CN101324753A - Radiation sensibility composition for forming staining layer, color filter and color liquid crystal display element - Google Patents

Radiation sensibility composition for forming staining layer, color filter and color liquid crystal display element Download PDF

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CN101324753A
CN101324753A CNA2008101255708A CN200810125570A CN101324753A CN 101324753 A CN101324753 A CN 101324753A CN A2008101255708 A CNA2008101255708 A CN A2008101255708A CN 200810125570 A CN200810125570 A CN 200810125570A CN 101324753 A CN101324753 A CN 101324753A
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methyl
acid
compound
formula
ethyl
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CN101324753B (en
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森下聪
庄田良平
依田杏介
角昭宽
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—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
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

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  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Structural Engineering (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
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Abstract

The invention relates to radiation sensitive composition for forming colored layer, comprises a colorant, an alkali soluble resin, a polyfunctional monomer and a photopolymerization initiator. The alkali soluble resin comprises a copolymer obtained by polymerizing a polymerizable mixture comprising at least one selected from the group consisting of an unsaturated carboxylic acid, an unsaturated carboxylic anhydride and an unsaturated phenol compound and an N-position substituted maleimide, in the presence of a compound having two or more thiol groups in a molecule. The composition does not undergo a reduction in film remaining percentage and chipping and undercutting of pattern even with low light exposure, provides pixels and a black matrix which are excellent in solvent resistance, adhesion to a substrate and other properties, and shows excellent storage stability as a liquid composition even when containing pigments in high concentration.

Description

Be used to form radiation-ray sensitive composition, color filter and the color liquid crystal display device of dyed layer
Technical field
The present invention relates to be used to form radiation-ray sensitive composition, color filter and the color liquid crystal display device of dyed layer, in more detail, relate to the radiation-ray sensitive composition that is used to form dyed layer, this dyed layer is used for the color filter in uses such as the color liquid crystal display arrangement of transmission-type or reflection-type, colour pick-up tube elements; Color filter with the dyed layer that uses this radiation-ray sensitive composition formation; And the color liquid crystal display device that possesses this color filter.
Background technology
In the past, when known use colored radiation-sensitive composition is made color filter, on the substrate or be pre-formed coating colored radiation-sensitive composition and dry on the substrate of light shield layer of desired pattern, then dry coating is shone radioactive ray (hereinafter referred to as " exposure ") by desired pattern form, develop, thereby obtain the method (referring to Japanese kokai publication hei 2-144502 communique and Japanese kokai publication hei 3-53201 communique) of versicolor pixel.
In addition, in recent years, in the technical field of color filter, main flow is to reduce exposure, shorten the productive temp time, requires the pixel that forms with low exposure and black matrix in pattern form, solvent resistance, and the aspect excellences such as adaptation of substrate.In Japanese kokai publication hei 10-31308 communique, Japanese kokai publication hei 10-300922 communique etc., proposed to improve development or thermotolerance, in colored radiation-sensitive composition, can contain the scheme of the multipolymer of N position-substituted maleimide amine monomers.But for this colored radiation-sensitive composition, if exposure reduces, the back residual film ratio that then develops reduces, be easy to produce the damaged or sidewall corrosion (ア Application ダ one カ Star ト) of pattern, owing to be easy to from strippable substrate etc. with the not enough pattern of adaptation of substrate, therefore, be difficult to when shortening the productive temp time, obtain the pixel and the black matrix of good pattern form.
Summary of the invention
The object of the present invention is to provide the novel radiation-ray sensitive composition that is used to form dyed layer, even its exposure is low, can do not produced also that residual film ratio reduces, pattern is damaged or the sidewall corrosion, and solvent resistance, with excellent pixel and black matrix such as the adaptation of substrate, contain under the condition of pigment on high concentration ground in addition, also excellent as the storage stability of fluid composition.
Other purposes of the present invention are to provide color filter with the dyed layer that is formed by radiation-ray sensitive composition of the present invention and the color liquid crystal display device that possesses this color filter.
Further purpose of the present invention and advantage will illustrate below.
According to the present invention, above-mentioned purpose of the present invention and advantage realize by following the 1st aspect,
Radiation-ray sensitive composition, it contains (A) colorant, (B) alkali soluble resins, (C) multi-functional monomer and (D) Photoepolymerizationinitiater initiater, it is used to form dyed layer, it is characterized in that: (B) alkali soluble resins contains following polymkeric substance, and described polymkeric substance has: be selected from the repetitive of at least a, following formula (1) expression of acidic functionality and anhydride group and the group of following formula (2) expression.
Figure A20081012557000051
(in the formula (1), R 7The alkyl of expression carbon number 1～12 or the aryl of carbon number 6～12),
(in the formula (2), X represents the organic group of n valency, R 8The alkylidene of expression methylene or carbon number 2～6, n represents 2～10 integer, " * " represents connecting key).
Among the present invention, so-called dyed layer is meant " layer that contains pixel and/or black matrix ".
According to the present invention, above-mentioned purpose of the present invention and advantage realize by following the 2nd aspect,
Color filter, it possesses the dyed layer that uses the radiation-ray sensitive composition that is used to form dyed layer of the present invention to form.
According to the present invention, above-mentioned purpose of the present invention and advantage realize by following the 3rd aspect,
Color liquid crystal display device, it possesses above-mentioned color filter.
Embodiment
Below the present invention is described in detail.
Be used to form the radiation-ray sensitive composition of dyed layer
-(A) colorant-
There is no particular limitation to tone for colorant of the present invention, can be suitably selected according to the purposes of gained color filter.Pigment, dyestuff or natural colouring matter all can.
Color filter requires high meticulous colour developing and thermotolerance, so as colorant of the present invention, preferred colour rendering height and the high colorant of thermotolerance, the high colorant of preferred especially heat-resisting decomposability, preferred organic pigment or the inorganic pigment of using especially preferably uses organic pigment, carbon black.
As above-mentioned organic pigment, can enumerate the compound that for example in color index, is categorized as pigment, specifically can enumerate the following compound that has color index (C.I.) numbering.
C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 17, C.I. pigment yellow 20, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 55, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 166, C.I. pigment yellow 168, C.I. pigment yellow 180, C.I. pigment yellow 211;
C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 61, C.I. pigment orange 64, C.I. pigment orange 68, C.I. pigment orange 70, C.I. pigment orange 71, C.I. pigment orange 72, C.I. pigment orange 73, C.I. pigment orange 74;
C.I. paratonere 1, C.I. paratonere 2, C.I. paratonere 5, C.I. paratonere 17, C.I. pigment red 31, C.I. pigment red 32, C.I. pigment red 41, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 149, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 170, C.I. paratonere 171, C.I. paratonere 175, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 178, C.I. paratonere 179, C.I. paratonere 180, C.I. paratonere 185, C.I. paratonere 187, C.I. paratonere 202, C.I. paratonere 206, C.I. Pigment Red 207, C.I. paratonere 209, C.I. pigment red 21 4, C.I. paratonere 220, C.I. paratonere 221, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 243, C.I. paratonere 254, C.I. paratonere 255, C.I. paratonere 262, C.I. paratonere 264, C.I. paratonere 272;
C.I. pigment violet 1, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 29, C.I. pigment violet 32, C.I. pigment violet 36, C.I. pigment violet 38; C.I. pigment blue 15, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment blue 60, C.I. alizarol saphirol 80; C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58; C.I. pigment brown 23, C.I. pigment brown 25; C.I. pigment black 1, C.I. pigment black 7.
These organic pigments for example can be by refining uses such as sulfuric acid recrystallization method, solvent wash method, salt mill method or their combinations.
Among these organic pigments, be preferably selected from C.I. pigment yellow 83, C.I. pigment yellow 13 9, C.I. pigment yellow 13 8, C.I. pigment yellow 150, C.I. pigment yellow 180, C.I. paratonere 166, C.I. paratonere 177, C.I. paratonere 242, C.I. paratonere 254, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4, C.I. pigment blue 15: 6, C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58; C.I. at least a kind of pigment Violet 23, C.I. pigment blue 60 and C.I. alizarol saphirol 80.
As above-mentioned inorganic pigment for example can enumerate that titanium dioxide, barium sulphate, lime carbonate, zinc white, lead sulfate, lead and yellow-collation, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine, Prussian blue, chrome oxide green, cobalt green, umber, titanium are black, iron oxide black (synthetic iron black), carbon black etc.
In the present invention, above-mentioned organic pigment and inorganic pigment can be used alone, or two or more kinds in combination respectively, also can use organic pigment and inorganic pigment together.When forming pixel, preferably use the organic pigment more than a kind, when forming black matrix, preferably use organic pigment and/or carbon black more than 2 kinds.
In the present invention, as required, can carry out modification to the particle surface of above-mentioned each pigment with polymkeric substance and use.As the polymkeric substance that the particle surface of pigment is carried out modification, for example can enumerate the special polymkeric substance of opening record in the flat 8-259876 communique etc., polymkeric substance that commercially available various dispersed colors are used or oligomer etc.
In the present invention, as required, colorant can use together with spreading agent.
As above-mentioned spreading agent, for example, can use suitable spreading agents such as cationic, anionic, nonionic or both sexes, the preferred polymers spreading agent.Particularly, can enumerate alkylammonium salt or phosphate ester salt, the cationic comb type graft polymer etc. of modified acroleic acid based copolymer, acrylic acid series copolymer, polyurethane, polyester, high-molecular copolymer.At this, cationic comb type graft polymer is meant in trunk polymkeric substance 1 molecule with a plurality of basic groups (cationic functional group), the polymkeric substance of the structure that the above branched polymer of grafting bonding 2 molecules obtains, for example can enumerate, be that polyvinylamine, branched polymer partly are the polymkeric substance that the ring-opening polymerization polymer of 6-caprolactone constitutes by the trunk polymer moieties.In these spreading agents, preferred modified acroleic acid based copolymer, polyurethane, cationic comb type graft polymer.
Such spreading agent can obtain by commercial sources, and for example can enumerate as the modified acroleic acid based copolymer has, Disperbyk-2000, Disperbyk-2001 (above, PVC Star Network ケ ミ one (BYK) society system); Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, (above, PVC Star Network ケ ミ one (BYK) society system) are arranged as polyurethane; ソ Le ス パ one ス 76500 (Le one Block リ ゾ Le (strain) system); ソ Le ス パ one ス 24000, ソ Le ス パ one ス 37500 (Le one Block リ ゾ Le (strain) system), ア ジ ス パ one PB821, ア ジ ス パ one PB822, ア ジ ス パ one PB880 (aginomoto Off ア イ Application テ Network ノ (strain) system) etc. are arranged as cationic comb type graft polymer.
These spreading agents can use separately also can mix more than 2 kinds and use.With respect to (A) colorant 100 weight portions, the content of spreading agent is generally below 100 weight portions, preferred 0.5～100 weight portion, more preferably 1～70 weight portion, preferred especially 10～50 weight portions.At this moment, if the content of spreading agent surpasses 100 weight portions, then have the possibility of infringement development etc.
-(B) alkali soluble resins-
Alkali soluble resins among the present invention contains following polymkeric substance (hereinafter referred to as " polymkeric substance (B) "), and described polymkeric substance has: be selected from the repetitive of at least a, above-mentioned formula (1) expression of acidic functionality and anhydride group and the group of above-mentioned formula (2) expression.Alkali soluble resins works as bonding agent with respect to (A) colorant, and has solubility with respect to the alkaline developer that uses in the development treatment operation when forming dyed layer.
In the above-mentioned formula (1), R 7The alkyl of carbon number 1～12 for example can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base, dodecyl, cyclopentyl, cyclohexyl etc.R 7The aryl of carbon number 6～12 for example can enumerate phenyl, o-tolyl, a tolyl, p-methylphenyl, 1-naphthyl, 2-naphthyl etc.R in the above-mentioned formula (1) 7Preferred cyclohexyl, phenyl etc., preferred especially phenyl.
The group of above-mentioned formula (2) expression for example can be enumerated the group of following formula (3) expression.
Figure A20081012557000081
(in the formula (3), Y represents the organic group of n valency, R 8With the R in n and the formula (2) 8With the n same meaning, " * " represents connecting key).
In above-mentioned formula (2) and (3), R 8The group etc. of straight chain shape alkylidene, following formula (R8) expression of the preferred carbon number 2～6 of alkylidene of carbon number 2～6.
Figure A20081012557000091
(in the formula (R8), R 10The straight chain shape alkylidene of expression singly-bound, methylene or carbon number 2～4, the connecting key of " * " expression and S bonding).
In above-mentioned formula (2) and (3), n is preferably 2～8, and more preferably 2～6.In the above-mentioned formula (3), Y is preferably the group of the alkylidene of carbon number 2～20, following formula (Y-1)～(Y-6) expression etc.
Figure A20081012557000092
Figure A20081012557000101
(in formula (Y-1), R 11Expression ethylidene or propylidene, m represents 1～20 integer.In formula (Y-6), R 12The alkylidene of representing methylene or carbon number 2～6 independently of each other.In whole formulas, " * " represents connecting key).
As polymkeric substance (B), for example can enumerate following multipolymer (hereinafter referred to as " multipolymer (B1) "), described multipolymer be with contain (b1) be selected from least a of unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and unsaturated phenolic compounds (following these potpourris are generically and collectively referred to as " unsaturated compound (b1) ") and (b2) polymerization in the presence of the compound of following formula (5) expression of the polymerism potpourri that forms of the compound (hereinafter referred to as " unsaturated compound (b2) ") of following formula (4) expression obtain
Figure A20081012557000102
(in the formula (4), R 7With the R in the formula (1) 7Same meaning),
Figure A20081012557000103
(in the formula (5), X, R 8With X, the R in n and the formula (2) 8With the n same meaning).In unsaturated compound (b1), unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides can exemplify: unsaturated monocarboxylics such as (methyl) acrylic acid, crotonic acid, α-Lv Bingxisuan, cinnamic acid;
Unsaturated dicarboxylic or its acid anhydrides such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid;
Unsaturated polybasic carboxylic acid more than 3 yuan or its acid anhydrides;
List [(methyl) acryloxyalkyl] ester of the polybasic carboxylic acids more than 2 yuan such as mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] ester;
ω-two ends such as carboxyl polycaprolactone list (methyl) acrylate have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl etc.
In these unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, mono succinate (2-acryloxy ethyl) ester and phthalic acid list (2-acryloxy ethyl) ester are commercially available with the trade name of ラ イ ト ス テ Le HOA-MS and ラ イ ト ス テ Le HOA-MPE (common prosperity society chemistry (strain) system) respectively.
Above-mentioned unsaturated phenolic compounds can exemplify: for example
Adjacent vinylphenol, a vinylphenol, to vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, adjacent isopropenyl phenol, an isopropenyl phenol, to unsaturated phenols such as isopropenyl phenols; 2-vinyl-1-naphthols, 3-vinyl-1-naphthols, 1-vinyl-beta naphthal, 3-vinyl-beta naphthal, 2-isopropenyl-1-naphthols, 3-isopropenyl-unsaturated aphthols such as 1-naphthols etc.
Among the present invention, preferred (methyl) acrylic acid of unsaturated compound (b1), to vinylphenol etc., preferred especially (methyl) acrylic acid.
As unsaturated compound (b2), for example, can enumerate
Hydroxy phenyl maleimide, N-p-hydroxybenzene maleimide, N-benzyl maleimide, N-cyclohexyl maleimide, N-succinimido-3-maleimide benzoate, N-succinimido-4-maleimide butyrate, N-succinimido-6-maleimide caproate, N-succinimido-3-maleimide propionate, N-(acridinyl) maleimide etc. between N-phenylmaleimide, N-o-hydroxy-phenyl maleimide, N-.
Among these N-position substituted maleimide amine, preferred N-phenylmaleimide, N-cyclohexyl maleimide etc., preferred especially N-phenylmaleimide.
In multipolymer (B1), unsaturated compound (b2) can use separately, also can mix more than 2 kinds and use.
Among the present invention, except unsaturated compound (b1) and unsaturated compound (b2), the polymerism potpourri that uses in multipolymer (B1) synthetic can also contain can with other unsaturated compounds of their copolymerization.
As above-mentioned other unsaturated compounds, be preferably selected from least a of unsaturated compound (hereinafter referred to as " unsaturated compound (b3-1) ") that (b3) have the oxetanes skeleton and unsaturated compound (hereinafter referred to as " unsaturated compound (b3-2) ") (following these compounds are generically and collectively referred to as " unsaturated compound (b3) ") with tetrahydrofuran skeleton.
As unsaturated compound (b3-1), preferably can enumerate the compound (hereinafter referred to as " unsaturated compound (b3-1a) ") of for example following formula (I) expression, the compound (hereinafter referred to as " unsaturated compound (b3-1b) ") of following formula (II) expression etc.
Figure A20081012557000121
[in the formula (I), R 1The alkyl of expression hydrogen atom or carbon number 1～4, R 2The alkyl of expression hydrogen atom or carbon number 1～4, R 3, R 4, R 5And R 6Represent the alkyl of hydrogen atom, fluorine atom, carbon number 1～4, the fluoro-alkyl of carbon number 1～4 or the aryl of carbon number 6～20 independently of each other, n is 0～6 integer.]
Figure A20081012557000122
[in the formula (II), R 1, R 2, R 3, R 4, R 5, R 6With n respectively with formula (I) in R 1, R 2, R 3, R 4, R 5, R 6With the n same meaning].
In formula (I) and the formula (II), as R 1, R 2, R 3, R 4, R 5And R 6The alkyl of carbon number 1～4, for example can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group etc.
In addition, as R 3, R 4, R 5And R 6The fluoro-alkyl of carbon number 1～4, for example can enumerate, fluoro methyl, two fluoro methyl, three fluoro methyl, 1-fluoro ethyl, 2-fluoro ethyl, 1,1-two fluoro ethyls, 2,2,2-three fluoro ethyls, five fluoro ethyls, seven fluoro n-pro-pyls, seven fluoro isopropyls, nine fluoro normal-butyls, nine fluoro isobutyls, nine fluoro sec-butyls, the nine fluoro tert-butyl groups etc.
In addition, as R 3, R 4, R 5And R 6The aryl of carbon number 6～20, for example can enumerate phenyl, o-tolyl, a tolyl, p-methylphenyl etc.
As the concrete example of unsaturated compound (b3-1a), can enumerate,
The 3-[(methyl) acryloyl-oxy ylmethyl] oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2-methyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-3-methyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2-ethyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-3-ethyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2-three fluoro methyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2-five fluoro ethyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2-phenyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2,2-two fluoro oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2,2,4-three fluoro oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2,2,4, the 4-tetrafluoro is for oxetanes;
3-[2-(methyl) acryloxy ethyl] oxetanes, 3-[2-(methyl) acryloxy ethyl]-2-methyl oxetanes, 3-[2-(methyl) acryloxy ethyl]-3-methyl oxetanes, 3-[2-(methyl) acryloxy ethyl]-2-ethyl oxetanes, 3-[2-(methyl) acryloxy ethyl]-3-ethyl oxetanes, 3-[2-(methyl) acryloxy ethyl]-2-three fluoro methyl oxetanes, 3-[2-(methyl) acryloxy ethyl]-2-five fluoro ethyl oxetanes, 3-[2-(methyl) acryloxy ethyl]-2-phenyl oxetanes, 3-[2-(methyl) acryloxy ethyl]-2,2-two fluoro oxetanes, 3-[2-(methyl) acryloxy ethyl]-2,2,4-three fluoro oxetanes, 3-[2-(methyl) acryloxy ethyl]-2,2,4, the 4-tetrafluoro is for (methyl) acrylate of oxetanes etc. etc.
In addition,, can enumerate as the concrete example of unsaturated compound (b3-1b),
The 2-[(methyl) acryloyl-oxy ylmethyl] oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-2-methyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-3-methyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-4-methyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-2-ethyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-3-ethyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-4-ethyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-2-three fluoro methyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-3-three fluoro methyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-4-three fluoro methyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-2-five fluoro ethyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-3-five fluoro ethyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-4-five fluoro ethyl oxetanes;
The 2-[(methyl) acryloyl-oxy ylmethyl]-2-phenyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-3-phenyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-4-phenyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-2,3-two fluoro oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-2,4-two fluoro oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-3,3-two fluoro oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-3,4-two fluoro oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-4,4-two fluoro oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-3,3,4-three fluoro oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-3,4,4-three fluoro oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-3,3,4, the 4-tetrafluoro is for oxetanes;
2-[2-(methyl) acryloxy ethyl] oxetanes, 2-[2-(methyl) acryloxy ethyl]-2-methyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-3-methyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-4-methyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-2-ethyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-3-ethyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-4-ethyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-2-three fluoro methyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-3-three fluoro methyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-4-three fluoro methyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-2-five fluoro ethyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-3-five fluoro ethyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-4-five fluoro ethyl oxetanes;
2-[2-(methyl) acryloxy ethyl]-2-phenyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-3-phenyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-4-phenyl oxetanes, 2-[2-(methyl) acryloxy ethyl]-2,3-two fluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-2,4-two fluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-3,3-two fluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-3,4-two fluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-4,4-two fluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-3,3,4-three fluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-3,4,4-three fluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-3,3,4, the 4-tetrafluoro is for (methyl) acrylate such as oxetanes etc.
Wide from the development surplus (マ one ジ Application) of the radiation-ray sensitive composition that obtains, and improve the angle of the chemical proofing of the dyed layer that obtains, among these unsaturated compounds (b3-1a) and the unsaturated compound (b3-1b), preferred 3-[(methyl) acryloyl-oxy ylmethyl] oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-3-ethyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2-three fluoro methyl oxetanes, the 3-[(methyl) acryloyl-oxy ylmethyl]-2-phenyl oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl] oxetanes, the 2-[(methyl) acryloyl-oxy ylmethyl]-4-three fluoro methyl oxetanes etc., preferred especially 3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-3-ethyl oxetanes, 3-(methacryloxy methyl)-2-three fluoro methyl oxetanes, 3-(methacryloxy methyl)-2-phenyl oxetanes, 2-(methacryloxy methyl) oxetanes, 2-(methacryloxy methyl)-4-three fluoro methyl oxetanes etc.
In addition, among the present invention, be unsaturated compound as oxetanes, except unsaturated compound (b3-1a) and unsaturated compound (b3-1b), for example also can use
(3-oxetanes ylmethoxy)-to vinyl benzene, [2-(3-oxetanyl) ethoxy]-to vinyl benzene, (2-oxetanes ylmethoxy)-to vinyl benzene, [2-(2-oxetanyl) ethoxy]-to (oxetanyl alkyl) ether of vinylphenols such as vinyl benzene;
(oxetanyl alkyl) vinyl ether of (3-oxetanes ylmethyl) vinyl ether, [2-(3-oxetanyl) ethyl] vinyl ether, (2-oxetanes ylmethyl) vinyl ether, [2-(2-oxetanyl) ethyl] vinyl ether etc. etc.
In the multipolymer (B1), unsaturated compound (b3-1) can use separately or mix more than 2 kinds and use.
In addition,, for example can enumerate as unsaturated compound (b3-2),
(methyl) acrylic acid tetrahydrofuran-2-base ester, (methyl) acrylic acid tetrahydrofuran-(methyl) acrylic acid tetrahydrofuran esters such as 3-base ester;
(methyl) acrylic acid esters that contain tetrahydrofurfuryl such as (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) acrylic acid 3-tetrahydro furfuryl ester, 2-(tetrahydrofurfuryl oxygen base) ethyl (methyl) acrylate, 2-(3-tetrahydrofurfuryl oxygen base) ethyl (methyl) acrylate;
The ester that contains tetrahydrofurfuryl of 2-(methyl) acryloxy propionic such as 2-(methyl) acryloxy propionic tetrahydro furfuryl ester, 2-(methyl) acryloxy propionic 3-tetrahydro furfuryl ester, 2-(methyl) acryloxy propionic 2-(tetrahydrofurfuryl oxygen base) ethyl ester, 2-(methyl) acryloxy propionic 2-(3-tetrahydrofurfuryl oxygen base) ethyl ester;
(tetrahydrofuran-2-yl) oxygen base to vinyl benzene, (tetrahydrofurfuryl) oxygen base to vinyl benzene, 2-(tetrahydrofurfuryl oxygen base) ethoxy to vinyl benzene derivants such as vinyl benzenes;
Vinyl ethers such as (tetrahydrofuran-2-yl) vinyl ether, (tetrahydrofurfuryl) vinyl ether, [2-(tetrahydrofurfuryl oxygen base) ethyl] vinyl ether, succinic acid [2-(methyl) acryloxy ethyl] (tetrahydrofurfuryl) ester etc.
Among these unsaturated compounds (b3-2), preferably (methyl) acrylic acid ester that contains tetrahydrofurfuryl, succinic acid [2-(methyl) acryloxy ethyl] (tetrahydrofurfuryl) ester etc., preferred especially tetrahydrofurfuryl (methyl) acrylate, succinic acid [2-(methyl) acryloxy ethyl] (tetrahydrofurfuryl) ester.
In the multipolymer (B1), unsaturated compound (b3-2) can use separately or mix more than 2 kinds and use.
In addition, among the present invention,, also can use unsaturated compound (b3) other unsaturated compounds (hereinafter referred to as " unsaturated compound (b3-3) ") in addition as other unsaturated compounds.
As unsaturated compound (b3-3), for example can enumerate,
Styrene, α-Jia Jibenyixi, adjacent vinyltoluene, a vinyltoluene, to vinyltoluene, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to aromatic ethenyl compounds such as vinyl benzyl glycidyl ethers;
Indenes classes such as indenes, 1-methyl indenes;
Single end of polymer molecular chains such as polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane has the macromonomer (below, only be called " macromonomer ") of (methyl) acryloyl group;
(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) acrylic acid 3-hydroxyl butyl ester, (methyl) acrylic acid 4-hydroxyl butyl ester, allyl methacrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) phenyl acrylate, (methyl) acrylic acid 2-methoxyl ethyl ester, (methyl) acrylic acid 2-phenoxy ethyl, (methyl) acrylic acid methoxyl diglycol ester, (methyl) acrylic acid methoxyl triethyleneglycol ester, (methyl) acrylic acid MPEG ester, (methyl) acrylic acid methoxyl dipropylene glycol ester, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring [5.2.1.0 2,6] esters of unsaturated carboxylic acids such as decane-8-base ester, (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester, list (methyl) acrylic acid glyceride;
Unsaturated carboxylic acid aminoalkyl esters such as (methyl) acrylic acid 2-amino ethyl ester, (methyl) acrylic acid 2-dimethylamino ethyl ester, the amino propyl ester of (methyl) acrylic acid 2-, (methyl) acrylic acid 2-dimethylamino propyl ester, the amino propyl ester of (methyl) acrylic acid 3-, (methyl) acrylic acid 3-dimethylamino propyl ester;
Unsaturated carboxylic acid ethylene oxidic esters such as (methyl) acrylic acid glycidyl esters;
Vinyl esters of carboxylic acids such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, EVE, allyl glycidyl ether;
Vinyl nitrile compounds such as (methyl) vinyl cyanide, α-Lv Bingxijing, ethenylidene dintrile;
Unsaturated amides such as (methyl) acrylamide, α-chloropropene acid amides, N-2-hydroxyethyl (methyl) acrylamide;
Aliphatics conjugated diolefines such as 1,3-butadiene, isoprene, chlorobutylene, isoprene sulfonic acid etc.
Among these unsaturated compounds (b3-3), optimization styrene, macromonomer, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) phenyl acrylate, (methyl) isobornyl acrylate, three ring [5.2.1.0 2,6] decane-8-base (methyl) acrylate, list (methyl) acrylic acid glyceride etc., in macromonomer, preferred especially polystyrene macromolecular monomer, poly-(methyl) methyl acrylate macromonomer.
In the multipolymer (B1), unsaturated compound (b3-3) can use separately or mix more than 2 kinds and use.
Among the present invention, during the multipolymer that multipolymer (B1) obtains for the polymerism polymerization of mixtures that will contain unsaturated compound (b3) (hereinafter referred to as " multipolymer (B1-1) "), the use-pattern of multipolymer (B1-1) can be following mode.
[I] contain unsaturated compound (b1), unsaturated compound (b2) and unsaturated compound (b3-1) or and then with the mode of multipolymer (B1-1) as the constituent of alkali soluble resins, described multipolymer (B1-1) obtains the polymerism polymerization of mixtures that contains unsaturated compound (b3-3);
[II] contain unsaturated compound (b1), unsaturated compound (b2) and unsaturated compound (b3-2) or and then with the mode of multipolymer (B1-1) as the constituent of alkali soluble resins, described multipolymer (B1-1) obtains the polymerism polymerization of mixtures that contains unsaturated compound (b3-3);
[III] contain unsaturated compound (b1), unsaturated compound (b2), unsaturated compound (b3-1) and unsaturated compound (b3-2) or and then with the mode of multipolymer (B1-1) as the constituent of alkali soluble resins, described multipolymer (B1-1) obtains the polymerism polymerization of mixtures that contains unsaturated compound (b3-3);
[IV] is with the potpourri of any multipolymer (B1-1) more than 2 of above-mentioned [I]～[III] mode as the constituent of alkali soluble resins.
In the multipolymer (B1), preferred 1～40 weight % of the copolymerization ratio of unsaturated compound (b1), preferred especially 5～35 weight %, preferred 1～40 weight % of the copolymerization ratio of unsaturated compound (b2), preferred especially 5～30 weight %.
In addition, during with unsaturated compound (b3) and unsaturated compound (b1) and unsaturated compound (b2) copolymerization, preferred 1～70 weight % of the copolymerization ratio of unsaturated compound (b3), preferred especially 1～40 weight %, the copolymerization ratio of unsaturated compound (b3-3), preferred 0～70 weight %, more preferably 1～60 weight %.
In addition, during with unsaturated compound (b3-1) and unsaturated compound (b3-2) both and unsaturated compound (b1) and unsaturated compound (b2) copolymerization, preferred 1～70 weight % of the copolymerization ratio of unsaturated compound (b3-1), preferred especially 1～40 weight %, preferred 1～60 weight % of the copolymerization ratio of unsaturated compound (b3-2), preferred especially 1～40 weight %, preferred 0～70 weight % of the copolymerization ratio of unsaturated compound (b3-3), more preferably 1～60 weight %.
In addition, with unsaturated compound (b3-1) and unsaturated compound (b3-2) during respectively with unsaturated compound (b1) and unsaturated compound (b2) copolymerization, preferred 1～70 weight % of the copolymerization ratio of unsaturated compound (b3-1), preferred especially 1～40 weight %, preferred 0～70 weight % of the copolymerization ratio of unsaturated compound (b3-3), more preferably 1～60 weight %, preferred 1～60 weight % of the copolymerization ratio of unsaturated compound (b3-2), preferred especially 1～40 weight %, preferred 0～70 weight % of the copolymerization ratio of unsaturated compound (b3-3), more preferably 1～60 weight %.
Among the present invention, the copolymerization ratio by making each unsaturated compound in the multipolymer (B1) is in above-mentioned scope, can obtain susceptibility, to the radiation-ray sensitive composition that is used to form dyed layer of excellences such as the adherence of substrate, solvent resistance.
Multipolymer (B1) can followingly synthesize, in the presence of the compound (hereinafter referred to as " multi-thiol compound ") of above-mentioned formula (5) expression, in appropriate solvent, use 2,2 '-azoisobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two radical polymerization initiators such as (4-methoxyl-2,4-methyl pentane nitriles) synthesizes each unsaturated polymerizable compound.
As above-mentioned multi-thiol compound, the compound of preferred following formula (6) expression.
Figure A20081012557000191
(in the formula (6), Y, R 8With Y, the R in n and the formula (3) 8With the n same meaning.)
As above-mentioned multi-thiol compound, for example can enumerate mercaptan carboxylic acid's classes such as mercaptoacetic acid, 3-mercaptopropionic acid, 3-sulfydryl butyric acid, 3-sulfydryl valeric acid and ethylene glycol, tetraethylene glycol, butylene glycol, trimethylolpropane, pentaerythrite, dipentaerythritol, tripentaerythritol, 1,3, the carboxylate of polyvalent alcohols such as 5-three (2-hydroxyethyl) cyanurate, D-sorbite etc.
Among the present invention, can enumerate as the concrete example of preferred multi-thiol compound,
Trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptopropionic acid ester), tetraethylene glycol two (3-mercaptopropionic acid ester), dipentaerythritol six (3-mercaptopropionic acid ester), pentaerythrite four (mercaptoacetate), 1; 4-two (3-sulfydryl bytyry oxygen base) butane, pentaerythrite four (3-sulfydryl butyric ester), 1; 3,5 ,-three (3-sulfydryl butyl oxygen base ethyls)-1; 3; 5-triazine-2,4,6 (1H; 3H, 5H)-triketone etc.
Above-mentioned multi-thiol compound can use separately or mix more than 2 kinds and use.
The composition that works as chain-transferring agent when the multi-thiol compound is the polymerization of synthetic copolymer (B1).The inventor finds by the multi-thiol compound is carried out polymerization as chain-transferring agent, can reduce unreacted unsaturated compound, raising is to in the conversion ratio of the polymkeric substance of the unsaturated compound of free radical polyalcohol, and can be at synthetic desired multipolymer (B1) of short time.By reducing unreacted unsaturated compound, think to prevent to spray and develop or the reduction of the solvent resistance of the reduction of the pattern residual film ratio that the volatilization the during baking of back is followed, unreacted unsaturated compound stripping and the pixel that causes.
The consumption of the multi-thiol compound the during polymerization of synthetic copolymer (B1), with respect to whole unsaturated compound 100 weight portions, preferred 0.5～20 weight portion, more preferably 1～10 weight portion, the consumption of radical polymerization initiator, whole unsaturated compound 100 weight portions, preferred 0.1～50 weight portion, more preferably 0.1～20 weight portion.In addition, preferred 0～150 ℃, more preferably 50～120 ℃ of polymerization temperatures, preferred 10 minutes～20 hours of polymerization time, more preferably 30 minutes～6 hours.
Among the present invention, during the polymerization of synthetic copolymer (B1), chain-transferring agent beyond the multi-thiol compound, for example, can be with uncle's lauryl mercaptan, α-Jia Jibenyixi dimer etc. more than a kind below the preferred 90 weight % with whole chain-transferring agents, more preferably amount and the usefulness below the 60 weight %.
Among the present invention, multipolymer (B1) with gel permeation chromatography (GPC, eluting solvent: tetrahydrofuran) weight-average molecular weight of the polystyrene conversion of Ce Dinging (hereinafter referred to as " Mw ") is preferred 3,000～300,000, more preferably 3,000～100,000.
In addition, multipolymer (B1) with gel permeation chromatography (GPC, eluting solvent: tetrahydrofuran) number-average molecular weight of the polystyrene conversion of Ce Dinging (hereinafter referred to as " Mn ") is preferred 3,000～60,000, more preferably 3,000～25,000.
In addition, the Mw of multipolymer (B 1) and the ratio (Mw/Mn) of Mn are preferred 1～5, and more preferably 1～4.Have specific like this Mw or the multipolymer of Mn (B1) by use, can obtain the radiation-ray sensitive composition of development property excellence, and can form dyed layer thus with clear pattern edge, be difficult to produce residue, scum (Di れ on the substrate of unexposed portion and on the light shield layer when developing simultaneously), residual film etc.
Among the present invention, multipolymer (B1) can use separately or mix more than 2 kinds and use.
In addition, among the present invention, can and use multipolymer (B1) and other alkali soluble resins.
As above-mentioned other alkali soluble resins, be not particularly limited, can be that addition polymerization arbitrarily is that resin, addition polymerization are that resin, polycondensation are resin etc., preferred addition polymerization is a resin.
As other alkali soluble resinss of above-mentioned addition polymerization system, for example can enumerate be selected from least a kind of above-mentioned unsaturated compound (b1) and be selected from above-mentioned unsaturated compound (b2) and the potpourri of at least a kind of unsaturated compound (b3-3) the multi-thiol compound not in the presence of the multipolymer that obtains of polymerization etc.
Among the present invention, the consumption of alkali soluble resins, with respect to (A) colorant 100 weight portions, preferred 10～1,000 weight portion, more preferably 20～500 weight portions.The consumption of alkali soluble resins is very few, then for example alkali-developable reduces, on the substrate of unexposed portion or the possibility that produces scum or residual film arranged on the light shield layer, if too much on the other hand, then since relatively colorant concentration reduce, the possibility of the aim colour concentration that is difficult to realize film is arranged.
In addition, the usage ratio of other alkali soluble resinss is with respect to whole alkali soluble resinss, below the preferred 80 weight %, more preferably below the 60 weight %.The usage ratio of other alkali soluble resinss surpasses 80 weight %, and then the desired effect of the present invention may reduce.
-(C) multi-functional monomer-
Multi-functional monomer of the present invention contains the monomer with 2 above polymerism unsaturated links.
As multi-functional monomer, for example can enumerate:
Two (methyl) acrylate of aklylene glycol such as ethylene glycol, propylene glycol; Two (methyl) acrylate of poly alkylene glycol such as polyglycol, polypropylene glycol;
Poly-(methyl) acrylate or their the dicarboxylic acid modifier of the polyvalent alcohols more than 3 yuan such as glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol; Oligomeric (methyl) acrylate such as polyester, epoxy resin, urethane resin, alkyd resin, organic siliconresin, spirane resin;
Two terminal hydroxyls are poly--two (methyl) acrylate, three [2-(methyl) acryloxy ethyl] phosphate of two terminal hydroxyl fluidized polymers such as 1,3-butadiene, two terminal hydroxyl polyisoprene, two terminal hydroxyl polycaprolactones etc.
In these multi-functional monomers, poly-(methyl) acrylate of preferred polyvalent alcohol more than 3 yuan, their dicarboxylic acid modifier, specifically, preferred trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate,
Compound shown in the following formula (III),
Figure A20081012557000211
Compound shown in the following formula (IV) etc.
Figure A20081012557000212
Wherein, good and be difficult to produce considerations such as scum, residual film on the substrate of unexposed portion and on the light shield layer, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol acrylate for the flatness on dyed layer intensity height, dyed layer surface.
Above-mentioned multi-functional monomer can use separately or use mixing more than 2 kinds.
With respect to 100 weight portions (B) alkali soluble resins, the consumption of multi-functional monomer is preferably 5～500 weight portions among the present invention, more preferably 20～300 weight portions.At this moment, multi-functional monomer consumption is very few, and the intensity of dyed layer, surface smoothing have the possibility of reduction, and if too much, have for example alkali-developable reduction, perhaps producing the possibility of scum, residual film etc. on the substrate of unexposed portion or on the light shield layer easily.
Among the present invention, can be with multi-functional monomer and simple function monomer with a polymerism unsaturated link and usefulness.
As above-mentioned simple function monomer; can enumerate with (B) alkali soluble resins in unsaturated compound (b1), unsaturated compound (b2) or unsaturated compound (b3-3) in the same compound that exemplified; or N-(methyl) acryloyl morpholine; the N-vinyl pyrrolidone; N-vinyl-epsilon-caprolactams; in addition, also has M-5600 (trade name, East Asia synthetic (strain) system) as commercially available product etc.
These simple function monomers can be used singly or two or more kinds mixed.
The usage ratio of simple function monomer is preferably below the 90 weight % with respect to the total amount of multi-functional monomer and simple function monomer, more preferably below the 50 weight %.If the usage ratio of simple function monomer is too much, the intensity of gained dyed layer or surface smoothing may be not enough.
With respect to 100 weight portions (B) alkali soluble resins, total consumption of multi-functional monomer of the present invention and simple function monomer is preferably 5～500 weight portions, more preferably 20～300 weight portions.If above-mentioned total consumption is very few, possibility that reduce of the intensity of dyed layer and surface smoothing existence then, and if too much, for example have then that alkali-developable reduces, perhaps be easy to produce the possible of scum, residual film etc. on the substrate of unexposed portion or on the light shield layer.
-(D) Photoepolymerizationinitiater initiater-
Photoepolymerizationinitiater initiater of the present invention is by visible light, ultraviolet ray, far ultraviolet, electron ray, the exposure of X ray isoradial, and generation can cause above-mentioned (C) the multi-functional monomer and the composition of the spike of the simple function monomer polymerization of use according to circumstances.
As such Photoepolymerizationinitiater initiater, for example can enumerate acetophenone based compound, bisglyoxaline based compound, triazine based compound, O-acyl group oxime compound, salt based compound, benzoin based compound, benzophenone based compound, α-diketone based compound, multinuclear quinone (multinuclear キ ノ Application) based compound, xanthone based compound, diazonium based compound, acid imide sulfonate (イ ミ De ス Le ホ Na one ト) based compound etc.These compounds are the compositions that produce living radical or live acid or living radical and live acid by exposure.
As Photoepolymerizationinitiater initiater of the present invention, be preferably selected from least a kind in acetophenone based compound, bisglyoxaline based compound, triazine based compound and the O-acyl group oxime compound.
Among the present invention, Photoepolymerizationinitiater initiater can use separately or use mixing more than 2 kinds.
With respect to the total amount of multi-functional monomer of 100 weight portions (C) and simple function monomer, the consumption of Photoepolymerizationinitiater initiater of the present invention is generally 0.01～120 weight portion, is preferably 1～100 weight portion.At this moment, if the consumption of Photoepolymerizationinitiater initiater is very few, then utilize the curing of exposure to become insufficient, have and obtain dyed layer pattern the become possibility of difficulty of the color filter of alignment arrangements in accordance with regulations, on the other hand, and if too much, the dyed layer that has formation when developing easily from substrate come off may.
Can enumerate 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 1-hydroxycyclohexylphenylketone, 2 as object lesson at the acetophenone based compound of preferred light polymerization initiator of the present invention, 2-dimethoxy-1,2-diphenylethane-1-ketone, 1,2-acetyl caproyl etc.
In these acetophenone based compounds, preferred especially 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone, 1,2-acetyl caproyl etc.
Above-mentioned acetophenone based compound can use separately or use mixing more than 2 kinds.
Among the present invention, total amount with respect to multi-functional monomer of 100 weight portions (C) and simple function monomer, consumption when using the acetophenone based compound as Photoepolymerizationinitiater initiater is preferably 0.01～80 weight portion, more preferably 1～70 weight portion, more preferably 1～60 weight portion.If the consumption of acetophenone based compound is very few, then utilize the curing of exposure to become insufficient, have to obtain dyed layer pattern the become possibility of difficulty of the color filter of alignment arrangements in accordance with regulations, on the other hand, if and too much, the dyed layer that has formation when developing easily from substrate come off may.
As the object lesson of above-mentioned bisglyoxaline based compound, can enumerate 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyls)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2-bromophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dibromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4,6-tribromo phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.
In these bisglyoxaline based compounds, preferred 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-two (2,4, the 6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc., preferred especially 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
These bisglyoxaline based compounds are good to the dissolubility of solvent, can not produce not impurity such as dissolved matter, precipitate, and susceptibility height, under the exposure of less energy, just can fully be cured reaction, curing reaction can not take place in unexposed portion simultaneously, therefore filming after the exposure can clearly be distinguished to the insoluble cured portion of developer solution with to developer solution and have the uncured portion of highly dissoluble, therefore can form the dyed layer pattern high-precision thin color filter of alignment arrangements according to the rules that does not have the sidewall corrosion.
Above-mentioned bisglyoxaline based compound can use separately or use mixing more than 2 kinds.
Among the present invention, total amount with respect to multi-functional monomer of 100 weight portions (C) and simple function monomer, consumption when using the bisglyoxaline based compound as Photoepolymerizationinitiater initiater is preferably 0.01～40 weight portion, more preferably 1～30 weight portion, more preferably 1～20 weight portion.Consumption as the bisglyoxaline based compound is very few, then because the curing that exposure causes becomes insufficient, have and obtain dyed layer pattern the become possibility of difficulty of the color filter of alignment arrangements in accordance with regulations, on the other hand, come off, cause easily the coarse possibility of film on dyed layer surface from substrate if too much, then have the dyed layer that when developing, forms.
Among the present invention, when using the bisglyoxaline based compound, consider, preferably with following hydrogen donor and usefulness from the further susceptibility that improves as Photoepolymerizationinitiater initiater.
Here alleged " hydrogen donor " is meant the compound that hydrogen atom can be provided to the free radical that is produced from the bisglyoxaline based compound by exposure.
As the hydrogen donor among the present invention, mercaptan based compound, the amine compound of preferred following definitions.
Above-mentioned mercaptan based compound comprises with phenyl ring or heterocycle as parent nucleus, has more than 1, preferred 1～3, more preferably 1～2 compound (hereinafter referred to as " mercaptan is hydrogen donor ") that is bonded directly to the sulfydryl on this parent nucleus.
Above-mentioned amine compound comprises with phenyl ring or heterocycle as parent nucleus, has more than 1, preferred 1～3, more preferably 1～2 compound (hereinafter referred to as " amine is hydrogen donor ") that is bonded directly to the amino on this parent nucleus.
In addition, these hydrogen donors can have sulfydryl and amino simultaneously.
Below be described more specifically hydrogen donor.
Mercaptan is that hydrogen donor can have 1 above phenyl ring or heterocycle respectively, can also have simultaneously phenyl ring and heterocycle the two, when having more than 2 these rings, can form fused rings.
Mercaptan is that hydrogen donor is when having 2 above sulfydryls, need only residual at least 1 the free sulfydryl that has, promptly can being replaced more than 1 of residual sulfydryl by alkyl, aralkyl or aryl, and then, can have structural unit by 2 sulphur atoms of divalent organic group bondings such as alkylidene or 2 sulphur atoms structural unit with the form bonding of disulfide as long as residual have at least 1 free sulfhydryl groups.
And then mercaptan is that the position of hydrogen donor beyond sulfydryl can be by replacements such as carboxyl, alkoxy carbonyl, substituted alkoxy carbonyl, phenyloxycarbonyl, substituent phenoxy carbonyl, itrile groups.
As such mercaptan is the object lesson of hydrogen donor, can enumerate 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-2,5-dimethyl aminopyridine etc.
These mercaptan are in the hydrogen donor, preferred 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, preferred especially 2-mercaptobenzothiazole.
Amine is that hydrogen donor can have 1 above phenyl ring or heterocycle respectively, can also have simultaneously phenyl ring and heterocycle the two, when having more than 2 these rings, can form fused rings.
Amine is that hydrogen donor can replace amino more than 1 with alkyl or substituted alkyl, and the position beyond amino also can be by replacements such as carboxyl, alkoxy carbonyl, substituted alkoxy carbonyl, phenyloxycarbonyl, substituent phenoxy carbonyl, itrile groups.
As such amine is the object lesson of hydrogen donor, can enumerate 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, ethyl-4-dimethylaminobenzoic acid ester, 4-dimethylaminobenzoic acid, 4-dimethylaminophenyl cyanogen etc.
At these amine is in the hydrogen donor, preferred 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, preferred especially 4,4 '-two (diethylamino) benzophenone.
In addition, even under the situation of the free radical generating agent beyond the bisglyoxaline based compound, amine is the effect that hydrogen donor also has sensitizer.
In the present invention, hydrogen donor can use separately or use mixing more than 2 kinds, since the dyed layer that forms when developing, be difficult to from substrate come off or dyed layer intensity and susceptibility also high, preferably be that hydrogen donor and the amine more than a kind are that hydrogen donor is used in combination with the mercaptan more than a kind.
As mercaptan is that hydrogen donor and amine are the object lesson of hydrogen donor combination, can enumerate 2-mercaptobenzothiazole/4,4 '-two (dimethylamino) benzophenone, 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (dimethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (diethylamino) benzophenone etc., preferred combination has 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (diethylamino) benzophenone, particularly preferred 2-mercaptobenzothiazole/4 that are combined as, 4 '-two (diethylamino) benzophenone.
At mercaptan is that hydrogen donor and amine are in the combination of hydrogen donor, mercaptan be hydrogen donor and amine be the weight ratio of hydrogen donor be preferably 1: 1～1: 4, more preferably 1: 1～1: 3.
In the present invention, with respect to (C) the multi-functional monomer of 100 weight portions and the total amount of simple function monomer, the consumption of hydrogen donor and bisglyoxaline based compound and time spent is preferably 0.01～40 weight portion, 1～30 weight portion more preferably, preferred especially 1～20 weight portion.Consumption as hydrogen donor is very few, then has the tendency that the susceptibility improved effect reduces, on the other hand, if too much, the dyed layer that then has formation when developing easily from substrate come off may.
Object lesson as above-mentioned triazine based compound, can enumerate 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(5-methylfuran-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(furans-2-yl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-ethoxybenzene vinyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-n-butoxy phenyl)-4, two (the trichloromethyl)-s-triazines of 6-etc. have the triazine based compound of halogenated methyl.
In these triazine based compounds, preferred especially 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4, two (the trichloromethyl)-s-triazines of 6-.
Above-mentioned triazine based compound can use separately or use mixing more than 2 kinds.
In the present invention, with respect to (C) the multi-functional monomer of 100 weight portions and the total amount of simple function monomer, consumption when using the triazine based compound as Photoepolymerizationinitiater initiater is preferably 0.01～40 weight portion, and more preferably 1～30 weight portion is preferably 1～20 weight portion especially.Consumption as the triazine based compound is very few, then, might be difficult to obtain the dyed layer pattern color filter of alignment arrangements in accordance with regulations, on the other hand because the curing that exposure causes becomes insufficient, if too much, then have the possibility that the dyed layer of formation when developing comes off from substrate easily.
Object lesson as above-mentioned O-acyl group oxime compound; can enumerate: 1-[4-(thiophenyl) phenyl]-heptane-1; 2-diketone 2-(O-benzoyl oximes); 1-[4-(thiophenyl) phenyl]-octane-1; 2-diketone 2-(O-benzoyl oximes); 1-[4-(benzoyl) phenyl]-octane-1; 2-diketone 2-(O-benzoyl oximes); 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-ethyl ketone (エ ノ Application) 1-(O-acetyl group oxime); 1-[9-ethyl-6-(3-methyl benzoyl)-9H-carbazole-3-yl]-ethyl ketone 1-(O-acetyl group oxime); 1-(9-ethyl-6-benzoyl-9H-carbazole-3-yl)-ethyl ketone 1-(O-acetyl group oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl benzoyl)-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime); ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1; 3-dioxolanyl (ジ オ キ ソ ラ ニ Le)) benzoyl }-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime); ethyl ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime); ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1, the 3-dioxolanyl) the methoxybenzoyl base }-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime) etc.
Among these O-acyl group oxime compounds; preferred especially 1-[4-(thiophenyl) phenyl]-octane-1; 2-diketone 2-(O-benzoyl oximes), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-ethyl ketone 1-(O-acetyl group oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1, the 3-dioxolanyl) the methoxybenzoyl base }-9.H.-carbazole-3-yl]-1-(O-acetyl group oxime) etc.
Above-mentioned O-acyl group oxime compound can use separately or use mixing more than 2 kinds.
In the present invention; with respect to (C) the multi-functional monomer of 100 weight portions and the total amount of simple function monomer; consumption when using O-acyl group oxime compound as Photoepolymerizationinitiater initiater is preferably 0.01～80 weight portion, and more preferably 1～70 weight portion is preferably 1～60 weight portion especially.Consumption as O-acyl group oxime compound is very few; then, might be difficult to obtain the dyed layer pattern color filter of alignment arrangements in accordance with regulations, on the other hand because the curing that exposure causes becomes insufficient; if too much, then have the possibility that the dyed layer of formation when developing comes off from substrate easily.
-adjuvant-
The radiation-ray sensitive composition that is used to form dyed layer of the present invention also can contain various adjuvants as required.
As above-mentioned adjuvant, for example can enumerate organic acid or organic amino compounds (still, above-mentioned hydrogen is supplied with except the body), hardening agent, auxiliary curing agent etc.
Above-mentioned organic acid or organic amino compounds are to show further to improve radiation-ray sensitive composition further suppresses the remaining effect etc. of dissolved matter not to the dissolubility of alkaline developer and after development composition.
As above-mentioned organic acid, preferably in molecule, have the aliphatic carboxylic acid of 1 above carboxyl or contain the carboxylic acid of phenyl.
As above-mentioned aliphatic carboxylic acid, for example can enumerate:
Formic acid, acetate, propionic acid, butyric acid, valeric acid, neopentanoic acid, caproic acid, diethacetic acid, enanthic acid, monocarboxylic acid such as sad;
Dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, Brazilian diacid, methylmalonic acid, ethyl malonic acid, dimethyl malonic acid, methylsuccinic acid, tetramethyl succinic acid, cyclohexane dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid; Tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoronic acid etc.
In addition, as the above-mentioned carboxylic acid that contains phenyl, can enumerate carboxyl for example directly and the compound of phenyl bonding, the carboxyl carboxylic acid by carbochain and phenyl bonding etc.
As the carboxylic acid that contains phenyl, for example can enumerate:
Benzoic acid, toluic acid, cumfrey, 2,3-mesitylenic acid, 3, aromatic monocarboxylates such as 5-mesitylenic acid; Aromatic dicarboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid (TPA); Aromatic multi-carboxy acids more than 3 yuan such as trimellitic acid, trimesic acid, mellophanic acid, pyromellitic acid, or phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, umbellic acid.
In these organic acids, from alkali dissolution, to the dissolubility of aftermentioned solvent, prevent on the substrate of unexposed portion or viewpoint such as the scum on the light shield layer and film be residual, as aliphatic carboxylic acid, the preferred aliphat dicarboxylic acid, preferred especially malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid etc.As the carboxylic acid that contains phenyl, the acid of optimization aromatic diacid, preferred especially phthalic acid.
Above-mentioned organic acid can be used singly or two or more kinds mixed.
The organic acid use amount is preferably below the 15 weight % with respect to the solid constituent of whole radiation-ray sensitive compositions, more preferably below the 10 weight %.At this moment, if the organic acid use amount is too much, there be the tendency of the dyed layer of formation to the adaptation reduction of substrate.
In addition, as above-mentioned organic amino compounds, preferably in molecule, have the fatty amine of the amino more than 1 or contain the amine of phenyl.
As above-mentioned fatty amine, for example can enumerate:
Single (ring) alkyl amines such as n-propylamine, isopropylamine, n-butylamine, isobutyl amine, sec-butylamine, tert-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane amine, n-dodecane amine, cyclohexylamine, 2-methyl cyclohexylamine, 3-methyl cyclohexylamine, 4-methyl cyclohexylamine, 2-ethyl cyclohexylamine, 3-ethyl cyclohexylamine, 4-ethyl cyclohexylamine;
Two (ring) alkyl amines such as Methylethyl amine, diethylamide, methyl n-pro-pyl amine, ethyl n-pro-pyl amine, di-n-propyl amine, diisopropylamine, di-n-butyl amine, diisobutyl amine, two sec-butylamine, di-t-butyl amine, two n-pentyl amine, di-n-hexyl amine, methyl cyclohexylamine, ethyl cyclohexylamine, dicyclohexyl amine;
Three (ring) alkyl amines such as dimethylethyl amine, methyl diethylamide, triethylamine, dimethyl n propyl group amine, diethyl n-pro-pyl amine, methyl di-n-propyl amine, ethyl di-n-propyl amine, three n-pro-pyl amine, triisopropylamine, tri-n-butyl amine, triisobutyl amine, three sec-butylamine, tri-tert amine, three n-pentyl amine, three n-hexyl amine, dimethyl cyclohexyl amine, diethyl cyclohexylamine, methyl bicyclic hexylamine, ethyl dicyclohexyl amine, tricyclohexyltin amine;
The 2-ethylaminoethanol, single (ring) alkanolamine such as 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 6-amino-1-hexanol, 4-amino-1-cyclohexanol;
Two (ring) alkanolamines such as diethanolamine, two n-propanol amine, diisopropanolamine, two normal butyl alcohol amine, two isobutyl hydramine, two n-amyl alcohol amine, two n-hexyl alcohol amine, two (4-cyclohexanol) amine;
Three (ring) alkanolamines such as triethanolamine, three n-propanol amine, triisopropanolamine, three normal butyl alcohol amine, three isobutyl hydramine, three n-amyl alcohol amine, three n-hexyl alcohol amine, three (4-cyclohexanol) amine;
3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1,2-butylene glycol, 4-amino-1,3 butylene glycol, 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propylene glycol, 3-diethylamino-1,2-propylene glycol, 2-dimethylamino-1, ammediol, 2-diethylamino-1, amino (ring) alkane glycol such as ammediol;
1-Aminocyclopentane methyl alcohol, 4-Aminocyclopentane methyl alcohol, 1-aminocyclohexane methyl alcohol, 4-aminocyclohexane methyl alcohol, 4-dimethylamino cyclopentane methyl alcohol, 4-diethylamino cyclopentane methyl alcohol, 4-dimethylamino cyclohexane methanol, 4-diethylamino cyclohexane methanol etc. contain amino cycloalkanes methyl alcohol;
Amino carboxylic acids such as Beta-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaprolc acid, 1-1-aminocyclopropane-1-carboxylic acid, 1-aminocyclohexane carboxylic acid, 4-aminocyclohexane carboxylic acid.
In addition, as the above-mentioned amine that contains phenyl, for example can enumerate amino directly with the compound of phenyl bonding, the amino compound by carbochain and phenyl bonding etc.
As the amine that contains phenyl, for example can enumerate:
Aniline, 2-aminotoluene, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-pro-pyl aniline, 4-isopropyl aniline, 4-n-butyl aniline, 4-tert-butyl group aniline, naphthalidine, 2-naphthylamines, N, accelerine, N, N-diethylaniline, 4-methyl-N, aromatic amines such as accelerine;
Aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylamino benzylalcohol, 4-diethylamino benzylalcohol;
Amino phenol such as 2-amino-phenol, 3-amino-phenol, 4-amino-phenol, 4-dimethylamino phenol, 4-diethylamino phenol.
In these organic amine compounds, from to the dissolubility of aftermentioned solvent, prevent on the substrate of unexposed portion or viewpoint such as the scum on the light shield layer and film be residual, as fatty amine, fatty amine, preferred single (ring) alkanolamine, amino (ring) alkane glycol, especially preferably the 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-propylene glycol, 2-amino-1, ammediol, 4-amino-1,2-butylene glycol etc.As the amine that contains phenyl, preferred amino-phenol, preferred especially 2-amino-phenol, 3-amino-phenol, 4-amino-phenol etc.
The use amount of organic amino compounds is preferably below the 15 weight % with respect to the solid constituent of whole radiation-ray sensitive compositions, more preferably below the 10 weight %.At this moment, if the use amount of organic amine compound is too much, there be the tendency of the dyed layer of formation to the adaptation reduction of substrate.
Above-mentioned hardening agent be with (B) alkali soluble resins in carboxyl and/or oxetanes ring reaction, make should the curing of (B) alkali soluble resins composition.
As such hardening agent, for example can enumerate epoxy compound, oxetane compound etc.
As above-mentioned epoxy compound, preferred multi-functional epoxy compound, its object lesson can be enumerated fragrant family epoxy resin such as bisphenol A epoxide resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, A Hydrogenated Bisphenol A F epoxy resin, phenolic resin varnish type epoxy resin; Alicyclic ring family epoxy resin, heterocyclic ring epoxy resins, ethylene oxidic ester are that resin, glycidyl amine are resin, other epoxy resin of epoxidation wet goods; The bromo derivative of these epoxy resin, in addition, can also enumerate the epoxide, (being total to) polymkeric substance that contains the unsaturated compound of glycidyl, isocyanic acid triglycidyl group ester etc. of (being total to) polymkeric substance of epoxide, the isoprene of (being total to) polymkeric substance of butadiene.
As above-mentioned epoxy compound, also preferably contain the unsaturated compound of epoxy radicals.Its object lesson can be enumerated (methyl) acrylic acid glycidyl esters, (methyl) acrylic acid 3,4-epoxy radicals butyl ester, (methyl) acrylic acid 6,7-epoxy radicals heptyl ester, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether etc.
As above-mentioned oxetane compound, preferred multifunctional oxetane compound, its object lesson can enumerate carbonic acid dioxetane ester, hexane diacid dioxetane ester, terephthalic acid (TPA) dioxetane ester, to inferior dimethylbenzene dicarboxylic acid dioxetane ester, 1, the oxetanes etherate of low molecular compounds such as 4-cyclohexane dicarboxylic acid dioxetane ester, phenol phenolic novolac, has (being total to) polymkeric substance macromolecular compounds such as (still, except multipolymer (B1)) of the unsaturated compound of oxetanes ring structure.Multipolymer (B1) with oxetanes ring structure is the composition that works as hardening agent.
As oxetane compound, preferably have the two compound of oxetanes ring structure and unsaturated double-bond, it is identical with the illustrated compound of above-mentioned unsaturated compound (b3-1) that its object lesson can be enumerated.
These hardening agent can use separately or use mixing more than 2 kinds.
The use amount of hardening agent is preferably below the 30 weight % with respect to the solid constituent of whole radiation-ray sensitive compositions, more preferably below the 20 weight %.If the use amount of hardening agent is too much, then there is the possibility of the storage stability reduction of the radiation-ray sensitive composition that obtains.
Above-mentioned auxiliary curing agent is by epoxy radicals that above-mentioned hardening agent has and/or oxetanes ring closed loop being promoted utilize the composition of the curing reaction that this hardening agent carries out.
As such auxiliary curing agent, for example can enumerate polybasic carboxylic acid, polybasic acid anhydride, amino-compound etc.
As the object lesson of carboxylic acid multicomponent carboxylic acid, can enumerate with above-mentioned organic acid in to have a compound of 2 above carboxyls same, as the object lesson of above-mentioned amino-compound, can enumerate with above-mentioned organic amino compounds same.
As the object lesson of above-mentioned polybasic acid anhydride, can enumerate phthalate anhydride, pyromellitic acid dianhydride, trimellitic anhydride, 3,3 ', 4, aromatic series polybasic acid anhydrides such as 4 '-benzophenone tetracarboxylic dianhydride; Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic acid acid anhydride, maleic anhydride, 1,2,3, aliphatics polybasic acid anhydrides such as 4-butane tetracarboxylic acid dianhydride; Hexahydrophthalic acid anhydride, 3,4-dimethyl tetrahydro phthalate anhydride, 1,2,4-cyclopentane tricarboxylic acid anhydride, 1,2,4-cyclohexane tricarboxylic acid anhydride, cyclopentane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, the acid of carbic anhydride (No water Ha イ ミ Star Network), the acid of tetrahydrochysene phthalate anhydride (No water Na ジ Application) etc. alicyclic polybasic acid anhydride; Ethylene glycol bisthioglycolate trimellitate acid anhydride (エ チ レ Application グ リ コ one Le PVC ス ト リ メ リ テ イ ト No water thing), glycerine three trimellitate acid anhydrides (グ リ セ リ Application ト リ ス ト リ メ リ テ イ ト No water thing) etc. contain the ester group carboxylic acid anhydrides, in addition, can also enumerate with commercially available epoxy curing agent of ア デ カ Ha one De Na one EH-700 (rising sun electrochemical industry (strain) system), リ カ シ Star De HH (new Japanese physics and chemistry (strain) system), MH-700 trade names such as (new Japanese physics and chemistry (strain) systems) etc.
Above-mentioned auxiliary curing agent can use separately or mix more than 2 kinds and use.
The use amount of auxiliary curing agent is preferably below the 15 weight % with respect to the solid constituent of whole radiation-ray sensitive compositions, more preferably below the 10 weight %.If the use amount of auxiliary curing agent is too much, the dyed layer that then exists the storage stability of the radiation-ray sensitive composition that obtains to reduce or form when developing, be easy to from substrate come off may.
As the adjuvant beyond above-mentioned, for example can enumerate:
Blue pigment derivants such as copper phthalocyanine derivative thing, yellow uitramarine derivant etc. disperse auxiliary agent;
Filling agent such as glass, aluminium oxide;
Macromolecular compounds such as polyvinyl alcohol (PVA), polyalkylene glycol monoalkyl ethers, poly-(fluoroalkyl acrylate) class;
Surfactants such as nonionic, cationic, anionic;
Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, driving fit promoter such as 3-sulfydryl propyl trimethoxy silicane;
2,2 '-thiobis (4-methyl-6-tert butyl phenol), 2, antioxidants such as 6-two-tert-butyl phenol;
Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole, alkoxy Benzophenones;
Anti-agglutinant such as sodium polyacrylate;
1,1 '-azo two (cyclohexane-1-nitrile), 2-phenylazos-4-methoxyl-2, thermal free radical initiators such as 4-methyl pentane nitrile etc.
Solvent
The radiation-ray sensitive composition that is used to form dyed layer of the present invention as must composition, can contain above-mentioned additive component with above-mentioned (A)～(D) composition as required, can cooperate solvent to make fluid composition usually.
Constitute radiation-ray sensitive composition (A)～(D) composition or additive component as long as above-mentioned solvent can disperse or dissolve, and do not react with these compositions, the volatility with appropriateness gets final product, and can suitably select to use.
As above-mentioned solvent, for example can enumerate:
The glycol monomethyl methyl ether, ethylene glycol monomethyl ether, the glycol monomethyl n-propyl ether, the glycol monomethyl n-butyl ether, the diglycol monotertiary methyl ether, carbiphene, the diglycol monotertiary n-propyl ether, the diglycol monotertiary n-butyl ether, the triethylene glycol monomethyl ether, triethylene glycol list ethylether, propylene glycol monomethyl ether, propylene glycol list ethylether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, the dipropylene glycol monomethyl ether, dipropylene glycol list ethylether, dipropylene glycol list n-propyl ether, dipropylene glycol list n-butyl ether, the tripropylene glycol monomethyl ether, (many) alkylene glycol monoalkyl ethers such as tripropylene glycol list ethylether;
(many) alkylene glycol monoalkyl ethers acetic acid esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, diglycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters;
Other ethers such as diethylene glycol dimethyl ether, diglycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; Ketone such as MEK, cyclohexanone, 2-heptanone, 3-heptanone;
Lactic acid alkyl ester such as methyl lactate, ethyl lactate;
2-hydroxy-2-methyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, acetate 3-methoxyl butyl ester, acetate 3-methyl-3-methoxyl butyl ester, propionic acid 3-methyl-3-methoxyl butyl ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other esters such as 2-ketobutyric acid ethyl ester;
Aromatic hydrocarbon such as toluene, dimethylbenzene;
N, acid amides or lactams such as dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone.
In these solvents, from dissolubility, pigment-dispersing, the coating equal angles is considered, preferred propylene glycol monomethyl ether, propylene glycol list ethylether, the ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, diethylene glycol dimethyl ether, the diglycol methyl ethyl ether, cyclohexanone, the 2-heptanone, the 3-heptanone, ethyl lactate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, acetate 3-methoxyl butyl ester, propionic acid 3-methyl-3-methoxyl butyl ester, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate.Above-mentioned solvent can use separately or use mixing more than 2 kinds.
Can also be with above-mentioned solvent, be used in combination high boiling solvents such as benzylisoeugenol, two n-hexyl ethers, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, acetate benzyl ester, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, glycol monomethyl phenyl ether acetic acid esters.
These high boiling solvents can use separately or use mixing more than 2 kinds.
The use amount of solvent is not particularly limited, consider from viewpoints such as the coating of the radiation-ray sensitive composition that obtains, stability, usually make each composition total concentration of removing the said composition solvent reach 5～50 weight % usually, preferably reach the amount of 10～40 weight %.
Color filter
Color filter of the present invention has the dyed layer that is formed by the radiation-ray sensitive composition that is used to form dyed layer of the present invention.
Below describe for the method that forms dyed layer in the color filter of the present invention.
At first, as required, on the surface of substrate, form light shield layer, the part that forms pixel is distinguished, and coating for example is dispersed with the fluid composition of the radiation-ray sensitive composition of red pigment on this substrate, carries out prebake conditions then, make solvent evaporation, formation is filmed.
Then, to this exposure of filming, use alkaline-based developer to develop via photomask then, the unexposed portion of filming is removed in dissolving, by the back baking, forms picture element matrix then, and this picture element matrix is that red pattern of pixels alignment arrangements according to the rules obtains.
Use the fluid composition of each radiation-ray sensitive composition that is dispersed with green or blue pigment then, with above-mentioned coating, prebake conditions, exposure, development and the back baking of similarly carrying out each fluid composition, on same substrate, form green pixel matrix and blue pixel matrix successively, red, green and blue trichromatic picture element matrix is disposed on the substrate, obtains color filter.Among the present invention, the order that forms each color pixel is not limited to above-mentioned.
In addition, black matrix is for example used the radiation-ray sensitive composition that is used to form dyed layer of the present invention, similarly forms with the situation of the formation of above-mentioned pixel.
The substrate that uses during as formation pixel and/or black matrix for example has glass, silicon, polycarbonate, polyester, aromatic poly amide, polyamidoimide, polyimide etc.
And,, can also implement to utilize suitable pre-treatments such as chemical reagent processing that silane coupling agent etc. carries out, Cement Composite Treated by Plasma, ion plating, sputter, gas-phase reaction method, vacuum evaporation to these substrates according to expectation.
When coating the fluid composition of radiation-ray sensitive composition on the substrate, can adopt spray-on process, rolling method, method of spin coating (spin-coating method), gap nozzle rubbing method, rod to be coated with suitable coating processes such as method, ink-jet method.Preferred especially spin-coating method, gap nozzle rubbing method.
The thickness of coating calculates according to the thickness that removes after desolvating, and is preferably 0.1～10 μ m, more preferably 0.2～8.0 μ m, preferred especially 0.2～6.0 μ m.
The radioactive ray that use during as the formation dyed layer can use for example visible light, ultraviolet ray, far ultraviolet, electron ray, X ray etc., and optimal wavelength is at the radioactive ray of 190～450nm scope.
The exposure of radioactive ray is preferably 10～10,000J/m 2
As above-mentioned alkaline-based developer, preference such as sodium carbonate, NaOH, potassium hydroxide, tetramethyl ammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecylene, 1, the aqueous solution of 5-diazabicyclo-[4.3.0]-5-nonene etc.
In above-mentioned alkaline-based developer, can also add for example water-miscible organic solvent such as methyl alcohol, ethanol or surfactant etc. in right amount.In addition, after alkaline development, wash usually.
As developing method, can adopt spray development method, spray development method, immersion development method, soak and put (liquid low-lying area) development method etc.Development conditions is preferably carried out about 5～300 seconds at normal temperatures.
The color filter of the present invention that obtains like this is for example extremely useful for transmission-type or reflection-type color liquid crystal display element, colour pick-up tube element, color sensor etc.
Color liquid crystal display device
Color liquid crystal display device of the present invention possesses color filter of the present invention.
A scheme of color liquid crystal display device of the present invention is to use the radiation-ray sensitive composition that is used to form dyed layer of the present invention, as mentioned above, on the thin film transistor base plate matrix, form pixel and/or black matrix, thereby can prepare color liquid crystal display device with excellent especially characteristic.
Embodiment
Below, enumerate embodiment, further specifically describe embodiments of the present invention.But the present invention is not subjected to the qualification of following embodiment.
Synthesizing of solidfied material (B1)
Synthesis example 1
Possess and add 3 weight portions in the flask of condenser pipe and stirring machine as 2 of polymerization initiator, 2 '-azoisobutyronitrile and 200 weight portions are as the propylene glycol monomethyl ether of solvent, then add 25 weight portion N-phenylmaleimides, 15 parts by weight of styrene, 30 weight portion methacrylic acids, 10 weight portion n-BMAs and 20 weight portion benzyl methacrylates and as the 7 weight portion pentaerythrites four (3-mercaptopropionic acid ester) (Sakai chemical industry (strain) system) of multi-thiol compound, nitrogen replacement as polymerizable unsaturated compound.Slowly stir afterwards, make the temperature of reaction solution rise to 80 ℃, keep carrying out polymerization in 5 hours, obtain the solution (solid component concentration=35.5 weight %, polymerisation conversion=100 weight %) of multipolymer (B1) thus in this temperature.With this multipolymer (B1) as " alkali soluble resins (B-1) ".
At this, polymerisation conversion is to be calculated by following formula in the actual addition of each composition of free radical polymerization and the solid component concentration (weight %) of the copolymer solution after the polymerization by confession.When the copolymer solution that weighing obtains in aluminum dish heats 2 hours on 180 ℃ hot plate, measure before and after the heating weight, calculate solid component concentration by (weight before the weight after the heating * 100/ heating).
The actual adding total amount of the composition beyond the actual adding total amount/solvent of the solid component concentration (weight %) of the copolymer solution after polymerisation conversion (weight %)=polymerization * whole compositions
Synthesis example 2
Except polymerizable unsaturated compound being become 25 weight portion N-phenylmaleimides, 15 parts by weight of styrene, 15 weight portion methacrylic acids, 20 weight portion n-BMAs and 25 weight portion 3-(methacryloxy methyl)-3-ethyl oxetanes, obtain the solution (solid component concentration=35.5 weight %, polymerisation conversion=100 weight %) of multipolymer (B1) in the same manner with synthesis example 1.With this multipolymer (B1) as " alkali soluble resins (B-2) ".
Synthesis example 3
Except polymerizable unsaturated compound being become 25 weight portion N-phenylmaleimides, 15 parts by weight of styrene, 15 weight portion methacrylic acids, 20 weight portion n-BMAs and 25 weight portion methacrylic acid tetrahydro furfuryl esters, obtain the solution (solid component concentration=35.5 weight %, polymerisation conversion=100 weight %) of multipolymer (B1) in the same manner with synthesis example 1.With this multipolymer (B1) as " alkali soluble resins (B-3) ".
Synthesis example 4
Except polymerizable unsaturated compound being become 25 weight portion N-phenylmaleimides, 15 parts by weight of styrene, 15 weight portion methacrylic acids, 20 weight portion n-BMAs, 15 weight portion 3-(methacryloxy methyl)-3-ethyl oxetanes and 10 weight portion methacrylic acid tetrahydro furfuryl esters, obtain the solution (solid component concentration=35.5 weight %, polymerisation conversion=100 weight %) of multipolymer (B1) in the same manner with synthesis example 1.With this multipolymer (B1) as " alkali soluble resins (B-4) ".
Synthesis example 5
Except the multi-thiol compound being become 7 weight portion tetraethylene glycols two (3-mercaptopropionic acid ester) (Sakai chemical industry (strain) system), obtain the solution (solid component concentration=35.5 weight %, polymerisation conversion=100 weight %) of multipolymer (B1) in the same manner with synthesis example 1.With this multipolymer (B1) as " alkali soluble resins (B-5) ".
Synthesis example 6
Except the multi-thiol compound being become 7 weight portion dipentaerythritols six (3-mercaptopropionic acid ester) (Sakai chemical industry (strain) system), obtain the solution (solid component concentration=35.5 weight %, polymerisation conversion=100 weight %) of multipolymer (B1) in the same manner with synthesis example 1.With this multipolymer (B1) as " alkali soluble resins (B-6) ".
Synthesis example 7
Except the multi-thiol compound being become 7 weight portions 1,4-two (3-sulfydryl butyryl acyloxy) butane (clear and electrician's (strain) system) in addition, obtain the solution (solid component concentration=35.4 weight %, polymerisation conversion=99.8 weight %) of multipolymer (B1) in the same manner with synthesis example 1.With this multipolymer (B1) as " alkali soluble resins (B-7) ".
Synthesis example 8
Except the multi-thiol compound being become 7 weight portion pentaerythrites four (3-sulfydryl butyric ester) (clear and electrician's (strain) system), obtain the solution (solid component concentration=35.3 weight %, polymerisation conversion=99.5 weight %) of multipolymer (B1) in the same manner with synthesis example 1.With this multipolymer (B1) as " alkali soluble resins (B-8) ".
Synthesis example 9
Except the multi-thiol compound being become 7 weight portions 1,3,5,-three (3-sulfydryl butyl oxygen base ethyls)-1,3,5 ,-triazine-2,4,6 (1H, 3H, 5H)-triketone (clear and electrician's (strain) system) is in addition, obtain the solution (solid component concentration=35.4 weight %, polymerisation conversion=99.8 weight %) of multipolymer (B1) in the same manner with synthesis example 2.
With this multipolymer (B1) as " alkali soluble resins (B-9) ".
Relatively use the synthetic of multipolymer
Synthesis example 10
Except polymerizable unsaturated compound being become 15 weight portion methacrylic acids, 15 parts by weight of styrene and 70 weight portion benzyl methacrylates, obtain the solution (solid component concentration=34.9 weight %, polymerisation conversion=98.4 weight %) of multipolymer in the same manner with synthesis example 1.With this multipolymer as " alkali soluble resins (B-10) "
Synthesis example 11
Except replacing pentaerythrite four (3-mercaptopropionic acid ester), use beyond the 7 weight portion uncle lauryl mercaptans, obtain the solution (solid component concentration=34.0 weight %, polymerisation conversion=95.8 weight %) of multipolymer in the same manner with synthesis example 1.With this multipolymer as " alkali soluble resins (B-11) ".
Synthesis example 12
Except replacing pentaerythrite four (3-mercaptopropionic acid ester), use 7 weight portions 2,4-diphenyl-4-methyl-1-pentene (Japanese grease (strain) system) obtains the solution (solid component concentration=31.0 weight %, polymerisation conversion=87.4 weight %) of multipolymer in the same manner with synthesis example 1 in addition.With this multipolymer as " alkali soluble resins (B-12) ".
The comparison of polymerization speed
Synthesis example 13
Except polymerizable unsaturated compound being become 15 weight portion N-phenylmaleimides, 8 parts by weight of styrene, 15 weight portion methacrylic acids, 15 weight portion 2-hydroxyethyl methacrylates, 28 weight portion methacrylic acid 2-Octyl Nitrites and 19 weight portion benzyl methacrylates, obtain the solution of multipolymer (B1) in the same manner with synthesis example 1.At this moment, make the temperature of reaction solution rise to 80 ℃ after, the solid component concentration of each sample was measured in the reaction solution sampling, is followed the trail of polymerisation conversion in per 1 hour.The results are shown in table 1.The temperature that makes reaction solution rises to polymerization 2 hours after 80 ℃ and the multipolymer that obtains is " alkali soluble resins (B-14) " for the multipolymer that " alkali soluble resins (B-13) ", polymerization obtained in 5 hours.The Mw=7000 of alkali soluble resins (B-14), Mn=4400.
Synthesis example 14
Except using 2,4-diphenyl-4-methyl-1-pentene replaces pentaerythrite four (3-mercaptopropionic acid ester) in addition, with the synthesis example 13 same polymerisation conversions of following the trail of, obtains copolymer solution.The temperature that makes reaction solution rises to polymerization 2 hours after 80 ℃ and the multipolymer that obtains is " alkali soluble resins (B-16) " for the multipolymer that " alkali soluble resins (B-15) ", polymerization obtained in 5 hours.The Mw=9000 of alkali soluble resins (B-16), Mn=4300.
Table 1
Figure A20081012557000391
The dispersible pigment dispersion preparation
Preparation example 1
To handle preparation dispersible pigment dispersion (R) by ball mill as the PB-821 of spreading agent with as solvent propylene glycol monomethyl ether 75 weight portions as C.I. paratonere 254/C.I. paratonere 177=80/20 (weight ratio) potpourri 20 weight portions, 6 weight portions (converting) of (A) colorant with solid constituent.
Preparation example 2
To handle preparation dispersible pigment dispersion (G) by ball mill as the BYK-2001 of spreading agent with as propylene glycol monomethyl ether 75 weight portions of solvent as C.I. pigment green 36/C.I. pigment yellow 150/C.I. pigment yellow 13 8=50/30/20 (weight ratio) potpourri 20 weight portions, 5 weight portions (converting) of (A) colorant with solid constituent.
Preparation example 3
To handle preparation dispersible pigment dispersion (BK) by ball mill as the BYK-2001 of spreading agent with as propylene glycol monomethyl ether 75 weight portions of solvent as carbon black 20 weight portions, 3 weight portions (converting) of (A) colorant with solid constituent.
Embodiment 1
To mix as 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholinyl propane-1-ketone 5 weight portions of Photoepolymerizationinitiater initiater with as the solvent propylene glycol monomethyl ether as dipentaerythritol acrylate 15 weight portions, (D) of multi-functional monomer as alkali soluble resins (B-1) 15 weight portions (converting), (C) of alkali soluble resins as dispersible pigment dispersion (R) 100 weight portions, (B) of (A) colorant with solid constituent, so that solid component concentration is 20 weight %, preparation fluid composition (R1).
For fluid composition (R1), form pattern according to following order and estimate.Evaluation result is as shown in table 6.
Pattern forms
Fluid composition (R1) is coated on the surface of glass substrate with spin coater after, under 90 ℃, carry out 4 minutes prebake conditions, form filming of thickness 1.3 μ m.Afterwards, 6 pieces of these substrates are cooled to room temperature, use high-pressure mercury-vapor lamp, by photomask to filming on each substrate with 100J/m 2, 200J/m 2, 300J/m 2, 400J/m, 500J/m 2, 750J/m or 1,000J/m 2Each exposure expose.Afterwards, to filming on each substrate, by 23 ℃ 0.04 weight % potassium hydroxide aqueous solutions with 1kgf/cm 2Development pressure (nozzle diameter 1mm) discharge and after spraying development, 220 ℃ carry out 30 minutes after baking, form the dot pattern of 200 * 200 μ m.
The evaluation of susceptibility
Dot pattern on each substrate that forms pattern with each exposure is observed with scanning electron microscope, pattern forms well, calculating residual film ratio (thickness before developing in the thickness after the development * 100/) with the Film Thickness Ratio before and after developing is that situation more than 90% is zero, pattern forms well, but residual film ratio is less than 90% or confirm that the defective situation of a part of pattern is △, the situation that does not form pattern for *, estimate.
The evaluation of solvent resistance
With 3 pieces with 1,000J/m 2The exposure substrate that exposes and obtain, 25 ℃ N-Methyl pyrrolidone (being designated as " NMP " in table 6～table 9), flooded respectively 30 minutes in 5 weight % sodium hydrate aqueous solutions (being designated as " NaOH " in table 6～table 9) or the 18 weight % hydrochloric acid (being designated as " HCl " in table 6～table 9), dot pattern before and after the dipping is observed with scanning electron microscope, pattern forms well, calculating residual film ratio (thickness before the thickness behind the dipping * 100/ dipping) with the Film Thickness Ratio before and after the dipping is that situation more than 95% is zero, Film Thickness Ratio before and after the dipping is less than 95%, or the defective situation of a part of confirming pattern is △, pattern behind the dipping all from the situation of strippable substrate be *, estimate.
The evaluation of adaptation
Fluid composition (R1) is coated on the surface of glass substrate with spin coater after, under 90 ℃, carry out 4 minutes prebake conditions, form filming of thickness 1.3 μ m.Afterwards, this substrate is cooled to room temperature after, use high-pressure mercury-vapor lamp, to filming with 2 000J/m 2Exposure expose.Afterwards, 0.04 weight % potassium hydroxide aqueous solution by 23 ℃ is with 1kgf/cm 2Development pressure (nozzle diameter 1mm) discharge and after spraying development, 220 ℃ carry out 30 minutes after baking.Afterwards, according to JIS K 5400 standards, will film and draw lattice is 100 gridiron patterns, carry out the evaluation of adaptation, the situation that gridiron pattern does not have to peel off is zero, and 1～10 situation about peeling off is △ in the gridiron pattern, surpass in the gridiron pattern 10 situations about peeling off for *, estimate.
Embodiment 2～41 and comparative example 1～20
In addition, prepare each fluid composition similarly to Example 1 except the kind of each composition and amount are shown in table 2～table 5 (still, part be weight basis), estimate.Evaluation result is shown in table 6～table 9.
In table 2～table 5, multi-functional single amount and theing contents are as follows of Photoepolymerizationinitiater initiater are stated.
Multi-functional single amount body
C-1: dipentaerythritol acrylate
C-2: trimethylolpropane triacrylate
Photoepolymerizationinitiater initiater
D-1:2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholinyl propane-1-ketone
D-2:2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone
D-3:1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl)-ethyl ketone 1-(O-acetyl group oxime)
D-4:4,4 '-two (diethylamino) benzophenone
D-5:2, the 4-diethyl thioxanthone
D-6:2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline
The D-7:2-mercaptobenzothiazoler
Table 2
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resins (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part)
Embodiment 1 R1 R(100) B-1(15) C-1(12) C-2(3) D-1(4) D-5(1)
Embodiment 2 R2 R(100) B-2(15) C-1(12) C-2(3) D-1(4) D-5(1)
Embodiment 3 R3 R(100) B-3(15) C-1(12) C-2(3) D-1(4) D-5(1)
Embodiment 4 R4 R(100) B-2(7.5) B-3(7.5) C-1(12) C-2(3) D-1(4) D-5(1)
Embodiment 5 R5 R(100) B-4(15) C-1(12) C-2(3) D-1(4) D-5(1)
Embodiment 6 R6 R(100) B-5(15) C-1(12) C-2(3) D-1(4) D-5(1)
Embodiment 7 R7 R(100) B-6(15) C-1(12) C-2(3) D-1(4) D-5(1)
Embodiment 8 R8 R(100) B-7(15) C-1(12) C-2(3) D-1(4) D-5(1)
Embodiment 9 R9 R(100) B-8(15) C-1(12) C-2(3) D-1(4) D-5(1)
Embodiment 10 R10 R(100) B-9(15) C-1(12) C-2(3) D-1(4) D-5(1)
Embodiment 11 R11 R(100) B-2(15) C-1(12) C-2(3) D-3(3) D-4(1)
Embodiment 12 R12 R(100) B-2(15) C-1(12) C-2(3) D-1(4) D-4(1) D-6(0.4) D-7(0.2)
Table 3
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resins (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part)
Embodiment 13 G1 G(100) B-1(10) C-1(10) D-2(4) D-4(1)
Embodiment 14 G2 G(100) B-2(10) C-1(10) D-2(4) D-4(1)
Embodiment 15 G3 G(100) B-3(10) C-1(10) D-2(4) D-4(1)
Embodiment 16 G4 G(100) B-2(5) B-3(5) C-1(10) D-2(4) D-4(1)
Embodiment 17 G5 G(100) B-4(10) C-1(10) D-2(4) D-4(1)
Embodiment 18 G6 G(100) B-5(10) C-1(10) D-2(4) D-4(1)
Embodiment 19 G7 G(100) B-6(10) C-1(10) D-2(4) D-4(1)
Embodiment 20 G8 G(100) B-7(10) C-1(10) D-2(4) D-4(1)
Embodiment 21 G9 G(100) B-8(10) C-1(10) D-2(4) D-4(1)
Embodiment 22 G10 G(100) B-9(10) C-1(10) D-2(4) D-4(1)
Embodiment 23 G11 G(100) B-2(10) C-1(10) D-3(3) D-4(1)
Embodiment 24 G12 G(100) B-2(10) C-1(10) D-2(4) D-4(1) D-6(0.4) D-7(0.2)
Table 4
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resins (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part)
Embodiment 25 BK1 BK(100) B-1(9) C-1(8) D-3(4) D-5(1)
Embodiment 26 BK2 BK(100) B-2(9) C-1(8) D-3(4) D-5(1)
Embodiment 27 BK3 BK(100) B-3(9) C-1(8) D-3(4) D-5(1)
Embodiment 28 BK4 BK(100) B-2(4.5) B-3(4.5) C-1(8) D-3(4) D-5(1)
Embodiment 29 BK5 BK(100) B-4(9) C-1(8) D-3(4) D-5(1)
Embodiment 30 BK6 BK(100) B-5(9) C-1(8) D-3(4) D-5(1)
Embodiment 31 BK7 BK(100) B-6(9) C-1(8) D-3(4) D-5(1)
Embodiment 32 BK8 BK(100) B-7(9) C-1(8) D-3(4) D-5(1)
Embodiment 33 BK9 BK(100) B-8(9) C-1(8) D-3(4) D-5(1)
Embodiment 34 BK10 BK(100) B-9(9) C-1(8) D-3(4) D-5(1)
Embodiment 35 BK11 BK(100) B-2(9) C-1(8) D-3(4) D-5(1) D-6(0.4) D-7(0.2)
Embodiment 36 R18 R(100) B-13(15) C-1(12) C-2(3) D-1(4) D-5(1)
Embodiment 37 R19 R(100) B-14(15) C-1(12) C-2(3) D-1(4) D-5(1)
Embodiment 38 G18 G(100) B-13(10) C-1(10) D-2(4) D-4(1)
Embodiment 39 G19 G(100) B-14(10) C-1(10) D-2(4) D-4(1)
Embodiment 40 BK16 BK(100) B-13(9) C-1(8) D-3(4) D-5(1)
Embodiment 41 BK17 BK(100) B-14(9) C-1(8) D-3(4) D-5(1)
Table 5
Fluid composition Dispersible pigment dispersion (part) Alkali soluble resins (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part)
Comparative example 1 R13 R(100) B-10(15) C-1(12) C-2(3) D-1(4) D-5(1)
Comparative example 2 R14 R(100) B-11(15) C-1(12) C-2(3) D-1(4) D-5(1)
Comparative example 3 R15 R(100) B-12(15) C-1(12) C-2(3) D-1(4) D-5(1)
Comparative example 4 R16 R(100) B-10(15) C-1(12) C-2(3) D-3(3) D-4(1)
Comparative example 5 R17 R(100) B-10(15) C-1(12) C-2(3) D-1(4) D-4(1) D-6(0.4) D-7(0.2)
Comparative example 6 G13 G(100) B-10(10) C-1(10) D-2(4) D-4(1)
Comparative example 7 G14 G(100) B-11(10) C-1(10) D-2(4) D-4(1)
Comparative example 8 G15 G(100) B-12(10) C-1(10) D-2(4) D-4(1)
Comparative example 9 G16 G(100) B-10(10) C-1(10) D-3(3) D-4(1)
Comparative example 10 G17 G(100) B-10(10) C-1(10) D-2(4) D-4(1) D-6(0.4) D-7(0.2)
Comparative example 11 BK12 BK(100) B-10(9) C-1(8) D-3(4) D-5(1)
Comparative example 12 BK13 BK(100) B-11(9) C-1(8) D-3(4) D-5(1)
Comparative example 13 BK14 BK(100) B-12(9) C-1(8) D-3(4) D-5(1)
Comparative example 14 BK15 BK(100) B-10(9) C-1(8) D-3(4) D-5(1) D-6(0.4) D-7(0.2)
Comparative example 15 R20 R(100) B-15(15) C-1(12) C-2(3) D-1(4) D-5(1)
Comparative example 16 R21 R(100) B-16(15) C-1(12) C-2(3) D-1(4) D-5(1)
Comparative example 17 G20 G(100) B-15(10) C-1(10) D-2(4) D-4(1)
Comparative example 18 G21 G(100) B-16(10) C-1(10) D-2(4) D-4(1)
Comparative example 19 BK18 BK(100) B-15(9) C-1(8) D-3(4) D-5(1)
Comparative example 20 BK19 BK(100) B-16(9) C-1(8) D-3(4) D-5(1)
Table 6
Figure A20081012557000461
Table 7
Figure A20081012557000462
Table 8
Table 9
Figure A20081012557000472
As mentioned above, even the radiation-ray sensitive composition exposure that is used to form dyed layer of the present invention is low, can do not produced also that residual film ratio reduces, pattern is damaged or the sidewall corrosion, and solvent resistance, with excellent pixel and black matrix such as the adaptation of substrate, multipolymer (B1) self memory that constitutes in addition as the principal ingredient of (B) alkali soluble resins of adhesive ingredients has good stability, even it is contain under the condition of pigment, also excellent as the storage stability of fluid composition on high concentration ground.
And the color filter that the radiation-ray sensitive composition that is used to form dyed layer of the present invention can be used for using with the color liquid crystal display device of electronics industry very suitably is in the manufacturing of various color filters of representative.

Claims (7)

1. radiation-ray sensitive composition, it contains (A) colorant, (B) alkali soluble resins, (C) multi-functional monomer and (D) Photoepolymerizationinitiater initiater, it is used to form dyed layer, it is characterized in that: (B) alkali soluble resins contains following polymkeric substance, described polymkeric substance has: be selected from the repetitive of at least a, following formula (1) expression of acidic functionality and anhydride group and the group of following formula (2) expression
Figure A2008101255700002C1
In the formula (1), R 7The alkyl of expression carbon number 1～12 or the aryl of carbon number 6～12,
Figure A2008101255700002C2
In the formula (2), X represents the organic group of n valency, R 8The alkylidene of expression methylene or carbon number 2～6, n represents 2～10 integer, " * " represents connecting key.
2. the described radiation-ray sensitive composition of claim 1, wherein, (B) group of the expression of the above-mentioned formula (2) in the alkali soluble resins is the group of following formula (3) expression,
Figure A2008101255700002C3
In the formula (3), Y represents the organic group of n valency, R 8With the R in n and the formula (2) 8With the n same meaning, " * " represents connecting key.
3. claim 1 or 2 described radiation-ray sensitive compositions, wherein, (B) alkali soluble resins is following multipolymer, described multipolymer be with contain (b1) be selected from least a of unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and unsaturated phenolic compounds and (b2) polymerization in the presence of the compound of following formula (5) expression of the polymerism potpourri that forms of the compound of following formula (4) expression obtain
Figure A2008101255700003C1
In the formula (4), R 7With the R in the formula (1) 7Same meaning,
Figure A2008101255700003C2
In the formula (5), X, R 8With X, the R in n and the formula (2) 8With the n same meaning.
4. any described radiation-ray sensitive composition of claim 1～3, wherein, above-mentioned polymerism potpourri also contains the unsaturated compound that (b3) has the unsaturated compound of oxetanes skeleton and/or have the tetrahydrofuran skeleton.
5. color filter, it has the dyed layer that uses any described radiation-ray sensitive composition of claim 1～4 to form and forms.
6. color liquid crystal display device, it possesses the described color filter of claim 5.
7. the manufacture method of alkali soluble resins, it is characterized in that, will contain (b1) and be selected from least a of unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and unsaturated phenolic compounds and (b2) the polymerism potpourri that forms of the compound of above-mentioned formula (4) expression polymerization in the presence of the compound of above-mentioned formula (5) expression.
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