CN105182686A - Photosensitive resin composition and application thereof - Google Patents

Photosensitive resin composition and application thereof Download PDF

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Publication number
CN105182686A
CN105182686A CN201510251424.XA CN201510251424A CN105182686A CN 105182686 A CN105182686 A CN 105182686A CN 201510251424 A CN201510251424 A CN 201510251424A CN 105182686 A CN105182686 A CN 105182686A
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compound
methyl
formula
group
weight portions
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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 and application thereof, in particular to a photosensitive resin composition for a black matrix, and a color filter and a liquid crystal display element formed by using the black matrix. The photosensitive resin composition comprises an alkali-soluble resin , an ethylenically unsaturated group-containing compound (B), a photoinitiator (C), a solvent (D), a black pigment (E), a compound (F) represented by the formula (a), and an epoxy resin (G) having a fluorene skeleton represented by the formula (B). The photosensitive resin composition for black matrix has the advantages of reducing film shrinkage and roughness.

Description

Photosensitive polymer combination and application thereof
Technical field
The present invention has the colored filter and liquid crystal display cells that are formed about a kind of black matrix" photosensitive polymer combination and use black matrix".Particularly provide a kind of reduce film contracting and reduce the black matrix" photosensitive polymer combination of roughness and use the colored filter that formed of black matrix" and liquid crystal display cells.
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 black matrix" can be placed in the striped (stripe) of colored filter in display and point (dot) gap.Contrast caused by light between above-mentioned black matrix" can prevent because of pixel leaks declines 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 complex process and the shortcomings such as material expensive.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 light lithography (photolithographic).
Current industry requires day by day to improve for the light-proofness of black matrix", and one of its solution is exactly the use amount 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 use amount, alkali soluble resin, photopolymerization initiator, 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 hiding while optical activity to increase in the mode promoting black pigment use amount, 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, photopolymerization initiator and the high use amount 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 use amount black pigment.
Although the photosensitive polymer combination that improve black pigment use amount in prior art can increase light-proofness etc., but, the photosensitive polymer combination of above-mentioned each prior art is after rear baking, and black matrix" produces serious film contracting, and its roughness fails to make industry accept.In view of this, the black matrix" photosensitive polymer combination needing to develop and can reduce film contracting and reduce roughness is still had.
Summary of the invention
The present invention utilizes the composition providing special alkali soluble resin and special compound, and obtains the black matrix" photosensitive polymer combination that can reduce film contracting and reduction roughness.
Therefore, the invention provides a kind of photosensitive polymer combination, it comprises:
Alkali soluble resin (A);
Containing the compound (B) of ethene unsaturated group;
Light initiator (C);
Solvent (D);
Black pigment (E);
Compound (F) shown in formula (a); And
There is shown in formula (b) epoxy resin (G) of fluorene skeleton;
Wherein:
Described alkali soluble resin (A) comprises the resin (A-1) with unsaturated group, and described in there is unsaturated group resin (A-1) be undertaken obtained by polyreaction by potpourri, and described potpourri contains the epoxy compound (i) with at least two epoxy radicals, and there is the compound (ii) of at least one carboxylic acid group and at least one ethene unsaturated group;
In formula (a):
R a, R band R cindependently represent the trialkoxy silane base (trialkoxysilylgroup) combined through alkylidene (alkylenegroup) or arlydene (arylenegroup) separately; And
In formula (b):
R 21represent cyano group, C 1to C 5alkyl or halogen atom;
R 22represent C 1to C 13alkylidene;
R 23represent hydrogen atom or methyl;
R 24represent C 1to C 5alkyl, C 6to C 12aryl or C 6to C 12aralkyl;
P represents the integer of 0 to 4;
Q represents the integer of 1 to 10; And
R represents the integer of 0 to 4.
The present invention also provides a kind of black matrix", and it formed by aforesaid Photosensitve resin composition.
The present invention provides again a kind of colored filter, and it comprises aforesaid black matrix".
The present invention reoffers a kind of LCD assembly, and it comprises aforesaid colored filter.
Embodiment
The invention provides a kind of photosensitive polymer combination, it comprises:
Alkali soluble resin (A);
Containing the compound (B) of ethene unsaturated group;
Light initiator (C);
Solvent (D);
Black pigment (E);
Compound (F) shown in formula (a); And
There is shown in formula (b) epoxy resin (G) of fluorene skeleton;
Wherein:
Described alkali soluble resin (A) comprises the resin (A-1) with unsaturated group, and described in there is unsaturated group resin (A-1) be undertaken obtained by polyreaction by potpourri, and described potpourri contains the epoxy compound (i) with at least two epoxy radicals, and there is the compound (ii) of at least one carboxylic acid group and at least one ethene unsaturated group;
In formula (a):
R a, R band R cindependently represent the trialkoxy silane base (trialkoxysilylgroup) combined through alkylidene (alkylenegroup) or arlydene (arylenegroup) separately; And
In formula (b):
R 21represent cyano group, C 1to C 5alkyl or halogen atom;
R 22represent C 1to C 13alkylidene;
R 23represent hydrogen atom or methyl;
R 24represent C 1to C 5alkyl, C 6to C 12aryl or C 6to C 12aralkyl;
P represents the integer of 0 to 4;
Q represents the integer of 1 to 10; And
R represents the integer of 0 to 4.
The epoxy compound (i) with at least two epoxy radicals according to the present invention can have as shown in the formula the structure shown in (I) or following formula (II).Herein, " epoxy compound (i) can have as shown in the formula the structure shown in (I) or following formula (II) " describe the situation also covering and have as shown in the formula the compound of the structure shown in (I) and the compound had as shown in the formula the structure shown in (II) exist simultaneously as epoxy compound (i).Specifically, the aforementioned epoxy compound (i) with at least two epoxy radicals is such as have the structure as shown in the formula shown in (I):
Wherein:
R 1, R 2, R 3with R 4independently represent hydrogen atom, halogen atom, C separately 1to C 5alkyl, C 1to C 5alkoxy, C 6to C 12aryl or C 6to C 12aralkyl.
The epoxy compound (i) with at least two epoxy radicals with formula (I) structure can comprise and react by bisphenol fluorene type compound (bisphenolfluorene) and halogenated epoxy propane (epihalohydrin) and the bisphenol fluorene type compound containing epoxy radicals that obtains, but is not limited to this.
Concrete example as above-mentioned bisphenol fluorene type compound is: 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.
Above-mentioned halogenated epoxy propane (epihalohydrin) can include but not limited to bromo-1, the 2-epoxypropane (epibromohydrin) of chloro-1, the 2-epoxypropane of 3-(epichlorohydrin) or 3-etc.
Above-mentionedly react the bisphenol fluorene type compound containing epoxy radicals of gained including but not limited to commodity manufactured by (1) Nippon Steel's chemistry (NipponSteelChemicalCo., Ltd): such as ESF-300 etc. by bisphenol fluorene type compound and halogenated epoxy propane; (2) commodity manufactured by Osaka gas (OsakaGasCo., Ltd): such as EG-210 etc.; (3) commodity manufactured by note science and technology (S.M.STechnologyCo., Ltd): such as SMS-F9PhPG, SMS-F9CrG, SMS-F914PG etc.
In another concrete example of the present invention, described in there are at least two epoxy radicals epoxy compound (i) have as shown in the formula the structure shown in (II):
Wherein:
R 5to R 18independently represent hydrogen atom, halogen atom, C separately 1to C 8alkyl or C 6to C 15aryl; And n represents the integer of 0 to 10.
The epoxy compound (i) with at least two epoxy radicals with formula (II) structure is such as by under existing at alkali metal hydroxide, and the compound and the halogenated epoxy propane that make to have following formula (II-1) structure carry out reacting and obtaining:
In formula (II-1), R 5to R 18and the definition of n respectively with the R in formula (II) 5to R 18and the definition of n is identical, does not separately repeat at this.
Moreover, the epoxy compound (i) with at least two epoxy radicals with formula (II) structure is such as in presence of an acid catalyst, use has after the compound of following formula (II-2) structure and phenol (phenol) class carry out condensation reaction, forms the compound with formula (II-1) structure.Then, carry out de-hydrogen halide (dehydrohalogenation) by adding excessive halogenated epoxy propane, and acquisition has the epoxy compound (i) with at least two epoxy radicals shown in formula (II) structure:
In above formula (II-2), R 19with R 20be respectively identical or different hydrogen atom, halogen atom, C 1to C 8alkyl or C 6to C 15aryl; X 1and X 2be respectively identical or different halogen atom, C 1to C 6alkyl or C 1to C 6alkoxy.Preferably, above-mentioned halogen atom can be such as chlorine or bromine, and abovementioned alkyl can be such as methyl, ethyl or the tert-butyl group, and above-mentioned alkoxy can be such as methoxy or ethoxy.
Concrete example as above-mentioned phenols is: 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.Above-mentioned phenols generally separately or can mix multiple use.
Be 1 mole based on the above-mentioned use amount with the compound of formula (II-2) structure, the use amount of phenols is 0.5 mole to 20 moles, wherein better to 15 moles with 2 moles.
As the concrete example of above-mentioned acid catalyst, can be enumerated as: hydrochloric acid, sulfuric acid, p-toluenesulfonic acid (p-toluenesulfonicacid), oxalic acid (oxalicacid), boron trifluoride (borontrifluoride), anhydrous Aluminum chloride (aluminiumchlorideanhydrous), zinc chloride (zincchloride) etc., wherein better with p-toluenesulfonic acid, sulfuric acid or hydrochloric acid.Above-mentioned acid catalyst separately or can mix multiple use.
In addition, though the use amount of above-mentioned acid catalyst is without particular limitation, but be 100 percentage by weights (wt%) based on the above-mentioned use amount with the compound of formula (II-2) structure, the use amount of acid catalyst is preferably 0.1wt% to 30wt%.
Above-mentioned condensation reaction can solvent-free or carry out in the presence of an organic.Secondly, the concrete example of above-mentioned organic solvent can be enumerated as: toluene (toluene), dimethylbenzene (xylene) or methyl isobutyl ketone (methylisobutylketone) etc.Above-mentioned organic solvent separately or can mix multiple use.
General assembly (TW) based on the compound and phenols with formula (II-2) structure is 100wt%, and the use amount of above-mentioned organic solvent is 50wt% to 300wt%, wherein better with 100wt% to 250wt%.In addition, the operating temperature of above-mentioned condensation reaction is 40 DEG C to 180 DEG C, and the running time of condensation reaction is 1 little of 8 hours.
After completing above-mentioned condensation reaction, neutralisation treatment or washing process can be carried out.Above-mentioned neutralisation treatment is that the pH value of reacted solution is adjusted to pH3 to pH7, wherein better with pH5 to pH7.Above-mentioned washing process can use neutralizing agent to carry out, this neutralizing agent is alkaline matter, and its concrete example can be enumerated as: the alkali metal hydroxides such as NaOH (sodiumhydroxide), potassium hydroxide (potassiumhydroxide); The alkaline-earth metal oxyhydroxide such as calcium hydroxide (calciumhydroxide), magnesium hydroxide (magnesiumhydroxide); The organic amines such as diethylene triamine (diethylenetriamine), trien (triethylenetetramine), aniline (aniline), phenylenediamine (phenylenediamine); And ammonia (ammonia), sodium dihydrogen phosphate (sodiumdihydrogenphosphate) etc.Above-mentioned washing process can adopt the method for prior art to carry out, 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, through heating under reduced pressure process, unreacted phenols and solvent are heated up in a steamer and is removed, and concentrated, the compound with formula (II-1) structure can be obtained.
As the concrete example of above-mentioned halogenated epoxy propane, can be exemplified by: chloro-1, the 2-epoxypropane (3-chloro-1,2-epoxypropane) of 3-, 3-bromo-1,2-epoxypropane (3-bromo-1,2-epoxypropane) or above-mentioned combination in any.Before carrying out above-mentioned de-hydrogen halide, can add in advance or in course of reaction, add the alkali metal hydroxide such as NaOH, potassium hydroxide.The operating temperature of above-mentioned de-hydrogen halide is 20 DEG C to 120 DEG C, and its running time scope is 1 little of 10 hours.
In one embodiment, the alkali metal hydroxide added in above-mentioned de-hydrogen halide also can use its aqueous solution.In this embodiment, above-mentioned alkali metal hydroxide aqueous solution is added into continuously de-hydrogen halide intrasystem while, can in decompression or normal pressure under, continuous still water outlet and halogenated epoxy propane, be separated by this and except anhydrating, halogenated epoxy propane can be back in reactive system continuously simultaneously.
Before above-mentioned de-hydrogen halide carries out, also the quarternary ammonium salt of tetramethyl-ammonium chloride (tetramethylammoniumchloride), tetramethylammonium bromide (tetramethylammoniumbromide), trimethyl benzyl ammonia chloride (trimethylbenzylammoniumchloride) etc. can be added as catalyzer, and at 50 DEG C at 150 DEG C, react 1 little of 5 hours, add alkali metal hydroxide or its aqueous solution again, at the temperature of 20 DEG C to 120 DEG C, it is made to react 1 little of 10 hours, to carry out de-hydrogen halide.
Be 1 equivalent based on the hydroxyl total yield in the above-mentioned compound with formula (II-1) structure, the use amount of above-mentioned halogenated epoxy propane can be 1 equivalent to 20 equivalent, wherein better with 2 equivalent to 10 equivalents.Be 1 equivalent based on the hydroxyl total yield in the above-mentioned compound with formula (II-1) structure, the use amount of the alkali metal hydroxide added in above-mentioned de-hydrogen halide can be 0.8 equivalent to 15 equivalent, wherein better with 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 polarity solvent etc. that also can add the aprotic (aprotic) such as dimethyl sulfone (dimethylsulfone), dimethyl sulfoxide (dimethylsulfoxide) reacts.When using alcohols, the use amount based on above-mentioned halogenated epoxy propane is 100wt%, and the use amount of alcohols can be 2wt% to 20wt%, is preferably 4wt% to 15wt%.In the example of polarity solvent using aprotic, the use amount based on halogenated epoxy propane is 100wt%, and the use amount of the polarity solvent of aprotic can be 5wt% to 100wt%, wherein, better with 10wt% to 90wt%.
After completing de-hydrogen halide, optionally carry out washing process.Afterwards, the mode of heating decompression is utilized to remove the polarity solvent etc. of halogenated epoxy propane, alcohols and aprotic.Above-mentioned heating decompression is such as be 110 DEG C to 250 DEG C in temperature, and pressure is carry out under 1.3kPa (10mmHg) environment below.
In order to avoid the epoxy resin formed contains hydrolyzable halogen, solution after de-hydrogen halide can be added toluene, methyl isobutyl ketone (methylisobutylketone) equal solvent, and add the alkali metal hydroxide aqueous solution such as NaOH, potassium hydroxide, again carry out de-hydrogen halide.In de-hydrogen halide, be 1 equivalent based on the hydroxyl total yield in the above-mentioned compound with formula (II-1) structure, the use amount of alkali metal hydroxide is 0.01 mole to 0.3 mole, wherein, better to 0.2 mole with 0.05 mole.In addition, the operating temperature range of above-mentioned de-hydrogen halide is 50 DEG C to 120 DEG C, and its running time scope is 0.5 little of 2 hours.
After completing de-hydrogen halide, by filter and the step such as washing removes salt.In addition, also can utilize the mode of heating decompression, by toluene, methyl isobutyl ketone equal solvent is heated up in a steamer removes, and can obtain such as formula the epoxy compound (i) with at least two epoxy radicals shown in (II).The epoxy compound (i) with at least two epoxy radicals of above-mentioned formula (II) can be called the commodity manufactured by the Japanese chemical drug such as NC-3000, NC-3000H, NC-3000S and NC-3000P (NipponKayakuCo.Ltd.) including but not limited to such as commodity.
The compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group according to the present invention is such as be selected from the group be made up of to (3) following (1): (1) acrylic acid, methacrylic acid, 2-methylacryoyloxyethyl succinic acid (2-methacryloyloxyethylbutanedioicacid), 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 is including but not limited to hexane diacid, succinic acid, maleic acid, phthalic acid, (3) half ester compound being reacted by (methyl) acrylate and the compound carboxylic acid anhydride (iii) of hydroxyl and obtained, wherein (methyl) acrylate of hydroxyl is 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.In addition, compound carboxylic acid anhydride described herein can with have unsaturated group resin (A-1) potpourri contained by compound carboxylic acid anhydride (iii) identical, therefore to repeat no more in this.
The potpourri with the resin (A-1) of unsaturated group according to the present invention more optionally comprises compound carboxylic acid anhydride (iii) and/or the compound (iv) containing epoxy radicals.The group that below above-mentioned compound carboxylic acid anhydride (iii) optional freedom, (1) forms to (2): (1) succinic anhydride (butanedioicanhydride), maleic anhydride (maleicanhydride), itaconic anhydride (Itaconicanhydride), phthalic anhydride (phthalicanhydride), tetrabydrophthalic anhydride (tetrahydrophthalicanhydride), hexahydrophthalic anhydride (hexahydrophthalicanhydride), methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylene tetrabydrophthalic anhydride (methylendo-methylenetetrahydrophthalicanhydride), chlorendic anhydride (chlorendicanhydride), glutaric anhydride or inclined three benzoyl oxides (1, the dicarboxylic acid anhydride compound such as 3-dioxoisobenzofuran-5-carboxylicanhydride), and the quaternary compound carboxylic acid anhydride such as (2) benzophenone tetracarboxylic dianhydride (benzophenonetetracarboxylicdianhydride, be called for short BTDA), two pyromellitic dianhydride or two phenylate tetracarboxylic acid dianhydrides.
The above-mentioned compound (iv) containing epoxy radicals is such as 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.The aforementioned compound (above be the long rapids commodity that change into Industrial Co., Ltd) of glycidyl ether compound including but not limited to trade name DenacolEX-111, EX-121Denacol, DenacolEX-141, DenacolEX-145, DenacolEX-146, DenacolEX-171, DenacolEX-192 etc. containing unsaturated group.
In a specific example of the present invention, the aforementioned resin (A-1) with unsaturated group can carry out polyreaction by the epoxy compound (i) with at least two epoxy radicals of formula (I) and the compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group, form the reaction product of hydroxyl,, then add obtained by compound carboxylic acid anhydride (iii) reacts then.Hydroxyl total yield based on the reaction product of above-mentioned hydroxyl is 1 equivalent, and the equivalent 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), can sequentially add in reaction or add simultaneously.When using dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride 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 range of above-mentioned reaction is such as the scope at 50 DEG C to 130 DEG C.
In another concrete example of the present invention, the aforementioned resin (A-1) with unsaturated group can be reacted 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, form the reaction product of hydroxyl, then, then by interpolation compound carboxylic acid anhydride (iii) and/or containing the compound (iv) of epoxy radicals carry out obtained by polyreaction.The epoxy radicals total yield had on the epoxy compound (i) of at least two epoxy radicals based on formula (II) is 1 equivalent, the above-mentioned 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.Hydroxyl use amount based on the reaction product of above-mentioned hydroxyl is 100 molar percentages (% by mole), the use amount of compound carboxylic acid anhydride (iii) is preferably 10 % by mole to 100 % by mole, be more preferred from 20 % by mole to 100 % by mole, You Jia is 30 % by mole to 100 % by mole.
Prepare above-mentioned there is resin (A-1) of unsaturated group time, in order to accelerated reaction, usually can add alkali compounds as catalysts in reaction solution.Above-mentioned catalysts can be used alone or as a mixture, and above-mentioned catalysts is including but not limited to triphenylphosphine (triphenylphosphine), antimony triphenyl (triphenylstibine), triethylamine (triethylamine), triethanolamine (triethanolamine), tetramethyl ammonium chloride (tetramethylammoniumchloride), benzyltriethylammonium chloride (benzyltriethylammoniumchloride) etc.Be 100 weight portions based on the above-mentioned epoxy compound (i) with at least two epoxy radicals and the general assembly (TW) 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, usually also polymerization inhibitor (polymerizationinhibitor) can be added in reaction solution.Above-mentioned polymerization inhibitor can be including but not limited to: methoxyl phenol (methoxyphenol), methylnaphthohydroquinone (methylhydroquinone), quinhydrones (hydroquinone), 2,6-BHT (2,6-di-t-butyl-p-cresol) or phenothiazine (phenothiazine) etc.Generally speaking, above-mentioned polymerization inhibitor separately or can mix multiple use.Be 100 weight portions based on the above-mentioned epoxy compound (i) with at least two epoxy radicals and the general assembly (TW) 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 preparation has resin (A-1) of unsaturated group, polymerization solvent can be used if desired.As the concrete example of above-mentioned polymerization solvent, can enumerate as alcohol compounds such as ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutyl alcohol, 2-butanols, hexanol or ethylene glycol; The ketone compounds such as MEK or cyclohexanone; The aromatic hydrocarbon such as toluene or dimethylbenzene compounds; The match such as match Luo element (cellosolve) or butyl match Luo element (butylcellosolve) Luo chlorins compound; Card must appropriate (carbitol) or butyl card must the card such as appropriate (butylcarbitol) must appropriate compounds; The propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether (propyleneglycolmonomethylether); Many propylene glycol alkyls ether [poly (propyleneglycol) alkylether] compounds such as dipropylene glycol monomethyl ether [di (propyleneglycol) methylether]; The acetic ester compounds such as ethyl acetate, butyl acetate, ethylene glycol ether acetate (ethyleneglycolmonoethyletheracetate) or 1-Methoxy-2-propyl acetate (propyleneglycolmethyletheracetate); Lactic acid alkane ester (alkyllactate) compounds such as ethyl lactate (ethyllactate) or butyl lactate (butyllactate); Or dialkyl group glycol ethers.Above-mentioned polymerization solvent generally separately or can mix multiple use.In addition, the above-mentioned 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 (A) is 100 weight portions, the aforementioned use amount with the resin (A-1) of unsaturated group is preferably 30 weight portion to 100 weight portions, be more preferred from 50 weight portion to 100 weight portions, You Jia is 70 weight portion to 100 weight portions.If when not using resin (A-1) with unsaturated group completely, then the Photosensitve resin composition of gained has serious film contracting phenomenon.
Alkali soluble resin according to the present invention (A) alternative comprises other alkali soluble resins (A-2).Other alkali soluble resins (A-2) are including but not limited to the resin containing carboxylic acid group or hydroxyl, specifically, can be enumerated as: the acrylic resin beyond the resin (A-1) with unsaturated group, urethane (urethane) are resin and phenolic varnish type (novolac) resin etc.
Use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of other alkali soluble resins (A-2) is preferably 0 weight portion to 70 weight portion, is more preferred from 0 weight portion to 50 weight portion, and You Jia is 0 weight portion to 30 weight portion.
Photosensitive polymer combination according to the present invention comprises the compound (B) containing ethene unsaturated group.
Compound (B) containing ethene unsaturated group according to the present invention can be selected from the compound with 1 ethene unsaturated group or the compound with more than 2 (containing 2) ethene unsaturated groups.
The aforesaid compound with 1 ethene unsaturated group can including but not limited to (methyl) acrylamide ((meth) acrylamide), (methyl) acryloyl morpholine, (methyl) acrylic acid-7-amido-3,7-dimethyl monooctyl ester, isobutoxymethyl (methyl) acrylamide, (methyl) isobomyl acrylate base 2-ethoxyethyl acetate, (methyl) isobornyl acrylate, (methyl) acrylic acid-2-ethyl caproite, ethyl diethylene glycol (methyl) acrylate, tertiary octyl group (methyl) acrylamide, two acetone (methyl) acrylamide, (methyl) DMAM, (methyl) dodecylacrylate, (methyl) acrylic acid dicyclopentenyl oxygen base ethyl ester, (methyl) acrylic acid dicyclopentenyl ester, nitrogen, nitrogen-dimethyl (methyl) acrylamide, (methyl) acrylic acid tetrachloro phenyl ester, (methyl) acrylic acid-2-tetrachloro phenoxy ethyl, (methyl) tetrahydrofurfuryl acrylate [tetrahydrofurfuryl (meth) 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, 2-hydroxyl-(methyl) ethyl acrylate, 2-hydroxyl-(methyl) propyl acrylate, caprolactam, nitrogen-vinyl pyrrolidone, (methyl) acrylate, (methyl) Pentachlorophenyl Acrylate, (methyl) acrylic acid pentabromo-phenyl ester, poly-single (methyl) acrylic acid second diester, poly-single (methyl) acrylic acid propylene diester, (methyl) acrylic acid norbornene ester etc.The aforesaid compound (B-1) with 1 ethene unsaturated group generally can be a kind of or mix multiple use separately.
The aforesaid compound with more than 2 (containing 2) ethene unsaturated groups is including but not limited to ethylene glycol bisthioglycolate (methyl) acrylate, two (methyl) acrylic acid dicyclopentenyl ester, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, three (2-hydroxyethyl) isocyanic acid two (methyl) acrylate, three (2-hydroxyethyl) isocyanic acid three (methyl) acrylate, three (2-hydroxyethyl) isocyanic acid three (methyl) acrylate of caprolactone upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester, three (methyl) acrylic acid trihydroxy methyl propyl ester of oxirane (being called for short EO) upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester of epoxypropane upgrading (being called for short PO), tripropylene 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, dipentaerythritol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate of caprolactone upgrading, dipentaerythritol five (methyl) acrylate of caprolactone upgrading, four (methyl) acrylic acid two trihydroxy methyl propyl ester [di (trimethylolpropane) tetra (meth) acrylate], bisphenol-A two (methyl) acrylate of ethane via epoxyethane upgrading, through bisphenol-A two (methyl) acrylate of epoxypropane upgrading, hydrogenated bisphenol A two (methyl) acrylate of ethane via epoxyethane upgrading, through hydrogenated bisphenol A two (methyl) acrylate of epoxypropane upgrading, through glycerine three (methyl) acrylate of epoxypropane upgrading, Bisphenol F two (methyl) acrylate of ethane via epoxyethane upgrading, novolaks polyglycidyl ether (methyl) acrylate etc.The aforesaid compound (B) with more than 2 (containing 2) ethene unsaturated groups generally can be a kind of or mix multiple use separately.
As the concrete example of the above-mentioned compound (B) containing ethene unsaturated group, can be enumerated as: three acrylic acid trihydroxy methyl propyl ester, three acrylic acid trihydroxy methyl propyl ester of ethane via epoxyethane upgrading, through three acrylic acid trihydroxy methyl propyl ester of epoxypropane 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 glycerol tri-acrylate or the above-mentioned combination in any of epoxypropane upgrading.
Use amount based on aforesaid alkali soluble resin (A) is 100 weight portions, use amount containing the compound (B) of ethene unsaturated group is preferably 40 weight portion to 300 weight portions, be more preferred from 50 weight portion to 250 weight portions, You Jia is 60 weight portion to 200 weight portions.
According to smooth initiator (C) of the present invention, there is no particular restriction, and it can be including but not limited to: O-acyl group oxime compound, triazine based compound, vinylbenzene ketone compounds, diimidazole compounds, benzophenone compound, α-cyclohexadione compounds, ketols compound, keto-alcohol ether compound, acyl phosphine oxide compounds, quinones, halogen-containing compounds, superoxide etc.
The concrete example of above-mentioned O-acyl group oxime compound is: 1-[4-(phenyl) phenyl]-heptane-1, 2-diketone 2-(O-benzoyl group oxime), 1-[4-(phenyl) phenyl]-octane-1, 2-diketone 2-(O-benzoyl group oxime), 1-[4-(benzoyl group) phenyl]-heptane-1, 2-diketone 2-(O-benzoyl group oxime), 1-[9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-substituting group]-ethane ketone 1-(O-acetyl group oxime), 1-[9-ethyl-6-(3-methylbenzene acyl group)-9H-carbazole-3-substituting group]-ethane ketone 1-(O-acetyl group oxime), 1-[9-ethyl-6-benzoyl group-9H-carbazole-3-substituting group]-ethane ketone 1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl benzoyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base benzoyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzene acyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl methoxybenzene acyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base methoxybenzene acyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-(2-methyl-5-THP trtrahydropyranyl methoxybenzene acyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxa penta cyclic group) benzoyl group }-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxa penta cyclic group) methoxybenzene acyl group }-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime) etc.
Above-mentioned O-acyl group oxime compound is preferably 1-[4-(phenyl) phenyl]-octane-1, 2-diketone 2-(O-benzoyl group oxime) (OXE01 such as manufactured by Ciba company limited (CibaSpecialtyChemicals)), 1-[9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-substituting group]-ethane ketone 1-(O-acetyl group oxime) (OXE02 such as manufactured by Ciba company limited), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran methoxybenzene acyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxa penta cyclic group) methoxybenzene acyl group }-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime) etc.Above-mentioned O-acyl group oxime compound separately or can mix multiple use, depending on actual needs.
Above-mentioned triazine based compound can include but not limited to vinyl-halogenated methyl-s-triazine compound, 2-(naphtho--1-substituting group)-4,6-pair-halogenated methyl-s-triazine compound and 4-(p-aminocarbonyl phenyl)-2,6-bis--halogenated methyl-s-triazine compound etc.
The concrete example of above-mentioned vinyl-halogenated methyl-s-triazine compound is: 2, two (the trichloromethyl)-6-p-methoxystyrene base-s-triazine, 2 of 4-, 4-two (trichloromethyl)-3-(the p-dimethyl amido phenyl-1,3-butadiene base of 1-)-s-triazine, 2-trichloromethyl-3-amido-6-p-methoxystyrene base-s-triazine etc.
Above-mentioned 2-(naphtho--1-substituting group)-4, the concrete example of 6-pair-halogenated methyl-s-triazine compound is: 2-(naphtho--1-substituting group)-4, 6-pair-trichloromethyl-s-triazine, 2-(4-methoxyl-naphtho--1-substituting group)-4, 6-pair-trichloromethyl-s-triazine, 2-(4-ethoxy-naphtho--1-substituting group)-4, 6-pair-trichloromethyl-s-triazine, 2-(4-butoxy-naphtho--1-substituting group)-4, 6-pair-trichloromethyl-s-triazine, 2-[4-(2-methoxy ethyl)-naphtho--1-substituting group]-4, 6-pair-trichloromethyl-s-triazine, 2-[4-(2-ethoxyethyl group)-naphtho--1-substituting group]-4, 6-pair-trichloromethyl-s-triazine, 2-[4-(2-butoxyethyl group)-naphtho--1-substituting group]-4, 6-pair-trichloromethyl-s-triazine, 2-(2-methoxyl-naphtho--1-substituting group)-4, 6-pair-trichloromethyl-s-triazine, 2-(6-methoxyl-5-methyl-naphtho--2-substituting group)-4, 6-pair-trichloromethyl-s-triazine, 2-(6-methoxyl-naphtho--2-substituting group)-4, 6-pair-trichloromethyl-s-triazine, 2-(5-methoxyl-naphtho--1-substituting group)-4, 6-pair-trichloromethyl-s-triazine, 2-(4, 7-dimethoxy-naphtho--1-substituting group)-4, 6-pair-trichloromethyl-s-triazine, 2-(6-ethoxy-naphtho--2-substituting group)-4, 6-pair-trichloromethyl-s-triazine, 2-(4, 5-dimethoxy-naphtho--1-substituting group)-4, 6-pair-trichloromethyl-s-triazine etc.
Above-mentioned 4-(p-aminocarbonyl phenyl)-2, the concrete example of 6-bis--halogenated methyl-s-triazine compound is: 4-[p-N, N-bis-(ethoxy carbonyl methyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-methyl-p-N, N-bis-(ethoxy carbonyl methyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[p-N, N-bis-(chloroethyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-methyl-p-N, N-bis-(chloroethyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-(p-N-chloroethyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(p-N-ethoxy carbonyl methyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-[p-N, N-bis-(phenyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-(p-N-chloroethyl carbonylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-[p-N-(p-methoxyphenyl) carbonylamino phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-N, N-bis-(ethoxy carbonyl methyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-bromo-p-N, N-bis-(ethoxy carbonyl methyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-chloro-p-N, N-bis-(ethoxy carbonyl methyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-fluoro-p-N, N-bis-(ethoxy carbonyl methyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-bromo-p-N, N-bis-(ethoxy carbonyl methyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-chloro-p-N, N-bis-(ethoxy carbonyl methyl) aminocarbonyl phenyl-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-fluoro-p-N, N-bis-(ethoxy carbonyl methyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-bromo-p-N, N-bis-(chloroethyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-chloro-p-N, N-bis-(chloroethyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[o-fluoro-p-N, N-bis-(chloroethyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-bromo-p-N, N-bis-(chloroethyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-chloro-p-N, N-bis-(chloroethyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-[m-fluoro-p-N, N-bis-(chloroethyl) aminocarbonyl phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-bromo-p-N-ethoxy carbonyl methyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-chloro-p-N-ethoxy carbonyl methyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-fluoro-p-N-ethoxy carbonyl methyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-bromo-p-N-ethoxy carbonyl methyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-chloro-p-N-ethoxy carbonyl methyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-ethoxy carbonyl methyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-bromo-p-N-chloroethyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-chloro-p-N-chloroethyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-fluoro-p-N-chloroethyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-bromo-p-N-chloroethyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-chloro-p-N-chloroethyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-chloroethyl aminocarbonyl phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 2, two (trichloromethyl)-6-[bromo-4-[N of 3-of 4-, two (ethoxy carbonyl methyl) amido of N-] phenyl]-1, 3, 5-triazine etc.
Above-mentioned triazine based compound is preferably 4-[m-bromo-p-N, N-bis-(ethoxy carbonyl methyl) aminocarbonyl phenyl]-2,6-bis-(trichloromethyl)-s-triazine, 2,4-two (trichloromethyl)-6-p-methoxystyrene base-s-triazines etc.Above-mentioned triazine based compound separately or can mix multiple use, depending on actual needs.
The concrete example of above-mentioned vinylbenzene ketone compounds is: to dimethylamine vinylbenzene ketone, α, α '-dimethoxy azoxy vinylbenzene ketone, 2,2'-dimethyl-2-phenyl vinylbenzene ketone, p-methoxybenzene ethane ketone, 2-methyl isophthalic acid-(4-methylthiophenyi)-2-morpholino-1-acetone (trade name IRGACURE907; Ciba company limited system), 2-benzyl-2-N, N dimethylamine-1-(4-morphlinophenyl)-1-butanone etc.Above-mentioned vinylbenzene ketone compounds is better with 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-good fortune quinoline generation-1-acetone, 2-benzyl-2-N, N dimethylamine-1-(4-morphlinophenyl)-1-butanone etc.Above-mentioned vinylbenzene ketone compounds separately or can mix multiple use, depending on actual needs.
The concrete example of above-mentioned diimidazole compounds is: 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 o-ethylphenyl)-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, 2, two (the 2-chlorphenyl)-4 of 2'-, 4', 5, 5'-tetraphenyl diimidazole, 2, 2'-two (2, 4-dichlorophenyl)-4, 4', 5, 5'-tetraphenyl diimidazole etc.Above-mentioned diimidazole compounds is better with two (2,4-dichlorophenyl)-4,4', 5, the 5'-tetraphenyl diimidazoles of 2,2'-.Above-mentioned diimidazole compounds separately or can mix multiple use, depending on actual needs.
The concrete example of above-mentioned benzophenone compound is: thioxanthones, 2,4-diethyl thioxanthones, thioxanthones-4-sulfone, benzophenone, 4,4'-two (dimethylamine) benzophenone, 4,4'-two (diethylamine) benzophenone etc.Above-mentioned benzophenone compound is better with two (diethylamine) benzophenone of 4,4'-.Above-mentioned benzophenone compound separately or can mix multiple use, depending on actual needs.
Above-mentioned α-cyclohexadione compounds concrete example is: benzil, acetyl group etc.Above-mentioned ketols compound can be enumerated as: diphenylhydroxyethanone.Above-mentioned keto-alcohol ether compound can be enumerated as: diphenylhydroxyethanone methyl ether, diphenylhydroxyethanone ether, diphenylhydroxyethanone isopropyl ether etc.Above-mentioned acyl phosphine oxide compounds can be enumerated as: 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, two-(2,6-dimethoxy benzoyl)-2,4,4-trimethylpentyl phosphine oxide etc.Above-mentioned quinones can be enumerated as: anthraquinone, 1,4-naphthoquinone etc.Above-mentioned halogen-containing compounds can be enumerated as: chloroacetophenone, trisbromomethyl benzene sulfone, three (trichloromethyl)-s-triazine etc.Above-mentioned superoxide can be enumerated as: di-tert-butyl peroxide etc.Above-mentioned α-cyclohexadione compounds, ketols compound, keto-alcohol ether compound, acyl phosphine oxide compounds, quinones, halogen-containing compounds, superoxide etc. separately or can mix multiple use, depending on actual needs.
Use amount according to smooth initiator (C) of the present invention can be allocated according to need, based on alkali soluble resin (A) 100 weight portion, the use amount of light initiator (C) is preferably 10 weight portion to 80 weight portions, be more preferred from 12 weight portion to 75 weight portions, You Jia is 15 weight portion to 70 weight portions.
The epoxy resin (G) and light initiator (C) shown in the compound (F) shown in solubilized alkali soluble resin (A), formula (a), formula (b) with fluorene skeleton is preferably according to solvent of the present invention (D), and do not react to each other with mentioned component, and there is suitable volatility.
The concrete example of above-mentioned solvent (D) is: the alkyl diol list alkane ether compounds such as glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol list positive propyl ether, dipropylene glycol mono-n-butyl ether, Tripropylene glycol monomethyl Ether or tripropylene glycol list ether, the alkyl diol list alkane ether acetate compounds such as glycol methyl ether acetate, ethylene glycol ether acetate or 1-Methoxy-2-propyl acetate or propylene-glycol ethyl ether acetate, other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether or tetrahydrofuran, the ketone compounds such as MEK, cyclohexanone, 2-HEPTANONE, 3-heptanone or diacetone alcohol, the lactic acid such as methyl lactate or ethyl lactate alkane ester type compound, 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, 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, other ester type compounds such as ethyl acetoacetate or 2-oxygen base ethyl butyrate, the aromatic hydrocarbon such as toluene or dimethylbenzene compounds, the amine carboxylic acid compounds such as 1-METHYLPYRROLIDONE, DMF or DMA, or above-mentioned combination in any.Above-mentioned solvent (D) generally separately or can mix multiple use.
Use amount based on above-mentioned alkali soluble resin (A) is 100 weight portions, the use amount of solvent (D) is preferably 1200 weight portion to 8000 weight portions, be more preferred from 1500 weight portion to 7500 weight portions, You Jia is 1800 weight portion to 7000 weight portions.
Be applicable to black pigment of the present invention (E) and be preferably the black pigment with thermotolerance, photostability and solvent resistance.
The concrete example of above-mentioned black pigment (E) is: the black organic pigments such as perylene black (peryleneblack), cyanine black (cyanineblack), nigrosine (anilineblack); By in the pigment such as redness, blueness, green, purple, yellow, cyanine (cyanine), fuchsin (magenta), the colour mixture organic pigment of the approximate black selecting two or more pigment to carry out mixing; The lightproof material such as carbon black (carbonblack), chromium oxide, iron oxide, titanium black (titaniumblack), graphite, wherein, above-mentioned carbon black including but not limited to C.I.pigmentblack7 etc., can enumerate the commercially available product (trade name MA100, MA230, MA8, #970, #1000, #2350, #2650) manufactured by Mitsubishi Chemical (MitsubishiChemicalCo.).Above-mentioned black pigment (E) generally separately or can mix multiple use.
Use amount based on above-mentioned alkali soluble resin (A) is 100 weight portions, the use amount of black pigment (E) is preferably 100 weight portion to 700 weight portions, be more preferred from 120 weight portion to 650 weight portions, You Jia is 150 weight portion to 600 weight portions.
Compound (F) according to black matrix" photosensitive polymer combination contained (a) of the present invention;
In its Chinese style (a):
R a, R band R cindependently represent the trialkoxy silane base (trialkoxysilylgroup) combined through alkylidene (alkylenegroup) or arlydene (arylenegroup) separately.
Wherein alkylidene or arlydene can have substituting group, and substituting group can be amino, hydroxyl, alkoxy or halogen atom.
According to the concrete example of alkylidene of the present invention be methylene, the carbon number such as ethylidene, propylidene, butylidene, pentylidene, hexylidene, sub-heptyl, Ya Xinji, sub-nonyl, sub-decyl is the alkylidene of 1 to 10.Be phenylene or naphthylene according to the concrete example of arlydene of the present invention.
The concrete example of the compound (F) according to formula (a) of the present invention is the compound shown in following formula (a-1) to (a-9):
In compound (F) shown in above-mentioned formula (a), better with formula (a-1), (a-4), (a-7) and (a-9).
Use amount based on above-mentioned alkali soluble resin (A) is 100 weight portions, the use amount of the compound (F) shown in formula (a) is preferably 5 weight portion to 40 weight portions, be more preferred from 6 weight portion to 35 weight portions, You Jia is 7 weight portion to 30 weight portions.
If when not using compound (F) shown in formula (a) completely, have serious film contracting phenomenon.Though be reluctant by theory is limited, the compound (F) shown in salty letter factor (a) and black photoresistance forms to produce and are cross-linked, and can reduce film and contract.
There is the epoxy resin (G) of fluorene skeleton according to formula (b) of the present invention, wherein:
In formula (b):
R 21represent cyano group, C 1to C 5alkyl or halogen atom;
R 22represent C 1to C 13alkylidene;
R 23represent hydrogen atom or methyl;
R 24represent C 1to C 5alkyl, C 6to C 12aryl or C 6to C 12aralkyl;
P represents the integer of 0 to 4;
Q represents the integer of 1 to 10; And
R represents the integer of 0 to 4.
There is shown in formula (b) synthesis mode of the epoxy resin (G) of fluorene skeleton, such as, under alkali metal hydroxide exists, with epihalohydrin (epihalohydrin), as chloropropylene oxide (epichlorohydrin), alcohol or phenol, and fluorene skeleton reacts and obtains.
The concrete example shown in formula (b) with the epoxy resin (G) of fluorene skeleton is 9, two [4-(the 2-glycidoxypropyl ethoxy) phenyl] fluorenes (9 of 9-, 9-bis [4-(2-glycidyloxyethoxy) phenyl] fluorene) etc. 9, two (glycidoxypropyl phenyl (gathering) alkoxyl phenyl) compound (9, the 9-bis (glycidyloxyphenyl (poly) alkoxyphenyl) of 9-, 9, 9-pair [4-(2-glycidoxypropyl ethoxy)-3-aminomethyl phenyl) fluorenes (9, 9-bis [4-(2-glycidyloxyethoxy)-3-methylphenyl] fluorene), 9, two [the 4-(2-glycidoxypropyl ethoxy)-3 of 9-, 5-3,5-dimethylphenyl] fluorenes (9, 9-bis [4-(2-glycidyloxyethoxy)-3, 5-dimethylphenyl] fluorene) etc. 9, two (alkyl-glycidoxypropyl phenyl (gathering) alkoxyl phenyl) fluorene compound (9 of 9-, 9-bis (alkyl-glycidyloxyphenyl (poly) alkoxyphenyl) fluorene), 9, two [4-(2-glycidoxypropyl the ethoxy)-3-phenyl] fluorenes (9 of 9-, 9-bis [4-(2-glycidyloxyethoxy)-3-phenylphenyl] fluorene) etc. 9, two (aryl-diglycidyl oxygen phenyl (gathering) alkoxyl phenyl) fluorene compound (9,9-bis (aryl-glycidyloxyphenyl (poly) alkoxyphenyl) fluorene) of 9-.
The concrete example shown in formula (b) with the epoxy resin (G) of fluorene skeleton is EG-200, EG-250, PG-100 that Osaka gas Chemical Co., Ltd. manufactures.
Use amount based on above-mentioned alkali soluble resin (A) is 100 weight portions, the use amount shown in formula (b) with the epoxy resin (G) of fluorene skeleton is preferably 3 weight portion to 30 weight portions, be more preferred from 4 weight portion to 27 weight portions, You Jia is 5 weight portion to 25 weight portions.
If when not using epoxy resin (G) shown in formula (b) with fluorene skeleton completely, roughness is not good.
According to photosensitive polymer combination of the present invention, goodly separately comprise the polysiloxane polymer (H) with anhydride group or epoxy radicals.
The polysiloxane polymer (H) with anhydride group or epoxy radicals choice for use silane monomer (silanemonomer), polysiloxane prepolymers (siloxaneprepolymer) or silane monomer can carry out being polymerized (being namely hydrolyzed (hydrolysis) and partial condensates (partiallycondensation)) and is formed with the combination of polysiloxane prepolymers.
The polymerization silane monomer with the polysiloxane polymer (H) of anhydride group or epoxy radicals of the present invention comprises the silane at least with formula (III) structure
Si (R 25) t(OR 26) 4-tformula (III)
T is the integer of 1 to 3, and when t represents 2 or 3, multiple R 25be identical or different separately; And when 4-t is 2 or 3, multiple R 26be identical or different separately;
At least one R 25represent the C replaced through anhydride group 1to C 10alkyl, through epoxy radicals replace C 1to C 10alkyl or the alkoxy that replaces through epoxy radicals, and all the other R 25represent hydrogen, C 1to C 10alkyl, C 2to C 10thiazolinyl or C 6to C 15aryl; And
R 26represent hydrogen, C 1to C 6alkyl, C 1to C 6acyl group or C 6to C 15aryl.
Replace and C through anhydride group 1to C 10the concrete example of alkyl, as: ethyl succinic acid acid anhydride, propyl succinimide acid anhydrides or propyl group glutaric anhydride etc.
Replace and C through epoxy radicals 1to C 10the concrete example of alkyl, as: epoxypropane base amyl group (oxetanylpentyl) or 2-(3,4-epoxycyclohexyl) ethyl [2-(3,4-epoxycyclohexyl) ethyl] etc.
Through the concrete example of the oxyalkyl that epoxy radicals replaces, as: glycidoxypropyl group (glycidoxypropyl) or 2-epoxypropane base butoxy (2-oxetanylbutoxy) etc.
In R 26in, aforesaid 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.Aryl then can including but not limited to phenyl.
Silane monomer shown in formula (III) can including but not limited to 3-glycidoxypropyltrime,hoxysilane (3-glycidoxypropyltrimethoxysilane, TMS-GAA), 3-glycidoxypropyl group triethoxysilane (3-glycidoxypropyltriethoxysilane), 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane [2-(3, 4-epoxycyclohexyl) ethyltrimethoxysilane], 2-epoxypropane base butoxypropyl triple phenoxyl silane (2-oxetanylbutoxypropyltriphenoxysilane), 3-(triple phenoxyl is silica-based) propyl succinimide acid anhydrides, 3-(trimethoxy is silica-based) propyl group glutaric anhydride (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-oxetanylbutoxypropyl) silane, DIDOS], two (3-epoxypropane base amyl group) dimethoxysilane [di (3-oxetanylpentyl) dimethoxysilane], (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) methoxysilane], (phenoxy group is silica-based) three (propyl succinimide acid anhydrides), (methyl methoxy base is silica-based) two (ethyl succinic acid acid anhydride), Toagosei Co., Ltd manufactures, model is 2-epoxypropane base butoxypropyl trimethoxy silane (2-oxetanylbutoxypropyltrimethoxysilane) of TMSOX-D, model is 2-epoxypropane base butoxypropyl triethoxysilane (2-oxetanylbutoxypropyltriethoxysilane) of TESOX-D, and model is 3-ethyl-3-{ [3-(trimethoxy the is silica-based) propoxyl group] methyl of TMSOX } epoxypropane, KCC of SHIN-ETSU HANTOTAI manufactures, and model is 3-(trimethoxy is silica-based) the propyl succinimide acid anhydrides of X-12-967, manufactured by WACKER company, model is 3-(triethoxy is silica-based) the propyl succinimide acid anhydrides etc. of GF-20.Silane monomer shown in above-mentioned formula (III) a kind ofly separately can use or mix multiple use.
In another preferred embodiment of the present invention, the polymerization silane monomer with the polysiloxane polymer (H) of anhydride group or epoxy radicals of the present invention also comprises the silane monomer shown in following structural (III-1):
Si (R 27) u(OR 28) 4-uformula (III-1)
Wherein:
R 27represent and be selected from by hydrogen atom, C 1to C 10alkyl, C 2to C 10thiazolinyl and C 6to C 15the group that forms of aryl, wherein C 1to C 10alkyl not containing carboxylic acid anhydrides substituting group;
R 28independently be selected from by hydrogen atom, C 1to C 6alkyl, C 1to C 6acyl group and C 6to C 15the group that forms of aryl; And
U represents the integer of 1 to 3; When u represents 2 or 3, multiple R 27can identical also can be different; When (4-u) represents 2,3 or 4, multiple R 28can be identical or different.
In R 27in, alkyl can including but not limited to methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl, positive decyl, trifluoromethyl, 3,3,3-trifluoro propyls, 3-amine propyl group, 3-mercapto propyl group or 3-isocyanatopropyl etc.Thiazolinyl can including but not limited to vinyl, 3-acryloxypropyl or 3-methacryloxypropyl etc.Aryl 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 28in, alkyl can including but not limited to methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl etc.Acyl group can including but not limited to acetyl group.Aryl can including but not limited to phenyl.
Silane monomer shown in formula (III-1) can including but not limited to tetramethoxy-silicane, tetraethoxysilane, four acetoxylsilanes, tetraphenoxy-silicane alkane, methyltrimethoxy silane, 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, phenyl triethoxysilane, 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, 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.Silane monomer shown in previously described formula (III-1) a kind ofly separately can use or mix multiple use.
Preferably, the polymerization polysiloxane prepolymers with the polysiloxane polymer (H) of anhydride group or epoxy radicals of the present invention comprises as shown in the formula the polysiloxane shown in (III-2):
Wherein:
R 29, R 30, R 31and R 32can be identical or different, and be selected from respectively by hydrogen atom, C 1to C 10alkyl, C 2to C 6thiazolinyl and C 6to C 15the group that forms of aryl; Wherein alkyl, thiazolinyl or aryl are better for substituting group; Wherein each R 29can be identical or different, and each R 30can be identical or different; Aforesaid alkyl can including but not limited to methyl, ethyl or n-pro-pyl etc.Thiazolinyl can including but not limited to vinyl, acryloxypropyl or methacryloxypropyl etc.Aryl can including but not limited to phenyl, tolyl or naphthyl etc.;
S is the integer between 1 to 1000; Preferably, s is the integer between 3 to 300; More preferably, s is the integer between 5 to 200.
R 33and R 34be selected from respectively by hydrogen atom, C 1to C 6alkyl, C 1to C 6acyl group and C 6to C 15the group that forms of aryl; Wherein alkyl, acyl group or aryl are better for substituting group.Preferably, alkyl is such as but not limited to methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl etc.; Acyl group is such as but not limited to acetyl group; Aryl is such as but not limited to phenyl.
Polysiloxane shown in formula (III-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, the silanol end polysiloxane that 3-diethoxy disiloxane or Gelest company manufacture, its model is respectively DM-S12 (molecular weight is 400 to 700), 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) or PDS-9931 (molecular weight is 1000 to 1400) etc.Polysiloxane shown in formula (III-2) a kind ofly separately can use or mix multiple use.
Preferably, the polysiloxane polymer (H) with anhydride group or epoxy radicals of the present invention can by described silane monomer and/or polysiloxane prepolymers via the incompatible preparation of copolymerization, or combination silica (silicondioxide) particle is prepared via copolymerization.
The mean grain size of silicon dioxide granule is not particularly limited, and its average particle size range is 2nm to 250nm.Preferably, its average particle size range is 5nm to 200nm.More preferably, its average particle size range is 10nm to 100nm.
Silicon dioxide granule can change into Co., Ltd. including but not limited to catalyst and manufacture, model is that (particle diameter is 12nm to OSCAR1132, and spreading agent is methyl alcohol), (particle diameter is 12nm to OSCAR1332, and spreading agent is n-propanol), (particle diameter is 60nm to OSCAR105, and spreading agent is gamma-butyrolacton) or the commodity of OSCAR106 (particle diameter is 120nm, and spreading agent is diacetone alcohol) etc.; KCC of Japan manufactures, model is that (particle diameter is 13nm to QuartronPL-1-IPA, and spreading agent is isopropyl acetone), (particle diameter is 13nm to QuartronPL-1-TOL, and spreading agent is toluene), (particle diameter is 18nm to QuartronPL-2L-PGME, and spreading agent is propylene glycol monomethyl ether) or the commodity of QuartronPL-2L-MEK (particle diameter is 18nm, and spreading agent is MEK) etc.; Misao Kusano manufactures, model is that (particle diameter is 12nm to IPA-ST, 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) or the commodity of IPA-ST-ZL (particle diameter is 100nm, and spreading agent is isopropyl alcohol) etc.Silicon dioxide granule a kind ofly separately can use or mix multiple use.
Aforesaid partial condensates reaction can use general method, such as: in silane monomer and/or polysiloxane prepolymers, add solvent and water, and optionally add catalyzer.Then, at 50 DEG C to 150 DEG C, thermal agitation 0.5 is added little of 120 hours.During stirring, react and remove accessory substance (alcohols or water etc.) by distillation.
Total use amount based on silane monomer and/or polysiloxane prepolymers is 100 grams, and the use amount of solvent is 15 grams to 1200 grams.Preferably, the use amount of solvent is 20 grams to 1100 grams.More preferably, the use amount of solvent is 30 grams to 1000 grams.
Be 1 mole based on hydrolyzable groups contained in silane monomer and/or polysiloxane prepolymers, the use amount being hydrolyzed the water used is 0.5 mole to 2 moles.
Above-mentioned catalyzer has no particular limits.Preferably, catalyzer can be selected from acid catalyst or base catalyst.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 class, or ion exchange resin etc.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 with amido or ion exchange resin etc.
Total amount based on silane monomer and/or polysiloxane prepolymers is the use amount scope of 100 grams of catalyzer is 0.005 gram to 15 grams.Preferably, the use amount scope of catalyzer is 0.01 gram to 12 grams.More preferably, the use amount scope of catalyzer is 0.05 gram to 10 grams.
Based on the viewpoint of stability, the polysiloxane polymer (H) obtained by after condensation reaction with anhydride group or epoxy radicals is to be not good containing accessory substance (as alcohols or water) and catalyzer, and the polysiloxane polymer (H) therefore with anhydride group or epoxy radicals optionally carries out purifying.There is no particular restriction for purification process, and the better hydrophobic solvent that uses dilutes the polysiloxane polymer (H) with anhydride group or epoxy radicals, then concentrates through water washing organic layer for several times, to remove alcohols or water with evaporator.In addition, spent ion exchange resin can be made to remove catalyzer.
According to photosensitive polymer combination of the present invention, wherein, the use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of polysiloxane polymer (H) is 5 to 40 weight portions, be preferably 6 weight portion to 38 weight portions, be more preferred from 7 weight portion to 35 weight portions.If use the polysiloxane polymer (H) with anhydride group or epoxy radicals, roughness can be improved further.
Under the prerequisite not affecting effect of the present invention, photosensitive polymer combination of the present invention optionally adds adjuvant (I) further.Adjuvant (I) is including but not limited to surfactant, filling agent, adherence promoter, bridging agent, antioxidant, anti-agglutinant, or other can improve the polymkeric substance etc. of various character (as engineering properties).
The group that the optional free kation system of above-mentioned surfactant, negative ion system, nonionic system, both sexes, polysiloxane series, fluorine prime system surfactant or above-mentioned combination in any form.Furthermore, above-mentioned surfactant can be including but not limited to: the polyethoxy alkyl ethers such as polyethoxy lauryl ether, polyethoxy hard ester acyl ether or polyethoxy oil ether; The polyethoxy alkyl phenyl ethers such as polyethoxy octyl phenyl ether or polyethoxy nonylplenyl ether; The polyethylene glycol di classes such as polyethylene glycol dilaurate or polyglycol two hard acid ester; Sorbitan fatty acid ester class; The polyesters of fatty acid upgrading; And the polyurethane class of tertiary amine upgrading.Above-mentioned surfactant separately or can mix multiple use.
As the concrete example of above-mentioned surfactant, can be enumerated as: KP (SHIN-ETSU HANTOTAI chemical industry (Shin-EtsuChemicalCo., Ltd.) make), SF-8427 (eastern beautiful DOW CORNING silicon profit Kanggong department (TorayDowCorningSiliconeCo., Ltd.) make), Polyflow (common prosperity society oil chemical industry (KyoeishaOilChemicalCo., Ltd.) make), F-Top (holder Chemical Co., Ltd (TochemProductCo., Ltd.) make), Megafac (large Japanese ink chemical industry (DainipponInkandChemicals (DIC) Co., Ltd.) make), Fluorade (Sumitomo 3M (Sumitomo3M, Ltd.) make), AsahiGuard (Asahi Glass (AsahiglassCo., Ltd.) make), Surflon (Asahi Glass system) or SINOPOLE8008 (Sino-Japan synthetic chemistry (Sino-JapanChemicalCo., Ltd.) make) etc.
Filling agent can be enumerated as glass or aluminium etc., but is not limited to this.
The concrete example of adherence promoter is: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amido ethyl)-3-aminocarbonyl propyl methyl dimethoxysilane, N-(2-amido ethyl)-3-aminocarbonyl propyl trimethoxy silane, 3-amine propyl-triethoxysilicane, 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 trimethoxysilane etc.
The concrete example of antioxidant is 2,2-thiobis (4-methyl-6-tert-butylphenol) or 2,6-, bis--tert-butyl phenol etc.
The concrete example of anti-agglutinant is sodium polyacrylate etc.
The concrete example of bridging agent is the epoxy compound or resin etc. of 1031S, 157S-70 etc. of japan epoxy resin Inc..
Use amount based on above-mentioned alkali soluble resin (A) is 100 weight portions, the use amount scope of the polymkeric substance beyond the filling agent in adjuvant (I), adherence promoter, antioxidant, anti-agglutinant or alkali soluble resin (A) is preferably below 10 weight portions, is more preferred from below 6 weight portions.
Use amount based on above-mentioned alkali soluble resin (A) is 100 weight portions, and the use amount scope of the surfactant in adjuvant (I) is preferably below 6 weight portions, is more preferred from below 4 weight portions.
Use amount based on above-mentioned alkali soluble resin (A) is 100 weight portions, and the use amount scope of the bridging agent in adjuvant (I) is preferably below 100 weight portions, is more preferred from below 80 weight portions.
Photosensitive polymer combination of the present invention is such as by being positioned in stirrer stirring having the epoxy resin (G) of fluorene skeleton, light initiator (C), solvent (D) and black pigment (E) shown in the compound (F) shown in above-mentioned alkali soluble resin (A), formula (a), formula (b), making it be uniformly mixed into solution state and obtain.If desired, also can in wherein adding the adjuvant (I) such as compound (B), surfactant, filling agent, adherence promoter, bridging agent, antioxidant, anti-agglutinant containing ethene unsaturated group, after carrying out Homogeneous phase mixing, the photosensitive polymer combination in solution state can be obtained.
The preparation method of photosensitive polymer combination of the present invention is not particularly limited, such as, black pigment (E) directly can be added dispersion in photosensitive polymer combination to form, also can in advance the black pigment (E) of a part be scattered in a part containing in the medium (medium) of alkali soluble resin (A) and solvent (D), after forming dispersible pigment dispersion, again with the compound (F) shown in formula (a), there is shown in formula (b) epoxy resin (G) of fluorene skeleton, all the other parts of light initiator (C) and solvent (D) carry out mixing and obtaining.The dispersion steps of above-mentioned black pigment (E) is then undertaken by the such as mixer mixing mentioned component such as ball mill (beadsmill) or roller mill (rollmill).
The present invention also provides a kind of black matrix", and it formed by aforesaid Photosensitve resin composition.
Black matrix" according to the present invention obtains by roasting (postexposurebaking, PEB) process after Photosensitve resin composition as above sequentially being bestowed to pre-baked (pre-baking), exposing, develop and expose to the sun.The thickness of obtained black matrix" can be different according to purposes, specifically, during for black matrix" is applied to LCD, its thickness is such as in the scope of 0.8 μm to 1.2 μm, and during for black matrix" is applied to contact panel, its thickness is such as in the scope of 1.5 to 2.5 μm, but is not limited to this.Wherein, when thickness is 1 μm, the optical density (OD) scope of this black matrix" is preferably more than 3.0, and being more preferred from 3.2 to 5.5, You Jia is 3.5 to 5.5.
More specifically, above-mentioned photosensitive polymer combination, by the coating process such as rotary coating or cast coat, is coated on substrate by black matrix" of the present invention, and through drying under reduced pressure and pre-baked process by removal of solvents, and then on substrate, form pre-baked film.Aforesaid vacuum drying and pre-baked condition can be determined according to composition kind and allotment ratio.Generally speaking, above-mentioned drying under reduced pressure can carry out 1 second to 20 seconds under the pressure being less than 200mmHg, and pre-baked process then can carry out 1 minute to 15 minutes at 70 DEG C to 110 DEG C temperature.After pre-baked process, aforementioned film is exposed via the light shield of specifying (mask), then at the temperature of 23 ± 2 DEG C, the film through exposure to be impregnated in developer solution 15 seconds to 5 minutes, unwanted part to be removed, thus form specific pattern.The light used in above-mentioned step of exposure is preferably the ultraviolets such as g line, h line or i line, the ultraviolet lamp used can be (surpassing) high-pressure mercury-vapor lamp or metal halid lamp etc.
As the concrete example of above-mentioned developer solution, can be enumerated as: 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 etc. of-7-hendecene etc.The concentration of developer solution is generally 0.001 percentage by weight (wt%) to 10wt%, is preferably 0.005wt% to 5wt%, is more preferred from 0.01wt% to 1wt%.
Generally speaking, after processing with developer solution, first clean pattern with water, then with pressurized air or compressed nitrogen pattern is air-dry after, the heating arrangements such as hot plate (hotplate) or baking oven can be utilized to carry out rear roasting process.Rear roasting temperature is generally in the scope of 150 DEG C to 250 DEG C, and wherein, if use hot plate, the heat time is about 5 minutes to 60 minutes; If use baking oven, the heat time is then about 15 minutes to 150 minutes.After above treatment step, black matrix" can be formed on substrate.
As the concrete example of aforesaid substrate, can be enumerated as: for alkali-free glass, soda-lime glass, hard glass (as: Pai Lesi glass), quartz glass and the person that adheres to nesa coating on above-mentioned glass of liquid crystal display etc.; Or for the photo-electric conversion device substrate (as: silicon substrate) etc. of solid-state image sensor etc.
The present invention provides again a kind of colored filter, and it comprises aforesaid black matrix".
According to the formation method of colored filter of the present invention by coating methods such as rotary coating, cast coat or print roll coatings, the above-mentioned colored filter photosensitive composite being mixed into solution state is coated on substrate.Wherein, on substrate, utilize above-mentioned Photosensitve resin composition in advance and be formed with the black matrix" of isolating each pixel shader layer.After coating, first remove most solvent in the mode of drying under reduced pressure, then with pre-bake mode, removal of solvents is formed pre-baked film.
Aforesaid vacuum drying and pre-baked condition can be determined according to each composition kind and allotment ratio.Generally speaking, drying under reduced pressure can carry out for 1 second in second to 60 under the pressure of 0mmHg to 200mmHg, and pre-bakedly can carry out 1 minute to 15 minutes at 70 DEG C to 110 DEG C temperature.After pre-baked, film is exposed via the light shield of specifying, and at 23 ± 2 DEG C of temperature, the film through exposure be impregnated in developer solution and within 15 seconds, developed to 5 minutes, unwanted part to be removed, thus form specific pattern.The light used in above-mentioned step of exposure is preferably the ultraviolets such as g line, h line, i line, the ultraviolet lamp used can be (surpassing) high-pressure mercury-vapor lamp or metal halid lamp etc.
After development, first can clean pattern with water, then with pressurized air or compressed nitrogen pattern is air-dry, next, the heating arrangement such as hot plate or baking oven can be utilized to carry out rear roasting process, and the condition of rear roasting process is known as aforementioned, therefore in repeating no more herein.
Assorted photosensitive composite (mainly comprising red, green, blue three look) sequentially repeats above-mentioned steps, just can obtain the pixel layer of colored filter.Next, under the vacuum environment in 220 DEG C to 250 DEG C temperature ranges, pixel layer forms tin indium oxide (ITO) vapor-deposited film.If desired, can after ITO plated film being etched and connect up, then coating of liquid crystalline alignment film polyimide, and then burn till, namely obtain and can be used as colored filter used for liquid crystal display element.
The present invention reoffers a kind of liquid crystal display cells, and it comprises aforesaid colored filter.
Liquid crystal display cells according to the present invention by such as under type formed: by make by the manufacture method of above-mentioned colored filter formed colored filter substrate, be provided with thin film transistor (TFT) (thinfilmtransistor; TFT) driving substrate is to have (structure cell interval, space between the two, cellgap) mode subtend configuration, surrounding's position sealing agent in above-mentioned two substrates is fitted, and at substrate surface and sealing agent insert liquid crystal in the gap that separates out, formed liquid crystal cell (cell) to seal filling orifice.Then, at the outside surface of liquid crystal cell, that is form on other sides of each substrate of liquid crystal cell, laminating Polarizer, thus obtained LCD assembly.
Foregoing liquid crystal can be liquid-crystal compounds or liquid-crystal composition, its specifically composition be not particularly limited, tool in field belonging to the present invention can be used usually to know any one liquid-crystal compounds known by the knowledgeable and liquid-crystal composition.
Moreover foregoing liquid crystal alignment film is for limiting the orientation of liquid crystal molecule, and its kind is not particularly limited, can be inorganics or organic any one.In addition, form the technology of liquid crystal orienting film known by persond having ordinary knowledge in the technical field of the present invention, therefore repeat no more in this.
Now be described in detail the present invention with following Examples, but do not mean the content that the present invention is only confined to these examples and discloses.
< synthesis example >
The synthesis > of < alkali soluble resin (A)
Synthesis example 1: the manufacture method with the resin (A-1-1) of unsaturated group
By fluorenes epoxy compound (model ESF-300, Nippon Steel's chemistry system of 100 weight portions; Epoxide equivalent 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 500mL continuously, and pan feeding speeds control 25 weight portions/minute, temperature is maintained in the scope of 100 DEG C to 110 DEG C, react after 15 hours, the pale yellow transparent mixed liquor that solid component concentration is 50wt% 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, 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, the resin (A-1-1) with unsaturated group that acid value is 98.0mgKOH/g can be obtained.
Synthesis example 2: the manufacture method with the resin (A-1-2) of unsaturated group
By fluorenes epoxy compound (model ESF-300, Nippon Steel's chemistry system of 100 weight portions; Epoxide equivalent 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 500mL continuously, and pan feeding speeds control 25 weight portions/minute, temperature is maintained in the scope of 100 DEG C to 110 DEG C, react after 15 hours, the pale yellow transparent mixed liquor that solid component concentration is 50wt% 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, add the benzophenone tetracarboxylic dianhydride of 13 weight portions simultaneously, 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, the resin (A-1-2) with unsaturated group that acid value is 99.0mgKOH/g can be obtained.
Synthesis example 3: the manufacture method with the resin (A-1-3) of unsaturated group
By epoxy compound (model NC-3000, Japanese chemical drug (strain) system of 400 weight portions; Epoxide equivalent 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 be placed in reaction bulb, temperature is maintained 95 DEG C, react after 9 hours, the intermediate product that acid value is 2.2mgKOH/g can be obtained.Then, add the tetrabydrophthalic anhydride (tetrahydrophthalicanhydride) of 151 weight portions, react 4 hours at 95 DEG C, can obtain acid value is 102mgKOH/g, and weight-average molecular weight is the resin (A-1-3) with unsaturated group of 3,200.
Synthesis example 4: the manufacture method of other alkali soluble resins (A-2-1)
By 2 of 1 weight portion, the N-phenylmaleimide of the styrene of the 1-Methoxy-2-propyl acetate of 2'-azobis isobutyronitrile, 240 weight portions, the methacrylic acid of 20 weight portions, 15 weight portions, the benzyl methacrylate of 35 weight portions, the glycerin monomethyl acrylic ester of 10 weight portions and 20 weight portions is placed in the round-bottomed flask that stirrer and condenser are housed, and makes flask interior be full of nitrogen.Afterwards, slowly stir and be warming up to 80 DEG C, make each reactant Homogeneous phase mixing and carry out polyreaction 4 hours.Afterwards, then reactant is warming up to 100 DEG C, and adds 2,2'-azoisobutyronitriles of 0.5 weight portion, after carrying out polymerization in 1 hour, after removing volatilizer, drying, alkali soluble resin (A-2-1) can be obtained.
Synthesis example 5: the manufacture method of other alkali soluble resins (A-2-2)
By 2 of 2 weight portions, the dipropylene glycol monomethyl ether of 2'-azobis isobutyronitrile, 300 weight portions, the methacrylic acid of 15 weight portions, the 2-hydroxyl ethyl acrylate of 15 weight portions and the benzyl methacrylate of 70 weight portions are placed in the round-bottomed flask that stirrer and condenser are housed, and make flask interior be full of nitrogen.Afterwards, slowly stir and be warming up to 80 DEG C, make each reactant Homogeneous phase mixing and carry out polyreaction 3 hours.Afterwards, then be warming up to 100 DEG C, and added 2,2'-azoisobutyronitriles of 0.5 weight portion, after carrying out polymerization in 1 hour, after removing volatilizer, drying, alkali soluble resin (A-2-2) can be obtained.Synthesis example 6: the synthesis of polysiloxane polymer (H)
Be in the three-neck flask of 500 milliliters at volume, add the 4-hydroxy-4-methyl-2-pentanone (hereinafter referred to as DAA) of the methyltrimethoxy silane (hereinafter referred to as MTMS) of 0.5 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 and 180 grams, and stir under room temperature added oxalic acid aqueous solution (dissolving oxalic acid of 0.4 gram is in the water of 75 grams) in 30 minutes.Then, be impregnated in by flask in the oil bath of 30 DEG C, stir after 30 minutes, above-mentioned reaction solution is heated to 110 DEG C, Keep agitation is to carry out polycondensation reaction.React after 6 hours, utilize distillation mode to remove solvent in solution, polysiloxane polymer (H-1) can be obtained.
Synthesis example 7 to 9:
Synthesis example 7 to 9 (H-2, H-3, H-4) uses the preparation method identical with the method for making of the polysiloxane polymer (H-1) of synthesis example 6, difference is that synthesis example 7 to 9 changes the kind of polysiloxane polymer Raw and use amount and polymerizing condition, its formula and polymerizing condition are distinguished as shown in table 1, separately do not repeat herein.
The formation > of < black matrix" is by the composition of the black matrix" described in following table 2 and 3 by photosensitive polymer combination embodiment and comparative example, and (model is MS-A150 to insert a coating machine; Purchased from new light trade), in the mode of rotary coating, be coated on the glass substrate of 100mm × 100mm, then carry out drying under reduced pressure with 100mmHg, lasted for 5 seconds, then pre-baked 2 minutes with 100 DEG C in baking oven, pre-baked film can be formed.Then, with ultraviolet light, (exposure machine model is for AG500-4N; M & RNanoTechnology system) 100mJ/cm 2irradiate pre-baked film, impregnated in the developer solution (0.04% potassium hydroxide) 2 minutes of 23 DEG C afterwards, clean with pure water, then carry out latter roasting 30 minutes with 240 DEG C in baking oven, photomask can be formed on the glass substrate.
< film contracting evaluation method >
Film after aforementioned exposure is taken up an official post and is got a measuring point and record thickness (δ d1), then the baking oven being placed in 240 DEG C gives baking after 30 minutes (i.e. above-mentioned rear roasting step), records another thickness (δ d2) at identical measuring point.Finally, can be calculated film shrinkage through following formula (IV).
Film shrinkage (%)=[(δ d1-δ d2)/(δ d1)] × 100 (IV)
"○": film Suo Shuais≤and 10%
" △ ": 10% < film Suo Shuais≤and 15%
" X ": 15% < film shrinkage
< surfaceness evaluation method >
Use contactless white light interferometer (BMT system; Model is WLILAB) measure the surface of black matrix", can record its surface roughness (Ra), unit is nm.
「◎」：Ra≦40nm
「○」：40nm＜Ra≦70nm
「△」：70nm＜Ra≦100nm
「X」：100nm＜Ra
Table 2:
Table 3:
In table 2 and table 3:
Above-described embodiment is only and principle of the present invention and effect thereof is described, and unrestricted the present invention.The amendment that those skilled in the art makes above-described embodiment and change are still without prejudice to spirit of the present invention.

Claims (9)

1. a photosensitive polymer combination, it comprises:
Alkali soluble resin (A);
Containing the compound (B) of ethene unsaturated group;
Light initiator (C);
Solvent (D);
Black pigment (E);
Compound (F) shown in formula (a); And
There is shown in formula (b) epoxy resin (G) of fluorene skeleton;
Wherein:
Described alkali soluble resin (A) comprises the resin (A-1) with unsaturated group, and described in there is unsaturated group resin (A-1) be undertaken obtained by polyreaction by potpourri, and described potpourri contains the epoxy compound (i) with at least two epoxy radicals, and there is the compound (ii) of at least one carboxylic acid group and at least one ethene unsaturated group;
In formula (a):
R a, R band R cthe trialkoxy silane base that respective independent representative combines through alkylidene or arlydene; And
In formula (b):
R 21represent cyano group, C 1to C 5alkyl or halogen atom;
R 22represent C 1to C 13alkylidene;
R 23represent hydrogen atom or methyl;
R 24represent C 1to C 5alkyl, C 6to C 12aryl or C 6to C 12aralkyl;
P represents the integer of 0 to 4;
Q represents the integer of 1 to 10; And
R represents the integer of 0 to 4.
2. photosensitive polymer combination according to claim 1, the wherein said epoxy compound (i) with at least two epoxy radicals has as shown in the formula the structure shown in (I):
Wherein:
R 1, R 2, R 3with R 4independently represent hydrogen atom, halogen atom, C separately 1to C 5alkyl, C 1to C 5alkoxy, C 6to C 12aryl or C 6to C 12aralkyl.
3. photosensitive polymer combination according to 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):
Wherein: ()
R 5to R 18independently represent hydrogen atom, halogen atom, C separately 1to C 8alkyl or C 6to C 15aryl; And
N represents the integer of 0 to 10.
4. photosensitive polymer combination according to claim 1, wherein, the use amount based on alkali soluble resin (A) is 100 weight portions, described in there is the resin (A-1) of unsaturated group use amount be 30 to 100 weight portions; Use amount containing the compound (B) of ethene unsaturated group is 40 to 300 weight portions; The use amount of light initiator (C) is 10 to 80 weight portions; The use amount of solvent (D) is 1200 to 8000 weight portions; The use amount of black pigment (E) is 100 to 700 weight portions; The use amount of the compound (F) shown in formula (a) is 5 to 40 weight portions; The use amount shown in formula (b) with the epoxy resin (G) of fluorene skeleton is 3 to 30 weight portions.
5. photosensitive polymer combination according to claim 1, it also comprises the polysiloxane polymer (H) with anhydride group or epoxy radicals, and the polymerization silane monomer of described polysiloxane polymer comprises at least one silane with formula (III) structure
Si (R 25) t(OR 26) 4-tformula (III)
T is the integer of 1 to 3, and when t represents 2 or 3, multiple R 25be identical or different separately; And when 4-t is 2 or 3, multiple R 26be identical or different separately;
At least one R 25represent the C replaced through anhydride group 1to C 10alkyl, through epoxy radicals replace C 1to C 10alkyl or the alkoxy that replaces through epoxy radicals, and all the other R 25represent hydrogen, C 1to C 10alkyl, C 2to C 10thiazolinyl or C 6to C 15aryl; And R 26represent hydrogen, C 1to C 6alkyl, C 1to C 6acyl group or C 6to C 15aryl.
6. photosensitive polymer combination according to claim 5, wherein, the use amount based on alkali soluble resin (A) is 100 weight portions, and the use amount of described polysiloxane polymer (H) is 5 to 40 weight portions.
7. a black matrix", it formed by according to the Photosensitve resin composition in claim 1 to 6 described in any one.
8. a colored filter, it comprises black matrix" according to claim 7.
9. a liquid crystal display cells, it comprises colored filter according to claim 8.
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CN103019031A (en) * 2011-09-22 2013-04-03 东京应化工业株式会社 A photosensitive resin composition, and a coating film and color filter using the composition
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