CN1570764A - Light-sensitive resin composition for black matrix - Google Patents

Light-sensitive resin composition for black matrix Download PDF

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CN1570764A
CN1570764A CN 200410042228 CN200410042228A CN1570764A CN 1570764 A CN1570764 A CN 1570764A CN 200410042228 CN200410042228 CN 200410042228 CN 200410042228 A CN200410042228 A CN 200410042228A CN 1570764 A CN1570764 A CN 1570764A
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methyl
compound
acid
weight portions
alkali soluble
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CN1260619C (en
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李俊贤
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Chi Mei Industrial Co Ltd
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Chi Mei Industrial Co Ltd
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Abstract

This invention relates to light-sensitive resin compound used in black matrix, which is excellent in sensitivity when in exposure and in resolution power and leveling margin of image after developing and will not easily drop out of base plate. This compound comprises alkali soluble resin (A), ethylene unsaturated group compound (B), optical initiation reagent (C) with general formula (c-1), solvent (D) and black colorant. The alkali soluble resin (A) which includes function group represented by general formula (a-1) wherein, R represents independent hydrogen atoms, straight chain with one to five carbon, bifurcationalkyl, phenyl group or halogen atom) and general formula (c-1) wherein, Z1 represents Ra, Rb-S, Rc-O and Ra is hydrogen atom, alkyl, aromatic group; Z2 represents hydrogen atom, C1-C4 alkyl, halogen).

Description

Photosensitive resin composition for black matrix
Technical field
The present invention system comprises LCD (Liquid crystal display is called for short LCD) and plasma display panel (plasma display is called for short PDP) about a kind of display that is applicable to, particularly is applicable to the photosensitive resin composition for black matrix of LCD.
Background technology
In recent years, employed colored filter when the colorize of LCD is handled all has meticulous, the high-quality requirement of image quality height.Wherein, be contrast and the correlation properties thereof that improve this display, the general employing in the striped (stripe) of colored filter and point (dot) gap placed photomask.For example, between the picture element such as red, blue, green of colored filter, form black matrix" with the usefulness as photomask, this black matrix" can prevent that the contrast that is caused descends because of the light between picture element leaks, degradation lacks under the excitation.
Yet the employed material of black matrix" in the past all based on the vapor-deposited film of chromium or chromium oxide etc., but with the material of this vapor-deposited film as black matrix", all has shortcomings such as processing procedure complexity, material expensive.Being the head it off point, is to propose the mode of photosensitive resin composition with light lithography (photo lithographic) formed black matrix".
Above-mentioned have photosensitive resin composition with the relevant patent that the lithographic mode of light forms black matrix": (1) is with each layer photoresist plies such as red, green and bluenesss, form the method (be disclosed in Japanese kokai publication sho 59-204009 communique, the spy opens clear 63-40101 communique and the spy opens flat 2-287303 communique) of light shield layer; (2) photoresist is formed pattern after, the method that pattern is dyeed (be disclosed in the spy opens clear 62-14103 communique and the spy opens clear 62-14104 communique); (3) photoresist (photoresist) with carbon black black pigments such as (carbon black) forms method of patterning (be disclosed in the spy and open flat 4-177202) or the like.
In the right above-mentioned method, with the overlay method of (1) and the formed black matrix" of decoration method of (2), it is not good that it hides rerum naturas such as optical activity and thermotolerance; And the pigment dispersing method of (3) is compared (1) and (2) method owing to used black pigment, and it has higher shading rate.
The method of above-mentioned (3), the resin that main system will contain phenol (phenol) and the formed alkali soluble resin of bridging agent of holding N-methylol (N-methylol) structure are as cementing agent, and collocation light acid propellant and black pigment and form the photosensitive resin composition that a black matrix" is used, and this photosensitive resin composition is formed a black matrix" with the light lithography.
And the manufacturing process of above-mentioned (3), the system earlier with this photosensitive resin composition for black matrix with the revolution coating method, coat glass baseplate surface, form a photomask, then with pre-bake mode, after the solvent drying, form pre-roasting filming, will be somebody's turn to do the pre-roasting exposure between between specified light shield (mask) of filming again, make the exposed portion sclerosis, and the stripping of unexposed position is formed pattern with weak alkaline aqueous solution, dry dry processing after carrying out again at last.
But the method for making of above-mentioned (3) has the problem that edge shape presents undercutting.
For solving the above problems, be have proposition with the alkali soluble resin that contains fluorenes (fluorene) functional group as cementing agent, and the collocation black pigment is (as the black organic pigment, black inorganic pigment or light screening material) and form the photosensitive resin composition that a black matrix" is used, and this photosensitive resin composition is formed the method (be disclosed in the spy and open flat 8-278629) of a black matrix" with the light lithography.This mode can solve the problem that edge shape presents undercutting really.
But above-mentioned with the alkali soluble resin that contains the fluorenes functional group as cementing agent, and collocation black pigment and form the photosensitive resin composition that a black matrix" is used, problem generation such as sensitivity is low when still having exposure during use, development is poor, edge planarization, the resolution of the back pattern that forms that develops are not good; Especially, the requirement to black matrix" recently trends towards film and high shading rate, and this constituent can't satisfy the demand of industry.
Summary of the invention
The present invention's purpose is to provide a kind of photosensitive resin composition for black matrix that is applicable to display.Sensitivity when a kind of exposure particularly is provided is good, good, the no undercutting of edge planarization, resolution of the pattern that the back of developing forms and the difficult photosensitive resin composition for black matrix that comes off from substrate.
The technical solution used in the present invention is that this constituent comprises: alkali soluble resin (A), contain the ethene unsaturated group compound (B), contain down represented light initiator (C), solvent (D) and the black pigment (E) of note general expression (c-1); Wherein, this alkali soluble resin (A) is to contain the represented functional group of note general expression (a-1) down.
Figure A20041004222800051
General expression (a-1)
(in the formula, R represents separately independently straight chain or difference alkyl, phenyl or the halogen atom of hydrogen atom, carbon number 1～5) General expression (c-1)
(in the formula, Z 1Expression Ra, Rb-S, Rc-O, wherein Ra, Rb, Rc represent hydrogen atom, alkyl (alkyl), aromatic series base (aryl); Z 2Expression hydrogen atom, C 1～C 4Alkyl, halogen (halide)).
Beneficial effect of the present invention is that the light sensitivity in this constituent when exposure is good, and edge planarization, the resolution of the pattern (pattern) that the back of developing forms are good, no undercutting (underctu) and difficultly come off from substrate.
Description of drawings
Fig. 1 is the edge of acute angle side status figure of photoresist pattern.
Fig. 2 is edge, the obtuse angle side status figure of photoresist pattern.
Embodiment
Below one by one each composition of the present invention is done detailed explanation:
(A) alkali soluble resin
Alkali soluble resin of the present invention (A) is to contain the represented functional group of note general expression (a-1) down, and it is to be formed through reaction by the represented functional group's of note general expression (a-1) under containing the compound and the compound of other copolymerizable reaction.
Figure A20041004222800061
General expression (a-1)
(in the formula, R represents the hydrogen atom of independence separately, straight chain or difference alkyl, phenyl or the halogen atom of carbon number 1～5).
Last note contains the represented functional group's of general expression (a-1) the concrete example of compound as bisphenol fluorene (bisphenol fluorene) the type compound (hereinafter to be referred as compound (a-3)) of the hydroxyl (hydroxy) shown in the bisphenol fluorene that contains epoxy radicals (epoxy) shown in the general expression (a-2) (bisphenol fluorene) type compound (hereinafter to be referred as compound (a-2)) and the general expression (a-3):
General expression (a-2)
(in the formula, R is identical with the expression of preceding note)
Figure A20041004222800063
General expression (a-3)
In the formula, R is identical with the expression of preceding note; R 1, R 2Expression is selected at least a independent separately, and the alicyclic functional group of alkylidene of carbon number 1～20 (alkylene) or carbon number 1～20; K, l shows separately the independently integer more than 1.
But the compound of above-mentioned other copolyreaction can be exemplified below: acrylic acid, methacrylic acid, butenoic acid, α-Lv Bingxisuan, the unsaturated monocarboxylic acid class of ethylacrylic acid and cinnamic acid etc.; Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrobenzene dioctyl phthalate, the hexahydrobenzene dioctyl phthalate, the methyltetrahydro phthalic acid, methyl hexahydrobenzene dioctyl phthalate, methyl endo-methylene group tetrahydrobenzene dioctyl phthalate (methyl endo-methylenetetrahydro phthalic acid), chlorine mattress acid (chlorendic acid), the dicarboxylic acids class of glutaric acid etc. and sour anhydride thereof; 1,2, the tricarboxylic acid class and the sour anhydride thereof of 4-benzenetricarboxylic acid (trimellitic acid) etc.; 1,2,4,5 benzenetetracarboxylic acid (pyromellitic acid), The benzophenone tetrabasic carboxylic acid(benzophenone tetracarboxylic acid), two benzene tertacarbonic acids (biphenyl tetracarboxylic acid), the quaternary carboxylic acids and sour two anhydrides thereof of two phenylate tetrabasic carboxylic acids (biphenylethertetracarboxylic acid) etc.
Alkali soluble resin of the present invention (A) there is no special restriction on method for making, below enumerate three kinds of method for makings (method for making I～method for making III) and be illustrated.
Method for making I
Compound (a-2) is reacted with (methyl) acrylic acid earlier, make down represented bisphenol fluorene (bisphenol fluroene) type epoxy (methyl) acrylate (epoxy (meth) acrylate) compound (hereinafter to be referred as compound (a-4)) of note general expression (a-4).
General expression (a-4)
In the following formula, R is with aforesaid identical, R 3Expression hydrogen (H) or methyl (CH 3).
Then with polybasic carboxylic acid or its sour anhydride reaction of compound (a-4) and single kind and make.For example, the sour anhydride of compound (a-4) and dicarboxylic acids class is added thermal response in ester class solvents such as ethoxyethyl acetate(EA) or butoxy acetic acid ethyl ester, make the alkali soluble resin (A) that contains ethene unsaturated double-bond and carboxyl simultaneously, the available following general expression of this alkali soluble resin (A) (A-1) is represented (hereinafter to be referred as resin (A-1)).
Figure A20041004222800072
General expression (A-1)
In the formula, X can represent (following Jane Said compound (a-5)) by following note general expression (a-5);
Figure A20041004222800081
General expression (a-5)
(in the following formula, R and R 3With aforesaid identical)
Remove the remaining residue of anhydride group in the sour anhydride compound of Y table dicarboxylic acids class, promptly the sour anhydride of this dicarboxylic acids class can be represented (hereinafter to be referred as compound (a-6)) by following general expression (a-6);
General expression (a-6)
The integer that m table 1 is above is preferably 1～20 integer.
In above-mentioned, the meaning of " polybasic carboxylic acid of single kind or its sour anhydride " represents promptly in the course of reaction that the kind of polybasic carboxylic acid or its sour anhydride only can be selected dicarboxylic acids or its sour anhydride, tricarboxylic acid or its sour anhydride, quaternary carboxylic acid or its sour two anhydrides etc. wherein a kind of.
Method for making II
The potpourri of acid two anhydrides of the sour anhydride of compound (a-4) and dicarboxylic acids class and quaternary carboxylic acids is added thermal response in ester class solvents such as ethoxyethyl acetate(EA) or butoxy acetic acid ethyl ester, make the alkali soluble resin (A) that contains ethene unsaturated double-bond and carboxyl simultaneously.The available following general expression of the alkali soluble resin of method for making II (A) (A-2) is represented (hereinafter to be referred as resin (A-2)).
General expression (A-2)
Remove the dicarboxylic anhydride base and last residue in the acid two anhydride compounds of Z table quaternary carboxylic acids, promptly sour two anhydrides of this quaternary carboxylic acids can be represented by following general expression (a-7);
General expression (a-7)
P and q represent the integer more than 1, are preferably 1～20 integer.
P and q represent the degree of polymerization, and the ratio of p/q is preferably 1/99～90/10 for good, is more preferred from 5/95～80/20.
In above-mentioned, " potpourri " represents that promptly the sour anhydride of dicarboxylic acids class and sour two anhydrides of quaternary carboxylic acids need to react under the condition of existence at the same time.
Method for making III
Sour two anhydrides of compound (a-4) elder generation and quaternary carboxylic acids are added thermal response in ester class solvents such as ethoxyethyl acetate(EA) or butoxy acetic acid ethyl ester, after the reaction, the sour anhydride that adds the dicarboxylic acids class again, add thermal response, make the alkali soluble resin (A) that contains ethene unsaturated double-bond and carboxyl simultaneously.The available following general expression of the alkali soluble resin of method for making III (A) (A-3) is represented (hereinafter to be referred as resin (A-3)).
General expression (A-3)
In the following formula, X, Y and Z be with aforesaid identical, the integer that r table 1 is above, but preferable with 1～20 integer.
In the synthetic reaction process of the alkali soluble resin of above-mentioned method for making I～III (A), the temperature of reaction of compound (a-4) and polybasic carboxylic acid class and sour anhydride thereof is preferably 50～130 ℃, is more preferred from 70～120 ℃.
In the synthetic reaction process of the alkali soluble resin of above-mentioned method for making I～III (A), based on hydroxyl 1 equivalent of compound (a-4), the contained sour anhydride base of the sour anhydride of its employed polybasic carboxylic acid class is preferably 0.4～1 equivalent, is more preferred from 0.75～1 equivalent.
In the synthetic reaction process of the alkali soluble resin of above-mentioned method for making II and method for making III (A), the molar ratio of acid two anhydrides of the sour anhydride of dicarboxylic acids class and quaternary carboxylic acids is preferably 1/99～90/10, is more preferred from 5/95～80/20.
(B) contain the compound of ethene unsaturated group
Based on alkali soluble resin (A) 100 weight portions, the use amount that the present invention contains the compound (B) of ethene unsaturated group is generally 5～220 weight portions, is preferably 10～160 weight portions, is more preferred from 15～120 weight portions.
The above-mentioned compound (B) that contains the ethene unsaturated group is the ethene unsaturated compound with at least one ethene unsaturated group.
The concrete example that wherein has the compound of an ethene unsaturated group has acrylamide, (methyl) acryloyl morpholine, (methyl) acrylic acid-7-amino-3,7-dimethyl monooctyl ester, isobutoxy methyl (methyl) acrylamide, (methyl) acrylic acid isobornyl 2-ethoxyethyl acetate, (methyl) isobornyl acrylate, (methyl) acrylic acid-2-ethyl caproite, ethyl diglycol (methyl) acrylate, uncle's octyl group (methyl) acrylamide, two acetone (methyl) acrylamide, (methyl) acrylic acid dimethylamino ester, (methyl) dodecylacrylate, (methyl) acrylic acid two cyclopentene 2-ethoxyethyl acetates, (methyl) acrylic acid two cyclopentene esters, N, N-dimethyl (methyl) acrylamide, (methyl) acrylic acid tetrachloro phenyl ester, (methyl) acrylic acid-2-tetrachloro phenoxy ethyl, (methyl) tetrahydrofurfuryl acrylate, (methyl) tetrabromophenyl acrylate, (methyl) acrylic acid-2-tetrabromo phenoxy ethyl, (methyl) acrylic acid-2-Trichlorophenoxy ethyl ester, (methyl) acrylic acid tribromophenyl, (methyl) acrylic acid-2-tribromophenoxy ethyl ester, (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) acrylic acid-2-hydroxypropyl acrylate, caprolactam, N-vinyl skin junket alkane ketone, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid pentachlorophenyl ester, (methyl) acrylic acid pentabromo-phenyl ester, poly-single (methyl) acrylic acid glycol ester, poly-single (methyl) acrylic acid propylene glycol ester, (methyl) acrylic acid norbornene ester.
The concrete example of ethene unsaturated compound with 2 or 2 above ethene unsaturated groups is as follows: ethylene glycol bisthioglycolate (methyl) acrylate, two (methyl) acrylic acid, two cyclopentene esters, triethylene glycol diacrylate, tetraethylene glycol two (methyl) acrylate, three (2-hydroxyethyl) isocyanates two (methyl) acrylate, three (2-hydroxyethyl) isocyanates three (methyl) acrylate, three (2-hydroxyethyl) isocyanates three (methyl) acrylate of caprolactone upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester, three (methyl) acrylic acid trihydroxy methyl propyl ester of oxirane (hereinafter to be referred as EO) upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester of epoxypropane (hereinafter to be referred as PO) upgrading, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, polyester two (methyl) acrylate, polyglycol two (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate of caprolactone upgrading, dipentaerythritol five (methyl) acrylate of caprolactone upgrading, four (methyl) acrylic acid, two trihydroxy methyl propyl ester, bisphenol-A two (methyl) acrylate of EO upgrading, bisphenol-A two (methyl) acrylate of PO upgrading, hydrogenated bisphenol A two (methyl) acrylate of EO upgrading, hydrogenated bisphenol A two (methyl) acrylate of PO upgrading, the glycerin tripropionate of PO upgrading, Bisphenol F two (methyl) acrylate of EO upgrading, phenolic aldehyde polyglycidyl ether (methyl) acrylate or the like.
In the aforementioned ethene unsaturated compound, the preferably is dipentaerythritol acrylate, the tetrapropylene acid two trihydroxy methyl propyl ester of three acrylic acid trihydroxy methyl propyl ester, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, dipentaerythritol five acrylate, dipentaerythritol tetraacrylate, the caprolactone upgrading of three acrylic acid trihydroxy methyl propyl ester, the PO upgrading of three acrylic acid trihydroxy methyl propyl ester, EO upgrading, the glycerin tripropionate of PO upgrading.
(C) light initiator
The present invention's light initiator (C) is to contain the represented compound of note general expression (c-1) down.
General expression (c-1)
Wherein, Z 1The functional group of expression Ra, Rb-S, Rc-O is preferably Ra, Rb-S; Wherein Ra, Rb, Rc represent hydrogen atom, alkyl, aromatic series base; Z 2Expression hydrogen atom, C 1～C 4Alkyl, halogen.
Based on the compound that contains the ethene unsaturated group (B) 100 weight portions, the use amount of light initiator of the present invention (C) is generally 2～120 weight portions, is preferably 5～70 weight portions, is more preferred from 10～60 weight portions.
The present invention's light initiator (C) preferable concrete example is as ethane ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9 hydrogen-carbazole-3-substituting group]-; 1-(oxygen-acetyl oxime) [Ethanone; 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-; 1-(O-acetyl oxime)] (trade name: CGI-242; Ciba Specialty Chemicals system; structural formula is shown in general expression (c-1-1)); ethane ketone; 1-[9-ethyl-6-(2-chloro-4 benzene sulfo group benzoyls)-9 hydrogen-carbazole-3-substituting group]-; 1-(oxygen-acetyl oxime) [Ethanone; 1-[9-ethyl-6-(2-chloro-4-benzylsulfonyl benzoyl)-9H-carbazole-3-yl]-; 1-(O-acetyl oxime)] (rising sun electrification corporate system, structural formula is shown in general expression (c-1-2)).
Figure A20041004222800121
General expression (c-1-1)
General expression (c-1-2)
In the present invention's the photosensitive resin composition for black matrix, when (1) alkali soluble resin (A) contains the represented functional group of general expression (a-1), and when (2) light initiator (C) contains the represented compound of general expression (c-1), then this photosensitive resin composition is after coating, sensitivity during exposure is good, good, the no undercutting of edge planarization, resolution of the pattern that the back of developing forms and difficultly come off from substrate.
In addition, employed smooth initiator also can contain in addition light initiator of light initiator (C) (C ') among the present invention.This light initiator (C ') for example: the acetophenone based compound.
Wherein, the concrete example of acetophenone based compound is as Right dimethylamine acetophenone (p-dimethylamino-acetophenone), α, α '-dimethoxy azoxy acetophenone (α, α ' Wen Biao-dimethoxyazoxyacetophenone), 2,2 '-dimethyl-2-phenyl acetophenone (2,2 '-dimethyl-2-phenylacetophenone), Right methoxyacetophenone (p-methoxy acetophenone), 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-Do quinoline generation-1-acetone (2-methyl-1-(4-methylthiophenyl)-2-morpholino propane-1-on), 2-benzyl-2-N, N dimethylamine-1-(4-Do quinoline is for phenyl)-1-butanone [2-benzyl-2-N, N-dimethylamino-1-(4-morpholinophenyl)-1-butanone].
These light initiators (C ') can independent a kind of use, also can mix two or more use.The aforementioned lights initiator (C ') be with 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino-1-acetone, 2-benzyl-2-N, (4-morpholino phenyl)-the 1-butanone is preferable for N dimethylamine-1-.
Based on the compound that contains the ethene unsaturated group (B) 100 weight portions, the use amount of light initiator of the present invention (C ') is generally 0.5～60 weight portion, is preferably 1～50 weight portion, is more preferred from 2～40 weight portions.
In the present invention, especially containing being used in combination of light initiator (C) shown in the above-mentioned general expression (c-1) and acetophenone based compound class light initiator (C ') to good, this combination and photosensitive resin composition through coating, exposure, after the video picture, the resolution of formed pattern is higher.
In the photosensitive resin composition for black matrix of the present invention, in addition light initiator of note light initiator (C) and (C ') before can further adding (C ").For example: 2,2 '-two (neighbour-chlorphenyl)-4,4 ', 5, and 5 '-tetraphenyl diimidazole [2,2 '-bis (o-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-two (ortho-fluorophenyl base)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (o-fluorophenyl)-4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-two (neighbour-aminomethyl phenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (o-methyl phenyl)-4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-two (neighbour-methoxyphenyl)-4,4 ', 5, and 5 '-tetraphenyl diimidazole [2,2 '-bis (o-methoxyphenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole], 2,2 '-two (p-methoxyphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (p-methoxyphenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole], 2,2 '-two (2,2 ', 4,4 '-tetramethoxy phenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (2,2 ', 4,4 '-tetramethoxyphenyl)-4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole], 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-biimidazole] etc. diimidazole based compound (biimidazole); 1-(4-phenyl-sulfo--phenyl)-butane-1,2-diketone 2-oxime-oxygen-benzoic ether [1-(4-phenyl-thio-phenyl)-butane-1,2-dion 2-oxime-O-benzoate], 1-(4-phenyl-sulfo--phenyl)-octane-1,2-diketone 2-oxime-oxygen-benzoic ether [1-(4-phenyl-thio-phenyl)-octane-1,2-dion 2-oxime-O-benzoate] (trade name: CGI-1 24, Ciba Specialty Chemicals system, structural formula is shown in postscript general expression (c "-1)); 1-(4-phenyl-sulfo--phenyl)-octane-1-ketoxime-oxygen-acetate [1-(4-phenyl-thio-phenyl)-octane-1-on oxime-O-acetate]; oximes (oxime) compound of 1-(4-phenyl-sulfo--phenyl)-butane-1-ketoxime-oxygen-acetate [1-(4-phenyl-thio-phenyl)-butane-1-on oxime-O-acetate] etc.; Thioxanthones (thioxanthone), 2,4-diethyl thioxanthone (2,4-diethylthioxanthanone), thioxanthones-4-sulfone (thioxanthone-4-sulfone), benzophenone (benzophenone), 4,4 '-two (dimethylamine) benzophenone [4,4 '-bis (dimethylamino) benzophenone], 4, benzophenone (benzophenone) compounds of 4 '-two (diethylamine) benzophenone [4,4 '-bis (diethylamino) benzophenone] etc.; Benzil (benzil), acetyl group (acetyl) etc. α-diketone (compounds of α-diketone); Keto-alcohol (acyloin) compounds of diphenylhydroxyethanone (benzoin) etc.; Keto-alcohol ether (acyloin ether) compounds of diphenylhydroxyethanone methyl ether (benzoin methylether), diphenylhydroxyethanone ether (benzoin ethylether), diphenylhydroxyethanone isopropyl ether (benzoin isopropyl ether) etc.; 2,4,6-trimethyl benzoyl diphenyl phosphine oxide (2,4,6-trimethyl-benzoyl diphenylphosphineoxide), two-(2,6-dimethoxy benzoyl)-2,4, and 4-trimethylphenyl phosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethylbenzyl phosphineoxide] etc. acyl phosphine oxide (acylphosphineoxide) compounds; Anthraquinone (anthraquinone), 1, and the 4-naphthoquinones (1, the 4-naphthoquinone) quinone of Denging (quinone) compounds; The halide compound of chloroacetophenone (phenacyl chloride), trisbromomethyl benzene sulfone (tribromomethylphenylsulfone), three (trichloromethyl)-s-triazines [tris (trichloromethyl)-s-triazine] etc.; The superoxide of two-tert-butyl peroxide (di-tertbutylperoxide) etc.
Figure A20041004222800141
General expression (c "-1)
(D) solvent
Photosensitive resin composition for black matrix of the present invention system with aforementioned alkali soluble resin (A), contain compound (B) the light initiator (C) of ethene unsaturated group, and the black pigment (E) of solvent (D) and aftermentioned is neccessary composition, can add the additive composition of aftermentioned in case of necessity.
In the selection of aforementioned solvents (D), need are selected solubilized alkali soluble resin (A), are contained the compound (B) of ethene unsaturated group, and light initiator (C), and do not react to each other with these compositions, and have suitable volatility person.
Based on 100 weight portion alkali soluble resins (A), the use amount of the solvent of photosensitive resin composition for black matrix of the present invention (D) is generally 500～3, and 500 weight portions are preferably 800～3,200 weight portions, are more preferred from 1,000～3,000 weight portion.
Photosensitive resin composition for black matrix of the present invention with the concrete example of solvent as ethylene glycol monomethyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, DGDE, the diglycol positive propyl ether, the diglycol n-butyl ether, the triethylene glycol methyl ether, the triethylene glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, the dipropylene glycol methyl ether, the dipropylene glycol ether, the dipropylene glycol positive propyl ether, the dipropylene glycol n-butyl ether, tripropylene glycol methyl ether (tripropylene glycol mono methyl ether), (gathering) alkylene glycol mono alkane ethers of tripropylene glycol ether (tripropylene glycol monoethyl ether) etc.; (gathering) alkylene glycol mono alkane ether acetate classes such as glycol methyl ether acetate, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetate; Other ethers such as diethylene glycol dimethyl ether, diglycol ethyl methyl ether, diethyl carbitol, tetrahydrofuran; Ketones such as MEK, cyclohexanone, 2-heptanone, 3-heptanone; Lactic acid alkane ester classes such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester; 2-hydroxy-2-methyl methyl propionate, 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, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butyl propionic ester, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other ester classes such as 2-oxygen base ethyl butyrate; Aromatic hydrocarbons such as toluene, dimethylbenzene class; N-Methyl pyrrolidone, N, carboxylic acyloxy amines such as dinethylformamide, N,N-dimethylacetamide or the like.This equal solvent can independent a kind of use, also can mix two or more use.Be preferable in the aforementioned solvents with 1-Methoxy-2-propyl acetate, diethylene glycol dimethyl ether, 3-ethoxyl ethyl propionate.
(E) black pigment
Based on alkali soluble resin (A) 100 weight portions, the use amount of black pigment of the present invention (E) is generally 20～500 weight portions, is preferably 40～400 weight portions, is more preferred from 60～300 weight portions.
The black pigment of used (E) composition among the present invention, requirement need have preferable thermotolerance, photostability and solvent resistance.The concrete example of this black pigment as: perylene is deceived (perylene black), and cyanine is deceived (cyanineblack), nigrosine black organic pigments such as (aniline black); By red, blue, green, purple, yellow, cyanine (cyanine), in the fuchsin pigment such as (magenta), select two or more pigment to mix, make it become the colour mixture organic pigment of approximate blackization; Carbon black (carbon black), chromium oxide, iron oxide, titanium is deceived (titaniumblack), graphite black inorganic pigment such as (graphite).The material of lifting can a kind of independent use, also can two or more merging use.
Black pigment in the present invention (E) according to desired person, also can be followed the use spreading agent.The interfacial agent that these spreading agents can be lifted kation system, negative ion system, nonionic system, both sexes, polysiloxane series, fluorine system etc. is an example.
Wherein interfacial agent for example has: polyethylene oxide lauryl ether, polyethylene oxide stearoyl ether, the polyethylene oxide alkyl ethers class of polyethylene oxide oil ether etc.; Polyethylene oxide octyl group phenylate, the polyethylene oxide alkyl benzene ethers of polyethylene oxide nonyl phenylate etc.; Polyethylene glycol dilaurate, the polyethylene glycol di class of polyglycol distearate etc.; The sorbitan fatty acid ester class; The polyesters of fatty acid upgrading; The polyurethane class of 3 grades of amine upgradings; Below be trade name: KP (SHIN-ETSU HANTOTAI's chemical industry system), SF-8427 (Toray Dow Corning Silicon system), Puli's furlong (Polyflow, common prosperity society oil chemistry industry system), Ai Fuduopu [F-Top, De Kemupuluo is big make now in the storehouse (Tochem Products Co., Ltd.)], Mei Kafuke (Megafac, the black chemical industry system of big Japan's seal), Fu Luoduo (Fluorade, Sumitomo 3M system), asafoetide card many (Asahi Guard), Sa Fulong (Surflon, Asahi Glass system) or the like.These interfacial agents can separately or mix plural number and plant above the use.
Be the raising coating in the photosensitive resin composition for black matrix of the present invention, and can follow the use interfacial agent.Based on alkali soluble resin (A) 100 weight portions, the use amount of this interfacial agent generally is 0～6 weight portion, be preferably 0～4 weight portion, be more preferred from 0～3 weight portion, above-mentioned interfacial agent for example with employed interfacial agent in the aforementioned black pigment (E).
In addition, in the photosensitive resin composition for black matrix of the present invention, can concoct various additives in case of necessity, for example in addition macromolecular compound of filling agent, alkali soluble resin (A), adherence promoter, antioxidant, ultraviolet light absorber, anti-agglutinant, bridging agent etc.Wherein, based on alkali soluble resin (A) 100 weight portions, the use amount of additives such as in addition macromolecular compound of filling agent of the present invention, alkali soluble resin (A), adherence promoter, antioxidant, ultraviolet light absorber, anti-agglutinant is generally 0～10 weight portion, be preferably 0～6 weight portion, be more preferred from 0～3 weight portion; And the use amount of bridging agent is generally 0～100 weight portion, is preferably 0～80 weight portion, is more preferred from 0～50 weight portion.
The concrete example of these additives has: the filling agent of glass, aluminium; Alkali soluble resin (A) macromolecular compound in addition of polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, poly-perfluoroalkyl acrylate alkane ester etc.; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxyethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-epoxy prapanol propyl trimethoxy silicane, 3-epoxy prapanol propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, 3-metacryloxy propyl trimethoxy silicane, adherence promoter such as 3-mercapto propyl trimethoxy silicane; 2,2-thiobis (4-methyl-6-tert butyl phenol), 2, the antioxidant of 6-two-tert-butyl phenol etc.; Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorphenyl nitrine, alkoxy benzophenone; Reach anti-agglutinants such as sodium polyacrylate; The compound of the epoxy system of trade name 1031S, 157S-70 (oiling Shell system) etc. or the bridging agent of resin.
Photosensitive resin composition for black matrix of the present invention is that mentioned component (A)～(E) is uniformly mixed into solution state in stirrer, can add other adjuvants such as interfacial agent, adherence promoter, bridging agent in case of necessity.
Secondly, by coating methods such as revolution coating, curtain coating coating or print roll coatings above-mentioned black matrix" is coated on the substrate with photosensitive compoistion.After the coating,, remove the solvent of major part, removal of solvents is formed pre-roasting filming in pre-roasting (pre-bake) mode more earlier in the mode of drying under reduced pressure.Wherein, drying under reduced pressure and pre-roasting condition according to the kind of each composition, cooperate ratio and different, and usually, drying under reduced pressure is to carry out for 1 second～10 second under the pressure of 0～26.7kPa, and pre-roasting be under 70～110 ℃ of temperature, to carry out 1 minute～15 minutes.After pre-roasting, this roasting in advance exposure between between specified light shield (mask) of filming, impregnated in developer solution under 23 ± 2 ℃ of temperature developed in 15 seconds～5 minutes, and the part of not wanting is removed and is formed pattern.The light that exposure is used be good with the ultraviolet ray of g line, h line, i line etc., and UV-device can be (surpassing) high-pressure mercury-vapor lamp and metal halid lamp.
Substrate of the present invention, for example be useful on the alkali-free glass, soda-lime glass, hard glass (Pai Lesi glass), quartz glass of liquid crystal indicator etc. and in these persons that adheres to the nesa coating on glass, or be used for photo-electric conversion device substrate (as: silicon substrate) of solid-state image sensor etc. or the like.
Moreover, developer solution system use as: NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sal tartari, saleratus, sodium silicate, sodium methyl silicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrroles, the croak pyridine, 1,8-diazabicylo-(5,4,0)-and alkali compounds such as 7-hendecene, the concentration of developer solution is generally 0.001～10 weight %, is preferably 0.005～5 weight %, is more preferred from the alkaline aqueous solution that 0.01～1 weight % is constituted.
When using the developer solution that these alkaline aqueous solutions constitute, generally lie in after the video picture clean to wash again.Secondly with pressurized air or compressed nitrogen that pattern is air-dry.
Make last heat treated with heating arrangements such as hot plate or baking ovens more afterwards.To decide heating-up temperature be 150～250 ℃, be 5 minutes～60 minutes heat time heating time when using hot plate, be 15 minutes～90 minutes the heat time heating time when using baking oven for heating.Through behind the above treatment step, get final product display black matrix" of the present invention.
Aforementioned and other technology contents, characteristics and effect of the present invention in the explanation of following cooperation embodiment and comparative example, can be known and understand.
(synthesis example of alkali soluble resin (A))
Synthesis example a
In 500 milliliters the separated type flask (separable flask) air intake is set, stirrer, well heater, condenser pipe and thermometer, and importing air, add the feed composition thing, this feed composition thing comprises: bisphenol fluorene (bisphenol fluorene) the type compound 100 weight portions (compound shown in the general expression (a-2) that contains epoxy radicals (epoxy), epoxide equivalent is 230), tetramethyl amine chlorine (tetramethyl ammonium chloride) 0.3 weight portion, 2,6-two-tert-butyl group-paracresol (2,6-di-t-butyl-p-cresol) 0.1 weight portion, acrylic acid 30 weight portions and propylene glycol monomethyl ether acetate 130 weight portions.Wherein, the enter material way of feed composition thing is to add continuously, the pan feeding speed control in 25 weight portions/minute.The temperature of reaction of polymerization process is kept 100～110 ℃, polymerization time 15 hours.After finishing, reaction can make the faint yellow transparent mixed solution (being the mixed solution of compound (a-4)) of bisphenol fluorene type epoxy (methyl) acrylate (epoxy (meth) acrylate) compound of solid constituent concentration 50 weight %.
Secondly, mixed solution 100 weight portions that in 300 milliliters of separated type flasks, add above-mentioned gained compound (a-4), propylene glycol monomethyl ether acetate 25 weight portions, the acid of benzophenone tetrabasic carboxylic acid does not have two water things, 13 weight portions, and 1,2,3, sour anhydride 6 weight portions of 6-tetrahydrobenzene dioctyl phthalate, reaction is 2 hours under 110～115 ℃ temperature, makes the alkali soluble resin solution (being the solution of general expression (A-2)) of yellow transparent.The acid number of this resin is 98.0mgKOH/g, and weight average molecular weight is 4100, p/q=5/5.
After polymerization is finished, product of polymerization is taken out from the separated type flask,, promptly make alkali soluble resin a the solvent devolatilization.
Synthesis example b
In 300 milliliters of separable flasks, mixed solution 100 weight portions that add the compound (a-4) of synthesis example a gained, propylene glycol monomethyl ether acetate 25 weight portions, and the acid of benzophenone tetrabasic carboxylic acid does not have two water things, 13 weight portions, reaction is 2 hours under 90～95 ℃ temperature, after determining that with IR spectrum anhydride group disappears, in reactant liquor, add 1 again, 2,3, sour anhydride 6 weight portions of 6-tetrahydrobenzene dioctyl phthalate, and under 90～95 ℃ temperature, reacted 4 hours, make faint yellow transparent alkali soluble resin solution (being the solution of general expression (A-3)).The acid number of this resin is 99.0mgKOH/g, and weight average molecular weight is 3900.
After polymerization is finished, product of polymerization is taken out from the separated type flask,, promptly make alkali soluble resin b the solvent devolatilization.
Synthesis example c
On four cervical vertebra bottles of 300 milliliters of volumes, nitrogen inlet, stirrer, well heater, condenser pipe and thermometer are set, and importing nitrogen, add the feed composition thing, this feed composition thing comprises: methacrylic acid monomer 25 weight portions, methacrylic acid benzene methyl monomer 50 weight portions, methacrylate monomer 25 weight portions, polymerization are with initiator 2, and 2 '-azo is two-2-methylbutyronitrile 2.4 weight portions and 1-Methoxy-2-propyl acetate 240 weight portions.Wherein, monomer and polymerization are once all interpolations with the enter material way of the potpourri of initiator.The temperature of reaction of polymerization process is kept 100 ℃, polymerization time 6 hours.After finishing polymerization, polymerizate is taken out in four cervical vertebra bottles,, can get alkali soluble resin c the solvent devolatilization.
The embodiment of photosensitive resin composition for black matrix and comparative example
Embodiment 1
Use alkali soluble resin a 100 weight portions (solid) of synthesis example gained; with the dipentaerythritol acrylate shown in the table one (hereinafter to be referred as B-1) 50 weight portions; dipentaerythritol tetraacrylate (hereinafter to be referred as B-2) 10 weight portions; ethane ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9 hydrogen-carbazole-3-substituting group]-; 1-(oxygen-acetyl oxime) [Ethanone; 1-[9-ehtyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-; 1-(O-acetyloxime)] (hereinafter to be referred as C-1) 15 weight portions; pigment C.I.7 (hereinafter to be referred as E-1) 150 weight portions; adherence promoter (3-metacryloxy propyl trimethoxy silicane) 1 weight portion; the potpourri of bridging agent [trade name 1031S (oiling Shell system)] 15 weight portions; after adding solvent 1-Methoxy-2-propyl acetate (hereinafter to be referred as D-1) 1200 weight portions and 3-ethoxyl ethyl propionate (hereinafter to be referred as D-2) 300 weight portions; with swing-out stirrer; dissolved mixing; can modulate and photosensitive resin composition for black matrix; each evaluation of measuring mode of the following note of this photosensitive resin composition is estimated, and the gained result as shown in Table 1.
Embodiment 2
With the method for operating of embodiment 1, difference system changes the kind of alkali soluble resin (A) and the use amount of light initiator (C), and its prescription and evaluation result are stated from table one.
Embodiment 3
Method of operating with embodiment 1, difference system changes the kind and the use amount of light initiator, be respectively C-1 20 weight portions, 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino-1-acetone (hereinafter to be referred as C '-1) 5 weight portions, solvent (D) uses (D-1) 1500 weight portions, and do not add bridging agent, its prescription and evaluation result are stated from table one.
Embodiment 4
Method of operating with embodiment 2, difference system changes the kind and the use amount of light initiator, be respectively C-1 20 weight portions, 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone (hereinafter to be referred as C-2) 7 weight portions, solvent (D) uses (D-1) 1500 weight portions, and do not add adherence promoter, its prescription and evaluation result are stated from table one.
Embodiment 5
Use alkali soluble resin a 50 weight portions (solid) and alkali soluble resin b 50 weight portions (solid) of synthesis example gained, with B-1 60 weight portions shown in the table one, C-1 20 weight portions, C '-1 5 weight portion, E-1 150 weight portions, adherence promoter (3-metacryloxy propyl trimethoxy silicane) 1 weight portion, the potpourri of bridging agent [trade name 1031S (oiling Shell system)] 15 weight portions, after adding solvent D-1 1500 weight portions, with swing-out stirrer, dissolved mixing, can modulate and photosensitive resin composition for black matrix, each evaluation of measuring mode of the following note of this photosensitive resin composition is estimated, and the gained result as shown in Table 1.
Comparative example 1
Use alkali soluble resin c 100 weight portions (solid) of synthesis example gained, with B-1 50 weight portions shown in the table one, B-2 10 weight portions, C '-2 20 weight portion, 4,4 '-two (diethylamine) benzophenone (hereinafter to be referred as C "-1) 20 weight portions; 2; 2 '-two (neighbour-chlorphenyl)-4; 4 '; 5; 5 '-tetraphenyl diimidazole (hereinafter to be referred as C "-2) 20 weight portions, E-1 150 weight portions, adherence promoter (3-metacryloxy propyl trimethoxy silicane) 1 weight portion, the potpourri of bridging agent [trade name 1031S (oiling Shell system)] 15 weight portions, after adding solvent D-1 1500 weight portions, with swing-out stirrer, dissolved mixing, can modulate and photosensitive resin composition for black matrix, each evaluation of measuring mode of the following note of this photosensitive resin composition is estimated, and the gained result as shown in Table 1.
Comparative example 2
With the method for operating of comparative example 1, difference system changes the kind and the use amount of light initiator, is respectively its prescription of C-1 20 weight portions and evaluation result and is stated from table one.
Comparative example 3
Method of operating with embodiment 1, difference system changes the kind and the use amount of light initiator, be respectively 1-(4-phenyl-sulfo--phenyl)-octane-1,2-diketone 2-oxime-oxygen-benzoic ether [1-(4-phenyl-thio-phenyl)-octane-1,2-dion 2-oxime-O-benzoate] (Ciba system, trade name CGI-124 is hereinafter to be referred as C "-3) 20 weight portions; solvent (D) uses (D-1) 1500 weight portions, and its prescription and evaluation result are stated from table one.
Comparative example 4
With 1 method of operating relatively, difference system change alkali soluble resin kind, its prescription and evaluation result are stated from table one.
Evaluation method
(1), sensitivity
With the mode of photosensitive resin composition with rotary coating (spin coating), be coated on the glass substrate of 100mm * 100mm, carry out drying under reduced pressure with 13.3kPa earlier, the time was 5 seconds, pre-baking 3 minutes under 85 ℃ of temperature forms the roasting in advance of a thickness 2 μ m and films then.
(transparent step wedge, Stouffer corporate system, optical concentration rank difference are divided into 21 etc.) is adjacent to above-mentioned pre-roasting filming with the optical concentration rank difference table of model T2115, with the 20W high-pressure mercury-vapor lamp with 800mJ/cm 2Light quantity irradiation.The developer solution that impregnated in 23 ℃ again developed in 2 minutes, cleaned with pure water, observed the situation (as the foundation of judging sensitivity, in this Evaluation Method, number of degrees multilist more shows that sensitivity is high more with number of degrees) of developing.
Zero: number of degrees 9～21
△: number of degrees 7～8
*: number of degrees 1～6
(2), edge planarization
With pre-roasting the filming between between specified light shield in the evaluation method (), with ultraviolet light (exposure machine CanonPLA-501F) 300mJ/cm 2Irradiation, the developer solution that impregnated in 23 ℃ afterwards developed in 2 minutes, and unexposed partly removing on substrate cleaned with pure water, bakes 40 minutes after 200 ℃ again, can form the photoresist pattern of being wanted on glass substrate.Observe with optical microscope (500 times) again, determine the planarization at edge.
Zero: the edge is a near linear, and planarization is good
△: the marginal portion is uneven, and planarization is poor slightly
*: the edge is seriously uneven, and planarization is poor
(3), resolution
With pre-roasting the filming in the evaluation method (), the in-service evaluation resolution is with the light shield (Japanese Filcon corporate system) of line/space (line and space), with 200mJ/cm 2Irradiate light after, with the potassium hydroxide aqueous solution of 0.4 weight %, under 28 ℃ * 2 minutes condition, develop again.After the development, the lines at exposure position do not lack to land and are retained on the substrate, and remove through development at unexposed position, its minimum value of the lines amplitude that can form be decided to be resolution.
◎: below the wire spoke 10 μ m
Zero: wire spoke 10～20 μ m
△: wire spoke 20～30 μ m
*: more than the wire spoke 30 μ m
(4), undercutting
See also Fig. 1 and Fig. 2.
With the photoresist pattern of gained in the evaluation method (two), observe with sweep electron microscope (SEM), determine the shape of side, edge (edge profile).
Zero: consult Fig. 1, the edge angle θ of photoresist pattern 12 1(inner pattern 12 sidewalls of resin are with respect to the angle of substrate 14) is the acute angle of 0～90 degree.
*: consult Fig. 2, the edge angle θ of photoresist pattern 22 2(inner pattern 22 sidewalls of resin are with respect to the angle of substrate 14) is the obtuse angle of 90 degree～180 degree.
(5), come off
With the photoresist pattern of gained in the evaluation method (two),, determine whether resin pattern comes off from substrate with observation by light microscope.
Zero: nothing comes off
△: part comes off
*: seriously come off
Evaluation result according to above evaluation method is shown in table one.
The above person of thought, it only is preferred embodiment of the present invention, when not limiting scope of the invention process with this, promptly the simple equivalent of doing according to claims of the present invention and description generally changes and modifies, and all should still belong in the scope that patent of the present invention contains.
The subordinate list explanation
Table one: each embodiment of resin combination of the present invention and the proportion of composing and the evaluation result of comparative example.
Each embodiment of table one resin combination of the present invention and the proportion of composing and the evaluation result of comparative example
Composition Embodiment Comparative example
????1 ????2 ????3 ????4 ????5 ????1 ????2 ????3 ????4
Alkali soluble resin (A) (weight portion) a ????100 ????100 ????50 ????100 ????100
b ????100 ????100 ????50
c ????100 ????100
The compound (B) (weight portion) that contains the ethene unsaturated group B-1 ????50 ????50 ????50 ????50 ????60 ????50 ????50 ????50 ????50
B-2 ????10 ????10 ????10 ????10 ????10 ????10 ????10 ????10
Light initiator (C) (weight portion) C-1 ????15 ????30 ????20 ????20 ????20 ????20
The light initiator (C ') (weight portion) C’-1 ????5 ????10
C’-2 ????7 ????20 ????20
Light initiator (C ") (weight portion) C″-1 ????20 ????20
C″-2 ????20 ????20
C″-3 ????20
Solvent (D) (weight portion) D-1 ????1200 ????1200 ????1500 ????1500 ????1500 ????1500 ????1500 ????1500 ????1500
D-2 ????300 ????300
Pigment (E) (weight portion) E-1 ????150 ????150 ????150 ????150 ????150 ????150 ????150 ????150 ????150
Adjuvant (weight portion) Adherence promoter ????1 ????1 ????1 ????1 ????1 ????1 ????1 ????1
Bridging agent ????15 ????15 ????15 ????15 ????15 ????15 ????15 ????15
Assessment item Sensitivity ????○ ????○ ????○ ????○ ????○ ????× ????△ ????△ ????×
The edge planarization ????○ ????○ ????○ ????○ ????○ ????× ????× ????○ ????○
Resolution ????○ ????○ ????◎ ????◎ ????◎ ????× ????× ????× ????×
Undercutting ????○ ????○ ????○ ????○ ????○ ????× ????× ????× ????×
Come off ????○ ????○ ????△ ????△ ????○ ????× ????△ ????△ ????×
B-1 dipentaerythritol acrylate dipentaerythritol hexaacrylate
B-2 dipentaerythritol tetraacrylate dipentaerythritol tetraacrylate
C-1 ethane ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9 hydrogen-carbazole-3-substituting group]-; 1-(oxygen-acetyl oxime) Ethanone, 1-[9-ehtyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime)
C '-1 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino-1-acetone 2-methyl-1-(4-methylthio phenyl)-2-morpholino propane-1-on
C '-2 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone 2-benzyl-2-N, N-dimethylamino-1-(4-morpholinophenyl)-1-butanone
C " 14,4 '-two (diethylamine) hexichol first 4,4 '-bis (diethylamino) benzophenone
C " 22,2 '-two (neighbour-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole 2,2 '-bis (o-chlorophenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole
C " 3 1-(4-phenyl-sulfo--phenyl)-octane-1,2-ketone 2-oxime-oxygen-benzoic ether 1-(4-phenylsulfonyl-phenyl)-octane-1,2-dion 2-oxime-0-benzoate
D-1 1-Methoxy-2-propyl acetate propylene glycol monomethyl ether acetate
D-2 3-ethoxyl ethyl propionate Ethyl 3-ethoxypropionate
E-1 black pigment C.I.7
Adherence promoter 3-metacryloxy propyl trimethoxy silicane 3-methacryloxypropyltrimethoxysilane
Bridging agent trade name 1031S (oiling Shell system)

Claims (2)

1. a photosensitive resin composition for black matrix is characterized in that, its constituent comprises:
(A) alkali soluble resin
(B) contain the compound of ethene unsaturated group
(C) contain the represented light initiator of note general expression (c-1) down
(D) solvent and
(E) black pigment;
Wherein, this alkali soluble resin (A) is to contain the represented functional group of note general expression (a-1) down;
Figure A2004100422280002C1
General expression (a-1)
In the formula, R represents separately independently straight chain or difference alkyl, phenyl or the halogen atom of hydrogen atom, carbon number 1～5;
General expression (c-1)
In the formula, Z 1The functional group of expression Ra, Rb-S, Rc-O, wherein, Ra, Rb, Rc represent hydrogen atom, alkyl, aromatic series base; Z 2Expression hydrogen atom, C 1～C 4Alkyl, halogen.
2. photosensitive resin composition for black matrix according to claim 1, this constituent more comprise the light initiator (C ') of acetophenone based compound class.
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CN101634807B (en) * 2008-07-24 2012-08-08 奇美实业股份有限公司 Photosensitive resin composition for black matrix and liquid crystal display element
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CN103135344A (en) * 2011-11-25 2013-06-05 奇美实业股份有限公司 Photosensitive resin composition, black matrix, color filter and liquid crystal display element thereof
CN103885289A (en) * 2012-12-20 2014-06-25 奇美实业股份有限公司 Photosensitive resin composition, color filter and liquid crystal display element thereof
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CN101128774B (en) * 2005-02-24 2011-07-20 东京应化工业株式会社 Photosensitive resin composition for forming light shielding layer, light shielding layer and color filter
CN101114124B (en) * 2006-07-26 2013-05-01 富士胶片株式会社 Photosensitive composition, photosensitive resin transfer film, manufacturing method of photo spacer, substrate for liquid crystal display device, and liquid crystal display device
CN101634807B (en) * 2008-07-24 2012-08-08 奇美实业股份有限公司 Photosensitive resin composition for black matrix and liquid crystal display element
CN103135344A (en) * 2011-11-25 2013-06-05 奇美实业股份有限公司 Photosensitive resin composition, black matrix, color filter and liquid crystal display element thereof
CN103135344B (en) * 2011-11-25 2015-07-08 奇美实业股份有限公司 Photosensitive resin composition, black matrix, color filter and liquid crystal display element thereof
CN103885289A (en) * 2012-12-20 2014-06-25 奇美实业股份有限公司 Photosensitive resin composition, color filter and liquid crystal display element thereof
CN103885289B (en) * 2012-12-20 2017-01-04 奇美实业股份有限公司 Photosensitive resin composition, color filter and liquid crystal display element thereof
US9791773B2 (en) 2012-12-20 2017-10-17 Chi Mei Corporation Photosensitive resin composition, color filter and liquid crystal display device
WO2016058545A1 (en) * 2014-10-15 2016-04-21 奇美实业股份有限公司 Photosensitive resin composition, color filter and liquid crystal display element thereof
US10591816B2 (en) 2014-10-15 2020-03-17 Chi Mei Corporation Photosensitive resin composition, color filter, and liquid crystal display element thereof

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