CN104570598A - Photosensitive resin composition, color filter and liquid crystal display element thereof - Google Patents

Photosensitive resin composition, color filter and liquid crystal display element thereof Download PDF

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CN104570598A
CN104570598A CN201410527841.8A CN201410527841A CN104570598A CN 104570598 A CN104570598 A CN 104570598A CN 201410527841 A CN201410527841 A CN 201410527841A CN 104570598 A CN104570598 A CN 104570598A
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compound
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weight portions
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acid
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曾靖渊
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Chi Mei Corp
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Chi Mei Corp
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Abstract

The invention relates to a photosensitive resin composition for a color filter, a color filter comprising a black matrix formed by using the photosensitive resin composition and a liquid crystal display element. 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 black pigment (E), and a black dye (F). The alkali-soluble resin comprises a resin (A-1) with unsaturated groups and a polysiloxane polymer (A-2), and the resin (A-1) with unsaturated groups 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 obtained by the invention has good reliability, high optical density and high impedance value.

Description

Photosensitive polymer combination, colored filter and liquid crystal display cells thereof
Technical field
The present invention is about a kind of black matrix" photosensitive polymer combination and the colored filter using this black matrix" to be formed and liquid crystal display cells.The black matrix" photosensitive polymer combination of good, the high optical density (OD) of a kind of reliability and high impedance and the colored filter using this black matrix" to be formed and liquid crystal display cells are particularly provided.
Background technology
In recent years, lcd technology miscellaneous is flourish, and in order to the contrast that improves current liquid crystal display and display quality, generally in display, black matrix" can be placed in the striped (stripe) of colored filter and the gap of point (dot).Above-mentioned black matrix" can prevent light between pixel leak caused by contrast decline and the problem such as color purity decline.The material that uses of black matrix" was all based on the vapor-deposited film containing chromium or chromium oxide etc. in the past, but, during using above-mentioned vapor-deposited film as the material of black matrix", there is the complicated and shortcomings such as material expensive of processing procedure.In order to head it off, previously proposed to have to utilize photosensitive polymer combination to form the technology of black matrix" by the mode of lithographic process (photolithography).
Current industry requires day by day to improve for the light-proofness of black matrix", and one of its solution is exactly the content increasing black pigment, improves the light-proofness of black matrix" by this.For example, Japanese Patent Laid-Open 2006-259716 publication discloses a kind of photosensitive polymer combination of black matrix", and it comprises the black pigment of high-load, alkali soluble resin, Photoepolymerizationinitiater initiater, the reactive monomer with two functional groups and organic solvent.Wherein, the reactive monomer with two functional groups can improve the reaction between compound, to form the pattern of fine.By this, in photosensitive polymer combination, when in the mode promoting black pigment content with while increasing light-proofness, still can keep the sensitivity of photosensitive polymer combination.
In addition, Japanese Patent Laid-Open 2008-268854 publication discloses a kind of photosensitive polymer combination of black matrix".This photosensitive polymer combination comprises the black pigment having carboxylic acid group and contain the alkali soluble resin of unsaturated group, photo polymerization monomer, Photoepolymerizationinitiater initiater and the high-load containing ethene unsaturated group.In this black matrix" photosensitive polymer combination, by the resolution using specific alkali soluble resin to improve the photosensitive polymer combination of high-load black pigment.
Although the photosensitive polymer combination that improve black pigment content in prior art can increase light-proofness etc., but the photosensitive polymer combination of above-mentioned each front case still has that reliability is not good, optical density (OD) (opticaldensity; OD) problem that value is not enough and resistance value is too low.In view of this, the black matrix" photosensitive polymer combination needing good for reliability, the high OD of exploitation and high impedance is still had.
Summary of the invention
Therefore, one aspect of the present invention is to provide a kind of photosensitive polymer combination, and this photosensitive polymer combination has good reliability, high optical density (OD) and high impedance value.
Another aspect of the present invention is to provide a kind of black matrix", and it utilizes made by aforesaid photosensitive polymer combination.
Another aspect of the present invention is to provide a kind of colored filter, and it comprises aforesaid black matrix".
Another aspect of the invention is to provide a kind of liquid crystal display cells, and it comprises aforesaid colored filter.
According to above-mentioned aspect of the present invention, a kind of photosensitive polymer combination is proposed, this photosensitive polymer combination comprises: alkali soluble resin (A), the compound (B) with ethene unsaturated group, light trigger (C), solvent (D), black pigment (E) and black dyes (F), below analyses and states it.
Photosensitive polymer combination
Alkali soluble resin (A)
Alkali soluble resin of the present invention (A) comprises the resin (A-1) and polysiloxane macromolecule (A-2) with unsaturated group.
There is the resin (A-1) of unsaturated group
This resin (A-1) with unsaturated group can be undertaken obtained by polyreaction by a potpourri, and wherein 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).Preferably, this potpourri optionally comprises compound carboxylic acid anhydride (iii) and/or has the compound (iv) of epoxy radicals.
There is the epoxy compound (i) of at least two epoxy radicals
The aforementioned epoxy compound (i) with at least two epoxy radicals can have as shown in the formula the structure shown in (II) or formula (III):
In formula (II), B 1, B 2, B 3and B 4be respectively identical or different, and B 1, B 2, B 3and B 4represent hydrogen atom respectively, alkoxy that alkyl that halogen atom, carbon number are 1 to 5, carbon number are 1 to 5, carbon number be 6 to 12 aromatic radical or carbon number be the aralkyl of 6 to 12.
The epoxy compound (i) with at least two epoxy radicals of this formula (II) is including but not limited to the bisphenol fluorene type compound (bisphenol fluorene) with epoxy radicals (epoxy).This bisphenol fluorene type compound with epoxy radicals is by 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 and halogenated epoxy propane (epihalohydrin) react and obtain.This halogenated epoxy propane is including but not limited to bromo-1, the 2-epoxypropane (epibromohydrin) of chloro-1, the 2-epoxypropane of 3-(epichlorohydrin) or 3-etc.Should manufacture including but not limited to (1) Nippon Steel chemistry containing the bisphenol fluorene type compound of epoxy radicals, model is the commodity of ESF-300 etc.; (2) Osaka gas manufactures, and model is the commodity of PG-100, EG-210 etc.; (3) S.M.S Technology Co. manufactures, and model is the commodity of SMS-F9PhPG, SMS-F9CrG, SMS-F914PG etc.
In formula (III), D 1to D 14be respectively identical or different, and 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.
Preferably, be under alkali metal hydroxide exists such as formula the epoxy compound (i) with at least two epoxy radicals shown in (III), make to have and carry out reacting as shown in the formula the compound of the structure shown in (IV) and halogenated epoxy propane and obtain:
In formula (IV), D 1to D 14and n respectively as previously mentioned, separately do not repeat at this.
Preferably, in presence of an acid catalyst such as formula the epoxy compound (i) with at least two epoxy radicals shown in (III), after making to have and carrying out condensation reaction as shown in the formula the compound of the structure shown in (V) and phenol (phenol) compounds, and form the compound of the structure had as shown in above-mentioned formula (IV).Then, add excessive halogenated epoxy propane and carry out de-hydrogen halide (dehydrohalogenation), can obtain such as formula the epoxy compound (i) with at least two epoxy radicals shown in (III):
In formula (V), D 15with D 16for identical or different, and D 15with D 16represent hydrogen atom respectively, halogen, carbon number be 1 to 8 alkyl or carbon number be the aromatic radical of 6 to 15; X 1and X 2for identical or different, and X 1and X 2represent halogen respectively, carbon number be 1 to 6 alkyl or carbon number be the alkoxy of 1 to 6.This halogen represents chlorine or bromine.This alkyl represents methyl (methyl), ethyl (ethyl) or the tert-butyl group (t-butyl).This alkoxy represents methoxyl (methoxy) or ethoxy (ethoxy).
Aforesaid phenolic compound can including but not limited to phenol (phenol), cresols (cresol), diethylstilbestrol (ethylphenol), n-pro-pyl phenol (n-propylphenol), isobutyl phenol (isobutylphenol), tert-butyl phenol (t-butylphenol), octyl phenol (octylphenol), nonylphenol (nonylphenol), stubble phenol (xylenol), methyl butyl phenol (methylbutylphenol), dual-tert-butyl phenol (di-t-butylphenol), vinylphenol (vinylphenol), allyl phenol (propenylphenol), acetylene phenol (ethnylphenol), cyclopentyl phenol (cyclopentylphenol), cyclohexyl phenol (cyclohexylphenol) or cyclohexyl cresols (cyclohexylcresol) etc.This phenolic compound can be a kind of or mix multiple use separately.
The use amount had such as formula the compound of the structure shown in (V) based on this is 1 mole, and the use amount of this phenolic compound is preferably 0.5 mole to 20 moles, is more preferred from 2 moles to 15 moles.
Aforesaid acid catalyst can including but not limited to hydrochloric acid, sulfuric acid, p-toluenesulfonic acid (p-toluenesulfonicacid), oxalic acid (oxalic acid), boron trifluoride (boron trifluoride), anhydrous Aluminum chloride (aluminiumchloride anhydrous) or zinc chloride (zinc chloride) etc.This acid catalyst can be a kind of or mix multiple use separately.This acid catalyst is preferably and is selected from p-toluenesulfonic acid, sulfuric acid or hydrochloric acid.
Though the use amount of this acid catalyst is without particular limitation, be 100 percentage by weights based on having such as formula the use amount of the compound of the structure shown in (V), the use amount of this acid catalyst is preferably 0.1 percentage by weight to 30 percentage by weight.
Aforesaid condensation reaction under solvent-free, or can be carried out under the existence of organic solvent.This organic solvent can including but not limited to toluene (toluene), dimethylbenzene (xylene) or methyl isobutyl ketone (methyl isobutylketone) etc.This organic solvent can be a kind of or mix multiple use separately.
Be 100 percentage by weights based on having such as formula the compound of the structure shown in (V) and total use amount of phenolic compound, the use amount of this organic solvent is preferably 50 percentage by weight to 300 percentage by weights, is more preferred from 100 percentage by weight to 250 percentage by weights.Preferably, the operating temperature of this condensation reaction is 40 DEG C to 180 DEG C, and the running time of this condensation reaction is 1 little of 8 hours.
After aforesaid condensation reaction terminates, 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 uses neutralizing agent to carry out, and this neutralizing agent is an alkaline matter, it is including but not limited to the alkali metal hydroxide of NaOH (sodiumhydroxide), potassium hydroxide (potassium hydroxide) etc.; The alkaline-earth metal oxyhydroxide of calcium hydroxide (calcium hydroxide), magnesium hydroxide (magnesium hydroxide) etc.; The compound of the organic amine compound of diethylene triamine (diethylene triamine), trien (triethylenetetramine), aniline (aniline), phenylenediamine (phenylene diamine) etc. or ammonia (ammonia), sodium dihydrogen phosphate (sodium dihydrogen phosphate) etc.This washing process can adopt the method in the past used, and such as, in solution after the reaction, adds the aqueous solution containing neutralizing agent, repeatedly carries out extracting.After neutralisation treatment or washing process, under heating under reduced pressure, unreacted phenolic compound and solvent are heated up in a steamer and is removed, and concentrated, the compound had such as formula the structure shown in (IV) can be obtained.
Aforesaid halogenated epoxy propane is preferably the combination in any being selected from chloro-1, the 2-epoxypropane of 3-, bromo-1, the 2-epoxypropane of 3-or above-claimed cpd.
Having such as formula the hydroxyl total yield in the compound of the structure shown in (IV) based on this is 1 equivalent, and the use amount of this halogenated epoxy propane is 1 mole to 20 moles, is preferably 2 moles to 10 moles.
The alkali metal hydroxide such as NaOH, potassium hydroxide can be added in advance before this de-hydrogen halide carries out, or add in the process of reaction.The operating temperature of this de-hydrogen halide is preferably 20 DEG C to 120 DEG C.Running time of this de-hydrogen halide is preferably 1 little of 10 hours.
The alkali metal hydroxide added in this de-hydrogen halide also can use its aqueous solution, in the case, continuously this alkali metal hydroxide aqueous solution is added into de-hydrogen halide intrasystem while, water outlet and halogenated epoxy propane is distilled continuously under decompression or under normal pressure, and further Separation of Water and halogenated epoxy propane, halogenated epoxy propane is back in reactive system continuously simultaneously.
Having such as formula the hydroxyl total yield in the compound of the structure shown in (IV) based on this is 1 equivalent, and the use amount of the alkali metal hydroxide added in this de-hydrogen halide is 0.8 mole to 15 moles, is preferably 0.9 mole to 11 moles.
The quaternary ammonium salt of tetramethyl-ammonium chloride (tetramethyl ammoniumchloride), tetramethylammonium bromide (tetramethyl ammonium bromide), trimethyl benzyl ammonia chloride (trimethyl benzyl ammonium chloride) etc. can be added as catalyzer before this de-hydrogen halide carries out, and at 50 DEG C at 150 DEG C, react 1 little of 5 hours, add alkali metal hydroxide or its aqueous solution again, at the temperature of 20 DEG C to 120 DEG C, react 1 little of 10 hours, to carry out de-hydrogen halide.
In addition, carry out smoothly to make de-hydrogen halide, except can adding the alcohols such as methyl alcohol (methanol), ethanol (ethanol), the polar solvent etc. that also can add the aprotic (aprotic) such as dimethyl sulfone (dimethyl sulfone), dimethyl sulfoxide (dimethylsulfoxide) reacts.When using alcohols, the total use amount based on this halogenated epoxy propane is 100 percentage by weights, and the use amount of this 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 this halogenated epoxy propane is 100 percentage by weights, the use amount of the polar solvent of this aprotic is 5 percentage by weight to 100 percentage by weights, is preferably 10 percentage by weight to 90 percentage by weights.
Physical property is affected as halogenated epoxy propane in order to avoid having unreacted initiation raw material, further the solution after de-hydrogen halide can be added toluene (toluene), methyl isobutyl ketone (methyl isobutylketone) equal solvent, and add the alkali metal hydroxide aqueous solution such as NaOH, potassium hydroxide and again carry out de-hydrogen halide.Preferably, in de-hydrogen halide, having such as formula the hydroxyl total yield in the compound of the structure shown in (IV) based on this is 1 equivalent, and the use amount of this alkali metal hydroxide is 0.01 mole to 0.3 mole, is more preferred from 0.05 mole to 0.2 mole.Preferably, the operating temperature of this de-hydrogen halide is 50 DEG C to 120 DEG C.Preferably, the running time of this de-hydrogen halide is 0.5 little of 2 hours.
After de-hydrogen halide terminates, optionally carry out filtration treatment or washing process.Afterwards, by the mode of heating decompression, in temperature be 110 DEG C to 250 DEG C and pressure be 1.3kPa (10mmHg) below, remove the polar solvent etc. of halogenated epoxy propane, alcohols and aprotic, then can obtain the epoxy compound (i) such as formula having at least two epoxy radicals shown in (III).The commodity that the epoxy compound (i) with at least two epoxy radicals of this formula (II) is made including but not limited to Japanese chemical drug (strain): NC-3000, NC-3000H, NC-3000S and NC-3000P.
There is the compound (ii) of at least one carboxylic acid group and at least one ethene unsaturated group
This compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group is selected from (1) acrylic acid, methacrylic acid, 2-methylacryoyloxyethyl succinic acid (2-methaacryloyloxyethylsuccinic 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-methacryl oxygen-butyl 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, (3) half ester compound being reacted by (methyl) acrylate and the compound carboxylic acid anhydride of hydroxyl and obtained.
Aforesaid dicarboxylic acid compound can including but not limited to hexane diacid, maleic acid, succinic acid, phthalic acid.(methyl) acrylate of this 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] or pentaerythritol acrylate trimethyl etc.
Aforesaid compound carboxylic acid anhydride with the compound carboxylic acid anhydride (iii) contained by potpourri in the following resin (A-1) that this has a unsaturated group for identical, separately can not repeat at this.
Compound carboxylic acid anhydride (iii)
This compound carboxylic acid anhydride (iii) is preferably and is selected from succinic anhydride (succinic anhydride), maleic anhydride (maleic anhydride), itaconic anhydride (Itaconic anhydride), phthalic anhydride (phthalicanhydride), tetrabydrophthalic anhydride (tetrahydrophthalic anhydride), hexahydrophthalic anhydride (hexahydrophthalic anhydride), methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylene tetrabydrophthalic anhydride (methyl endo-methylene tetrahydrophthalic anhydride), chlorendic anhydride (chlorendic anhydride), glutaric anhydride or inclined three benzoyl oxides (1, 3-dioxoisobenzofuran-5-carboxylic anhydride) etc. dicarboxylic acid anhydride compound, 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 (iv) of epoxy radicals
This compound (iv) with epoxy radicals be preferably be selected from glytidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, containing unsaturated group glycidyl ether compound, other is containing the unsaturated compound of epoxy radicals or the combination in any of above-claimed cpd.Can should manufacture including but not limited to the long rapids Industrial Co., Ltd that changes into containing the glycidyl ether compound of unsaturated group, model is the commodity of Denacol EX-111, EX-121Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192 etc.
In the present invention, this resin (A-1) with unsaturated group can carry out polyreaction by the epoxy compound (i) with at least two epoxy radicals of formula (II) and the compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group, and form the reaction product of a hydroxyl,, then add obtained by this compound carboxylic acid anhydride (iii) reacts then.Be 1 equivalent based on the hydroxyl total yield in the reaction product of this hydroxyl, the equivalents of the upper contained anhydride group of this compound carboxylic acid anhydride (iii) is preferably 0.4 equivalent to 1 equivalent, is more preferred from 0.75 equivalent to 1 equivalent.When compound carboxylic acid anhydride (iii) uses multiple, the mode of adding in time reacting can adopt the mode of sequentially adding or adding simultaneously.Preferably, this compound carboxylic acid anhydride (iii) is that when using dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride, the molar ratio of this dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride is 1/99 to 90/10, is more preferred from 5/95 to 80/20.Preferably, the operating temperature of this reaction is 50 DEG C to 130 DEG C.
In the present invention, this resin (A-1) with unsaturated group can be reacted by the epoxy compound (i) with at least two epoxy radicals of formula (III) and the compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group, after forming the reaction product of a hydroxyl, then add compound carboxylic acid anhydride (iii) and/or carry out obtained by polyreaction containing the compound (iv) of epoxy radicals.The epoxy radicals total yield had on the epoxy compound (i) of at least two epoxy radicals based on formula (III) is 1 equivalent, this acid value equivalent 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.Be 100 molar percentages based on the hydroxyl total amount in the reaction product of this hydroxyl, 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 this and there is resin (A-1) of unsaturated group, be accelerated reaction, usually can add alkali compounds as catalysts in reaction solution.This catalysts can including but not limited to triphenylphosphine (triphenyl phosphine), antimony triphenyl (triphenyl stibine), triethylamine (triethylamine), triethanolamine (triethanolamine), tetramethyl ammonium chloride (tetramethylammonium chloride), benzyltriethylammonium chloride (benzyltriethylammonium chloride) etc.This catalysts can be a kind of or mix multiple use separately.Be 100 weight portions based on this 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 this 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, usually also polymerization inhibitor can be added in reaction solution.This polymerization inhibitor can including but not limited to methoxyl phenol (p-methoxyphenol), methylnaphthohydroquinone (methylhydroquinone), quinhydrones (hydroquinone), 2,6-BHT (2,6-di-t-butyl-p-cresol) or phenothiazine (phenothiazine) etc.This polymerization inhibitor can be a kind of or mix multiple use separately.
Be 100 weight portions based on this epoxy compound (i) with at least two epoxy radicals and the use amount summation of the compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group, the use amount of this 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 and there is resin (A-1) of unsaturated group, polymerization solvent can be used if desired.This polymerization solvent can including but not limited to the alcohol compound of ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutyl alcohol, 2-butanols, hexanol or ethylene glycol etc.; The ketone compounds of MEK or cyclohexanone etc.; The aromatic hydrocarbon compounds of toluene or dimethylbenzene etc.; Match Luo element (cellosolve) compounds of match Luo element or butyl match Luo element (butyl cellosolve) etc.; Card must appropriate or butyl card must be appropriate etc. card must appropriate compounds; The propylene glycol alkyl ether compound of methyl proxitol etc.; Many propylene glycol alkyls ether [poly (propylene glycol) alkyl ether] compounds of dipropylene glycol methyl ether [di (propylene glycol) methylether] etc.; The acetic ester compounds of ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate (ethylene glycol monoethyl ether acetate) or propylene glycol monomethyl ether acetate (propylene glycol methyl ether acetate) etc.; Lactate (lactate) compounds of ethyl lactate (ethyl lactate) or butyl lactate (butyl lactate) etc. or dialkyl group glycol ethers compound.This polymerization solvent can be a kind of or mix multiple use separately.
This acid value with the resin (A-1) of unsaturated group is preferably 50mgKOH/g to 200mgKOH/g, is more preferred from 60mgKOH/g to 150mgKOH/g.
Use amount based on alkali soluble resin is 100 weight portions, and this use amount with the resin (A-1) of unsaturated group is 30 weight portion to 90 weight portions, is preferably 35 weight portion to 87 weight portions, is more preferred from 40 weight portion to 85 weight portions.
In photosensitive polymer combination of the present invention, the resin (A-1) having unsaturated group if do not use completely, then obtained photosensitive polymer combination has the not good defect of reliability under hot and humid environment.
Polysiloxane macromolecule (A-2)
Polysiloxane macromolecule (A-2) of the present invention is formed by the capable polymerization of an anti-Ying Wu Jin [being namely hydrolyzed (hydrolysis) and partial condensates (partially condensation)] reaction, and this reactant can comprise silane monomer (silane monomer), polysiloxane prepolymers (siloxane prepolymer), or the combination of silane monomer and polysiloxane prepolymers.
This silane monomer can comprise at least one silane monomer had as shown in the formula the structure shown in (I):
Si(R 1) t(OR 2) 4-t(I)
In formula (I), t represents the integer of 1 to 3, when t represents 2 or 3, and multiple R 1can be identical or different separately, wherein at least one R 1represent through anhydride group (Anhydride group) replace and carbon number be 1 to 10 alkyl, to replace and carbon number is the alkyl of 1 to 10 or the oxyalkyl that replaces through epoxy radicals, and all the other R through epoxy radicals (Epoxy group) 1represent hydrogen atom, carbon number be 1 to 10 alkyl, carbon number be 2 to 10 thiazolinyl or carbon number be the aromatic radical of 6 to 15.When (4-t) represents 2 or 3, multiple R 2be identical or different separately, and R 2represent hydrogen atom, carbon number be 1 to 6 alkyl, carbon number be 1 to 6 acyl group or carbon number be the aromatic radical of 6 to 15.
When polysiloxane macromolecule (A-2) has anhydride group or epoxy radicals, the SiOH functional group of polysiloxane macromolecule and glass surface has good affinity, and adherence can be promoted, and then the moisture-proof promoted under hot and humid environment and reliability.If aforesaid R 1when not comprising the functional group replaced through anhydride group or epoxy radicals, obtained photosensitive polymer combination has the not good shortcoming of reliability under hot and humid environment.
This is through anhydride group replacement and the alkyl that carbon number is 1 to 10 can including but not limited to ethyl succinic acid acid anhydride, propyl succinimide acid anhydrides or propyl group glutaric anhydride etc.
This is through epoxy radicals replacement and the alkyl that carbon number is 1 to 10 can including but not limited to epoxypropane base amyl group (oxetanylpentyl) or 2-(3,4-epoxycyclohexyl) ethyl (2-(3,4-epoxycyclohexyl) ethyl) etc.
The oxyalkyl replaced through epoxy radicals can including but not limited to glycidoxypropyl group (glycidoxypropyl), 2-epoxypropane base butoxy (2-oxetanylbutoxy) etc.
In above-mentioned R 2in, alkyl can including but not limited to methyl, ethyl, n-pro-pyl, isopropyl or normal-butyl etc.Acyl group can including but not limited to acetyl group.Aromatic radical can including but not limited to phenyl.
Can including but not limited to 3-glycidoxypropyltrime,hoxysilane (3-glycidoxypropyltrimethoxysilane such as formula the siloxanyl monomers shown in (I), TMS-GAA), 3-glycidoxypropyl group triethoxysilane (3-glycidoxypropyltriethoxysilane), 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane [2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane], 2-epoxypropane base butoxypropyl triple phenoxyl silane (2-oxetanylbutoxypropyltriphenoxysilane), commercially available product manufactured by East Asia is synthesized: 2-epoxypropane base butoxypropyl trimethoxy silane (2-oxetanylbutoxypropyltrimethoxysilane, its commodity are called TMSOX-D), 2-epoxypropane base butoxypropyl triethoxysilane (2-oxetanylbutoxypropyltriethoxysilane, its commodity are called TESOX-D), 3-(triple phenoxyl is silica-based) propyl succinimide acid anhydrides, commercially available product by manufactured by SHIN-ETSU HANTOTAI's chemistry: 3-(trimethoxy is silica-based) propyl succinimide acid anhydrides (commodity are called X-12-967), commercially available product by manufactured by WACKER company: 3-(triethoxy is silica-based) propyl succinimide acid anhydrides (its commodity are called GF-20), 3-(trimethoxy is silica-based) propyl group glutaric anhydride (referred to as TMSG), 3-(triethoxy is silica-based) propyl group glutaric anhydride, 3-(triple phenoxyl is silica-based) propyl group glutaric anhydride, diisopropoxy-two (2-epoxypropane base butoxypropyl) silane [diisopropoxy-di (2-oxetanylbutoxy propyl) silane, DIDOS], two (3-epoxypropane base amyl group) dimethoxysilane [di (3-oxetanylpentyl) dimethoxy silane], (two n-butoxies are silica-based) two (propyl succinimide acid anhydrides), (dimethoxy is silica-based) two (ethyl succinic acid acid anhydride), 3-glycidoxypropyl group dimethyl methoxy silane (3-glycidoxypropyldimethylmethoxysilane), 3-glycidoxypropyl group dimethylethoxysilane (3-glycidoxypropyldimethylethoxysilane), two (2-epoxypropane base butyloxypentyl)-2-epoxypropane base amyl group Ethoxysilane [di (2-oxetanylbutoxypentyl)-2-oxetanylpentylethoxysilane], three (2-epoxypropane base amyl group) methoxy silane [tri (2-oxetanylpentyl) methoxy silane], (phenoxy group is silica-based) three (propyl succinimide acid anhydrides) and (methyl methoxy base is silica-based) two (ethyl succinic acid acid anhydride) etc.Aforementioned can be a kind of or mix multiple use separately such as formula the siloxanyl monomers shown in (I).
Preferably, this siloxanyl monomers optionally comprises as shown in the formula the siloxanyl monomers shown in (I-1):
Si(R 3) u(OR 4) 4-u(I-1)
In formula (I-1), u represents the integer of 0 to 3.When u represents 2 or 3, multiple R 3be identical or different separately, and R 3represent hydrogen atom, carbon number be 1 to 10 alkyl, carbon number be 2 to 10 thiazolinyl or carbon number be the aromatic radical of 6 to 15.When (4-u) represents 2,3 or 4, multiple R 4be identical or different separately, and R 4represent hydrogen atom, carbon number be 1 to 6 alkyl, carbon number be 1 to 6 acyl group or carbon number be the aromatic radical of 6 to 15.
In R 3in, alkyl can including but not limited to methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, positive certain herbaceous plants with big flowers base, trifluoromethyl, 3,3,3-trifluoro propyls, 3-amine propyl group, 3-mercapto propyl group or 3-isocyanatopropyl.Thiazolinyl can including but not limited to vinyl, 3-acryloxypropyl or 3-methacryloxypropyl etc.Aromatic radical can including but not limited to phenyl, tolyl, p-hydroxy phenyl, 1-(p-hydroxy phenyl) ethyl, 2-(p-hydroxy phenyl) ethyl, 4-hydroxyl-5-(p-hydroxy phenyl carbonyl oxygen base) amyl group or naphthyl etc.
In R 4in, alkyl can including but not limited to methyl, ethyl, n-pro-pyl, isopropyl or normal-butyl etc.Acyl group can including but not limited to acetyl group.Aromatic radical can including but not limited to phenyl.
Can including but not limited to tetramethoxy-silicane such as formula the siloxanyl monomers shown in (I-1), tetraethoxysilane, four acetoxylsilanes, tetraphenoxy-silicane alkane, methyltrimethoxy silane (being called for short MTMS), methyl triethoxysilane, methyl three isopropoxy silane, methyl three n-butoxy silane, ethyl trimethoxy silane, ethyl triethoxysilane, ethyl three isopropoxy silane, ethyl three n-butoxy silane, n-pro-pyl trimethoxy silane, n-pro-pyl triethoxysilane, n-butyltrimethoxysilane, ne-butyltriethoxysilaneand, n-hexyl trimethoxy silane, n-hexyl triethoxysilane, decyl trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, phenyltrimethoxysila,e (being called for short PTMS), phenyl triethoxysilane (being called for short PTES), p-hydroxy phenyl trimethoxy silane, 1-(p-hydroxy phenyl) ethyl trimethoxy silane, 2-(p-hydroxy phenyl) ethyl trimethoxy silane, 4-hydroxyl-5-(p-hydroxy phenyl carbonyl oxygen base) amyltrimethoxysilane, trifluoromethyl trimethoxy silane, trifluoromethyl triethoxysilane, 3,3,3-trifluoro propyl trimethoxy silane, 3-amine propyl trimethoxy silicane, 3-amine propyl-triethoxysilicane, dimethyldimethoxysil,ne (being called for short DMDMS), dimethyldiethoxysilane, dimethyldiacetoxy silane, di-n-butyl dimethoxysilane, dimethoxydiphenylsilane, trimethylmethoxysilane, three normal-butyl Ethoxysilanes, 3-mercaptopropyl trimethoxysilane, 3-acryloxypropyl trimethoxy silane, 3-methacryloxypropyl trimethoxy silane or 3-methacryloxypropyl etc.Above-mentioned can be a kind of or mix multiple use separately such as formula the siloxanyl monomers shown in (I-1).
Preferably, this polysiloxane prepolymers optionally comprises as shown in the formula the polysiloxane shown in (I-2):
In formula (I-2), R 5, R 6, R 7and R 8for identical or different.When the integer of behalf 2 to 1000, each R 5or R 6can be identical or different.
Aforesaid R 5, R 6, R 7and R 8represent hydrogen atom respectively, carbon number be 1 to 10 alkyl, carbon number be 2 to 6 thiazolinyl or carbon number be the aromatic radical of 6 to 15, any one wherein in alkyl, thiazolinyl and aromatic radical optionally has substituting group.This alkyl can including but not limited to methyl, ethyl or n-pro-pyl etc.This thiazolinyl can including but not limited to vinyl, acryloxypropyl or methacryloxypropyl etc.This aromatic radical can including but not limited to phenyl, tolyl or naphthyl etc.
Aforesaid R 9with R 10represent hydrogen atom respectively, carbon number be 1 to 6 alkyl, carbon number be 1 to 6 acyl group or carbon number be the aromatic radical of 6 to 15, and any one in this alkyl, acyl group and aromatic radical optionally has substituting group.This alkyl can including but not limited to methyl, ethyl, n-pro-pyl, isopropyl or normal-butyl etc.This acyl group can including but not limited to acetyl group.This aromatic radical can including but not limited to phenyl.
Further, the s shown in formula (I-2) is the integer of 1 to 1000.Preferably, s is the integer of 3 to 300.More preferably, s is the integer of 5 to 200.
Polysiloxane as shown in this formula (I-2) can including but not limited to 1, 1, 3, 3-tetramethyl-1, 3-dimethoxy disiloxane, 1, 1, 3, 3-tetramethyl-1, 3-diethoxy disiloxane, 1, 1, 3, 3-tetraethyl-1, 3-diethoxy disiloxane, [its trade name is as DM-S12 (molecular weight is 400 to 700 to the commercially available product of Gelest Inc. silanol end polysiloxane), DMS-S15 (molecular weight is 1500 to 2000), DMS-S21 (molecular weight is 4200), DMS-S27 (molecular weight is 18000), DMS-S31 (molecular weight is 26000), DMS-S32 (molecular weight is 36000), DMS-S33 (molecular weight is 43500), DMS-S35 (molecular weight is 49000), DMS-S38 (molecular weight is 58000), DMS-S42 (molecular weight is 77000), PDS-9931 (molecular weight is 1000 to 1400) etc.] etc.Polysiloxane shown in this formula (I-2) can be a kind of or mix multiple use separately.
Preferably, the polysiloxane macromolecule (A-1) with anhydride group or epoxy radicals of the present invention can be prepared via polyreaction by described silane monomer and/or polysiloxane prepolymers, or optionally comprises silicon dioxide (silicon dioxide) particle to carry out polyreaction to prepare.
The mean grain size of this silicon dioxide granule is not particularly limited, and its mean grain size can be 2nm to 250nm, is preferably 5nm to 200nm, is more preferred from 10nm to 100nm.
This silicon dioxide granule can [(its particle diameter be 12nm to trade name such as OSCAR 1132 including but not limited to the commercially available product changed into by catalyst manufactured by company, and spreading agent is methyl alcohol), (particle diameter is 12nm to OSCAR 1332, and spreading agent is n-propanol), (particle diameter is 60nm to OSCAR 105, and spreading agent is gamma-butyrolacton), (particle diameter is 120nm to OSCAR 106, and spreading agent is diacetone alcohol) etc.], [(particle diameter is 13nm to trade name such as Quartron PL-1-IPA to commercially available product manufactured by chemical company of Japan, and spreading agent is isopropyl acetone), (particle diameter is 13nm to Quartron PL-1-TOL, and spreading agent is toluene), (particle diameter is 18nm to Quartron PL-2L-PGME, and spreading agent is propylene glycol monomethyl ether), (particle diameter is 18nm to Quartron PL-2L-MEK, and spreading agent is MEK) etc.], [(particle diameter is 12nm to trade name such as IPA-ST to commercially available product manufactured by Nissan Chemical company, and spreading agent is isopropyl alcohol), (particle diameter is 12nm to EG-ST, and spreading agent is ethylene glycol), (particle diameter is 45nm to IPA-ST-L, and spreading agent is isopropyl alcohol), (particle diameter is 100nm to IPA-ST-ZL, and spreading agent is isopropyl alcohol) etc.].
This condensation reaction can use general method.Such as, in siloxanyl monomers component, add solvent, water, or optionally add catalyzer further, at 50 DEG C to 150 DEG C, then add thermal agitation 0.5 little of 120 hours.During stirring, further can by distillation removing accessory substance (alcohols, water etc.).
Above-mentioned solvent is not particularly limited, can be identical or different with the solvent (D) of following photosensitive polymer combination of the present invention.Total use amount based on this siloxanyl monomers is 100 grams, and the use amount of this solvent is 15 grams to 1200 grams, is preferably 20 grams to 1100 grams, is more preferred from 30 grams to 1000 grams.
Be 1 mole based on hydrolyzable groups contained in this siloxanyl monomers, this use amount being used for the water be hydrolyzed is 0.5 mole to 2 moles.
Aforesaid catalyzer has no particular limits, and this catalyzer is preferably and is selected from acid catalyst or base catalyst.This acid catalyst can including but not limited to hydrochloric acid, nitric acid, sulfuric acid, fluoric acid, oxalic acid, phosphoric acid, acetic acid, trifluoracetic acid, formic acid, polybasic carboxylic acid or its acid anhydride or ion exchange resin etc.This base catalyst can including but not limited to diethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, triamylamine, trihexylamine, three heptyl amices, trioctylamine, diethanolamine, triethanolamine, NaOH, potassium hydroxide, the alkoxy silane containing amino or ion exchange resin etc.
Total use amount based on this siloxanyl monomers is 100 grams, and the use amount of this catalyzer is 0.005 gram to 15 grams, is preferably 0.01 gram to 12 grams, is more preferred from 0.05 gram to 10 grams.
Based on the viewpoint of stability, polysiloxane macromolecule (A-2) obtained after condensation reaction is to be not good containing accessory substance (as alcohols or water), catalyzer, and therefore obtained polysiloxane macromolecule (A-2) optionally carries out purifying.There is no particular restriction for purification process, preferably, hydrophobic solvent can be used to dilute this polysiloxane macromolecule (A-2), then concentrate the organic layer returned through water washing number with evaporator, to remove alcohols or water.In addition, spent ion exchange resin can be made to remove catalyzer.
Use amount based on alkali soluble resin is 100 weight portions, and the use amount of polysiloxane macromolecule (A-2) is 10 weight portion to 70 weight portions, is preferably 13 weight portion to 65 weight portions, is more preferred from 15 weight portion to 60 weight portions.
Because polysiloxane macromolecule (A-2) has good resistance to aqueous vapor character, and the swelling effect of the resin combination that can desensitize, and then improve adherence.Therefore, if alkali soluble resin (A) not simultaneously and with when having resin (A-1) and polysiloxane macromolecule (A-2) of unsaturated group, obtained photosensitive polymer combination has the not good shortcoming of reliability.
Other alkali soluble resin (A-3)
Alkali soluble resin of the present invention (A) can comprise other alkali soluble resin (A-3).This other alkali soluble resin (A-3) can including but not limited to the resin with carboxylic acid group or hydroxyl, its concrete example, as: the acrylic acid (Acrylic) had beyond unsaturated group (A-1) and polysiloxane macromolecule (A-2) is resin, Polyurethane (urethane) is resin and phenolic varnish type (novolac) resin etc.
This acrylic resin can be Toagosei Co., Ltd and manufactures, and model is the commodity of ARUFON UC-3910 or ARUFON UH-2032.This Polyurethane system resin can be Negami Chemical Ind Co., Ltd. and manufactures, and model is the commodity of UN-904, UN-952, UN-333 or UN1255.Phenolic varnish type resin can be Asahi Organic Chem Ind and manufactures, and model is the commodity of EP4020G, EP4080G, TR40B45G or EP30B50.
Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of other alkali soluble resin (A-3) is 0 weight portion to 40 weight portion, is preferably 0 weight portion to 30 weight portion, is more preferred from 0 weight portion to 20 weight portion.
There is the compound (B) of ethene unsaturated group
This compound (B) with ethene unsaturated group is selected from the compound (B-1) with 1 ethene unsaturated group or the compound (B-2) with more than 2 (containing 2) ethene unsaturated groups.
This compound (B-1) with 1 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, NVP, 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.This compound (B-1) with 1 ethene unsaturated group can be a kind of or mix multiple use separately.
This compound (B-2) with more than 2 (containing 2) ethene unsaturated groups can 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, or phenolic aldehyde poly epihydric alcohol ether metacrylic acid ester etc.This compound (B-2) with more than 2 (containing 2) ethene unsaturated groups can be a kind of or mix multiple use separately.
Preferably, this compound (B) with ethene unsaturated group be 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, through the glycerol tri-acrylate of epoxypropane upgrading or the combination of these compounds.
Total use amount based on alkali soluble resin (A) is 100 weight portions, this use amount with the compound (B) of ethene unsaturated group is 20 weight portion to 180 weight portions, be preferably 25 weight portion to 160 weight portions, be more preferred from 30 weight portion to 140 weight portions.
Light trigger (C)
Light trigger of the present invention (C) is the combination in any being selected from oxime (oxime) based compound (C-1), acetophenone based compound (C-2), other light trigger (C-3) or above-mentioned material.
This oxime compound (C-1) can (such as Ciba Specialty Chemicals company makes including but not limited to 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-ethane ketone-1-(O-acetyl group oxime) { 1-[9-ethyl-6-(2-methylbezoyl)-9H-carbozole-3-yl]-ethanone-1-(o-acetyl oxime) }, model is the commodity of OXE-02), 1-[9-ethyl-6-(2-chloro-4-benzene sulfobenzoyl)-9H-carbazole-3-base]-ethane ketone-1-(O-acetyl group oxime) { 1-[9-ethyl-6-(2-chloro-4-benzylsulfonyl benzoyl)-9H-carbozole-3-yl]-ethanone-1-(o-acetyl oxime) } (such as: the commodity that rising sun electrification company manufactures), 1-(4-benzene-sulfo phenyl)-butane-1, 2-diketone 2-oxime-oxygen-benzoate, 1-(4-benzene-sulfo phenyl)-octane-1, 2-diketone 2-oxime-oxygen-benzoic ether is (as Ciba Specialty Chemicals company manufactures, model is the commodity of OXE-01), 1-(4-benzene-sulfo phenyl)-octane-1-ketoxime-oxygen-acetate, 1-(4-benzene-sulfo phenyl)-butane-1-ketoxime-oxygen-acetate etc.This oxime compound (C-1) can be a kind of or mix multiple use separately.
This acetophenone based compound (C-2) can including but not limited to p-dimethylamine acetophenone, α, α '-dimethoxy azobenzene ethyl ketone, 2, 2'-dimethyl-2-acetophenone, p methoxyacetophenone, 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone (2-methyl-1-(4-methylthiophenyl)-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] etc.This acetophenone based compound (C-2) can be a kind of or mix multiple use separately.Preferably, this acetophenone based compound (C-2) is selected from 2-methyl isophthalic acid-(4-methylthiophenyi)-2-agate quinoline generation-1-acetone or 2-benzyl-2-N, N dimethylamine-1-(4-agate quinoline is for phenyl)-1-butanone.
This other light trigger (C-3) can including but not limited to 2, two (the o-chlorphenyl)-4 of 2'-, 4', 5, 5'-tetraphenyl diimidazole, 2, two (the ortho-fluorophenyl base)-4 of 2'-, 4', 5, 5'-tetraphenyl diimidazole, 2, two (the o-aminomethyl phenyl)-4 of 2'-, 4', 5, 5'-tetraphenyl diimidazole, 2, two (the o-methoxyphenyl)-4 of 2'-, 4', 5, 5'-tetraphenyl diimidazole, 2, two (the p-methoxyphenyl)-4 of 2'-, 4', 5, 5'-tetraphenyl diimidazole, 2, 2'-two (2, 2', 4, 4'-tetramethoxy phenyl)-4, 4', 5, 5'-tetraphenyl diimidazole or 2, 2'-two (2, 2'-dichlorophenyl)-4, 4', 5, diimidazole (biimidazole) based compound of 5'-tetraphenyl diimidazole etc., the benzophenone based compound of thioxanthones (thioxantone), 2,4-diethyl thioxanthones, thioxanthones-4-sulfone, benzophenone, 4,4'-two (dimethylamine) benzophenone or two (diethylamine) benzophenone of 4,4'-etc., α-diketone (α-diketone) compounds of benzil (benzil) or acetyl group etc., keto-alcohol (acyloin) compounds of diphenylhydroxyethanone (benzoin) etc., keto-alcohol ether (acyloin ether) compounds of diphenylhydroxyethanone methyl ether, diphenylhydroxyethanone ether or diphenylhydroxyethanone isopropyl ether etc., the compound with acyl phosphine oxide (acylphosphine oxide) of 2,4,6-trimethyl benzoyl diphenyl phosphine oxide or two-(2,6-dimethoxy benzoyl)-2,4,4-trimethyl benzyl phosphine oxides etc., the quinones of anthraquinone or 1,4-naphthoquinone etc., the halide compound of chloroacetophenone (phenacyl chloride), trisbromomethyl benzene sulfone or three (trichloromethyl)-s-triazine (tris (trichloro methyl)-s-triazine) etc., the superoxide of two-tert-butyl peroxide etc. or the combination in any of above-claimed cpd.
Use amount based on this alkali soluble resin (A) is 100 weight portions, and the use amount of this light trigger (C) is 10 weight portion to 80 weight portions, is preferably 12 weight portion to 75 weight portions, is more preferred from 15 weight portion to 70 weight portions.
Solvent (D)
Solvent of the present invention (D) is with solubilized alkali soluble resin (A), the compound (B) with ethene unsaturated group and light trigger (C), and do not react to each other with these compositions, and to have suitable evaporative be good.
This solvent (D) can including but not limited to ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, TC, diethylene glycol list n-propyl ether, diethylene glycol list n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl (referred to as PGEE), DPGME, dihydroxypropane single-ethyl ether, dipropylene glycol list n-propyl ether, dipropylene glycol list n-butyl ether, tripropylene glycol monomethyl ether, the alkyl diol list alkane ether compound of tripropylene glycol list ethylether etc., ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (propylene glycol monomethylether acetate, PGMEA), the alkyl diol list alkane ether acetate compounds of propylene glycol monoethyl acetate etc., other ether compound of diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran etc., the ketone compounds of MEK, cyclohexanone, 2-HEPTANONE, 3-heptanone, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone (referred to as DAA) etc., the lactic acid alkane ester type compound 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 (3-ethoxyethylpropionate, EEP), ethoxy ethyl acetate, hydroxacetic acid ethyl ester, 2-hydroxy-3-methyl methyl butyrate, 3-methyl-3-methoxybutyl acetate, 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 ester type compound of 2-oxygen base ethyl butyrate etc., the aromatic hydrocarbon compounds of toluene or dimethylbenzene etc., the amides compound of 1-METHYLPYRROLIDONE, DMF, DMA etc. or the combination in any of above-mentioned solvent.This solvent (D) can be a kind of or mix multiple use separately.
Total use amount based on this alkali soluble resin (A) is 100 weight portions, the use amount of this solvent (D) is 1000 weight portion to 7000 weight portions, be preferably 1300 weight portion to 6000 weight portions, be more preferred from 1600 weight portion to 5000 weight portions.
Black pigment (E)
Be applicable to black pigment of the present invention (E) there is the black pigment of thermotolerance, photostability and solvent resistance for better.
The concrete example of aforesaid black pigment (E), as: the black organic pigments such as perylene black (perylene black), cyanine black (cyanine black), nigrosine (aniline black); By in the pigment such as red, blue, green, purple, yellow, cyanine (cyanine), fuchsin (magenta), select two or more pigment to mix, make it become closely blackened colour mixture organic pigment; The lightproof material such as carbon black (carbon black), chromium oxide, iron oxide, titanium black (titanium black), graphite, wherein aforesaid carbon black can including but not limited to C.I.pigment black 7 etc., the commercially available product of concrete example manufactured by Mitsubishi Chemical (its commodity are called MA100, MA230, MA8, #970, #1000, #2350 or #2650) of aforesaid carbon black.Aforesaid black pigment (E) can be a kind of or mix multiple use separately.
Use amount based on aforesaid alkali soluble resin (A) is 100 weight portions, the use amount of black pigment (E) is 100 weight portion to 600 weight portions, be preferably 130 weight portion to 550 weight portions, be more preferred from 150 weight portion to 500 weight portions.
In photosensitive polymer combination of the present invention, if do not use black pigment (E), obtained photosensitive polymer combination has the not good shortcoming of reliability under hot and humid condition.
Black dyes (F)
Black dyes of the present invention (F) is advisable with the dyestuff beyond black pigment (E), can including but not limited to the combination in any of acid dyes, basic-dyeable fibre, disperse dyes, oil-soluble dyes or above-mentioned dyestuff.
Preferably, black dyes (F) can be acid dyes or basic-dyeable fibre.Acid dyes can be the azo system metal complex dyes of chromium, copper, cobalt etc.Basic-dyeable fibre can be polymethine (Polymethine) dyestuff, azo dyes, azomethine dyes, anthraquinone dye or the kiton colors with amino or the amino quaternary ammonium salt replaced.
The concrete example of aforementioned azo system metal complex dyes, as: Baotugu Chemical Industrial Co., Ltd manufactures, and model is the commodity of Aizen Spilon Black BNH, MH, RLH, BH; BASF AG manufactures, and model is the commodity of the azo system chromium metal complex dyes of NeoZapon X55, NeoZapon X51, BasantolBlack X82 etc.
The concrete example of aforementioned base dyestuff, as: Baotugu Chemical Industrial Co., Ltd manufactures, and model is the commodity of AizenCathilon Black SBH, BXH, SH, NH, MH, AWH, KBH.
The concrete example of aforementioned disperse dyes can manufacture including but not limited to Mitsui BASF dyestuff Co., Ltd., and model is the commodity of Miketon Polyester dyestuff, Miketon Fast dyestuff, Dispersol dyestuff, Palanil dyestuff etc.; Sumitomo Chemical Co manufactures, and model is the commodity of Sumikaron dyestuff; Nippon Kayaku K. K manufactures, and model is the commodity of Kayal on Polyester dyestuff; Dystar Co., Ltd. manufactures, and model is the commodity of Dianix dyestuff; Ciba Speciality Chemical company manufactures, and model is the commodity of Terasil dyestuff; Clariant company manufactures, and model is the commodity of Foron dyestuff.
The concrete example of aforementioned oil-soluble dyes, as: BASF AG manufactures, and model is the commodity of Sudan Black X60; Orient Chemical Industries company manufactures, and model is the commodity of Nubian Black PC-0850, Oil Black HBB etc.; C.I.Solvent Black-3 ,-7 ,-22:1 ,-27 ,-29 ,-34, the commercially available product of-50 etc.
Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of black dyes (F) is 20 weight portion to 200 weight portions, is preferably 25 weight portion to 180 weight portions, is more preferred from 30 weight portion to 160 weight portions.
If when photosensitive polymer combination does not comprise black dyes (F), obtained photoresist has optical density value and the lower defect of resistance value.
Adjuvant (G)
Do not affecting effect of the present invention, photosensitive polymer combination of the present invention optionally comprises adjuvant (G).Adjuvant (G) can increase the polymkeric substance etc. of various character (as engineering properties) including but not limited to other beyond surfactant, filling agent, adherence promoter, antioxidant, ultraviolet light absorber, anti-agglutinant or alkali soluble resin (A).
Preferably, this surfactant is the combination in any being selected from kation system, negative ion system, nonionic system, both sexes, polysiloxane series, fluorine prime system or above-mentioned surfactant.This surfactant can including but not limited to the polyethoxy alkyl ether surfactant of polyethoxy lauryl ether, polyethoxy hard ester acyl ether or polyethoxy oil ether etc.; The polyethoxy alkyl phenyl ethers surfactant of polyethoxy octyl phenyl ether or polyethoxy nonylplenyl ether etc.; The polyethylene glycol di class surfactant of polyethylene glycol dilaurate or polyglycol two hard acid ester etc.; Sorbitan fatty acid ester class surfactant; The polyesters surfactant of fatty acid upgrading and the polyurethanes surfactant of tertiary amine upgrading.This surfactant can be a kind of or mix multiple use separately.
This surfactant can manufacture including but not limited to SHIN-ETSU HANTOTAI's chemical industry, and model is the commodity of KP; Toray Dow Corning Silicon company manufactures, and model is the commodity of SF-8427; Oil chemical industry company of common prosperity society manufactures, and model is the commodity of Polyflow; Tochem Product Co., Ltd. manufactures, and model is the commodity of F-Top; Large Japanese INK chemical industrial company manufactures, and model is the commodity of Megafac; Sumitomo 3M manufactures, and model is the commodity of Fluorade; Asahi Glass manufactures, and model is the commodity of Asahi Guard, Surflon; Sino-Japan synthetic chemistry manufactures, and model is the commodity of SINOPOL E8008.
Total use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of this surfactant is 0 weight portion to 6 weight portion, is preferably 0 weight portion to 4 weight portion.
This filling agent can including but not limited to glass or aluminium etc.This adherence promoter can including but not limited to vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) 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 diethoxy silane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methylpropionyloxy propyl trimethoxy silicane or 3-mercaptopropyl trimethoxy silane etc.This antioxidant can including but not limited to 2,2-thiobis (4-methyl-6-tert-butylphenol) or 2,6-, bis--tert-butyl phenol etc.This ultraviolet light absorber can including but not limited to 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzotriazole [2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chloro benzotriazole] or alkoxy benzophenone etc.This anti-agglutinant can including but not limited to sodium polyacrylate etc.
Total use amount based on this alkali soluble resin (A) is 100 weight portions, the use amount of the polymkeric substance beyond aforementioned filling agent, adherence promoter, antioxidant, ultraviolet light absorber, anti-agglutinant or alkali soluble resin (A) is 0 weight portion to 10 weight portion, is preferably 0 weight portion to 6 weight portion.
The preparation of photosensitive polymer combination
The preparation method of photosensitive polymer combination of the present invention is by aforesaid alkali soluble resin (A), there is the compound (B) of ethene unsaturated group, light trigger (C), solvent (D), black pigment (E) and black dyes (F) are positioned in stirrer and stir, it is made to be uniformly mixed into solution state, also optionally surfactant is added if desired, ?fill agent, adherence promoter, antioxidant, ultraviolet light absorber, other beyond anti-agglutinant or alkali soluble resin (A) can increase the adjuvants (G) such as the polymkeric substance of various character (as engineering properties).
The preparation of black matrix" and pixel layer
Black matrix" of the present invention is by above-mentioned photosensitive polymer combination sequentially being bestowed to pre-baked, exposure, development and rear roasting process and obtaining.
This photosensitive polymer combination can be coated on substrate by the coating process such as rotary coating or cast coat by the preparation of black matrix", and with drying under reduced pressure and pre-baked process by removal of solvents wherein, and then form a pre-baked film on the substrate.Wherein, drying under reduced pressure and pre-baked condition, according to the kind of each composition, compounding ratio and different, drying under reduced pressure is generally carry out under pressure is less than the environment of 200mmHg 1 second to 20 seconds, and pre-baked process is then carry out 1 minute to 15 minutes at the temperature of 70 DEG C to 110 DEG C.Then, expose under this film being positioned over the mask of specifying, and impregnated at the temperature of 21 DEG C to 25 DEG C in a developer, last 15 seconds to 5 minutes, form specific pattern to remove part not.Exposing the light used, be good, and ultraviolet lamp can be (surpassing) high-pressure mercury-vapor lamp and metal halid lamp with the ultraviolet of g line, h line or i line etc.
The developer that the making of black matrix" of the present invention uses can including but not limited to NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sal tartari, saleratus, sodium silicate, sodium methyl silicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethylphosphonihydroxide hydroxide amine, tetraethylamine hydroxide, choline, pyrroles, piperidines or 1,8-diazabicylo-[5,4,0] alkali compounds of-7-hendecene etc.The concentration of this developer is 0.001wt% to 10wt%, is preferably 0.005wt% to 5wt%, is more preferred from 0.01wt% to 1wt%.
During the developer using aforesaid alkali compounds to form, usually in development after with water clean, and with pressurized air or compressed nitrogen air-dry.Then, use the heating arrangement such as hot plate or baking oven to carry out rear roasting process, and heating-up temperature is generally 150 DEG C to 250 DEG C.Wherein, the heat time using hot plate is 1 minute to 60 minutes, and the heat time using baking oven is 5 minutes to 90 minutes.A black matrix" can be formed after above treatment step.
The glass substrate that making black matrix" uses can be the alkali-free glass be applied in liquid crystal display, soda-lime glass, tempered glass (Pyrex glass), quartz glass, has adhered to the glass of nesa coating, the components of photo-electric conversion substrate (as: silicon substrate) etc. for solid photographic element etc. on the surface.
The preparation of colored filter
Colored filter of the present invention comprises above-mentioned black matrix", and wherein the surface resistance value of this black matrix" is 10 10Ω/cm 2to 10 17Ω/cm 2.
Colored filter can obtain according to the mode of general preparation, such as: on a substrate, first form above-mentioned black matrix", again assorted (mainly comprising red, green and Lan Sanse) is formed on this substrate with identical generation type, and then obtains the pixel shader layer of a colored filter.Secondly, under the vacuum environment of 220 DEG C to 250 DEG C, a tin indium oxide (Inidium Tin Oxide is formed; ITO) vapor-deposited film is on this pixel shader layer, if desired, after etching and wiring are implemented to ITO vapor-deposited film, then coating of liquid crystalline alignment film polyimide, the colored filter of a liquid crystal display can be obtained.
The preparation of liquid crystal display cells
Liquid crystal display cells of the present invention comprises above-mentioned colored filter, and can obtain according to mode in the past, such as: first by above-mentioned colored filter and be provided with thin film transistor (TFT) (Thin Film Transistor; TFT) driving substrate toward each other, between two plate bases, get involved cell gap (cell gap) do subtend configuration, and fit with the surrounding position of sealing agent by this two plate base, only leave a Liquid crystal pour hole, then, in the gap that these substrate surfaces and sealing agent are distinguished, liquid crystal is injected in filling, and seals this Liquid crystal pour hole and form liquid crystal cell (cell).Then, at the outside surface of liquid crystal cell, that is form on other side of substrate of liquid crystal cell, laminating Polarizer, can obtain a liquid crystal display cells.
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.
Accompanying drawing explanation
Fig. 1 is the side view of the evaluation method illustrated according to optical density value of the present invention;
Wherein, symbol description:
110 incident lights
120 black matrix"s
130 emergent lights.
Embodiment
Preparation has the resin (A-1) of unsaturated group
Synthesis example A-1-1
By the fluorenes epoxy compound of 100 weight portions, (Nippon Steel's chemistry manufactures, model is the commodity of ESF-300, and its 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 propylene glycol monomethyl ether acetate of 6-BHT and 130 weight portions adds in the four-hole boiling flask of 500mL with continous way addition manner, and be 100 weight portions based on the use amount of this fluorenes epoxy compound, the pan feeding speeds control of propylene glycol monomethyl ether acetate 25 weight portions/minute, the temperature of this course of reaction maintains 100 DEG C to 110 DEG C, react after 15 hours, the pale yellow transparent mixed liquor that a solid constituent concentration is 50 percentage by weights can be obtained.
Then, the above-mentioned pale yellow transparent mixed liquor of 100 weight portions is dissolved in the ethylene glycol ether acetate of 25 weight portions, and add 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, a resin (A-1-1) with unsaturated group, and its acid value is 98.0mgKOH/g.
Synthesis example A-1-2
By the fluorenes epoxy compound of 100 weight portions, (Nippon Steel's chemistry manufactures, model is the commodity of ESF-300, and its 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, 6-BHT, and 130 the propylene glycol monomethyl ether acetate of weight portion add in the four-hole boiling flask of 500mL with continous way addition manner, and be 100 weight portions based on the use amount of this fluorenes epoxy compound, the pan feeding speeds control of propylene glycol monomethyl ether acetate 25 weight portions/minute, the temperature of this course of reaction maintains 100 DEG C to 110 DEG C, react after 15 hours, the pale yellow transparent mixed liquor that a solid constituent concentration is 50 percentage by weights can be obtained.
Then, the above-mentioned pale yellow transparent mixed liquor of 100 weight portions is dissolved in the ethylene glycol ether acetate of 25 weight portions, and adds the benzophenone tetracarboxylic dianhydride of 13 weight portions, react 2 hours at 90 DEG C to 95 DEG C.Then, add the tetrabydrophthalic anhydride of 6 weight portions, and react 4 hours at 90 DEG C to 95 DEG C, a resin (A-1-2) with unsaturated group, and its acid value is 99.0mgKOH/g.
Synthesis example A-1-3
By the epoxy compound of 400 weight portions, (Nippon Kayaku K. K manufactures, model is NC-3000, and its epoxide equivalent is 288), the acrylic acid of 102 weight portions, the triphenylphosphine to methoxyl phenol, 5 weight portions of 0.3 weight portion, and 264 the propylene glycol monomethyl ether acetate of weight portion be placed in reaction bulb, the temperature of this course of reaction maintains 95 DEG C, react after 9 hours, the intermediate product that an acid value is 2.2mgKOH/g can be obtained.Then, add the tetrabydrophthalic anhydride of 151 weight portions, react 4 hours at 95 DEG C, can obtain the resin (A-1-3) that has unsaturated group, its acid value is 102mgKOH/g, and weight average molecular weight is 3200.
Prepare polysiloxane macromolecule (A-2)
It is below the polysiloxane macromolecule preparing synthesis example A-2-1 to A-2-6 according to table 1
Synthesis example A-2-1
In the three-neck flask of a volume 500 milliliters, add the methyltrimethoxy silane (hereinafter referred to as MTMS) of 0.30 mole, the phenyltrimethoxysila,e (hereinafter referred to as PTMS) of 0.45 mole, 3-(triethoxy is silica-based) propyl succinimide acid anhydrides (hereinafter referred to as GF-20) of 0.05 mole, 3-(trimethoxy the is silica-based) propyl methacrylate (hereinafter referred to as KBM-503) of 0.20 mole and the 4-hydroxy-4-methyl-2-pentanone (hereinafter referred to as DAA) of 180 grams, and stir under room temperature while added oxalic acid aqueous solution (0.4 gram of oxalic acid/75 gram water) in 30 minutes.Then, flask to be impregnated in the oil bath of 30 DEG C and to stir 30 minutes, then in 30 minutes, oil bath is warming up to 120 DEG C, when the interior temperature of solution reaches 110 DEG C, continuous heating stirs and carries out polycondensation 6 hours, recycling distillation mode removes solvent, polysiloxane macromolecule (A-2-1).Raw material type and the use amount thereof of preparation example A-2-1 are as shown in table 1.
Synthesis example A-2-2 is to synthesis example A-2-6
Synthesis example A-2-2 to A-2-6 uses the preparation method identical with the high molecular method for making of the polysiloxane of synthesis example A-2-1, difference is that synthesis example A-2-2 to A-2-6 is the kind and the use amount that change polysiloxane macromolecule 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 9 according to table 2 and table 3.
Embodiment 1
By the resin (A-1-1) with unsaturated group of the synthesis example A-1-1 of 30 weight portions, the polysiloxane macromolecule of the synthesis example A-2-1 of 35 weight portions, the polysiloxane macromolecule of the synthesis example A-2-4 of 35 weight portions, three acrylic acid trihydroxy methyl propyl ester (hereinafter referred to as B-1) of 20 weight portions, (CibaSpecialty Chemicals company manufactures 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-the substituting group]-ethane ketone 1-(oxy-acetyl oxime) of 10 weight portions, model is the commodity of OXE-02, hereinafter referred to as C-1), the 1-Methoxy-2-propyl acetate (hereinafter referred to as D-1) of 1000 weight portions, MA100 (the black pigment that Mitsubishi Chemical manufactures of 100 weight portions, hereinafter referred to as E-1) and 20 weight portions NeoZapon X55 (BASF AG manufacture black dyes, hereinafter referred to as F-1), homogeneous solution state is formed with swing-out stirrer, the 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 reliability, surface resistance value and optical density value repeats after holding.
Embodiment 2 to 7 and comparative example 1 to 9
Embodiment 2 to 7 and comparative example 1 to 9 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 9 are the kind and the use amount that change photosensitive polymer combination Raw, wherein comparative example 6 and 7 adds other dyestuff (F '), and its formula and evaluation result are respectively as shown in table 2 and table 3, separately do not repeat herein.
Prepare black matrix"
In coating machine, (model is MS-A150; Purchased from new light trade) in, in the mode of rotary coating, aforesaid photosensitive polymer combination is coated on and is of a size of on the glass substrate of 100mm × 100mm, and carry out drying under reduced pressure with 100mmHg, lasted for 5 seconds.Then, pre-baked 2 minutes with 100 DEG C in baking oven, the pre-baked film that thickness is 1.2 μm can be formed.Then, with ultraviolet light, (exposure machine model is for AG500-4N; M & R Nano Technology system) irradiate this pre-baked film, wherein the intensity of ultraviolet light is 100mJ/cm 2.Afterwards, impregnated in the developer solution (potassium hydroxide of 0.04%) of 23 DEG C.After 2 minutes, clean with pure water, and carry out latter roasting 60 minutes with 230 DEG C in baking oven, the black matrix" that thickness is 1.0 μm can be formed on the glass substrate.
Evaluation method
1. reliability
The black matrix" utilized made by the photosensitive polymer combination of above-described embodiment 1 to 7 and comparative example 1 to 9 is positioned over temperature is 121 DEG C, pressure is for 2atm and relative humidity is in the baking oven of 100%, after 8 hours, according to the basal disc order method of the 8.5.2 in the adherence test method(s) of JIS.5400 (1900) 8.5, after aforesaid black matrix" is cut into 100 basal disc orders with pocket knife, tear after sticking with adhesive tape, observe the situation that basal disc order is residual, and evaluate according to following benchmark:
○：＞4B。
△: 3B to 2B.
╳: 1B to 0B.
Wherein, basal disc order Shuo Liang≤5% of > 4B:0%≤come off.
Basal disc order Shuo Liang≤15% of 3B:5%≤come off.
Basal disc order Shuo Liang≤35% of 2B:15%≤come off.
Basal disc order Shuo Liang≤65% of 1B:35%≤come off.
Basal disc order Shuo Liang≤100% of 0B:65%≤come off.
2. surface resistance value
(model is MCP-HT450 type Hiresta-UP to use high impedance rate meter; Mitsubishi Chemical's system) measure the black matrix" utilizing above-mentioned thickness 1.0 μm obtained by embodiment 1 to 7 and comparative example 1 to 9 respectively.During measurement, take up an official post in above-mentioned black matrix" and get three measuring points, measure the mean value (Ω of surface resistance value (surface resistance) s), and evaluate according to following benchmark:
○：1.0E+10≦Ω S。
△：1.0E+8≦Ω S＜1.0E+10。
╳：Ω S＜1.0E+8。
3. optical density value (Optical Density Value)
Please refer to Fig. 1, it is the side view of the evaluation method illustrated according to optical density value of the present invention.First, take intensity as I 0incident light 110 irradiate black matrix" 120 (thickness is 1.0 μm) obtained by above-described embodiment 1 to 7 and comparative example 1 to 9, and measure the intensity (I) penetrating the emergent light 130 of black matrix" 120.Then, calculate the optical density value of black matrix" 120 with following formula (VI), and evaluate according to following benchmark:
Zero: 4.0≤optical density value.
△: 3.8≤optical density value < 4.0.
╳: optical density value < 3.8.
From the result of table 2 and table 3, when photosensitive polymer combination and with have the resin (A-1) of unsaturated group, polysiloxane macromolecule (A-2), black pigment (E) and black dyes (F) time, obtained photosensitive polymer combination has good reliability, surface resistance value and optical density value under hot and humid environment.
Secondly, when photosensitive polymer combination and with when having resin (A-1) and polysiloxane macromolecule (A-2) of unsaturated group, obtained photosensitive polymer combination can have good reliability.Wherein, when polysiloxane macromolecule (A-2) has anhydride group or epoxy radicals, this anhydride group or epoxy radicals can the reliability of promotion feeling photosensitive resin composition under hot and humid environment further.
Moreover, when photosensitive polymer combination comprises black pigment (E), obtained photosensitive polymer combination can have preferably reliability under hot and humid environment, and when photosensitive polymer combination comprises black dyes (F), black dyes (F) can the surface resistance value of promotion feeling photosensitive resin composition and optical density value.
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 (6)

1. a photosensitive polymer combination, comprises:
Alkali soluble resin (A), comprises:
There is the resin (A-1) of unsaturated group, be undertaken obtained by polyreaction by a potpourri, and described potpourri comprise 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); And
Polysiloxane macromolecule (A-2), be by a reactant be hydrolyzed reaction and partial condensates react formed, wherein said reactant comprises the combination in any of silane monomer, polysiloxane prepolymers and above-mentioned material, and described silane monomer comprises at least one silane monomer had as shown in the formula the structure shown in (I)
Si(R 1) t(OR 2) 4-t(I)
In formula (I), t represents the integer of 1 to 3, when t represents 2 or 3, and multiple R 1be identical or different separately, wherein at least one R 1represent through anhydride group replace and carbon number be 1 to 10 alkyl, to replace and carbon number is the alkyl of 1 to 10, the oxyalkyl that replaces through epoxy radicals, and all the other R through epoxy radicals 1represent hydrogen atom, carbon number be 1 to 10 alkyl, carbon number be 2 to 10 thiazolinyl or carbon number be the aromatic radical of 6 to 15; When (4-t) represents 2 or 3, multiple R 2be identical or different separately, and R 2represent hydrogen atom, carbon number be 1 to 6 alkyl, carbon number be 1 to 6 acyl group or carbon number be the aromatic radical of 6 to 15;
There is the compound (B) of ethene unsaturated group;
Light trigger (C);
Solvent (D);
Black pigment (E); And
Black dyes (F).
2. 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 3and B 4be respectively identical or different, and B 1, B 2, B 3and B 4represent hydrogen atom respectively, 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, and 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. photosensitive polymer combination as claimed in claim 1, use amount wherein based on alkali soluble resin (A) is 100 weight portions, the described use amount with the resin (A-1) of unsaturated group is 30 weight portion to 90 weight portions, the use amount of described polysiloxane macromolecule (A-2) is 10 weight portion to 70 weight portions, the described use amount with the compound (B) of ethene unsaturated group is 20 weight portion to 180 weight portions, the use amount of described light trigger (C) is 10 weight portion to 80 weight portions, the use amount of described solvent (D) is 1000 weight portion to 7000 weight portions, the use amount of described black pigment (E) is 100 weight portion to 600 weight portions, and the use amount of described black dyes (F) is 20 weight portion to 200 weight portions.
4. a black matrix" formed by photosensitive polymer combination as claimed any one in claims 1 to 3.
5. a colored filter, comprises black matrix" as claimed in claim 4.
6. a liquid crystal display cells, comprises colored filter as claimed in claim 5.
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KR20210112060A (en) * 2020-03-04 2021-09-14 삼성에스디아이 주식회사 Photosensitive resin composition, photosensitive resin layer using the same and color filter
KR102586091B1 (en) * 2020-03-04 2023-10-05 삼성에스디아이 주식회사 Photosensitive resin composition, photosensitive resin layer using the same and color filter

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