CN101067723B - Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device - Google Patents

Radiation sensitive composition for forming a colored layer, color filter and color liquid crystal display device Download PDF

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CN101067723B
CN101067723B CN2007100966816A CN200710096681A CN101067723B CN 101067723 B CN101067723 B CN 101067723B CN 2007100966816 A CN2007100966816 A CN 2007100966816A CN 200710096681 A CN200710096681 A CN 200710096681A CN 101067723 B CN101067723 B CN 101067723B
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methyl
acid
oxetanes
unsaturated compound
composition
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CN101067723A (en
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森下聪
依田杏介
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JSR Corp
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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
    • G03F7/0005—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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a radiation sensitive composition for forming a colored layer comprising: (A) colorant, (B) alkali soluble resins, (C) multi-functional monomer and (D) photopolymerization initiating agent, wherein (B) alkali soluble resins contains the copolymer consisted by the following compositions: (b1) at least one selected from the unsaturated carboxylic acid, the unsaturated carboxylic acid anhydride and unsaturated phenol compound; (b2) unsaturated compound with alicyclic carbocycle structure; (b3) unsaturated compound with oxacyclobutane cycle structure. In the composition, the save stability of the alkali soluble resins itself is good, the save stability of the colorant dispersion liquid and the liquid composition are excellent even under high pigment concentration, it will not have the problems of that the fogging ratio is lower in the low light exposure, the pattern edge is crumbling or sunken, it can obtain the excellent pixel and black matrix having good solvent resistance and joint performance with the base plate.

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 radiation-ray sensitive composition, color filter (color filter) and color liquid crystal display device.More particularly, the present invention relates in transmission-type or Reflexible color LCD, colour pick-up tube element etc. to use, the radiation-ray sensitive composition that can be used for being formed on dyed layer useful in the color filter, the color liquid crystal display device that has the color filter of the dyed layer that forms by this radiation-ray sensitive composition and possess this color filter.
Background technology
In the past; Known when using colored radiation-sensitive composition to make color filter have a following method: on the substrate or be pre-formed on the substrate of light shield layer of required pattern and be coated with colored radiation-sensitive composition; Dry then; Again to dry coating irradiation radioactive ray, form required pattern form (below be called " exposure "), obtain versicolor pixel (with reference to japanese kokai publication hei 2-144502 communique, japanese kokai publication hei 3-53201 communique) through development.
In recent years in the color filter technique field, reduce exposure, shorten the productive temp time and become main flow, the pixel that requires to form and the pattern form of black matrix, solvent resistance with low exposure, with the excellences such as stickiness of substrate.But in colored radiation-sensitive composition in the past; Taking place easily to develop if exposure reduces, the back residual film ratio is low, pattern is damaged or depression, pattern are peeled off etc. from substrate, therefore is difficult in and shortens productive temp obtains to form good pattern form again in the time of the time pixel and black matrix.In addition, anti-solvent, and the aspects such as stickiness of substrate also not enough.And; In recent years in order to realize higher color reprodubility; The colored radiation-sensitive composition that in color filter forms, uses has adopted high pigment levels; This aspect the production management of color filter except the storage stability of the storage stability that requires dispersible pigment dispersion and the fluid composition form that contains solvent, also require the storage stability of alkali soluble resins itself good.But, colored radiation-sensitive composition in the past can not satisfy above-mentioned some.
Summary of the invention
The object of the present invention is to provide the storage stability of alkali soluble resins itself good; Even high pigment levels; The storage stability of dispersible pigment dispersion and fluid composition is also excellent; Residual film ratio is low, pattern edge is damaged or depression even under low exposure, also can not take place, can obtain solvent resistance, with the aspects such as stickiness of the substrate also pixel of excellence or the new radiation-ray sensitive composition that is used to form dyed layer of black matrix (black matrix).
Another object of the present invention is to provide color filter with the dyed layer that forms by above-mentioned composition of the present invention and the color liquid crystal display device that possesses this color filter.
Another purpose of the present invention and advantage such as following explanation.
According to the present invention; The above-mentioned purpose of first aspect present invention and advantage realize through the radiation-ray sensitive composition that is used to form dyed layer; The said radiation-ray sensitive composition that is used to form dyed layer contains (A) colorant, (B) alkali soluble resins, (C) multi-functional monomer and (D) Photoepolymerizationinitiater initiater, it is characterized in that: (B) alkali soluble resins contains unsaturated compound, (b3) that at least a, (b2) that are selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and unsaturated phenolic compounds with (b1) have ester ring type carbocyclic ring structure and has the multipolymer of the unsaturated compound of oxetanes ring structure as constituent.
Among the present invention, dyed layer is meant " pixel and/or black matrix ".
According to the present invention, the above-mentioned purpose of second aspect of the present invention and advantage realize that through color filter this color filter has the dyed layer that uses the above-mentioned radiation-ray sensitive composition that is used to form dyed layer to form.
According to the present invention, the above-mentioned purpose of the third aspect of the invention and advantage realize through the color liquid crystal display device that possesses above-mentioned color filter.
Embodiment
Below the present invention is elaborated.
Be used to form the radiation-ray sensitive composition of dyed layer
-(A) colorant-
The not special restriction of its tone of colorant of the present invention can suitably be selected according to the purposes of gained color filter, and pigment, dyestuff or natural colouring matter all can.
Color filter requires high meticulous colour developing and thermotolerance, therefore as colorant of the present invention, and 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 and carbon black.
As above-mentioned organic pigment, for example have at カ ラ-イ Application デ ッ Network ス (C.I.; The compound of the pigment (pigment) that is categorized as the distribution of The Society ofDyers and Colourists company) can be enumerated the compound that following Colour Index (C.I.) is numbered specifically.
C.I. pigment yellow 1; C.I. pigment yellow 3; C.I. pigment Yellow 12; C.I. pigment yellow 13; C.I. pigment Yellow 14; C.I. pigment yellow 15; C.I. pigment yellow 16; 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 60; C.I. pigment yellow 61; C.I. pigment yellow 65; C.I. pigment yellow 71; C.I. pigment yellow 73; C.I. pigment yellow 74; C.I. pigment yellow 81; C.I. pigment yellow 83; C.I. pigment yellow 93; C.I. pigment yellow 95; C.I. pigment yellow 97; C.I. pigment yellow 98; C.I. pigment yellow 100; C.I. pigment yellow 101; C.I. pigment yellow 104; C.I. pigment yellow 106; C.I. pigment yellow 108; C.I. pigment yellow 109; C.I. pigment yellow 110; C.I. pigment yellow 113; C.I. pigment yellow 114; C.I. pigment yellow 116; C.I. pigment yellow 117; C.I. pigment yellow 119; C.I. pigment Yellow 12 0; C.I. pigment Yellow 12 6; C.I. pigment Yellow 12 7; C.I. pigment Yellow 12 8; C.I. pigment Yellow 12 9; C.I. pigment yellow 13 8; C.I. pigment yellow 13 9; C.I. pigment yellow 150; C.I. pigment yellow 151; C.I. pigment yellow 152; C.I. pigment yellow 153; C.I. pigment yellow 154; C.I. pigment yellow 155; C.I. pigment yellow 156; C.I. pigment yellow 166; C.I. pigment yellow 168; C.I. pigment yellow 17 5; C.I. pigment yellow 180; C.I. pigment yellow 185;
C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, 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 51, C.I. pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73;
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. paratonere 1; C.I. paratonere 2; C.I. pigment red 3; C.I. pigment red 4; C.I. paratonere 5; C.I. paratonere 6; C.I. paratonere 7; C.I. pigment Red 8; C.I. Pigment Red 9; C.I. paratonere 10; C.I. paratonere 11; C.I. paratonere 12; C.I. paratonere 14; C.I. paratonere 15; C.I. paratonere 16; C.I. paratonere 17; C.I. paratonere 18; C.I. paratonere 19; C.I. pigment red 21; C.I. paratonere 22; C.I. paratonere 23; C.I. pigment red 30; C.I. pigment red 31; C.I. pigment red 32; C.I. pigment red 37; C.I. pigment red 38; C.I. pigment red 40; C.I. pigment red 41; C.I. pigment red 42; C.I. pigment red 4 8:1; C.I. pigment red 4 8:2; C.I. pigment red 4 8:3; C.I. pigment red 4 8:4; C.I. pigment red 4 9:1; C.I. pigment red 4 9:2; C.I. paratonere 50:1; C.I. paratonere 52:1; C.I. paratonere 53:1; C.I. paratonere 57; C.I. paratonere 57:1; C.I. paratonere 57:2; C.I. paratonere 58:2; C.I. paratonere 58:4; C.I. paratonere 60:1; C.I. paratonere 63:1; C.I. paratonere 63:2; C.I. paratonere 64:1; C.I. pigment red 81: 1; C.I. pigment Red 83; C.I. pigment Red 88; C.I. Pigment Red 9 0:1; C.I. Pigment Red 97;
C.I. paratonere 101; C.I. paratonere 102; C.I. paratonere 104; C.I. paratonere 105; C.I. paratonere 106; C.I. paratonere 108; C.I. pigment red 112; C.I. paratonere 113; C.I. paratonere 114; C.I. pigment red 122; C.I. pigment red 123; C.I. paratonere 144; C.I. pigment red 146; C.I. pigment red 149; C.I. paratonere 150; C.I. paratonere 151; C.I. paratonere 166; C.I. paratonere 168; C.I. paratonere 170; C.I. paratonere 171; C.I. paratonere 172; C.I. paratonere 174; 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 188; C.I. paratonere 190; C.I. paratonere 193; C.I. paratonere 194; C.I. paratonere 202; C.I. paratonere 206; C.I. Pigment Red 207; C.I. paratonere 208; C.I. paratonere 209; C.I. pigment red 21 5; C.I. pigment red 21 6; C.I. paratonere 220; C.I. paratonere 224; C.I. paratonere 226; C.I. paratonere 242; C.I. paratonere 243; C.I. paratonere 245; C.I. paratonere 254; C.I. paratonere 255; C.I. paratonere 264; C.I. paratonere 265;
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. pigment Green 7, C.I. pigment green 36;
C.I. pigment brown 23, C.I. pigment brown 25;
C.I. pigment black 1, C.I. pigment black 7.
Above-mentioned organic pigment can use through the purifying such as method of for example sulfuric acid recrystallization method, solvent wash method or their combination.
In addition, inorganic pigment for example can be enumerated titanium dioxide, barium sulphate, lime carbonate, zinc white, lead sulfate, lead and yellow-collation (yellow
Figure S07196681620070518D00004183037QIETU
), zinc yellow, iron oxide red, cadmium red, ultramarine, Prussian blue, chrome oxide green, cobalt green, Ang Bai (ア Application バ-), black, the synthetic iron oxide black of titanium, carbon black etc.
Among the present invention, above-mentioned organic pigment and inorganic pigment can be distinguished independent use or use mixing more than 2 kinds.Can also and use organic pigment and inorganic pigment.When for example forming pixel, preferably use more than one organic pigment, in addition, form when deceiving matrix, preferably use organic pigment and/or carbon black more than 2 kinds.
Among the present invention, above-mentioned each pigment can be as required uses its particle surface after with polymer modification.Be used for polymkeric substance that particle surface to pigment carries out modification and for example can be the polymkeric substance of records such as japanese kokai publication hei 8-259876 communique or polymkeric substance that commercially available various pigment dispersing are used or oligomer etc.
Among the present invention, colorant can use with spreading agent as required.Above-mentioned spreading agent for example has surfactants such as cationic, anionic species, nonionic class, both sexes, type siloxane, fluorine class.
As the object lesson of above-mentioned surfactant, can enumerate polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether; Polyethylene glycol di such as polyethylene glycol dilaurate, polyglycol distearate; Sorbitan fatty acid esters; Fatty acid modified polyester; The tertiary amine modified polyurethane; Polyethyleneimine: amines etc. are discussed KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturings) that the name of an article representes, Port リ Off ロ-(common prosperity chemistry (strain) is made), エ Off ト ッ プ (ト-ケ system プ ロ ダ Network Star (strain) is made), メ ガ Off ァ ッ Network (big Japanese イ Application キ chemical industry (strain) manufacturings), Off ロ ラ-De (Sumitomo ス リ-エ system (strain) is made), ア サ ヒ ガ-De, サ-Off ロ Application (above by Asahi Glass (strain) manufacturing), Disperbyk (PVC ッ Network ケ ミ-ジ ャ パ Application (strain) manufacturing), ソ Le ス パ-ス (セ ネ カ (strain) manufacturing) etc. face to face below also having in addition.
These surfactants can use separately or use mixing more than 2 kinds.
Among the present invention, radiation sensitive resin composition can be through the appropriate method preparation.When using pigment as colorant; Preferably in solvent, in the presence of spreading agent; Use for example ball mill, roller mill etc.; This pigment is pulverized and is mixed, disperses, process dispersible pigment dispersion, with its with after (B) composition, (C) composition of stating with (D) composition and further replenish as required the solvent that adds or after other adjuvant of stating be mixed with.
The use amount of preparation spreading agent during dispersible pigment dispersion is with respect to 100 weight portion pigment optimizations, 100 weight portions or following, more preferably 0.5-100 weight portion, further preferred 1-70 weight portion, preferred especially 10-50 weight portion.The use amount of spreading agent surpasses 100 weight portions, and then development property maybe be impaired.
The solvent that preparation is used during dispersible pigment dispersion for example can be with after the cited identical solvent of solvent in the fluid composition of the radiation sensitive resin composition stated.
During the preparation dispersible pigment dispersion, with respect to 100 weight portion pigment, the preferred 200-1 of the use amount of solvent, 000 weight portion, more preferably 300-800 weight portion.
During the preparation dispersible pigment dispersion; If use ball mill to prepare; Beaded glass about for example can using diameter as 0.5-10mm or titania pearl etc., the pigment mixed liquor of pigment, solvent and spreading agent is preferred to carry out mixed and dispersed with coolings such as chilled waters on one side Yi Bian will contain.
At this moment, the filling rate of pearl is preferably the 50-80% of grinding machine capacity, and the injection rate IR of pigment mixed liquor is preferably about the 20-50% of grinding machine capacity.Preferred 2-200 of processing time hour, more preferably 2-100 hour.
When using roller mill to prepare, for example can use triple-roller mill or two roller mills etc., preferred one side implements to handle to the pigment mixed liquor with coolings such as chilled waters on one side.
At this moment, below the preferred 10 μ m, shearing force is generally 10 to roller at interval 8Dyn/ is about second.Preferred 2-50 of processing time hour, more preferably 2-25 hour.
-(B) alkali soluble resins-
Alkali soluble resins of the present invention contains with (b1) and is selected from unsaturated carboxylic acid; Unsaturated carboxylic acid anhydrides and unsaturated phenolic compounds (following these compounds are referred to as " acid unsaturated compound ") at least a; (b2) has the unsaturated compound (below be called " ester ring type unsaturated compound ") of ester ring type carbocyclic ring structure; (b3) has the unsaturated compound (below be called " oxetanes unsaturated compound ") of oxetanes ring structure as the multipolymer of constituent (below be called " multipolymer (BI) ").Should play the bonding agent effect to (A) colorant by (B) composition, and have solubility for the developer solution that in the development treatment step that forms dyed layer, uses.
Above-mentioned unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides for example have:
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;
Ternary or above unsaturated polybasic carboxylic acid or its acid anhydrides;
List [(methyl) acryloxyalkyl] ester of 2 yuan of mono succinate [2-(methyl) acryloxy ethyl] ester, phthalic acid list [2-(methyl) acryloxy ethyl] esters etc. or above polybasic carboxylic acid;
ω-two ends such as carboxyl polycaprolactone list (methyl) acrylic ester have list (methyl) acrylic ester of the polymkeric substance of carboxyl and hydroxyl etc.
In these unsaturated carboxylic acids, the unsaturated carboxylic acid anhydrides, mono succinate (2-acryloxy ethyl ester) and phthalic acid list (2-acryloxy ethyl ester) are sold with the trade name of ラ イ ト エ ス テ Le HOA-MS and ラ イ ト エ ス テ Le HOA-MPE (above is common prosperity society chemistry (strain) preparation) respectively.
In addition, above-mentioned unsaturated phenolic compounds for example has:
Adjacent vinylphenol, a vinylphenol, to vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, neighbour-isopropenyl phenol ,-isopropenyl phenol, right-unsaturated phenol such as isopropenyl phenol;
2-vinyl-1-naphthols, 3-vinyl-1-naphthols, 1-vinyl-beta naphthal, 3-vinyl-beta naphthal, 2-isopropenyl-1-naphthols, 3-isopropenyl-unsaturated naphthols such as 1-naphthols etc.
Among the present invention, preferred (methyl) acrylic acid of acid unsaturated compound, to vinylphenol etc., preferred especially (methyl) acrylic acid.
The ester ring type unsaturated compound for example has:
(methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-9-base ester, (methyl) acrylic acid three ring [5.2.1.0 2,6] last of the ten Heavenly stems-3-alkene-8-base ester, (methyl) acrylic acid three ring [5.2.1.0 2,6] last of the ten Heavenly stems-3-alkene-9-base ester, (methyl) acrylic acid 2-cyclohexyl oxygen base ethyl ester, (methyl) acrylic acid 2-(three ring [5.2.1.0 2,6] decane-8-base oxygen base) ethyl ester, (methyl) acrylic acid 2-(three ring [5.2.1.0 2,6] decane-9-base oxygen base) ethyl ester, (methyl) acrylic acid 2-(three ring [5.2.1.0 2,6] last of the ten Heavenly stems-3-alkene-8-base oxygen base) ethyl ester, (methyl) acrylic acid 2-(three ring [5.2.1.0 2,6] last of the ten Heavenly stems-3-alkene-9-base oxygen base) ethyl ester, hexahydrophthalic acid list [2-(methyl) acryloxy ethyl] ester, hexahydrophthalic acid 1-hydroxyethyl-2-(methyl) acryloxy ethyl ester, hexahydrophthalic acid 1-methyl-2-(methyl) acryloxy ethyl ester, hexahydrophthalic acid 1-ethyl-2-(methyl) acryloxy ethyl ester;
Cyclohexyl vinyl ether, isobornyl vinyl ether, three ring [5.2.1.0 2,6] decane-8-base vinyl ether, three ring [5.2.1.0 2,6] decane-9-base vinyl ether, three ring [5.2.1.0 2,6] last of the ten Heavenly stems-3-alkene-8-base vinyl ether, three ring [5.2.1.0 2,6] last of the ten Heavenly stems-3-alkene-9-base vinyl ether, 2-cyclohexyl oxygen base ethyl vinyl ether, 2-(three ring [5.2.1.0 2,6] decane-8-base oxygen base) ethyl vinyl ether, 2-(three ring [5.2.1.0 2,6] decane-9-base oxygen base) ethyl vinyl ether, 2-(three ring [5.2.1.0 2,6] last of the ten Heavenly stems-3-alkene-8-base oxygen base) ethyl vinyl ether, 2-(three ring [5.2.1.0 2,6] last of the ten Heavenly stems-3-alkene-9-base oxygen base) ethyl vinyl ether, hexahydrophthalic acid list (2-vinyl oxygen base ethyl) ester, hexahydrophthalic acid 1-hydroxyethyl-2-vinyl oxygen base ethyl ester, hexahydrophthalic acid 1-methyl-2-vinyl oxygen base ethyl ester, hexahydrophthalic acid 1-ethyl-vinyl ether such as 2-vinyl oxygen base ethyl ester etc.
Among the present invention, preferred (methyl) cyclohexyl acrylate of ester ring type unsaturated compound, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, cyclohexyl vinyl ether, isobornyl vinyl ether, three ring [5.2.1.0 2,6] decane-8-base vinyl ether etc., preferred especially (methyl) cyclohexyl acrylate, (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, (methyl) isobornyl acrylate.
Above-mentioned ester ring type unsaturated compound can use separately or with two or more mixing.
Oxetanes unsaturated compound preference is as shown in the formula compound shown in compound shown in (1) (below be called " oxetanes unsaturated compound (1) "), the following formula (2) (below be called " oxetanes unsaturated compound (2) ") etc.
Figure S07196681620070518D000081
[in the formula (1), R representes the alkyl of hydrogen atom or carbon atom 1-4, R 1The alkyl of expression hydrogen atom or carbon number 1-4, R 2, R 3, R 4And R 5Independent separately, expression hydrogen atom, fluorine atom, the alkyl of carbon number 1-4, the fluoroalkyl of carbon number 1-4 or the aryl of carbon number 6-20, n representes the integer of 0-6].
[in the formula (2), R, R 1, R 2, R 3, R 4, R 5With n respectively with following formula (1) in R, R 1, R 2, R 3, R 4, R 5Identical with the n implication].
In formula (1) and the formula (2), R, R 1, R 2, R 3, R 4And R 5The alkyl of carbon number 1-4 methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group etc. are for example arranged.
R 2, R 3, R 4And R 5The fluoroalkyl of carbon number 1-4 methyl fluoride, difluoromethyl, trifluoromethyl, 1-fluoro ethyl, 2-fluoro ethyl, 1 are for example arranged; 1-two fluoro ethyls, 2; 2,2-trifluoroethyl, pentafluoroethyl group, seven fluoro-n-pro-pyls, seven fluoro-1-propyl group, nine fluoro-normal-butyls, nine fluoro-isobutyls, nine fluoro-sec-butyls, the nine fluoro-tert-butyl groups etc.
R 2, R 3, R 4And R 5The aryl of carbon number 6-20 phenyl, o-tolyl, a tolyl, p-methylphenyl etc. are for example arranged.
Oxetanes unsaturated compound (1) for example has:
3-[(methyl) acryloyl-oxy ylmethyl] oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2-methyl oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-3-methyl oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2-ethyl oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-3-ethyl oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2-trifluoromethyl oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2-pentafluoroethyl group oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2-phenyl oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2; 2-difluoro oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2; 2; 4-trifluoro oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2; 2; 4,4-tetrafluoro 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-trifluoromethyl oxetanes, 3-[2-(methyl) acryloxy ethyl]-2-pentafluoroethyl group oxetanes, 3-[2-(methyl) acryloxy ethyl]-2-phenyl oxetanes, 3-[2-(methyl) acryloxy ethyl]-2; 2-difluoro oxetanes, 3-[2-(methyl) acryloxy ethyl]-2; 2; 4-trifluoro oxetanes, 3-[2-(methyl) acryloxy ethyl]-2; 2; 4,4-tetrafluoro oxetanes etc. (methyl) acrylic ester etc.
Oxetanes unsaturated compound (2) for example has:
2-[(methyl) acryloyl-oxy ylmethyl] oxetanes; 2-[(methyl) acryloyl-oxy ylmethyl]-2-methyl oxetanes; 2-[(methyl) acryloyl-oxy ylmethyl]-3-methyl oxetanes; 2-[(methyl) acryloyl-oxy ylmethyl]-4-methyl oxetanes; 2-[(methyl) acryloyl-oxy ylmethyl]-2-ethyl oxetanes; 2-[(methyl) acryloyl-oxy ylmethyl]-3-ethyl oxetanes; 2-[(methyl) acryloyl-oxy ylmethyl]-4-ethyl oxetanes; 2-[(methyl) acryloyl-oxy ylmethyl]-2-trifluoromethyl oxetanes; 2-[(methyl) acryloyl-oxy ylmethyl]-3-trifluoromethyl oxetanes; 2-[(methyl) acryloyl-oxy ylmethyl]-4-trifluoromethyl oxetanes; 2-[(methyl) acryloyl-oxy ylmethyl]-2-pentafluoroethyl group oxetanes; 2-[(methyl) acryloyl-oxy ylmethyl]-3-pentafluoroethyl group oxetanes; 2-[(methyl) acryloyl-oxy ylmethyl]-4-pentafluoroethyl group oxetanes;
2-[(methyl) acryloyl-oxy ylmethyl]-2-phenyl oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl]-3-phenyl oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl]-4-phenyl oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl]-2,3-difluoro oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl]-2,4-difluoro oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl]-3; 3-difluoro oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl]-3; 4-difluoro oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl]-4,4-difluoro oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl]-3,3; 4-trifluoro oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl]-3; 4,4-trifluoro oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl]-3,3; 4,4-tetrafluoro 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-trifluoromethyl oxetanes; 2-[2-(methyl) acryloxy ethyl]-3-trifluoromethyl oxetanes; 2-[2-(methyl) acryloxy ethyl]-4-trifluoromethyl oxetanes; 2-[2-(methyl) acryloxy ethyl]-2-pentafluoroethyl group oxetanes; 2-[2-(methyl) acryloxy ethyl]-3-pentafluoroethyl group oxetanes; 2-[2-(methyl) acryloxy ethyl]-4-pentafluoroethyl group 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-difluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-2; 4-difluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-3,3-difluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-3,4-difluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-4; 4-difluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-3; 3,4-trifluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-3,4; 4-trifluoro oxetanes, 2-[2-(methyl) acryloxy ethyl]-3; 3,4,4-tetrafluoro oxetanes etc. (methyl) acrylic ester etc.
In these oxetanes unsaturated compounds (1) and the oxetanes unsaturated compound (2); Angle wide from the development latitude of gained radiation-ray sensitive composition and that the chemical reagent resistance gained dyed layer is high is considered; Preferred 3-[(methyl) acryloyl-oxy ylmethyl] oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-3-ethyl oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2-trifluoromethyl oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2-phenyl oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl] oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl]-4-trifluoromethyl oxetanes etc., preferred especially 3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-3-ethyl oxetanes, 3-(methacryloxy methyl)-2-trifluoromethyl oxetanes, 3-(methacryloxy methyl)-2-phenyl oxetanes, 2-(methacryloxy methyl) oxetanes, 2-(methacryloxy methyl)-4-trifluoromethyl oxetanes etc.
Among the present invention; Outside oxetanes unsaturated compound deoxygenation heterocycle butane unsaturated compound (1) and the oxetanes unsaturated compound (2), for example can also use in (3-oxa-cyclobutyl methoxy base)-to vinyl benzene, [2-(3-oxa-cyclobutyl) ethoxy]-to vinyl benzene, (2-oxa-cyclobutyl methoxy base)-to vinyl benzene, [2-(2-oxa-cyclobutyl) ethoxy]-to (oxa-cyclobutyl alkyl) ether of vinylphenols such as vinyl benzene;
(oxa-cyclobutyl alkyl) vinyl ether such as (3-oxa-cyclobutylmethyl) vinyl ether, [2-(3-oxa-cyclobutyl) ethyl] vinyl ether, (2-oxa-cyclobutylmethyl) vinyl ether, [2-(2-oxa-cyclobutyl) ethyl] vinyl ether etc.
Above-mentioned oxetanes unsaturated compound can use separately or with two or more mixing.
Multipolymer (BI) can according to circumstances further contain unsaturated compound beyond acid unsaturated compound, ester ring type unsaturated compound and the oxetanes unsaturated compounds (below be called " other unsaturated compound ") as constituent.
Other unsaturated compound for example has:
Styrene, AMS, 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;
Unsaturated acyl imines such as maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, clothing health acid imide, citraconimide;
(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; (methyl) allyl acrylate; (methyl) acrylic acid benzyl ester; (methyl) cyclohexyl 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) IBOA; (methyl) acrylic acid bicyclopentadiene ester; (methyl) acrylic acid 2-hydroxyl-3-phenoxy group propyl ester; Esters of unsaturated carboxylic acids such as glycerine list (methyl) acrylic ester;
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;
Acrylonitrile compounds such as (methyl) vinyl cyanide, α-Lv Bingxijing, vinylidene cyanide;
Unsaturated amides such as (methyl) acrylic amide, α-chloropropene acid amides, N-2-hydroxyethyl (methyl) acrylic amide;
Vinyl carboxylates such as vinyl acetate, propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, EVE, allyl glycidyl ether;
Aliphatics conjugated diolefines such as 1,3-butadiene, isoprene, chlorbutadiene;
Polystyrene, gather (methyl) methyl acrylate, gather (methyl) n-butyl acrylate, polysiloxane etc. and on the polymer molecule chain end, have macromonomer of list (methyl) acryloyl group etc.
Above-mentioned other unsaturated compound can use separately or use mixing more than 2 kinds.
Among the present invention; The preferred following multipolymer of multipolymer (BI) (below be called multipolymer (BII)), this multipolymer (BII) with following compositions as necessary constituent: (b1) be selected from (methyl) cyclohexyl acrylate, (methyl) IBOA and (methyl) acrylic acid three ring [5.2.1.0 as at least a acid unsaturated compound, (b2) that must composition with (methyl) acrylic acid 2,6] at least a ester ring type unsaturated compound, (b3) in the decane-8-base ester be selected from least a oxetanes unsaturated compound in 3-[(methyl) acryloyl-oxy ylmethyl] oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-3-ethyl oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2-trifluoromethyl oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2-phenyl oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl] oxetanes and 2-[(methyl) acryloyl-oxy ylmethyl]-4-trifluoromethyl oxetanes, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid allyl ester, (methyl) acrylic acid benzyl ester, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer.
In particular, multipolymer (BII) for example has:
Multipolymer (BII-1): this multipolymer (BII-1) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) cyclohexyl acrylate as ester ring type unsaturated compound that must composition, (b3) with 3-[(methyl) acryloyl-oxy ylmethyl] oxetanes as the oxetanes unsaturated compound of necessary composition as necessary composition, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer;
Multipolymer (BII-2): this multipolymer (BII-2) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) cyclohexyl acrylate as ester ring type unsaturated compound that must composition, (b3) with the oxetanes unsaturated compound of 3-[(methyl) acryloyl-oxy ylmethyl]-3-ethyl oxetanes as necessary composition, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer;
Multipolymer (BII-3): this multipolymer (BII-3) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) cyclohexyl acrylate as ester ring type unsaturated compound that must composition, (b3) with the oxetanes unsaturated compound of 3-[(methyl) acryloyl-oxy ylmethyl]-2-trifluoromethyl oxetanes as necessary composition, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer;
Multipolymer (BII-4): this multipolymer (BII-4) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) cyclohexyl acrylate as ester ring type unsaturated compound that must composition, (b3) with the oxetanes unsaturated compound of 3-[(methyl) acryloyl-oxy ylmethyl]-2-phenyl oxetanes as necessary composition, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer;
Multipolymer (BII-5): this multipolymer (BII-5) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) cyclohexyl acrylate as ester ring type unsaturated compound that must composition, (b3) with the oxetanes unsaturated compound of 2-[(methyl) acryloyl-oxy ylmethyl] oxetanes as necessary composition, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer;
Multipolymer (BII-6): this multipolymer (BII-6) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) cyclohexyl acrylate as ester ring type unsaturated compound that must composition, (b3) with the oxetanes unsaturated compound of 2-[(methyl) acryloyl-oxy ylmethyl]-4-trifluoromethyl oxetanes as necessary composition, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer;
Multipolymer (BII-7): this multipolymer (BII-7) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) isobornyl acrylate as ester ring type unsaturated compound that must composition, (b3) with the oxetanes unsaturated compound of 3-[(methyl) acryloyl-oxy ylmethyl] oxetanes as necessary composition, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer;
Multipolymer (BII-8): this multipolymer (BII-8) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) isobornyl acrylate as ester ring type unsaturated compound that must composition, (b3) with the oxetanes unsaturated compound of 3-[(methyl) acryloyl-oxy ylmethyl]-3-ethyl oxetanes as necessary composition, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer;
Multipolymer (BII-9): this multipolymer (BII-9) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) isobornyl acrylate as ester ring type unsaturated compound that must composition, (b3) with the oxetanes unsaturated compound of 3-[(methyl) acryloyl-oxy ylmethyl]-2-trifluoromethyl oxetanes as necessary composition, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer;
Multipolymer (BII-10): this multipolymer (BII-10) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) isobornyl acrylate as ester ring type unsaturated compound that must composition, (b3) with the oxetanes unsaturated compound of 3-[(methyl) acryloyl-oxy ylmethyl]-2-phenyl oxetanes as necessary composition, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer;
Multipolymer (BII-11): this multipolymer (BII-11) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) isobornyl acrylate as ester ring type unsaturated compound that must composition, (b3) with the oxetanes unsaturated compound of 2-[(methyl) acryloyl-oxy ylmethyl] oxetanes as necessary composition, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer;
Multipolymer (BII-12): this multipolymer (BII-12) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) isobornyl acrylate as ester ring type unsaturated compound that must composition, (b3) with the oxetanes unsaturated compound of 2-[(methyl) acryloyl-oxy ylmethyl]-4-trifluoromethyl oxetanes as necessary composition, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer;
Multipolymer (BII-13): this multipolymer (BII-13) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer with the oxetanes unsaturated compound of 3-[(methyl) acryloyl-oxy ylmethyl] oxetanes as necessary composition as ester ring type unsaturated compound that must composition, (b3);
Multipolymer (BII-14): this multipolymer (BII-14) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer with the oxetanes unsaturated compound of 3-[(methyl) acryloyl-oxy ylmethyl]-3-ethyl oxetanes as necessary composition as ester ring type unsaturated compound that must composition, (b3);
Multipolymer (BII-15): this multipolymer (BII-15) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer with the oxetanes unsaturated compound of 3-[(methyl) acryloyl-oxy ylmethyl]-2-trifluoromethyl oxetanes as necessary composition as ester ring type unsaturated compound that must composition, (b3);
Multipolymer (BII-16): this multipolymer (BII-16) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer with the oxetanes unsaturated compound of 3-[(methyl) acryloyl-oxy ylmethyl]-2-phenyl oxetanes as necessary composition as ester ring type unsaturated compound that must composition, (b3);
Multipolymer (BII-17): this multipolymer (BII-17) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer with the oxetanes unsaturated compound of 2-[(methyl) acryloyl-oxy ylmethyl] oxetanes as necessary composition as ester ring type unsaturated compound that must composition, (b3);
Multipolymer (BII-18): this multipolymer (BII-18) with following compositions as necessary constituent: (b1) with (methyl) acrylic acid as acid unsaturated compound that must composition, (b2) with (methyl) acrylic acid three ring [5.2.1.0 2,6] decane-8-base ester, according to circumstances can also contain (b4) and be selected from least a other unsaturated compound in styrene, N-cyclohexyl maleimide, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer with the oxetanes unsaturated compound of 2-[(methyl) acryloyl-oxy ylmethyl]-4-trifluoromethyl oxetanes as necessary composition as ester ring type unsaturated compound that must composition, (b3).
In these multipolymers (BII), special preferred copolymer (BII-1), multipolymer (BII-2), multipolymer (BII-7), multipolymer (BII-8), multipolymer (BII-13), multipolymer (BII-14) etc.
In the multipolymer (BI), the copolymerization ratio of acid unsaturated compound is with respect to the preferred 1-40 weight of multipolymer %, preferred especially 5-30 weight %; The preferred 1-50 weight of the copolymerization ratio % of ester ring type unsaturated compound, preferred especially 1-30 weight %; The copolymerization ratio of oxetanes unsaturated compound is with respect to the preferred 1-60 weight of multipolymer %, preferred especially 10-45 weight %; The copolymerization ratio of other unsaturated compound is with respect to the preferred 0-50 weight of multipolymer %, more preferably 1-50 weight %, preferred especially 5-40 weight %.
Among the present invention; Copolymerization ratio through making each unsaturated compound in the multipolymer (BI) is in above-mentioned scope; Can obtain making the excellent storage stability of alkali soluble resins itself, sensitivity under the high pigment levels simultaneously, solvent resistance, with the also excellent radiation-ray sensitive composition of storage stability of the stickiness of substrate etc. and dispersible pigment dispersion or fluid composition.
Among the present invention, multipolymer (BI) can also be used with other alkali soluble resins.
Above-mentioned other alkali soluble resins is so long as to the performance bonding agent effect of (A) colorant and when forming dyed layer, have solubility to the alkaline developer that in the development treatment step, uses and get final product, not special the qualification.The alkali soluble resins that for example preferably has carboxyl.Its example has: in the unsaturated carboxylic acid of enumerating in the multipolymer (BI) at least a be selected from the ester ring type unsaturated compound enumerated in the multipolymer (BI) and at least a multipolymer of other unsaturated compound etc.
Preferred alkali soluble resins more specifically has: (i) with (methyl) acrylic acid as must composition at least aly contain the carboxyl unsaturated compound and (ii) be selected from least a multipolymer in styrene, N-phenylmaleimide, (methyl) methyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) acrylic acid benzyl ester, list (methyl) acrylic acid glyceride, polystyrene macromolecular monomer and the polymethylmethacrylate macromonomer etc.
Among the present invention, (GPC, eluting solvent: the polystyrene conversion weight-average molecular weight of tetrahydrofuran) measuring (below be called " Mw ") is preferred respectively 2,000-300 through gel permeation chromatography for multipolymer (BI) and other alkali soluble resins; 000; More preferably 3,000-100,000.
(GPC, eluting solvent: the polystyrene conversion number-average molecular weight of tetrahydrofuran) measuring (below be called " Mn ") is also distinguished preferred 1,000-60,000, more preferably 2,000-25,000 through gel permeation chromatography for multipolymer (BI) and other alkali soluble resins.
Among the present invention, have the multipolymer (BI) of above-mentioned specific Mw or Mn through use, perhaps through with this multipolymer (BI) with have other alkali soluble resins and the usefulness of above-mentioned specific Mw or Mn, can obtain the good radiation-ray sensitive composition of development property.Can form pixel and black matrix thus with taper (sharp) pattern edge, when developing simultaneously on the substrate of unexposed portion be difficult to produce residue, scum, film residual etc. on the light shield layer.
Multipolymer (BI) distinguishes preferred 1～5, further preferred 1～4 with the Mw of other alkali soluble resins and the ratio (Mw/Mn) of Mn.
In the present invention, multipolymer (BI) can use separately or use mixing more than 2 kinds, and other alkali soluble resins too.
Among the present invention, with respect to 100 weight portions (A) colorant, preferred 10～1,000 weight portion of total consumption of alkali soluble resins, more preferably 20～500 weight portions.Total consumption of alkali soluble resins is lower than 10 weight portions; Have then that alkali-developable for example reduces, on the substrate of unexposed portion or produce scum, the residual possibility of film on the light shield layer; And if surpass 1; 000 weight portion then because colorant concentration reduces relatively, is difficult to reach the aim colour concentration of film sometimes.
The preferred 10-100 weight of the usage ratio % of the multipolymer in the alkali soluble resins (BI), more preferably 20-100 weight %.The usage ratio of multipolymer (BI) is lower than 10 weight %, then possibly damage effect of the present invention.
-(C) multi-functional monomer-
Multi-functional monomer of the present invention contains the monomer that has 2 or above polymerism unsaturated link in the molecule.
Multi-functional monomer for example has:
Two (methyl) acrylic ester of alkylene glycol such as monoethylene glycol, propylene glycol;
Two (methyl) acrylic ester of ployalkylene glycol such as polyglycol, polypropylene glycol;
3 yuan of glycerine, trimethylolpropane, pentaerythrite, dipentaerythritols etc. or above polyvalent alcohol gather (methyl) acrylic ester and their dicarboxylic acid modifier;
Oligomeric (methyl) acrylic ester of polyester, epoxy resin, urethane resin, alkyd resin, organic siliconresin, spirane resin etc.;
Two (methyl) acrylic ester of the polyisoprene of the gathering of two ends hydroxylation-1,3-butadiene, two ends hydroxylation, the two ends hydroxylation polymkeric substance such as polycaprolactone of two ends hydroxylation,
Tricresyl phosphate [2-(methyl) acryloxy ethyl] ester etc.
In these multi-functional monomers; Preferred 3 yuan or above polyvalent alcohol gather (methyl) acrylic ester, their dicarboxylic acid modifier; Specifically, compound shown in preferred trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylic ester, dipentaerythritol five acrylic ester, dipentaerythritol pentamethyl acrylic ester, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylic ester, the following formula (3),
Compound shown in the following formula (4) etc.,
Figure S07196681620070518D000202
Flatness wherein high from dyed layer intensity, that dyed layer is surperficial is good and be difficult to produce considerations such as scum, film be residual, preferred especially trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol acrylate on the substrate of unexposed portion and on the light shield layer.
These multi-functional monomers can use separately or use mixing more than 2 kinds.
With respect to 100 weight portions (B) alkali soluble resins, preferred 5～500 weight portions of the consumption of the multi-functional monomer among the present invention, more preferably 20～300 weight portions.Multi-functional monomer consumption is lower than the words of 5 weight portions; The intensity of dyed layer, surface smoothing property have the tendency of reduction; And if surpass 500 weight portions, for example have that alkali-developable reduces, perhaps producing residual etc. the tendency of scum, film on the substrate of unexposed portion or on the light shield layer easily.
Can also be among the present invention with multi-functional monomer and with simple function property monomer with 1 polymerism unsaturated link.
Above-mentioned simple function property monomer for example has the same compound of the compound enumerated in acid unsaturated compound, ester ring type unsaturated compound or other unsaturated compound in (B) and the alkali soluble resins or N-(methyl) acryloyl morpholine, N-vinyl pyrrolidone, N-vinyl-'epsilon '-hexanolactam; Also has commercially available commodity M-5600 (trade name, East Asia synthetic (strain) preparation) etc. in addition.
These simple function property monomers can use separately or use mixing more than 2 kinds.With respect to the total amount of multi-functional monomer or itself and simple function property monomer, the usage ratio of simple function property monomer is preferably 90 weight % or following, more preferably 50 weight % or following.If the usage ratio of simple function property monomer surpasses 90 weight %, then the intensity of the dyed layer of gained, surface smoothing property maybe be not enough.
With respect to 100 weight portions (B) alkali soluble resins, the total consumption of multi-functional monomer of the present invention and simple function property monomer is preferably the 5-500 weight portion, more preferably the 20-300 weight portion.This total consumption is lower than 5 weight portions, and then the intensity of dyed layer or surface smoothing property have and reduce tendency, and surpass 500 weight portions, and then for example alkali-developable reduces, or generations such as scum, film be residual are arranged on the substrate of unexposed portion or on the light shield layer.
-(D) Photoepolymerizationinitiater initiater-
Photoepolymerizationinitiater initiater of the present invention is the compound that produces spike through the exposure of rays such as visible light, ultraviolet ray, far ultraviolet, electron ray, X ray, and wherein said spike can cause above-mentioned (C) multi-functional monomer and the polymerization of the simple function property monomer of use according to circumstances.
Above-mentioned Photoepolymerizationinitiater initiater for example has acetophenone compounds, bisglyoxaline compounds, compound in triazine class, benzoin compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear quinones, xanthone compounds, diazonium compounds, O-acyl group oxime compound, salt compounds, imido sulphonate (compounds etc. of イ ミ De ス Le ホ Na-ト).These compounds are the compositions that produce living radical or live acid or living radical and live acid through exposure.
Among the present invention, Photoepolymerizationinitiater initiater can use separately or with two or more mixing, and Photoepolymerizationinitiater initiater of the present invention is preferably selected from least a of acetophenone compounds, bisglyoxaline compounds, compound in triazine class and O-acyl group oxime compound.
Among the present invention, measure 100 weight portions, the preferred 0.01-120 weight portion of the use amount of Photoepolymerizationinitiater initiater, more preferably 1-100 weight portion with respect to the total of (C) multi-functional monomer or itself and simple function property monomer.The use amount of Photoepolymerizationinitiater initiater is lower than 0.01 weight portion, and then deficiency is solidified in exposure, is difficult to obtain the color filter of dyed layer pattern alignment arrangements according to the rules, and the dyed layer that then forms above 120 weight portions comes off from substrate when developing easily.
Among the present invention in the preferred Photoepolymerizationinitiater initiater; The object lesson of acetophenone compounds has: 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; 2-dimethoxy-1; 2-diphenylethane-1-ketone, 1,2-octane diketone etc.
In these acetophenone 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-octane diketone etc.
Above-mentioned acetophenone compounds can use separately or with two or more mixing.
Among the present invention; When using acetophenone compounds as Photoepolymerizationinitiater initiater, measure 100 weight portions with respect to the total of (C) multi-functional monomer or itself and simple function property monomer, its use amount is preferably the 0.01-80 weight portion; More preferably 1-60 weight portion, further preferred 1-30 weight portion.The use amount of acetophenone compounds is lower than 0.01 weight portion then makes public and solidifies not enoughly, is difficult to obtain the dyed layer pattern color filter of series arrangement configuration according to the rules, surpasses the dyed layer that 80 weight portions then form and when developing, comes off from substrate easily.
As the concrete example of above-mentioned bisglyoxaline compounds, can enumerate as 22 '-two (2-chlorphenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-bisglyoxaline, 2; 2 '-two (2-bromophenyl)-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 compounds, be preferably 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 '-bisglyoxalines etc. are preferably 2 especially; 2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline.
The dissolubility of these bisglyoxaline compounds in solvent is excellent; Can not produce not impurity such as dissolved matter, precipitate; And exposure highly sensitive, through little energy can fully be cured reaction; Unexposed portion can not produce curing reaction simultaneously; Therefore filming after the exposure can be divided into the cured portion that is insoluble to developer solution clearly and developer solution is had the uncured portion of highly dissoluble, can form thus depression (ア Application ダ-カ ッ ト) not, the dyed layer pattern high meticulous color filter of series arrangement configuration according to the rules.
Above-mentioned bisglyoxaline compounds can use separately or with two or more mixing.
Among the present invention; When using the bisglyoxaline compounds, measure 100 weight portions, the preferred 0.01-40 weight portion of its use amount with respect to the total of (C) multi-functional monomer or itself and simple function property monomer as Photoepolymerizationinitiater initiater; More preferably 1-30 weight portion, further preferred 1-20 weight portion.The use amount of bisglyoxaline compounds be lower than 0.01 weight portion then make public solidify not enough; Be difficult to obtain the dyed layer pattern color filter of series arrangement configuration according to the rules, surpass the dyed layer that forms when 40 weight portions then develop and come off or cause the film on dyed layer surface coarse easily from substrate easily.
Among the present invention, when using the bisglyoxaline compounds, consider, be preferably and following hydrogen donor and usefulness from the angle that can further improve sensitivity as Photoepolymerizationinitiater initiater.
At this so-called " hydrogen donor " is the compound that hydrogen atom can be provided the free radical that produces from the bisglyoxaline compounds through exposure.
As hydrogen donor of the present invention, be preferably with undefined sulfur alcohol compound, aminated compounds etc.
Above-mentioned sulfur alcohol compound is to be parent nucleus with phenyl ring or heterocycle, have 1 or above, be preferably 1～3, the compound of further preferred 1～2 sulfydryl that directly combines with this parent nucleus (below, be called " thio-alcohol hydrogen donor ").
Above-mentioned aminated compounds be with phenyl ring or heterocycle as parent nucleus, have 1 or above, preferred 1～3, more preferably the compound of 1～2 amino that directly combines with this parent nucleus (below, be called " amine hydrogen donor ").
In addition, these hydrogen donors can have sulfydryl and amino simultaneously.
Below, these hydrogen donors are explained more specifically.
The thio-alcohol hydrogen donor can have 1 or above phenyl ring or heterocycle respectively, can also have phenyl ring and heterocycle concurrently.The time can form condensed ring when having 2 or above these rings.
In addition, when the thio-alcohol hydrogen donor had 2 or above sulfydryl, as long as residual at least 1 free sulfhydryl groups, remaining 1 or above sulfydryl can be replaced by alkyl, aralkyl, aryl.And, perhaps have the structural unit of 2 sulphur atoms with the form combination of disulfide bond as long as residual at least 1 free sulfhydryl groups can have 2 sulphur atoms across the structural unit that divalent organic groups such as alkylene base combine.
And the position of thio-alcohol hydrogen donor beyond sulfydryl can be by replacements such as carboxyl, alkoxy carbonyl, substituted alkoxy carbonyl, phenyloxycarbonyl, (replacement) phenyloxycarbonyl, cyanic acid.
As the concrete example of this thio-alcohol hydrogen donor, can enumerate like 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2 5-dimercapto-1,3,4-thiadiazoles, 2-sulfydryl-2,5-dimethyl aminopyridine etc.
In these thio-alcohol hydrogen donors, preferred 2-mercaptobenzothiazole, 2-mercaptobenzoxazole are preferably 2-mercaptobenzothiazole especially.
The amine hydrogen donor can have 1 or above phenyl ring or heterocycle respectively, can also have phenyl ring and heterocycle concurrently.The time can form condensed ring when having 2 or above these rings.
In addition, 1 of amine hydrogen donor or above amino can be replaced by alkyl or substituted alkyl, and amino part in addition also can be by replacements such as carboxyl, alkoxy carbonyl, (replacement) alkoxy carbonyl, phenyloxycarbonyl, (replacement) phenyloxycarbonyl, cyanic acid.
Concrete example as this amine hydrogen donor; Can enumerate as 4; 4 '-two (dimethylamino) benzophenone, 4,4 '-two (lignocaine) benzophenone, 4-lignocaine acetophenone, 4-dimethylamino propiophenone, ethyl-4-dimethylaminobenzoic acid ester, 4-dimethylaminobenzoic acid, 4-dimethylamino cyanobenzene etc.
In these amine hydrogen donors, preferred 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (lignocaine) benzophenone, preferred especially 4,4 '-two (lignocaine) benzophenone.
In addition, under the situation that adopts the Photoepolymerizationinitiater initiater beyond the bisglyoxaline compounds, the amine hydrogen donor also has the effect of sensitizer.
Among the present invention; Hydrogen donor can use separately also and can use mixing more than 2 kinds; When developing, be not easy to come off, consider aspect the intensity of dyed layer and sensitivity are also high, from the dyed layer that forms preferably with thio-alcohol hydrogen donor more than a kind and the combination of the amine hydrogen donor more than a kind use from substrate.
Concrete example as the preferred compositions of thio-alcohol hydrogen donor and amine hydrogen donor has 2-mercaptobenzothiazole/4,4 '-two (dimethylamino) benzophenone, 2-mercaptobenzothiazole/4; 4 '-two (lignocaine) benzophenone, 2-mercaptobenzoxazole/4; 4 '-two (dimethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (lignocaine) benzophenone etc., further preferred combination has 2-mercaptobenzothiazole/4; 4 '-two (lignocaine) benzophenone, 2-mercaptobenzoxazole/4; 4 '-two (lignocaine) benzophenone etc., preferred especially combination has 2-mercaptobenzothiazole/4,4 '-two (lignocaine) benzophenone.
In the combination of thio-alcohol hydrogen donor and amine hydrogen donor, the preferred 1:1～1:4 of weight ratio of thio-alcohol hydrogen donor and amine hydrogen donor is more preferably 1:1～1:3.
Among the present invention; With hydrogen donor and bisglyoxaline compounds and time spent, measure 100 weight portions, the preferred 0.01-40 weight portion of its use amount with respect to the total of (C) multi-functional monomer or itself and simple function property monomer; Further preferred 1-30 weight portion, preferred especially 1-20 weight portion.The use amount of hydrogen donor is lower than the then improved effect reduction of sensitivity of 0.01 weight portion, and the dyed layer that then forms above 40 weight portions comes off from substrate when developing easily.
As the concrete example of above-mentioned compound in triazine class, can enumerate as 2,4; 6-three (trichloromethyl)-s-triazine, 2-methyl-4; 6-two (trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-[2-(furans-2-yl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4; [2-(3 for 6-two (trichloromethyl)-s-triazine, 2-; The 4-Dimethoxyphenyl) vinyl]-4,6-two (trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-two (trichloromethyl)-s-triazine, 2-(4-ethoxybenzene vinyl)-4; 6-two (trichloromethyl)-s-triazine, 2-(4-n-butoxy phenyl)-4,6-two (trichloromethyl)-s-triazine etc. has the compound in triazine class of halogenated methyl.
In these compound in triazine class, preferred especially 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4,6-two (trichloromethyl)-s-triazine.
Above-mentioned compound in triazine class can use separately or with two or more mixing.
Among the present invention; When using compound in triazine class as Photoepolymerizationinitiater initiater, measure 100 weight portions with respect to the total of (C) multi-functional monomer or itself and simple function property monomer, its use amount is preferably the 0.01-40 weight portion; Further preferred 1-30 weight portion, preferred especially 1-20 weight portion.Then making public when the use amount of compound in triazine class is lower than 0.01 weight portion, it is not enough to solidify, and is difficult to obtain the dyed layer pattern color filter of sequence configuration according to the rules, and the dyed layer that then forms above 40 weight portions comes off from substrate when developing easily.
The object lesson of above-mentioned O-acyl group oxime compound has: 1-[4-(thiophenyl) phenyl]-heptane-1; 2-diketone 2-(O-benzoyl oxime), 1-[4-(thiophenyl) phenyl]-octane-1; 2-diketone 2-(O-benzoyl oxime), 1-[4-(benzoyl) phenyl]-octane-1,2-diketone 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-ethyl ketone 1-(O-acetyl oxime), 1-[9-ethyl-6-(3-methyl benzoyl)-9H-carbazole-3-yl]-ethyl ketone 1-(O-acetyl oxime), 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl]-ethyl ketone 1-(O-acetyl oxime) etc.
In these O-acyl group oxime compounds, preferred especially 1-[4-(thiophenyl) phenyl]-heptane-1,2-diketone 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-ethyl ketone 1-(O-acetyl oxime) etc.
Above-mentioned O-acyl group oxime compound can use separately or with two or more mixing.
Among the present invention; When using O-acyl group oxime compound, measure 100 weight portions, the preferred 0.01-40 weight portion of its use amount with respect to the total of (C) multi-functional monomer or itself and simple function property monomer as Photoepolymerizationinitiater initiater; Further preferred 1-30 weight portion, preferred especially 1-20 weight portion.The use amount of O-acyl group oxime compound is lower than 0.01 weight portion then makes public and solidifies not enoughly, is difficult to obtain the dyed layer pattern color filter of sequence configuration according to the rules, surpasses the dyed layer that 40 weight portions then form and when developing, comes off from substrate easily.
Above-mentioned salt compounds for example has diaryl group iodized salt, triarylsulfonium salt, Er Fang Ji phosphonium salt etc.
The object lesson of above-mentioned diaryl group iodized salt has: tetrafluoro boric acid diphenyl iodine; Hexafluoro phosphonic acids diphenyl iodine; Hexafluoroarsenate diphenyl iodine; TFMS diphenyl iodine; Trifluoroacetic acid diphenyl iodine; P-toluenesulfonic acid diphenyl iodine; Tetrafluoro boric acid 4-methoxyphenyl phenyl-iodide; Hexafluoro phosphonic acids 4-methoxyphenyl phenyl-iodide; Hexafluoroarsenate 4-methoxyphenyl phenyl-iodide; TFMS 4-methoxyphenyl phenyl-iodide; Trifluoroacetic acid 4-methoxyphenyl phenyl-iodide; P-toluenesulfonic acid 4-methoxyphenyl phenyl-iodide; Two (4-tert-butyl-phenyl) iodine of tetrafluoro boric acid; Two (4-tert-butyl-phenyl) iodine of hexafluoroarsenate; Two (4-tert-butyl-phenyl) iodine of TFMS; Two (4-tert-butyl-phenyl) iodine of trifluoroacetic acid; Two (4-tert-butyl-phenyl) iodine of p-toluenesulfonic acid etc.
The object lesson of above-mentioned triarylsulfonium salt has: the tetrafluoro boric acid triphenylsulfonium; Hexafluoro phosphonic acids triphenylsulfonium; The hexafluoroarsenate triphenylsulfonium; The TFMS triphenylsulfonium; The trifluoroacetic acid triphenylsulfonium; The p-toluenesulfonic acid triphenylsulfonium; Tetrafluoro boric acid 4-methoxyphenyl diphenyl sulfonium; Hexafluoro phosphonic acids 4-methoxyphenyl diphenyl sulfonium; Hexafluoroarsenate 4-methoxyphenyl diphenyl sulfonium; TFMS 4-methoxyphenyl diphenyl sulfonium; Trifluoroacetic acid 4-methoxyphenyl diphenyl sulfonium; P-toluenesulfonic acid 4-methoxyphenyl diphenyl sulfonium; Tetrafluoro boric acid 4-thiophenyl phenyl diphenyl sulfonium; Hexafluoro phosphonic acids 4-thiophenyl phenyl diphenyl sulfonium; Hexafluoroarsenate 4-thiophenyl phenyl diphenyl sulfonium; TFMS 4-thiophenyl phenyl diphenyl sulfonium; Trifluoroacetic acid 4-thiophenyl phenyl diphenyl sulfonium; P-toluenesulfonic acid 4-thiophenyl phenyl diphenyl sulfonium etc.
The object lesson of above-mentioned Er Fang Ji phosphonium salt has: hexafluoro phosphonic acids (1-6-η-cumene) (η-cyclopentadienyl group) iron etc.
In the above-mentioned salt compounds, preferred especially hexafluoro phosphonic acids diphenyl iodine, TFMS triphenylsulfonium etc.Above-mentioned salt compounds can use separately or with two or more mixing.
Among the present invention; When using salt compounds, measure 100 weight portions, the preferred 0.01-40 weight portion of its use amount with respect to the total of (C) multi-functional monomer or itself and simple function property monomer as Photoepolymerizationinitiater initiater; Further preferred 1-30 weight portion, preferred especially 1-20 weight portion.The use amount of salt compounds is lower than 0.01 weight portion then makes public and solidifies not enoughly, is difficult to obtain the dyed layer pattern color filter of sequence configuration according to the rules, surpasses the dyed layer that 40 weight portions then form and when developing, comes off from substrate easily.
-adjuvant-
The radiation-ray sensitive composition that is used to form dyed layer of the present invention can contain various adjuvants as required.
Above-mentioned adjuvant for example has organic acid or organic amino compounds (except the above-mentioned hydrogen donor), hardening agent, auxiliary curing agent etc.
Above-mentioned organic acid and organic amino compounds be further improve radiation-ray sensitive composition in alkaline developer dissolubility and show further suppress to develop after the composition of the residual effect of dissolved matter not.
Have the aliphatic carboxylic acid of or above carboxyl in the preferred molecule of above-mentioned organic acid or contain the carboxylic acid of phenyl.
Above-mentioned aliphatic carboxylic acid for example has:
Monocarboxylic acids such as formic acid, acetate, propionic acid, butyric acid, valeric acid, trimethylace tonitric, caproic acid, diethacetic acid, enanthic acid, capric acid;
Dicarboxylic acids 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 cyclohexanedimethanodibasic, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Tricarboxylic acids such as equal propanetricarboxylic acid, aconitic acid, camphoronic acid etc.
The above-mentioned carboxylic acid that contains phenyl for example has the direct compound that combines with phenyl of carboxyl, the carboxylic acid that carboxyl combines with phenyl via carbochain etc.
The carboxylic acid that contains phenyl for example has:
Benzoic acid, toluic acid, cumic acid, 2,3-mesitylenic acid, 3, one dollar aromatic carboxylic acids such as 5-mesitylenic acid;
Aromatic dicarboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid (TPA);
Ternary or above aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, inclined to one side benzene tetracarboxylic acid, Pyromellitic Acid, or
Phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, inferior cinnamic acid, coumaric acid (Network マ Le
Figure S07196681620070518D00027183942QIETU
), umbellic acid etc.
In these organic acids; From alkali dissolution property, after state dissolubility the solvent, prevent on the substrate at unexposed portion or light shield layer forms scum or the residual equal angles of film is considered; Aliphatic carboxylic acid aliphatic dicarboxylic acid, preferred especially malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid etc.In addition, contain the preferred aromatic dicarboxylic acid of carboxylic acid of phenyl, preferred especially phthalic acid.
Above-mentioned organic acid can use separately or with two or more mixing.
All with respect to radiation-ray sensitive composition, the preferred 15 weight % or following of organic acid use amount, more preferably 10 weight % or following.The organic acid use amount surpasses 15 weight %, and the stickiness of then formed dyed layer and substrate has the tendency of reduction.
Have the aliphatic amine of or above amino in the preferred molecule of above-mentioned organic amino compounds or contain the amine of phenyl.
Above-mentioned aliphatic amine for example has:
One (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 base amine, dodecyl 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, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-iso-butylmanice, di-sec-butylamine, two tert-butylamines, two n-amylamines, two n-hexylamines, methyl cyclohexylamine, ethyl cyclohexylamine, dicyclohexyl amine;
Three (ring) alkyl amines such as dimethyl amine, methyl-diethyl-amine, triethylamine, dimethyl n propylamine, diethyl n-propylamine, methyl di-n-propylamine, ethyl di-n-propylamine, Tri-n-Propylamine, tri-isopropyl amine, tri-n-butylamine, triisobutylamine, tri sec-butylamine, three tert-butylamines, tri-n-amyl amine, three n-hexylamines, dimethyl cyclohexyl amine, diethyl cyclohexylamine, methyl bicyclic hexylamine, ethyl dicyclohexyl amine, tricyclohexyltin amine;
The 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 1-amino-2-propyl alcohol, 4-amino-1-butanols, 5-amino-1-amylalcohol, 6-amino-1-hexanol, 4-amino-one (ring) alkanolamines such as 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-cyclohexane diol, 4-amino-1; 3-cyclohexane diol, 3-dimethylamino-1,2-propylene glycol, 3-diethylamino-1,2-propylene glycol, 2-dimethylamino-1; 3-propane diol, 2-diethylamino-1, amino (ring) alkane glycol such as 3-propane diol;
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, 3-aminobutyric, 4-aminobutyric, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaprolc acid, 1-amino-cyclopropane formic acid, 1-aminocyclohexane formic acid, 4-aminocyclohexane formic acid etc.
The above-mentioned amine that contains phenyl for example has: the compound that the amino compound that directly combines with phenyl, amino combine with phenyl via carbochain etc.
The amine that contains phenyl for example has:
Aniline, 2-aminotoluene, 3-methylaniline, 4-methylaniline, 4-MEA, 4-n-pro-pyl aniline, 4-isopropyl aniline, 4-n-butyl aniline, 4-tert-butyl group aniline, 1-naphthylamine, 2-naphthylamine, 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 benzyl alcohol, 4-diethylamino benzyl alcohol;
Amino phenols such as 2-amino-phenol, 3-amino-phenol, 4-amino-phenol, 4-dimethylamino phenol, 4-diethylamino phenol etc.
In these organic amino compounds; From after state dissolubility the solvent, prevent on the substrate of unexposed portion or angle that light shield layer produces scum or residual film etc. is considered; Aliphatic amine preferred one (ring) alkanolamine, amino (ring) alkane glycol, preferred especially 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-is amino-1,2-propylene glycol, 2-amino-1; Ammediol, 4-amino-1,2-butylene glycol etc.The preferred aminophenols of amine that contains phenyl, preferred especially 2-amino-phenol, 3-amino-phenol, 4-amino-phenol etc.
Above-mentioned hardening agent be with (B) alkali soluble resins in the reaction of carboxylic acid and/or oxetanes ring, make should the curing of (B) alkali soluble resins composition.
Above-mentioned hardening agent for example has epoxy compound, oxetane compound etc.
The preferred multi-functional epoxy compound of above-mentioned epoxy compound, its object lesson has aromatic species 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; Alicyclic based epoxy resin, hetero ring type epoxy resin, glycidyl esters resin, glycidyl amine resins, other epoxy resin of epoxidation wet goods; The brominated derivative of above-mentioned epoxy resin; And epoxide of (being total to) polymkeric substance of the epoxide of (being total to) polymkeric substance of butadiene, isoprene, (being total to) polymkeric substance that contains the unsaturated compound of glycidyl, triglycidyl group isocyanuric acid ester etc.
Above-mentioned epoxy compound preferably contains the unsaturated compound of epoxy radicals; Its object lesson has (methyl) glycidyl acrylate, (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.
The preferred multifunctional oxetane compound of above-mentioned oxetane compound; Its object lesson has: carbonic acid dioxygen heterocycle butyl ester, hexane diacid dioxygen heterocycle butyl ester, terephthalic acid (TPA) dioxygen heterocycle butyl ester, terephthaldehyde's base dioctyl phthalate dioxygen heterocycle butyl ester, 1; Low molecular compounds such as 4-cyclohexane cyclohexanedimethanodibasic dioxygen heterocycle butyl ester, or the oxetanes ether compound of novolac resin, have (being total to) polymkeric substance macromolecular compounds such as (except the multipolymers (BI)) of the unsaturated compound of oxetanes ring structure.Multipolymer (BI) has the oxetanes ring structure, belongs to the category as the oxetane compound of hardening agent.
Oxetane compound preferably has the compound of oxetanes ring structure and unsaturated double-bond, and its object lesson has above-mentioned oxetanes unsaturated compounds.
These hardening agent can use separately or with two or more mixing.
With respect to all solids composition of radiation-ray sensitive composition, the preferred 30 weight % or following of the use amount of hardening agent, more preferably 20 weight % or following.The use amount of hardening agent surpasses 30 weight %, and then the storage stability of gained radiation-ray sensitive composition reduces.
Above-mentioned auxiliary curing agent is the composition through making epoxy radicals that above-mentioned hardening agent has and/or the open loop of oxetanes ring promote the curing reaction that this hardening agent causes.
Said auxiliary curing agent for example has polybasic carboxylic acid, polybasic acid anhydride, amino-compound, hot acid propellant etc.
The object lesson of above-mentioned polybasic carboxylic acid have with above-mentioned organic acid in have the identical example of compound of two or above carboxyl, the object lesson of above-mentioned amino-compound has the example identical with above-mentioned amino-compound.
The object lesson of above-mentioned polybasic acid anhydride has: phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, 3,3 ', 4, aromatic polycarboxylic acid acid anhydrides such as 4 '-benzophenone tetracarboxylic acid dianhydride; Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, propanetricarboxylic acid acid anhydride, maleic anhydride, 1,2,3, aliphatic multi-anhydrides such as 4-ethylene-dimalonic acid dianhydride; Hexahydrophthalic anhydride, 3,4-dimethyl tetrahydro phthalic anhydride, 1,2,4-cyclopentane front three acid anhydrides, 1,2,4-cyclohexane front three acid anhydrides, cyclopentane tetracarboxylic acid dianhydride, 1,2,4, alicyclic polybasic acid anhydrides such as 5-cyclohexane tetracarboxylic acid dianhydride; Two trimellitic anhydride glycol esters, three (trimellitic anhydride) glyceride etc. contain the carboxylic acid anhydrides of ester group, the epoxy curing agent of in addition selling with ア デ カ Ha-De Na-EH-700 (rising sun electrochemical industry (strain) preparation), リ カ シ ッ De HH (new Japanese physics and chemistry (strain) preparation), MH-700 trade names such as (new Japanese physics and chemistry (strain) preparations) in addition etc.
Above-mentioned hot acid propellant for example has sulfonium salt (except the triarylsulfonium salt of being put down in writing in above-mentioned (D) Photoepolymerizationinitiater initiater), benzothiazolium salt, ammonium salt 、 phosphonium salt, sulfonate compound, sulfimine compound, double n-formyl sarcolysine hydride compounds etc., wherein preferred sulfonium salt, benzothiazolium salt, sulfonate compound, sulfimine compound, double n-formyl sarcolysine hydride compounds etc.
The object lesson of above-mentioned sulfonium salt has:
Hexafluoro-antimonic acid 4-acetylphenyl dimethyl sulfonium, hexafluoroarsenate 4-acetoxyl group phenyl dimethyl sulfonium, hexafluoro-antimonic acid dimethyl-4-(benzyloxycarbonyloxy base) phenyl sulfonium, hexafluoro-antimonic acid dimethyl-4-(benzoyl oxygen base) phenyl sulfonium, hexafluoroarsenate dimethyl-4-(benzoyl oxygen base) phenyl sulfonium, hexafluoro-antimonic acid-dimethyl-alkyl sulfonium salts such as 3-chloro-4-acetoxyl group phenyl sulfonium;
Hexafluoro-antimonic acid benzyl-4-hydroxy phenyl methyl sulfonium, hexafluorophosphoric acid benzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl benzyl methyl sulfonium, hexafluoro-antimonic acid benzyl-4-methoxybenzene ylmethyl sulfonium, hexafluoro-antimonic acid benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium, hexafluoroarsenate benzyl-3-chloro-4-hydroxy phenyl methyl sulfonium, hexafluorophosphoric acid 4-methoxy-benzyl-benzyl sulfonium salts such as 4-hydroxy phenyl methyl sulfonium;
Hexafluoro-antimonic acid dibenzyl-4-hydroxy phenyl sulfonium, hexafluorophosphoric acid dibenzyl-4-hydroxy phenyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl dibenzyl sulfonium, hexafluoro-antimonic acid dibenzyl-4-methoxyphenyl sulfonium, hexafluoroarsenate dibenzyl-3-chloro-4-hydroxy phenyl sulfonium, hexafluoro-antimonic acid dibenzyl-3-methyl-4-hydroxyl-5-tert-butyl-phenyl sulfonium, hexafluorophosphoric acid benzyl-4-methoxy-benzyl-dibenzyl sulfonium salts such as 4-hydroxy phenyl sulfonium;
Hexafluoro-antimonic acid p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid to nitrobenzyl-4-hydroxy phenyl methyl sulfonium, hexafluorophosphoric acid p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid to nitrobenzyl-3-methyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid 3,5-dichloro benzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid o-chlorobenzyl-substituted benzyl sulfonium salts such as 3-chloro-4-hydroxy phenyl methyl sulfonium etc.
The object lesson of above-mentioned benzothiazolium salt has: benzyl benzothiazolium salts such as hexafluoro-antimonic acid 3-benzyl benzothiazole, hexafluorophosphoric acid 3-benzyl benzothiazole, tetrafluoro boric acid 3-benzyl benzothiazole, hexafluoro-antimonic acid 3-(to methoxy-benzyl) benzothiazole, hexafluoro-antimonic acid 3-benzyl-2-methyl mercapto benzo thiazole, hexafluoro-antimonic acid 3-benzyl-5-chloro benzothiazole etc.
The object lesson of above-mentioned sulfonate compound has: benzoin p-toluenesulfonic esters, alpha-hydroxymethyl benzoin p-toluenesulfonic esters, alpha-hydroxymethyl benzoin normal octane sulphonic acid ester, pyrogallol three (triflate), pyrogallol three (nine fluorine normal butane sulphonic acid esters), pyrogallol three (methanesulfonates), nitrobenzyl-9,10-diethoxy anthracene-2-sulphonic acid ester etc.
The object lesson of above-mentioned sulfimine compound has: N-(trifluoro-methanesulfonyl oxy) succinimide, N-(trifluoro-methanesulfonyl oxy) dicyclo [2.2.1] heptan-5-alkene-2; 3-dicarboximide, N-(10-camphor sulfonyloxy) succinimide, N-(10-camphor sulfonyloxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, N-[(5-methyl-5 carboxyl methane dicyclo [2.2.1] heptan-2-yl) sulfonyloxy] succinimide etc.
The object lesson of above-mentioned double n-formyl sarcolysine alkyl compound has: two (cyclohexane sulfonyl) double n-formyl sarcolysine alkane, two (tert-butyl group sulfonyl) double n-formyl sarcolysine alkane, two (1,4-dioxo spiro [4.5]-decane-7-sulfonyl) double n-formyl sarcolysine alkane etc.
In these hot acid propellants; Preferred especially hexafluoroarsenate 4-acetoxyl group phenyl dimethyl sulfonium, hexafluoro-antimonic acid benzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl benzyl methyl sulfonium, hexafluoro-antimonic acid dibenzyl-4-hydroxy phenyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl benzyl sulfonium, hexafluoro-antimonic acid 3-benzyl benzothiazole, N-(trifluoro-methanesulfonyl oxy) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide etc.
Above-mentioned auxiliary curing agent can use separately or with two or more mixing.
With respect to all solids composition of radiation-ray sensitive composition, the preferred 15 weight % or following of the use amount of auxiliary curing agent, more preferably 10 weight % or following.The use amount of auxiliary curing agent surpasses 15 weight %, and then the storage stability of gained radiation-ray sensitive composition reduces, and the dyed layer of formation comes off from substrate when developing easily.
Adjuvant beyond above-mentioned for example has:
Blue pigment derivant such as ketone phthalocyanine derivates or yellow uitramarine derivant etc. disperse auxiliary agent;
Filling agent such as glass, aluminium oxide;
Polyvinyl alcohol (PVA), polyglycol one alkyl ether, gather macromolecular compounds such as (fluoroalkyl acrylic ester);
Surfactants such as nonionic system, kation system, negative ion system;
Driving fit promoter such as vinyltrimethoxy silane, VTES, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane;
2, anti-oxidants such as 2-thiobis (4-methyl-6-tert butyl phenol), 2,6 di t butyl phenol;
Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorinated benzotriazole, alkoxy benzophenone;
Anti-coagulants such as sodium polyacrylate;
1,1 '-azo two (cyclohexane-1-nitrile), 2-phenylazo-4-methoxyl-2, thermal free radical initiators such as 4-methyl pentane nitrile etc.
Solvent
The radiation-ray sensitive composition that the present invention is used to form dyed layer be with above-mentioned (A)-(D) composition as must composition, can contain above-mentioned additive component as required, preferably cooperate solvent to process fluid composition.
Above-mentioned solvent be so long as can disperse or dissolve (A)-(D) composition or the additive component that constitutes radiation-ray sensitive composition, and not with these compositions reactions, the volatility with appropriateness get final product, can suitably select use.
Above-mentioned solvent for example has:
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; 3 third glycol monomethyl ether; (gathering) alkylene glycol monoalky lethers such as 3 third glycol list ethylethers;
(gathering) alkylene glycol monoalky lether acetic acid esters such as monoethylene 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-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; Other esters such as 2-ketobutyric acid ethyl ester;
Aromatic hydrocarbon such as toluene, xylene;
N, acid amides such as dinethylformamide, DMAC N,N, N-Methyl pyrrolidone or lactams etc.
In these solvents; Consider preferred propylene glycol monomethyl ether, monoethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, diethylene glycol dimethyl ether, diglycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, propionic acid 3-methyl-3-methoxyl butyl ester, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate etc. from dissolubility, pigment-dispersing, coating equal angles.
Above-mentioned solvent can use separately or use mixing more than 2 kinds.
Can also be with above-mentioned solvent and with 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 special to be limited; Consider from viewpoints such as the coating of the radiation-ray sensitive composition that obtains, stability; Preferably make in the said composition to reach 5～50 weight %, especially preferably reach the amount of 10～40 weight % except that each composition total concentration of desolvating.
Color filter
Color filter of the present invention has the dyed layer that uses radiation-ray sensitive composition of the present invention to form.
Below describe for the method for the dyed layer that forms color filter of the present invention.
At first, as required, on the surface of substrate, form light shield layer; In order to divide the part that forms pixel, coating for example is dispersed with the fluid composition of the radiation-ray sensitive composition of red pigment on this substrate, carries out preliminary drying then; Evaporation removes and desolvates, and formation is filmed.
Then, to this exposure of filming, use alkaline developer to develop via photomask, the unexposed portion of filming is removed in dissolving, forms the picture element matrix of red pattern of pixels sequence configuration according to the rules then through the back baking.
Use the fluid composition of each radiation-ray sensitive composition that is dispersed with green or blue pigment then; With above-mentioned coating, preliminary drying, exposure, development and the back baking of likewise carrying out each fluid composition; On same substrate, form green pixel matrix and blue pixel matrix successively, obtain redness, green and blue trichromatic picture element matrix and be disposed at the color filter on the substrate.Among the present invention, the order that forms each color pixel is not limited to above-mentioned.
In addition, black matrix for example can use the fluid composition of the radiation-ray sensitive composition that is dispersed with black pigment, likewise forms with 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, as required, can also implement to utilize suitable pre-treatments such as chemical reagent processing that silane coupling agent etc. carries out, plasma treatment, ion plating, sputter, gas-phase reaction method, vacuum evaporation to these substrates.
When coating the fluid composition of radiation-ray sensitive composition on the substrate, for example 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, slit shower nozzle rubbing method.
The thickness of coating calculates according to dried thickness, preferred 0.1-10 μ m, more preferably 0.2-8.0 μ m, especially preferably 0.2-6.0 μ m.
The radioactive ray that use during as formation pixel and/or black matrix can be enumerated for example visible light, ultraviolet ray, far ultraviolet, electron ray, X ray etc.Optimal wavelength is at the radioactive ray of 190～450nm scope.
The exposure of radioactive ray is preferably 10～10,000J/m 2About.
As above-mentioned alkaline developer, preference such as sodium carbonate, NaOH, potassium hydroxide, tetramethyl ammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecylene, 1, the 5-diazabicyclo-WS such as [4.3.0]-5-nonene.
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, preferably, washes in alkali after developing.
Can adopt spray development method, sputter development method, immersion development method, stirring (liquid is contained り) development method etc. as developing method.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.
An embodiment 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 stated; On the thin film diode substrate matrix, form pixel and/or black matrix, thereby can prepare color liquid crystal display device with excellent especially characteristic.
The radiation-ray sensitive composition that is used to form dyed layer of the present invention contains above-mentioned (A)-(D) composition as must composition, below specifically provides special preferred compositions, like following (1)-(5).
(1) (B) alkali soluble resins contains the radiation-ray sensitive composition that is used to form dyed layer of multipolymer (BII).
(2) multipolymer (BII) is the radiation-ray sensitive composition that is used to form dyed layer that is selected from least a above-mentioned (1) of multipolymer (BII-1)-(BII-18).
(3) radiation-ray sensitive composition that is used to form dyed layer of above-mentioned (1) or (2), wherein, (C) multi-functional monomer is selected from least a of trimethylolpropane triacrylate, pentaerythritol triacrylate and six acrylic acid dipentaerythritol ester.
(4) radiation-ray sensitive composition that is used to form dyed layer of above-mentioned (1), (2) or (3), wherein, (D) Photoepolymerizationinitiater initiater is selected from least a of acetophenone compounds, bisglyoxaline compounds and compound in triazine class.
(5) radiation-ray sensitive composition that is used to form dyed layer of above-mentioned (1), (2), (3) or (4), wherein, (A) colorant contains organic pigment or carbon black.
In addition, the preferred color filter of the present invention is:
(6) possess pixel and/or the black matrix that the radiation-ray sensitive composition that is used to form dyed layer by above-mentioned (1), (2), (3), (4) or (5) forms.
In addition, the preferred color liquid crystal display device of the present invention is:
(7) possesses the color filter of above-mentioned (6).
The color liquid crystal display device that the present invention is more preferably is:
(8) possesses the color filter of above-mentioned (6) on the thin film transistor base plate array.
Specify as above; In the radiation-ray sensitive composition that is used to form dyed layer of the present invention; The storage stability of alkali soluble resins itself is good; Particularly the storage stability of dispersible pigment dispersion and fluid composition is also excellent under the high pigment levels, can not take place also under low exposure that residual film ratio is low, pattern edge is damaged or depression, can form solvent resistance, with the excellent pattern of pixels and the black matrix pattern such as stickiness of substrate.
Therefore, the radiation-ray sensitive composition utmost point of the present invention is suitable for using in the manufacturing of color filter as the various color filters of representative with the color liquid crystal display device in the electronics industry.
Embodiment
Below provide embodiment, further specify the present invention.The present invention does not receive the qualification of following embodiment.
Synthesizing of alkali soluble resins
Synthetic example 1
In the flask that possesses condenser pipe and stirrer, add 3 weight portions 2; 2 '-azoisobutyronitrile, 200 weight portion propylene glycol methyl ether acetates then add 15 weight portion methacrylic acids, 60 weight portion methacrylic acid benzyl esters, 15 weight portion 3-(methacryloxy methyl)-3-ethyl oxetanes, 10 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base ester and 3 weight portions are as the α-Jia Jibenyixierjuwu of molecular weight regulator, with the nitrogen displacement, light and slow then stirring is warming up to 80 ℃ with reaction solution, and this temperature is kept carrying out polymerization in 5 hours, obtains the solution of multipolymer (BII).With this multipolymer (BII) as " alkali soluble resins (B-1) ".
Synthetic example 2
In the flask that possesses condenser pipe and stirrer, add 3 weight portions 2; 2 '-azoisobutyronitrile, 200 weight portion propylene glycol methyl ether acetates then add 15 weight portion methacrylic acids, 20 weight portion methacrylic acid benzyl esters, 30 weight portion 3-(methacryloxy methyl)-3-ethyl oxetanes, 10 parts by weight of styrene, 25 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base ester and 3 weight portions are as the α-Jia Jibenyixierjuwu of molecular weight regulator, with the nitrogen displacement, light and slow then stirring is warming up to 80 ℃ with reaction solution, and this temperature is kept carrying out polymerization in 5 hours, obtains the solution of multipolymer (BII).With this multipolymer (BII) as " alkali soluble resins (B-2) ".
Synthetic example 3
In the flask that possesses condenser pipe and stirrer, add 3 weight portions 2; 2 '-azoisobutyronitrile, 200 weight portion propylene glycol methyl ether acetates then add 15 weight portion methacrylic acids, 20 weight portion N-phenylmaleimides, 30 weight portion 3-(methacryloxy methyl)-3-ethyl oxetanes, 10 parts by weight of styrene, 25 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base ester and 3 weight portions are as the α-Jia Jibenyixierjuwu of molecular weight regulator, with the nitrogen displacement, light and slow then stirring is warming up to 80 ℃ with reaction solution, and this temperature is kept carrying out polymerization in 5 hours, obtains the solution of multipolymer (BII).With this multipolymer (BII) as " alkali soluble resins (B-3) ".
Synthetic example 4
In the flask that possesses condenser pipe and stirrer, add 3 weight portions 2; 2 '-azoisobutyronitrile, 200 weight portion propylene glycol methyl ether acetates then add 15 weight portion methacrylic acids, 20 weight portion N-phenylmaleimides, 30 weight portion 3-(methacryloxy methyl) oxetanes, 10 parts by weight of styrene, 25 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base ester and 3 weight portions are as the α-Jia Jibenyixierjuwu of molecular weight regulator, with the nitrogen displacement, light and slow then stirring is warming up to 80 ℃ with reaction solution, and this temperature is kept carrying out polymerization in 5 hours, obtains the solution of multipolymer (BII).With this multipolymer (BII) as " alkali soluble resins (B-4) ".
Relatively more synthetic example 1
In the flask that possesses condenser pipe and stirrer, add 3 weight portions 2; 2 '-azoisobutyronitrile, 200 weight portion propylene glycol methyl ether acetates; Then add 15 weight portion methacrylic acids, 70 weight portion benzyl methacrylates, 15 weight portion 3-(methacryloxy methyl)-3-ethyl oxetanes and 3 weight portions α-Jia Jibenyixierjuwu as molecular weight regulator; With the nitrogen displacement, light and slow then stirring is warming up to 80 ℃ with reaction solution; This temperature is kept carrying out polymerization in 5 hours, obtain the solution of alkali soluble resins.With this alkali soluble resins as " alkali soluble resins (B-5) ".
Relatively more synthetic example 2
In the flask that possesses condenser pipe and stirrer, add 3 weight portions 2; 2 '-azoisobutyronitrile, 200 weight portion propylene glycol methyl ether acetates; Then add 15 weight portion methacrylic acids, 25 weight portion benzyl methacrylates, 30 weight portion 3-(methacryloxy methyl)-3-ethyl oxetanes, 10 parts by weight of styrene, 20 weight portion N-phenylmaleimides and 3 weight portions α-Jia Jibenyixierjuwu as molecular weight regulator; With the nitrogen displacement, light and slow then stirring is warming up to 80 ℃ with reaction solution; This temperature is kept carrying out polymerization in 5 hours, obtain the solution of alkali soluble resins.With this alkali soluble resins as " alkali soluble resins (B-6) ".
Relatively more synthetic example 3
In the flask that possesses condenser pipe and stirrer, add 3 weight portions 2; 2 '-azoisobutyronitrile, 200 weight portion propylene glycol methyl ether acetates; Then add 15 weight portion methacrylic acids, 70 weight portion benzyl methacrylates, 15 weight portion 3-(methacryloxy methyl) oxetanes and 3 weight portions α-Jia Jibenyixierjuwu as molecular weight regulator; With the nitrogen displacement, light and slow then stirring is warming up to 80 ℃ with reaction solution; This temperature is kept carrying out polymerization in 5 hours, obtain the solution of alkali soluble resins.With this alkali soluble resins as " alkali soluble resins (B-7) ".
The storage stability evaluation of alkali soluble resins
The solution of each alkali soluble resins that obtains in above-mentioned synthetic example or the relatively synthetic example is packed in the vial; In 40 ℃ constant temperature and humidity cabinet, preserved for three weeks; The ELD type viscosity apparatus (25 ℃) that uses Tokyo gauge (strain) to make is measured the solution viscosity of preserving front and back, calculates viscosity rate of change (viscosity before preserve the viscosity after the preservation * 100/) and evaluation.Evaluation result is as shown in table 1.
Table 1
Alkali soluble resins Storage stability (viscosity rate of change, %)
B-1 102
B-2 100
B-3 100
B-4 101
B-5 169
B-6 175
B-7 239
The preparation of dispersible pigment dispersion
Preparation example 1
20 weight portions are handled preparation dispersible pigment dispersion (R1) with ball mill as the propylene glycol monomethyl ether of solvent as BYK-2001 (being converted into solid constituent), 75 weight portions of spreading agent as C.I. paratonere 254/C.I. paratonere 177=80/20 (weight ratio) potpourri, 5 weight portions of (A) colorant.
Preparation example 2
Use 5 weight portion ソ Le ス パ-ス, 24000 (being converted into solid constituent) to replace BYK-2001, in addition likewise prepare dispersible pigment dispersion (R2) with preparation example 1 as spreading agent.
Preparation example 3
20 weight portions are handled preparation dispersible pigment dispersion (G1) with ball mill as the propylene glycol monomethyl ether of solvent as BYK-2001 (being converted into solid constituent), 75 weight portions of spreading agent as C.I. pigment green 36/C.I. pigment yellow 150=50/50 (weight ratio) potpourri, 5 weight portions of (A) colorant.
Preparation example 4
Use 5 weight portion ソ Le ス パ-ス, 24000 (being converted into solid constituent) to replace BYK-2001, in addition likewise prepare dispersible pigment dispersion (G2) with preparation example 3 as spreading agent.
Preparation example 5
With the C.I. pigment blue 15 of 20 weight portions as (A) colorant: 6/C.I. pigment Violet 23=90/10 (weight ratio) potpourri, 5 weight portions are handled with ball mill as the propylene glycol monomethyl ether of solvent as BYK-2001 (being converted into solid constituent), 75 weight portions of spreading agent, preparation dispersible pigment dispersion (B1).
Preparation example 6
Use 5 weight portion ソ Le ス パ-ス, 24000 (being converted into solid constituent) to replace BYK-2001, in addition likewise prepare dispersible pigment dispersion (B2) with preparation example 5 as spreading agent.
Embodiment 1
With 100 weight portions as the dispersible pigment dispersion (R1) of (A) colorant, 15 weight portions (being converted into solid constituent) as the alkali soluble resins (B-1) of (B) alkali soluble resins, 15 weight portions as the six acrylic acid dipentaerythritol ester of (C) multi-functional monomer, 5 weight portions as 2-methyl isophthalic acid-[4-(methyl mercapto) the phenyl]-2-morpholino propane-1-ketone of (D) Photoepolymerizationinitiater initiater, mix as the propylene glycol monomethyl ether of solvent; Making solid component concentration is 25 weight %, preparation fluid composition (R1-1).
Form pattern for fluid composition (R1-1) according to following order, estimate.Evaluation result is as shown in table 8.
The formation of pattern
On glass baseplate surface,, under 90 ℃, carry out 4 minutes preliminary drying then, form filming of thickness 1.3 μ m with spin coating appearance coating fluid composition (R1-1).Then 6 these substrates are cooled to room temperature, with the high pressure pumping lamp via photomask respectively with 300J/m 2, 400J/m 2, 500J/m 2, 750J/m 2, 1,000J/m 2Or 2,000J/m 2Exposure filming on each substrate made public, then with 23 ℃ 0.04 weight % potassium hydroxide aqueous solution with 1kgf/cm 2Development pressure (nozzle diameter 1mm) be sprayed onto on the filming of each substrate, spray development, then 220 ℃ of back bakings of carrying out 30 minutes, form the dot pattern of 200 * 200 μ m.
Sensitivity is estimated
With scanning electron microscope the dot pattern on each substrate that forms pattern under each exposure is observed; The residual film ratio (thickness before developing in the thickness after the development * 100/) that pattern is formed well, calculates with the Film Thickness Ratio before and after developing is 90% or above is evaluated as zero; With pattern form good but with the residual film ratio that Film Thickness Ratio before and after developing is calculated be lower than 90% or the visible part of pattern damaged be evaluated as Δ, do not form being evaluated as of pattern *.
Solvent resistance is estimated
Above-mentioned 6 plate bases that under each exposure, make public are immersed in 25 ℃ the N-Methyl pyrrolidone 30 minutes respectively; Soak the dot pattern of front and back with sem observation; Film Thickness Ratio (thickness before soak the thickness after the immersion * 100/) before and after pattern do not had to change, soak is 95% or above is evaluated as zero; Be lower than 95% or some damaged Δ that is evaluated as of pattern with the Film Thickness Ratio before and after soaking, with soak the back pattern fully from being evaluated as of coming off of substrate *.When can't well forming because sensitivity is not enough, substrate estimates (being labeled as "-" among the table 8-11).
Stickiness is estimated
(R1-1) is coated on the glass baseplate surface with the spin coating appearance with fluid composition, under 90 ℃, carries out 4 minutes preliminary drying then, forms filming of thickness 1.3 μ m, then this substrate is cooled to room temperature, with the high pressure pumping lamp with 2,000J/m 2Exposure this filmed make public, then with 23 ℃ 0.04 weight % potassium hydroxide aqueous solution with 1kgf/cm 2Development pressure (nozzle diameter 1mm) be sprayed onto film on, spray development, then 220 ℃ of back bakings of carrying out 30 minutes.According to JIS K5400 specification, will film to intersect and be cut into 100 grids, carry out the stickiness evaluation, do not take place to be evaluated as zero when grid is peeled off, be evaluated as Δ when having 1-10 to peel off in the grid, grid have when peeling off more than 10 be evaluated as *.
The storage stability evaluation of fluid composition
Fluid composition (R1-1) is packed in the vial, in 40 ℃ constant temperature and humidity cabinet, preserve a week, measure the viscosity before and after preserving, calculate viscosity rate of change (viscosity before preserve the viscosity after the preservation * 100/).
Embodiment 2-40 and comparative example 1-30
Each composition kind of fluid composition and amount according to shown in the table 2-7 (wherein " part " is to be benchmark with weight), are in addition likewise prepared fluid composition with embodiment 1, estimate.
Evaluation result is shown in table 8-table 11.
Among the table 2-7, shown in the theing contents are as follows of multi-functional monomer, Photoepolymerizationinitiater initiater, adjuvant and solvent.
Multi-functional monomer
C-1: six acrylic acid dipentaerythritol ester
Photoepolymerizationinitiater initiater
D-1:2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone
D-2:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-ethyl ketone-1-(O-acetyl oxime)
D-3:2, the 4-diethyl thioxanthone
Adjuvant
E-1: bisphenol-A novolac-type epoxy resin (trade name 157S65, ジ ャ パ Application エ Port キ シ レ ジ Application (strain) preparation)
E-2: trimellitic anhydride
E-3:N-(trifluoro-methanesulfonyl oxy) dicyclo [2.2.1] heptan-5-alkene-2, the 3-dicarboximide
Table 2
Dispersible pigment dispersion (part) Alkali soluble resins (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Embodiment 1 R1(100) B-1(15) C-1(15) D-1(5) ——
Embodiment 2 R1(100) B-1(15) C-1(15) D-2(5) ——
Embodiment 3 R1(100) B-1(15) C-1(15) D-1(5) E-1(3)
Embodiment 4 R1(100) B-1(15) C-1(15) D-1(5) E-2(1)
Embodiment 5 R1(100) B-1(15) C-1(15) D-1(5) E-3(2)
Embodiment 6 R1(100) B-2(15) C-1(15) D-1(5) ——
Embodiment 7 R1(100) B-2(15) C-1(15) D-2(5) ——
Embodiment 8 R1(100) B-2(15) C-1(15) D-1(5) E-1(3)
Embodiment 9 R1(100) B-2(15) C-1(15) D-1(5) E-2(1)
Embodiment 10 R1(100) B-2(15) C-1(15) D-1(5) E-3(2)
Embodiment 11 R1(100) B-3(15) C-1(15) D-1(5) ——
Embodiment 12 R1(100) B-3(15) C-1(15) D-2(5) ——
Embodiment 13 R1(100) B-3(15) C-1(15) D-1(5) E-1(3)
Embodiment 14 R1(100) B-3(15) C-1(15) D-1(5) E-2(1)
Embodiment 15 R1(100) B-3(15) C-1(15) D-1(5) E-3(2)
Embodiment 16 R1(100) B-4(15) C-1(15) D-1(5) ——
Embodiment 17 R1(100) B-4(15) C-1(15) D-2(5) ——
Embodiment 18 R1(100) B-4(15) C-1(15) D-1(5) E-1(3)
Embodiment 19 R1(100) B-4(15) C-1(15) D-1(5) E-2(1)
Embodiment 20 R1(100) B-4(15) C-1(15) D-1(5) E-3(2)
Embodiment 21 R2(100) B-1(15) C-1(15) D-1(5) ——
Embodiment 22 R2(100) B-2(15) C-1(15) D-1(5) ——
Embodiment 23 R2(100) B-3(15) C-1(15) D-1(5) ——
Embodiment 24 R2(100) B-4(15) C-1(15) D-1(5) ——
Table 3
Dispersible pigment dispersion (part) Alkali soluble resins (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Embodiment 25 G1(100) B-1(10) C-1(10) D-1(5) ——
Embodiment 26 G1(100) B-2(10) C-1(10) D-1(5) ——
Embodiment 27 G1(100) B-3(10) C-1(10) D-1(5) ——
Embodiment 28 G1(100) B-4(10) C-1(10) D-1(5) ——
Embodiment 29 G2(100) B-1(10) C-1(10) D-1(5) ——
Embodiment 30 G2(100) B-2(10) C-1(10) D-1(5) ——
Embodiment 31 G2(100) B-3(10) C-1(10) D-1(5) ——
Embodiment 32 G2(100) B-4(10) C-1(10) D-1(5) ——
Table 4
Dispersible pigment dispersion (part) Alkali soluble resins (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Embodiment 33 B1(100) B-1(20) C-1(10) D-1(4)D-3(1) ——
Embodiment 34 B1(100) B-2(20) C-1(10) D-1(4)D-3(1) ——
Embodiment 35 B1(100) B-3(20) C-1(10) D-1(4)D-3(1) ——
Embodiment 36 B1(100) B-4(20) C-1(10) D-1(4)D-3(1) ——
Embodiment 37 B2(100) B-1(20) C-1(10) D-1(4)D-3(1) ——
Embodiment 38 B2(100) B-2(20) C-1(10) D-1(4)D-3(1) ——
Embodiment 39 B2(100) B-3(20) C-1(10) D-1(4)D-3(1) ——
Embodiment 40 B2(100) B-4(20) C-1(10) D-1(4)D-3(1) ——
Table 5
Dispersible pigment dispersion (part) Alkali soluble resins (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Comparative example 1 R1(100) B-5(15) C-1(15) D-1(5) ——
Comparative example 2 R1(100) B-5(15) C-1(15) D-2(5) ——
Comparative example 3 R1(100) B-5(15) C-1(15) D-1(5) E-1(3)
Comparative example 4 R1(100) B-5(15) C-1(15) D-1(5) E-2(1)
Comparative example 5 R1(100) B-5(15) C-1(15) D-1(5) E-3(2)
Comparative example 6 R1(100) B-6(15) C-1(15) D-1(5) ——
Comparative example 7 R1(100) B-6(15) C-1(15) D-2(5) ——
Comparative example 8 R1(100) B-6(15) C-1(15) D-1(5) E-1(3)
Comparative example 9 R1(100) B-6(15) C-1(15) D-1(5) E-2(1)
Comparative example 10 R1(100) B-6(15) C-1(15) D-1(5) E-3(2)
Comparative example 11 R1(100) B-7(15) C-1(15) D-1(5) ——
Comparative example 12 R1(100) B-7(15) C-1(15) D-2(5) ——
Comparative example 13 R1(100) B-7(15) C-1(15) D-1(5) E-1(3)
Comparative example 14 R1(100) B-7(15) C-1(15) D-1(5) E-2(1)
Comparative example 15 R1(100) B-7(15) C-1(15) D-1(5) E-3(2)
Comparative example 16 R2(100) B-5(15) C-1(15) D-1(5) ——
Comparative example 17 R2(100) B-6(15) C-1(15) D-1(5) ——
Comparative example 18 R2(100) B-7(15) C-1(15) D-1(5) ——
Table 6
Dispersible pigment dispersion (part) Alkali soluble resins (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Comparative example 19 G1(100) B-5(10) C-1(10) D-1(5) ——
Comparative example 20 G1(100) B-6(10) C-1(10) D-1(5) ——
Comparative example 21 G1(100) B-7(10) C-1(10) D-1(5) ——
Comparative example 22 G2(100) B-5(10) C-1(10) D-1(5) ——
Comparative example 23 G2(100) B-6(10) C-1(10) D-1(5) ——
Comparative example 24 G2(100) B-7(10) C-1(10) D-1(5) ——
Table 7
Dispersible pigment dispersion (part) Alkali soluble resins (part) Multi-functional monomer (part) Photoepolymerizationinitiater initiater (part) Adjuvant (part)
Comparative example 25 B1(100) B-5(20) C-1(10) D-1(4)D-3(1) ——
Comparative example 26 B1(100) B-6(20) C-1(10) D-1(4)D-3(1) ——
Comparative example 27 B1(100) B-7(20) C-1(10) D-1(4)D-3(1) ——
Comparative example 28 B2(100) B-5(20) C-1(10) D-1(4)D-3(1) ——
Comparative example 29 B2(100) B-6(20) C-1(10) D-1(4)D-3(1) ——
Comparative example 30 B2(100) B-7(20) C-1(10) D-1(4)D-3(1) ——
Table 8
Figure S07196681620070518D000471
Table 9
Figure S07196681620070518D000481
Table 10
Figure S07196681620070518D000491
Table 11
Figure S07196681620070518D000501

Claims (4)

1. be used to form the radiation-ray sensitive composition of dyed layer, said composition contains (A) colorant, (B) alkali soluble resins, (C) multi-functional monomer and (D) Photoepolymerizationinitiater initiater, it is characterized in that: (B) alkali soluble resins contain with
(b1) be selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and the unsaturated phenolic compounds at least a,
(b2) have ester ring type carbocyclic ring structure unsaturated compound,
(b3) have the oxetanes ring structure unsaturated compound and
(b4) unsaturated acyl imines
Multipolymer as necessary constituent.
2. the described radiation-ray sensitive composition that is used to form dyed layer of claim 1, wherein said (B) alkali soluble resins contain with
(b1) with (methyl) acrylic acid as at least a acid unsaturated compound of neccessary composition,
(b2) be selected from least a ester ring type unsaturated compound in (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate and (methyl) acrylic acid three ring [5.2.1.02, the 6] decane-8-base ester,
(b3) be selected from 3-[(methyl) acryloyl-oxy ylmethyl] oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-3-ethyl oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2-trifluoromethyl oxetanes, 3-[(methyl) acryloyl-oxy ylmethyl]-2-phenyl oxetanes, 2-[(methyl) acryloyl-oxy ylmethyl] oxetanes and 2-[(methyl) acryloyl-oxy ylmethyl]-4-trifluoromethyl oxetanes at least a oxetanes ring system unsaturated compound and
(b4) N-phenylmaleimide
Multipolymer as necessary constituent.
3. color filter, this color filter have the dyed layer that the radiation-ray sensitive composition that is used to form dyed layer with claim 1 forms.
4. color liquid crystal display device, this color liquid crystal display device has the color filter of claim 4.
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