CN105467756A - Photosensitive resin compound - Google Patents
Photosensitive resin compound Download PDFInfo
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- CN105467756A CN105467756A CN201510618503.XA CN201510618503A CN105467756A CN 105467756 A CN105467756 A CN 105467756A CN 201510618503 A CN201510618503 A CN 201510618503A CN 105467756 A CN105467756 A CN 105467756A
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Abstract
The invention provides a photosensitive resin compound suitable for forming a black matrix layer; the formed photosensitive resin layer is high in resistance value, and excellent in photoetching property when patterns are formed; the photosensitive resin compound comprises resin (A) containing Cardo frame, photopolymerization initiator (B), silane coupling agent (C), and a colorant (D); the photosensitive resin compound is characterized in that the colorant comprises carbon black having epoxy resin coating treatment.
Description
Technical field
The present invention relates to photosensitive polymer combination.
Background technology
The liquid crystal board of liquid crystal board, especially TN mode, STN mode etc., and touch sensor panel (touchsensorpanel) possessing the black-matrix layer of the contrast for strengthening image, being usually formed with the colored filter of the dyed layer of RGB (comprise red (R), green (G), blue (B) is assorted).This black-matrix layer and dyed layer are formed by repeating following operation, described operation is: be coated on substrate by the photosensitive polymer combination of the colorant being dispersed with black or shades of colour, after carrying out drying, by the film exposure obtained, develop, the pattern desired by formation.
All the time, black-matrix layer be formed by the method (such as patent documentation 1) lithographically waiting the organic resin film patterning that will be dispersed with the black pigments such as carbon black.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2006-330209 publication
Summary of the invention
Although the optical density of black-matrix layer (OD value) improves by the content increasing the black pigment such as carbon black, there is the problem that the resistance value that more increases the charcoal then black-matrix layer with electric conductivity is lower.
Especially for movement terminal, because metal line directly contacts with black-matrix layer, so require high resistance value to black-matrix layer.
The present invention completes in view of the foregoing, problem of the present invention is to provide a kind of photosensitive polymer combination, it is the photosensitive polymer combination being suitable for being formed black-matrix layer, wherein, the intrinsic volume resistivity value of the photo-sensitive resin formed is high, and photolithographic characteristics when forming pattern is also excellent.
The present invention is a kind of photosensitive polymer combination, it contains resin (A), Photoepolymerizationinitiater initiater (B), silane coupling agent (C) and the colorant (D) with Cardo skeleton (Cardo-skeleton), it is characterized in that, above-mentioned colorant (D) comprises the carbon black through epoxy resin coating treatment.
In this instructions and these claims, " aliphatics " is the relative concept for aromatic series, and it is defined as follows: refer to the group, compound etc. without aromaticity.
So-called " alkyl ", unless otherwise specified, then comprises the univalent saturated hydrocarbon radical of straight-chain, branched and ring-type.
So-called " alkylidene ", unless otherwise specified, then comprises the divalent saturated hydrocarbon base of straight-chain, branched and ring-type.Alkyl in alkoxy is also like this.
" haloalkyl " is part or all group replaced by halogen atom of the hydrogen atom of alkyl, as this halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, atomic iodine.
" fluoro-alkyl " or " fluorianted alkylene " refers to part or all group be replaced by fluorine atoms of the hydrogen atom of alkyl or alkylidene.
So-called " structural unit ", refers to the monomeric unit forming macromolecular compound (resin, polymkeric substance, multipolymer).
So-called " from the structural unit that acrylate is derivative ", refers to that the ethylenic double bond of acrylate ruptures and the structural unit of formation.
" acrylate " is acrylic acid (CH
2=CH-COOH) the compound that replaced by organic group of the hydrogen atom of carboxyl terminal.
With regard to acrylate, can be substituted with a substituent with the hydrogen atom of the carbon atom bonding of α position.Replace the substituting group (R of the hydrogen atom of the carbon atom bonding of this and α position
α) be the atom beyond hydrogen atom or group, such as can enumerate the haloalkyl, hydroxy alkyl etc. of the alkyl of carbon number 1 ~ 5, carbon number 1 ~ 5.It should be noted that, the carbon atom of the α position of so-called acrylate, unless otherwise specified, then refer to the carbon atom of carbonyl institute bonding.
Below, sometimes the acrylate that the hydrogen atom of the carbon atom bonding with α position is substituted with a substituent is called α substituted acrylate.In addition, sometimes acrylate and α substituted acrylate are referred to as " (α replacement) acrylate ".
So-called " structural unit from hydroxy styrenes or hydroxy styrenes derivant derive ", refers to that the ethylenic double bond of hydroxy styrenes or hydroxy styrenes derivant ruptures and the structural unit of formation.
So-called " hydroxy styrenes derivant ", refers to the concept of the product that the hydrogen atom of the α position comprising hydroxy styrenes is replaced by other substituting groups such as alkyl, haloalkyl and their derivant.As their derivant, the substituting group on the product that the hydrogen atom organic group can enumerating the hydroxyl of the hydroxy styrenes be optionally substituted with a substituent by the hydrogen atom of α position replaces and obtains, the phenyl ring of hydroxy styrenes that is optionally substituted with a substituent at the hydrogen atom of α position beyond bonded hydroxy and the product etc. that obtains.It should be noted that so-called α position (carbon atom of α position) unless otherwise specified, then refers to the carbon atom of phenyl ring institute bonding.
The alternatively substituting group of the hydrogen atom of the α position of hydroxy styrenes, can enumerate the group identical with the group enumerated as the substituting group of α position in above-mentioned α substituted acrylate.
So-called " structural unit from vinyl benzoic acid or vinyl benzoic acid derivant derive ", refers to that the ethylenic double bond of vinyl benzoic acid or vinyl benzoic acid derivant ruptures and the structural unit of formation.
So-called " vinyl benzoic acid derivant ", refers to the concept of the product that the hydrogen atom of the α position comprising vinyl benzoic acid is replaced by other substituting groups such as alkyl, haloalkyl and their derivant.As their derivant, the substituting group on the product that the hydrogen atom organic group can enumerating the carboxyl of the vinyl benzoic acid be optionally substituted with a substituent by the hydrogen atom of α position replaces and obtains, the phenyl ring of vinyl benzoic acid that is optionally substituted with a substituent at the hydrogen atom of α position beyond bonded hydroxy and carboxyl and the product etc. that obtains.It should be noted that so-called α position (carbon atom of α position) unless otherwise specified, then refers to the carbon atom of phenyl ring institute bonding.
So-called " styrene derivative ", refers to the product that the hydrogen atom of cinnamic α position is replaced by other substituting groups such as alkyl, haloalkyl.
So-called " structural unit from styrene derived ", " from the structural unit that styrene derivative is derivative ", refer to that the ethylenic double bond of styrene or styrene derivative ruptures and the structural unit of formation.
The above-mentioned substituent alkyl as α position is preferably the alkyl of straight-chain or branched, specifically can enumerate the alkyl (methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl) etc. of carbon number 1 ~ 5.
In addition, as the substituent haloalkyl of α position, specifically can enumerate part or all group obtained with halogen atom replacement of the hydrogen atom of above-mentioned " the substituent alkyl as α position ".As this halogen atom, fluorine atom, chlorine atom, bromine atoms, atomic iodine etc. can be enumerated, be particularly preferably fluorine atom.
In addition, as the substituent hydroxy alkyl of α position, specifically can enumerate part or all group obtained with hydroxyl replacement of the hydrogen atom of above-mentioned " the substituent alkyl as α position ".Hydroxyl value in this hydroxy alkyl is preferably 1 ~ 5, most preferably is 1.
When being recited as " optionally there is substituting group ", comprise with univalent perssad replace hydrogen atom (-H) situation and with divalent group substituted methylene (-CH
2-) both situations.
" exposure " refers to the concept comprising all radiation exposures.
According to the present invention, can provide a kind of photosensitive polymer combination, it is suitable for forming black-matrix layer, and the intrinsic volume resistivity value of the photo-sensitive resin of formation is high, and photolithographic characteristics when forming pattern is also excellent.
Accompanying drawing explanation
Fig. 1 is the figure of the pattern angles that the photosensitive resin pattern formed in embodiments of the invention is described.
description of reference numerals
1... substrate
2... photosensitive resin pattern
Embodiment
" photosensitive polymer combination "
The present invention is a kind of photosensitive polymer combination, it contains resin (A), Photoepolymerizationinitiater initiater (B), silane coupling agent (C) and the colorant (D) with Cardo skeleton, it is characterized in that, above-mentioned colorant (D) comprises the carbon black through epoxy resin coating treatment.
[there is the resin (A) of Cardo skeleton]
As the resin with Cardo skeleton, as long as have the resin of Cardo skeleton as basic framework, be not particularly limited, wherein, the resin that following formula (a-1) represents is preferred.Because thermotolerance, the chemical proofing with the resin of Cardo structure are high, therefore, it is possible to improve thermotolerance and the chemical proofing of photosensitive polymer combination.
<X
a>
In above formula (a-1), X
arepresent the group that following formula (a-2) represents.In following formula (a-2), * represents that binding site is (hereinafter same.)。
<R
a1、R
a2>
In above formula (a-2), R
a1represent alkyl or the halogen atom of hydrogen atom, carbon number 1 ~ 6 independently of one another, R
a2represent hydrogen atom or methyl independently of one another, W
arepresent the group that singly-bound or following formula (a-3) represent.
<Y
a>
In addition, in above formula (a-1), Y
arepresent from the residue after dicarboxylic anhydride removing anhydride group (-CO-O-CO-).As the example of dicarboxylic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, phthalate anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic tetrabydrophthalic anhydride, chlorendic anhydride (ChlorendicAnhydride), methyl tetrahydrophthalic anhydride, glutaric anhydride etc. can be enumerated.
<Z
a>
In addition, in above formula (a-1), Z
arepresent and remove the residue after 2 anhydride group from tetracarboxylic dianhydride.As the example of tetracarboxylic dianhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, bibenzene tetracarboxylic dianhydride, diphenyl ether tetraformic dianhydride etc. can be enumerated.
In addition, in above formula (a-1), m represents the integer of 0 ~ 20.
The ratio of the resin (A) with Cardo skeleton contained by photosensitive polymer combination of the present invention is 10 ~ 50 quality %, the scope being preferably 15 ~ 40 quality %, more preferably 20 ~ 35 quality % relative to solid state component (composition after the aftermentioned solvent (S) in removing photosensitive polymer combination is overall).
In addition, the weight-average molecular weight (Mw) of resin (A) is preferably more than 1000, less than 40000, is more preferably more than 2000, less than 30000.By making weight-average molecular weight be more than 1000, thermotolerance, film strength can being improved, in addition, by being less than 40000, the sufficient dissolubility relative to developer solution can be obtained.
[Photoepolymerizationinitiater initiater (B)]
As this Photoepolymerizationinitiater initiater, such as, can enumerate 2-((benzoyl oxygen base) imino group)-1-(4-(thiophenyl) phenyl) octane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-(4-(2-hydroxyl-oxethyl) phenyl)-2-hydroxy-2-methyl-1-propane-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone, 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-ketone, two (4-dimethylaminophenyl) ketone, 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholinopropane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, TMDPO, 4-benzoyl-4 '-methyl dimethoxy base thioether, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid butyl ester, benzoic acid 4-dimethylamino-2-Octyl Nitrite, benzoic acid 4-dimethylamino-2-isopentyl ester, benzyl-'beta '-methoxy ethyl acetal, benzil dimethyl ketal, 1-phenyl-1,2-propanedione-2-(O-ethoxy carbonyl) oxime, o-benzoyl yl benzoic acid methyl esters, 2,4-diethyl thioxanthone, CTX, 2,4-dimethyl thioxanthone (2,4-dimethylthioxanthone), the chloro-4-propoxythioxanthone of 1-, thioxanthene, 2-diuril ton, 2,4-diethyl thioxanthene, 2-methyl thioxanthene, 2-isopropylthioxanthones, 2-EAQ, prestox anthraquinone, 1,2-benzo anthraquinone (1,2-benzanthraquinone), 2,3-diphenyl anthraquinone, azobis isobutyronitrile, benzoyl peroxide, dicumyl peroxide (cumeneperoxide), 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-(Chloro-O-Phenyl)-4,5-bis-(m-methoxyphenyl)-imidazole radicals dipolymer, benzophenone, 2-chlorobenzophenone, 4,4 '-bis-dimethylamino benzophenone, 4,4 '-bis-diethylamino benzophenone, 4,4 '-dichloro benzophenone, 3,3-dimethyl-4-methoxy benzophenone, benzil, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, benzoin butyl ether, acetophenone, 2,2-diethoxy acetophenone, to dimethyl acetophenone, to dimethylamino propiophenone, dichloroacetophenone, trichloroacetophenone, p-tert.-butyl acetophenone, to dimethylamino benzoylformaldoxime, to tert-butyl group trichloroacetophenone, to tert-butyl group dichloroacetophenone, α, α,α-dichloro-4-phenoxy acetophenone, thioxanthones, 2-methyl thioxanthones, ITX, Dibenzosuberone (dibenzosuberone), 4-dimethylaminobenzoic acid pentyl ester, 9-phenylacridine, two (9-acridinyl) heptane of 1,7-, two (9-acridinyl) pentane of 1,5-, two (9-acridinyl) propane of 1,3-, to methoxyl triazine, 2,4,6-tri-(trichloromethyl) s-triazine, two (trichloromethyl) s-triazine of 2-methyl-4,6-, two (trichloromethyl) s-triazine of 2-[2-(5-methylfuran-2-base) vinyl]-4,6-, two (trichloromethyl) s-triazine of 2-[2-(furans-2-base) vinyl]-4,6-, two (trichloromethyl) s-triazine of 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4,6-, two (trichloromethyl) s-triazine of 2-[2-(3,4-Dimethoxyphenyl) vinyl]-4,6-, two (trichloromethyl) s-triazine of 2-(4-methoxyphenyl)-4,6-, two (trichloromethyl) s-triazine of 2-(4-ethoxystyrene base)-4,6-, two (trichloromethyl) s-triazine of 2-(4-n-butoxyphenyl)-4,6-, two (trichloromethyl)-6-(the bromo-4-methoxyl of 3-) the phenyl s-triazine of 2,4-, two (trichloromethyl)-6-(the bromo-4-methoxyl of 2-) the phenyl s-triazine of 2,4-, two (trichloromethyl)-6-(the bromo-4-methoxyl of 3-) the styryl phenyl s-triazine of 2,4-, two (trichloromethyl)-6-(the bromo-4-methoxyl of 2-) the styryl phenyl s-triazine of 2,4-etc.
In addition, in above-mentioned Photoepolymerizationinitiater initiater, combined light auxiliary agent can be caused.
As above-mentioned light-initiated auxiliary agent, such as triethanolamine can be enumerated, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoic acid methyl esters, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid-2-Octyl Nitrite, benzoic acid-2-dimethylamino ethyl ester, N, N-dimethyl-p-toluidine, 4, 4 '-bis-(dimethylamino) benzophenone (common name Michler's keton (Michler ' sketone)), 4, 4 '-bis-(diethylamino) benzophenone, 9, 10-dimethoxy anthracene, 2-ethyl-9, 10-dimethoxy anthracene, 9, 10-diethoxy anthracene, 2-ethyl-9, 10-diethoxy anthracene etc.Above-mentioned light-initiated auxiliary agent can be used alone or in combination of two or more kinds.
The ratio of the Photoepolymerizationinitiater initiater (B) contained by photosensitive polymer combination of the present invention is 1 ~ 20 quality %, the scope being preferably 1 ~ 15 quality %, more preferably 2 ~ 7 quality % relative to solid state component (composition after the aftermentioned solvent (S) in removing photosensitive polymer combination is overall).
[silane coupling agent (C)]
Photosensitive polymer combination of the present invention contains silane coupling agent (C).
In the present invention, silane coupling agent (C) is not particularly limited, but such as preferably containing the compound that following general formula (C0) represents.
[in above formula, Yc
01for the alkylidene of carbon number 1 ~ 6 that can be replaced by amino, R
c1~ R
c3be the alkoxy of carbon number 1 ~ 6, the alkyl of carbon number 1 ~ 10, the naphthenic base of carbon number 3 ~ 7, the aryl of carbon number 6 ~ 10, the aralkyl of carbon number 7 ~ 10 independently of one another, R
c1~ R
c3in at least 1 be alkoxy, R
c4for the group that (C-1) or (C-2) represents, R
c5for the alkyl of the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl, ring-type, heterocycle or carbon number 1 ~ 20, R
c6for the alkyl of the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl, ring-type, heterocycle or carbon number 1 ~ 20, * is binding site.]
<Yc
01>
Yc
01for the alkylidene of carbon number 1 ~ 6 that can be replaced by amino.
As the alkylidene of carbon number 1 ~ 6, specifically, methylene [-CH can be enumerated
2-];-CH (CH
3)-,-CH (CH
2cH
3)-,-C (CH
3)
2-,-C (CH
3) (CH
2cH
3)-,-C (CH
3) (CH
2cH
2cH
3)-,-C (CH
2cH
3)
2-wait alkylmethylene; Ethylidene [-CH
2cH
2-];-CH (CH
3) CH
2-,-CH (CH
3) CH (CH
3)-,-C (CH
3)
2cH
2-,-CH (CH
2cH
3) CH
2-wait alkyl ethylidene; 1,3-propylidene (sub-n-pro-pyl) [-CH
2cH
2cH
2-];-CH (CH
3) CH
2cH
2-,-CH
2cH (CH
3) CH
2-wait alkyl-1,3-propylidene; Isosorbide-5-Nitrae-butylidene [-CH
2cH
2cH
2cH
2-];-CH (CH
3) CH
2cH
2cH
2-,-CH
2cH (CH
3) CH
2cH
2-wait alkyl-Isosorbide-5-Nitrae-butylidene; 1,5-pentylidene [-CH
2cH
2cH
2cH
2cH
2-] etc.
In the present invention, Yc
01be preferably the alkylidene of carbon number 1 ~ 4, this alkylidene is preferably straight-chain, is particularly preferably 1,3-propylidene.
In addition, in the present invention, Yc
01during the group replaced by amino for a part for the alkylidene of carbon number 1 ~ 6, the group that the part being preferably the alkylidene of the straight-chain of carbon number 1 ~ 6 is replaced by amino.
<R
c1～R
c3>
R
c1~ R
c3be the alkoxy of carbon number 1 ~ 6, the alkyl of carbon number 1 ~ 10, the naphthenic base of carbon number 3 ~ 7, the aryl of carbon number 6 ~ 10, the aralkyl of carbon number 7 ~ 10 independently of one another, R
c1~ R
c3in at least 1 be alkoxy.
(alkoxy of carbon number 1 ~ 6)
As the alkoxy of carbon number 1 ~ 6, be preferably the alkoxy of carbon number 1 ~ 5, be more preferably methoxyl, ethoxy, positive propoxy, isopropoxy, n-butoxy, tert-butoxy, most preferably be methoxyl, ethoxy.
(alkyl of carbon number 1 ~ 10)
As the alkyl of carbon number 1 ~ 10, be preferably the alkyl of straight-chain or branched, specifically, methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl, 1 can be enumerated, 1-dimethyl ethyl, 1,1-diethylpropyl, 2,2-dimethyl propyls, 2,2-dimethylbutyls etc.
(naphthenic base of carbon number 3 ~ 7)
As the naphthenic base of carbon number 3 ~ 7,2-methyl-2-adamantyl, 2-ethyl-2-adamantyl, 1-methyl isophthalic acid-naphthenic base, 1-ethyl-1-naphthenic base etc. can be enumerated, more specifically, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 2-methyl-2-adamantyl, 2-ethyl-2-adamantyl etc. can be enumerated.
(aryl of carbon number 6 ~ 10)
As the aryl of carbon number 6 ~ 10, phenyl, benzyl, tolyl, o-xylene base can be enumerated.
(aralkyl of carbon number 7 ~ 10)
As the aralkyl of carbon number 7 ~ 10, the aryl alkyls such as benzyl, phenethyl, 1-naphthyl methyl, 2-naphthyl methyl, 1-naphtylethyl group, 2-naphtylethyl group can be enumerated.
In the present invention, R
c1~ R
c3in at least 1 be alkoxy.For the present invention, preferred R
c1~ R
c3in at least 1 be the alkoxy of carbon number 1 ~ 3, be wherein particularly preferably methoxyl.In addition, preferred R
c1~ R
c3in at least 2 be methoxyl, particularly preferably R
c1~ R
c3it is all methoxyl.
<R
c4>
R
c4for the group that following general formula (C-1) or (C-2) represent.
[in above formula, R
c5for the alkyl of the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl, ring-type, heterocycle or carbon number 1 ~ 20, R
c6for the alkyl of the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl, ring-type, heterocycle or carbon number 1 ~ 20, * is binding site.]
<R
c5、R
c6>
R
c5for the alkyl of the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl, ring-type, heterocycle or carbon number 1 ~ 20, R
c6for the alkyl of the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl, ring-type, heterocycle or carbon number 1 ~ 20.
Below, to as R
c5or R
c6aromatic hydrocarbyl, the aliphatic alkyl of ring-type, heterocycle or carbon number 1 ~ 20 alkyl be described.
(aromatic hydrocarbyl)
Aromatic hydrocarbyl is the alkyl with aromatic rings.
In the present invention, the carbon number of aromatic hydrocarbyl is preferably 3 ~ 30, is more preferably 5 ~ 30, and more preferably 5 ~ 20, be particularly preferably 6 ~ 15, most preferably be 6 ~ 10.Wherein, this carbon number does not comprise substituent carbon number.
As the aromatic rings that aromatic hydrocarbyl has, specifically the aromatic hydrocarbon rings such as benzene, biphenyl, fluorenes, naphthalene, anthracene, phenanthrene can be enumerated; Form a part for the carbon atom of above-mentioned aromatic hydrocarbon ring by the heteroaromatic etc. of hybrid atom MCM-41.As the heteroatoms in heteroaromatic, oxygen atom, sulphur atom, nitrogen-atoms etc. can be enumerated.
As aromatic hydrocarbyl, specifically can enumerate and remove 1 hydrogen atom from above-mentioned aromatic hydrocarbon ring and the group (such as, benzyl, phenethyl, 1-naphthyl methyl, 2-naphthyl methyl, 1-naphtylethyl group, 2-naphtylethyl group etc. remove 1 hydrogen atom again from the aryl aryl alkyl and the group obtained) that replaced by alkylidene of 1 hydrogen atom of the group (aryl) obtained; 2 hydrogen atoms are removed and the group etc. that obtains from the aromatics (such as biphenyl, fluorenes etc.) containing the aromatic rings of more than 2.The carbon number of above-mentioned alkylidene (alkyl chain in aryl alkyl) is preferably 1 ~ 4, is more preferably 1 ~ 2, is particularly preferably 1.
In the present invention, as aromatic hydrocarbyl, be preferably phenyl, naphthyl etc.
(aliphatic alkyl of ring-type)
The aliphatic alkyl of ring-type can be polycycle, also can be monocyclic.As the ester ring type alkyl of monocyclic, from monocycle alkane, preferably eliminate the group of 1 hydrogen atom.As this monocycle alkane, the monocycle alkane of preferred carbon number 3 ~ 6, specifically can enumerate cyclopentane, cyclohexane etc.As the ester ring type alkyl of polycycle, from polycyoalkane, preferably eliminate the group of 2 hydrogen atoms, as this polycyoalkane, the polycyoalkane of preferred carbon number 7 ~ 12, specifically can enumerate diamantane, norbornane, isoborneol alkane (isobornane), tristane, tetracyclododecane etc.
(heterocycle)
As heterocycle, the hetero ring type group shown in following (r-hr-1) ~ (r-hr-62) can be enumerated.
(alkyl of carbon number 1 ~ 20)
As the alkyl of carbon number 1 ~ 20, be more preferably the alkyl of carbon number 1 ~ 10, be particularly preferably the alkyl of carbon number 1 ~ 5; Be preferably the alkyl of straight-chain or branched, specifically can enumerate methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl, neopentyl, 1,1-dimethyl ethyl, 1,1-diethylpropyl, 2,2-dimethyl propyl, 2,2-dimethylbutyls etc.
In above-mentioned group, preferable methyl or ethyl.
In the present invention, as R
c5or R
c6, be preferably hydrogen atom, the alkyl of carbon number 1 ~ 5, hetero ring type group or aromatic hydrocarbyl.
Below record the concrete example of the compound that general formula (C0) represents.In formula, Me refers to methyl (hereinafter same).
The ratio of the silane coupling agent (C) that photosensitive polymer combination of the present invention contains, for solid state component (composition except following solvents (S) in photosensitive polymer combination is overall), be 0.05 ~ 10 quality %, the scope being preferably 0.1 ~ 8 quality %, more preferably 0.5 ~ 5 quality %.
With regard to photosensitive polymer combination of the present invention, by comprising the colorant containing the carbon black through epoxy resin coating treatment hereinafter described, the volume resistivity value of the photo-sensitive resin of formation can be made very high.
On the other hand, when using the carbon black through epoxy resin coating treatment, the reduction of the water tolerance caused by epoxy radicals becomes problem.This is because, because water tolerance reduces, the volume resistivity value of photo-sensitive resin is also reduced.
Therefore, inferring by making photosensitive polymer combination of the present invention contain above-mentioned silane coupling agent (C), the water tolerance of photo-sensitive resin can be improved.Especially, infer when above-mentioned silane coupling agent (C) has urea skeleton (-N-C (=O)-N-), very large contribution can be made to raising water tolerance.
In addition, infer that by containing silane coupling agent (C), can make also to improve relative to the adaptation of substrate, therefore, it is possible to prevent photo-sensitive resin after patterning from strippable substrate, elching resistant also improves.
[colorant (D)]
The present invention contains colorant (D), and above-mentioned colorant (D) comprises the carbon black through epoxy resin coating treatment.
Epoxy resin, relative to the amount of coating of carbon black, is preferably 1 ~ 30wt% relative to the total amount of carbon black and epoxy resin.
By for more than above-mentioned lower limit, dispersiveness, dispersion stabilization, the insulativity higher than untreated carbon black can be obtained.In addition, by for below above-mentioned higher limit, favorable dispersibility can be made.
In addition, use through the carbon black of epoxy resin coating treatment as colorant (D) time, preferably carry out adjusting to make OD (OpticalDensity, the optical density) value of every 1 μm of thickness of the film formed become more than 3.0, be preferably more than 3.5.If the OD value of every 1 μm of thickness is more than 3.5, then when being used as the black matrix" of colored filter, sufficient display comparison degree can be obtained, necessary performance can be obtained.
When the photo-sensitive resin using photosensitive polymer combination of the present invention to be formed is used as black matrix", if increase the content of carbon black, then the optical density (OD value) as black matrix" improves.
On the other hand, increase the content with the carbon black of electric conductivity, will the reason of the intrinsic volume resistivity value reducing black matrix" be become.
Infer because the present invention adopts through the carbon black of epoxy resin coating treatment as the black colorant added in photosensitive polymer combination, so increase formed photo-sensitive resin, black matrix" OD value while, also can realize increasing intrinsic volume resistivity value.
As except the colorant except the carbon black of epoxy resin coating treatment, such as, can enumerate the pigment or dyestuff recorded in Japanese Laid-Open Patent Publication 60-237403 publication and Japanese Unexamined Patent Publication 4-310901 publication.
Such as, Colour Index (C.I. can be enumerated; TheSocietyofDyersandColourists corporation issues) in be classified as the compound of pigment (Pigment), specifically can enumerate the compound being endowed Colour Index (C.I.) as described below number.
C.I. (following, " C.I. pigment yellow " is identical, only records numbering for pigment yellow 1.)、3、11、12、13、14、15、16、17、20、24、31、53、55、60、61、65、71、73、74、81、83、86、93、95、97、98、99、100、101、104、106、108、109、110、113、114、116、117、119、120、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、166、167、168、175、180、185；
C.I. (following, " C.I. pigment orange " is identical, only records numbering for pigment orange 1.)、5、13、14、16、17、24、34、36、38、40、43、46、49、51、55、59、61、63、64、71、73；
C.I. (following, " C.I. pigment violet " is identical, only records numbering for pigment violet 1.)、19、23、29、30、32、36、37、38、39、40、50；
C.I. (following, " C.I. paratonere " is identical, only records numbering for paratonere 1.)、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48：1、48：2、48：3、48：4、49：1、49：2、50：1、52：1、53：1、57、57：1、57：2、58：2、58：4、60：1、63：1、63：2、64：1、81：1、83、88、90：1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、155、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、192、193、194、202、206、207、208、209、215、216、217、220、223、224、226、227、228、240、242、243、245、254、255、264、265；
C.I. (following, " C.I. alizarol saphirol " is identical, only records numbering for pigment blue 1.), 2,15,15:3,15:4,15:6,16,22,60,64,66; C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 37;
C.I. pigment brown 23, C.I. pigment brown 25, C.I. pigment brown 26, C.I. pigment brown 28; C.I. pigment black 1, pigment black 7.
The ratio of the colorant (D) that photosensitive polymer combination of the present invention contains, for solid state component (composition except following solvents (S) in photosensitive polymer combination is overall), be 30 ~ 80 quality %, the scope being preferably 40 ~ 75 quality %, more preferably 45 ~ 70 quality %.
The ratio of the carbon black through epoxy resin coating treatment in colorant (D), is preferably more than 80 quality %, is more preferably more than 90 quality %, more preferably 95 ~ 100 quality %.
By being above-mentioned scope, can be maintained as the function of colored filter, sensitivity is good, and the thermotolerance of the film after solidification and chemical proofing become good.
[solvent (S)]
Photosensitive polymer combination of the present invention is preferably containing solvent (S).Solvent (S) is preferably the solvent (S1) of more than 200 DEG C and boiling point lower than the solvent (S2) of 200 DEG C containing boiling point.
As solvent (S2), be preferably selected from more than a kind in cyclohexanone (AN) and propylene glycol methyl ether acetate (PGMEA), acetic acid 3-methoxybutyl (MA), dimethyl ether (DMM) and cyclohexyl acetate (CHXA).Wherein, acetic acid 3-methoxybutyl and propylene glycol methyl ether acetate (PGMEA) is more preferably.
Relative to solvent (S) generally speaking, the use level of (S2) can be 90 ~ 99 quality %, is preferably 92 ~ 98 quality %, is more preferably 94 ~ 97 quality %.
In the present invention, solvent (S) is preferably the solvent (S1) of more than 200 DEG C containing boiling point.
As the solvent (S1) that boiling point is more than 200 DEG C, can 1 be enumerated, 4-butyldiglycol diacetate esters (1,4-butyldiglycoldiacetate), ethyl diglycol acetic acid esters (ethyldiglycolacetate), gamma-butyrolacton (GBL), dipropylene glycol methyl ether acetic acid esters (DPMA), 1,3-butylene glycol diacetate esters (1,3-BGA), diethylene glycol monoethyl ether acetic acid esters (EDGAC) or butyl carbitol acetate (BDGAC).
In above-mentioned solvent, Isosorbide-5-Nitrae-butyldiglycol diacetate esters, butyldiglycol acetic acid esters, ethyl diglycol acetic acid esters are preferred.These solvents can be used alone separately, or can combine two or more use.
Relative to solvent (S) generally speaking, the use level of (S1) can be 1 ~ 10 quality %, is preferably 2 ~ 8 quality %, is more preferably 3 ~ 6 quality %.
The use level of solvent (S) is preferably 70 quality % ~ 90 quality % relative to photosensitive polymer combination entirety of the present invention.That is, the solid component concentration of photosensitive polymer combination of the present invention is preferably 10 quality % ~ 30 quality %.
Can think, when to contain boiling point be solvent (S1) of more than 200 DEG C to photosensitive polymer combination of the present invention, when preliminary drying, solvent remains in photosensitive resin film, therefore the curable epoxide reaction in unexposed portion is slack-off, not easily produce the obstruction to unexposed portion developing solution dissolution, therefore, be not easy when pattern is formed to produce residue.
The volume resistivity value of photosensitive polymer combination of the present invention is preferably 1.0 × 10
13more than (Ω cm).
Volume resistivity value calculates as follows.
Sectional area (the cm of volume resistivity value (Ω cm)=carbon black powder
2the stack height (cm) of) × resistance value (Ω)/carbon black powder
Because the black matrix" using photosensitive polymer combination of the present invention to be formed have employed above-mentioned colorant (D), so intrinsic volume resistivity value can be made very high.Especially when volume resistivity value is 1.0 × 10
13time more than (Ω cm), movement terminal metal line directly being contacted to black matrix" is useful.
< optional member >
Photosensitive polymer combination of the present invention can also contain photopolymerizable compound (E).
Photopolymerizable compound is subject to the irradiation of the light such as ultraviolet and the material being polymerized, solidifying.As photopolymerizable compound, preferably there is the compound of ethylenic double bond, specifically can enumerate acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monomethyl ester, 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, glycol monoethyl ether acrylate, glycol monoethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glyceral methacrylate, acrylamide, Methacrylamide, vinyl cyanide, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, β-dimethyl-aminoethylmethacrylate, isobutyl acrylate, isobutyl methacrylate, acrylic acid-2-ethyl caproite, methacrylic acid-2-Octyl Nitrite, benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, Ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, TEGDMA, tetraethylene glycol diacrylate, TEG dimethylacrylate, butanediol dimethylacrylate, propylene glycol diacrylate, dimethacrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, tetra methylol tetraacrylate, tetra methylol propane tetramethyl acrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate (DPTA), pentaerythritol tetramethylacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol pentamethacrylates, dipentaerythritol acrylate (DPHA), dipentaerythritol hexamethacrylate, 1,6-hexanediyl ester, HDDMA, the monomers such as Cardo epoxy radicals diacrylate, oligomer class, polyester (methyl) acrylate that the polyester prepolyer that polyalcohols and monoacid or polyprotonic acid condensation obtain and (methyl) acrylic acid are obtained by reacting, polyvalent alcohol and rear polyurethane (methyl) acrylate be obtained by reacting with (methyl) acrylic acid of compound reaction with 2 isocyanate group, epoxy (methyl) acrylate resin etc. that the epoxy resin such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol-novolac type or cresols-novolac type epoxy resin, resol type epoxy resin, triphenol methylmethane type epoxy resin, poly carboxylic acid poly epihydric alcohol base ester, polyvalent alcohol poly epihydric alcohol base ester, aliphatics or alicyclic epoxy resin, amine epoxy resin and dihydroxy benzene-type epoxy resin and (methyl) acrylic acid are obtained by reacting.And then the resin making above-mentioned epoxy (methyl) acrylate resin and multi-anhydride react and obtain also can use suitably.
The ratio of the photopolymerizable compound (E) that photosensitive polymer combination of the present invention contains, for solid state component (composition except following solvents (S) in photosensitive polymer combination is overall), be 1 ~ 40 quality %, the scope being preferably 3 ~ 30 quality %, more preferably 5 ~ 25 quality %.
In addition, thermal polymerization inhibitor, defoamer, surfactant etc. can also be added in photosensitive polymer combination of the present invention.They can be used alone or and with multiple.
As above-mentioned thermal polymerization inhibitor, can be existing known thermal polymerization inhibitor, quinhydrones, quinhydrones list ether etc. can be enumerated.
As above-mentioned defoamer, can be existing known defoamer, polysiloxane-based, fluoride compound can be enumerated.
As above-mentioned surfactant, can be existing known surfactant, the compound of anionic species, cationic, nonionic class etc. can be enumerated.
The preparation method > of < photosensitive polymer combination
Photosensitive polymer combination of the present invention is prepared by following methods.
Add resin (A), Photoepolymerizationinitiater initiater (B), silane coupling agent (C) and the colorant (D) with Cardo skeleton and the organic additive etc. added as required, the stirring machines such as three-roll grinder, bowl mill, sand mill are used to carry out mixing (dispersion milling), use such as 5 μm of membrane filters to filter, thus prepare photosensitive polymer combination.
The formation method > of < light shield layer (black matrix")
Below, as a kind of embodiment using photosensitive polymer combination of the present invention to form the method for light shield layer, the example of the method forming black matrix" is described.
First, use the non-contact type apparatus for coating such as contact transfer printing type apparatus for coating, spinner (rotary apparatus for coating), curtain coater such as roll coater, reverse roll coater (reversecoater), bar coater, photosensitive polymer combination of the present invention is applied on substrate.Substrate can use the substrate with photopermeability, such as glass substrate.
After being coated with above-mentioned photosensitive polymer combination, carrying out drying thus remove desolventizing.
Next, via female mask irradiation ultraviolet radiation, excimer laser isoreactivity energy line, partly expose.Exposure can use high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp, carbon arc lamp etc. to send ultraviolet light source.The difference that the energy line amount of irradiating form according to photosensitive polymer combination and different, but such as preferably 30 ~ 2000mJ/cm
2left and right.
By the film developing liquid developing after exposure, form black matrix" thus.Developing method is not particularly limited, such as, can use infusion process, spray-on process etc.In addition, also can adopt prewet (Pre-Wet).After image is formed, in order to improve the effect of the drying of developer solution, the solidification of resist film, rear baking, posterior photocuring etc. can be adopted.As the concrete example of developer solution, the organic developer solutions such as monoethanolamine, diethanolamine, triethanolamine can be enumerated, the aqueous solution of NaOH, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt etc.
embodiment
Below, further illustrate the present invention by embodiment, but the present invention is not limited to following examples.
The preparation > of < photosensitive polymer combination
Each composition shown in table 1 is mixed and dissolved, and the mode becoming to be divided into 85 overall quality % with (S) prepares photosensitive polymer combination.
[table 1]
Each abbreviation in upper table has following implication.In addition, the numerical value in [] is use level (mass parts).
(A)-1: the resin (A)-1 obtained as described below
(A)-2: following macromolecular compound (A)-2
(B)-1: following compound (B)-1
(C)-1 ~ (C)-7: following compound (C)-1 ~ (C)-7
(D)-1: the carbon black being coated with epoxy resin
(D)-2: carbon black
(E)-1: dipentaerythritol acrylate
(S) mixed solvent of-1: acetic acid 3-methoxybutyl/PGMEA/ cyclohexanone/BDO diacetate esters=55/20/20/5.
(S) mixed solvent of-2: acetic acid 3-methoxybutyl/PGMEA/ cyclohexanone/butyldiglycol acetic acid esters=55/20/20/5.
(S) mixed solvent of-3: acetic acid 3-methoxybutyl/PGMEA/ cyclohexanone=60/20/20.
(manufacture of macromolecular compound (A)-1)
First, load in 500ml four-necked bottle 235g bisphenol fluorene type epoxy resin (epoxide equivalent is 235), 110mg tetramethyl ammonium chloride, 100mg 2,6-di-tert-butyl-4-methy phenol and 72.0g acrylic acid, while being blown into air wherein with the speed of 25ml/ minute, carry out heating for dissolving in 90 ~ 100 DEG C.Then, slowly heat up under the state that solution is gonorrhoea, be heated to 120 DEG C and make it dissolve completely.Now, solution becomes clear viscous gradually, in this condition Keep agitation.During this period, measure acid number, continuous heating stirs until acid number becomes be less than 1.0mgKOH/g.12 hours are needed to acid number reaches desired value.Then, be cooled to room temperature, the bisphenol fluorene type epoxy acrylate that the following formula (a-4) obtaining water white solid shape represents.
Next, add in the above-mentioned bisphenol fluorene type epoxy acrylate that 307.0g obtains as mentioned above 600g acetic acid 3-methoxybutyl and after dissolving, mixing 80.5g benzophenone tetracarboxylic dianhydride and 1g tetraethylammonium bromide, heat up lentamente, reacts 4 hours at 110 ~ 115 DEG C.After confirming anhydride group disappearance, 1,2,3, the 6-tetrabydrophthalic anhydride of mixing 38.0g, reacts 6 hours, obtains resin (A)-1 at 90 DEG C.The disappearance of anhydride group is confirmed by IR spectrum.It should be noted that, this resin (A)-1 is equivalent to the resin that above formula (a-1) represents.
The formation > of < photosensitive resin pattern
Spin coater (TR25000: (strain) system should be changed in Tokyo) is used to be coated on glass substrate (100mm × 100mm) by the photosensitive polymer combination prepared in embodiment and comparative example, at 100 DEG C, carry out the preliminary drying of 120 seconds, form the film that thickness is 1.0 μm.Then, use mirror surface projection to aim at exposer (mirrorprojectionaligner) (goods name: TME-150RTO, Co., Ltd. TOPCON system), exposing clearance is set to 50 μm, via mask to film irradiation ultraviolet radiation.Exposure is set to 100mJ/cm
2.Use the 0.04 quality %KOH aqueous solution of 26 DEG C that the painting film development after exposure, after 40 seconds, is carried out the rear baking of 20 minutes at 230 DEG C, formed thus and comprise the photosensitive resin pattern (black matrix") that live width is the line of 10 μm.Then, 230 DEG C of circulating baking ovens of-20min are used to carry out rear baking.The thickness of each photosensitive resin pattern made is 1.0 μm.
In addition, following evaluation is carried out to each photosensitive resin pattern made.Result is shown in table 2.
[mensuration of OD value]
OD determinator D-200II (GretagMacbeth Inc.) is used to measure.
[Water Resistance Test]
For photosensitive resin pattern obtained above, implement PCT test (PressureCookerTest, pressure cooker testing) further, that is, place 12 hours in the environment of humidity 100%-2 air pressure at 120 DEG C.
Then return to room temperature, draw cross-cut trace (the cancellate cut channel of wide 1mm) on photosensitive resin pattern surface, carry out the scotch tape test specified in JISZ1522, confirm that photosensitive resin pattern is with or without stripping.Be 5B by the average evaluation do not peeled off completely, the average evaluation being less than 5% by stripping is 4B, by peel off be greater than 5% and be less than 15% average evaluation be 3B, by peel off be greater than 15% and be less than 35% average evaluation be 2B, by peel off be greater than 35% and be less than 65% average evaluation be 1B, being 0B by peeling off the average evaluation being greater than 65%, recording in table 2.
[volume resistivity value]
Volume resistivity value calculates as follows.
Sectional area (the cm of volume resistivity value (Ω cm)=carbon black powder
2the stack height (cm) of) × resistance value (Ω)/carbon black powder
[residue]
Utilize and survey long SEM (scanning electron microscope, accelerating potential 800V, trade name: S-9220, Inc. of Hitachi), observe photosensitive resin pattern obtained above, confirm with or without residue.
Being zero by the average evaluation can not observing residue on SEM, is △ by the average evaluation that observed residue slightly on SEM, by the average evaluation that observed residue on SEM for ×, record in table 2.
[advancing property of pattern lines]
Utilize and survey long SEM (scanning electron microscope, accelerating potential 800V, trade name: S-9220, Inc. of Hitachi), observe photosensitive resin pattern obtained above, advancing property of pattern lines (mask fidelity) is evaluated.
Be good by the average evaluation defining good pattern according to mask as former state, the average evaluation do not formed well by pattern is bad, records in table 2.
[pattern stripping]
Utilize and survey long SEM (scanning electron microscope, accelerating potential 800V, trade name: S-9220, Inc. of Hitachi), observe photosensitive resin pattern obtained above, the average evaluation peeled off not having pattern is zero, has 1 ~ 2 average evaluation peeled off to be △ by every 10 lines, by have in every 10 lines 5 ~ 10 average evaluations peeled off for ×, record in table 2.
[pattern form]
Utilize and survey long SEM (scanning electron microscope, accelerating potential 800V, trade name: S-9220, Inc. of Hitachi), observe photosensitive resin pattern obtained above, the cross sectional shape of pattern is evaluated.Be ◎ by average evaluation very good for the rectangularity of pattern, being zero by average evaluation good for the rectangularity of pattern, is △ by average evaluation bad for the rectangularity of pattern, by the average evaluation of non-for the rectangularity of pattern constant be ×, record in table 2.
[pattern angles]
As shown in Figure 1, the angle of angle θ formed by substrate 1 and pattern 2 is measured.Result is shown in table 2.
As shown in the above results, the intrinsic volume resistivity value of the photosensitive resin pattern using photosensitive polymer combination of the present invention to be formed is high, and photolithographic characteristics when forming pattern is excellent.
Claims (4)
1. a photosensitive polymer combination, it contains resin (A), Photoepolymerizationinitiater initiater (B), silane coupling agent (C) and the colorant (D) with Cardo skeleton, it is characterized in that, described colorant (D) comprises the carbon black through epoxy resin coating treatment.
2. photosensitive polymer combination as claimed in claim 1, wherein, the compound that described silane coupling agent (C) represents containing following general formula (C0),
In formula (C0),
Yc
01for the alkylidene of carbon number 1 ~ 6 that can be replaced by amino,
R
c1~ R
c3be the alkoxy of carbon number 1 ~ 6, the alkyl of carbon number 1 ~ 10, the naphthenic base of carbon number 3 ~ 7, the aryl of carbon number 6 ~ 10, the aralkyl of carbon number 7 ~ 10 independently of one another, R
c1~ R
c3in at least 1 be alkoxy,
R
c4for the group that following formula (C-1) or (C-2) represent,
R
c5for the alkyl of the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl, ring-type, heterocycle or carbon number 1 ~ 20,
R
c6for the alkyl of the aliphatic alkyl of hydrogen atom, aromatic hydrocarbyl, ring-type, heterocycle or carbon number 1 ~ 20,
* be binding site,
3. photosensitive polymer combination as claimed in claim 1 is also the solvent (S1) of more than 200 DEG C containing boiling point.
4. photosensitive polymer combination as claimed in claim 1, wherein, volume intrinsic resistance rate value is 1.0 × 10
13more than (Ω cm).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1928716A (en) * | 2005-09-06 | 2007-03-14 | 东京应化工业株式会社 | Photosensitive composition |
| JP2009075446A (en) * | 2007-09-21 | 2009-04-09 | Mitsubishi Chemicals Corp | Resin black matrix, light shielding photosensitive resin composition and liquid crystal display |
| CN102103327A (en) * | 2009-12-22 | 2011-06-22 | 株式会社Lg化学 | Black matrix composition with high light-shielding and improved adhesion properties |
| JP2013065000A (en) * | 2011-08-30 | 2013-04-11 | Mitsubishi Chemicals Corp | Photosensitive colored resin composition, color filter and liquid crystal display |
| JP2013174714A (en) * | 2012-02-24 | 2013-09-05 | Mitsubishi Chemicals Corp | Photosensitive colored resin composition, color filter, and liquid crystal display device |
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| JP2013011845A (en) * | 2011-05-31 | 2013-01-17 | Mitsubishi Chemicals Corp | Photosensitive colored resin composition for color filter, color filter, liquid crystal display device, and organic electroluminescent display |
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| CN1928716A (en) * | 2005-09-06 | 2007-03-14 | 东京应化工业株式会社 | Photosensitive composition |
| JP2009075446A (en) * | 2007-09-21 | 2009-04-09 | Mitsubishi Chemicals Corp | Resin black matrix, light shielding photosensitive resin composition and liquid crystal display |
| CN102103327A (en) * | 2009-12-22 | 2011-06-22 | 株式会社Lg化学 | Black matrix composition with high light-shielding and improved adhesion properties |
| JP2013065000A (en) * | 2011-08-30 | 2013-04-11 | Mitsubishi Chemicals Corp | Photosensitive colored resin composition, color filter and liquid crystal display |
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