) is 5~80 mass parts； Summation more preferably relative to (A) ingredient and (B) ingredient, the resin (A) containing epoxy group and acidic group are 80~20 mass %, contain The polynary acid monoester (B) of the multifunctional (methyl) acrylate of hydroxyl is 20~80 mass %；If will remove in resin combination The summation of ingredient of solvent (C) be set as 100 mass parts, then solvent (C) is 50~800 mass parts；If by (A) ingredient and (B) The summation of ingredient is set as 100 mass parts, then Photoepolymerizationinitiater initiater (D) is 0.5~20 mass parts；If will remove in resin combination The summation of ingredient of solvent (C) be set as 100 mass parts, then colorant (E) is 5~70 mass parts；It is further preferably opposite In the summation of (A) ingredient and (B) ingredient, the resin (A) containing epoxy group and acidic group be 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) at The summation divided is set as 100 mass parts, then solvent (C) is 100~700 mass parts；If (A) ingredient and the summation of (B) ingredient are set For 100 mass parts, then Photoepolymerizationinitiater initiater (D) is 1~15 mass parts；If by remove resin combination in solvent (C) at The summation divided is set as 100 mass parts, then colorant (E) is 10~60 mass parts.
Even if when resin combination of the invention is free of colorant (E), resin (A) containing epoxy group and acidic group contains hydroxyl The additive amount of the polynary acid monoester (B) of the multifunctional (methyl) acrylate of base, solvent (C) and Photoepolymerizationinitiater initiater (D) can also It is applicable in above-mentioned numerical value.
Similarly, even if containing ring when resin combination of the invention is free of Photoepolymerizationinitiater initiater (D) and colorant (E) The resin (A) of oxygroup 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 well known to coupling agent, levelling agent, thermal polymerization inhibitor for knowing etc..If in the range of not hindering effect of the present invention, The additive amount of the additive is not particularly limited.
Well known mixing arrangement can be used in resin combination of the invention, is manufactured by mixing mentioned component.
In addition, resin combination of the invention can also be prepared formerly containing resin (A), hydroxyl containing epoxy group and acidic group The polynary acid monoester (B) of multifunctional (methyl) acrylate and the resin combination of solvent (C) after, mixing photopolymerization cause Agent (D) and arbitrary colorant (E) and manufacture.In addition, resin combination of the invention, except can be used to form colored filter Except colored pattern, it can also be used to other purposes.
Resin combination of the invention obtained as described above has alkali development, therefore can be by using alkaline water Solution develops.The sensitivity of resin combination especially of the invention and developability are excellent, and are capable of forming 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, solid-state imager colored filter colored pattern and use against corrosion Agent.In addition, resin combination of the invention is capable of forming the cured coating film of the excellents such as solvent resistance, therefore can also be used in each Kind smears, bonding agent, adhesive for printing ink etc..
Then, the colored filter for using resin combination of the invention to manufacture is illustrated.Colored filter of the invention Mating plate has the colored pattern obtained by above-mentioned resin combination.
Attached drawing used below is illustrated the colored filter of one embodiment of the present invention.
Fig. 1 is the sectional view of the colored filter of an embodiment of the invention.In Fig. 1, colored filter is by substrate 1, it forms the pixel 2 of RGB on substrate 1 and is formed in the stain matrix 3 on the boundary of pixel 2 and is formed in pixel 2 and black Protective film 4 on dot matrix 3 is constituted.In this configuration, in addition at least one of pixel 2 and stain matrix 3 (colored pattern) make It is formed with above-mentioned resin combination, well known structure can be used in other structures.In addition, colored filter shown in Fig. 1 For an example, it is not limited to the structure.
Then, the manufacturing method of the colored filter of one embodiment of the present invention is illustrated.
Firstly, forming colored pattern on substrate 1.Specifically, sequentially forming stain matrix 3 and pixel on substrate 1 2.Here, be not particularly limited as substrate 1, can be used glass substrate, silicone substrate, polycarbonate substrate, polyester substrate, Polyamide substrate, polyamideimide-based plate, polyimide substrate, aluminum substrate, printed circuit board, array substrate etc..
Colored pattern can be formed by using photoetching process.Specifically, above-mentioned resin combination is coated on substrate 1 On, after forming coated film, the photomask across predetermined pattern is exposed coated film, makes exposed portion photocuring.Then, make After being developed with alkaline aqueous solution to unexposed portion, by baking, defined pattern can be formed.
It as the coating method of resin combination, is not particularly limited, screen printing process, rolling method, curtain can be used to apply Cloth method, spray coating method, spin-coating method etc..In addition, can also be as needed, after being coated with resin combination, circulating baking oven, infrared be used The heating equipments such as line heater, electric furnace are heated, and the volatile ingredients such as solvent (C) is thus made to volatilize.Heating condition, without special It limits, can be appropriately configured according to the type of the resin combination used.Usually 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 carries out appropriate adjustment.
As the alkaline aqueous solution used in development, be not particularly limited, can be used sodium carbonate, potassium carbonate, calcium carbonate, The aqueous solutions 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-hydroxy ethyl aniline, 3- methyl -4- amino - N- ethyl-N- β-methylsulphur amine ethyl aniline, 3- methyl -4- amino-N- ethyl-N- 'beta '-methoxy ethyl aniline and these substances The aqueous solution etc. of the P- pHENYLENE dI AMINEs class compound such as sulfate, hydrochloride or tosilate.Wherein, it is preferable to use to Asia The aqueous solution of phenylenediamine class compound.In addition, defoaming agent or surface-active can be added as needed in these aqueous solutions Agent.Furthermore it is preferred that being washed and being made it dry after being developed using above-mentioned alkaline aqueous solution.
The condition of baking, is not particularly limited, as long as being heated i.e. according to the type of the resin combination used Can, by using resin combination of the invention, can be toasted than previous lower temperature, preferably 215 DEG C or less, It is heated 10~60 minutes more preferably at 130~215 DEG C.Due to even if can under than previous lower baking temperature Sufficient solvent resistance, therefore the non-serviceable dyestuff for the deterioration problem as caused by heat are obtained, it also can be with more kinds of Class uses.
By using the resin combination for stain matrix 3 and for the resin combination of pixel 2, it is repeated in Coating, exposure, development and the baking stated, are capable of forming desired colored pattern.
In addition, the method for forming colored pattern by photocuring is illustrated among the above, still, if using Resin combination added with curing accelerator and well 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, protective film 4 is formed on colored pattern (pixel 2 and stain matrix 3).As protective film 4, do not limit especially It is fixed, as long as being formed using well known substance.
The colored filter manufactured through the above way, due to using sensitivity and developability excellent and be capable of forming 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 value is according to JIS The acid value of the resin (A) containing epoxy group and acidic group of K6901:2008 5.3.2 measurement refers to and neutralizes 1g containing epoxy group and acidic group Resin (A) contained in potassium hydroxide needed for acid ingredient mg number.In addition, weight average molecular weight, is referred to and is seeped using gel Saturating chromatography (GPC), the weight average molecular weight for being converted into standard polystyren measured by following conditions.
Column: Shodex (registered trademark) LF-804+LF-804 (SHOWA DENKO K.K. manufacture)
Column temperature: 40 DEG C
Sample: 0.2% tetrahydrofuran solution of resin
Eluent: tetrahydrofuran
Detector: Differential refractometer (Shodex (registered trademark) RI-71S) (SHOWA DENKO K.K. manufacture)
Flow velocity: 1mL/min
1 > of < synthesis example
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 stirs while carrying out nitrogen displacement, is warming up to 80 DEG C.It then, will be to by 86 mass The monomer mixing that the methacrylic acid of part (1 mole) and the glycidyl methacrylate of 71 mass parts (0.5 mole) are formed 2,2- azo bis- (2,4- methyl pentane nitriles) (polymerization initiator, Wako Pure Chemical of 17 mass parts is added in object Industries, Ltd. manufacture V-65) made of substance, be added dropwise in flask with 2 hours from dropping funel.After the completion of titration, It is futher stirred at 80 DEG C 2 hours, carries out copolyreaction, obtain resinous liquid (the solid component acid value 320mgKOH/ of No.1 G, weight average molecular weight 10000).In addition, 1 mole of acidic group relative to the resin in obtained resinous liquid, mole of epoxy group Number is 0.5.
2~5 > of < synthesis example
In addition to according to shown in table 1, changing propylene glycol methyl ether acetate (PGMEA), methacrylic acid (MAa) and methyl Other than the usage amount of glycidyl acrylate (GMA), in a manner of identical with synthesis example 1, the resinous of No.2~5 is obtained Liquid.
[table 1]
PGMEA: propylene glycol methyl ether acetate
MAa: methacrylic acid
GMA: glycidyl methacrylate
6 > of < synthesis example
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 stirs while carrying out nitrogen displacement, is warming up to 80 DEG C.It then, will be to by 86 mass The monomer mixture that the methacrylic acid of part (1 mole) and the glycidyl methacrylate of 142 mass parts (1 mole) are formed In be added to 2,2- azo bis- (2,4- methyl pentane nitriles) (polymerization initiator, Wako Pure Chemical of 25 mass parts Industries, Ltd. manufacture V-65) made of substance, be added dropwise in flask with 2 hours from dropping funel.After the completion of titration, It is futher stirred at 80 DEG C 2 hours, carries 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. manufacture), after carrying out stirring in 1 hour, the propylene glycol methyl ether acetate of 160 mass parts is put into, obtains No.6's Resinous liquid (solid component acid value 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 group are 2.
7 > of < synthesis example
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 stirs while carrying out nitrogen displacement, is warming up to 80 DEG C.It then, will be to by 86 mass The methacrylic acid, the styrene of 104 mass parts (1 mole) and the methacrylic acid of 284 mass parts (2 moles) of part (1 mole) Being added to the 2,2- azos bis- (2,4- methyl pentane nitriles) of 52 mass parts in the monomer mixture that ethylene oxidic ester is formed, (polymerization is drawn Send out agent, Wako Pure Chemical Industries, Ltd. manufactures V-65) made of substance, with 2 hours from dropping funel It is added dropwise in flask.It after the completion of titration, is futher stirred at 80 DEG C 2 hours, carries out copolyreaction, obtain the resinous of No.7 Liquid (solid component acid value 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 group are 2.
The preparation > of < resin combination
Using mixed proportion shown in table 2 as basic addition, the change resin as shown in table 3 and 4 contains liquid and polymerism The type of monomer prepares the resin combination of Examples 1 to 10 and comparative example 1~7.
[table 2]
[table 3]
PETA-SA: succinate modified object (degree of modification 50~60%, the KYOEISHA of pentaerythritol triacrylate CHEMICAL Co., LTD manufacture)
DPEPA-SA: succinate modified object (degree of modification 35~60%, the 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 hexaacrylate
DPHA: dipentaerythritol hexaacrylate (KYOEISHA CHEMICAL Co., LTD manufacture)
PETA-SA: succinate modified object (degree of modification 50~60%, the KYOEISHA of pentaerythritol triacrylate CHEMICAL Co., LTD manufacture)
DPEPA-SA: succinate modified object (degree of modification 35~60%, the KYOEISHA of Dipentaerythritol Pentaacrylate CHEMICAL Co., LTD manufacture)
The evaluation > of < solvent resistance
To the n-methyl-2-pyrrolidone as usually used solvent in the protective film 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 at 210 DEG C toast after with a thickness of 2.5 μm Mode heated 3 minutes at 90 DEG C after the resin combination of preparation is carried out spin coating, solvent made to volatilize.Then, using wave The light of long 365nm is exposed (light exposure 300mJ/cm to coated film2), after making exposed portion photocuring, in baking temperature It is placed 20 minutes in 210 DEG C of drier, makes cured coating film.Use spectrophotometer UV-1650PC (Shimadzu Corporation manufacture), transmissivity of test film of the measurement with cured coating film at wavelength 675nm.Then, to training with cover Support and the n-methyl-2-pyrrolidone (NMP) of 55 mass parts be added in ware, by the test film dipping with cured coating film wherein it Afterwards, transmissivity of the measurement after 30 minutes at 60 DEG C.The results are shown in Table 5.The rising of transmissivity, it is meant that colorant to N-methyl-2-pyrrolidone (NMP) dissolution, it may be said that initial stage transmissivity transmits after being impregnated with n-methyl-2-pyrrolidone (NMP) The small side of the difference of rate, solvent resistance are high.
The evaluation > of < alkali development
It, will in a manner of after making to expose with a thickness of 2.5 μm on the glass substrate (alkali-free glass substrate) of 5cm square After the resin combination of preparation carries out spin coating, is heated 3 minutes at 90 DEG C, solvent is made to volatilize.Then, away from 100 μm of coated film Distance configuration predetermined pattern photomask, (light exposure 150mJ/cm is exposed to coated film across the photomask2), make to expose Light part photocuring.Then, it will be sprayed containing the aqueous solution of 0.1 mass % sodium carbonate with 23 DEG C of temperature and the pressure of 0.3MPa Mist after dissolving unexposed portion and being developed, by toasting 30 minutes at 210 DEG C, forms predetermined pattern, confirms that alkalinity 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 evaluation criteria is as described below.As a result such as table 5 It is shown.
Zero: without residue
×: there is residue
The evaluation > of < sensitivity
The spraying alkaline development of above-mentioned use in 30 seconds is carried out, contact pin type segment difference meter ET4000M (Kosaka is passed through Laboratory Ltd. manufacture) reduction amount of pattern thickness before and after alkaline development is measured, thus determine the excellent of sensitivity It is bad.It may be said that the reduction amount of the pattern thickness is smaller, then sensitivity is better, therefore the evaluation criteria is as described below.As a result such as table 5 It is shown.
Zero: less than 0.20 μm
×: 0.20 μm or more
[table 5]
As shown in Table 5, if using Examples 1 to 10 resin combination, 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
From the above results, it can be seen that, according to the present invention, it is possible to provide a kind of sensitivity and developability are good and be capable of forming 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 resin combination of the invention, the colored pattern with excellent solvent resistance can be obtained , the colored filter that reliability is high.
Description of symbols
1: substrate；2: pixel；3: stain matrix；4: protective film.

Claims (13)

1. a kind of resin combination for the colored pattern for being used to form colored filter, contains: the tree containing epoxy group and acidic group Polynary acid monoester (B), solvent (C) and the colorant (E) of the multifunctional (methyl) acrylate of rouge (A), hydroxyl, feature It is, relative to 1 mole of acidic group in the resin (A) containing epoxy group and acidic group, epoxy group is 0.5~3.0 mole.
2. resin combination according to claim 1, contain to come from has olefinic carbon-to-carbon double bond and ring in a molecule The monomeric unit of the monomer (a-1) of oxygroup, the structures alone unit as the resin (A) containing epoxy group and acidic group.
3. resin combination according to claim 1 or 2 contains the monomeric unit from unsaturated carboxylic acid (a-2), make For the structures alone unit of the resin (A) containing epoxy group and acidic group.
4. resin combination according to claim 3, wherein the resin (A) containing epoxy group and acidic group contains: coming From a part of the carboxyl of the unsaturated carboxylic acid (a-2), addition has and has the functional group reacted with carboxyl in a molecule With the monomer (a-3) of olefinic carbon-to-carbon double bond, structures alone unit with olefinic carbon-to-carbon double bond.
5. resin combination according to claim 2, wherein described that there is olefinic carbon-to-carbon double bond and ring in a molecule The monomer (a-1) of oxygroup is (methyl) acrylate containing epoxy group.
6. resin combination according to claim 4, wherein described that there is the functional group reacted with carboxyl in a molecule With the monomer (a-3) of olefinic carbon-to-carbon double bond, for selected from (methyl) acrylate containing epoxy group and containing the (first of isocyanate group Base) it is one kind or two or more in acrylate.
7. resin combination according to claim 1 or 2, wherein the multifunctional (methyl) acrylate of the hydroxyl Polynary acid monoester (B), for selected from polynary acid monoester, the dipentaerythritol by the two of pentaerythrite or three (methyl) acrylate Two, three, four or five (methyl) acrylate polynary acid monoester composed by it is one kind or two or more in group.
8. resin combination according to claim 1 or 2, wherein the acid value of the resin (A) containing epoxy group and acidic group For 10~350mgKOH/g.
9. resin combination according to claim 1 or 2 further contains Photoepolymerizationinitiater initiater (D).
10. resin combination according to claim 1, wherein the colorant (E) is selected from by dyestuff and pigment institute group At group in it is at least one kind of.
11. a kind of colored filter, what the cured coating film with the resin combination as described in claim 1 or 10 was formed Colored pattern.
12. a kind of image-displaying member has colored filter described in claim 11.
13. a kind of manufacturing method of colored filter comprising following process:
Resin combination described in claim 1 or 10 is coated on substrate, expose and is carried out by alkaline aqueous solution The process of development；And
It is toasted under the conditions of 215 DEG C of temperature below, the process for forming colored pattern.
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