CN104914666A - Colored photosensitive resin composition for color filter, color filter and liquid crystal display device having the same - Google Patents

Colored photosensitive resin composition for color filter, color filter and liquid crystal display device having the same Download PDF

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Publication number
CN104914666A
CN104914666A CN201510103384.4A CN201510103384A CN104914666A CN 104914666 A CN104914666 A CN 104914666A CN 201510103384 A CN201510103384 A CN 201510103384A CN 104914666 A CN104914666 A CN 104914666A
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mentioned
weight
antioxidant
photosensitive composition
pigment
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CN104914666B (en
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申泳璨
安大熙
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • 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
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

The invention relates to a colored photosensitive resin composition for a color filter, a color filter and a liquid crystal display device having the same, concretely a colored photosensitive resin composition for a red filter used in manufacturing a red filter used for a color LCD display unit.

Description

Color filter photosensitive composition, color filter and possess its liquid crystal indicator
Technical field
The present invention relates to photosensitive composition, in more detail, relating to the red color filter photosensitive composition used when manufacturing the red color filter for color liquid crystal display arrangement etc.
Background technology
Color filter (color filter) is widely used in Plasmia indicating panel (PDP), liquid crystal indicator (LCD), Field Emission Display (FEL) and light emitting diode indicator (LED) etc., and the range of application of color filter also expands rapidly.Especially, purposes in an lcd expands further recently, and therefore, color filter is considered to be in one of most important parts in tone aspect reproducing LCD.
This color filter is formed by the method manufacture utilizing the photosensitive composition that contain toner and form required colored pattern.Particularly, by repeatedly performing the coating being formed on substrate and be made up of photosensitive composition, and carry out exposing and developing at above-mentioned coating formation pattern, and carry out heating and make a series of processes such as its heat curing, thus manufacture color filter.
In the recent period, in order to realize high color purity, the concentration for the manufacture of the colorant of the photosensitive composition of color filter continues to rise, and is studying method pigment and dyestuff being used as colorant simultaneously.On the other hand, in order to improve throughput rate in operation and yield, needing there is high developing powder and to low exposure, also there is excellent sensitivity and the photosensitive composition of reliability.
To this; provide in No. 2002-0006441st, KR published patent and use hindered phenol system antioxidant to make the color filter of pattern precision excellence; but pigment is only used as colorant by foregoing invention; thus there is the problem etc. of pigment particle; and when there is red color filter, after high-temperature process, produce the problem of variable color.
Prior art document
Patent documentation
Patent documentation 1: No. 2008-0103590, KR published patent
Patent documentation 2: No. 2002-0006441, KR published patent
Summary of the invention
The object of the invention is to, the red color filter photosensitive composition of the color filter that can obtain transmission excellence is provided.Especially, the object of the invention is to, there is provided because transmission is excellent, the minimise issues that thus transmissivity of the generation when carrying out subsequent handling can be declined, and due to sensitivity, adaptation and developing powder excellence, thus the red pixel photosensitive composition that pattern is not peeled off in developing procedure.
Further, the object of the invention is to, be provided in the few and red pixel photosensitive composition of brightness excellence of variable color in redness.
To achieve these goals, the invention provides a kind of red pixel photosensitive composition, it is characterized in that, contain toner (A), alkali soluble resin (B), photopolymerizable compound (C), Photoepolymerizationinitiater initiater (D), the photosensitive composition of antioxidant (E) and solvent (F), above-mentioned colorant (A) comprises more than one pigment and more than one dyestuff, more than one in above-mentioned pigment or dyestuff are red series, above-mentioned Photoepolymerizationinitiater initiater (D) comprises the oxime ester system light trigger containing hexichol sulfenyl represented by following chemical formula 1, above-mentioned antioxidant (E) comprises the phenol system antioxidant of more than a kind and the phosphorous antioxidant of more than a kind, above-mentioned phenol system antioxidant is not deteriorated for more than 200 hours in 150 DEG C.
[chemical formula 1]
In above-mentioned formula, alkyl, phenyl, substituted or unsubstituted phenyl, the substituted or unsubstituted benzyl of R1 can be following chemical formula 2, R2 can be C1 ~ C8, R3 can be diphenyl sulfide base.
[chemical formula 2]
-R 4-R 5
Wherein, R4 can be the alkylidene of C1 ~ C4, and R5 can be the alkyl or cycloalkyl of C3 ~ C8.
According to a preferred embodiment of the invention, in above-mentioned antioxidant, the weight ratio of phenol system antioxidant and phosphorous antioxidant can be 1:1 ~ 5:1.
In the present invention, mark meter by weight, relative to the total solid composition in above-mentioned photosensitive composition, can comprise the colorant (A) of 5 ~ 60 % by weight, the alkali soluble resin (B) of 10 ~ 80 % by weight and 5 ~ 45 % by weight photopolymerizable compound (C); Take solid constituent as benchmark, relative to above-mentioned alkali soluble resin (B) and photopolymerizable compound (C) sum 100 weight portion, the Photoepolymerizationinitiater initiater (D) of 0.1 ~ 40 weight portion can be comprised.
The invention provides the color filter be made up of above-mentioned red pixel photosensitive composition.
The invention provides the liquid crystal indicator comprising above-mentioned color filter.
The color filter manufactured by photosensitive composition of the present invention, due to excellent adhesion, does not thus produce the problem that pattern is peeled off, and has the effect that developing powder is fast, aberration is few, transmission is excellent.
Further, the color filter manufactured by photosensitive composition of the present invention variable color in redness is few, and brightness is excellent.
Embodiment
The invention provides a kind of red pixel photosensitive composition, it is characterized in that, contain toner (A), alkali soluble resin (B), photopolymerizable compound (C), Photoepolymerizationinitiater initiater (D), the photosensitive composition of antioxidant (E) and solvent (F), above-mentioned colorant (A) comprises more than one pigment (a1) and more than one dyestuff (a2), more than one in above-mentioned pigment or dyestuff are red series, above-mentioned Photoepolymerizationinitiater initiater (D) comprises the oxime ester system Photoepolymerizationinitiater initiater containing hexichol sulfenyl represented by following chemical formula 1, above-mentioned antioxidant (E) comprises the phenol system antioxidant of more than a kind and the phosphorous antioxidant of more than a kind, above-mentioned phenol system antioxidant is not deteriorated for more than 200 hours in 150 DEG C,
[chemical formula 1]
In above-mentioned formula, R1 can be following chemical formula 2, R2 can be the alkyl of C1 ~ C8, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, and R3 can be diphenyl sulfide base;
[chemical formula 2]
-R 4-R 5
In above-mentioned formula, R4 can be the alkylidene of C1 ~ C4, and R5 can be the alkyl or cycloalkyl of C3 ~ C8.
Red pixel photosensitive composition of the present invention comprises pigment as colorant and fuel, and be together used in the phenol system antioxidant and phosphorous antioxidant that within 150 DEG C more than 200 hours, are not deteriorated, and the oxime ester system Photoepolymerizationinitiater initiater comprised containing hexichol sulfenyl, thus the color filter manufactured by above-mentioned photosensitive composition is due to excellent adhesion, thus do not produce the problem that pattern is peeled off, and there is the effect that developing powder is fast, aberration is few, transmission is excellent.
Below, each composition forming red pixel photosensitive composition of the present invention is described.
Colorant (A)
Above-mentioned colorant (A) using more than one pigment (a1) and more than one dyestuff (a2) as neccessary composition.
Pigment (a1)
Can by normally used organic pigment or inorganic pigment are used as above-mentioned pigment in the art.
Above-mentioned organic pigment can use the various pigment for printing-ink, jetted ink etc., particularly, water-soluble azo pigment, insoluble azo colour, phthalocyanine color, quinoline Azone pigment, isoindolenone pigments, isoindoline pigment, perylene dye, purple cyclic ketones pigment, two can be enumerated piperazine pigment, anthraquinone pigment, dianthraquinone pigment, anthrapyrimidine pigment, three benzos [cd, jk] pyrene-5,10-diketone (anthanthrone) pigment, indanthrone (indanthrone) pigment, yellow anthrone pigment, pyranthrone (pyranthrone) pigment, diketopyrrolo-pyrrole pigment etc.
As above-mentioned inorganic pigment, the metallic compound such as metal oxide or metallic complex salt can be enumerated, particularly, the oxide or composite metal oxide etc. of the metal of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black etc. can be enumerated.
Especially, above-mentioned organic pigment and inorganic pigment specifically can enumerate the compound being divided into pigment in color index (Britain's dyeing is published with colourist association (The society of Dyers and Colourists)), more specifically, the pigment that following color index (C.I.) is numbered can be enumerated, but be not limited thereto.
As C.I. pigment yellow 13,20,24,31,53,83,86,93,94,109,110,117,125,137,138,139,147,148,150,153,154,166,173,180 and 185; C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65 and 71;
C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,208,215,216,224,242,254,255 and 264.
In above-mentioned illustrative C.I. pigment, preferably can use the pigment selected from C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 185, C.I. pigment orange 38, C.I. pigment red 122, C.I. paratonere 166, C.I. paratonere 177, C.I. paratonere 208, C.I. paratonere 242, C.I. paratonere 254 and C.I. paratonere 255.
Above-mentioned pigment can use the normally used organic pigment in this area or inorganic pigment, and individually can use or combine two or more pigment to use.
Above-mentioned pigment preferably uses with the dispersible pigment dispersion of the uniform particle sizes of above-mentioned pigment dispersion.As an example of the method making the uniform particle sizes of pigment disperse, the method etc. comprising pigment dispersing agent (a3) to carry out dispersion treatment can be enumerated, utilize the method, the dispersible pigment dispersion that pigment is dispersed in the state in solution can be obtained.
Pigment dispersing agent (a3)
Above-mentioned pigment dispersing agent (a3) is in order to the anti-freezing of pigment gathers add with maintenance stability, the normally used pigment dispersing agent in this area can be used without restriction, concrete example, the surfactants etc. such as kation system, negative ion system, nonionic system, both sexes, Polyester, polyamine system can be exemplified.Preferably, above-mentioned pigment dispersing agent comprises acrylic ester spreading agent, and aforesaid propylene acid esters system spreading agent comprises BMA (butyl methacrylate) or DMAEMA (methacrylic acid N, N-dimethylaminoethyl).Now, as as suggested in No. 2004-0014311, KR published patent, preferably manufacture aforesaid propylene acid esters system spreading agent by active control method, the acrylic ester spreading agent manufactured by above-mentioned active control method commercially sold can enumerate DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150 etc.
Above-mentioned illustrative acrylic ester spreading agent can individually use or combine two or more use.
Except aforesaid propylene acid esters system spreading agent, also the pigment dispersing agent of other resinous type can be used as above-mentioned pigment dispersing agent (a3).The pigment dispersing agent of other resinous type above-mentioned can enumerate the pigment dispersing agent of known resinous type, especially can enumerate with polyurethane, polyacrylate is the polycarboxylate of representative, unsaturated polyester acid amides, poly carboxylic acid, (part) amine salt of poly carboxylic acid, the ammonium salt of poly carboxylic acid, the alkylamine salt of poly carboxylic acid, polysiloxane, long-chain polyaminoamide phosphate salt, the ester of hydroxyl poly carboxylic acid and their modification product, or the amine that the polyester with freedom (free) carboxyl is formed with the reaction of poly-(rudimentary alkyleneimines), or the emulsifying dispersant of their salt and so on, the water soluble resin of (methyl) acrylic styrene copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol (PVA) or polyvinylpyrrolidone and so on or water-soluble polymers, polyester, the polyacrylate of modification, the additional product of ethylene oxide/propylene oxide and phosphate etc.
As the commercially available product of above-mentioned resinous type spreading agent, such as, can enumerate the trade name of BYK chemical industry: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; The trade name of BASF (BASF) company: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA-4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; The trade name of Lubirzol company: SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; The trade name of KAWAKEN Fine chemical company: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; The trade name of Ajinomoto company: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; The trade name of chemical company of common prosperity society: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44 etc.
The pigment dispersing agent of other resinous type except aforesaid propylene acid esters system spreading agent can individually use or combine two or more use, also can use with acrylic ester spreading agent.
The use amount of above-mentioned pigment dispersing agent (a3), relative to solid constituent 100 weight portion of used pigment (a1), is 5 ~ 60 weight portions, is more preferably the scope of 15 ~ 50 weight portions.By above-mentioned benchmark, if the content of pigment dispersing agent (a3) is more than 60 weight portions, then likely make viscosity uprise, if be less than 5 weight portions, then likely make pigment be difficult to micronize, or likely cause pigment to disperse the problems such as rear gelation.
Dyestuff (a2)
As long as have dissolubility to organic solvent, then the use of above-mentioned dyestuff (a2) is unrestricted.Preferred use has dissolubility to organic solvent and can guarantee the dyestuff of dissolubility to alkaline developer and the reliability such as thermotolerance, solvent resistance.
As above-mentioned dyestuff, the acid dyes of acidic-group, acid dyes and the salt of nitrogen-containing compound, the sulfonamide body of acid dyes etc. and choice for use their derivant can be had, in addition the acid dyes of optional nitrogen system of choosing spouse, xanthene system, phthalocyanine system and their derivant from sulfonic acid or carboxylic acid etc.From color, preferably select the dyestuff of redness, purple, peony series, have and be divided into the compound of dyestuff or be recorded in the orchil, blue dyes, the cudbear that dye in the known dyestuff of this (dyeing history) in color index (Britain's dyeing is published with colourist association (The Society of Dyers and Colourists)).
As the concrete example of above-mentioned dyestuff, first have as C.I. solvent dye, have C.I. solvent red 8,45,49,89,111,122,125,130,132,146, the orchils such as 179, wherein, be preferably in C.I. solvent dye to the C.I. solvent red 8 of the dissolubility excellence of organic solvent, 49,89,111,122,132,146,179, be wherein more preferably C.I. solvent red 8,122,132.
And, as C.I. acid dyes, there is C.I. azogeramine, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426 orchils such as grade, wherein, be preferably the C.I. acid red 52 to the solubleness excellence of organic solvent, 92.And, be preferably C.I. acid blue 80,90, C.I. acid violet 66.
And, as C.I. direct dyes, the C.I. directly orchils such as red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250 can be enumerated.
Further, the orchils such as C.I. medium red 1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37,38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94,95 can also be enumerated.
In the present invention, above-mentioned dyestuff can individually use or combine two or more use.
Mark meter by weight, the content of above-mentioned dyestuff (a2), relative to the total solid composition in above-mentioned colorant (A), preferably comprises 0.5 ~ 80 % by weight, more preferably comprises 0.5 ~ 60 % by weight, especially preferably comprises 1 ~ 50 % by weight.By said reference, if the content of the dyestuff in above-mentioned colorant (A) is in above-mentioned scope, then can prevent the problem of the reliability decrease making dyestuff stripping after forming pattern due to organic solvent, and due to sensitivity excellence, thus preferably.
Mark meter by weight, the content of above-mentioned colorant (A), relative to the total solid composition in photosensitive composition of the present invention, comprises 5 ~ 60 % by weight, preferably comprises 10 ~ 45 % by weight.
This is because, with said reference, when above-mentioned colorant (A) comprises 5 ~ 60 % by weight, even if form film, the color depth of pixel is also full, the omission of non-pixel portion during development also can not decline, thus be difficult to produce residue, therefore preferably.
In the present invention, the content of the total solid composition in photosensitive composition means the total content of all the other compositions desolventized in photosensitive composition.
Alkali soluble resin (B)
In order to there is solubility to the alkaline developer utilized in development treatment operation when forming pattern, carry out copolymerization using the ethylene unsaturated monomer (b1) with carboxyl as neccessary composition.Further, in order to ensure with the compatibility of dyestuff (a2) and the storage stability of photosensitive composition of the present invention, the acid number of alkali soluble resin (B) is 30 ~ 150mgKOH/g.
If the acid number of alkali soluble resin (B) is less than 30mgKOH/g, then photosensitive composition is difficult to guarantee sufficient developing powder, if be greater than 150mgKOH/g, then because the adaptation between substrate declines, thus the short circuit of pattern is easily produced, and because the compatibility between dyestuff has problems, thus the dyestuff in photosensitive composition can be caused to separate out, or decline due to the storage security of photosensitive composition, thus easily make viscosity increase.
The concrete example of the carboxylic ethylene unsaturated monomer of above-mentioned bag (b1) can enumerate the monocarboxylic acid classes such as acrylic acid, methacrylic acid, crotonic acid; The acid anhydride of the dicarboxylic acids classes such as fumaric acid, mesaconic acid, itaconic acid and their dicarboxylic acids; ω-carboxyl-polycaprolactone list (methyl) acrylate etc. have list (methyl) esters of acrylic acid etc. of the polymkeric substance of carboxyl and hydroxyl at two ends; Wherein, acrylic acid, methacrylic acid is preferably.
In order to give hydroxyl to alkali soluble resin (B), by making the ethylene unsaturated monomer (b1) with carboxyl manufacture with ethylene unsaturated monomer (b2) copolymerization with hydroxyl, and by making the ethylene unsaturated monomer (b1) with carboxyl react to manufacture with the compound (b3) with glycidyl.Further, also react to manufacture above-mentioned alkali soluble resin (B) further with the compound (b3) with glycidyl by the multipolymer of the ethylene unsaturated monomer (b1) that makes to have carboxyl and the ethylene unsaturated monomer (b2) with hydroxyl.
The above-mentioned concrete example with the ethylene unsaturated monomer (b2) of hydroxyl can enumerate (methyl) hydroxy-ethyl acrylate classes such as (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid-4-hydroxybutyl ester, (methyl) acrylic acid-2-hydroxyl-3-phenoxy-propyl, N-hydroxyethyl acrylamide.
The above-mentioned concrete example with the compound (b3) of glycidyl has butyl glycidyl ether, glycidylpropyl ether, phenyl glycidyl ether, 2-hexyl glycidyl ether, Glycidyl butyrate, Glycidyl methyl ether, ethyl glycidyl ether, diglycidyl isopropyl ether, tertiary butyl glycidyl ether, benzyl glycidyl ether, benzoic acid glycidyl 4-tertiary butyl ester, stearic acid ethylene oxidic ester, arylolycidyl ethers, glycidyl methacrylate etc., wherein be preferably butyl glycidyl ether, arylolycidyl ethers, glycidyl methacrylate.And the above-mentioned illustrative compound (b3) with glycidyl can be used alone or combine two or more use.
And, when manufacturing above-mentioned alkali soluble resin (B), the above-mentioned ethylene unsaturated monomer (b1) with carboxyl except with there is the ethylene unsaturated monomer (b2) of hydroxyl and there is compound (b3) copolymerization of glycidyl, also can with unsaturated monomer (b4) copolymerization that can realize copolymerization.
Below exemplified with the above-mentioned kind that can realize the unsaturated monomer (b4) of copolymerization, but be not limited thereto.
The concrete example that can realize the unsaturated monomer (b4) of copolymerization has: styrene, vinyltoluene, α-methyl styrene, to chlorostyrene, o-methoxystyrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinylbenzyl glycidyl ether, a vinylbenzyl glycidyl ether, to aromatic ethylene compounds such as vinylbenzyl glycidyl ether;
N-N-cyclohexylmaleimide, N-benzyl maleimide, N-phenylmaleimide, N-o-hydroxy-phenyl maleimide, hydroxyphenyl-maleimides between N-, N-p-hydroxybenzene maleimide, N-o-methyl-phenyl-maleimide, methylphenylmaleimide between N-, N-p-methylphenyl maleimide, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, the N-substituted maleimide amine compounds such as N-p-methoxyphenyl maleimide,
(methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate; Alicyclic (methyl) acrylic compounds such as (methyl) acrylic acid cyclopentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methylcyclohexyl ester, three rings [5.2.1.02,6]-8-base in the last of the ten Heavenly stems (methyl) acrylate, (methyl) acrylic acid 2-bicyclopentyl oxygen base ethyl ester, (methyl) isobornyl acrylate;
(methyl) benzyl acrylate classes such as (methyl) phenyl acrylate, (methyl) benzyl acrylate;
The unsaturated oxetane compounds such as 3-(methacryloxymethyl) oxetanes, 3-(methacryloxymethyl)-3-Ethyloxetane, 3-(methacryloxymethyl)-2-trifluoromethyl oxetanes, 3-(methacryloxymethyl)-2-phenyl oxetanes, 2-(methacryloxymethyl) oxetanes, 2-(methacryloxymethyl)-4-trifluoromethyl oxetanes; Deng.
As above-mentioned can copolymerization unsaturated monomer (b4) come illustrative monomer can individually use or combine two or more use.
In weight fraction, the content of above-mentioned alkali soluble resin (B) comprises 10 ~ 80 % by weight relative to the total solid composition in photosensitive polymer combination of the present invention, preferably comprises the scope of 10 ~ 70 % by weight.By above-mentioned benchmark, if the content of above-mentioned alkali soluble resin (B) is 10 ~ 80 % by weight, then above-mentioned alkali soluble resin (B) has sufficient dissolubility in developer solution, thus easily pattern is formed, and the film of the pixel portion in exposure portion reduces when preventing from developing, it is good that the omission of non-pixel portion becomes, thus preferably.
Photopolymerizable compound (C)
Above-mentioned photopolymerizable compound (C) is effect by following Photoepolymerizationinitiater initiater (D) and the compound that can be polymerized, monofunctional monomer (c1), two functional monomers (c2) or polyfunctional monomer (c3) can be used, preferably, the polyfunctional monomer (c3) of more than two senses can be used.
The concrete example of above-mentioned monofunctional monomer (c1) has nonylphenol acrylate phenyl carbitol ester, acrylic acid 2-hydroxyl-3-phenoxy-propyl, acrylic acid 2-ethylhexyl carbitol ester, acrylic acid 2-hydroxy methacrylate or NVP etc., but is not limited thereto.
The concrete example of above-mentioned two functional monomers (c2) has 1, two (acrylyl oxy-ethyl) ether or 3-methyl pentanediol two (methyl) acrylate etc. of 6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A, but be not limited thereto.
The concrete example of above-mentioned polyfunctional monomer (c3) has trimethylolpropane tris (methyl) acrylate, ethoxy trimethylolpropane tris (methyl) acrylate, propoxyl group trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, ethoxy dipentaerythritol six (methyl) acrylate, propoxyl group dipentaerythritol six (methyl) acrylate or dipentaerythritol six (methyl) acrylate etc., but be not limited thereto.
Mark meter by weight, above-mentioned photopolymerizable compound (C), relative to the total solid composition in photosensitive composition of the present invention, preferably comprises 5 ~ 45 % by weight, more preferably comprises 7 ~ 45 % by weight.If by said reference, when above-mentioned photopolymerizable compound (C) comprises 5 ~ 45 % by weight, then the intensity in pixel portion or flatness become good, thus preferably.
Photoepolymerizationinitiater initiater (D)
Above-mentioned Photoepolymerizationinitiater initiater (D) with the Photoepolymerizationinitiater initiater (d1) of the structure of following chemical formula 1 for composition.
[chemical formula 1]
[chemical formula 2]
-R 4-R 5
In above-mentioned chemical formula 1, R1 is represented by above-mentioned chemical formula 2, in above-mentioned chemical formula 2, R4 can be the alkyl of C1 ~ C4, R5 can be the alkyl or cycloalkyl of C3 ~ C8, above-mentioned R2 can be alkyl, phenyl, substituted or unsubstituted phenyl, the substituted or unsubstituted benzyl of C1 ~ C8, and R3 can be diphenyl sulfide base.
The Photoepolymerizationinitiater initiater (d1) with the structure of above-mentioned chemical formula 1 by preventing the decline of sensitivity because dyestuff causes and transmissivity, thus can make to comprise dyestuff and expresses effective photopolymerization characteristic as the photosensitive composition of colorant.
The example of the Photoepolymerizationinitiater initiater (d1) of above-mentioned chemical formula 1 has TR-PBG-305 etc.
And, in the scope not damaging effect of the present invention, also can also with Photoepolymerizationinitiater initiater (d2) apart from the above, representative ground preferably uses more than one the compound be selected from acetophenone based compound, benzophenone based compound, triazine based compound, bisglyoxaline based compound and thioxanthones based compound.
The concrete example of above-mentioned acetophenone based compound, diethoxy acetophenone can be enumerated, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl dimethyl ketal, 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methylpropane-1-ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino-propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morphlinophenyl) butane-1-ketone etc.
As above-mentioned benzophenone based compound, such as, there are benzophenone, O-benzoyl methyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'-methyldiphenyl thioether, 3,3'; 4; 4'-tetra-(t-butyl peroxy carbonyl) benzophenone, 2,4,6-tri-methyl benzophenones etc.
The concrete example of above-mentioned triazine based compound, can 2 be enumerated, two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl naphthyl)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-piperonyl-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(5-methylfuran-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(furans-2-base) vinyl]-1 of 4-, 3, 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-1 of 4-, 3, 5-triazine, 2, two (trichloromethyl)-6-[2-(3 of 4-, 4-Dimethoxyphenyl) vinyl]-1, 3, 5-triazine etc.
The concrete example of above-mentioned united imidazole has two (the 2-chlorphenyl)-4,4' of 2,2'-, 5,5'-tetraphenyl bisglyoxaline, 2,2'-two (2,3-dichlorophenyl)-4,4', 5,5'-tetraphenyl bisglyoxaline, 2,2'-two (2-chlorphenyls)-4,4', 5,5'-tetra-(alkoxyl phenyl) bisglyoxaline, 2,2'-two (2-chlorphenyls)-4,4', 5,5'-tetra-(tri-alkoxy phenyl) bisglyoxaline, 2, two (2, the 6-dichlorophenyl)-4,4' of 2'-, 5,5'-tetraphenyl-1,2'-bisglyoxaline or 4,4', the imidazolium compounds etc. that the phenyl of 5,5' position is replaced by carbonyl alkyl.Wherein, two (the 2-chlorphenyl)-4 of 2,2'-is preferably used, 4', 5,5'-tetraphenyl bisglyoxaline, 2, two (2, the 3-dichlorophenyl)-4,4' of 2'-, 5,5'-tetraphenyl bisglyoxaline, 2,2'-two (2,6-dichlorophenyl)-4,4', 5,5'-tetraphenyl-1,2'-bisglyoxaline.
As above-mentioned thioxanthones based compound, if any ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones, the chloro-4-propoxythioxanthone of 1-etc.
Further, in order to improve the sensitivity of photosensitive composition of the present invention, above-mentioned Photoepolymerizationinitiater initiater (D) also can comprise photopolymerization and cause auxiliary agent (d3).Photosensitive composition of the present invention causes auxiliary agent (d3) by comprising photopolymerization, makes sensitivity higher, thus can boost productivity.
Above-mentioned photopolymerization initiation auxiliary agent (d3) preferably can use and be selected from amines, carboxylic acid compound, more than one the compound had in the organosulfur compound of mercapto.
Above-mentioned amines preferably uses aromatic amines compound, specifically can use aliphatic amine compound, 4-dimethylaminobenzoic acid methyl esters, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylamino ethyl ester, the N such as triethanolamine, methyldiethanolamine, triisopropanolamine, N-dimethyl-p-toluidine, 4, two (dimethylamino) benzophenone of 4'-(being referred to as: michaelis ketone), 4,4'-two (lignocaine) benzophenone etc.
Above-mentioned carboxylic acid compound is preferably heteroaromatic acetic acid class, specifically can enumerate thiophenyl acetic acid, aminomethyl phenyl ethyl thioglycollic acid, ethylphenyl ethyl thioglycollic acid, ethyl methyl benzene ethyl thioglycollic acid, dimethyl benzene ethyl thioglycollic acid, Methoxv-phenylsulfanvl acetic acid, dimethoxyphenylthio acetic acid, chlorophenylsulfanyl acetic acid, dichloro-benzenes ethyl thioglycollic acid, N-phenylglycine, phenoxy acetic acid, naphthalene ethyl thioglycollic acid, N-naphthyl glycocoll, naphthoxy acetic acid etc.
The above-mentioned concrete example with the organosulfur compound of mercapto can enumerate 2-mercaptobenzothiazole, 1, two (the 3-sulfydryl butoxy) butane, 1 of 4-, 3,5-tri-(3-sulfydryl butoxyethyl group)-1,3,5-triazine-2,4,6, (1H, 3H, 5H)-triketone, trimethylolpropane tris (3-mercaptopropionic acid ester), pentaerythrite four (3-mercaptobutylate), pentaerythrite four (3-mercaptopropionic acid ester), dipentaerythritol six (3-mercaptopropionic acid ester), TEG two (3-mercaptopropionic acid ester) etc.
Take solid constituent as benchmark, relative to alkali soluble resin (B) and photopolymerizable compound (C) sum 100 weight portion, above-mentioned Photoepolymerizationinitiater initiater (D) can comprise 0.1 ~ 40 weight portion, preferably comprises 1 ~ 30 weight portion.If the content of above-mentioned Photoepolymerizationinitiater initiater (D) is in the scope of 0.1 ~ 40 weight portion, then photosensitive composition is by high-sensitivity, shortens the time shutter thus, thus improves throughput rate, and can maintain high resolving power, thus preferably.
Further, the flatness on the intensity in pixel portion that the composition meeting above-mentioned condition by use is formed and the surface in above-mentioned pixel portion can become good.Further, in total Photoepolymerizationinitiater initiater (D), the Photoepolymerizationinitiater initiater (d1) with the structure of above-mentioned chemical formula 1 of 10 ~ 100 % by weight should be comprised, preferably comprise 20 ~ 100 % by weight.
If in total Photoepolymerizationinitiater initiater, the ratio with the Photoepolymerizationinitiater initiater (d1) of the structure of above-mentioned chemical formula 1 is less than 10 % by weight, then cannot suppress the decline of the sensitivity caused by dyestuff, and easily produces pattern short circuit in developing procedure
And, if also use above-mentioned photopolymerization to cause auxiliary agent (d3), it is then benchmark with solid constituent, relative to alkali soluble resin (B) and photopolymerizable compound (C) sum 100 weight portion, above-mentioned photopolymerization causes auxiliary agent (d3) can comprise 0.1 ~ 40 weight portion, preferably comprises 1 ~ 30 weight portion.
If above-mentioned photopolymerization causes the use amount of auxiliary agent (d3) in the scope of 0.1 ~ 40 above-mentioned weight portion, then more can improve the sensitivity of photosensitive composition, and the effect of the throughput rate improved by the color filter using above-mentioned composition to be formed is provided.
Antioxidant (E)
Antioxidant (E) is using more than one of more than one and phosphorous antioxidant of phenol system antioxidant as neccessary composition, and phenol system antioxidant should not be deteriorated for more than 200 hours in the baking oven of 150 DEG C.
As red colored photosensitive polymer combination, the problem that most transmission declines causes due to the xanthochromia produced when firmly toasting, this reduction by using above-mentioned antioxidant (E) to suppress transmission, especially carry out more than 220 degree owing to firmly toasting major part, thus in order to the maximum effect by antioxidant, when firmly toasting, antioxidant should not be deteriorated at the corresponding temperature.
But, if use the antioxidant that thermotolerance is low, in order to the effect of the xanthochromia that is inhibited, then need use 2 ~ 3 times to the amount of the strong antioxidant of thermotolerance, use excessive antioxidant like this, antioxidant xanthochromia can be caused, thus cause transmission to decline, thus be difficult to the effect expecting the decline of suppression transmission.
On the other hand, if use the phenol system antioxidant meeting the above-mentioned condition that more than 200 hours are not deteriorated in the baking oven of 150 DEG C, then also continue to play a role in subsequent handling, thus the minimise issues that the transmissivity of the generation when carrying out subsequent handling can be declined.
Therefore, in the present invention, be used in the phenol system antioxidant be not deteriorated in the baking oven of 150 DEG C more than 200 hours, preferably use hindered phenol system antioxidant, and concrete example be as follows.
3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl (Octadecyl 3-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) (264 hours), 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene (1, 3, 5-Trimethyl-2, 4, 6-tris (3, 5-di-tert-b utyl-4-hydroxybenzyl) benzene) (240 hours), four (3, 5-di-t-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester (Pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hyd roxyhydrocinnamate)) (960 hours), the time that time representation phenol system antioxidant in above-mentioned bracket is not deteriorated in the baking oven of 150 degree.
The concrete example of above-mentioned phosphorous antioxidant is as follows.
Triphenyl phosphate (Triphenyl phosphate), isodecyl diphenyl phosphate (Isodecyl diphenyl phosphate), three (2, 4-di-tert-butyl-phenyl) phosphate (Tris (2, 4-di-te rt-butylphenyl) phosphate), 3, two (the octadecane oxygen base)-2 of 9-, 4, 8, 10-tetra-oxa--3, 9-bis-phospha spiral shell [5.5] undecane (3, 9-Bis (octadecyloxy)-2, 4, 8, 10-tetraoxa-3, 9-diphosp haspiro [5.5] undecane), 2, 2'-di-2-ethylhexylphosphine oxide (4, 6-di-tert-butyl-phenyl)-ethylhexyl dihydrogen phosphate (2, 2'-methylenebis (4, 6-di-tert-butyl-phenyl)-2-ethylhexyl phospha te).
According to a preferably embodiment of the present invention, in above-mentioned antioxidant, the weight ratio of phenol system antioxidant and phosphorous antioxidant can be 1:1 ~ 5:1, and more preferably weight ratio can be 1.5:1 ~ 3:1.When weight ratio is in above-mentioned scope, can prevent xanthochromia and transmission from declining.Further, in the present compositions, because the seizure playing the free radical of phenol system antioxidant action will produce larger impact, thus preferably the amount of phenol system antioxidant is greater than phosphorous antioxidant.But due to when phenol system antioxidant is excessive, the problem of also generating portion transmission decline, thus preferably suitably uses.
Take solid constituent as benchmark, relative to the Photoepolymerizationinitiater initiater (D) of 100 weight portions, above-mentioned antioxidant (E) can comprise 1 ~ 100 weight portion, preferably comprises 2 ~ 50 weight portions.If the content of above-mentioned antioxidant (E) is in the scope of 1 ~ 100 above-mentioned weight portion, then can expect that photosensitive composition improves transmissivity when sensitivity does not decline, thus preferably.If the content of above-mentioned antioxidant (E) is less than 1 weight portion, then be difficult to expect to improve transmissivity, if the content of above-mentioned antioxidant (E) is greater than 100 weight portions, then be difficult to the decline of the sensitivity that suppression causes because of dyestuff, thus be difficult to realize high sensitivity, and easily in developing procedure, produce pattern short circuit.
Solvent (F)
Above-mentioned solvent (F) effectively can dissolve other composition being contained in photosensitive composition, as long as be generally used for the solvent (F) of photosensitive composition, then not by particular restriction, especially, ethers, aromatic hydrocarbon based, ketone, alcohols, ester class or amide-type etc. are preferably.
Above-mentioned solvent (F) specifically can enumerate the ethylene glycol monoalkyl ether classes such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether; The diethylene glycol dialkyl ether classes such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether; The ethylene glycol such as ethylene glycol monomethyl ether acetate, ethyl cellosolve acetate alkylether acetates class; The aklylene glycol alkylether acetates classes such as propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether ethylene glycol, methoxybutyl acetic acid esters, methoxypentyl acetic acid esters; Benzene,toluene,xylene, sym-trimethyl benzene etc. are aromatic hydrocarbon based; The ketones such as methyl ethyl ketone, acetone, methylpentanone, hexone, cyclohexanone; The alcohols such as ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, ethylene glycol, glycerine; And the cyclic ester class etc. such as the ester such as 3-ethoxyl ethyl propionate, 3-methoxy methyl propionate class, gamma-butyrolacton.
Consider in screening characteristics and drying property, above-mentioned solvent (F) is preferably the organic solvent that boiling point is 100 DEG C to 200 DEG C, more preferably uses propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, 3-ethoxyl ethyl propionate and 3-methoxy methyl propionate etc.
Above-mentioned illustrative solvent (F) can individually use or mix two or more use, with the general assembly (TW) of photosensitive composition of the present invention for benchmark, solvent (F) can comprise 60 ~ 90 % by weight, preferably comprises 70 ~ 85 % by weight.
If the content of above-mentioned solvent (F) is in the scope of above-mentioned 60 ~ 90 % by weight, then when using the applying device such as roll coater, spin coater, slit and spin coater, slit coater (being also called extrusion coater), ink jet printer to apply, the effect that screening characteristics becomes good can be provided.
Adjuvant (G)
Photosensitive composition of the present invention in addition to the aforementioned ingredients, in the scope not hindering object of the present invention, can according to the needs of technician and with adjuvants (G) such as filling agent (g1), other macromolecular compound (g2), hardening agent (g3), closely sealed promoter (g4), ultraviolet light absorber (g5) and anticoalescents (g6).
Above-mentioned filling agent (g1) specifically can use glass, silicon dioxide, aluminium oxide etc., but is not limited thereto.
Above-mentioned other macromolecular compound (g2) specifically can use the curable resin such as epoxy resin, maleimide resin; The thermoplastic resins etc. such as polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, Polyfluoroalkyl acrylate, polyester, polyurethane, but be not limited thereto.
Above-mentioned hardening agent (g3), for realizing deeply-curing and improving mechanical strength, specifically can use epoxy compound, polyfunctional isocyanate compound, melamine compound, oxetane compound etc., but be not limited thereto.Above-mentioned epoxy compound specifically can use bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, A Hydrogenated Bisphenol A F type epoxy resin, phenolic resin varnish type epoxy resin, other fragrant family epoxy resin, alicyclic ring family epoxy resin, ethylene oxidic ester system resin, glycidyl amine system resin, or the brominated derivative of these epoxy resin, aliphatics outside epoxy resin and brominated derivative thereof and alicyclic or aromatic epoxy compound, the epoxide of butadiene (being total to) polymkeric substance, the epoxide of isoprene (being total to) polymkeric substance, (methyl) glycidyl acrylate (being total to) polymkeric substance, triglycidyl isocyanurate etc., but be not limited thereto.Above-mentioned oxetane compound specifically can use carbonic ester dioxygen azetidine, dimethylbenzene dioxygen azetidine, adipate dioxygen azetidine, terephthalate dioxygen azetidine, cyclohexane dicarboxylic acid dioxygen azetidine etc., but is not limited thereto.
Above-mentioned hardening agent can with hardening agent together also with the solidification auxiliary compounds that the oxetanes scaffolds open of the epoxy radicals of epoxy compound and oxetane compound can be made to be polymerized.Above-mentioned solidification auxiliary compounds specifically can use polybasic carboxylic acid class, polybasic acid anhydride class, acid agent etc.Above-mentioned carboxyanhydrides can utilize the epoxy curing agent commercially sold.The above-mentioned epoxy curing agent that market is sold such as can enumerate ADEKA HARDENER EH-700 (trade name) (manufacture of Adek Industrial Co., Ltd), RIKACID HH (trade name) (New Japan Chem Co., Ltd's manufacture), MH-700 (trade name) (New Japan Chem Co., Ltd's manufacture) etc.
Illustrative hardening agent and solidification auxiliary compounds can individually use or mix two or more use in above-mentioned.
Above-mentioned closely sealed promoter (g4) specifically can be used alone and is selected from vinyl trimethoxy silane, vinyl three ethoxy silane, vinyl three (2-methoxy ethoxy) silane, N-(2-aminoethyl)-3-aminopropyltriethoxy dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, APTES, 3-glycidylpropyl trimethoxy silane, 3-glycidylpropyl methyl dimethoxysilane, 2-(3, 4-7-oxa-bicyclo[4.1.0) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methyl allyl acyloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, material in 3-isocyanate group propyl trimethoxy silicane and 3-isocyanate group propyl-triethoxysilicane or their potpourri.
Mark meter by weight, relative to the total solid composition of photosensitive composition of the present invention, above-mentioned closely sealed promoter can comprise 0.01 ~ 10 % by weight, preferably comprises 0.05 ~ 2 % by weight.
Particularly, above-mentioned ultraviolet light absorber (g5) can use 2-(the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole, alkoxy benzene ketone etc., but is not limited thereto.
Particularly, above-mentioned anticoalescent (g6) can use sodium polyacrylate etc., but is not limited thereto.
The manufacture method of photosensitive composition of the present invention can be illustrated as follows.
First, mix the pigment (a1) in above-mentioned colorant (A) and solvent (F), and utilize ball mill etc. to disperse, until the mean grain size of pigment reaches less than 0.2 μm degree.Now, as required can with part or all or dyestuff (a2) of solvent (F) together hybrid pigment spreading agent (a3), alkali soluble resin (B), carry out dissolving or disperseing.
Dyestuff (a2), remaining alkali soluble resin (B), photopolymerizable compound (C), Photoepolymerizationinitiater initiater (D) and antioxidant (E) is added in the dispersion liquid of above-mentioned mixing, also add adjuvant (G) and solvent (F) if desired, make it reach predetermined concentration, thus photosensitive composition of the present invention can be manufactured.
Below, be described in more details based on embodiments of the invention, but following disclosed embodiments of the present invention are only exemplary, scope of the present invention is not by the restriction of these embodiments.Claims of the present invention illustrate scope of the present invention, especially comprise and have the meaning equal with the record of application claims protection domain and all changes in the scope equal with the record of application claims protection domain.Further, if there is no special explanation, in following examples, comparative example, represent that " % " and " part " of content is weight basis.
Experimental example
Make paints dispersive composition
< pigment dispensing composition M1>
By the AJISPUR PB821 (manufacture of Ajinomoto FineTechno Co., Ltd.) of the C.I. paratonere 254 of ball mill to 10.85 weight portions, 3.80 weight portions as spreading agent, to carry out mixing and the dispersion of 12 hours as the propylene glycol methyl ether acetate of 76.90 weight portions of solvent and the cyclohexanone of 8.45 weight portions, thus manufacture dispersible pigment dispersion M1.
The synthesis of alkali soluble resin
< synthesis example 1>
Drop into propylene glycol methyl ether acetate, the propylene glycol monomethyl ether of 80 weight portions, the azoisobutyronitrile (AIBN) of 2 weight portions, 13.0 parts by weight of acrylic acid, the benzyl methacrylate of 10 weight portions, the 4-methyl styrene of 57.0 weight portions, the methyl methacrylate of 20 weight portions, the n-dodecyl mercaptan of 3 weight portions of 120 weight portions to the flask possessing stirrer, thermometer, backflow cooling tube, tap funnel and nitrogen ingress pipe, and carry out nitrogen displacement.Stir afterwards, and be 110 DEG C by the temperature increase of reactant liquor, carried out the reaction of 6 hours.The acid number of the solid constituent of the alkali soluble resin of such synthesis is 100.2mgKOH/g, and the weight-average molecular weight Mw utilizing gel permeation chromatography (GPC) to measure is about 15110.
The manufacture of photosensitive composition
< embodiment 1>
Mix the above-mentioned < pigment dispensing composition M1> of 36.50 weight portions, acid red (the Acid Red 52 of 0.54 weight portion, TCI America company), the resin of the < synthesis example 1> of 10.11 weight portions, the KAYARAD DPHA (Japanese chemical drug Inc. makes) of 3.86 weight portions, the TR-PBG-305 (manufacture of TRONLY company) of 1.00 weight portions, as 1 of 0.23 weight portion of phenol system antioxidant, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene (1, 3, 5-Trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene) (240 hours, aldrich company), as triphenyl phosphate (Triphenyl phosphate) (the aldrich company) of 0.15 weight portion of phosphorous antioxidant, the 4-hydroxy-4-methyl-2-pentanone of 12.75 weight portions, the propylene glycol methyl ether acetate of 34.85 weight portions produces photosensitive composition.
< embodiment 2>
Mix the above-mentioned < pigment dispensing composition M1> of 36.50 weight portions, acid red (the Acid Red 52 of 0.54 weight portion, TCI America company), the resin of the < synthesis example 1> of 10.11 weight portions, the KAYARAD DPHA (Japanese chemical drug Inc. makes) of 3.86 weight portions, the TR-PBG-305 (manufacture of TRONLY company) of 1.00 weight portions, as the 3-(3 of 0.23 weight portion of phenol system antioxidant, 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl (Octadecyl3-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) (264 hours, aldrich company), as triphenyl phosphate (Triphenyl phosphate) (the aldrich company) of 0.15 weight portion of phosphorous antioxidant, the 4-hydroxy-4-methyl-2-pentanone of 12.75 weight portions, the propylene glycol methyl ether acetate of 34.85 weight portions produces photosensitive composition.
< embodiment 3>
Mix the above-mentioned < pigment dispensing composition M1> of 36.50 weight portions, acid red (the Acid Red 52 of 0.54 weight portion, TCI America company), the resin of the < synthesis example 1> of 10.11 weight portions, the KAYARAD DPHA (Japanese chemical drug Inc. makes) of 3.86 weight portions, the TR-PBG-305 (manufacture of TRONLY company) of 1.00 weight portions, as four (3 of 0.23 weight portion of phenol system antioxidant, 5-di-t-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester (Pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate)) (960 hours, aldrich company), as triphenyl phosphate (Triphenyl phosphate) (the aldrich company) of 0.15 weight portion of phosphorous antioxidant, the 4-hydroxy-4-methyl-2-pentanone of 12.75 weight portions, the propylene glycol methyl ether acetate of 34.85 weight portions produces photosensitive composition.
< comparative example 1>
Mix the above-mentioned < pigment dispensing composition M1> of 36.50 weight portions, acid red (the Acid Red 52 of 0.54 weight portion, TCI America company), the resin of the < synthesis example 1> of 10.56 weight portions, the KAYARAD DPHA (Japanese chemical drug Inc. makes) of 4.03 weight portions, the TR-PBG-305 (manufacture of TRONLY company) of 1.05 weight portions, the 4-hydroxy-4-methyl-2-pentanone of 12.75 weight portions, the propylene glycol methyl ether acetate of 34.85 weight portions produces photosensitive composition.
< comparative example 2>
Mix the above-mentioned < pigment dispensing composition M1> of 36.50 weight portions, acid red (the Acid Red 52 of 0.54 weight portion, TCI America company), the resin of the < synthesis example 1> of 10.28 weight portions, the KAYARAD DPHA (Japanese chemical drug Inc. makes) of 3.93 weight portions, the TR-PBG-305 (manufacture of TRONLY company) of 1.02 weight portions, as four (3 of 0.24 weight portion of phenol system antioxidant, 5-di-t-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester (Pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate)) (960 hours, aldrich company), the 4-hydroxy-4-methyl-2-pentanone of 12.75 weight portions, the propylene glycol methyl ether acetate of 34.74 weight portions produces photosensitive composition.
< comparative example 3>
Mix the above-mentioned < pigment dispensing composition M1> of 36.50 weight portions, acid red (the Acid Red 52 of 0.54 weight portion, TCI America company), the resin of the < synthesis example 1> of 10.37 weight portions, the KAYARAD DPHA (Japanese chemical drug Inc. makes) of 3.96 weight portions, the TR-PBG-305 (manufacture of TRONLY company) of 1.03 weight portions, as triphenyl phosphate (Triphenyl phosphate) (the aldrich company) of 0.16 weight portion of phosphorous antioxidant, the 4-hydroxy-4-methyl-2-pentanone of 12.75 weight portions, the propylene glycol methyl ether acetate of 34.69 weight portions produces photosensitive composition.
< comparative example 4>
Mix the above-mentioned < pigment dispensing composition M1> of 36.50 weight portions, acid red (the Acid Red 52 of 0.54 weight portion, TCI America company), the resin of the < synthesis example 1> of 10.11 weight portions, the KAYARAD DPHA (Japanese chemical drug Inc. makes) of 3.86 weight portions, the TR-PBG-305 (manufacture of TRONLY company) of 1.00 weight portions, as 2 of 0.23 weight portion of phenol system antioxidant, 6-di-tert-butyl-4-methy phenol (2, 6-Di-tert-butyl-4-methylphenol) (48 hours, aldrich company), as triphenyl phosphate (Triphenyl phosphate) (the aldrich company) of 0.15 weight portion of phosphorous antioxidant, the 4-hydroxy-4-methyl-2-pentanone of 12.75 weight portions, the propylene glycol methyl ether acetate of 34.85 weight portions produces photosensitive composition.
< comparative example 5>
Mix the above-mentioned < pigment dispensing composition M1> of 36.50 weight portions, acid red (the Acid Red 52 of 0.54 weight portion, TCI America company), the resin of the < synthesis example 1> of 10.11 weight portions, the KAYARAD DPHA (Japanese chemical drug Inc. makes) of 3.86 weight portions, the TR-PBG-305 (manufacture of TRONLY company) of 1.00 weight portions, as 4 of 0.23 weight portion of phenol system antioxidant, two (the 6-tert-butyl-m-cresol) (4 of 4'-butylidene, 4'-Butylidenebis (6-tert-butyl-m-cresol)) (48 hours, aldrich company), as triphenyl phosphate (Triphenyl phosphate) (the aldrich company) of 0.15 weight portion of phosphorous antioxidant, the 4-hydroxy-4-methyl-2-pentanone of 12.75 weight portions, the propylene glycol methyl ether acetate of 34.85 weight portions produces photosensitive composition.
< comparative example 6>
Mix the above-mentioned < pigment dispensing composition M1> of 36.50 weight portions, acid red (the Acid Red 52 of 0.54 weight portion, TCI America company), the resin of the < synthesis example 1> of 10.11 weight portions, the KAYARAD DPHA (Japanese chemical drug Inc. makes) of 3.86 weight portions, the TR-PBG-305 (manufacture of TRONLY company) of 1.00 weight portions, as 1 of 0.23 weight portion of phenol system antioxidant, 1, 3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (1, 1, 3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane) (120 hours, aldrich company), as triphenyl phosphate (Triphenyl phosphate) (the aldrich company) of 0.15 weight portion of phosphorous antioxidant, the 4-hydroxy-4-methyl-2-pentanone of 12.75 weight portions, the propylene glycol methyl ether acetate of 34.85 weight portions produces photosensitive composition.
< experimental example 1> measures adaptation, aberration and transmissivity
The photosensitive composition manufactured in above-described embodiment 1 to 3 and comparative example 1 to 6 is utilized to produce color filter.
Particularly, utilize spin-coating method to apply above-mentioned each photosensitive composition respectively on the glass substrate (Corning Incorporated manufactures, " EAGLE XG ") of 2 inch square, be positioned over afterwards on heating plate, and maintain 3 minutes at the temperature of 100 DEG C, thus define film.Then, the test photomask with the line/intermittent pattern making the pattern of the stepped change of transmissivity and have 1 μm to 100 μm in the scope of 1% to 100% is positioned on above-mentioned film, with and the test photomask mode that forms the interval of 300 μm irradiated ultraviolet.Now, ultraviolet light source uses the high-pressure sodium lamp comprising the 1KW of g, h, i line in the lump, and with 100mJ/cm 2illumination irradiate, and do not use special optical filter.The above-mentioned film of irradiation ultraviolet radiation is soaked in the KOH aqueous development solution 2 minutes that pH is 10.5, develops.Utilize after distilled water washs the above-mentioned glass plate being coated with film, blow nitrogen to carry out drying, and heat 25 minutes in the heated oven of 230 DEG C, thus produce color filter.
The thickness of the film of the color filter produced in above-mentioned is 2.0 μm.
< adaptation >
When being evaluated generated pattern by optical microscope, by peeling off on following standard evaluation pattern phenomenon degree, and be presented at following < table 1>.
Zero: pattern does not peel off.
△: pattern peels off 1 ~ 3.
×: pattern peels off more than 4.
< aberration and transmissivity measure >
(Olympus Corp manufactures to utilize colorimeter, OSP-200) after being determined at the transmissivity of 100 μm of patterns of the substrate manufactured in < experimental example 1>, the hard baking carried out each 25 minutes is added under 230 degree, carry out 6 times altogether, measure transmissivity more afterwards, and average transmission rate of change is presented at table 1.
The result of above-mentioned experimental example 1 is presented at table 1.
< developing powder >
Measure non-exposed part when developing and be dissolved in the time needed for developer solution completely, and be presented at following table 1.
Table 1
Adaptation Developing powder (second) Aberration (△ y) Transmissivity Average transmission rate of change
Embodiment 1 ○ 14 0.0025 17.56 97.6％
Embodiment 2 ○ 14 0.0021 17.57 97.9％
Embodiment 3 ○ 14 0.0017 17.66 98.5％
Comparative example 1 △ 18 0.0033 17.35 96.8％
Comparative example 2 △ 18 0.0029 17.38 97.2％
Comparative example 3 ○ 14 0.0031 17.37 97.0％
Comparative example 4 ○ 15 0.0025 17.48 97.2％
Comparative example 5 ○ 14 0.0020 17.46 97.1％
Comparative example 6 ○ 14 0.0020 17.50 97.4％
With reference to above-mentioned table 1, can confirm, the color filter manufactured by the photosensitive composition of embodiment 1,2 and 3, due to excellent adhesion, thus do not produce pattern and peel off, and developing powder be fast, aberration is few, transmission is excellent.

Claims (9)

1. a red pixel photosensitive composition, it is characterized in that, contain toner A, alkali soluble resin B, photopolymerizable compound C, Photoepolymerizationinitiater initiater D, the photosensitive composition of antioxidant E and solvent F, described colorant A comprises more than one pigment a1 and more than one dyestuff a2, more than one in described pigment a1 or dyestuff a2 are red series, described Photoepolymerizationinitiater initiater D comprises the oxime ester system light trigger containing hexichol sulfenyl represented by following chemical formula 1, described antioxidant E comprises the phenol system antioxidant of more than a kind and the phosphorous antioxidant of more than a kind, described phenol system antioxidant is not deteriorated for more than 200 hours in 150 DEG C,
Chemical formula 1:
In above-mentioned formula,
R1 is following chemical formula 2,
R2 is alkyl, phenyl, substituted or unsubstituted phenyl, the substituted or unsubstituted benzyl of C1 ~ C8,
R3 is hexichol sulfenyl;
Chemical formula 2:
-R 4-R 5
Wherein, R4 is the alkylidene of C1 ~ C4,
R5 is the alkyl or cycloalkyl of C3 ~ C8.
2. red pixel photosensitive composition according to claim 1, is characterized in that, take solid constituent as benchmark, relative to the Photoepolymerizationinitiater initiater D of 100 weight portions, comprises the described antioxidant E of 1 ~ 100 weight portion.
3. red pixel photosensitive composition according to claim 1, it is characterized in that, described phenol system antioxidant comprises and is selected from 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, 1,3,5-trimethyl-2,4, more than one in 6-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) benzene and four (3,5-di-t-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester.
4. red pixel photosensitive composition according to claim 1, it is characterized in that, described phosphorous antioxidant comprises and is selected from triphenyl phosphate, isodecyl diphenyl phosphate, three (2,4-di-tert-butyl-phenyl) phosphate, 3,9-two (octadecane oxygen bases)-2,4,8,10-tetra-oxa--3,9-bis-phospha spiral shell [5.5] undecane and 2, more than one in 2'-di-2-ethylhexylphosphine oxide (4,6-di-tert-butyl-phenyl)-ethylhexyl dihydrogen phosphate.
5. red pixel photosensitive composition according to claim 1, is characterized in that, in described antioxidant, the weight ratio of phenol system antioxidant and phosphorous antioxidant is 1:1 ~ 5:1.
6. red pixel photosensitive composition according to claim 1, it is characterized in that, mark meter by weight, relative to the total solid composition in described photosensitive composition, comprise the colorant A of 5 ~ 60 % by weight, 10 ~ 80 % by weight the photopolymerizable compound C of alkali soluble resin B and 5 ~ 45 % by weight; Take solid constituent as benchmark, relative to described alkali soluble resin B and photopolymerizable compound C sum 100 weight portion, comprise the Photoepolymerizationinitiater initiater D of 0.1 ~ 40 weight portion.
7. red pixel photosensitive composition according to claim 1, is characterized in that, by weight mark meter, relative to the total solid composition in colorant A, comprises the described dyestuff a2 of 0.5 ~ 80 % by weight.
8. a color filter, is characterized in that, is made up of red pixel photosensitive composition according to claim 1.
9. a liquid crystal indicator, is characterized in that, comprises color filter according to claim 8.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106959576A (en) * 2015-11-25 2017-07-18 捷恩智株式会社 Photosensitive composite and its application
CN107656423A (en) * 2016-07-26 2018-02-02 株式会社Lg化学 Photosensitive polymer combination and the colour filter containing the photosensitive polymer combination

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KR20090066076A (en) * 2007-12-18 2009-06-23 제일모직주식회사 Photosensitive resin composition for color filter and color filter using same
KR20140016650A (en) * 2012-07-30 2014-02-10 동우 화인켐 주식회사 Colored photosensitive resin composition

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
KR20090066076A (en) * 2007-12-18 2009-06-23 제일모직주식회사 Photosensitive resin composition for color filter and color filter using same
KR20140016650A (en) * 2012-07-30 2014-02-10 동우 화인켐 주식회사 Colored photosensitive resin composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106959576A (en) * 2015-11-25 2017-07-18 捷恩智株式会社 Photosensitive composite and its application
CN107656423A (en) * 2016-07-26 2018-02-02 株式会社Lg化学 Photosensitive polymer combination and the colour filter containing the photosensitive polymer combination
CN107656423B (en) * 2016-07-26 2020-11-10 株式会社Lg化学 Photosensitive resin composition and color filter containing the same

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