CN104423162A

CN104423162A - Photosensitive resin composition for color filter and application thereof

Info

Publication number: CN104423162A
Application number: CN201410421321.9A
Authority: CN
Inventors: 王端志; 许荣宾
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 2013-09-03
Filing date: 2014-08-25
Publication date: 2015-03-18
Also published as: TWI486709B; TW201510652A

Abstract

The invention relates to a photosensitive resin composition for a color filter and application thereof. The photosensitive resin composition comprises an alkali-soluble resin , a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), an organic solvent (D), a pigment (E), and a compound (F). The alkali-soluble resin comprises a first alkali-soluble resin (A-1), and the first alkali-soluble resin (A-1) is prepared by polymerizing a mixture, wherein the mixture comprises an epoxy compound (i) with at least two epoxy groups and a compound (ii) with at least one carboxylic acid group and at least one ethylene unsaturated group. The photosensitive resin composition for a color filter has good development resistance and viscosity stability over time.

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.A kind of resistance to developability and the good colored filter photosensitive polymer combination of viscosity ageing stability are particularly provided.

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.

Usually, colored filter can by decoration method, print process, electricity the method such as method, pigment dispersion method, the pixels such as red, green, blue are formed on transparent glass substrate, and obtained colored filter.Generally speaking, in order to improve the contrast of colored filter, light shield layer (or claiming black matrix") is configurable between pixel layer.

The processing procedure of above-mentioned pigment dispersion method is first dispersed in by pigment in ray hardening resin to form photosensitive composition.Then, this resin combination is formed pixel layer.Furthermore, the processing procedure of pigment dispersion method, normally first on the transparent supports such as glass substrate, light shield layer (black matrix) is formed with the metal such as chromium, chromium oxide or photoresist photomask, and then the photoresist (colorama resist) comprising red pigment will be coated on transparent support by rotary coating mode, and expose by mask, carry out after exposure development treatment red pixel.Then, the step repeating to be coated with, to expose and to develop with same mode of operation can obtain the three-color pixel such as red, green, blue respectively on support.

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, and causes the crosslinking degree after exposure to decline, and causes the problem of the not good grade of resistance to developability to occur.

As Japanese Patent Laid-Open 2004-138950 publication disclose, use specific alkali soluble resin, the pixel layer that surface is smooth can be formed, the colored filter that pattern form, resistance to developability and brightness performance are excellent, but the problem such as but have the viscosity ageing stability of photosensitive polymer combination not good.

Therefore, how to promote resistance to developability and viscosity ageing stability, 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, and this photosensitive polymer combination has good resistance to developability and viscosity ageing stability.

Another aspect of the present invention is the manufacture method providing a kind of colored filter, and it utilizes the photosensitive polymer combination of above-mentioned colored filter to form pixel layer.

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

Another aspect of the invention is to provide a kind of liquid crystal display, 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, the compound (F) that this colored filter photosensitive polymer combination comprises alkali soluble resin (A), has the compound (B) of ethene unsaturated group, light initiator (C), organic solvent (D), pigment (E) and have as shown in the formula the structure shown in (I), below analyses and states it.

Colored filter photosensitive polymer combination

Alkali soluble resin (A)

First alkali soluble resin (A-1)

Alkali soluble resin of the present invention (A) comprises first alkali soluble resin (A-1) with unsaturated group, and this first alkali soluble resin (A-1) with unsaturated group is undertaken obtained by polyreaction by a potpourri, and this potpourri comprises the epoxy compound (i) with at least two epoxy radicals and the compound with at least one carboxylic acid group and at least one ethene unsaturated group (ii).In addition, this potpourri more optionally comprises compound carboxylic acid anhydride (iii) and/or the compound (iv) containing epoxy radicals.

There is the epoxy compound (i) of at least two epoxy radicals

This epoxy compound (i) with at least two epoxy radicals can have as shown in the formula the structure shown in (II) or formula (III).The describing also to cover to have of aforementioned " epoxy compound (i) can have as shown in the formula the structure shown in (II) or following formula (III) " exists as shown in the formula the compound of the structure shown in (II) and the compound had as shown in the formula the structure shown in (III) simultaneously, and as the situation of epoxy compound (i).Specifically, the aforementioned epoxy compound (i) with at least two epoxy radicals has as shown in the formula the structure shown in (II):

In formula (II), B ₁, B ₂, B ₃with B ₄can be identical or different, and B ₁, B ₂, B ₃with B ₄represent hydrogen atom, alkoxy that alkyl that halogen atom, carbon number are 1 to 5, carbon number are 1 to 5, carbon number be 6 to 12 aryl or carbon number be the aralkyl of 6 to 12.

The bisphenol fluorene type compound containing epoxy radicals that the epoxy compound (i) with the structure as shown in previously described formula (II) can include but not limited to be reacted by bisphenol fluorene type compound (bisphenol fluorene) and halogenated epoxy propane (epihalohydrin) and obtain.

This bisphenol fluorene type compound can including but not limited to 9, two (4-hydroxy phenyl) fluorenes [9 of 9-, 9-bis (4-hydroxyphenyl) fluorene], 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] etc. compound.

Aforesaid halogenated epoxy propane (epihalohydrin) can including but not limited to bromo-1, the 2-epoxypropane (epibromohydrin) of chloro-1, the 2-epoxypropane of 3-(epichlorohydrin) or 3-etc.

The aforementioned concrete example being reacted the bisphenol fluorene type compound containing epoxy radicals of gained by bisphenol fluorene type compound and halogenated epoxy propane can including but not limited to Nippon Steel's chemistry (Nippon Steel Chemical Co., Ltd) manufacture, model is the commodity of ESF-300; Osaka rock gas (Osaka Gas Co., Ltd) manufactures, and model is the commodity of PG-100 or EG-210; Note science and technology (S.M.S Technology Co., Ltd) manufactures, and model is the commodity of SMS-F9PhPG, SMS-F9CrG or SMS-F914PG.

The aforementioned epoxy compound (i) that this has at least two epoxy radicals also can have as shown in the formula the structure shown in (III):

In formula (III), D ₁to D ₁₄can be identical or different, and D ₁to D ₁₄hydrogen atom can be represented respectively, halogen atom, carbon number be 1 to 8 alkyl or carbon number be the aromatic radical of 6 to 15; N can represent the integer of 0 to 10.

The epoxy compound (i) with the structure shown in formula (III) can in the presence of an alkali metal hydroxide, carries out reacting by having and obtain as shown in the formula the compound of the structure shown in (III-1) and halogenated epoxy propane:

In formula (III-1), D ₁to D ₁₄with n as previously mentioned, separately do not repeat at this.

Moreover, in presence of an acid catalyst such as formula the epoxy compound (i) with at least two epoxy radicals shown in (III), after use has and carries out condensation reaction as shown in the formula the compound of the structure shown in (III-2) and phenol (phenol) compounds, and form the compound had such as formula the structure shown in (III-1).Then, excessive halogenated epoxy propane is added to carry out de-hydrogen halide (dehydrohalogenation), to obtain such as formula the epoxy compound (i) with at least two epoxy radicals shown in (III):

In formula (III-2), D ₁₅with D ₁₆can be identical or different, and D ₁₅with D ₁₆hydrogen atom can be represented, halogen atom, carbon number be 1 to 8 alkyl or carbon number be the aromatic radical of 6 to 15; D ₁₇with D ₁₈can be identical or different, and D ₁₇with D ₁₈halogen atom can be represented, carbon number be 1 to 6 alkyl or carbon number be the alkoxy of 1 to 6.Preferably, above-mentioned halogen atom can be chlorine atom or bromine atoms, and alkyl can be methyl, ethyl or the tert-butyl group, and alkoxy can be methoxy or ethoxy.

This phenolic compound can including but not limited to phenol (phenol), cresols (cresol), diethylstilbestrol (ethylphenol), n-third phenol (n-propylphenol), isobutyl phenol (isobutylphenol), t-fourth 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.

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

The concrete example of above-mentioned acid catalyst, as: hydrochloric acid, sulfuric acid, p-toluenesulfonic acid (p-toluenesulfonicacid), oxalic acid (oxalic acid), boron trifluoride (boron trifluoride), anhydrous Aluminum chloride (aluminiumchloride anhydrous), zinc chloride (zinc chloride) etc.This acid catalyst is preferably p-toluenesulfonic acid, sulfuric acid or hydrochloric acid.This acid catalyst can be a kind of or mix multiple use separately.

The use amount of this acid catalyst is without particular limitation, but is 100 percentage by weights based on the aforementioned use amount had such as formula the compound of the structure shown in (III-2), and 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 under the situation with organic solvent.The concrete example of this organic solvent can including but not limited to toluene (toluene), dimethylbenzene (xylene), methyl isobutyl ketone (methyl isobutyl ketone) etc.This organic solvent can be a kind of or mix multiple use separately.

Having such as formula the compound of the structure shown in (III-2) and the general assembly (TW) of phenolic compound based on this is 100 percentage by weights, the use amount of this organic solvent is 50 percentage by weight to 300 percentage by weights, is preferably 100 percentage by weight to 250 percentage by weights.The operating temperature of this condensation reaction is 40 DEG C to 180 DEG C, and the running time of condensation reaction is 1 little of 8 hours.

After this condensation reaction terminates, this reaction solution can carry out neutralisation treatment or washing process.This neutralisation treatment is that the pH value of this reaction solution is adjusted to 3 to 7, is preferably 5 to 7.This washing process can use neutralizing agent to carry out.This neutralizing agent is alkaline matter, and can including but not limited to alkali metal hydroxides such as NaOH (sodiumhydroxide), potassium hydroxide (potassium hydroxide); The alkaline-earth metal oxyhydroxide such as calcium hydroxide (calcium hydroxide), magnesium hydroxide (magnesium hydroxide); Two stretch second triamine (diethylene triamine), three stretches the organic amines such as second tetramine (triethylenetetramine), aniline (aniline), phenylenediamine (phenylene diamine), and ammonia (ammonia), sodium dihydrogen phosphate (sodium dihydrogen phosphate) etc.Above-mentioned washing process can adopt known method to carry out, such as: add aqueous solution containing neutralizing agent in this reaction solution.Then, repeatedly extract.After neutralisation treatment or washing process, utilize the mode of heating under reduced pressure to remove unreacted phenolic compound and solvent, and concentrate, the compound had such as formula the structure shown in (III-1) can be obtained.

The concrete example of this halogenated epoxy propane, as: chloro-1, the 2-epoxypropane (3-chloro-1,2-epoxypropane) of 3-, bromo-1, the 2-epoxypropane (3-bromo-1,2-epoxypropane) of 3-or above-mentioned combination in any.Before carrying out this de-hydrogen halide or in course of reaction, the alkali metal hydroxide such as NaOH, potassium hydroxide can be added in this reaction solution.The temperature of this de-hydrogen halide is 20 DEG C to 120 DEG C, and the time is 1 little of 10 hours.

In one embodiment, the alkali metal hydroxide added also can use alkali metal hydroxide aqueous solution.In this embodiment, when above-mentioned alkali metal hydroxide aqueous solution is added in de-hydrogen halide system continuously, can under decompression or normal pressure, the mode by distillation distills water outlet and halogenated epoxy propane, and water can be removed, and halogenated epoxy propane is back in reactive system continuously simultaneously.

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

The total yield number had such as formula the hydroxyl in the compound of the structure shown in (III-1) based on this is 1 equivalent, and the use amount of this halogenated epoxy propane can be 1 equivalent to 20 equivalent, is preferably 2 equivalent to 10 equivalents.The total yield number had such as formula the hydroxyl in the compound of the structure shown in (III-1) based on this is 1 equivalent, the use amount of the alkali metal hydroxide added in this de-hydrogen halide can be 0.8 equivalent to 15 equivalent, is preferably 0.9 equivalent to 11 equivalent.

In addition, carry out smoothly to make above-mentioned de-hydrogen halide, except can adding the alcohols such as methyl alcohol, ethanol, the polar solvent that also can add the aprotic (aprotic) such as dimethyl sulfone (dimethyl sulfone), dimethyl sulfoxide (dimethyl sulfoxide) reacts.When using alcohols, the total use amount based on this halogenated epoxy propane is 100 percentage by weights, and the use amount of alcohols can be 2 percentage by weight to 20 percentage by weights, is preferably 4 percentage by weight to 15 percentage by weights.Total use amount based on halogenated epoxy propane is 100 percentage by weights, and the use amount of the polar solvent of aprotic can be 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, the mode of decompression distillation is utilized to remove the polar solvent etc. of halogenated epoxy propane, alcohols and aprotic.Above-mentioned decompression distillation can be such as 110 DEG C to 250 DEG C in temperature, and pressure carries out under being less than or equal to the environment of 1.3kPa (10mmHg).

In formed epoxy resin, there is hydrolyzable halogen, can toluene, methyl isobutyl ketone (methyl isobutyl ketone) equal solvent be added in the solution after de-hydrogen halide, add the alkali metal hydroxide aqueous solution such as NaOH, potassium hydroxide, and again carry out de-hydrogen halide.In de-hydrogen halide, be 1 equivalent based on the above-mentioned total yield number had such as formula the hydroxyl in the compound of the structure 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.In addition, the temperature of above-mentioned de-hydrogen halide is 50 DEG C to 120 DEG C, and the time is 0.5 little of 2 hours.

After completing de-hydrogen halide, the salt in reaction solution can be removed by steps such as filtration and washings, and utilize the mode of decompression distillation to remove toluene, methyl isobutyl ketone equal solvent, the epoxy compound (i) with at least two epoxy radicals had such as formula the structure shown in (III) can be obtained.

The epoxy compound (i) with at least two epoxy radicals had such as formula the structure shown in (III) can manufacture including but not limited to by Japanese chemical drug (Nippon Kayaku Co.Ltd.), and model is the commodity of NC-3000, NC-3000H, NC-3000S and NC-3000P etc.

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

The aforementioned compound (ii) with 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 the dicarboxylic acid compound of hydroxyl and obtained, wherein dicarboxylic acid compound can including but not limited to hexane diacid, succinic acid, maleic acid or phthalic acid, (3) half ester compound being reacted by (methyl) acrylate and the aforesaid compound carboxylic acid anhydride (iii) of hydroxyl and obtained, wherein (methyl) acrylate of hydroxyl can including but not limited to 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], pentaerythritol acrylate trimethyl etc.In addition, compound carboxylic acid anhydride described herein can be identical with compound carboxylic acid anhydride (iii) contained in the potpourri of aforementioned first alkali soluble resin (A-1), repeats after appearance.

Compound carboxylic acid anhydride (iii) and the compound (iv) containing epoxy radicals

The potpourri of above-mentioned first alkali soluble resin (A-1) more optionally comprises compound carboxylic acid anhydride (iii) and/or the compound (iv) containing epoxy radicals.This compound carboxylic acid anhydride (iii) can be selected from the group be made up of to (2) following (1): (1) succinic anhydride (butanedioic anhydride), maleic anhydride (maleicanhydride), 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 phthalicanhydride), chlorendic anhydride (chlorendic anhydride), glutaric anhydride, 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, two phenylate tetracarboxylic acid dianhydrides etc.

Should be selected from the group that glytidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, the glycidyl ether compound containing unsaturated group, the unsaturated compound containing epoxy radicals or above-mentioned combination in any form containing compound (iv) of epoxy radicals.

The aforementioned glycidyl ether compound containing unsaturated group can manufacture including but not limited to the long rapids Industrial Co., Ltd that changes into, and model is the commodity of Denacol EX-111, EX-121 Denacol, Denacol EX-141, DenacolEX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192 etc.

Aforesaid first alkali soluble resin (A-1) can be the reaction product that the epoxy compound (i) with at least two epoxy radicals and the compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group carry out the hydroxyl that polyreaction is formed, and the epoxy compound (i) wherein with at least two epoxy radicals has such as formula the structure shown in (II).Then, compound carboxylic acid anhydride (iii) 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 contained by compound carboxylic acid anhydride (iii) is preferably 0.4 equivalent to 1 equivalent, is more preferred from 0.75 equivalent to 1 equivalent.When using multiple compound carboxylic acid anhydride (iii), these compound carboxylic acid anhydrides 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 (iii), the molar ratio of dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride is preferably 1/99 to 90/10, is more preferred from 5/95 to 80/20.In addition, the operating temperature of above-mentioned reaction can be 50 DEG C to 130 DEG C.

Aforesaid first alkali soluble resin (A-1) can be the reaction product that the epoxy compound (i) with at least two epoxy radicals and the compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group carry out reacting formed hydroxyl, and the epoxy compound (i) wherein with at least two epoxy radicals has such as formula the structure shown in (II).Then, by add compound carboxylic acid anhydride (iii) and/or containing the compound (iv) of epoxy radicals in reaction solution, to carry out polyreaction.Be 1 equivalent based on the total yield number had such as formula the epoxy radicals had in the epoxy compound (i) of at least two epoxy radicals of structure (II) Suo Shi, the above-mentioned acid value equivalents with the compound (ii) of at least one carboxylic acid group and at least one ethene unsaturated group is preferably 0.8 equivalent to 1.5 equivalent, is more preferred from 0.9 equivalent to 1.1 equivalent.Total use amount based on the hydroxyl of the reaction product of above-mentioned hydroxyl is 100 molar percentages, the use amount of this compound carboxylic acid anhydride (iii) 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 first alkali soluble resin (A-1), 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 (tetramethylammoniumchloride), 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 (i) with at least two epoxy radicals and total use amount of the compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group, the use amount of catalysts is preferably 0.01 weight portion to 10 weight portion, is more preferred from 0.3 weight portion to 5 weight portion.

In addition, in order to control the degree of polymerization, be generally add polymerization inhibitor (polymerization inhibitor) in reaction solution.This polymerization inhibitor can including but not limited to methoxyl phenol (methoxyphenol), methylnaphthohydroquinone (methylhydroquinone), quinhydrones (hydroquinone), 2,6-BHT (2,6-di-t-butyl-p-cresol), phenothiazine (phenothiazine) etc.This polymerization inhibitor can be a kind of or mix multiple use separately.

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

When preparing this first alkali soluble resin (A-1), polymerization solvent is optionally used.This polymerization solvent can including but not limited to the alcohols solvent of ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutyl alcohol, 2-butanols, hexanol, ethylene glycol etc.; The ketones solvent of MEK, cyclohexanone etc.; The aromatic hydrocarbon solvent of toluene, dimethylbenzene etc.; The match Luo element kind solvent of match Luo element (cellosolve), butyl match Luo element (butyl cellosolve) etc.; Card must appropriate (carbitol), 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 ether acetate (ethylene glycol monoethyl ether acetate), 1-Methoxy-2-propyl acetate (propyleneglycol methyl ether acetate) etc.; Lactic acid alkane ester (alkyl lactate) kind solvent of ethyl lactate (ethyl lactate), butyl lactate (butyl lactate) etc.; Dialkyl group glycol ethers solvent.This polymerization solvent can be a kind of or mix multiple use separately.

In addition, the acid value of the first alkali soluble resin (A-1) is preferably 50mgKOH/g to 200mgKOH/g, is more preferred from 60mgKOH/g to 150mgKOH/g.

Use amount based on alkali soluble resin (A) is 100 weight portions, the use amount of aforementioned first alkali soluble resin (A-1) is 30 weight portion to 100 weight portions, be preferably 50 weight portion to 100 weight portions, be more preferred from 70 weight portion to 100 weight portions.If when alkali soluble resin (A) does not use the first alkali soluble resin (A-1), obtained Photosensitve resin composition has the not good shortcoming of resistance to developability.

Second alkali soluble resin (A-2)

Alkali soluble resin of the present invention (A) also optionally comprises the second alkali soluble resin (A-2).This second alkali soluble resin (A-2) is formed by the ethylene unsaturated monomer with at least one carboxylic acid group (a-1) and other copolymerizable ethylene unsaturated monomer (a-2) institute copolymerizations, and wherein having the ethylene unsaturated monomer (a-1) of at least one carboxylic acid group with total use amount of other copolymerizable ethylene unsaturated monomers (a-2) is 100 weight portions.

This has the concrete example of the ethylene unsaturated monomer (a-1) of at least one carboxylic acid group, as: the unsaturated monocarboxylic acid compound of acrylic acid, methacrylic acid, butenoic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2-methacryloyl ethoxy succinate etc.; Unsaturated dicarboxylic acid (acid anhydride) compound of maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride etc.; Unsaturated polyvalent carboxylic acid (acid anhydride) compound more than trivalent.The above-mentioned ethylene unsaturated monomer (a-1) with at least one carboxylic acid group can be a kind of or mix multiple use separately.

Preferably, this ethylene unsaturated monomer (a-1) with at least one carboxylic acid group is selected from acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate or 2-methacryloyl ethoxy succinate.When using the ethylene unsaturated monomer containing carboxylic acid group of 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2-methacryloyl ethoxy succinate etc., this ethylene unsaturated monomer (a-1) with at least one carboxylic acid group can improve pigment-dispersing, the enhancement developability of colored filter photosensitive polymer combination, and reduces the generation of residue.

The concrete example of this other copolymerizable ethylene unsaturated monomer (a-2), as: Bicvclopentyl acrylate, Bicvclopentyl ethoxy acrylate, double cyclopentenyl acrylate (dicyclopentenyl acrylate, hereinafter referred to as FA-511A), double cyclopentenyl ethoxy acrylate (dicyclopentenyloxyethylacrylate, hereinafter referred to as FA-512A), Bicvclopentyl methacrylate, Bicvclopentyl polyethoxymethacrylate, double cyclopentenyl methacrylate, double cyclopentenyl polyethoxymethacrylate, styrene, α-methyl styrene, vinyltoluene, to chlorostyrene, the aromatic ethenyl compound of methoxy styrene etc., the maleimide compound of the o-hydroxyphenyl-maleimides of N-phenylmaleimide, 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 methacrylate, benzyl 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, phenyl acrylate, phenyl methacrylate, acrylic acid triethylene glycol methoxyethoxy ester (methoxytriethylene glycol acrylate), methacrylic acid triethylene glycol methoxyethoxy ester (methoxy triethyleneglycol methacrylate), lauryl methacrylate (lauryl methacrylate), methacrylic acid myristyl ester (tertadecyl methacrylate), methacrylic acid cetyl ester (cetylmethacrylate), octadecyl methacrylate (octadecylmethacrylate), methacrylic acid eicosyl ester (eicosyl methacrylate), the unsaturated carboxylic ester compound of methacrylic acid docosyl ester (docosyl methacrylate) etc., 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, methacrylic acid-N-isobutylamino ethyl ester, 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 based compound of methoxy ethylene, ethyl vinyl ether, allyl glycidyl ethers, methylallyl glycidyl ethers etc., the vinyl cyanide based 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, isopentene, chlorination butadiene etc.The concrete example of this other copolymerizable ethylene unsaturated monomer (a-2) can be a kind of or mix multiple use separately.

Preferably, this copolymerizable ethylene unsaturated monomer (a-2) is selected from Bicvclopentyl acrylate, Bicvclopentyl ethoxy acrylate, double cyclopentenyl acrylate, double cyclopentenyl ethoxy acrylate, Bicvclopentyl methacrylate, Bicvclopentyl polyethoxymethacrylate, double cyclopentenyl methacrylate, double cyclopentenyl polyethoxymethacrylate, styrene, N-phenylmaleimide, methyl acrylate, methyl methacrylate, 2-Hydroxy ethyl acrylate, methacrylic acid-2-hydroxy methacrylate, benzyl acrylate or benzyl methacrylate.

Solvent in order to prepare this alkali soluble resin (A) 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, tripropylene glycol methyl ether (tripropylene glycol mono methyl ether), (gathering) alkylene glycol mono alkane ether solvent of tripropylene glycol ether (tripropylene glycolmono ethyl ether) etc., (gathering) alkylene glycol mono alkane ether acetate kind solvent of glycol methyl ether acetate, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetate etc., other ether solvents of diethylene glycol dimethyl ether, diglycol ethyl methyl ether, diethyl carbitol, tetrahydrofuran etc., the ketones solvent of the first and second alkane ketone, cyclohexanone, 2-HEPTANONE, 3-heptanone etc., the lactic acid alkane esters solvent of 2 hydroxy propanoic acid methyl esters, 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, 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, ethyl acetoacetate, other esters solvents of 2-oxygen base ethyl butyrate etc., the aromatic hydrocarbons solvent of toluene, dimethylbenzene etc., the carboxylic acid amide solvent of 1-METHYLPYRROLIDONE, DMF, DMA etc.Above-mentioned solvent can be a kind of or mix multiple use separately.

Preferably, be selected from 1-Methoxy-2-propyl acetate or 3-ethoxyl ethyl propionate in order to prepare the solvent of this alkali soluble resin (A).

Initiator in order to prepare this alkali soluble resin (A) is generally radical-type polymerization initiator, and this initiator can including but not limited to 2, 2 '-azobis isobutyronitrile (2, 2 '-azobisisobutyronitrile), 2, 2 '-azo two (2, 4-methyl pentane nitrile) [2, 2 '-azobis-(2, 4-dimethylvaleronitrile)], 2, two (the 4-methoxyl-2 of 2 '-azo, 4-methyl pentane nitrile) [2, 2 '-azobis-(4-methoxy-2, 4-dimethylvaleronitrile)], 2, two-2-the methylbutyronitrile (2 of 2 '-azo, 2 '-azobis-2-methyl butyronitrile) etc. azo (azo) compound, the per-compound of dibenzoyl peroxide (benzoylperoxide) etc.

There is the compound (B) of ethene unsaturated group

The compound (B) with ethene unsaturated group of the present invention can comprise the first compound (B-1), and wherein this first compound (B-1) is (methyl) acrylate based compound being reacted with (methyl) acrylic acid by the polyvalent alcohol through caprolactone upgrading and obtain.

This polyvalent alcohol through caprolactone upgrading is obtained by this caprolactone and the polyol reaction with more than 4 functional groups.This caprolactone can be γ-hexalactone, δ-caprolactone or 6-caprolactone, is wherein better with 6-caprolactone.This polyvalent alcohol with more than 4 functional groups can be pentaerythrite, two trimethylolpropanes or dipentaerythritol.Be 1 mole based on this use amount with the polyvalent alcohol of more than 4 functional groups, the use amount of this caprolactone is preferably 1 mole to 12 moles.

This first compound (B-1) can be the compound had as shown in the formula the structure shown in (IV):

In formula (IV), E ₁and E ₂represent hydrogen atom or methyl respectively, p represents the integer of 1 to 2, and a+b=2 to 6, a represent the integer of 1 to 6, and b represents the integer of 0 to 5.

This first compound (B-1) can including but not limited to many (methyl) acrylate compounds of four (methyl) acrylate compounds of four (methyl) acrylate compounds of pentaerythrite caprolactone upgrading, two trimethylolpropane caprolactone upgradings or dipentaerythritol caprolactone upgrading.Wherein, many (methyl) acrylate compounds of this dipentaerythritol caprolactone upgrading can be six (methyl) acrylate compounds of two (methyl) acrylate compounds of dipentaerythritol caprolactone upgrading, three (methyl) acrylate compounds of dipentaerythritol caprolactone upgrading, four (methyl) acrylate compounds of dipentaerythritol caprolactone upgrading, five (methyl) acrylate compounds of dipentaerythritol caprolactone upgrading or dipentaerythritol caprolactone upgrading.

This first compound (B-1) can be Nippon Kayaku K. K and manufactures, and model is the product of DPCA-20, DPCA-30, DPCA-60 or DPCA-120.

Total use amount based on this alkali soluble resin (A) is 100 weight portions, and the use amount of this first compound (B-1) is 5 weight portion to 50 weight portions, is preferably 8 weight portion to 40 weight portions, is more preferred from 10 weight portion to 30 weight portions.When the compound (B) with ethene unsaturated group does not use the first compound (B-1), colored filter photosensitive polymer combination has poor resistance to developability.

The compound (B) with ethene unsaturated group of the present invention optionally comprises the second compound (B-2), and wherein the second compound (B-2) has as shown in the formula the structure shown in (V):

In formula (V), M can represent hydrogen atom or methyl.

This second compound (B-2) can be selected from acrylamide, (methyl) acryloyl morpholine, amino-3, the 7-dimethyl monooctyl esters of (methyl) acrylic acid-7-, isobutoxymethyl (methyl) acrylamide, (methyl) isobomyl acrylate base 2-ethoxyethyl acetate, (methyl) isobornyl acrylate, (methyl) acrylic acid-2-ethyl caproite, ethyl diglycol (methyl) acrylate, tertiary octyl group (methyl) acrylamide, two acetone (methyl) acrylamide, (methyl) acrylate ester, (methyl) dodecylacrylate, (methyl) acrylic acid dicyclopentenyl 2-ethoxyethyl acetate, (methyl) acrylic acid dicyclopentenyl ester, N, N-dimethyl (methyl) acrylamide, (methyl) acrylic acid tetrachloro phenyl ester, (methyl) acrylic acid-2-tetrachloro phenoxy ethyl, (methyl) tetrahydrofurfuryl acrylate, (methyl) tetrabromophenyl acrylate, (methyl) acrylic acid-2-tetrabromo phenoxy ethyl, (methyl) acrylic acid-2-Trichlorophenoxy ethyl ester, (methyl) tribromophenyl acrylate, (methyl) acrylic acid-2-tribromophenoxy ethyl ester, (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, caprolactam, N-vinyl skin junket alkane ketone, (methyl) acrylate, (methyl) Pentachlorophenyl Acrylate, (methyl) acrylic acid pentabromo-phenyl ester, poly-single (methyl) acrylic acid glycol ester, poly-single (methyl) acrylic acid propylene glycol ester, (methyl) acrylic acid norbornene ester, ethylene glycol bisthioglycolate (methyl) acrylate, two (methyl) acrylic acid dicyclopentenyl ester, triethylene glycol diacrylate, tetraethylene glycol two (methyl) acrylate, three (2-hydroxyethyl) isocyanates two (methyl) acrylate, three (2-hydroxyethyl) isocyanates three (methyl) acrylate, three (2-hydroxyethyl) isocyanates three (methyl) acrylate of caprolactone upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester, three (methyl) acrylic acid trihydroxy methyl propyl ester of oxirane (hereinafter referred to as EO) upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester of epoxypropane (hereinafter referred to as PO) upgrading, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, BDO two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, polyester two (methyl) acrylate, polyglycol two (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate (Japanese Toagosei Co., Ltd manufactures, and model is the commodity of TO-1382), dipentaerythritol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate of caprolactone upgrading, the dipentaerythritol acrylate (Nippon Kayaku K. K manufactures, and model is the commodity of DPEA-12) of EO upgrading, dipentaerythritol five (methyl) acrylate of caprolactone upgrading, four (methyl) acrylic acid two trihydroxy methyl propyl ester, bisphenol-A two (methyl) acrylate of EO upgrading, bisphenol-A two (methyl) acrylate of PO upgrading, hydrogenated bisphenol A two (methyl) acrylate of EO upgrading, hydrogenated bisphenol A two (methyl) acrylate of PO upgrading, the glycerin tripropionate of PO upgrading, Bisphenol F two (methyl) acrylate of EO upgrading or phenolic aldehyde polyglycidyl ether (methyl) acrylate.

This second compound (B-2) 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, Toagosei Co., Ltd of Japan manufactures, model is the commodity of TO-1382 or the combination of these compounds.

Total use amount based on this alkali soluble resin (A) is 100 weight portions, the use amount of this second compound (B-2) is 15 weight portion to 150 weight portions, be preferably 17 weight portion to 120 weight portions, be more preferred from 20 weight portion to 90 weight portions.When the compound (B) with ethene unsaturated group comprises the second compound (B-2), the second compound (B-2) can improve the resistance to developability of colored filter photosensitive polymer combination.

Total use amount based on this alkali soluble resin (A) is 100 weight portions, this use amount with the compound (B) of ethene unsaturated group is 20 weight portion to 200 weight portions, be preferably 25 weight portion to 160 weight portions, be more preferred from 30 weight portion to 120 weight portions.

Light initiator (C)

Smooth initiator (C) of the present invention can be selected from the combination of acetophenone based compound (acetophenone), diimidazole based compound (biimidazole), acyl oxime compound (acyl oxime) or these compounds.

Above-mentioned acetophenone based compound is selected from dimethylamine acetophenone (p-dimethylamino-acetophenone), α, α '-dimethoxy azoxy acetophenone (α, α '-dimethoxyazoxy-acetophenone), 2, 2 '-dimethyl-2-phenyl acetophenone (2, 2 '-dimethyl-2-phenyl-acetophenone), acetanisole (p-methoxy-acetophenone), 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone [2-methyl-1-(4-methylthio phenyl)-2-morpholino-1-propanone], 2-benzyl-2-N, N dimethylamine-1-(4-morphlinophenyl)-1-butanone [2-benzyl-2-N, N-dimethylamino-1-(4-morpholinophenyl)-1-butanone].

Above-mentioned diimidazole based compound is selected from 2, 2 '-bis-(o-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole [2, 2 '-bis (o-chlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl-biimidazole], 2, 2 '-bis-(ortho-fluorophenyl base)-4, 4, 5, 5 '-tetraphenyl diimidazole [2, 2 '-bis (o-fluorophenyl)-4, 4 ', 5, 5 '-tetraphenyl-biimidazole], 2, 2 '-bis-(o-aminomethyl phenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole [2, 2 '-bis (o-methylphenyl)-4, 4 ', 5, 5 '-tetraphenyl-biimidazole], 2, 2 '-bis-(o-methoxyphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole [2, 2 '-bis (o-methoxyphenyl)-4, 4 ', 5, 5 '-tetraphenyl-biimidazole], 2, 2 '-bis-(o-ethylphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole [2, 2 '-bis (o-ethylphenyl)-4, 4 ', 5, 5 '-tetraphenyl-biimidazole], 2, 2 '-bis-(p-methoxyphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole [2, 2 '-bis (p-methoxyphenyl)-4, 4 ', 5, 5 '-tetraphenyl-biimidazole], 2, 2 '-bis-(2, 2 ', 4, 4 '-tetramethoxy phenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole [2, 2 '-bis (2, 2 ', 4, 4 '-tetramethoxyphenyl)-4, 4 ', 5, 5 '-tetraphenyl-biimidazole], 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole [2, 2 '-bis (2-chlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl-biimidazole], 2, 2 '-bis-(2, 4-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole [2, 2 '-bis (2, 4-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl-biimidazole].

Above-mentioned acyl oxime compound is selected from ethane ketone, 1-[9-ethyl-6-(2-methyl benzoyl)-9-hydrogen-carbazole-3-substituting group]-, 1-(oxygen-acetyl oxime) { Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), such as Ciba Specialty Chemicals company manufactures, model is the commodity of CGI-242, its structure is as shown in the formula (VI) Suo Shi }, 1-[4-(phenyl) phenyl]-octane-1, 2-diketone-2-(O-benzoyl group oxime) { 1-[4-(benzoyl) phenyl]-heptane-1, 2-dione-2-(O-benzoyloxime), such as Ciba Specialty Chemicals company manufactures, model is the commodity of CGI-124, its structure is as shown in the formula (VII) Suo Shi }, ethane ketone, 1-[9-ethyl-6-(the chloro-4-benzyl-sulfo--benzoyl of 2-)-9-hydrogen-carbazole-3-substituting group]-, 1-(oxygen-acetyl oxime) { Ethanone, 1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), the commodity that such as rising sun electrification company manufactures, its structure is as shown in the formula (VIII) Suo Shi }:

Preferably; this light initiator (C) can be 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone, 2-benzyl-2-N; N dimethylamine-1-(4-morphlinophenyl)-1-butanone, 2; 2 '-bis-(o-chlorphenyl)-4; 4 '; 5; 5 '-tetraphenyl diimidazole, ethane ketone; 1-[9-ethyl-6-(2-methyl benzoyl)-9-hydrogen-carbazole-3-substituting group]-, the combination of 1-(oxygen-acetyl oxime) or these compounds.

This light initiator (C) of the present invention optionally adds following compound: thioxanthones (thioxanthone), 2, 4-diethyl thioxanthone (2, 4-diethyl-thioxanthanone), thioxanthones-4-sulfone (thioxanthone-4-sulfone), benzophenone (benzophenone), 4, 4 '-bis-(dimethylamine) benzophenone [4, 4 '-bis (dimethylamino) benzophenone], 4, 4 '-bis-(diethylamine) benzophenone [4, 4 '-bis (diethylamino) benzophenone] etc. benzophenone (benzophenone) compound, α-diketone (α-diketone) compound of benzil (benzil), acetyl group (acetyl) etc., keto-alcohol (acyloin) compound of diphenylhydroxyethanone (benzoin) etc., keto-alcohol ether (acyloin ether) compound of diphenylhydroxyethanone methyl ether (benzoin methylether), diphenylhydroxyethanone ether (benzoin ethylether), diphenylhydroxyethanone isopropyl ether (benzoin isopropyl ether) etc., 2,4,6-trimethyl benzoyl diphenyl phosphine oxide (2,4,6-trimethyl-benzoyl-diphenyl-phosphineoxide), two-(2,6-dimethoxy benzoyl)-2,4,4-trimethylpentyl phosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-benzyl-phosphineoxide] etc. acyl phosphine oxide (acylphosphineoxide) compound, quinonyl (quinone) compound of anthraquinone (anthraquinone), 1,4-naphthoquinone (Isosorbide-5-Nitrae-naphthoquinone) etc., the halogenide of chloroacetophenone (phenacyl chloride), trisbromomethyl benzene sulfone (tribromomethyl-phenylsulfone), three (trichloromethyl)-s-triazine [tris (trichloromethyl)-s-triazine] etc., the superoxide of two-tert-butyl peroxide (di-tertbutylperoxide) etc.Above-mentioned compound is preferably benzophenone (benzophenone) compound, is wherein better with 4,4 '-bis-(diethylamine) benzophenone.

Total use amount based on this alkali soluble resin (A) is 100 weight portions, and the use amount of this light initiator (C) 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 (D)

This alkali soluble resin (A), this compound (B) with ethene unsaturated group can dissolve with this light initiator (C) by organic solvent of the present invention (D), do not react with above-mentioned compound, and there is suitable volatility.

This organic solvent (D) can be 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, tripropylene glycol methyl ether (tripropylene glycol mono methylether), (gathering) alkylene glycol mono alkane ether solvent of tripropylene glycol ether (tripropylene glycol mono ethyl ether) etc., (gathering) alkylene glycol mono alkane ether acetate kind solvent of glycol methyl ether acetate, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetate etc., other ether solvents of diethylene glycol dimethyl ether, diglycol ethyl methyl ether, diethyl carbitol, tetrahydrofuran etc., the ketones solvent of MEK, cyclohexanone, 2-HEPTANONE, 3-heptanone etc., the lactic acid alkane esters solvent of 2 hydroxy propanoic acid methyl esters, 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, 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-butyl 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, ethyl acetoacetate, other esters solvents of 2-oxygen base ethyl butyrate etc., the aromatic hydrocarbons kind solvent of toluene, dimethylbenzene etc., the carboxylic acid amide kind solvent etc. of 1-METHYLPYRROLIDONE, DMF, DMA etc.

This organic solvent (D) is better be can be 1-Methoxy-2-propyl acetate, 3-ethoxyl ethyl propionate or mixes multiple use.

Total use amount based on this alkali soluble resin (A) is 100 weight portions, the use amount of this organic solvent (D) is 500 weight portion to 3000 weight portions, be preferably 600 weight portion to 2500 weight portions, be more preferred from 700 weight portion to 2000 weight portions.

Pigment (E)

Pigment of the present invention (E) can be the combination of inorganic pigment, organic pigment or these pigment.

Above-mentioned inorganic pigment can be the metallic compound such as metal oxide, metal complex, and it can be selected from the oxide of metal and the composite oxides of aforementioned metal such as iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, sub-lead, antimony.

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.This organic pigment can be a kind of or mix multiple use separately.

The averaged particles footpath of the primary particle of this pigment (E) is preferably 10nm ~ 200nm, is more preferred from 20nm ~ 150nm, and the best is 30nm ~ 130nm.

Total use amount based on this alkali soluble resin (A) is 100 weight portions, and the use amount of this pigment (E) is 20 weight portion to 300 weight portions, is preferably 40 weight portion to 250 weight portions, is more preferred from 60 weight portion to 200 weight portions.

If desired, this pigment (E) also optionally can use spreading agent, such as: the interfacial agent of kation system, negative ion system, nonionic system, both sexes, polysiloxane series, 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, polyethylene oxide oil ether etc.; The polyethylene oxide alkyl benzene ethers interfacial agent of polyethylene oxide octyl group phenylate, polyethylene oxide nonyl phenylate etc.; The polyethylene glycol di class interfacial agent of polyethylene glycol dilaurate, polyglycol distearate etc.; Sorbitan fatty acid ester class interfacial agent; The polyesters interfacial agent of fatty acid upgrading; The polyurethane class interfacial agent of tertiary amine upgrading; SHIN-ETSU HANTOTAI's chemical industry manufactures, model is the commodity of KP, Toray DowCorning Silicon manufactures, model is commodity, the oil chemical industry manufacture of common prosperity society of SF-8427, model is commodity, get Ke Mu company (the Tochem Products Co. of Polyflow, Ltd.) manufacture, model is the commodity of F-Top, the manufacture of large Japanese ink chemical industry, model is the product of Megafac, Sumitomo 3M manufactures, model is product, the Asahi Glass manufacture of Fluorad, and model is the commodity of Asahi Guard and Surflon.This interfacial agent can be a kind of or mix multiple use separately.

There is the compound (F) as shown in the formula the structure shown in (I)

In formula (I), A ₁independently represent the fluorinated alkyl that carbon number is 1 to 4, A ₂be independently represent methyl or ethyl, and m represent the integer of 2 to 100.

The compound (F) had such as formula the structure shown in (I) can including but not limited to the fluorine system interfacial agent with hydroxyl.Be preferably that to have carbon number be the fluorinated alkyl of 1 to 4 and the compound of at least two hydroxyls.

In addition, in above-mentioned formula (I), in order to effect of promotion feeling photosensitive resin composition, A ₁goodly represent the perfluoroalkyl that carbon number is 1 to 4.Preferably, A ₁can be CF ₃cH ₂-, CF ₃cH ₂cH ₂-, CF ₃cF ₂cH ₂-, CF ₃cF ₂cH ₂cH ₂-, CF ₃cF ₂cF ₂cH ₂-, CF ₃cF ₂cF ₂cH ₂cH ₂-, CF ₃cF ₂cF ₂cF ₂cH ₂-or CF ₃cF ₂cF ₂cF ₂cH ₂cH ₂-.

If when m represents the integer of 2 to 100, then the viscosity ageing stability of obtained photosensitive polymer combination is better.Preferably, m can represent the integer of 3 to 70.More preferably, m can represent the integer of 4 to 40.

The concrete example had such as formula the compound (F) of the structure shown in (I) can be the manufacture of OMNOVA company, and model is PF-636 (wherein A ₁represent CF ₃cH ₂-, A ₂represent methyl, and m represents 6), PF-6320 (wherein A ₁represent CF ₃cH ₂-, A ₂represent methyl, and m represents 20), PF-656 (wherein A ₁represent CF ₃cF ₂cH ₂-, A ₂represent methyl, and m represents 6), PF-6520 (wherein A ₁represent CF ₃cF ₂cH ₂-, A ₂represent methyl, and m represents 20) etc. commodity.The aforementioned compound (F) had such as formula the structure shown in (I) can be a kind of or mix multiple use separately.

Total use amount based on alkali soluble resin (A) is 100 weight portions, the use amount had such as formula the compound of the structure shown in (I) is 0.5 weight portion to 10 weight portion, be preferably 0.5 weight portion to 8 weight portion, be more preferred from 1 weight portion to 5 weight portion.

If when colored filter photosensitive polymer combination of the present invention does not comprise compound (F) had such as formula the structure shown in (I), the viscosity ageing stability of obtained photosensitive polymer combination is not good.

Adjuvant (G)

Colored filter photosensitive polymer combination of the present invention can optionally use adjuvant (G) according to need, such as: macromolecular compound, adherence promoter, antioxidant, ultraviolet light absorber, anti-agglutinant etc. beyond filling agent, alkali soluble resin (A).

Based on alkali soluble resin (A) 100 weight portion, the use amount of aforesaid adjuvant (G) is generally 0 weight portion to 10 weight portion, is preferably 0 to 5 weight portion, is more preferred from 0 weight portion to 3 weight portion.

The concrete example of this adjuvant, as: the filling agent of glass, aluminium, macromolecular compound beyond the alkali soluble resin (A) of polyvinyl alcohol (PVA), polyalkylene glycol monoalkyl ether, poly-perfluoroalkyl acrylate alkane ester etc., 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, 3-metacryloxy propyl trimethoxy silicane, the adherence promoter of 3-mercaptopropyl trimethoxy silane etc., the antioxidant of 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-bis--tert-butyl phenols etc., 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorphenyl changes the ultraviolet light absorber of nitrogen, alkoxy benzophenone etc., the anti-agglutinant of sodium polyacrylate etc.

Colored filter photosensitive polymer combination

Above-mentioned alkali soluble resin (A), the compound (B) with ethene unsaturated group, light initiator (C), organic solvent (D), pigment (E) and the compound (F) had such as formula the structure shown in (I) are positioned in stirrer to stir by the preparation method of colored filter photosensitive polymer combination of the present invention, make it be uniformly mixed into solution state, also optionally add the adjuvants such as filling agent, antioxidant, ultraviolet light absorber, anti-agglutinant and interfacial agent if desired.

The generation type of the pixel layer of colored filter

Colored filter of the present invention comprises the pixel layer formed after photoetching treatment by above-mentioned colored filter photosensitive polymer combination.

When the making carrying out this pixel layer is shaped, can by coating methods such as revolution coating, cast coat or print roll coatings, the colored filter photosensitive polymer combination of above-mentioned solution state is coated on substrate, wherein this substrate can be for the alkali-free glass of liquid crystal indicator, soda-lime glass, hard glass (Pai Lesi glass), quartz glass, is attached with the above-mentioned glass of nesa coating, or for the substrate (such as silicon substrate) of photo-electric conversion device (such as solid-state image sensor).In addition, before the colored filter photosensitive polymer combination of solution state is coated on this substrate, the black matrix" (black matrix) isolating the shading of the pixel layers such as red, green, blue in advance shapes on this substrate.

After being coated with, the mode by drying under reduced pressure removes the organic solvent contained by this photosensitive polymer combination.The operating conditions of drying under reduced pressure is different according to the kind of each composition and compounding ratio, and this drying under reduced pressure is under the pressure of 0mmHg to 200mmHg, carried out for 1 second in second to 60 usually.

After drying under reduced pressure, with the mask with specific pattern, this film is exposed.The light used in exposure process is preferably the ultraviolet of g line, h line, i line etc., and can be (surpassing) high-pressure mercury-vapor lamp and metal halid lamp in order to send ultraviolet equipment.

After exposure, this film being impregnated in temperature is in the developer solution of 21 DEG C to 25 DEG C, carries out the development of about 15 seconds to 5 minutes, to remove the unwanted part of this film, and forms predetermined pattern on this substrate.The developer solution used can be by NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sal tartari, saleratus, sodium silicate, sodium methyl silicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrroles, croak pyridine 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 % by weight to 10 % by weight, be preferably 0.005 % by weight to 5 % by weight, be more preferred from 0.01 % by weight to 1 % by weight.

Then, with water, the pattern on substrate is cleaned, then with pressurized air or compressed nitrogen this pattern air-dry.Then, with the heating arrangement such as hot plate or baking oven, pattern is heated (post-bake), heating-up temperature is set in 150 DEG C to 250 DEG C, the time of hot plate heating is 5 minutes to 60 minutes, the time of baking oven heating is then 15 minutes to 150 minutes, uses and makes this pattern fixedly be configured as a pixel layer.

Then, above-mentioned steps is repeated sequentially to form the pixel layers such as red, green, blue on the substrate.

The generation type of colored filter

Be under the vacuum environment of 220 DEG C to 250 DEG C in temperature, the surperficial sputter in above-mentioned pixel layer forms an ITO diaphragm.Then, etching and wiring are implemented to this ITO diaphragm, and is coated with an alignment film in the surface of this ITO diaphragm, colored filter of the present invention can be produced.

The generation type of liquid crystal display

Liquid crystal display of the present invention (such as liquid crystal panel) comprises above-mentioned colored filter.First, get one and be inlaid with thin film transistor (TFT) (Thin Film Transistor; TFT) and be coated with the glass substrate of an alignment film, between this colored filter aforesaid and this glass substrate, get involved gap make subtend and configure, and inject liquid crystal molecule in this gap.Then, to fit a Polarizer at an outside surface of colored filter and glass substrate respectively, this liquid crystal display can be obtained.

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 alkali soluble resin (A)

Synthesis example A-1-1

By the fluorenes epoxy compound of 100 weight portions, (Nippon Steel's chemistry manufactures, and model is ESF-300; Epoxide equivalent is 231), the acrylic acid of 30 weight portions, the benzyltriethylammonium chloride of 0.3 weight portion, 2 of 0.1 weight portion, the 1-Methoxy-2-propyl acetate of 6-BHT and 130 weight portions is added in the four-hole boiling flask of 500 milliliters continuously, and pan feeding speeds control 25 weight portions/minute, and temperature to be maintained in the scope of 100 DEG C to 110 DEG C.React after 15 hours, can obtain pale yellow transparent mixed liquor, its solid component concentration is 50 percentage by weights.

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 alkali soluble resin (A-1-1), its acid value is 98mgKOH/g, and weight average molecular weight is 2205.

Synthesis example A-1-2

By the fluorenes epoxy compound of 100 weight portions, (Nippon Steel's chemistry manufactures, and model is ESF-300; Epoxide equivalent is 231), the acrylic acid of 30 weight portions, the benzyltriethylammonium chloride of 0.3 weight portion, 2 of 0.1 weight portion, the 1-Methoxy-2-propyl acetate of 6-BHT and 130 weight portions is added in the four-hole boiling flask of 500 milliliters continuously, and pan feeding speeds control 25 weight portions/minute, temperature is maintained in the scope of 100 DEG C ~ 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, the above-mentioned mixed liquor of 100 weight portions is dissolved in the ethylene glycol ether acetate of 25 weight portions, adds 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 alkali soluble resin (A-1-2), its acid value is 99.0mgKOH/g, and weight average molecular weight is 2630.

Synthesis example A-1-3

By the epoxy compound of 400 weight portions, (Japanese chemical drug (strain) manufactures, and model is NC-3000; 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 1-Methoxy-2-propyl 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, alkali soluble resin (A-1-3) can be obtained, its acid value is 102mgKOH/g, and weight average molecular weight is 3200.

Synthesis example A-2-1

Four cervical vertebra bottles of a volume 1000 milliliters arrange nitrogen inlet, stirrer, well heater, condenser pipe and thermometer, and imports nitrogen.Then, by the 2-methacryloyloxyethyl succinate (hereinafter referred to as HOMS) of 5 weight portions, the double cyclopentenyl acrylate (dicyclopentenyacrylate of 5 weight portions, hereinafter referred to as FA-511A), the styrene (hereinafter referred to as SM) of 40 weight portions and the methyl methacrylate (hereinafter referred to as MMA) of 50 weight portions be dissolved in the 3-ethoxyl ethyl propionate (hereinafter referred to as EEP) of 200 weight portions, wherein the mode of monomer mixture pan feeding is continuous interpolation.

After stirring, by the temperature increase to 100 of oil bath DEG C.Then, polymerization initiators 2, the 2 '-even dinitrogen-2-methylbutyronitrile (hereinafter referred to as AMBN) of 6 weight portions is dissolved in EEP, and is added in four cervical vertebra bottles with the deal of five equal portions interval in a hour.

The temperature of reaction of polymerization process is maintained at 100 DEG C.After 6 hours, polymerizate is taken out in four cervical vertebra bottles, and by solvent devolatilization, alkali soluble resin A-2-1 can be obtained.

Synthesis example A-2-2 and A-2-3

Synthesis example A-2-2 and A-2-3 uses the system identical with the method for making of the alkali soluble resin (A-2-1) of synthesis example A-2-1 by method, difference is that synthesis example A-2-2 and A-2-3 is the kind and the use amount that change alkali soluble resin Raw, its formula is as shown in table 1, does not separately repeat herein.

Prepare photosensitive polymer combination

It is below the photosensitive polymer combination preparing embodiment 1 to 7 and comparative example 1 to 7 according to table 2 and table 3.

Embodiment 1

By the dipentaerythritol acrylate of the alkali soluble resin of the above-mentioned synthesis example A-1-1 of 100 weight portions, the caprolactone upgrading of 5 weight portions, (Nippon Kayaku K. K manufactures, and model is the commodity of DPCA-120, hereinafter referred to as B-1-1), 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone (hereinafter referred to as C-1) of 2 weight portions, 2 of 5 weight portions, 2 '-bis-(2, 4-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole (hereinafter referred to as C-2), 4 of 3 weight portions, two (diethylamine) benzophenone (hereinafter referred to as C-3) of 4'-, pigment C.I.Pigment R254/C.I.Pigment Y139=80/20 (hereinafter referred to as E-1) of 20 weight portions and the OMNOVA company of 1 weight portion manufacture, model is that the commodity (hereinafter referred to as F-1) of PF-636 add in the 1-Methoxy-2-propyl acetate of 500 weight portions, and dissolve mixing with swing-out stirrer, the colored filter photosensitive polymer combination of embodiment 1 can be obtained.The photosensitive polymer combination of gained is evaluated with following evaluation method, and its result is as shown in table 2, and wherein the detection method of resistance to developability and viscosity ageing stability repeats after holding.

Embodiment 2 to 7 and comparative example 1 to 7

Embodiment 2 to 7 and comparative example 1 to 7 use the preparation method identical with the method for making of the photosensitive polymer combination of embodiment 1, difference is that embodiment 2 to 7 and comparative example 1 to 7 are the kind and the use amount that change colored filter photosensitive polymer combination Raw, its formula and evaluation result, respectively as shown in table 2 and table 3, separately do not repeat herein.

Evaluation method

1. viscosity ageing stability

Be 25 DEG C with E type viscosity meter (Dong Ji industry society system " ELD type viscosity meter (RE-80L) ") in temperature, under rotational speed is the condition of 20rpm, measure the viscosity of photosensitive polymer combination.The viscosity measuring the photosensitive polymer combination just manufactured the respectively viscosity that to be initial stage viscosity (a) deposit 7 with photosensitive polymer combination at 45 DEG C be through time viscosity (b).Utilize following formula (IX) to calculate viscosity B coefficent rate, and evaluate according to following benchmark:

◎: 0%≤viscosity B coefficent rate < 5%.

Zero: 5%≤viscosity B coefficent rate < 10%.

△: 10%≤viscosity B coefficent rate < 15%.

╳: 15%≤viscosity B coefficent rate < 30%.

2. 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 (X) to calculate colourity change (Δ Eab*), wherein Δ L, Δ a, Δ b are respectively the changing value of colourity L, a, b, and evaluate according to following benchmark:

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

◎：1≦ΔEab*＜2。

○：2≦ΔEab*＜3。

△：3≦ΔEab*＜6。

╳：6≦ΔEab*。

From the result of table 2 and table 3, when the alkali soluble resin (A) in colored filter photosensitive polymer combination comprises the first alkali soluble resin (A-1), made photosensitive polymer combination has good resistance to developability.

Moreover when the compound (B) with ethene unsaturated group in photosensitive polymer combination comprises the first compound (B-1), obtained photosensitive polymer combination has preferably resistance to developability.When the compound (B) if above-mentioned with ethene unsaturated group more comprises the second compound (B-2), obtained photosensitive polymer combination then has better resistance to developability.

In addition, when colored filter photosensitive polymer combination comprises compound (F) had such as formula the structure shown in (I), obtained photosensitive polymer combination has preferably viscosity ageing stability.

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 2

Table 3

Claims

1. a colored filter photosensitive polymer combination, comprises:

-alkali soluble resin (A), comprise first alkali soluble resin (A-1) with unsaturated group, and described in there is unsaturated group the first alkali soluble resin (A-1) be undertaken obtained by polyreaction by a potpourri, wherein said potpourri contains the epoxy compound (i) with at least two epoxy radicals, and has the compound (ii) of at least one carboxylic acid group and at least one ethene unsaturated group;

-there is the compound (B) of ethene unsaturated group, comprise the first compound (B-1), wherein said first compound (B-1) is reacted with (methyl) acrylic acid by the polyvalent alcohol through caprolactone upgrading and obtains;

-light initiator (C);

-organic solvent (D);

-pigment (E); And

-there is compound (F) as shown in the formula the structure shown in (I)

2. colored filter photosensitive polymer combination as claimed in claim 1, the wherein said epoxy compound (i) with at least two epoxy radicals has as shown in the formula the structure shown in (II) or formula (III):

In formula (II), B ₁, B ₂, B ₃with B ₄be respectively identical or different, and R ₁, R ₂, R ₃with R ₄represent hydrogen atom, alkoxy that alkyl that halogen atom, carbon number are 1 to 5, carbon number are 1 to 5, carbon number be 6 to 12 aryl or carbon number be the aralkyl of 6 to 12,

In formula (III), D ₁to D ₁₄be respectively identical or different, D ₁to D ₁₄represent hydrogen atom respectively, 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.

3. colored filter photosensitive polymer combination as claimed in claim 1, wherein said first compound (B-1) has as shown in the formula the structure shown in (IV):

4. colored filter photosensitive polymer combination as claimed in claim 1, the wherein said compound (B) with ethene unsaturated group more comprises the second compound (B-2), and described second compound (B-2) has as shown in the formula the structure shown in (V):

In formula (V), M represents hydrogen atom or methyl.

5. colored filter photosensitive polymer combination as claimed in claim 1, total use amount wherein based on alkali soluble resin (A) is 100 weight portions, the use amount with the compound (B) of ethene unsaturated group is 5 weight portion to 200 weight portions, the use amount of light initiator (C) is 10 weight portion to 100 weight portions, the use amount of organic solvent (D) is 500 weight portion to 3000 weight portions, the use amount of pigment (E) is 20 weight portion to 300 weight portions, and the use amount had such as formula the compound (F) of the structure shown in (I) is 0.5 weight portion to 10 weight portion.

6. colored filter photosensitive polymer combination as claimed in claim 1, total use amount wherein based on alkali soluble resin (A) is 100 weight portions, and the use amount with first alkali soluble resin (A-1) of unsaturated group is 30 weight portion to 100 weight portions.

7. colored filter photosensitive polymer combination as claimed in claim 1, the total use amount wherein based on alkali soluble resin (A) is 100 weight portions, and the use amount of the first compound (B-1) is 5 weight portion to 50 weight portions.

8. colored filter photosensitive polymer combination as claimed in claim 4, the total use amount wherein based on alkali soluble resin (A) is 100 weight portions, and the use amount of the second compound (B-2) is 15 weight portion to 150 weight portions.

9. a manufacture method for colored filter, it is that the colored filter photosensitive polymer combination of utilization according to any one of claim 1 to 8 is to form the pixel layer of colored filter.

10. a colored filter, it utilizes the manufacture method of colored filter as claimed in claim 9 to make.

11. 1 kinds of liquid crystal display, comprise colored filter as claimed in claim 10.