CN102844712B - Addition copolymer, photosensitive resin composition, and color filter - Google Patents

Addition copolymer, photosensitive resin composition, and color filter Download PDF

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Publication number
CN102844712B
CN102844712B CN201180018942.7A CN201180018942A CN102844712B CN 102844712 B CN102844712 B CN 102844712B CN 201180018942 A CN201180018942 A CN 201180018942A CN 102844712 B CN102844712 B CN 102844712B
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methyl
monomer
acrylic acid
photosensitive polymer
anhydride
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CN102844712A (en
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木下健宏
小森康広
川口恭章
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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
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • 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
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F232/04—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having one carbon-to-carbon double bond

Abstract

Disclosed is a photosensitive resin composition which is characterized by containing a solvent (B) and an addition copolymer (A) that is obtained by adding a monomer (a-4) having a hydroxyl group to a copolymer that is obtained by copolymerizing 2-60% by mole of a monomer (a-1) that has a bridged cyclic hydrocarbon group having 10-20 carbon atoms and/or a monomer (a-1') that is represented by general formula (1), 30-88% by mole of an unsaturated polybasic acid anhydride (a-2) and 10-68% by mole of a copolymerizable monomer (a-3) that is other than the components (a-1), (a-1') and (a-2). The photosensitive resin composition is capable of providing a color pattern that exhibits good sensitivity and developability, while having excellent thermal decomposition resistance and solvent resistance. (In general formula (1), X and Y each independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1-4 carbon atoms; R1 and R2 each independently represents a hydrogen atom, a hydrocarbon group having 1-20 carbon atoms or a carboxyl group; and R1 and R2 may combine together to form a cyclic structure.)

Description

Addition copolymer, photosensitive polymer combination and color filter
Technical field
The present invention relates to addition copolymer, photosensitive polymer combination and color filter, particularly relate to for the manufacture of being loaded into OLED display, liquid crystal indicator, the addition copolymer of color filter of solid photographic device and photosensitive polymer combination, and the color filter using these addition copolymers and photosensitive polymer combination to manufacture.
Background technology
In recent years, from the viewpoint of saving resource, save energy, in the fields such as various coating, printing, coating, bonding agent, widely use the photosensitive polymer combination that ultraviolet, electron ray isoreactivity can be used energy ray curing.Further, in the field of electronic materials such as printed circuit board (PCB), the photosensitive polymer combination by active energy ray-curable is also used as solder resist, color filter resist (resist) etc.
Color filter usually by transparency carriers such as glass substrates, form red (R), green (G) on the transparent substrate, blue (B) pixel, the black matrix being formed in pixel boundary and the diaphragm be formed on pixel and black matrix are formed.The color filter with this formation is manufactured by the mode forming black matrix, pixel and diaphragm on the transparent substrate successively usually.(following as pixel and black matrix, pixel and black matrix are called " colored pattern ") formation method, proposition has various manufacture method, wherein photosensitive polymer combination is used as resist, repeatedly carry out being coated with, exposing, developing and toasting (ベ ー キ Application グ) photoetching process of operation, due to the excellent in te pins of durability such as photostability, thermotolerance of formed colored pattern, and the defects such as pin hole are less, thus become present main flow.
Usually, the photosensitive polymer combination used in photoetching process contains alkali soluble resins, reactive diluent, Photoepolymerizationinitiater initiater, colorant and solvent.As alkali soluble resins, propose to have use by the unsaturated monomer containing carboxyl, maleic anhydride and except the unsaturated monomer containing carboxyl and maleic anhydride can the unsaturated monomer of copolymerization according to the scheme (such as, see patent documentation 1) setting the product that ratio copolymerization obtains.In addition, also propose to have and be used in the product that obtained by the compound of addition hydroxyl in maleic anhydride and the multipolymer that can obtain with the monomer of the maleic anhydride scheme (such as, see patent documentation 2 ~ 5) as alkali soluble resins.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-148720 publication
Patent documentation 2: Japanese Unexamined Patent Publication 10-293402 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2007-79294 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2007-133032 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2009-223127 publication
Summary of the invention
Technical matters
But existing photosensitive polymer combination there is sensitivity or developability does not meet the demands, cannot obtain the situation of the colored pattern of resistance to pyrolytic and excellent solvent resistance.
Therefore, the present invention proposes to solve the problem, and its object is to provide sensitivity, developability well and the photosensitive polymer combination providing the colored pattern of resistance to pyrolytic and excellent solvent resistance.In addition, the object of the present invention is to provide that to be used in sensitivity, developability good and provide the alkali soluble resins (addition copolymer) of the photosensitive polymer combination of the colored pattern of resistance to pyrolytic and excellent solvent resistance.And then, the object of the present invention is to provide a kind of color filter with the colored pattern of resistance to pyrolytic and excellent solvent resistance.
Technical scheme
The present inventor etc., in order to solve above-mentioned problem, concentrate on studies.It found that, specific addition copolymer is most suitable as the alkali soluble resins for photosensitive polymer combination, completes the present invention based on this opinion.
That is, the present invention is as shown in following [1] ~ [13].
[1] a kind of photosensitive polymer combination, it is characterized in that containing addition copolymer A and solvent B, this addition copolymer A is can addition has a hydroxyl in the multipolymer that formed of monomer (a-3) copolymerization of copolymerization monomer (a-4) be formed except (a-1), (a-1 ') and (a-2) with the monomer (a-1) that carbon number is the crosslinked ring type alkyl of 10 ~ 20 and/or the monomer represented by following general formula (1) (a-1 '), the unsaturated multi-anhydride (a-2) of 30 ~ 88 % by mole and 10 ~ 68 % by mole making 2 ~ 60 % by mole.
[chemical formula 1]
(wherein, X and Y independently, represents that hydrogen atom or carbon number are the straight or branched alkyl of 1 ~ 4, R 1and R 2independently, expression hydrogen atom, carbon number are alkyl or the carboxyl of 1 ~ 20, also can form R 1and R 2the ring texture be connected.）
[2] photosensitive polymer combination recorded in aforementioned [1], is characterized in that described monomer (a-1) is for methacrylic acid bicyclopentyl ester (ジ シ Network ロ ペ Application タ ニ Le メ タ Network リ レ mono-ト).
[3] photosensitive polymer combination recorded in aforementioned [1] or [2], is characterized in that described unsaturated multi-anhydride (a-2) is maleic anhydride.
[4] photosensitive polymer combination in aforementioned [1] to [3] described in any one, is characterized in that described monomer (a-3) comprises the vinyltoluene of 10 ~ 40 % by mole.
[5] photosensitive polymer combination in aforementioned [1] to [4] described in any one, is characterized in that described monomer (a-4) is more than one the material selected from the group be made up of (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, trimethylolpropane two (methyl) acrylate and pentaerythritol triacrylate.
[6] photosensitive polymer combination in aforementioned [1] to [5] described in any one, is characterized in that further containing more than one the material selected from the group be made up of reactive diluent C, Photoepolymerizationinitiater initiater D and colorant E.
[7] photosensitive polymer combination recorded in aforementioned [6], is characterized in that described colorant E comprises dyestuff.
[8] an addition copolymer A, it is characterized in that make 2 ~ 60 % by mole have the monomer (a-1) that carbon number is the crosslinked ring type alkyl of 10 ~ 20 and/or the monomer represented by following general formula (1) (a-1 '), the unsaturated multi-anhydride (a-2) of 30 ~ 88 % by mole and 10 ~ 68 % by mole addition can have the monomer (a-4) of hydroxyl in the multipolymer that formed of monomer (a-3) copolymerization of copolymerization except (a-1), (a-1 ') and (a-2).
[chemical formula 2]
(wherein, X and Y independently, represents that hydrogen atom or carbon number are the straight or branched alkyl of 1 ~ 4, R 1and R 2independently, expression hydrogen atom, carbon number are alkyl or the carboxyl of 1 ~ 20, also can form R 1and R 2the ring texture be connected.）
[9] the addition copolymer A recorded in aforementioned [8], is characterized in that described monomer (a-1) is for methacrylic acid bicyclopentyl ester (ジ シ Network ロ ペ Application タ ニ Le メ タ Network リ レ mono-ト).
[10] the addition copolymer A recorded in aforementioned [8] or [9], is characterized in that described unsaturated multi-anhydride (a-2) is maleic anhydride.
[11] the addition copolymer A in aforementioned [8] to [10] described in any one, is characterized in that described monomer (a-3) comprises the vinyltoluene of 10 ~ 40 % by mole.
[12] the addition copolymer A in aforementioned [8] to [11] described in any one, is characterized in that described monomer (a-4) is more than one the material selected from the group be made up of (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, trimethylolpropane two (methyl) acrylate and pentaerythritol triacrylate.
[13] color filter, is characterized in that having the colored pattern that the photosensitive polymer combination described in any one in aforementioned [1] to [7] is formed.
Beneficial effect
According to the present invention, sensitivity, developability can be provided good and the photosensitive polymer combination of the colored pattern of resistance to pyrolytic and excellent solvent resistance is provided.In addition, according to the present invention, can provide that to be used in sensitivity, developability good and provide the alkali soluble resins (addition copolymer) of the photosensitive polymer combination of the colored pattern of resistance to pyrolytic and excellent solvent resistance.And then, according to the present invention, a kind of color filter with the colored pattern of resistance to pyrolytic and excellent solvent resistance can be provided.
Accompanying drawing explanation
Fig. 1 is the cut-open view of the color filter of embodiment 3.
Embodiment
Embodiment 1
The addition copolymer A of present embodiment, by making to have the monomer (a-1) that carbon number is the crosslinked ring type alkyl of 10 ~ 20 and/or the monomer represented by following general formula (1) (a-1 '), unsaturated multi-anhydride (a-2) and can addition has a hydroxyl in the multipolymer that formed of monomer (a-3) copolymerization of copolymerization monomer (a-4) obtain except (a-1), (a-1 ') and (a-2).
[chemical formula 3]
(wherein, X and Y independently, represents that hydrogen atom or carbon number are the straight or branched alkyl of 1 ~ 4, R 1and R 2independently, expression hydrogen atom, carbon number are alkyl or the carboxyl of 1 ~ 20, also can form R 1and R 2the ring texture be connected.）
For monomer (a-1), as long as have the crosslinked ring type alkyl that carbon number is 10 ~ 20, be not particularly limited.At this, so-called crosslinked ring type hydrocarbon refer to diamantane, norbornane representatively, the material with the structure represented by following general formula (2) or (3), so-called crosslinked ring type alkyl refers to the group be equivalent to from the remainder after remove portion hydrogen atom this structure.
[chemical formula 4]
[chemical formula 5]
In general formula (2), A 1and B 1both can be identical, also can be different, represent straight or branched alkylene (comprising ring type) respectively, R 3represent hydrogen atom or methyl.At this, also can by making A 1and B 1branch be combined with each other and form ring-type.In addition, in general formula (3), A 2, B 2both can be identical with L, also can be different, represent straight or branched alkylene (comprising ring type) respectively, R 4represent hydrogen atom or methyl.At this, also can by making A 2, B 2be combined with each other with the branch of L and form ring-type.
As the example of monomer (a-1), (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid bicyclopentyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid diamantane ester etc. can be enumerated.Wherein, resistance to pyrolytic, cohesive, developability etc. are considered, preferable methyl acrylic acid bicyclopentyl ester.These materials can be used alone, and also can be used in combination of two or more.
For monomer (a-1 '), as long as have the chemical constitution that above-mentioned general formula (1) represents, be not particularly limited.In general formula (1), as representing that carbon number is the example of X and Y of the straight or branched alkyl of 1 ~ 4, can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group etc.Further, as representing that carbon number is the R of the alkyl of 1 ~ 20 1and R 2example, can enumerate: the straight or branched alkyl such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, the tert-butyl group, tertiary pentyl, octadecyl, dodecyl, 2-ethylhexyl; The aryl such as phenyl; The alicyclic group such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, three ring decyls, isobornyl, adamantyl, 2-methyl-2-adamantyl; The alkyl that 1-methoxy ethyl, 1-ethoxyethyl group etc. replace with alkoxy; The alkyl etc. that benzyl etc. replace with aryl.
As the example of monomer (a-1 ') with the chemical constitution represented with general formula (1), norborene (two rings [2.2.1] hept-2-ene"), 5-methyl bicyclic [2.2.1] hept-2-ene", 5-ethyl two ring [2.2.1] hept-2-ene", Fourth Ring [4.4.0.1 can be enumerated 2,5.1 7,10] 12-3-alkene, 8-methyl Fourth Ring [4.4.0.1 2,5.1 7,10] 12-3-alkene, 8-ethyltetracyclo [4.4.0.1 2,5.1 7,10] 12-3-alkene, bicyclopentadiene, three ring [5.2.1.0 2,6] ten-8-alkene, three ring [5.2.1.0 2,6] ten-3-alkene, three ring [4.4.0.1 2,5] 11-3-alkene, three ring [6.2.1.0 1,8] 11-9-alkene, three ring [6.2.1.0 1,8] 11-4-alkene, Fourth Ring [4.4.0.1 2,5.1 7,10.0 1,6] 12-3-alkene, 8-methyl Fourth Ring [4.4.0.1 2,5.1 7,10.0 1,6] 12-3-alkene, 8-ethylidene Fourth Ring [4.4.0.1 2,5.1 7,12] 12-3-alkene, 8-ethylidene Fourth Ring [4.4.0.1 2,5.1 7,10.0 1,6] 12-3-alkene, five rings [6.5.1.1 3,6.0 2,7.0 9,13] 15 (ペ Application タ デ カ)-4-alkene, five rings [7.4.0.1 2,5.1 9,12.0 8,13] 15-3-alkene, 5-norborene-2-carboxylic acid, 5-norborene-2,3-dicarboxylic acid, 5-norborene-2,3-dicarboxylic anhydride etc.Wherein, resistance to pyrolytic, cohesive, developing property etc. are considered, preferred norborene, bicyclopentadiene, 5-norborene-2,3-dicarboxylic anhydride.These materials can be used alone, and also can be used in combination of two or more.
When the summation of monomer (a-1) and/or monomer (a-1 '), unsaturated multi-anhydride (a-2) and monomer (a-3) is counted 100 % by mole, the mixing ratio of monomer (a-1) and/or monomer (a-1 ') is 2 ~ 60 % by mole, is preferably 5 ~ 20 % by mole.If the mixing ratio of monomer (a-1) and/or monomer (a-1 ') is less than 2 % by mole, then cannot obtain the resistance to pyrolytic of wishing.On the other hand, if this mixing ratio is more than 60 % by mole, then the mixing ratio of unsaturated multi-anhydride (a-2) diminishes, and cannot obtain the sensitivity of hope, developability.
As unsaturated multi-anhydride (a-2), be not particularly limited, material well known in the art can be used.As the example of unsaturated multi-anhydride (a-2), maleic anhydride, itaconic anhydride, citraconic anhydride etc. can be enumerated.Wherein, consider and can be easy to acquisition, repeatability, reactivity etc., preferred maleic anhydride.
When the summation of monomer (a-1) and/or monomer (a-1 '), unsaturated multi-anhydride (a-2) and monomer (a-3) is counted 100 % by mole, the mixing ratio of unsaturated multi-anhydride (a-2) is 30 ~ 88 % by mole, is preferably 35 ~ 70 % by mole.If the mixing ratio of unsaturated multi-anhydride (a-2) is less than 30 % by mole, then the quantitative change of the double bond in addition copolymer A is few, cannot obtain the sensitivity wished.On the other hand, if this mixing ratio is more than 88 % by mole, then unreacted unsaturated multi-anhydride (a-2) can remain in a large number.
For monomer (a-3), as long as except (a-1), (a-1 ') and (a-2) can the material of copolymerization, be not particularly limited.Monomer (a-3) is generally the free-radical polymerised compound with ethene unsaturated group, as its concrete example, can enumerate: the dienes such as butadiene, 2,3-dimethyl butadienes, isoprene, chlorbutadiene, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) acrylic acid peopentyl ester, (methyl) benzyl acrylate, (methyl) isoamyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid-2-ethyl caproite, (methyl) lauryl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic methyl cyclohexyl, (methyl) acrylic acid ethyl cyclohexyl, 1,4-CHDM list (methyl) acrylate, (methyl) acrylic acid rosin ester, (methyl) acrylic acid norborneol ester, (methyl) acrylic acid 5-methyl norborneol ester, (methyl) acrylic acid 5-ethyl norborneol ester, (methyl) allyl acrylate, (methyl) propargylacrylate, (methyl) acrylic acid pepper ester, (methyl) acrylic acid salicyl ester, (methyl) acrylic acid furans ester, (methyl) acrylic acid chaff ester, (methyl) acrylic acid tetrahydrofuran ester, (methyl) acrylic acid pyrans ester, (methyl) phenylethyl, (methyl) CA, (methyl) acrylic acid 1,1,1-trifluoro ethyl ester, (methyl) perfluoroethyl ethyl ester, (methyl) perfluoroethyl n-propyl, (methyl) perfluoroethyl isopropyl ester, (methyl) acrylic acid triphenylmethyl, (methyl) acrylic acid cumene ester, 3-(N, N-dimethylamino) propyl group (methyl) acrylate, glycerine list (methyl) acrylate, butantriol list (methyl) acrylate, penta triol list (methyl) acrylate, (methyl) acrylic acid naphthalene ester, (methyl) esters of acrylic acids such as (methyl) acrylic acid anthracene ester, (methyl) acrylamide, (methyl) acrylic acid N, N-dimethylformamide, (methyl) acrylic acid N, N-diethylamide, (methyl) acrylic acid N, N-dipropyl acid amides, (methyl) acrylic acid N, (methyl) acrylamides such as N-diisopropylamide, (methyl) acrylic acid anthryl acid amides, the vinyl compound such as (methyl) acryloyl aniline ((メ タ) ア Network リ Le acid ア ニ リ De), (methyl) vinyl cyanide ((メ タ) ア Network リ ロ イ Le ニ ト リ Le), acryl aldehyde, vinyl chloride, vinylidene chloride, fluorothene, vinylidene, NVP, vinylpyridine, vinyl acetate, vinyltoluene, styrene, cinnamic α-, adjacent, to alkyl, nitro, cyano group, amide derivatives, the unsaturated dicarboxylic diester such as citraconic acid diethylester, diethyl maleate, DEF, diethyl itaconate, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-lauryl maleimide, N-(4-hydroxyphenyl) single maleimide such as maleimide, N-(methyl) acryloyl group phthalimide, (methyl) acrylic acid, butenoic acid, cinnamic acid etc. have the compound etc. of carboxyl.These materials can be used alone, and also can be used in combination of two or more.
Especially, when using maleic anhydride as unsaturated multi-anhydride (a-2), because maleic anhydride is electron-withdrawing stronger compound, therefore monomer (a-3) preferably pushes away electro monomer.Thisly push away electro monomer by using, between the materials such as maleic anhydride, produce alternating copolymerization, each unit configures more randomly, the raisings such as its result developability, sensitivity, and can form the colored pattern of resistance to pyrolytic excellence.As pushing away electro monomer, ethene ethers, vinyl sulfide class, phenylethylene etc. can be enumerated.In these materials, consider copolymerizable, optimization styrene class, consider resistance to decomposability, more preferably vinyltoluene.At this, when using vinyltoluene, (methyl) esters of acrylic acid can be used together, developability can be improved further thus.
When the summation of monomer (a-1) and/or monomer (a-1 '), unsaturated multi-anhydride (a-2) and monomer (a-3) is counted 100 % by mole, the mixing ratio of monomer (a-3) is 10 ~ 68 % by mole, is preferably 20 ~ 50 % by mole.If the mixing ratio of monomer (a-3) is less than 10 % by mole, then cannot realize the balance of resistance to pyrolytic and developability.On the other hand, if this mixing ratio is more than 68 % by mole, then can desensitization and thermotolerance.
Especially, when using vinyltoluene as monomer (a-3), when the summation of monomer (a-1) and/or monomer (a-1 '), unsaturated multi-anhydride (a-2) and monomer (a-3) is counted 100 % by mole, monomer (a-3) preferably comprises the vinyltoluene of 10 ~ 40 % by mole.
Using the copolyreaction that monomer (a-1) and/or monomer (a-1 '), unsaturated multi-anhydride (a-2) and monomer (a-3) use as raw material, can carry out according to free radical polymerisation process well known in the art.Such as, after can monomer (a-1) and/or monomer (a-1 '), unsaturated multi-anhydride (a-2) and monomer (a-3) being dissolved in solvent, in this solution, adding polymerization initiator, at 50 ~ 130 DEG C, make it react 1 ~ 20 hour.
For the solvent that can use in this copolyreaction, be not particularly limited, such as, can enumerate: the glycol ethers solvent such as propylene glycol monomethyl ether, propylene glycol methyl ether acetate (the molten drug of グ リ コ ー ル エ ー テ Le system); The varsol such as toluene, dimethylbenzene, ethyl acetate etc. do not have the solvent of reactive functional groups.These materials can be used alone, and also can be used in combination of two or more.Further, in these materials, preferably glycol ethers solvent is used.
For the use level of solvent, as long as can raw material be dissolved, be not particularly limited, relative monomer (a-1) and/or monomer (a-1 '), unsaturated multi-anhydride (a-2) and monomer (a-3) total metering 100 mass parts, be generally 30 ~ 1000 mass parts, be preferably 50 ~ 800 mass parts.Especially, by making the use level of solvent be no more than 1000 mass parts, according to chain migration, suppressing the reduction of the molecular weight of multipolymer, and the viscosity of multipolymer can be controlled in suitable scope.In addition, by making the use level of solvent be more than or equal to 30 mass parts, abnormal polyreaction can be prevented, stably carrying out polyreaction, and painted, the gelation of multipolymer can be prevented.
For the polymerization initiator that can use in this copolyreaction, be not particularly limited, such as, can enumerate: azoisobutyronitrile, AMBN, benzoyl peroxide, the peroxidating-2-ethyl acid tert-butyl ester etc.These materials can be used alone, and also can be used in combination of two or more.
For the use level of polymerization initiator, total metering 100 mass parts of relative monomer (a-1) and/or monomer (a-1 '), unsaturated multi-anhydride (a-2) and monomer (a-3), is generally 0.5 ~ 20 mass parts, is preferably 1.0 ~ 10 mass parts.
At this, also can not with an organic solvent, and use monomer (a-1) and/or monomer (a-1 '), unsaturated multi-anhydride (a-2) and monomer (a-3) to carry out bulk polymerization with polymerization initiator.
By the multipolymer that above-mentioned copolymer reaction obtains, by addition, there is the monomer (a-4) of hydroxyl and import carboxyl and double bond at the side chain of multipolymer.Thus, sensitivity and the developability of photosensitive polymer combination is improved.
As the example of monomer (a-4), (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) acrylic acid 2,3-bis-hydroxypropyl acrylate, glycerol dimethacrylate, 2-hydroxyl-3-(methyl can be enumerated) acrylic acid acryloxy propyl ester, 2-acryloyl-oxyethyl-2-hydroxyethyl-phthalic acid, trimethylolpropane two (methyl) acrylate, pentaerythritol triacrylate etc.These materials can be used alone, and also can be used in combination of two or more.
Especially, consider the reactivity with the anhydride group in multipolymer, monomer (a-4) preferably has primary hydroxyl (the 1st Grade water acidic group).Further, when considering the sensitivity of photosensitive polymer combination, in order to increase the amount of the double bond in addition copolymer A, monomer (a-4) is preferably material or multifunctional (methyl) acrylate of molecular weight.As the monomer meeting these conditions, (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, trimethylolpropane two (methyl) acrylate, pentaerythritol triacrylate etc. can be enumerated.
Monomer (a-4) is proportional relative to adding of the anhydride group in multipolymer, is preferably 10 ~ 100%.In order to carry out the addition reaction of this monomer (a-4), adding monomer (a-4), making when the molar equivalent of the anhydride group of multipolymer counts 1, make the molar equivalent of the hydroxyl of monomer (a-4) fall into the scope of 0.1 ~ 1, carry out in the case reacting.Proportionally be less than 10% if added, then the amount importing to the carboxyl of the side chain of multipolymer and double bond is too small, cannot obtain the sensitivity wished and developability.
With regard to monomer (a-4) relative to the anhydride group in multipolymer addition reaction with regard to, add monomer (a-4), polymerization inhibitor and catalyzer in the copolymer, at 50 ~ 150 DEG C, preferably carry out reacting at 80 ~ 130 DEG C.At this, even if comprise the solvent used in copolyreaction in this addition reaction also do not have special problem, after therefore copolyreaction terminates, without the need to removing solvent, addition reaction can be carried out.
At this, polymerization inhibitor adds to prevent the gelation caused by the polymerization of multipolymer.As polymerization inhibitor, be not particularly limited, such as, can enumerate p-dihydroxy-benzene, methyl hydroquinone, hydroquinone monomethyl ether etc.In addition, as catalyzer, be not particularly limited, such as, can enumerate the huge legendary turtle compound etc. of the phosphorus compound of the quaternary amine of the tertiary amine of such as triethylamine, such as triethyl benzyl ammonia chloride, such as triphenylphosphine, chromium.In these materials, in the reaction of acid anhydrides and hydroxyl, preferably use the tertiary amines such as triethylamine, triethylenediamine, DMAP, dimethylaminoethyl acrylate methyl ammonia ethyl ester.
The acid number of the addition copolymer A obtained by the way, is preferably 50 ~ 400KOH mg/g, is more preferably 150 ~ 300KOH mg/g.If this acid number is less than 50KOH mg/g, then the developability of photosensitive polymer combination is caused to reduce.On the other hand, if this acid number is more than 400KOH mg/g, then relative to alkaline-based developer, exposed portion (photo-cured portion) easily dissolves.
Further, the molecular weight (being converted into the weight-average molecular weight of polystyrene) of addition copolymer A is preferably 1000 ~ 40000, is more preferably 3000 ~ 20000.If this molecular weight is less than 1000, then easily there is the disappearance of colored pattern after development.On the other hand, if this molecular weight is more than 40000, then cause development time to become long, lack practicality.
The addition copolymer A of present embodiment is most suitable as the alkali soluble resins for photosensitive polymer combination, can manufacture sensitivity, developability good and provide the photosensitive polymer combination of the colored pattern of resistance to pyrolytic and excellent solvent resistance.
Embodiment 2
The photosensitive polymer combination of present embodiment contains addition copolymer A and the solvent B of embodiment 1.
For solvent B, as long as the inactive solvent do not reacted with addition copolymer A, be not particularly limited.
As solvent B, the material identical with the solvent that when manufacturing addition copolymer A (copolyreaction) uses can be used.Specifically, as the example of solvent B, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether acetic acid esters, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Tripropylene glycol monomethyl Ether, glycol monoethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methylisobutylketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ether acetic acid esters etc. can be enumerated.These materials can be used alone, and also can be used in combination of two or more.Further, in these materials, the glycol ethers solvent such as propylene glycol monomethyl ether, propylene glycol methyl ether acetate that when manufacturing addition copolymer A, (copolyreaction) uses is preferably used in.
The use level of the solvent B in the photosensitive polymer combination of present embodiment, solid constituent (that is, except the composition of desolventizing) 100 mass parts in relative photosensitive polymer combination, elect 30 ~ 1000 mass parts usually as, be preferably 50 ~ 800 mass parts, be more preferably 100 ~ 700 mass parts.When adopting the use level of this scope, the photosensitive polymer combination with suitable viscosity can be become.
The photosensitive polymer combination of present embodiment, on the basis of mentioned component, can contain reactive diluent C, Photoepolymerizationinitiater initiater D and colorant E further.
As reactive diluent C, as long as the material reacted with addition copolymer A, be just not particularly limited.As the example of reaction diluent, can enumerate: the aromatic vinyl base class monomer class such as styrene, α-methyl styrene, α-1-chloro-4-methyl-benzene, vinyltoluene, divinylbenzene, diallyl phthalate, phenyl-phosphonic acid diallyl, the polycarboxylic acid such as vinyl acetate, hexanedioic acid vinyl ester monomer class, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) propenoic acid beta-hydroxy ethyl ester, (methyl) hydroxypropyl acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, (methyl) acrylic ester monomers such as three (methyl) acrylate of three (hydroxyethyl) chlorinated isocyanurates, triallyl cyanurate etc.These materials can be used alone, and also can be used in combination of two or more.
The use level of the reactive diluent C in the photosensitive polymer combination of present embodiment, solid constituent (that is, except the composition of desolventizing) 100 mass parts in relative photosensitive polymer combination, elect 10 ~ 90 mass parts usually as, be preferably 20 ~ 80 mass parts, be more preferably 25 ~ 70 mass parts.When adopting the use level of this scope, can become and there is suitable photo-curable and the photosensitive polymer combination of viscosity.
As Photoepolymerizationinitiater initiater D, be not particularly limited, such as, can enumerate: benzoin and its alkyl ethers such as benzoin, benzoin methylether, benzoin ethyl ether; Acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 4-(1-tert-butyl group dioxy-1-Methylethyl) acetophenones such as acetophenone; The Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone; The thioxanthene ketones such as 2,4-dimethyl thioxanthone, 2,4-diisopropylthioxanthone, CTX; The ketal classes such as acetophenone dimethyl ketal, benzyl dimethyl ketal; Benzophenone, 4-(1-tert-butyl group dioxy-1-Methylethyl) benzophenone, 3, the benzophenones such as 3 ', 4,4 '-four (tert-butyl group dioxy carbonyl) benzophenone; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine-propane-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butanone-1; Acylphosphine oxide class and xanthene ketone etc.These materials can be used alone, and also can be used in combination of two or more.
With regard to the use level of the Photoepolymerizationinitiater initiater D in the photosensitive polymer combination of present embodiment, solid constituent in relative photosensitive polymer combination (namely, composition except desolventizing) 100 mass parts, usually 0.1 ~ 30 mass parts is elected as, be preferably 0.5 ~ 20 mass parts, be more preferably 1 ~ 10 mass parts.When adopting the use level of this scope, the photosensitive polymer combination with suitable photo-curable can be become.
For colorant E, as long as the material that can be dissolved by solvent B, be just not particularly limited, such as, can enumerate dyestuff, pigment etc.
Especially, in photosensitive polymer combination in the past, if use dyestuff, although the colored pattern of high brightness can be obtained, compared with during use pigment, there is the problem of the thermotolerance step-down of colored pattern.To this, in the photosensitive polymer combination of present embodiment, because the compatibility of dyestuff is good, even if therefore use dyestuff, also can obtain the colored pattern of excellent heat resistance.
As dyestuff, consider the dissolubility of relative solvent B, alkaline-based developer, with the interaction, thermotolerance etc. of other compositions in photosensitive polymer combination, preferably use carboxylic acid etc. have the acid dyes of acidic groups, acid dyes with the salt of nitrogen compound, the sulfanilamide (SN) thing (ス Le ホ Application ア ミ De body) etc. of acid dyes.As the concrete example of these dyestuffs, can enumerate: acid alizarine purple N(Acid alizarin violetN); Acid black 1,2,24,48; Blue VRS, 7,9,25,29,40,45,62,70,74,80,83,90,92,112,113,120,129,147; Chromic acid purple K(acid chrome violet K); Acid fuchsin; Acid green 1,3,5,25,27,50; Acid orange 6,7,8,10,12,50,51,52,56,63,74,95; Azogeramine, 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 6B, 7,9,17,19; Indian yellow 1,3,9,11,17,23,25,29,34,36,42,54,72,73,76,79,98,99,111,112,114,116; Food yellow 3 and their derivant etc.In these materials, the acid dyes of preferred azo, xanthene class, Anthraquinones or phthalocyanines.These materials, according to the color of the pixel as object, can be used alone, and also can be used in combination of two or more.
As the concrete example of pigment, can enumerate: the yellow uitramarines such as C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214; C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71, the orange pigments such as 73; C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215,216,224,242,254,255,264, the red pigments such as 265; C.I. pigment blue 15,15:3,15:4,15:6, the blue pigments such as 60; C.I. pigment violet l, 19,23,29,32,36, the violet pigments such as 38; C.I. pigment Green 7,36, the viridine greens such as 58; C.I. the brown such as pigment brown 23,25; C.I. pigment black 1,7, the black pigment etc. such as black, the iron oxide of carbon black, titanium.These pigment, according to the color of the pixel as object, can be used alone, and also can be used in combination of two or more.
At this, according to the color of the pixel as object, above-mentioned dyestuff and pigment can also be combinationally used.
The use level of the colorant E in the photosensitive polymer combination of present embodiment, solid constituent (that is, except the composition of desolventizing) 100 mass parts in relative photosensitive polymer combination, elect 5 ~ 80 mass parts usually as, be preferably 5 ~ 70 mass parts, be more preferably 10 ~ 60 mass parts.
When using pigment as colorant E, in order to improve the dispersiveness of pigment, also known spreading agent can be added in photosensitive polymer combination.As spreading agent, preferably use the macromolecule dispersing agent of dispersion stabilization excellence in time.As the concrete example of macromolecule dispersing agent, can enumerate: polyurethanes spreading agent, polyethyleneimine: amine spreading agent, polyoxyethylene alkyl ether class spreading agent, polyoxyethylene alcohol diester (Port リ オ キ シ エ チ レ Application グ リ コ ー Le ジ エ ス テ Le) class spreading agent, Sorbitan fatty esters class spreading agent, aliphatic modified ester class spreading agent etc.As this macromolecule dispersing agent, can use and manufacture with EFKA(エ Off カ ー ケ ミ カ Le ズ PVC ー Block イ (EFKA) company), Disperbyk(PVC ッ Network ケ ミ ー company manufactures), デ ィ ス パ ロ Application (nanmu originally change into Co., Ltd. manufacture), SOLSPERSE(ゼ ネ カ company manufacture) etc. trade name product sold.
With regard to the use level of the spreading agent in the photosensitive polymer combination of present embodiment, the kind according to used pigment etc. suitably sets.
With regard to the photosensitive polymer combination of present embodiment, on the basis of mentioned component, in order to give predetermined characteristic, the known adjuvants such as known coupling agent, levelling agent, thermal polymerization inhibitor can be coordinated further.The use level of these adjuvants, as long as fall into the scope not hindering effect of the present invention, is just not particularly limited.
The photosensitive polymer combination of present embodiment, can be prepared by utilizing the mode of known mixing arrangement mixing mentioned component.
The photosensitive polymer combination of the present embodiment obtained by the way has alkali development, therefore easily can develop by using alkaline aqueous solution.Especially, the photosensitive polymer combination of present embodiment has excellent sensitivity, developability and can provide the colored pattern of resistance to pyrolytic and excellent solvent resistance.Therefore, the photosensitive polymer combination of present embodiment is suitable as various resist (resist), is especially suitable as and is loaded into OLED display, liquid crystal indicator, the color filter of solid photographic device and the resist used to manufacture.In addition, the photosensitive polymer combination of present embodiment provides the cured film with various characteristics such as excellent resistance to pyrolytic and solvent resistances, therefore can also be used for various coating, bonding agent, printing-ink cementing agent etc.
Embodiment 3
The color filter of present embodiment has the colored pattern obtained by above-mentioned photosensitive polymer combination.
Below, utilize accompanying drawing that the color filter of present embodiment is described.
Fig. 1 is the cut-open view of the color filter of present embodiment.In Fig. 1, color filter by substrate 1, form rgb pixel 2 on substrate 1, the black matrix 3 being formed in pixel 2 border and the diaphragm 4 be formed on pixel 2 and black matrix 3 and form.In this formation, form pixel 2 and black matrix 3(colored pattern except using above-mentioned photosensitive polymer combination) except, other formations can adopt known formation.At this, the color filter shown in Fig. 1 is only an example, is not only defined in this formation.
Next, the manufacture method of the color filter of present embodiment is described.
First, colored pattern is formed on substrate 1.Specifically, black matrix 3 and pixel 2 is formed on substrate 1 successively.At this, as substrate 1, be not particularly limited, glass substrate, silicon substrate, polycarbonate substrate, polyester substrate, polyamide substrate, polyamide-imides substrate, polyimide substrate, aluminium base, printed circuit board (PCB), array base palte etc. can be used.
Colored pattern can lithographically be formed.Specifically, be coated with above-mentioned photosensitive polymer combination on substrate 1 and after forming coated film, utilize the photomask exposure coated film of predetermined pattern, make exposed portion generation photocuring.Then, unexposed portion is utilized after alkaline aqueous solution develops, toast, predetermined pattern can be formed thus.
As the coating process of photosensitive polymer combination, be not particularly limited, silk screen print method, rolling method, curtain coating method, spraying process, spin-coating method etc. can be used.Further, after photosensitive resin coating composition, as required, the heater meanses such as circulating baking oven, infrared heater, hot plate can be utilized to carry out heating and solvent flashing B.For heating condition, be not particularly limited, the kind according to the photosensitive polymer combination used suitably sets.Usually, with the heating temperatures 30 seconds ~ 30 minutes of 50 DEG C ~ 120 DEG C.
As exposing the light source used, being not particularly limited, Cooper-Hewitt lamp, middle medium pressure mercury lamp, high-pressure mercury-vapor lamp, xenon lamp, metal halide lamp etc. can be used.In addition, exposure is also not particularly limited, and the kind according to the photosensitive polymer combination used suitably adjusts.
As the alkaline aqueous solution used in development, be not particularly limited, can use: the aqueous solution of sodium carbonate, sal tartari, calcium carbonate, NaOH, potassium hydroxide etc.; The aqueous solution of the aminated compoundss such as ethamine, diethylamine, dimethylethanolamine; 3-methyl-4-amino-N, the aqueous solution etc. of the oxidations such as N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-beta-hydroxyethyl aniline, 3-methyl-4-amino-N-ethyl-N-β-Methanesulfomide ethylaniline, 3-methyl-4-amino-N-ethyl-N-'beta '-methoxy ethylaniline and their sulfate, hydrochloride or tosilate.In these materials, preferably use the aqueous solution of oxidation.At this, defoamer, surfactant can be added as required in these aqueous solution.Further, utilizing after above-mentioned alkaline aqueous solution develops, after being preferably washing, drying is carried out.
For the condition of baking, be not particularly limited, the kind according to the photosensitive polymer combination used carries out heating.Usually, heat 10 ~ 60 minutes at 130 DEG C ~ 250 DEG C.
Utilize the photosensitive polymer combination of black matrix 3 and the photosensitive polymer combination of pixel 2, repeat coating as above, exposure, development and baking successively, desired colored pattern can be formed thus.
At this, foregoing illustrate the colored pattern formation method according to photocuring, if but use replaces Photoepolymerizationinitiater initiater D and has coordinated the photosensitive polymer combination of hardening accelerator and known epoxy resin, heat after then utilizing ink-jet method coating, also can form desired colored pattern.
Next, at colored pattern (pixel 2 and black matrix 3) upper formation diaphragm 4.As diaphragm 4, be not particularly limited, use known material to be formed.
The color filter of manufacture like this, is use sensitivity, developability is excellent and provides the photosensitive polymer combination of the colored pattern of resistance to pyrolytic and excellent solvent resistance to manufacture, therefore has the colored pattern of resistance to pyrolytic and excellent solvent resistance.
Embodiment
Below, describe the present invention in detail with reference to embodiment, but the present invention is not limited to these embodiments.It should be noted that, in this embodiment, about " part " and number percent, unless otherwise noted, entirely for quality.
The modulation > of < photosensitive polymer combination
Add propylene glycol methyl ether acetate (solvent 1) 426.1g and maleic anhydride (a-2) 176.4g in the flask possessing stirring apparatus, tap funnel, condenser, thermometer and gas introduction tube after, while carry out nitrogen displacement, while stir, be warming up to 120 DEG C.Then, in the monomer mixture be made up of methacrylic acid bicyclopentyl ester (a-1) 66.0g and vinyltoluene (a-3) 106.2g, add the peroxidating-2-ethyl acid tert-butyl ester (polymerization initiator) 24.4g, it is added drop-wise to aforementioned flask from tap funnel.After completing dropping, stir 2 hours at 120 DEG C, carry out copolyreaction, generate multipolymer.
Then, after aforementioned flask interior is replaced as air, add acrylic acid 2-hydroxyl ethyl ester (a-4) 139.2g, triethylamine (catalyzer) 1.5g and methyl hydroquinone (polymerization inhibitor) 1.5g, at 120 DEG C, carry out the addition reaction of 6 hours, generate addition copolymer A.
Then, add propylene glycol monomethyl ether (solvent 2) 305.6g to this addition copolymer A, obtain photosensitive polymer combination (No. 1 sample).
Except feed change kind and amount except, according to the mode identical with aforesaid way, modulated the photosensitive polymer combination (No. 2 ~ No. 19 samples) of multiple kind.
The raw material and use level thereof that use in the modulation of photosensitive polymer combination (No. 1 ~ No. 19 samples) have been shown in table 1.
Table 1
In table 1, each raw material of (a-1), (a-1 '), (a-2) and (a-3) % by mole for the summation of (a-1), (a-1 '), (a-2) and (a-3) raw material being counted 100 % by mole time each raw material % by mole.In addition, the molar equivalent of (a-4) is the molar equivalent of the hydroxyl of monomer (a-4) when the molar equivalent of the anhydride group of multipolymer being counted 1.In addition, the acid number of addition copolymer A of acid number for measuring according to JIS K69015.3, the mg number of the potassium hydroxide needed for acid ingredient contained in referring to and in 1g addition copolymer A.In addition, molecular weight (Mw) refers to and utilizes gel permeation chromatography, the polystyrene standard conversion weight-average molecular weight measured under the following conditions.
< molecule measuring fixed condition >
Post (カ ラ system): Shodex LF-804+LF-804(Showa Denko K. K manufactures)
Column temperature: 40 DEG C
Sample: the 0.2% tetrahydrofuran liquation of addition copolymer A
Developping agent: tetrahydrofuran
Detecting device: differential refractometer (Shodex RI-71S) (Showa Denko K. K's manufacture)
Flow velocity: 1mL/ divides
Use the photosensitive polymer combination of No. 1 ~ No. 19 samples, modulate transparent resist, colored resist (color type) and colored resist (dye-type).
The modulation > of the transparent resist of <
Solid constituent 100 mass parts of the photosensitive polymer combination of relative No. 1 ~ No. 19 samples, add tetramethylol methane tetraacrylate (reactive diluent) 30 mass parts, 2,2-dimethoxy-2-phenyl acetophenone (Photoepolymerizationinitiater initiater) 4 mass parts, modulates transparent resist (embodiment 1 ~ 14 and comparative example 1 ~ 5) thus.
< utilizes transparent resist to form hardened coating film >
In the length of side be 5cm tetragonal glass substrate (alkali-free glass substrate) on, be coated with modulated transparent resist in spin coating mode, reach 2.5 μm, after completing spin coating to make the thickness of final hardened coating film, heat 30 minutes at 90 DEG C, thus solvent is vapored away.Then, (exposure 50mJ/cm is exposed to the whole surface of obtained film 2) make it that photocuring occur, and then toast 30 minutes at 230 DEG C, thus obtain hardened coating film.
The evaluation > of the hardened coating film that < is formed by transparent resist
To the hardened coating film formed by transparent resist, evaluate its resistance to pyrolytic, the transparency and cohesive.
(1) evaluation of resistance to pyrolytic
Use the sample that the hardened coating film formed by transparent resist cutting is obtained, carry out thermogravimetric analysis (TGA), evaluate its resistance to pyrolytic thus.In this analysis, obtain this sample and sample is heated to 220 DEG C and weight rate between the sample keeping 2 hours.The standard of this evaluation is as follows.
Zero: be less than-2.0%
×: more than-2.0%
(2) evaluation of the transparency
To the hardened coating film formed by transparent resist with this hardened coating film is heated to 230 DEG C in dryer and places the hardened coating film of 1 hour, utilize spectrophotometric determination 400nm light transmittance, and check the rate of change of this transmissivity, evaluate its transparency thus.The standard of this evaluation is as follows.
Zero: the rate of change of transmissivity is less than 1%
×: the rate of change of transmissivity is more than 1%
(3) fusible evaluation
To the hardened coating film formed by transparent resist, carry out checker test (Acer Disk order Try test) according to JIS K5400, the stripping state of visual observations 100 checkers, evaluates its cohesive thus.The standard of this evaluation is as follows.
Zero: do not observe stripping completely
×: observe stripping
Above-mentioned resistance to pyrolytic, the transparency and fusible evaluation result have been shown in table 2.
Table 2
As shown in Table 2, the transparent resist of embodiment 1 ~ 14 provides all excellent hardened coating film of resistance to pyrolytic, the transparency and cohesive, and the hardened coating film that the transparent resist of comparative example 1 ~ 5 provides, at least some in its resistance to pyrolytic, the transparency, cohesive does not meet the demands.
The modulation > of the colored resist (color type) of <
Be in stainless steel (SUS) container of zirconium oxide bead 180 mass parts of 0.5mm being filled with diameter, add the C.I. pigment green 36 of 10.00 mass parts, the PGMEA(solvent of 33.75 mass parts) and the spreading agent (PVC ッ Network ケ ミ ー ジ ャ パ Application Co., Ltd. manufacture Disperbyk-161) of 6.25 mass parts, mix dispersion 3 hours with paint mixer (ペ イ Application ト シ ェ ー カ ー), obtain viridine green dispersion liquid thus.
Then, the viridine green dispersion liquid that mixing is modulated, the photosensitive polymer combination of No. 1 ~ No. 19 samples and other compositions, modulate colored resist (color type) (embodiment 15 ~ 28 and comparative example 6 ~ 10).The gradation composition of this colored resist (color type) shown in table 3 and use level thereof.
Table 3
< utilizes colored resist (color type) to form pattern >
In the length of side be 5cm tetragonal glass substrate (alkali-free glass substrate) on, be coated with modulated colored resist (color type) in spin coating mode, reach 2.2 μm with thickness when making drying, after completing spin coating, heat 3 minutes at 80 DEG C, make solvent vapor away thus, and dry.Then, with the photomask of coated film at a distance of the location arrangements predetermined pattern of 100 μm, by this photomask, (exposure 150mJ/cm is exposed to coated film 2), make exposed portion generation photocuring.Then, the aqueous solution of the sodium carbonate containing 0.1 quality % is sprayed with the pressure of the temperature of 23 DEG C and 0.3MPa, dissolve unexposed portion thus and develop, then toast 30 minutes at 230 DEG C, thus form predetermined pattern.
The evaluation > of the colored resist (color type) of < and pattern
To colored resist (color type) and pattern, evaluate its alkali development, sensitivity and solvent resistance.
(4) evaluation of alkali development
By the residue after alkaline development time, alkaline development and development form, alkali development is evaluated.
About the alkaline development time, determine by above-mentioned utilization spraying alkaline development can complete visual confirmation pattern time time.
About the residue after alkaline development, evaluated by the pattern after utilizing electron microscope observation alkaline development.The standard of this evaluation is as follows.
Zero: without residue
×: there is residue
About development form, by range estimation, the removal form of the unexposed portion produced by alkaline development is evaluated.At this, in the developing process of negative resist, uncured unexposed portion is dissolved by alkaline-based developer and departs from away from substrate, with regard to its development form, has the part that departs from away mainly in the exfoliated of large block and stripping with gradually dissolve and the lysotype spread.With regard to the former exfoliated, block becomes foreign matter and remains in system, easily pollutes the pixel of other colors, therefore not preferred.That is, the lysotype of preferred the latter, therefore its standard evaluated is as follows.
Zero: lysotype
×: exfoliated
(5) evaluation of sensitivity
About sensitivity, the alkaline development that above-mentioned utilization sprays was carried out for 30 seconds, measure the decrease of the pattern thickness before and after alkaline development.Can think, the decrease of this pattern thickness is less, and sensitivity is better, and therefore its standard evaluated is as follows.
Zero: be less than 0.20 μm
×: more than 0.20 μm
(6) evaluation of solvent resistance
About solvent resistance, formed through photocuring by the process identical with aforesaid way except the pattern sample used exposes whole surface except not using photomask, it is the n-N-methyl-2-2-pyrrolidone N-adding 200mL in the vial with cover of 500mL at capacity, after flooding pattern sample wherein, at 23 DEG C, measure the change of the color after 60 minutes with color difference meter.The standard of this evaluation is as follows.
Zero: Δ E*ab is less than 0.3
×: Δ E*ab is more than 0.3
The evaluation result of alkali development above-mentioned shown in table 4, sensitivity and solvent resistance.
Table 4
As shown in Table 4, alkali development and the sensitivity of the colored resist (color type) of embodiment 15 ~ 28 are good, provide the pattern of excellent solvent resistance, and the colored resist (color type) of comparative example 6 ~ 10 or alkali development or sensitivity bad, or provide the solvent resistance of pattern not meet the demands.
The modulation > of the colored resist (dye-type) of <
The photosensitive polymer combination of mixed dye (acid green 3), No. 1 ~ No. 19 samples and other compositions, modulate colored resist (dye-type) (embodiment 29 ~ 42 and comparative example 11 ~ 15) thus.The gradation composition of this colored resist (dye-type) shown in table 5 and use level thereof.
Table 5
< utilizes colored resist (dye-type) to form pattern >
Except using colored resist (dye-type), form predetermined pattern according to the processing mode identical with when utilizing colored resist (color type) to form pattern.
The evaluation > of the colored resist (dye-type) of < and pattern
According to the method identical with colored resist (color type), evaluate the alkali development of colored resist (dye-type) and pattern, sensitivity and solvent resistance.
The evaluation result of alkali development above-mentioned shown in table 6, sensitivity and solvent resistance.
Table 6
As shown in Table 6, alkali development and the sensitivity of the colored resist (dye-type) of embodiment 29 ~ 42 are good, provide the pattern of excellent solvent resistance, and the colored resist (dye-type) of comparative example 11 ~ 15 or alkali development or sensitivity bad, or provide the solvent resistance of pattern not meet the demands.
From above result, according to the present invention, can be provided for manufacturing sensitivity, developability good and the alkali soluble resins (addition copolymer) of the photosensitive polymer combination of the colored pattern of resistance to pyrolytic and excellent solvent resistance is provided.In addition, according to the present invention, sensitivity, developability can be provided good and the photosensitive polymer combination of the colored pattern of resistance to pyrolytic and excellent solvent resistance is provided.And then, according to the present invention, a kind of color filter with the colored pattern of resistance to pyrolytic and excellent solvent resistance can be provided.
At this, this International Application claim applying date is the right of priority of No. 2010-092286th, the Japanese patent application on April 13rd, 2010, and quotes the full content of this Japanese patent application in the application of border home.

Claims (13)

1. a photosensitive polymer combination, it is characterized in that containing addition copolymer A and solvent B, this addition copolymer A is at the monomer a-1 ' making the monomer a-1 of 2 ~ 60 % by mole and/or represented by following general formula (1), the unsaturated multi-anhydride a-2 of 30 ~ 88 % by mole, and 10 ~ 68 % by mole except a-1, can the monomer a-3 copolymerization of copolymerization and the monomer a-4 that in the multipolymer formed, addition has (methyl) acrylate of hydroxyl be formed outside a-1 ' and a-2, described monomer a-1 is from by (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid bicyclopentyl ester, (methyl) isobornyl acrylate and (methyl) acrylic acid diamantane ester composition group in select more than one, described unsaturated multi-anhydride a-2 is from by maleic anhydride, itaconic anhydride and citraconic anhydride composition group in select more than one, described monomer a-3 is from by ethene ethers, phenylethylene and (methyl) esters of acrylic acid composition group in select more than one,
Wherein, X and Y independently, represents that hydrogen atom or carbon number are the straight or branched alkyl of 1 ~ 4, R 1and R 2independently, represent that hydrogen atom or carbon number are the alkyl of 1 ~ 20.
2. photosensitive polymer combination according to claim 1, is characterized in that described monomer a-1 is methacrylic acid bicyclopentyl ester.
3. photosensitive polymer combination according to claim 1 and 2, is characterized in that described unsaturated multi-anhydride a-2 is maleic anhydride.
4. photosensitive polymer combination according to claim 1 and 2, is characterized in that the vinyltoluene that described monomer a-3 comprises 10 ~ 40 % by mole.
5. photosensitive polymer combination according to claim 1 and 2, is characterized in that described monomer a-4 is more than one the material selected from the group be made up of (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, trimethylolpropane two (methyl) acrylate and pentaerythritol triacrylate.
6. photosensitive polymer combination according to claim 1 and 2, is characterized in that further containing more than one the material selected from the group be made up of reactive diluent C, Photoepolymerizationinitiater initiater D and colorant E.
7. photosensitive polymer combination according to claim 6, is characterized in that described colorant E comprises dyestuff.
8. an addition copolymer A, it is characterized in that at the monomer a-1 ' making the monomer a-1 of 2 ~ 60 % by mole and/or represented by following general formula (1), the unsaturated multi-anhydride a-2 of 30 ~ 88 % by mole, and 10 ~ 68 % by mole except a-1, outside a-1 ' and a-2 can copolymerization monomer a-3 copolymerization and in the multipolymer formed addition there is the monomer a-4 of (methyl) acrylate of hydroxyl, described monomer a-1 is from by (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid bicyclopentyl ester, (methyl) isobornyl acrylate and (methyl) acrylic acid diamantane ester composition group in select more than one, described unsaturated multi-anhydride a-2 is from by maleic anhydride, itaconic anhydride and citraconic anhydride composition group in select more than one, described monomer a-3 is from by ethene ethers, phenylethylene and (methyl) esters of acrylic acid composition group in select more than one,
Wherein, X and Y independently, represents that hydrogen atom or carbon number are the straight or branched alkyl of 1 ~ 4, R 1and R 2independently, represent that hydrogen atom or carbon number are the alkyl of 1 ~ 20.
9. addition copolymer A according to claim 8, is characterized in that described monomer a-1 is methacrylic acid bicyclopentyl ester.
10. addition copolymer A according to claim 8 or claim 9, is characterized in that described unsaturated multi-anhydride a-2 is maleic anhydride.
11. addition copolymer A according to claim 8 or claim 9, is characterized in that the vinyltoluene that described monomer a-3 comprises 10 ~ 40 % by mole.
12. addition copolymer A according to claim 8 or claim 9, is characterized in that described monomer a-4 is more than one the material selected from the group be made up of (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, trimethylolpropane two (methyl) acrylate and pentaerythritol triacrylate.
13. 1 kinds of color filters, is characterized in that having the colored pattern formed by the photosensitive polymer combination in claim 1 to 7 described in any one.
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