CN104950571A - Photosensitive resin composition for color filter and application thereof - Google Patents

Abstract

The invention relates to a photosensitive resin composition for a color filter and application thereof. The photosensitive resin composition comprises a pigment , an alkali-soluble resin (B), a compound (C) having an ethylenically unsaturated group, a photoinitiator (D), and an organic solvent (E). The alkali-soluble resin (B) comprises a first alkali-soluble resin (B-1) and a second alkali-soluble resin (B-2). The photosensitive resin composition can improve the voltage holding ratio and the developing resistance of the color filter.

Description

Colored filter photosensitive polymer combination and application thereof

Technical field

The present invention is colored filter photosensitive polymer combination about a kind of liquid crystal display and the colored filter that formed thereof, particularly provides a kind of voltage retention and the good colored filter photosensitive polymer combination of resistance to developability.

Background technology

At present, colored filter has been widely used in the applications such as colour liquid crystal display device, colour facsimile apparatus, colour camera.Along with the market demand of the imaging equipments such as colour liquid crystal display device day by day expands, the manufacturing technology of colored filter also tends to variation.

Colored filter usually can by decoration method, print process, electricity the method such as method or pigment dispersion method, the pixels such as red, green, blue to be formed on transparent glass substrate obtained.Generally speaking, for improving the contrast of colored filter, the configurable light shield layer of pixel shader interlayer (or claiming black matrix", black matrix).

The processing procedure of above-mentioned pigment dispersion method is first dispersed in ray hardening resin by pigment to form photosensitive composition, finally this resin combination formed pixel shader layer.Furthermore, the processing procedure of pigment dispersion method, normally first on the transparent supports such as glass substrate, forms light shield layer with the metal such as chromium, chromium oxide or photoresist photomask.Then, this photoresist is coated on transparent support by rotary coating mode by the photoresist (colorama resist) being dispersed with red pigment, exposes by mask, and in exposure after carry out development treatment red pixel.Then, with same mode of operation, namely reuse coating, exposure, development mode can on support the three-color pixel such as obtained red, green, blue respectively.

In recent years, the purposes of colour liquid crystal display device is no longer confined in PC, also be widely used in (especially large-sized color liquid crystal screen) on color TV and various supervision screen, so more and more higher for the requirement of liquid crystal display color saturation.Therefore, the pigment proportion contained by photosensitive polymer combination is also more and more higher, and the relative usage quantitative change of alkali soluble resin and photo-sensitive monomer is few, causes the crosslinking degree after exposure to decline, and causes the problem of the not good grade of resistance to developability to occur.

In the content that Japanese Unexamined Patent Publication 2004-138950 publication discloses, it uses specific alkali soluble resin, the pixel shader layer that surface is smooth can be formed, the colored filter that pattern form, resistance to developability and brightness performance are excellent, but the method easily causes the voltage retention of this photosensitive polymer combination too low and causes the defect easily having image retention when display frame to exist.

Therefore, how to promote resistance to developability and voltage retention, to reach the requirement of current industry, for making great efforts the target studied in the technical field of the invention simultaneously.

Summary of the invention

Therefore, one aspect of the present invention is to provide a kind of colored filter photosensitive polymer combination.This photosensitive polymer combination can promote the voltage retention of colored filter and resistance to developability.

Another aspect of the present invention is to provide a kind of method manufacturing colored filter, and it utilizes aforesaid colored filter photosensitive polymer combination to form pixel layer.

Another aspect of the present invention is to provide a kind of colored filter, and it utilizes aforesaid method to obtain.

Another aspect of the invention is to provide a kind of liquid crystal indicator, and it comprises aforesaid colored filter.

According to above-mentioned aspect of the present invention, a kind of colored filter photosensitive polymer combination is proposed, this photosensitive polymer combination comprises pigment (A), alkali soluble resin (B), the compound (C) with ethene unsaturated group, light initiator (D) and organic solvent (E), below analyses and states it.

Photosensitive polymer combination

Pigment (A)

Pigment of the present invention (A) can be the combination in any of inorganic pigment, organic pigment or above-mentioned pigment.

Above-mentioned inorganic pigment can be the metallic compound of metal oxide or metal complex etc.This metal oxide can be the oxide of the metal of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc or antimony etc., and the composite oxides of aforementioned metal.

Above-mentioned organic pigment is selected from C.I. pigment yellow 1,3,11,12,13,14,15,16,17,20,24,31,53,55,60,61,65,71,73,74,81,83,93,95,97,98,99,100,101,104,106,108,109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,155,156,166,167,168,175, C.I. pigment orange 1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71,73, C.I. 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, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265, C.I. pigment violet 1,19,23,29,32,36,38,39, C.I. pigment blue 1,2,15,15:3,15:4,15:6,16,22,60,66, C.I. pigment Green 7,36,37, C.I. pigment brown 23,25,28, and C.I. pigment black 1,7.Aforesaid organic pigment can be a kind of or mix multiple use separately.

The mean grain size of the primary particle of this pigment (A) is 10nm to 200nm, is preferably 20nm to 150nm, is more preferred from 30nm to 130nm.

Total use amount based on aftermentioned alkali soluble resin (B) is 100 weight portions, and the use amount of this pigment (A) is 30 weight portion to 300 weight portions, is preferably 35 weight portion to 250 weight portions, is more preferred from 40 weight portion to 200 weight portions.

If desired, this pigment (A) optionally comprises spreading agent, its concrete example, as: the interfacial agent of kation system, negative ion system, nonionic system, both sexes, polysiloxane series or fluorine system etc.

This interfacial agent can including but not limited to the polyethylene oxide alkyl ethers class of polyethylene oxide lauryl ether, polyethylene oxide stearoyl ether or polyethylene oxide oil ether etc.; The polyethylene oxide alkyl benzene ethers interfacial agent of polyethylene oxide octyl group phenylate or polyethylene oxide nonyl phenylate etc.; The polyethylene glycol di class interfacial agent of polyethylene glycol dilaurate or polyglycol distearate etc.; Sorbitan fatty acid ester class interfacial agent; The polyesters interfacial agent of fatty acid upgrading; The polyurethanes interfacial agent of tertiary amine upgrading; Chemical industrial company of SHIN-ETSU HANTOTAI manufactures, and model is the commodity of KP; Toray Dow Corning Silicon manufactures, and model is the commodity of SF-8427; Common prosperity society oil chemical industry manufactures, and model is the commodity of Polyflow; get Ke Mu company (Tochem Products Co., Ltd.) manufactures, and model is the commodity of F-Top; Large Japanese ink chemical industry manufactures, and model is the product of Megafac; Sumitomo 3M manufactures, and model is the product of Fluorad; Asahi Glass manufactures, and model is the commodity of Asahi Guard or Surflon.This interfacial agent can be a kind of or mix multiple use separately.

Alkali soluble resin (B)

Alkali soluble resin of the present invention (B) can comprise the first alkali soluble resin (B-1) and the second alkali soluble resin (B-2).In addition, alkali soluble resin (B) optionally comprises the 3rd alkali soluble resin (B-3).

First alkali soluble resin (B-1)

First alkali soluble resin (B-1) is formed by potpourri institute copolymerization, and wherein this potpourri comprises the ethene monomer (b-1-1) with the structure of hindered amine and the ethylene unsaturated monomer (b-1-2) with one or more carboxylic acid groups.

In addition, aforesaid potpourri optionally comprises other the copolymerizable ethylene unsaturated monomer (b-1-3) beyond the ethene monomer (b-1-1) with the structure of hindered amine and the ethylene unsaturated monomer (b-1-2) with one or more carboxylic acid groups.

There is the ethene monomer (b-1-1) of the structure of hindered amine

The ethene monomer (b-1-1) with the structure of hindered amine can be the ethene monomer as shown in the formula having the structure of hindered amine shown in (I):

In formula (I), X ₁represent hydrogen atom, carbon number be 1 to 18 straight chained alkyl, branched alkyl or naphthenic base, the carbon number aromatic radical that is 6 to 20, carbon number be 7 to 12 aromatic alkyl, acyl group, oxygen radical, or-OX ₄; X ₄represent hydrogen atom, carbon number be 1 to 18 straight chained alkyl, branched alkyl or naphthenic base, carbon number be the aromatic radical of 6 to 20, or carbon number is the aromatic alkyl of 7 to 12; X ₂and X ₃represent methyl, ethyl, phenyl or mutual bond independently of one another and form the aliphatics ring that carbon number is 4 to 12; " * " represents covalent bond.

Work as X ₁and X ₄represent carbon number be 1 to 18 straight chained alkyl, branched alkyl or naphthenic base time, X ₁and X ₄can be straight chained alkyl or branched alkyl that carbon number is 1 to 18, or carbon number is the naphthenic base of 3 to 8, its concrete example, as: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, cyclohexyl, n-octyl or cetyl etc.Work as X ₁when to represent carbon number be the aromatic radical of 6 to 20, its concrete example can be phenyl, Alpha-Naphthyl or betanaphthyl.Work as X ₁and X ₄when to represent carbon number be the aromatic alkyl of 7 to 12, X ₁and X ₄can be and have the aromatic radical that carbon number is the alkyl bond of 1 to 8, and the carbon number of this aromatic radical is 6 to 10, its concrete example can be Benzyl base, phenethyl, α-first base Benzyl base or 2-phenyl-propane-2-base etc.Work as X ₁and X ₄represent acyl group, carbon number is when being alkanoyl or the aroyl of 2 to 8, its concrete example can be acetyl or benzoyl base.

X of the present invention ₁goodly can be hydrogen atom, carbon number be 1 to 5 alkyl or oxygen radical, be wherein better with hydrogen atom, oxygen radical and methyl.

Secondly, the X in formula (I) ₂and X ₃bond can form the structure of cycloaliphatic ring, its concrete example can be cyclopentane or cyclohexane etc.X ₂and X ₃goodly can be methyl.

Have and can be such as formula the ethene monomer shown in (I) with the structure of hindered amine the compound had as shown in the formula the structure shown in (I-1) and (I-2):

In formula (I-1) and (I-2), X ₅and X ₇separately represent hydrogen atom or methyl; X ₆represent methine or carbon number is the alkylidene of 2 to 5; X ₈representative is such as formula the structure shown in (I); X ₉representative-CONH-* ,-SO ₂-,-SO ₂nH-*, wherein " * " representative and X ₈the covalent bond of bond; X ₆being preferably ethylidine or propylidyne, is better with ethylidine; S is the integer of 0 to 8, is better with 0 to 6.

Concrete example such as formula the ethene monomer shown in (I-1) with the structure of hindered amine can be as shown in the formula the structure shown in (I-1-1) to (I-1-7):

In formula (I-1-1) in (I-1-7), X ₅definition as previously mentioned, separately do not repeat at this.

Concrete example such as formula the ethene monomer shown in (I-2) with the structure of hindered amine can be as shown in the formula the structure shown in (I-2-1) to (I-2-4):

In formula (I-2-1) in (I-2-4), X ₇definition as previously mentioned, separately do not repeat at this.

The ethene monomer (b-1-1) that the present invention has the structure of hindered amine can be 4-methacrylamido-2,2,6,6-tetramethyl-piperidines (4-methacrylamido-2,2,6,6-tetramethylpiperidine), or Hitachi Chemical Co., Ltd. manufactures, model is FA-712HM [2,2,6,6-tetramethyl-4-piperidyl methyl acrylate; I.e. previously described formula (I-1-1), and X ₅represent methyl] or FA-711MM [1,2,2,6,6-pentamethyl-piperidyl methyl acrylate; I.e. previously described formula (I-1-2), and X ₅represent methyl].

The aforementioned ethene monomer (b-1-1) with the structure of hindered amine can be a kind of or mix multiple use separately.

Based on there is the ethene monomer (b-1-1) of the structure of hindered amine and aftermentioned to have the ethylene unsaturated monomer (b-1-2) of one or more carboxylic acid groups and total use amount of other copolymerizable ethylene unsaturated monomer (b-1-3) be 100 weight portions, this use amount with the ethene monomer (b-1-1) of the structure of hindered amine is 3 weight portion to 45 weight portions, be preferably 4 weight portion to 40 weight portions, be more preferred from 5 weight portion to 35 weight portions.

There is the ethylene unsaturated monomer (b-1-2) of one or more carboxylic acid groups

This ethylene unsaturated monomer (b-1-2) with one or more carboxylic acid groups can including but not limited to acrylic acid, methacrylic acid (methacrylic acid; MAA), butenoic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid, 2-acryloyloxyethyl succinate or 2-methacryloyloxyethyl succinate (2-methacryloyloxyethyl succinate monoester; Etc. HOMS) unsaturated monocarboxylic acid compound; Unsaturated dicarboxylic acid (acid anhydride) compound of maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid or citraconic anhydride etc.; Unsaturated polybasic carboxylic acid (acid anhydride) compounds more than three carboxylic acid groups.The aforementioned ethylene unsaturated monomer (b-1-2) with one or more carboxylic acid groups can be a kind of or mix multiple use separately.

Preferably, this ethylene unsaturated monomer (b-1-2) with one or more carboxylic acid groups is selected from acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinate or 2-methacryloyloxyethyl succinate.Wherein, be better with 2-acryloyloxyethyl succinate or 2-methacryloyloxyethyl succinate.

The ethene monomer (b-1-1) that there is the structure of hindered amine based on aforementioned, there is the ethylene unsaturated monomer (b-1-2) of one or more carboxylic acid groups and total use amount of other copolymerizable ethylene unsaturated monomer (b-1-3) aftermentioned is 100 weight portions, this use amount with the ethylene unsaturated monomer (b-1-2) of one or more carboxylic acid groups is 15 weight portion to 55 weight portions, be preferably 20 weight portion to 50 weight portions, be more preferred from 25 weight portion to 45 weight portions.

Other copolymerizable ethylene unsaturated monomer (b-1-3)

This ethene monomer (b-1-1) with the structure of hindered amine and there are one or more carboxylic acid groups ethylene unsaturated monomer (b-1-2) beyond other copolymerizable ethylene unsaturated monomer (b-1-3) can including but not limited to styrene (styrene, SM), α-methyl styrene, vinyltoluene, aromatic ethenyl compound to chlorostyrene, methoxy styrene etc., N-phenylmaleimide (N-phenylmaleimide, PMI), the maleimide compound of the o-hydroxyphenyl-maleimides of N-, the m-hydroxyphenyl-maleimides of N-, the p-hydroxyphenyl-maleimides of N-, the o-methylphenylmaleimide of N-, the m-methylphenylmaleimide of N-, the p-methylphenylmaleimide of N-, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, the p-methoxyphenyl maleimide of N-, N-N-cyclohexylmaleimide etc., methyl acrylate (methyl acrylate, MA), methyl methacrylate, ethyl acrylate, β-dimethyl-aminoethylmethacrylate, n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, the secondary butyl ester of methacrylic acid, tert-butyl acrylate, Tert-butyl Methacrylate, 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, 2-hydroxypropyl acrylate, methacrylic acid-2-hydroxy propyl ester, acrylic acid-3-hydroxy propyl ester, methacrylic acid-3-hydroxy propyl ester, acrylic acid-2-hydroxybutyl, methacrylic acid-2-hydroxybutyl, acrylic acid-3-hydroxybutyl, methacrylic acid-3-hydroxybutyl, acrylic acid-4-hydroxybutyl, methacrylic acid-4-hydroxybutyl, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate (benzyl methacrylate, BzMA), phenyl acrylate, phenyl methacrylate, acrylic acid triethylene glycol methoxyethoxy ester, methacrylic acid triethylene glycol methoxyethoxy ester, lauryl methacrylate, methacrylic acid myristyl ester, methacrylic acid cetyl ester, octadecyl methacrylate, methacrylic acid eicosyl ester, methacrylic acid docosyl ester, acrylic acid double cyclopentenyl oxidation ethyl ester (dicyclopentenyloxyethyl acrylate, etc. DCPOA) unsaturated carboxylic ester compound, acrylic acid-N, N-dimethylamino ethyl ester, methacrylic acid-N, N-dimethylamino ethyl ester, acrylic acid-N, N-diethylamino propyl ester, methacrylic acid-N, N-dimethylamino propyl ester, acrylic acid-N, N-dibutylamino propyl ester, the iso-butylaminoethyl of N-methacrylic acid, the unsaturated carboxylic acid glycidyl ester compounds of acrylic acid epoxy propyl diester, glycidyl propyl diester etc., the generating vinyl carboxylate ester compounds of vinyl acetate, propionate, vinyl butyrate etc., the unsaturated ethers compound of methoxy ethylene, ethyl vinyl ether, allyl glycidyl ethers, methylallyl glycidyl ethers etc., the nitrilation vinyl compound of vinyl cyanide, methacrylonitrile, α-chloro-acrylonitrile, the sub-ethene of cyaniding etc., the unsaturated acyl amines of acrylamide, Methacrylamide, α-chloroacrylamide, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide etc., the aliphatic conjugated diene compound of 1,3-butadiene, isoprene, chlorination butadiene etc.Other copolymerizable ethylene unsaturated monomer (b-1-3) aforementioned can be a kind of or mix multiple use separately.

Preferably, this other copolymerizable ethylene unsaturated monomer (b-1-3) is any mixing being selected from styrene, N-phenylmaleimide, methyl acrylate, methyl methacrylate, 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, benzyl acrylate, benzyl methacrylate, acrylic acid double cyclopentenyl oxidation ethyl ester or above-claimed cpd.

The ethene monomer (b-1-1) that there is the structure of hindered amine based on aforementioned, there is the ethylene unsaturated monomer (b-1-2) of one or more carboxylic acid groups and total use amount of other copolymerizable ethylene unsaturated monomer (b-1-3) is 100 weight portions, the use amount of this other copolymerizable ethylene unsaturated monomer (b-1-3) is 0 weight portion to 82 weight portion, be preferably 10 weight portion to 70 weight portions, be more preferred from 20 weight portion to 60 weight portions.

If when alkali soluble resin (B) does not use aforementioned first alkali soluble resin (B-1), obtained panel easily produces ion under driving for a long time, and reduces voltage retention.

Second alkali soluble resin (B-2)

Second alkali soluble resin (B-2) is reacted by the first potpourri to obtain, this first potpourri comprises the epoxy compound (b-2-1) with at least two epoxy radicals, and has the compound (b-2-2) of at least one carboxylic acid group and at least one ethene unsaturated group.

In addition, this first potpourri optionally comprises compound carboxylic acid anhydride (b-2-3), has the combination in any of the compound (b-2-4) of epoxy radicals or above-mentioned material.

There is the epoxy compound (b-2-1) of at least two epoxy radicals

This epoxy compound (b-2-1) with at least two epoxy radicals comprises as shown in the formula the compound shown in (II), any mixing as shown in the formula the compound shown in (III) or above-mentioned material:

In formula (II), Y ₁, Y ₂, Y ₃and Y ₄separately represent hydrogen atom, halogen atom, carbon number be 1 to 5 alkyl or alkoxy, or carbon number is aromatic radical or the aralkyl of 6 to 12.

Compound as shown in previously described formula (II) can be undertaken reacting by bisphenol fluorene type compound (bisphenol fluorene) and halogenated epoxy propane (epihalohydrin) and obtain.

The concrete example of above-mentioned bisphenol fluorene type compound can be 9, two (4-hydroxy phenyl) fluorenes [9 of 9-, 9-bis (4-hydroxyphenyl) fluorine], 9, two (the 4-hydroxy-3-methyl phenyl) fluorenes (9 of 9-, 9-bis (4-hydroxy-3-methylphenyl) fluorene), 9, two (4-hydroxyl-3-chlorphenyl) fluorenes (9 of 9-, 9-bis (4-hydroxy-3-chlorophenyl) fluorene), 9, two (4-hydroxyl-3-bromophenyl) fluorenes (9 of 9-, 9-bis (4-hydroxy-3-bromophenyl) fluorene), 9, two (4-hydroxyl-3-fluorophenyl) fluorenes (9 of 9-, 9-bis (4-hydroxy-3-fluorophenyl) fluorene), 9, two (the 4-hydroxy 3-methoxybenzene base) fluorenes (9 of 9-, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene), 9, two (the 4-hydroxyl-3 of 9-, 5-3,5-dimethylphenyl) fluorenes (9, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene), 9, two (the 4-hydroxyl-3 of 9-, 5-dichlorophenyl) fluorenes (9, 9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene), 9, two (the 4-hydroxyl-3 of 9-, 5-dibromo phenyl) fluorenes (9, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene), or the combination in any of above-claimed cpd.

The concrete example of aforementioned halogenated epoxy propane (epihalohydrin) can including but not limited to 3-chloro-1, the combination in any of 2-epoxypropane (epichlorohydrin) or bromo-1, the 2-epoxypropane (epibromohydrin) of 3-or above-claimed cpd.

The concrete example with the bisphenol fluorene type compound of epoxy radicals can comprise chemical company of Nippon Steel (Nippon steel chemical Co., Ltd) and manufacture, and model is the commodity of ESF-300; Osaka natural gas companies (Osaka Gas Co., Ltd) manufactures, and model is the commodity of PG-100 or EG-210; Note scientific & technical corporation (S.M.S Technology Co., Ltd) manufactures, and model is the commodity of SMS-F9PhPG, SMS-F9CrG or SMS-F914PG.

In formula (III), this R ₁to R ₁₄separately represent hydrogen atom, halogen atom, carbon number be 1 to 8 alkyl or carbon number be the aromatic radical of 6 to 15, and n represents the integer of 0 to 10.

Compound as shown in previously described formula (III) in the presence of an alkali metal hydroxide, can use and react as shown in the formula the compound shown in (III-1) and halogenated epoxy propane:

In formula (III-1), R ₁to R ₁₄and the definition of n respectively as previously mentioned, separately do not repeat at this.

Synthetic method such as formula the compound shown in (III-1) is first in the presence of acid catalyst, condensation reaction is carried out, to be formed such as formula the compound shown in (III-1) by as shown in the formula the compound shown in (III-2) and phenol (phenol) compounds.Then, add excessive halogenated epoxy propane, to make halogenated epoxy propane and to carry out de-hydrogen halide (dehydrohalogenation) such as formula the compound shown in (III-1), can obtain such as formula the compound shown in (III):

In formula (III-2), R ₃to R ₆definition as previously mentioned, separately do not repeat at this; R ₁₅and R ₁₆separately represent halogen atom, or carbon number is alkyl or the alkoxy of 1 to 6.Above-mentioned halogen atom can be chlorine atom or bromine atoms.Alkyl is preferably methyl, ethyl or the tert-butyl group.Alkoxy is preferably methoxy or ethoxy.

The concrete example of aforesaid phenolic compound can including but not limited to phenol (phenol), cresols (cresol), diethylstilbestrol (ethylphenol), positive third phenol (n-propylphenol), isobutyl phenol (isobutylphenol), tertiary butyl phenol (t-butylphenol), octyl phenol (octylphenol), nonyl phenol (nonylphenol), stubble phenol (xylenol), methyl butyl phenol (methylbutylphenol), di-tert-butylphenol (di-t-butylphenol), phenol ethylene (vinylphenol), propylene phenol (propenylphenol), acetylene phenol (ethinylphenol), ring penta phenol (cyclopentylphenol), cyclohexyl phenol (cyclohexylphenol) or cyclohexyl cresols (cyclohexylcresol) etc.This phenolic compound can be a kind of or mix multiple use separately.

Be 1 mole based on the above-mentioned use amount such as formula the compound shown in (III-2), the use amount of phenolic compound is 0.5 mole to 20 moles, is preferably 2 moles to 15 moles.

The concrete example of acid catalyst can comprise the compound of hydrochloric acid, sulfuric acid, p-toluenesulfonic acid (p-toluenesulfonic acid), oxalic acid (oxalic acid), boron trifluoride (boron trifluoride), anhydrous Aluminum chloride (aluminium chloride anhydrous) or zinc chloride (zinc chloride) etc.Acid catalyst is preferably any mixing of p-toluenesulfonic acid, sulfuric acid, hydrochloric acid or above-claimed cpd.

Though the use amount of above-mentioned acid catalyst is without particular limitation.But be 100 percentage by weights based on the above-mentioned use amount such as formula the compound shown in (III-2), the use amount of acid catalyst is preferably 0.1 percentage by weight to 30 percentage by weight.

Above-mentioned condensation reaction can solvent-free or carry out in presence of organic solvent.The concrete example of this organic solvent can including but not limited to the organic solvent of toluene (toluene), dimethylbenzene (xylene) or methyl isobutyl ketone (methyl isobutyl ketone) etc.Above-mentioned organic solvent can be a kind of or mix multiple use separately.

Be 100 percentage by weights based on the total use amount such as formula the compound shown in (III-2) and phenols, the use amount of organic solvent is 50 percentage by weight to 300 percentage by weights, is preferably 100 percentage by weight to 250 percentage by weights.In addition, the operating temperature of above-mentioned condensation reaction is 40 DEG C to 180 DEG C, and the running time of condensation reaction is 1 little of 8 hours.

After completing above-mentioned condensation reaction, neutralisation treatment or washing process can be carried out.This neutralisation treatment is that the pH value of reacted solution is adjusted to 3 to 7, is preferably 5 to 7.This washing process can use neutralizing agent to carry out, and this neutralizing agent is alkaline matter, its concrete example, as: the alkali metal hydroxide of NaOH (sodium hydroxide) or potassium hydroxide (potassium hydroxide) etc.; The alkaline-earth metal oxyhydroxide of calcium hydroxide (calcium hydroxide) or magnesium hydroxide (magnesium hydroxide) etc.; The organic amine of secondary second triamine (diethylene triamine), three second tetramines (triethylenetetramine), aniline (aniline) or phenylenediamines (phenylene diamine) etc.; The combination in any of ammonia (ammonia), sodium dihydrogen phosphate (sodium dihydrogen phosphate) or above-claimed cpd.Above-mentioned neutralizing agent can be a kind of or mix multiple use separately.Above-mentioned washing process can adopt prior art method to carry out, and such as, adds the aqueous solution containing neutralizing agent in solution after the reaction, and repeatedly carries out extracting.

After carrying out aforesaid neutralisation treatment or washing process, can heat up in a steamer except unreacted phenols and solvent by heating under reduced pressure process, and concentrate.Thus, just can obtain such as formula the compound shown in (III-1).

The concrete example of above-mentioned halogenated epoxy propane can including but not limited to the combination in any of chloro-1, the 2-epoxypropane of 3-, bromo-1, the 2-epoxypropane of 3-or above-claimed cpd.Before carrying out above-mentioned de-hydrogen halide, can add or add in course of reaction the alkali metal hydroxide of NaOH, potassium hydroxide etc. in advance.The operating temperature of above-mentioned de-hydrogen halide can be 20 DEG C to 120 DEG C, and its running time can be 1 little of 10 hours.

In one embodiment, the alkali metal hydroxide added in above-mentioned de-hydrogen halide also can be its aqueous solution.In this embodiment, above-mentioned alkali metal hydroxide aqueous solution is added into continuously de-hydrogen halide intrasystem while, can in decompression or normal pressure under, continuous still water outlet and halogenated epoxy propane, use except anhydrating, and halogenated epoxy propane can be back in reactive system continuously.

Before above-mentioned de-hydrogen halide carries out, also the quarternary ammonium salt of tetramethyl-ammonium chloride (tetramethyl ammonium chloride), tetramethylammonium bromide (tetramethyl ammonium bromide) or trimethyl benzyl ammonia chloride (trimethyl benzyl ammonium chloride) etc. can be added as catalyzer, and at 50 DEG C at 150 DEG C, react 1 little of 5 hours, add alkali metal hydroxide or its aqueous solution.Then, at the temperature of 20 DEG C to 120 DEG C, reaction 1 is little of 10 hours, to carry out de-hydrogen halide.

Based on above-mentioned be 1 equivalent such as formula the hydroxyl total yield in the compound shown in (III-1), the use amount of halogenated epoxy propane is 1 equivalent to 20 equivalent, is preferably 2 equivalent to 10 equivalents.Based on above-mentioned be 1 equivalent such as formula the hydroxyl total yield in the compound shown in (III-1), the use amount of the alkali metal hydroxide added in aforementioned de-hydrogen halide is 0.8 equivalent to 15 equivalent, is preferably 0.9 equivalent to 11 equivalent.

In order to make above-mentioned de-hydrogen halide carry out smoothly, the alcohols solvent of methyl alcohol or ethanol etc. also can be added.In addition, de-hydrogen halide also can use the polar solvent of the aprotic (aprotic) of dimethyl sulfone (dimethyl sulfone) or dimethyl sulfoxide (dimethyl sulfoxide) etc. to react.When using alcohols solvent, the total use amount based on halogenated epoxy propane is 100 percentage by weights, and the use amount of alcohols is 2 percentage by weight to 20 percentage by weights, is preferably 4 percentage by weight to 15 percentage by weights.When using the polar solvent of aprotic, total use amount based on halogenated epoxy propane is 100 percentage by weights, the use amount of the polar solvent of aprotic is 5 percentage by weight to 100 percentage by weights, is preferably 10 percentage by weight to 90 percentage by weights.

After completing de-hydrogen halide, optionally carry out washing process.Then, utilize the mode of decompression distillation, such as in temperature be 110 DEG C to 250 DEG C and pressure is less than in the environment of 1.3kPa [10 mm Hg (mmHg)], remove the polar solvent of halogenated epoxy propane, alcohols and aprotic.

In order to avoid obtained epoxy resin has the halogen of hydrolyzable, toluene or methyl isobutyl ketone (methyl isobutyl ketone) equal solvent and the alkali metal hydroxide aqueous solution such as NaOH or potassium hydroxide can be added in the solution after de-hydrogen halide, and again carry out de-hydrogen halide.In de-hydrogen halide, based on above-mentioned be 1 equivalent such as formula the hydroxyl total yield in the compound shown in (III-1), the use amount of alkali metal hydroxide is 0.01 mole to 0.3 mole, is preferably 0.05 mole to 0.2 mole.The operating temperature of above-mentioned de-hydrogen halide is 50 DEG C to 120 DEG C, and the running time is 0.5 little of 2 hours.

After completing de-hydrogen halide, salt removes by steps such as filtration and washings.In addition, utilize the mode of decompression distillation to remove the solvent of toluene or methyl isobutyl ketone etc., can obtain such as formula the compound shown in (III).The above-mentioned concrete example such as formula the compound shown in (III) can be made including but not limited to Japanese chemical drug Inc., and model is the commodity of NC-3000, NC-3000H, NC-3000S and NC-3000P.

There is the compound (b-2-2) of at least one carboxylic acid group and at least one ethene unsaturated group

The concrete example with the compound (b-2-2) of at least one carboxylic acid group and at least one ethene unsaturated group is selected from the group be made up of to (3) following (1): (1) acrylic acid, methacrylic acid, 2-methylacryoyloxyethyl succinic acid (2-methacryloyloxyethylbutanedioic acid), 2-methacryl oxygen-butyl succinic acid, 2-methylacryoyloxyethyl hexane diacid, 2-methacryl oxygen-butyl hexane diacid, 2-methylacryoyloxyethyl hexahydrophthalic acid, 2-methylacryoyloxyethyl maleic acid, 2-methacryloxypropyl maleic acid, 2-methacryl oxygen-butyl maleic acid, 2-methacryloxypropyl succinic acid, 2-methacryloxypropyl hexane diacid, 2-methacryloxypropyl tetrahydrophthalic acid, 2-methacryloxypropyl phthalic acid, 2-methacryl oxygen-butyl phthalic acid or 2-methacryl oxygen-butyl hydrogen phthalic acid, (2) compound being reacted by (methyl) acrylate and dicarboxylic acid compound with hydroxyl and obtained, wherein dicarboxylic acid compound comprises hexane diacid, succinic acid, maleic acid or phthalic acid, and the half ester compound that (3) are reacted by (methyl) acrylate and compound carboxylic acid anhydride described later (b-2-3) with hydroxyl and obtained, (methyl) acrylate wherein with hydroxyl comprises 2-hydroxyethylmethacry,ate [(2-hydroxyethyl) acrylate], 2-HEMA [(2-hydroxyethyl) methacrylate], 2-acrylate [(2-hydroxypropyl) acrylate], 2-hydroxy propyl methacrylate [(2-hydroxypropyl) methacrylate], 4-hydroxybutyl acrylate [(4-hydroxybutyl) acrylate], 4-hydroxybutyl methacrylate [(4-hydroxybutyl) methacrylate] or pentaerythritol acrylate trimethyl etc.

Compound carboxylic acid anhydride (b-2-3)

Compound carboxylic acid anhydride (b-2-3) can be selected from the group be made up of (1) described later and (2): (1) succinic anhydride (butanedioic anhydride), maleic anhydride (maleic anhydride), itaconic anhydride (Itaconic anhydride), phthalic anhydride (phthalic anhydride), tetrabydrophthalic anhydride (tetrahydrophthalic anhydride), hexahydrophthalic anhydride (hexahydrophthalic anhydride), methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylene tetrabydrophthalic anhydride (methyl endo-methylene tetrahydro phthalic anhydride), chlorendic anhydride (chlorendic anhydride), glutaric anhydride or inclined three benzoyl oxides (1, 3-dioxoisobenzofuran-5-carboxylic anhydride) etc. dicarboxylic acid anhydride compound, and (2) benzophenone tetracarboxylic dianhydride (benzophenone tetracarboxylic dianhydride, BTDA), the quaternary compound carboxylic acid anhydride of two pyromellitic dianhydride or two phenylate tetracarboxylic acid dianhydrides etc.

There is the compound (b-2-4) of epoxy radicals

The compound (b-2-4) with epoxy radicals can be selected from glytidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, have unsaturated group glycidyl ether compound, there is the unsaturated compound of epoxy radicals or the combination in any of above-claimed cpd.

The above-mentioned glycidyl ether compound with unsaturated group can comprise the long rapids Industrial Co., Ltd that changes into and manufacture, and model is the commodity of Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171 or Denacol EX-192 etc.

This second alkali soluble resin (B-2) can be the epoxy compound (b-2-1) with at least two epoxy radicals and the compound (b-2-2) with at least one carboxylic acid group and at least one ethene unsaturated group and carries out the reaction product with hydroxyl that polyreaction formed, and the epoxy compound (b-2-1) wherein with at least two epoxy radicals comprises such as formula the compound shown in (II), any mixing such as formula the compound shown in (III) or above-mentioned material.Then, compound carboxylic acid anhydride (b-2-3) is added in reaction solution, to carry out polyreaction.Total yield number based on the hydroxyl of the reaction product of above-mentioned hydroxyl is 1 equivalent, and the equivalents of the anhydride group that compound carboxylic acid anhydride (b-2-3) has is 0.4 equivalent to 1 equivalent, is preferably 0.75 equivalent to 1 equivalent.When using multiple compound carboxylic acid anhydride (b-2-3), this little compound carboxylic acid anhydride can sequentially add or add simultaneously in reaction.When using dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride to be used as compound carboxylic acid anhydride (b-2-3), the mol ratio of dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride is 1/99 to 90/10, is preferably 5/95 to 80/20.The operating temperature of above-mentioned reaction can be 50 DEG C to 130 DEG C.

Second alkali soluble resin (B-2) can be the epoxy compound (b-2-1) with at least two epoxy radicals to carry out reacting the formed reaction product with hydroxyl with the compound (b-2-2) with at least one carboxylic acid group and at least one ethene unsaturated group, and the epoxy compound (b-2-1) wherein with at least two epoxy radicals can be such as formula the compound shown in (II) and formula (III).Then, be incorporated in reaction solution, to carry out polyreaction by interpolation compound carboxylic acid anhydride (b-2-3), the compound (b-2-4) with epoxy radicals or the two.Be 1 equivalent based on the total yield number such as formula the epoxy radicals in the compound shown in (II) and formula (III), the above-mentioned acid value equivalents with the compound (b-2-2) of at least one carboxylic acid group and at least one ethene unsaturated group is 0.8 equivalent to 1.5 equivalent, is preferably 0.9 equivalent to 1.1 equivalent.Be 100 molar percentages based on above-mentioned total use amount with the hydroxyl of the reaction product of hydroxyl, the use amount of compound carboxylic acid anhydride (b-2-3) is 10 molar percentage to 100 molar percentages, be preferably 20 molar percentage to 100 molar percentages, be more preferred from 30 molar percentage to 100 molar percentages.

When preparing above-mentioned the second alkali soluble resin (B-2), in order to Reaction time shorten, generally can add alkali compounds in reaction solution, using as catalysts.This catalysts can including but not limited to triphenylphosphine (triphenyl phosphine), antimony triphenyl (triphenyl stibine), triethylamine (triethylamine), triethanolamine (triethanolamine), tetramethyl ammonium chloride (tetramethylammonium chloride) or benzyltriethylammonium chloride (benzyltriethylammonium chloride) etc.This catalysts can be a kind of or mix multiple use separately.

Be 100 weight portions based on the above-mentioned epoxy compound (b-2-1) with at least two epoxy radicals and total use amount of the compound (b-2-2) with at least one carboxylic acid group and at least one ethene unsaturated group, the use amount of this catalysts is 0.01 weight portion to 10 weight portion, is preferably 0.3 weight portion to 5 weight portion.

Secondly, in order to control the degree of polymerization, reaction can add polymerization inhibitor (polymerization inhibitor) in reaction solution.Polymerization inhibitor can comprise methoxyl phenol (methoxyphenol), methylnaphthohydroquinone (methylhydroquinone), quinhydrones (hydroquinone), 2,6-BHT (2,6-di-t-butyl-p-cresol) or phenothiazine (phenothiazine) etc.Polymerization inhibitor can be a kind of or mix multiple use separately.

Be 100 weight portions based on the above-mentioned epoxy compound (b-2-1) with at least two epoxy radicals and total use amount of the compound (b-2-2) with at least one carboxylic acid group and at least one ethene unsaturated group, the use amount of this polymerization inhibitor is 0.01 weight portion to 10 weight portion, is preferably 0.1 weight portion to 5 weight portion.

When preparing the second alkali soluble resin (B-2), polymerization solvent is optionally used.Polymerization solvent can comprise the alcohols solvent of ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutyl alcohol, 2-butanols, hexanol or ethylene glycol etc.; The ketones solvent of MEK or cyclohexanone etc.; The aromatic hydrocarbon solvent of toluene or dimethylbenzene etc.; The match Luo element kind solvent of match Luo element (cellosolve) or butyl match Luo element (butyl cellosolve) etc.; Card must appropriate (carbitol) or butyl card must the card of appropriate (butyl carbitol) etc. must appropriate kind solvent; The propylene glycol alkyl ether solvent of propylene glycol monomethyl ether (propylene glycol monomethyl ether) etc.; Many propylene glycol alkyls ether [poly (propylene glycol) alkyl ether] kind solvent of dipropylene glycol monomethyl ether [di (propylene glycol) methyl ether] etc.; The acetates solvent of ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate (ethylene glycol monoethyl ether acetate) or propylene glycol monomethyl ether acetate (propylene glycol methyl ether acetate) etc.; Lactic acid alkane ester (alkyl lactate) kind solvent of ethyl lactate (ethyl lactate) or butyl lactate (butyl lactate) etc.; Or dialkyl group glycol ethers solvent.This polymerization solvent can be a kind of or mix multiple use separately.

The acid value of the second alkali soluble resin (B-2) is 50 milligrams of KOH/ gram to 200 milligrams KOH/ gram, is preferably 60 milligrams of KOH/ gram to 150 milligrams KOH/ gram.

When alkali soluble resin (B) does not use the second alkali soluble resin (B-2), obtained colored filter photosensitive polymer combination has the not good defect of resistance to developability.

When aforementioned first alkali soluble resin (B-1) is 10/90 to 90/10 with the weight ratio of the second alkali soluble resin (B-2), obtained colored filter photosensitive polymer combination has preferably resistance to developability.

3rd alkali soluble resin (B-3)

3rd alkali soluble resin (B-3) is formed by potpourri institute copolymerization, wherein this potpourri comprises the ethylene unsaturated monomer (b-3-1) with one or more carboxylic acid groups, and other the copolymerizable ethylene unsaturated monomer (b-3-2) beyond the aforementioned ethylene unsaturated monomer (b-3-1) with one or more carboxylic acid groups.

There is the ethylene unsaturated monomer (b-3-1) of one or more carboxylic acid groups

This ethylene unsaturated monomer (b-3-1) with one or more carboxylic acid groups is that to be same as the aforementioned ethylene unsaturated monomer (b-1-2) with one or more carboxylic acid groups identical, therefore does not separately repeat at this.

Other copolymerizable ethylene unsaturated monomer (b-3-2)

This other copolymerizable ethylene unsaturated monomer (b-3-2) is same as aforementioned this have the ethene monomer (b-1-1) of the structure of hindered amine and have ethylene unsaturated monomer (b-1-2) other copolymerizable ethylene unsaturated monomer (b-1-3) in addition of one or more carboxylic acid groups, separately do not repeat at this.

There is the compound (C) of ethene unsaturated group

This compound (C) with ethene unsaturated group refers to the unsaturated compound with at least one ethene unsaturated group or has the unsaturated compound of ethene unsaturated group of more than 2 or 2.

This unsaturated compound with at least one ethene unsaturated group can including but not limited to acrylamide, acryloyl morpholine, metering system morpholide, amino-3, the 7-dimethyl monooctyl esters of acrylic acid-7-, amino-3, the 7-dimethyl monooctyl esters of methacrylic acid-7-, isobutoxymethyl acrylamide, isobutoxymethyl Methacrylamide, isobomyl acrylate base 2-ethoxyethyl acetate, methacrylic acid isobornyl 2-ethoxyethyl acetate, isobornyl acrylate, isobornyl methacrylate, acrylic acid-2-ethyl caproite, methacrylic acid-2-Octyl Nitrite, ethyl diglycol acrylate, ethyl diglycol methacrylate, tertiary octyl acrylamide, tertiary octyl methyl acrylamide, diacetone acrylamide, two acetone Methacrylamides, acrylate ester, dimethylaminoethyl ester, dodecylacrylate, lauryl methacrylate, acrylic acid dicyclopentenyl 2-ethoxyethyl acetate, methacrylic acid dicyclopentenyl 2-ethoxyethyl acetate, acrylic acid dicyclopentenyl ester, methacrylic acid dicyclopentenyl ester, N,N-DMAA, N, N-dimethylmethacryl amide, acrylic acid tetrachloro phenyl ester, methacrylic acid tetrachloro phenyl ester, acrylic acid-2-tetrachloro phenoxy ethyl, methacrylic acid-2-tetrachloro phenoxy ethyl, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, tetrabromophenyl acrylate, methacrylic acid tetrabromo phenyl ester, acrylic acid-2-tetrabromo phenoxy ethyl, methacrylic acid-2-tetrabromo phenoxy ethyl, acrylic acid-2-Trichlorophenoxy ethyl ester, methacrylic acid-2-Trichlorophenoxy ethyl ester, tribromophenyl acrylate, methacrylic acid tribromophenyl, acrylic acid-2-tribromophenoxy ethyl ester, methacrylic acid-2-tribromophenoxy ethyl ester, acrylic acid-2-hydroxyl ethyl ester, 2-hydroxyethyl methacry-late, 2-hydroxypropyl acrylate, Hydroxypropyl methacrylate, caprolactam, N-vinyl skin junket alkane ketone, acrylate, phenoxyethyl methacrylate, Pentachlorophenyl Acrylate, methacrylic acid pentachlorophenyl ester, acrylic acid pentabromo-phenyl ester, methacrylic acid pentabromo-phenyl ester, poly-single acrylic acid glycol ester, poly-monomethacrylate glycol ester, poly-mono acrylic acid propylene glycol ester, poly-monomethacrylate acid propylene glycol ester, acrylic acid norbornene ester or methacrylic acid norbornene ester etc.

The aforementioned unsaturated compound with at least one ethene unsaturated group can be a kind of or mix multiple use separately.

This unsaturated compound with more than 2 or 2 ethene unsaturated groups is including but not limited to glycol diacrylate, ethylene glycol dimethacrylate, diacrylate dicyclopentenyl ester, dimethacrylate dicyclopentenyl ester, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, three (2-hydroxyethyl) isocyanates diacrylate, three (2-hydroxyethyl) isocyanates dimethylacrylate, three (2-hydroxyethyl) isocyanurate triacrylate, three (2-hydroxyethyl) isocyanates trimethyl acrylic ester, three (2-hydroxyethyl) isocyanurate triacrylate of caprolactone upgrading, three (2-hydroxyethyl) isocyanates trimethyl acrylic ester of caprolactone upgrading, three acrylic acid trihydroxy methyl propyl ester, trimethacrylate acid trihydroxy methyl propyl ester, three acrylic acid trihydroxy methyl propyl ester of oxirane (hereinafter referred to as EO) upgrading, the trimethacrylate acid trihydroxy methyl propyl ester of EO upgrading, three acrylic acid trihydroxy methyl propyl ester of epoxypropane (hereinafter referred to as PO) upgrading, the trimethacrylate acid trihydroxy methyl propyl ester of PO upgrading, triethylene glycol diacrylate, triethylene glycol dimethacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, BDO diacrylate, BDO dimethylacrylate, 1,6-hexanediyl ester, HDDMA, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, polyester diacrylate, polyester dimethylacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, dipentaerythritol acrylate (dipentaerythritol hexaacrylate, DPHA), dipentaerythritol hexamethacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol pentamethacrylates, dipentaerythritol tetraacrylate, dipentaerythritol tetramethyl acrylate, the dipentaerythritol acrylate of caprolactone upgrading, the dipentaerythritol hexamethacrylate of caprolactone upgrading, the Dipentaerythritol Pentaacrylate of caprolactone upgrading, the dipentaerythritol pentamethacrylates of caprolactone upgrading, tetrapropylene acid two trihydroxy methyl propyl ester, tetramethyl acrylic acid two trihydroxy methyl propyl ester, the bisphenol a diacrylate of EO upgrading, the bisphenol a dimethacrylate of EO upgrading, the bisphenol a diacrylate of PO upgrading, the bisphenol a dimethacrylate of PO upgrading, the hydrogenated bisphenol A diacrylate of EO upgrading, the hydrogenated bisphenol A dimethylacrylate of EO upgrading, the hydrogenated bisphenol A diacrylate of PO upgrading, the hydrogenated bisphenol A dimethylacrylate of PO upgrading, the glycerin tripropionate of PO upgrading, the Bisphenol F diacrylate of EO upgrading, the Bisphenol F dimethylacrylate of EO upgrading, phenolic aldehyde polyglycidyl ether acrylate, phenolic aldehyde poly epihydric alcohol ether metacrylic acid ester, or Japanese Toagosei Co., Ltd manufactures, and model is the commodity etc. of TO-1382.

This compound (C) with ethene unsaturated group is preferably and is selected from three acrylic acid trihydroxy methyl propyl ester, three acrylic acid trihydroxy methyl propyl ester of EO upgrading, three acrylic acid trihydroxy methyl propyl ester of PO upgrading, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol tetraacrylate, the dipentaerythritol acrylate of caprolactone upgrading, tetrapropylene acid two trihydroxy methyl propyl ester, the glycerin tripropionate of PO upgrading or the combination in any of above-mentioned material.

Total use amount based on aforementioned bases soluble resin (B) is 100 weight portions, this use amount with the compound (C) of ethene unsaturated group is 60 weight portion to 600 weight portions, be preferably 80 weight portion to 500 weight portions, be more preferred from 100 weight portion to 400 weight portions.

Light initiator (D)

Smooth initiator (D) of the present invention can be O-acyl group oxime (oxime) compound, triazine (triazine) compound, vinylbenzene ketone (acetophenone) compound, diimidazole (biimidazole) compound or benzophenone (benzophenone) compound etc.This light initiator (D) can be a kind of or mix multiple use separately.

This O-acyl group oxime compound can including but not limited to 1-[4-(phenyl) phenyl]-heptane-1, 2-diketone-2-(O-benzoyl group oxime), 1-[4-(phenyl) phenyl]-octane-1, 2-diketone-2-(O-benzoyl group oxime), 1-[4-(benzoyl group) phenyl]-heptane-1, 2-diketone-2-(O-benzoyl group oxime), 1-[9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-base]-ethane ketone-1-(O-acetyl group oxime), 1-[9-ethyl-6-(3-methylbenzene acyl group)-9H-carbazole-3-base]-ethane ketone 1-(O-acetyl group oxime), 1-[9-ethyl-6-benzoyl group-9H-carbazole-3-base]-ethane ketone 1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl group)-9H-carbazole-3-base]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl benzoyl group)-9H-carbazole-3-base]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzene acyl group)-9H-carbazole-3-base]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzene acyl group)-9H-carbazole-3-base]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxa penta cyclic group) benzoyl group }-9H-carbazole-3-base]-1-(O-acetyl group oxime), or ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxa penta cyclic group) methoxybenzene acyl group }-9H-carbazole-3-base]-1-(O-acetyl group oxime) etc.Aforesaid O-acyl group oxime compound can be a kind of or mix multiple use separately.

This triaizine compounds can including but not limited to 2, two (trichloromethyl)-6-(p-methoxyl) styryl-s-triazine [2 of 4-, 4-Bis (trichloromethyl)-6-(p-methoxy) styryl-s-triazine], 2, two (trichloromethyl)-6-(the p-dimethylaminophenyl-1 of 1-of 4-, 3-butadienyl)-s-triazine [2, 4-Bis (trichloromethyl)-6-(1-p-dimethylaminophenyl-1, 3-butadienyl)-s-triazine] or 2-trichloromethyl-4-amino-6-p-methoxystyrene base-s-triazine [2-trichloromethyl-4-amino-6-(p-methoxy) styryl-s-triazine] etc.Aforesaid triaizine compounds can be a kind of or mix multiple use separately.

This vinylbenzene ketonic compound can including but not limited to dimethylamine vinylbenzene ketone, α, α '-dimethoxy azoxy vinylbenzene ketone, 2,2 '-dimethyl-2-phenyl vinylbenzene ketone, p-methoxybenzene ethane ketone, 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholine-1-acetone or 2-benzyl-2-N, N dimethylamine-1-(4-morpholinyl phenyl)-1-butanone etc.Aforesaid vinylbenzene ketonic compound can be a kind of or mix multiple use separately.

This diimidazole compound can including but not limited to 2, 2 '-bis-(o-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(ortho-fluorophenyl base)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-aminomethyl phenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-methoxyphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-ethylphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(p-methoxyphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(2, 2 ', 4, 4 '-tetramethoxy phenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole or 2, 2 '-bis-(2, 4-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole etc.Aforesaid diimidazole compound can be a kind of or mix multiple use separately.

This benzophenone cpd can including but not limited to thioxanthones, 2,4-diethyl thioxanthones, thioxanthones-4-sulfone, benzophenone, 4,4 '-bis-(dimethylamine) benzophenone or 4,4 '-bis-(diethylamine) benzophenone etc.Aforesaid benzophenone cpd can be a kind of or mix multiple use separately.

This light initiator (D) is better can be 1-[4-(phenyl) phenyl]-octane-1, 2-diketone-2-(O-benzoyl group oxime), 1-[9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-base]-ethane ketone-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzene acyl group)-9H-carbazole-3-base]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxa penta cyclic group) methoxybenzene acyl group }-9H-carbazole-3-base]-1-(O-acetyl group oxime), 2, two (trichloromethyl)-6-(p-methoxyl) styryl-s-triazine of 4-, 2-benzyl-2-N, N dimethylamine-1-(4-morpholinyl phenyl)-1-butanone, 2, 2 '-bis-(2, 4-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole [2, 2 '-bis (2, 4-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl-1, 2 '-biimidazole], 4, the combination in any of 4 '-bis-(diethylamine) benzophenone or above-mentioned material.

Under the physical property not affecting photosensitive polymer combination, photosensitive polymer combination of the present invention can add the initiator beyond this light initiator (D) further.The concrete example of this initiator, as: α-diketone (α-diketone) compound, keto-alcohol (acyloin) compound, keto-alcohol ether (acyloin ether) compound, acyl phosphine oxide (acylphosphineoxide) compound, quinone (quinone) compound, the compound with halogen or superoxide etc.

This α-dione compounds can be compound etc. including but not limited to benzil (benzil) or acetyl group (acetyl).Aforesaid α-dione compounds can be a kind of or mix multiple use separately.

This keto-alcohol compound can including but not limited to diphenylhydroxyethanone (benzoin) etc.Aforesaid keto-alcohol compound can be a kind of or mix multiple use separately.

This keto-alcohol ether compound can including but not limited to diphenylhydroxyethanone methyl ether (benzoin methylether), diphenylhydroxyethanone ether (benzoin ethylether) or diphenylhydroxyethanone isopropyl ether (benzoin isopropyl ether) etc.Aforesaid keto-alcohol ether compound can be a kind of or mix multiple use separately.

This acyl phosphine oxide compound can including but not limited to 2,4,6-trimethyl benzoyl diphenyl phosphine oxide (2,4,6-trimethyl-benzoyl diphenylphosphineoxide) or two-(2,6-dimethoxy benzoyl)-2,4,4-trimethylpentyl phosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethylbenzyl phosphineoxide] etc.Aforesaid acyl phosphine oxide compound can be a kind of or mix multiple use separately.

This quinones can including but not limited to anthraquinone (anthraquinone), 1,4-naphthoquinone (Isosorbide-5-Nitrae-naphthoquinone) etc.Aforesaid quinones can be a kind of or mix multiple use separately.

This compound with halogen can including but not limited to chloroacetophenone (phenacyl chloride), trisbromomethyl benzene sulfone (tribromomethyl phenylsulfone) or three (trichloromethyl)-s-triazine [tris (trichloromethyl)-s-triazine] etc.The aforementioned compound with halogen can be a kind of or mix multiple use separately.

This superoxide can including but not limited to two-tert-butyl peroxide (di-tertbutylperoxide) etc.Aforesaid superoxide can be a kind of or mix multiple use separately.

Total use amount based on aforementioned bases soluble resin (B) is 100 weight portions, and the use amount of this light initiator (D) is 10 weight portion to 100 weight portions, is preferably 15 weight portion to 90 weight portions, is more preferred from 20 weight portion to 80 weight portions.

Organic solvent (E)

Organic solvent of the present invention (E) can including but not limited to ethylene glycol monomethyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, DGDE, diglycol positive propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol positive propyl ether, dipropylene glycol n-butyl ether, (gathering) alkylene glycol mono alkane ether solvent of tripropylene glycol methyl ether or tripropylene glycol ether etc., glycol methyl ether acetate, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate (propylene glycol methyl ether acetate, or (gathering) alkylene glycol mono alkane ether acetate kind solvent of propylene-glycol ethyl ether acetate etc. PGMEA), other ether solvent of diethylene glycol dimethyl ether, diglycol ethyl methyl ether, diethyl carbitol or tetrahydrofuran etc., the ketones solvent of the first and second alkane ketone, cyclohexanone, 2-HEPTANONE or 3-heptanone etc., the lactic acid alkane esters solvent of 2 hydroxy propanoic acid methyl esters or 2 hydroxy propanoic acid ethyl ester etc., 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate (ethyl3-ethoxypropionate, EEP), ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methyl-3-methoxybutyl acetic acid esters, 3-methyl-3-methoxybutyl propionic ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, other esters solvent of ethyl acetoacetate or 2-methoxyl ethyl butyrate etc., the aromatic hydrocarbons kind solvent of toluene or dimethylbenzene etc., the amide solvents such as 1-METHYLPYRROLIDONE, DMF or DMA.

This organic solvent (E) is better can be 1-Methoxy-2-propyl acetate or 3-ethoxyl ethyl propionate.

Total use amount based on aforementioned bases soluble resin (B) is 100 weight portions, and the use amount of this organic solvent (E) is 500 weight portion to 5000 weight portions, is preferably 800 weight portions to 4,500 weight portions; Be more preferred from 1,000 weight portion to 4,000 weight portion.

Dyestuff (F)

Colored filter photosensitive polymer combination of the present invention optionally comprises dyestuff (F), and this dyestuff (F) has the orchil as shown in the formula the structure shown in (IV):

In formula (IV), Z ₁to Z ₄represent hydrogen atom ,-Z independently of one another ₆, carbon number be 6 to 10 aromatic hydroxy group or through halogen atom ,-Z ₆,-OH ,-OZ ₆,-SO ₃ ^-,-SO ₃h ,-SO ₃m ,-COOH ,-COOZ ₆,-SO ₃z ₆,-SO ₂nHZ ₈or-SO ₂nZ ₈z ₉replace the aromatic hydroxy group that carbon number is 6 to 10; Z ₅representative-SO ₃ ^-,-SO ₃h ,-SO ₃m ,-COOH ,-COOZ ₆,-SO ₃z ₆,-SO ₂nHZ ₈or-SO ₂nZ ₈z ₉; A represents halogen atom; A represent 0 or 1 and b represent 0 to 5 integer.When b represents 2 to 5, multiple Z ₅for identical or not identical.Aforesaid Z ₆, Z ₈, Z ₉as described below respectively with M.

Aforesaid Z ₆represent alkyl that carbon number is 1 to 10 or through halogen atom replace the alkyl that carbon number is 1 to 10, wherein this carbon number alkyl that is 1 to 10 or this through halogen atom to replace carbon number be-CH in the alkyl of 1 to 10 ₂-be not to be substituted or can by-O-, carbonyl or-NZ ₇-replaced.This Z ₇represent carbon number be 1 to 10 alkyl or through halogen atom replace carbon number be the alkyl of 1 to 10.

Aforesaid Z ₈and Z ₉represent straight chained alkyl, branched alkyl or naphthenic base that carbon number is 1 to 10 independently of one another, or-Q.This Q represent carbon number be 6 to 10 aromatic hydroxy group, carbon number be 5 to 10 assorted aromatic radical.Moreover Q also can represent through halogen atom ,-Z ₆,-OH ,-OZ ₆,-NO ₂,-CH=CH ₂or-CH=CH-Z ₆the carbon number replaced is the aromatic hydroxy group of 6 to 10, or through halogen atom ,-Z ₆,-OH ,-OZ ₆,-NO ₂,-CH=CH ₂or-CH=CH-Z ₆the carbon number replaced is the assorted aromatic radical of 5 to 10, wherein Z ₆definition as previously mentioned, separately do not repeat at this.

Adjuvant (G)

For meeting physical property and the voltinism demand of colored filter fragment, photosensitive polymer combination of the present invention optionally comprises adjuvant (G), such as: the macromolecular compound beyond filling agent, aforementioned bases soluble resin (B), adherence promoter, antioxidant, ultraviolet light absorber or anti-agglutinant etc.

This adjuvant (G) can including but not limited to the filling agent of glass or aluminium etc., macromolecular compound beyond the alkali soluble resins (B) such as polyvinyl alcohol (PVA), polyalkylene glycol monoalkyl ether or poly-perfluoroalkyl acrylate alkane ester, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxyethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-epoxy prapanol propyl trimethoxy silicane, 3-epoxy prapanol hydroxypropyl methyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, the adherence promoter of 3-metacryloxy propyl trimethoxy silicane or 3-mercaptopropyl trimethoxy silane etc., the antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol) or 2,6-, bis--tert-butyl phenol, 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorphenyl changes the ultraviolet light absorber of nitrogen or alkoxy benzophenone etc., the anti-agglutinant of sodium polyacrylate etc.

The preparation of photosensitive polymer combination

The preparation method of colored filter photosensitive polymer combination of the present invention is by above-mentioned pigment (A), alkali soluble resin (B), there is the compound (C) of ethene unsaturated group, light initiator (D) and organic solvent (E) are positioned in stirrer and stir, it is made to be uniformly mixed into solution state, also dyestuff (F) is optionally added if desired, or filling agent, macromolecular compound beyond alkali soluble resin (B), adherence promoter, antioxidant, the adjuvant (G) of ultraviolet light absorber or anti-agglutinant etc.

Total use amount based on alkali soluble resin (B) is 100 weight portions, the use amount of pigment (A) is 30 weight portion to 300 weight portions, the use amount with the compound (C) of ethene unsaturated group is 60 weight portion to 600 weight portions, the use amount of light initiator (D) is 10 weight portion to 100 weight portions, and the use amount of organic solvent (E) is 500 weight portion to 5000 weight portions.

The preparation of colored filter

The preparation of colored filter of the present invention utilizes aforementioned colored filter photosensitive polymer combination to form pixel layer, and utilize the method to obtain colored filter.

The aforementioned colored filter photosensitive polymer combination being mixed into solution state, mainly by coating methods such as revolution coating, cast coat, ink-jet application (ink-jet) or print roll coatings, is coated on substrate by the preparation of colored filter of the present invention.After coating, first in the mode of drying under reduced pressure, remove most solvent, and remove solvent in the mode of pre-baked (pre-bake) and form a pre-baked film.Wherein, drying under reduced pressure and pre-baked condition, according to the kind of each composition, formula ratio and different.Drying under reduced pressure is generally under the pressure of 0 to 200mmHg, carried out for 1 second in second to 60, and pre-baked be generally carry out 1 minute to 15 minutes at 70 DEG C to 110 DEG C temperature.Then, expose under this pre-baked film being positioned over the mask (mask) of specifying, wherein exposing the light used, be good, and UV-device can be (surpassing) high-pressure mercury-vapor lamp or metal halid lamp with the ultraviolet of g line, h line, i line etc.Then, at 23 ± 2 DEG C of temperature, the pre-baked film after exposure be impregnated in developer solution and developed to 5 minutes for 15 seconds, form pattern to remove part not, and form the substrate with photo-hardening film layer.

The concrete example of aforesaid base plate, as: for alkali-free glass, soda-lime glass, hard glass (Pai Lesi glass), quartz glass, the person that adheres to nesa coating on this little glass of liquid crystal indicator etc., or for the photo-electric conversion device substrate (as: silicon substrate) etc. of solid-state image sensor etc.These substrates are generally first form the black matrix" (black matrix) of isolating each pixel shader layer.

Moreover, the concrete example of developer solution, 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, piperidines or 1, 8-diazabicylo-(5, 4, 0) alkaline aqueous solution that forms of the alkali compounds such as-7-hendecene, its concentration is generally 0.001 percentage by weight to 10 percentage by weight, be preferably 0.005 percentage by weight to 5 percentage by weight, be more preferred from 0.01 percentage by weight to 1 percentage by weight.

When the developer solution using aforementioned base aqueous solution to form, be generally clean with water after development, and with pressurized air or the air-dry pattern of compressed nitrogen.

In air-dry there is the substrate of photo-hardening film layer after, utilize the heating arrangement such as hot plate or baking oven, at temperature 100 to 280 DEG C, heat this substrate 1 to 15 minute, to remove the volatile ingredient in film, and make unreacted ethene unsaturated double-bond in film carry out thermmohardening reaction.Use the photosensitive polymer combination of colors (mainly comprising red, green, blue three look) in predetermined pixel with same step repetitive operation three times, the photo-hardening pixel shader layer of red, green, blue three look can be obtained.

Secondly, on aforesaid pixel shader layer, under vacuum, ITO (tin indium oxide) vapor-deposited film is formed with the temperature of 220 DEG C to 250 DEG C.If desired, ITO vapor-deposited film is etched and connects up, and coating of liquid crystalline alignment film polyimide, and then burn till it, the colored filter of liquid crystal display can be obtained.

The preparation of liquid crystal indicator

Liquid crystal indicator of the present invention comprises aforesaid colored filter.

The colored filter substrate of liquid crystal indicator of the present invention mainly obtained by preceding method and be provided with thin film transistor (TFT) (Thin Film Transistor; TFT) driving substrate formed, and wherein between above-mentioned 2 plate bases, gets involved (structure cell interval, gap; Cell gap) do subtend configuration, and the surrounding position of 2 plate bases of fitting with sealing agent.Then, in the gap that the surface of 2 plate bases and sealing agent are distinguished, liquid crystal is injected in filling, and seals filling orifice, to form liquid crystal cell (cell).Then, at the outside surface of liquid crystal cell, that is form on other side of each substrate of liquid crystal cell, laminating Polarizer, with obtained liquid crystal indicator.

Below utilize several embodiment so that application of the present invention to be described, so itself and be not used to limit the present invention, have in the technology of the present invention field and usually know the knowledgeable, without departing from the spirit and scope of the present invention, when being used for a variety of modifications and variations.

Embodiment

Prepare the first alkali soluble resin (B-1)

It is below the first alkali soluble resin preparing synthesis example B-1-1 to B-1-8 according to table 1.

Synthesis example B-1-1

By 1 of 3 weight portions, 2, 2, 6, 6-pentamethyl-piperidyl methyl acrylate (hereinafter referred to as FA-711MM), the 2-methacryloyloxyethyl succinate (hereinafter referred to as HOMS) of 45 weight portions, the double cyclopentenyl acrylate (hereinafter referred to as FA-511A) of 12 weight portions, the styrene (hereinafter referred to as SM) of 20 weight portions, the benzyl methacrylate (hereinafter referred to as BzMA) of 5 weight portions, the methyl methacrylate (hereinafter referred to as MMA) of 15 weight portions, 2 of 4 weight portions, the 3-ethoxyl ethyl propionate (hereinafter referred to as EEP) of the two-2-methylbutyronitrile (hereinafter referred to as AMBN) of 2 '-azo and 200 weight portions is added in the four-hole boiling flask of 500mL continuously, and pan feeding speeds control 25 weight portions/minute, temperature is maintained 100 DEG C.React after 6 hours, the first alkali soluble resin (B-1-1) can be obtained.

Synthesis example B-1-2 to B-1-8

Synthesis example B-1-2 to B-1-8 uses the preparation method identical with the method for making of first alkali soluble resin of synthesis example B-1-1, difference is that synthesis example B-1-2 to B-1-8 is the kind of change first alkali soluble resin Raw and use amount and polymerizing condition, and its formula and polymerizing condition as shown in table 1, separately do not repeat at this.

Prepare the second alkali soluble resin (B-2)

Synthesis example B-2-1

First, by the fluorenes epoxy compound of 100 weight portions, (chemical company of Nippon Steel manufactures, model is the commodity of ESF-300, and its epoxide equivalent is 231), the propylene glycol monomethyl ether acetate of the acrylic acid of 30 weight portions, the benzyltriethylammonium chloride of 0.3 weight portion, the BHT of 0.1 weight portion and 130 weight portions is added in the four neck flasks of 500 milliliters with continous way addition manner.Pan feeding speeds control 25 weight portions/minute, and the temperature of course of reaction maintains 100 DEG C to 110 DEG C.React after 15 hours, the pale yellow transparent mixed liquor that solid constituent concentration is 50 percentage by weights can be obtained.

Then, the above-mentioned mixed liquor of 100 weight portions is added in the ethylene glycol ether acetate of 25 weight portions, adds the tetrabydrophthalic anhydride of 6 weight portions and the benzophenone tetracarboxylic dianhydride of 13 weight portions simultaneously, and be heated to 110 DEG C to 115 DEG C.React after 2 hours, can obtain the second alkali soluble resin (B-2-1), its acid value is 98mgKOH/g, and weight average molecular weight is 2205.

Synthesis example B-2-2

By the fluorenes epoxy compound of 100 weight portions, (chemical company of Nippon Steel manufactures, model is the commodity of ESF-300, and its epoxide equivalent is 231), the propylene glycol monomethyl ether acetate of the acrylic acid of 30 weight portions, the benzyltriethylammonium chloride of 0.3 weight portion, the BHT of 0.1 weight portion and 130 weight portions is added in the four neck flasks of 500 milliliters continuously.Pan feeding speeds control 25 weight portions/minute, and the temperature of course of reaction maintains 100 DEG C to 110 DEG C.React after 15 hours, the pale yellow transparent mixed liquor that solid component concentration is 50 percentage by weights can be obtained.

Then, add in the ethylene glycol ether acetate of 25 weight portions by molten for the above-mentioned mixed liquor of 100 weight portions, add the benzophenone tetracarboxylic dianhydride of 13 weight portions simultaneously, and be heated to 90 DEG C to 95 DEG C.React after 2 hours, add the tetrabydrophthalic anhydride of 6 weight portions, and react 4 hours at 90 DEG C to 95 DEG C, can obtain the second alkali soluble resin (B-2-2), its acid value is 99.0mgKOH/g, and weight average molecular weight is 2630.

Synthesis example B-2-3

By the epoxy compound of 400 weight portions, (Japanese chemical drug Inc. makes, model is the commodity of NC-3000, and its epoxide equivalent is 288), the methoxyl phenol (methoxyphenol) of the acrylic acid of 102 weight portions, 0.3 weight portion, the triphenylphosphine of 5 weight portions and the propylene glycol monomethyl ether acetate of 264 weight portions add in reaction bulb, and temperature maintained 95 DEG C.React after 9 hours, can obtain intermediate product, its acid value is 2.2mgKOH/g.Then, add the tetrabydrophthalic anhydride (tetrahydrophthalic anhydride) of 151 weight portions, and react 4 hours at 95 DEG C, the second alkali soluble resin (B-2-3) can be obtained, its acid value is 102mgKOH/g, and weight average molecular weight is 3200.

Prepare the 3rd alkali soluble resin (B-3)

It is below the 3rd alkali soluble resin preparing synthesis example B-3-1 to B-3-4 according to table 2.

Synthesis example B-3-1

Four cervical vertebra bottles of a volume 1000 milliliters arrange nitrogen inlet, stirrer, well heater, condenser pipe and thermometer, and imports nitrogen.Under the environment of nitrogen, the 3-ethoxyl ethyl propionate (hereinafter referred to as EEP) of the benzyl methacrylate (hereinafter referred to as BzMA) of the styrene (hereinafter referred to as SM) of the double cyclopentenyl acrylate (hereinafter referred to as FA-511A) of the 2-methacryloyloxyethyl succinate (hereinafter referred to as HOMS) of 45 weight portions, 15 weight portions, 20 weight portions, 5 weight portions, the methyl methacrylate (hereinafter referred to as MMA) of 15 weight portions and 200 weight portions is added in four cervical vertebra bottles continuously, and mixes.Then, by the temperature increase to 100 of oil bath DEG C, and by 2 of 4 weight portions, the two-2-methylbutyronitrile (hereinafter referred to as AMBN) of 2 '-azo is dissolved in 3-ethoxyl ethyl propionate, be divided equally into the weight of five equal portions, and be added in 1 hour in four cervical vertebra bottles.Temperature of reaction in polymerization process is maintenance 100 DEG C, and reacts 6 hours.Then, in four cervical vertebra bottles, take out polymerizate, and remove solvent, namely obtain the 3rd alkali soluble resin (B-3-1).

Synthesis example B-3-2 to B-3-4

Synthesis example B-3-2 to B-3-4 uses the preparation method identical with the method for making of the 3rd alkali soluble resin of synthesis example B-3-1, difference is that synthesis example B-3-2 to B-3-4 is the kind of change the 3rd alkali soluble resin Raw and use amount and polymerizing condition, and its formula and polymerizing condition as shown in table 2, separately do not repeat at this.

Prepare photosensitive polymer combination

It is below the photosensitive polymer combination preparing embodiment 1 to 11 and comparative example 1 to 6 according to table 3 and table 4.

Embodiment 1

By the pigment (A-1 of 30 weight portions, wherein the ratio of C.I.Pigment R254 and C.I.Pigment Yellow139 is 80/20), the first alkali soluble resin (hereinafter referred to as B-1-1) obtained by the aforementioned synthesis example B-1-1 of 10 weight portion, the second alkali soluble resin (hereinafter referred to as B-2-1) obtained by the aforementioned synthesis example B-2-1 of 90 weight portion, (East Asia Synesis Company manufactures the dipentaerythritol acrylate of 40 weight portions, hereinafter referred to as C-1), 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone (hereinafter referred to as D-1) of 3 weight portions, 2 of 3 weight portions, 2 '-bis-(2, 4-dichloro-benzenes dustpan)-4, 4 ', 5, 4 of 5 '-tetraphenyl diimidazole (with referred to as D-2) and 4 weight portions, 4 '-bis-(diethylamine) benzophenone (hereinafter referred to as D-3), add in the 3-ethoxyl ethyl propionate (hereinafter referred to as E-1) of 500 weight portions, mixing is dissolved with swing-out stirrer, the colored filter photosensitive polymer combination of embodiment 1 can be obtained.The colored filter photosensitive polymer combination of gained is evaluated with following each evaluation method, and acquired results is as shown in table 3, and wherein the detection method of resistance to developability and voltage retention repeats after holding.

Embodiment 2 to 11 and comparative example 1 to 6

Embodiment 2 to 11 and comparative example 1 to 6 use the preparation method identical with the method for making of the photosensitive polymer combination of embodiment 1, difference is that embodiment 2 to 11 and comparative example 1 to 6 are the kind and the use amount that change photosensitive polymer combination Raw, and its formula and evaluation result are respectively as shown in table 3 Yu table 4, separately do not repeat at this.

Evaluation method

1. resistance to developability

The colored filter photosensitive polymer combination of solution state is coated in the mode of rotary coating and is of a size of on the glass substrate of 100mm × 100mm, and under the pressure of about 100mmHg, carry out drying under reduced pressure about 30 second.Then, at temperature 80 DEG C pre-baked 2 minutes, the pre-baked film forming thickness 2.5 μm is used.Then, its colourity (L*, a*, b*) is measured with colorimeter (great Zhong electronics corporation manufactures, and model is MCPD).

Afterwards, irradiate above-mentioned pre-baked film with ultraviolet photoetching machine (Canon manufactures, and model is PLA-501F), wherein the light intensity of ultraviolet photoetching machine is set as 100mJ/cm ².Then, pre-baked film be impregnated in the developer solution 1 minute of 23 DEG C.After cleaning with pure water, again measure its colourity, utilize following formula (V) to calculate colourity change (Δ Eab*), and evaluate according to following benchmark, wherein obtained colourity change (Δ Eab*) is less, represents that resistance to developability is better:

Δ Eab ^*=[(Δ L) ²+ (Δ is a) ²+ (Δ b) ²] ^1/2formula (V)

◎：ΔEab*＜2。

○：2≦ΔEab*＜4。

△：4≦ΔEab*＜6。

╳：6≦ΔEab*。

2. voltage retention

Form the SiO in order to prevent sodion stripping ₂film, and indium tin oxide (the Inidium Tin Oxide of evaporation predetermined pattern on soda-lime glass substrate further; ITO) electrode.Photosensitive polymer combination obtained by previous embodiment 1 to 11 and comparative example 1 to 6 is coated on above-mentioned glass substrate in the mode of rotary coating.Then, carry out pre-baked 1 minute with the temperature of 100 DEG C, to form the pre-baked film that thickness is 2.0 μm.Then, not coverage mask, and with 700J/m ²illumination penetrate aforesaid pre-baked film.By the film leaching after exposure, to be placed in temperature be 23 DEG C, and in the developer solution that formed of the potassium hydroxide that concentration is 0.04 percentage by weight.After 1 minute, air-dry with milli-Q water.Then, bake 30 minutes after the film after development with the temperature of 230 DEG C, and form hardened coating film.

Then, the ITO electrode of utilize sealing agent to bond pixel substrate that aforementioned hardened coating film formed and evaporation predetermined pattern, and be that the beaded glass of 1.8mm is positioned between the two by particle diameter.Liquid crystal material (Merck & Co., Inc. manufactures, and its model is the liquid crystal material of MLC6608) is injected the gap between aforementioned sealing agent, pixel substrate and ITO electrode, to form liquid crystal cell.

Then, obtained liquid crystal cell is positioned in the thermostat of 60 DEG C, and with the voltage retention of the liquid crystal cell obtained by liquid crystal voltage conservation rate determining instrument (Toyo Co., Ltd. manufactures, and model is the instrument of VHR-1A type) measurement.The voltage measured is the square wave of 5.5 volts, and its measurement frequency is 60Hz.

Aforesaid voltage retention represents a numerical value, and this numerical value is representative (voltage that the potential difference (PD)/liquid crystal cell of liquid crystal cell after 16.7 milliseconds applies in 0 millisecond).When the voltage retention of liquid crystal cell is no more than 90%, obtained liquid crystal cell cannot stablize maintenance voltage in 16.7 milliseconds, and makes the liquid crystal molecule in liquid crystal cell easily produce the defect of ghost.Previous embodiment 1 to 11 and the voltage retention measured by comparative example 1 to 6 are evaluated according to following benchmark:

◎: 95% < voltage maintenance Shuai≤100%.

Zero: 90% < voltage maintenance Shuai≤95%.

△: 80% < voltage maintenance Shuai≤90%.

╳: voltage maintenance Shuai≤80%.

From the result of table 3 with table 4, when the alkali soluble resin (B) in photosensitive polymer combination of the present invention comprises the first alkali soluble resin (B-1), obtained photosensitive polymer combination has preferably voltage retention.Secondly, when alkali soluble resin (B) comprises the second alkali soluble resin (B-2), obtained photosensitive polymer combination has preferably resistance to developability.

Moreover, when the first alkali soluble resin (B-1) in alkali soluble resin (B) is 10/90 to 90/10 with the weight ratio of the second alkali soluble resin (B-2), obtained photosensitive polymer combination has better resistance to developability.

What need supplement is, though the present invention with specific compound, composition, reaction conditions, processing procedure, analytical approach or particular instrument illustratively, colored filter photosensitive polymer combination of the present invention and application thereof are described, only in the technical field of the invention any have usually know that the knowledgeable is known, the present invention is not limited to this, without departing from the spirit and scope of the present invention, colored filter photosensitive polymer combination of the present invention and application thereof also can use other compound, composition, reaction conditions, processing procedure, analytical approach or instrument to carry out.

Although the present invention discloses as above with embodiment; so itself and be not used to limit the present invention; in the technical field of the invention any have usually know the knowledgeable; without departing from the spirit and scope of the present invention; when being used for a variety of modifications and variations, the scope that therefore protection scope of the present invention ought define depending on accompanying claims is as the criterion.

Table 3

Be called for short Chinese

A-1 C.I.Pigment R254/C.I.Pigment Y139＝80/20

A-2 C.I.Pigment G36/C.I.Pigment Y150＝60/40

A-3 C.I.Pigment B15：6

C-1 dipentaerythritol acrylate (East Asia synthesis manufactures)

C-2 tri-acrylic acid trihydroxy methyl propyl ester

C-3 TO-1382 (Japanese Toagosei Co., Ltd manufactures)

D-1 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone

D-2 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole

D-3 4,4 '-bis-(diethylamino) benzophenone

D-4 1-[4-(phenyl) phenyl]-octane-1,2-diketone 2-(O-benzoyl group oxime)

E-1 3-ethoxyl ethyl propionate

E-2 1-Methoxy-2-propyl acetate

F-1 3-mercaptopropyl trimethoxy silane

F-2 2,2-thiobis (4-methyl-6-tert-butylphenol)

Table 4

Be called for short Chinese

A-1 C.I.Pigment R254/C.I.Pigment Y139＝80/20

A-2 C.I.Pigment G36/C.I.Pigment Y150＝60/40

A-3 C.I.Pigment B15：6

C-1 dipentaerythritol acrylate (East Asia synthesis manufactures)

C-2 tri-acrylic acid trihydroxy methyl propyl ester

C-3 TO-1382 (Japanese Toagosei Co., Ltd manufactures)

D-1 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone

D-2 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole

D-3 4,4 '-bis-(diethylamino) benzophenone

D-4 1-[4-(phenyl) phenyl]-octane-1,2-=diketone 2-(O-benzoyl group oxime)

E-1 3-ethoxyl ethyl propionate

E-2 1-Methoxy-2-propyl acetate

F-1 3-mercaptopropyl trimethoxy silane

F-2 2,2-thiobis (4-methyl-6-tert-butylphenol)

Claims (7)

1. a colored filter photosensitive polymer combination, comprises:

Pigment (A);

Alkali soluble resin (B), comprises:

First alkali soluble resin (B-1), has as shown in the formula the structure of hindered amine shown in (I):

In formula (I), X ₁represent hydrogen atom, carbon number be 1 to 18 straight chained alkyl, branched alkyl or naphthenic base, the carbon number aromatic radical that is 6 to 20, carbon number be 7 to 12 aromatic alkyl, acyl group, oxygen radical, or-OX ₄; X ₄represent hydrogen atom, carbon number be 1 to 18 straight chained alkyl, branched alkyl or naphthenic base, carbon number be the aromatic radical of 6 to 20, or carbon number is the aromatic alkyl of 7 to 12; X ₂and X ₃represent methyl, ethyl, phenyl or mutual bond independently of one another and form the aliphatics ring that carbon number is 4 to 12; * covalent bond is represented; And

Second alkali soluble resin (B-2), reacted by the first potpourri and obtain, wherein this first potpourri comprises the epoxy compound (b-2-1) with at least two epoxy radicals, and has the compound (b-2-2) of at least one carboxylic acid group and at least one ethene unsaturated group;

There is the compound (C) of ethene unsaturated group;

Light initiator (D); And

Organic solvent (E).

2. colored filter photosensitive polymer combination as claimed in claim 1, total use amount based on this alkali soluble resin (B) is 100 weight portions, the use amount of this pigment (A) is 30 weight portion to 300 weight portions, this use amount with the compound (C) of ethene unsaturated group is 40 weight portion to 400 weight portions, the use amount of this light initiator (D) is 10 weight portion to 100 weight portions, and the use amount of this organic solvent (E) is 500 weight portion to 5000 weight portions.

3. colored filter photosensitive polymer combination as claimed in claim 1, wherein this epoxy compound (b-2-1) with at least two epoxy radicals comprises as shown in the formula the compound shown in (II), combines as shown in the formula the compound shown in (III) or the two one:

In formula (II), Y ₁, Y ₂, Y ₃and Y ₄separately represent hydrogen atom, halogen atom, carbon number be 1 to 5 alkyl or alkoxy, or carbon number is aromatic radical or the aralkyl of 6 to 12; In formula (III), R ₁to R ₁₄separately represent hydrogen atom, halogen atom, carbon number be 1 to 8 alkyl or carbon number be the aromatic radical of 6 to 15, and n represents the integer of 0 to 10.

4. colored filter photosensitive polymer combination as claimed in claim 1, wherein this first alkali soluble resin (B-1) is 10/90 to 90/10 with the weight ratio of this second alkali soluble resin (B-2).

5. manufacture a method for colored filter, it utilizes the colored filter photosensitive polymer combination as described in any one in Claims 1-4 to form a pixel layer.

6. a colored filter, it obtains by method as claimed in claim 5.

7. a liquid crystal indicator, comprises colored filter as claimed in claim 6.