CN101634807A - Photosensitive resin composition for black matrix and liquid crystal display element - Google Patents
Photosensitive resin composition for black matrix and liquid crystal display element Download PDFInfo
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- CN101634807A CN101634807A CN200810130086A CN200810130086A CN101634807A CN 101634807 A CN101634807 A CN 101634807A CN 200810130086 A CN200810130086 A CN 200810130086A CN 200810130086 A CN200810130086 A CN 200810130086A CN 101634807 A CN101634807 A CN 101634807A
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Abstract
The invention discloses a photosensitive resin composition for a black matrix without a white dot defect after developing, a color filter formed thereby and a liquid crystal display element formed thereby. The photosensitive resin composition for the black matrix comprises an alkali-soluble resin (A), a compound (B) containing a vinyl unsaturated group, a photoinitiator (C), a solvent (D) and a black dye (E), wherein the water content of the photosensitive resin composition is less than 3,000ppm.
Description
Technical field
The invention relates to a kind of display that is applicable to and comprise LCD (Liquid crystaldisplay, be called for short LCD) and plasma scope (plasma display, abbreviation PDP), particularly be applicable to the photosensitive resin composition for black matrix of LCD.A kind of photosensitive resin composition for black matrix of the no white point in back that develops particularly is provided and uses formed colored filter of this black matrix" and liquid crystal display cells.
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 pixel such as red, blue, green of colored filter, form black matrix" with as photomask usefulness, this black matrix" can prevent that caused contrast descends because of the light between pixel leaks, degradation disappearance 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 complex process, material expensive.Be the head it off point, propose the mode of photosensitive resin composition with light lithography (photolithographic) formed black matrix".
Above-mentioned have photosensitive resin composition with the relevant patent that the lithographic mode of light forms black matrix": (1) overlaps each layer photo-sensitive resins such as red, green and blueness, 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 (be disclosed in Japanese kokai publication sho 62-14103 communique and spy and open clear 62-14104 communique) that pattern is dyeed; (3) photoresist (photoresist) with carbon black black pigments such as (carbon black) forms method of patterning (being disclosed in Japanese kokai publication hei 4-177202) or the like.
Yet in the said method, with the overlapping method of (1) and the formed black matrix" of decoration method of (2), rerum naturas such as its light-proofness and thermotolerance are not good; 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), mainly be that resin that 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), be 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.Its formed black matrix" has preferable light-proofness.
In addition, U.S.'s bulletin patent 5,721,076 record, with the alkali soluble resin that contains fluorenes (fluorene) functional group as cementing agent, and collocation black pigment and form the photosensitive resin composition that a black matrix" is used.This photosensitive resin composition forms the method for a black matrix" with the light lithography, this matrix has higher thermotolerance.
Generally speaking, LCD needs high screening rate with black matrix", for example this black matrix" is under the thickness of 1 μ m, its OD (Optical Density optical density (OD), in the back OD of abbreviation) be worth need more than 2.0, especially nearest, for high-quality LCD, particularly need the high-quality LCD of high contrast, its OD value is with better greater than 4.0.But as U.S.'s bulletin patent 5,721,076 put down in writing, in its photosensitive resin composition, though with the alkali soluble resin that contains the fluorenes functional group as cementing agent, when (for example, the OD value was greater than 2.0 when the pigment use amount reached the OD value to increase, particularly greater than 4.0), then this photosensitive resin composition can produce the problem of white point after coating, exposure, development.
Publication No.WO02/100903A1 for another PCT puts down in writing, in the photosensitive resin composition, use contains the compound of carboxylate (oxime ester) of oxime as the light initiator, and collocation black pigment and form the photosensitive resin composition that a black matrix" is used, this photosensitive resin composition has preferable sensitivity.
Publication No.WO02/100903A1 as PCT puts down in writing, in the photosensitive resin composition, the compound that can use the carboxylate (oxime ester) that contains oxime is as the light initiator, but when when increasing the pigment use amount and reach the OD value (for example, the OD value is greater than 2.0, particularly greater than 4.0), then this photosensitive resin composition still can produce the problem of white point after coating, exposure, development.
In addition, in the photosensitive resin composition for black matrix of high OD value (for example the OD value is greater than 4.0), even use and contain fluorenes functional group's alkali soluble resin as cementing agent, and the compound that uses the carboxylate contain oxime is as the light initiator, after development, also can produce the problem of white point, consequently the productive rate of product reduces.
Recently, the requirement of black matrix" trends towards film and high shading rate, on remember that constituent can't satisfy the demand of industry.
Summary of the invention
The object of the present invention is to provide a kind of photosensitive resin composition for black matrix that is applicable to display.Do not produce the photosensitive resin composition for black matrix of white point problem and use formed colored filter of this black matrix" and liquid crystal display cells after a kind of development particularly is provided.
For achieving the above object, photosensitive resin composition for black matrix provided by the invention, it comprises:
Alkali soluble resin (A), the compound (B) that contains the ethene unsaturated group, light initiator (C), solvent (D) and black pigment (E), wherein, the water cut of this photosensitive resin composition is less than 3000ppm.
Described photosensitive resin composition for black matrix, wherein, this alkali soluble resin (A) contains the represented functional group of note general expression (a-1) down;
In the formula, R represents separately independently straight chain or difference alkyl, phenyl or the halogen atom of hydrogen atom, carbon number 1～5.
Described photosensitive resin composition for black matrix, wherein, this light initiator (C) comprises the represented compound (C-1) of note general expression (c-1) down;
In the formula, the functional group of Z1 table Ra, Rb-S, Rc-O, wherein, Ra, Rb, Rc table hydrogen atom, alkyl, aromatic series base; Z2 table hydrogen atom, C
1～C
4Alkyl, halogen.
A kind of colored filter provided by the invention, this optical filter comprise the formed black matrix" of being put down in writing in above-mentioned of photosensitive resin composition for black matrix.
Described colored filter, wherein, the optical density (OD) of this black matrix" is greater than 4.0.
Liquid crystal display cells provided by the invention, this element comprise the above-mentioned colored filter of claim.
Below one by one each composition of the present invention is described in detail.
(1) alkali soluble resin (A)
Alkali soluble resin used in the present invention (A)
,For example: the condensate of acrylic acid series (acrylic) resin, novolaks (novolac) resin, phenolic aldehyde (cresol) resin, polyvinyl alcohol (PVA) (polyvinylalcohol), hydroxy styrenes (hydroxy styrene), tygon hydroxylphenyl ester (polyvinyl hydroxy benzoate) etc. wherein are preferably acrylic resin.
Aforesaid propylene acid is the preferred embodiment of resin, as the resin, the vinyl monomer that contains one or more carboxylic acid group and other the copolymerizable ethene that contain the represented functional group of following note general expression (a-1) be the unsaturated monomer copolymerization and must multipolymer etc., wherein, preferable to contain the resin of remembering the functional group that general expression (a-1) is represented down.
(in the formula, R represents separately independently straight chain or difference alkyl, phenyl or the halogen atom of hydrogen atom, carbon number 1～5)
The above-mentioned resin that contains the represented functional group of general expression (a-1) is to be formed through reaction by the compound that contains the represented functional group of general expression (a-1) and the compound of other copolymerizable reactions.
The above-mentioned concrete example that contains the represented functional group's of general expression (a-1) 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, represented identical of R and preceding note)
(in the formula, R is with aforementioned represented identical; R
1, R
2Expression is selected from least a independent separately, and the alicyclic functional group of alkylidene of carbon number 1 ~ 20 (alkylene) or carbon number 1 ~ 20; K, l represent separately the independently integer more than 1)
But the compound of above-mentioned other copolyreaction can be exemplified below: unsaturated monocarboxylic acid classes such as acrylic acid, methacrylic acid, butenoic acid, α-Lv Bingxisuan, ethylacrylic acid and cinnamic acid; Dicarboxylic acids class and sour anhydrides thereof such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrobenzene dioctyl phthalate, hexahydrobenzene dioctyl phthalate, methyltetrahydro phthalic acid, methyl hexahydrobenzene dioctyl phthalate, methyl endo-methylene group tetrahydrobenzene dioctyl phthalate (methyl endo-methylene tetrahydro phthalic acid), chlorine mattress acid (chlorendic acid), glutaric acid; 1,2,4-benzenetricarboxylic acid tricarboxylic acid class and sour anhydrides thereof such as (trimellitic acid); 1,2,4,5-benzene tetracarboxylic acid (pyromellitic acid), benzophenone tetrabasic carboxylic acid (benzophenone tetracarboxylicacid), two benzene tertacarbonic acid (biphenyl tetracarboxylic acid), two phenylate tetrabasic carboxylic acid quaternary carboxylic acids and sour two anhydrides thereof such as (biphenylether tetracarboxylic acid).
Alkali soluble resin of the present invention (A) is also without particular limitation on method for making, below enumerates three kinds of method for makings (method for making I～method for making III) and is illustrated.
Method for making I
Compound (a-2) is reacted with (methyl) acrylic acid earlier, make following general expression (a-4) represented bisphenol fluorene (bisphenol fluroene) type epoxy (methyl) acrylate (epoxy (meth) acrylate) compound (hereinafter to be referred as compound (a-4)).
(in the following formula, R is with aforementioned represented identical, R
3Expression hydrogen (H) or methyl (CH
3))
Then the polybasic carboxylic acid of compound (a-4) and single kind or its sour anhydride reaction are made alkali soluble resin (A).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)).
(in the formula, X can represent (hereinafter to be referred as compound (a-5)) by following general expression (a-5);
(in the following formula, R and R
3With aforementioned represented identical)
In the general expression (A-1), 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);
(in the formula, m represents the integer more than 1, is preferably 1～20 integer)
In above-mentioned, the meaning of " polybasic carboxylic acid of single kind or its sour anhydride " is promptly represented in the course of reaction, the kind of polybasic carboxylic acid or its sour anhydride, only can select dicarboxylic acids or its sour anhydride, tricarboxylic acid or its sour anhydride, quaternary carboxylic acid or its sour two anhydrides etc. are wherein a kind of.
Method for making II
Potpourri with acid two anhydrides of the sour anhydride of compound (a-4) and dicarboxylic acids class and quaternary carboxylic acids, in ester class solvents such as ethoxyethyl acetate(EA) or butoxy acetic acid ethyl ester, 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 II gained (A) (A-2) is represented (hereinafter to be referred as resin (A-2)).
General expression (A-2)
In the following formula, X, Y are with aforementioned represented identical; Z represents to remove the dicarboxylic anhydride base and last residue in the acid two anhydride compounds of quaternary carboxylic acids, and promptly acid two anhydrides of this quaternary carboxylic acids can be represented by following general expression (a-7);
In the general expression (A-2), 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 preferable to be good with 1/99～90/10, is more preferred from 5/95～80/20.
In the above-mentioned explanation about method for making II, " potpourri " promptly represents the sour anhydride of dicarboxylic acids class and acid two anhydrides of quaternary carboxylic acids, under the condition that needs to exist at the same time, reacts.
Method for making III
Acid 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 gained (A) (A-3) is represented (hereinafter to be referred as resin (A-3)).
In the following formula, X, Y and Z are with aforementioned represented identical, and r represents the integer more than 1, but preferable with 1～20 integer.
Carry out in the synthetic reaction process that above-mentioned method for making I～III makes alkali soluble resin (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 ℃.
Carry out in the synthetic reaction process that above-mentioned method for making I～III makes alkali soluble resin (A), hydroxyl 1 equivalent based on 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.
Carry out above-mentioned method for making II and method for making III and make in the synthetic reaction process of alkali soluble resin (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.
(2) contain the compound (B) 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 has the ethene unsaturated compound of at least one ethene unsaturated group.
Wherein, concrete example with 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, trioctylphosphine (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 glycerin tripropionate of the dipentaerythritol acrylate of three acrylic acid trihydroxy methyl propyl ester of preferable is three acrylic acid trihydroxy methyl propyl ester, EO upgrading, three acrylic acid trihydroxy methyl propyl ester of PO upgrading, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, dipentaerythritol five acrylate, dipentaerythritol tetraacrylate, caprolactone upgrading, tetrapropylene acid two trihydroxy methyl propyl ester, PO upgrading.
(3) light initiator (C)
Based on the compound that contains the ethene unsaturated group (B) 100 weight portions, the use amount of smooth initiator of the present invention (C) is generally 2～180 weight portions, is preferably 5～150 weight portions, is more preferred from 10～120 weight portions.
Smooth initiator used in the present invention (C) is for example: contain the represented compound (C-1) of note general expression (c-1) down, acetophenone based compound (C-2), other light initiator (C-3) etc.Wherein, be preferably and contain represented compound (C-1) of following general expression (c-1) and acetophenone based compound (C-2).
Wherein, Z1 represents the functional group of Ra, Rb-S, Rc-O, preferable expression Ra, Rb-S, wherein Ra, Rb, Rc table hydrogen atom, alkyl, aromatic series base; Z2 table 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-1) is generally 2～120 weight portions, is preferably 5～70 weight portions, is more preferred from 10～60 weight portions.
The concrete example of smooth initiator of the present invention (C-1) 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-benzyl sulfonylbenzoyl)-9H-carbazole-3-yl]-; 1-(O-acetyl oxime)] (rising sun electrification corporate system, structural formula is shown in general expression (c-1-2)).
General expression (c-1-1)
In the photosensitive resin composition for black matrix of the present invention, 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 (C-1) of general expression (c-1), then this photosensitive resin composition is through the pattern of coating, exposure, the back formation of developing, in the OD value greater than 4.0 o'clock, but then whole exposure, the range of work (ProcessWindow) broad of development, yield are higher.
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-2) is generally 0.5～60 weight portion, is preferably 1～50 weight portion, is more preferred from 2～40 weight portions.
The concrete example of the acetophenone based compound (C-2) of last note as: to dimethylamine acetophenone (p-dimethylamino-acetophenone), α, α '-dimethoxy azoxy acetophenone (α, α '-dimethoxyazoxyacetophenone), 2,2 '-dimethyl-2-phenyl acetophenone (2,2 '-dimethyl-2-phenylacetophenone), acetanisole (p-methoxyacetophenone), 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino-1-acetone (2-methyl-1-(4-methylthio phenyl)-2-morpholino propane-1-on), 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone [2-benzyl-2-N, N-dimethylamino-1-(4-morpholinophenyl)-1-butanone].
This light initiator (C-2) can independent a kind of use, also can mix two or more use.Aforementioned lights initiator (C-2) is with 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino-1-acetone, 2-benzyl-2-N, and (4-morpholino phenyl)-the 1-butanone is preferable for N dimethylamine-1-.
In the present invention, especially containing being used in combination of light initiator (C-1) shown in the above-mentioned general expression (c-1) and acetophenone based compound class light initiator (C-2) 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, note light initiator (C-1) and (C-2) in addition light initiator (C-3) before can further adding.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-methylphenyl)-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-124, CibaSpecialty Chemicals system, structural formula is shown in general expression (c-3-1)), 1-(4-phenyl-sulfo--phenyl)-octane-1-ketoxime-oxygen-acetate [1-(4-phenyl-thio-phenyl)-octane-1-on oxime-O-acetate], 1-(4-phenyl-sulfo--phenyl)-butane-1-ketoxime-oxygen-acetate oximes (oxime) compounds such as [1-(4-phenyl-thio-phenyl)-butane-1-on oxime-O-acetate]; 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], 4,4 '-two (diethylamine) benzophenone benzophenone (benzophenone) compounds such as [4,4 '-bis (diethylamino) benzophenone]; Benzil (benzil), acetyl group α-diketone such as (the acetyl) (compounds of α-diketone); Diphenylhydroxyethanone keto-alcohol (acyloin) compounds such as (benzoin); Diphenylhydroxyethanone methyl ether (benzoin methyl ether), diphenylhydroxyethanone ether (benzoinethylether), diphenylhydroxyethanone isopropyl ether keto-alcohol ether (acyloin ether) compounds such as (benzoin isopropyl ether); 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 (1,4-naphthoquinone) wait quinone (quinone) compounds; Chloroacetophenone (phenacylchloride), trisbromomethyl benzene sulfone (tribromomethyl phenylsulfone), three (trichloromethyl)-s-triazines halide compound such as [tris (trichloromethyl)-s-triazine]; Two-tert-butyl peroxide superoxide such as (di-tertbutylperoxide).
Photosensitive resin composition for black matrix of the present invention is with aforementioned alkali soluble resin (A), contains the compound (B) of ethene unsaturated group, and light initiator (C) and black pigment described later (E) be neccessary composition, and can add solvent described later (D) and concoct various additive composition described later according to need.
(4) solvent (D)
Photosensitive resin composition for black matrix of the present invention is in the selection of solvent (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 those 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 mono ethyl 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.Those solvents 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.
(5) black pigment (E)
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 100～400 weight portions, is more preferred from 180～350 weight portions.
Used black pigment (E) among the present invention, requirement need have preferable thermotolerance, photostability and solvent resistance.This black pigment (E) concrete example is deceived (perylene black), cyanine black (cyanine black), nigrosine black organic pigments such as (aniline black) as: perylene; In red, blue, green, purple, yellow, cyanine (cyanine), 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 black (titanium black), 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 desirable, also can be followed the use spreading agent.It is example that these a little spreading agents can be lifted interfacial agents such as kation system, negative ion system, nonionic system, both sexes, polysiloxane series, fluorine system.
Wherein, interfacial agent for example has: polyethylene oxide lauryl ether, polyethylene oxide stearoyl ether, polyethylene oxide alkyl ethers classes such as polyethylene oxide oil ether; Polyethylene oxide octyl group phenylate, polyethylene oxide alkyl benzene ethers such as polyethylene oxide nonyl phenylate; Polyethylene glycol dilaurate, polyethylene glycol di classes such as polyglycol distearate; 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 be big make now in the storehouse (TochemProducts 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 a little 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, is preferably 0～4 weight portion, is more preferred from 0～3 weight portion, giving an example of above-mentioned interfacial agent is 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 optionally concoct various additives, 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 a little 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.; 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorphenyl ultraviolet light absorbers such as nitrogen, alkoxy benzophenone that change; Reach anti-agglutinants such as sodium polyacrylate; Epoxy based compound or the resin bridging agent of trade name 1031S, 157S-70 (oiling Shell system) etc.
Photosensitive resin composition for black matrix of the present invention is that mentioned component (A)～(E) is uniformly mixed into solution state in stirrer, and can optionally adds other adjuvants such as interfacial agent, adherence promoter, bridging agent.
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, in the mode of drying under reduced pressure, remove most solvent earlier, removal of solvents is formed pre-roasting filming in pre-roasting (pre-bake) mode again.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 under the pressure of 0～200mm-Hg for 1 second～10 second, carries out under 70～110 ℃ of temperature 1 minute～15 minutes and bake in advance.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 ultraviolet rays such as g line, h line, i lines, and UV-device can be (surpassing) high-pressure mercury-vapor lamp and metal halid lamp.
Aforesaid base plate, 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 a little nesa coatings that adhere 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 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, croak pyridine, 1,8-diazabicylo-(5,4,0)-alkali compounds such as 7-hendecene, the concentration of developer solution is generally 0.001～10 weight %, be preferably 0.005～5 weight %, be more preferred from the alkaline aqueous solution that 0.01～1 weight % is constituted.
When using the developer solution that this a little alkaline aqueous solution constitutes, generally be clean to wash again after video picture.Secondly with pressurized air or compressed nitrogen that pattern is air-dry.
Afterwards, make last heat treated with heating arrangements such as hot plate or baking ovens again.To decide heating-up temperature be 150～250 ℃, be 5～60 minutes heat time heating time when using hot plate, be 15～90 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.
Among the present invention, for improving contrast and the quality thereof of LCD, its black matrix" needs higher screening rate.Generally speaking, this black matrix" is under the thickness of 1 μ m, and its OD value (Optical Density) is preferably more than 4.0, is more preferred from 4.0～5.5, and the best is 4.2～5.2.
In the photosensitive resin composition of the present invention, comprise alkali soluble resin (A), contain compound (B), light initiator (C), solvent (D) and the black pigment (E) of ethene unsaturated group.Wherein, a lot of for the method for the OD value that improves black matrix", comprise use amount that increases pigment or the particle size that reduces pigment.Yet after those methods but caused development, albomaculatus shortcoming produced and influences productive rate on black matrix".In order to reach the OD value more than 4.0, and do not have the generation of white point, the water cut of photosensitive resin composition for black matrix generally need be lower than 3, and 000ppm is preferably and is lower than 2, and 800ppm is more preferred from and is lower than 2,500ppm.
Manufacturing method of color filters of the present invention is prior on the substrate, forms above-mentioned black matrix", again with identical generation type, (mainly comprising red, green, blue three looks) of all kinds is repeated above-mentioned steps, just can make the pixel dyed layer of colored filter.Secondly, to the vacuum of 250 ℃ of temperature, forming ITO (tin indium oxide) vapor-deposited film with 220 ℃ on the pixel dyed layer, in case of necessity, after execution etching of ITO film and wiring, coating of liquid crystalline alignment film polyimide again, and then burn till, promptly can be used as the colored filter that LCD is used.
The manufacture method of liquid crystal display cells of the present invention, be with above-mentioned colored filter and be provided with thin film transistor (TFT) (TFT, Thin Film Transistor) driving substrate toward each other, (structure cell at interval to get involved the gap between 2 plate bases, cell gap) does the subtend configuration, around 2 plate bases fit with sealing agent in the position, and filling injection liquid crystal in the crack between substrate surface and sealing agent are distinguished is sealed filling orifice and constituted liquid crystal structure cell (cell).Then,, that is constitute on other sides of each substrate of liquid crystal structure cell applying Polarizer and making at the outside surface of liquid crystal structure cell.
Description of drawings
Fig. 1 be the embodiment of the invention 5 in the white point evaluation method, inspect being seen local state synoptic diagram by optical microscope.
Fig. 2 be comparative example 5 of the present invention in the white point evaluation method, inspect being seen local state synoptic diagram by optical microscope.
Fig. 3 is that the optical density (OD) of black matrix" that photosensitive resin composition forms is estimated view.
Main element symbol description in the accompanying drawing:
White point (1)
Black matrix" (2)
Embodiment
Aforementioned and other technologies content, characteristics and effect of the present invention in the explanation of following cooperation embodiment and comparative example, can clearerly be understood.
The synthesis example of alkali-soluble Trees fat (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.
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 1 (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) 190 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.Wherein, before this photosensitive resin composition preparation, earlier solvent (D-1) and the adding molecular sieve 4A of mixed solvent (D-2) (graininess) stirring were done to handle earlier in 6 hours, the weight ratio of molecular sieve and mixed solvent is 2/100, after carrying out the isolated by filtration molecular sieve under the nitrogen of drying, be mixed with photoresist again and rent into thing again.Each evaluation of measuring mode of the following note of this photosensitive resin composition is estimated, and the gained result is as shown in table 1.
With the method for operating of embodiment 1, difference is the use amount that changes kind, light initiator (C-1) and the pigment (E) of alkali soluble resin (A), and its prescription and evaluation result are stated from table 1.
Embodiment 3
With the method for operating of embodiment 1, difference be the use amount that changes pigment (E), and the photosensitive resin composition after the preparation reduced its water cut in 2 hours through nitrogen purge (purge).Replenish with neat solvent (fresh solvent) again because of the solvent that evaporation is reduced and purify the back, make it reach original solid.Its prescription and evaluation result are stated from table 1.
Embodiment 4
With the method for operating of embodiment 1, difference comprises following three: (1) changes the kind and the use amount of the compound (B), light initiator (C) and the pigment (E) that contain the ethene unsaturated group; (2) before the photosensitive resin composition preparation, earlier solvent (D-1) is added molecular sieve 4A (graininess), stir and did in 6 hours to handle earlier, the weight ratio of molecular sieve and mixed solvent is 2/100, under the nitrogen of drying, filter again, isolate molecular sieve, be mixed with photosensitive resin composition again; (3) after the photosensitive resin composition preparation is finished, photosensitive resin composition is added molecular sieve 4A (graininess) again, stirred 12 hours, the weight ratio of molecular sieve and mixed solvent is 3/500, filters under the nitrogen of drying again, isolates molecular sieve.Its prescription and evaluation result are stated from table 1.
Embodiment 5
Method of operating with embodiment 4, difference is that the photosensitive resin composition after further will finally preparing reduced its water cut in 2 hours through nitrogen purge (purge), and the solvent that evaporation is reduced after purifying replenishes with neat solvent (fresh solvent) again, make it reach original solid, its prescription and evaluation result are stated from table 1.In addition, Fig. 1 demonstration is estimated embodiment 5 with white point evaluation method described later, inspect being seen local state by optical microscope with 50 times multiplying power, and the white point evaluation result of embodiment 5 is no white point.
Comparative example 1
Use alkali soluble resin a 100 weight portions (solid) of synthesis example gained, with B-1 50 weight portions shown in the table 1, B-2 10 weight portions, C-1-1 15 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 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 is as shown in table 1.Fig. 2 demonstration is estimated comparative example 1 with white point evaluation method described later, inspect being seen local state by optical microscope with 50 times multiplying power, and the white point evaluation result of comparative example 1 is for there being white point (1).
Comparative example 2
With the method for operating of comparative example 1, difference is to change the use kind of alkali soluble resin (A) and the use amount of light initiator (C-1), and its prescription and evaluation result are stated from table 1.
Comparative example 3
With the method for operating of comparative example 1, difference is to change the use kind of light initiator (C) and the use amount of pigment (E), and its prescription and evaluation result are stated from table 1.
Comparative example 4
With the method for operating of comparative example 1, difference is to change alkali soluble resin (A), the use kind of light initiator (C) and the use amount of pigment (E), and its prescription and evaluation result are stated from table 1.
Evaluation method
(1) OD value (Optical Density value)
With mode (the coating machine new light trade system of photosensitive resin composition with rotary coating (spin coating), model MS-A150), be coated on the glass substrate of 100mm * 100mm, earlier carry out drying under reduced pressure with 100mmHg, 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.
With above-mentioned pre-roasting filming between between specified light shield, with ultraviolet light (exposure machine Canon system, model PLA-501F) 300mJ/cm
2Irradiation, the developer solution that impregnated in 23 ℃ afterwards developed in 2 minutes, and unexposed part is removed on substrate, cleans with pure water, bakes 40 minutes after 200 ℃ again, can form the pattern of a thickness 1 μ m on glass substrate.And the OD value can following calculating formula be calculated.
O.D＝-log(I/I
0)
As shown in Figure 3, in the aforementioned calculation formula, I
0Be the incident light intensity, and I is through outgoing light intensity behind the black matrix", among the figure, the thickness of black matrix" (2) is 1 μ m.
(2) water cut (unit: ppm) of photosensitive resin composition
Photosensitive resin composition is put into moisture titrator (Mettler society system, model E665), then by Karl Fischer reagent SS (hereinafter to be referred as KF reagent SS, titration equivalent weight=0.7～1.0mgH
2O/milliliter) in addition titration, the water cut of this photosensitive resin composition can be calculated and get by following formula.
Water cut (ppm)=[titration equivalent weight (the mg H of KF reagent SS
2O/ml) * total amount (mg) of titer (ml)/photoresist of KF reagent SS] * 10
6
(3) white point
Get the film after the development of evaluation method (1), utilize optical microscope to amplify with 50 multiplying powers and observe and calculate the sum of observing the finding white point, its evaluation method as shown below.This evaluation method is based on the pattern on 100mm * 100mm glass substrate.
Zero: the white point number is 0
△: the white point number is between 1～3
*: the white point number is more than or equal to 4
Evaluation result according to above evaluation method is shown in table 1.
The above, it only is preferred embodiment of the present invention, when not limiting scope of the invention process with this, promptly the simple equivalent of being done according to the present patent application claim and description of the invention content generally changes and modifies, and all should still belong in the scope that claim of the present invention contains.
Table 1: each embodiment of resin combination of the present invention and the proportion of composing and the evaluation result of comparative example.
Claims (6)
1. photosensitive resin composition for black matrix, it comprises:
Alkali soluble resin (A), the compound (B) that contains the ethene unsaturated group, light initiator (C), solvent (D) and black pigment (E), wherein, the water cut of this photosensitive resin composition is less than 3000ppm.
2. according to the described photosensitive resin composition for black matrix of claim 1, wherein, this alkali soluble resin (A) contains the represented functional group of note general expression (a-1) down;
In the formula, R represents separately independently straight chain or difference alkyl, phenyl or the halogen atom of hydrogen atom, carbon number 1～5.
3. according to the described photosensitive resin composition for black matrix of claim 1, wherein, this light initiator (C) comprises the represented compound (C-1) of note general expression (c-1) down;
In the formula, the functional group of Z1 table Ra, Rb-S, Rc-O, wherein, Ra, Rb, Rc table hydrogen atom, alkyl, aromatic series base; Z2 table hydrogen atom, C
1～C
4Alkyl, halogen.
4. colored filter, this optical filter comprises the formed black matrix" of each photosensitive resin composition for black matrix of putting down in writing in the claim 1～3.
5. according to the described colored filter of claim 4, wherein, the optical density (OD) of this black matrix" is greater than 4.0.
6. liquid crystal display cells, this element comprises claim 4 or 5 colored filters of being put down in writing.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102221777A (en) * | 2010-04-16 | 2011-10-19 | 奇美实业股份有限公司 | White photosensitive resin component and white matrix as well as colorful optical filter and reflection type displayer component thereof |
| CN103838083A (en) * | 2012-11-20 | 2014-06-04 | 奇美实业股份有限公司 | Photosensitive resin composition, color filter formed by same and liquid crystal display element |
| CN104076608A (en) * | 2013-03-29 | 2014-10-01 | 奇美实业股份有限公司 | Photosensitive resin composition, white matrix, filter and display module |
| 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 |
| CN112684662A (en) * | 2021-01-03 | 2021-04-20 | 尚健 | Black matrix for liquid crystal display device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI235890B (en) * | 2003-03-31 | 2005-07-11 | Chi Mei Corp | photosensitive resin composition for color filter |
| CN1260619C (en) * | 2004-04-30 | 2006-06-21 | 奇美实业股份有限公司 | Light-sensitive resin composition for black matrix |
| TWI261728B (en) * | 2004-10-28 | 2006-09-11 | Chi Mei Corp | Photosensitive resin composition for a color filter |
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2008
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102221777A (en) * | 2010-04-16 | 2011-10-19 | 奇美实业股份有限公司 | White photosensitive resin component and white matrix as well as colorful optical filter and reflection type displayer component thereof |
| CN103838083A (en) * | 2012-11-20 | 2014-06-04 | 奇美实业股份有限公司 | Photosensitive resin composition, color filter formed by same and liquid crystal display element |
| CN103838083B (en) * | 2012-11-20 | 2017-01-04 | 奇美实业股份有限公司 | Photosensitive resin composition, color filter formed by same and liquid crystal display element |
| CN104076608A (en) * | 2013-03-29 | 2014-10-01 | 奇美实业股份有限公司 | Photosensitive resin composition, white matrix, filter and display module |
| 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 |
| CN112684662A (en) * | 2021-01-03 | 2021-04-20 | 尚健 | Black matrix for liquid crystal display device |
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| CN101634807B (en) | 2012-08-08 |
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