CN104062848A - Photosensitive resin composition, black matrix, color filter and liquid crystal display element - Google Patents

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

Info

Publication number
CN104062848A
CN104062848A CN201410076078.1A CN201410076078A CN104062848A CN 104062848 A CN104062848 A CN 104062848A CN 201410076078 A CN201410076078 A CN 201410076078A CN 104062848 A CN104062848 A CN 104062848A
Authority
CN
China
Prior art keywords
compound
pigment
methyl
resin composition
photosensitive resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410076078.1A
Other languages
Chinese (zh)
Inventor
曾靖渊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chi Mei Corp
Original Assignee
Chi Mei Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chi Mei Corp filed Critical Chi Mei Corp
Publication of CN104062848A publication Critical patent/CN104062848A/en
Pending legal-status Critical Current

Links

Abstract

The invention relates to a photosensitive resin composition, a black matrix, a color filter and a liquid crystal display element. A photosensitive resin composition comprises an alkali-soluble resin component, a compound containing an ethylenically unsaturated group, a photoinitiator, a pigment component and a solvent. The alkali-soluble resin component comprises resin with unsaturated groups, which is prepared by the polymerization reaction of a mixture, wherein the mixture comprises an epoxy compound with at least two epoxy groups and a compound with at least one carboxylic acid group and at least one ethylene unsaturated group. The pigment component comprises a black pigment and a blue pigment. The composition uses resin with unsaturated group, and the weight ratio of the black pigment to the blue pigment is regulated to be 0.5-10, so that the composition has high sensitivity, and a black matrix formed by the composition has high light-shielding property and high resolution.

Description

Photosensitive resin composition, black matrix", colored filter and liquid crystal display cells
Technical field
The present invention relates to a kind of photosensitive resin composition that is used to form black matrix", particularly a kind of photosensitive resin composition that comprises alkali soluble resin and pigment component, pigment component comprises black pigment and blue pigment.
Background technology
For improving contrast and the display quality of current liquid crystal display, general employing in the striped (stripe) of colored filter and point (dot) gap arranges black matrix".Acting as of this black matrix": prevent from leaking degradation disappearance under caused contrast decline and excitation because of the light between pixel.The mode of in the past making black matrix" is to utilize the material that contains chromium or chromium oxide etc. on substrate, to form vapor-deposited film, but this mode has the shortcomings such as processing procedure complexity and material expensive.For solving above-mentioned shortcoming, and proposition forms in the mode of light lithography (photo lithographic) photosensitive resin composition the technology of black matrix" on substrate.
Industry is more and more high to the light-proofness requirement of black matrix" at present, and solution has the content by increasing black pigment, improves whereby the light-proofness of black matrix".Japanese Patent Application Laid-Open 2006-259716 discloses the photosensitive resin composition that a kind of black matrix" is used.Black pigment, alkali soluble resin, photopolymerization initiator, the reactive monomer with two functional groups and organic solvent that this photosensitive resin composition comprises high-load, this reactive monomer with two functional groups is the acrylate monomers that contain fluorenyl.When the sensitization perception resin combination of this Japanese patent application uses the high light-proofness of black pigment demand of high-load, need to use this acrylate monomer that contains fluorenyl, to promote the crosslinking degree of this photosensitive resin composition in the time exposing, then improve sensitivity, to form the black matrix" with fine pattern.
Japanese Patent Application Laid-Open 2008-268854 discloses the photosensitive resin composition that a kind of black matrix" is used.This photosensitive resin composition comprises the black pigment that has the alkali soluble resin of carboxylic acid group and polymerism unsaturated group, gathers property monomer, light initiator and high-load containing the light of ethene unsaturated group.When the photosensitive resin composition of this Japanese patent application uses the high light-proofness of black pigment demand of high-load, use the specific alkali soluble resin with carboxylic acid group and polymerism unsaturated group, to promote the crosslinking degree of this photosensitive resin composition in the time exposing, then improve sensitivity, and make the black matrix" being formed by this photosensitive resin composition can also maintain required resolution.
But, cause now industry is required to be the resolution below 10 μ m to the minimum wire spoke of the requirement of black matrix", think that liquid crystal display cells provides more high-resolution image quality, so the black matrix" that the photosensitive resin composition for black matrix that above-mentioned two sections of patented claims disclose forms cannot meet the requirement of industry for resolution.
In view of above-mentioned, improvement photosensitive resin composition thinks that black matrix" provides more high resolving power, and the liquid crystal display cells of high image quality is provided then, is the problem that this technical field person skilled need break through again.
Summary of the invention
The first object of the present invention is to provide a kind of photosensitive resin composition.This photosensitive resin composition has high sensitivity, and can form high light-proofness and high-resolution black matrix".
Photosensitive resin composition of the present invention, comprises:
Alkali soluble resin component (A), comprise the resin (A-1) with unsaturated group, this resin (A-1) with unsaturated group is obtained through polyreaction by potpourri, this potpourri comprises the epoxy compound (i) with at least two epoxy radicals, and has the compound (ii) of at least one carboxylic acid group and at least one ethene unsaturated group;
Containing the compound (B) of ethene unsaturated group;
Light initiator (C);
Pigment component (D); And
Solvent (E);
This pigment component (D) comprises black pigment (D-1) and blue pigment (D-2), and the weight ratio scope of this black pigment (D-1) use amount and blue pigment (D-2) use amount is 0.5 to 10.
Photosensitive resin composition of the present invention, this epoxy compound (i) with at least two epoxy radicals is selected from the epoxy compound with at least two epoxy radicals shown in the epoxy compound with at least two epoxy radicals shown in formula (I), formula (II), or their combination:
R 1, R 2, R 3and R 4represent independently of one another hydrogen, halogen, C 1to C 5alkyl, C 1to C 5alkoxy, C 6to C 12aromatic radical or C 7to C 12aralkyl,
R 5to R 18represent independently of one another hydrogen, halogen, C 1to C 8alkyl or C 6to C 15aromatic radical, n represents 0 to 10 integer.
Photosensitive resin composition of the present invention, this epoxy compound (i) with at least two epoxy radicals is the epoxy compound with at least two epoxy radicals shown in formula (I):
R 1, R 2, R 3and R 4represent independently of one another hydrogen, halogen, C 1to C 5alkyl, C 1to C 5alkoxy, C 6to C 12aromatic radical or C 7to C 12aralkyl.
Photosensitive resin composition of the present invention, this epoxy compound (i) with at least two epoxy radicals is the epoxy compound with at least two epoxy radicals shown in formula (II):
R 5to R 18represent independently of one another hydrogen, halogen, C 1to C 8alkyl or C 6to C 15aromatic radical, n represents 0 to 10 integer.
Photosensitive resin composition of the present invention, total amount based on this alkali soluble resin component (A) is 100 weight portions, this content range with the resin (A-1) of unsaturated group is 50 to 100 weight portions, should be 30 to 300 weight portions containing the use amount scope of the compound (B) of ethene unsaturated group, the use amount scope of this pigment component (D) is 100 to 1000 weight portions, and the use amount scope of this solvent (E) is 1000 to 5000 weight portions.
Photosensitive resin composition of the present invention, is 100 weight portions based on this total amount containing the compound (B) of second unsaturated group, and the use amount scope of this light initiator (C) is 10 to 60 weight portions.
Photosensitive resin composition of the present invention, total amount based on this alkali soluble resin component (A) is 100 weight portions, the use amount scope of this black pigment (D-1) is 50 to 600 weight portions, and the use amount scope of this blue pigment (D-2) is 50 to 400 weight portions.
The second object of the present invention is to provide one to have high light-proofness and high-resolution black matrix".
Black matrix" of the present invention photosensitive resin composition from the above mentioned forms.
The 3rd object of the present invention is to provide a kind of colored filter.
Colored filter of the present invention comprises above-mentioned black matrix".
The 4th object of the present invention is to provide a kind of liquid crystal display cells.
Liquid crystal display cells of the present invention comprises above-mentioned colored filter.
Beneficial effect of the present invention is: by using this resin with unsaturated group (A-1), black pigment (D-1) and blue pigment (D-2), and the weight ratio scope of black pigment (D-1) use amount and blue pigment (D-2) use amount is 0.5 to 10, make this photosensitive resin composition there is high sensitivity, and the black matrix" being formed by this photosensitive resin composition has high light-proofness and high resolving power, and then make the liquid crystal display cells that comprises this black matrix" there is the display quality of good contrast and high image quality.
Embodiment
In this article, should represent acrylic acid (acrylic acid) and/or methacrylic acid (methacrylic acid) by (methyl) acrylic acid [(meth) acrylic acid]; Should represent acrylate (acrylate) and/or methacrylate (methacrylate) by (methyl) acrylate [(meth) acrylate]; Should represent acryloyl group (acryloyl group) and/or methacryl (methacryloyl group) by (methyl) acryloyl group [(meth) acryloyl group].
Photosensitive resin composition of the present invention, comprises:
Alkali soluble resin component (A), comprise the resin (A-1) with unsaturated group, this resin (A-1) with unsaturated group is obtained through polyreaction by potpourri, this potpourri comprises the epoxy compound (i) with at least two epoxy radicals, and has the compound (ii) of at least one carboxylic acid group and at least one ethene unsaturated group;
Containing the compound (B) of ethene unsaturated group;
Light initiator (C);
Pigment component (D); And
Solvent (E);
This pigment component (D) comprises black pigment (D-1) and blue pigment (D-2), and the weight ratio scope of this black pigment (D-1) use amount and blue pigment (D-2) use amount is 0.5 to 10.
Preferably, total amount based on this alkali soluble resin component (A) is 100 weight portions, this content range with the resin (A-1) of unsaturated group is 50 to 100 weight portions, should be 30 to 300 weight portions containing the use amount scope of the compound (B) of ethene unsaturated group, the use amount scope of this pigment component (D) is 100 to 1000 weight portions, and the use amount scope of this solvent (E) is 1000 to 5000 weight portions.
Below by one by one for each composition further instruction in photosensitive resin composition of the present invention:
<< alkali soluble resin component (A) >>
[thering is the resin (A-1) of unsaturated group]
Same as above, it is obtained that this resin (A-1) with unsaturated group carries out polyreaction by this potpourri, this potpourri is except comprising this epoxy compound with at least two epoxy radicals (i), and this has outside the compound (ii) of at least one carboxylic acid group and at least one ethene unsaturated group, this potpourri also optionally comprises carboxylic acid anhydrides based compound (iii) and/or has the epoxy compound (iv) of an epoxy radicals.To be described further for this epoxy compound (iv) that there is the epoxy compound (i) of at least two epoxy radicals, the compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group, carboxylic acid anhydrides based compound (iii) and there is an epoxy radicals below.
< has epoxy compound (i) > of at least two epoxy radicals
Preferably, this epoxy compound (i) with at least two epoxy radicals is selected from the epoxy compound with at least two epoxy radicals shown in the epoxy compound with at least two epoxy radicals shown in formula (I), formula (II), or their combination:
R 1, R 2, R 3and R 4represent independently of one another hydrogen, halogen, C 1to C 5alkyl, C 1to C 5alkoxy, C 6to C 12aromatic radical or C 7to C 12aralkyl (aralkyl group).
R 5to R 18represent independently of one another hydrogen, halogen, C 1to C 8alkyl or C 6to C 15aromatic radical, n represents 0 to 10 integer.
Preferably, this epoxy compound (i) with at least two epoxy radicals is the epoxy compound with at least two epoxy radicals shown in formula (I).The epoxy compound with at least two epoxy radicals shown in this formula (I) is same as above, so repeat no more.
Preferably, this epoxy compound (i) with at least two epoxy radicals is the epoxy compound with at least two epoxy radicals shown in formula (II).The epoxy compound with at least two epoxy radicals shown in this formula (II) is same as above, so repeat no more.
In more detail, the epoxy compound with at least two epoxy radicals shown in this formula (I) such as but not limited to: made through polyreaction by the first reactant that comprises bisphenol fluorene type compound (bisphenol fluorene) and halogenation epoxypropane (epihalohydrin) containing the bisphenol fluorene type compound of epoxy radicals.
This bisphenol fluorene type compound can be used alone or as a mixture, such as but not limited to: 9, two (4-hydroxy phenyl) fluorenes [9 of 9-, 9-bis (4-hydroxyphenyl) fluorene], 9, two (the 4-hydroxy-3-methyl phenyl) fluorenes [9 of 9-, 9-bis (4-hydroxy-3-methylphenyl) fluorene], 9, two (4-hydroxyl-3-chlorphenyl) fluorenes [9 of 9-, 9-bis (4-hydroxy-3-chlorophenyl) fluorene], 9, two (4-hydroxyl-3-bromophenyl) fluorenes [9 of 9-, 9-bis (4-hydroxy-3-bromophenyl) fluorene], 9, two (4-hydroxyl-3-fluorophenyl) fluorenes [9 of 9-, 9-bis (4-hydroxy-3-fluorophenyl) fluorene], 9, two (the 4-hydroxy 3-methoxybenzene base) fluorenes [9 of 9-, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene], 9, two (4-hydroxyl-3 of 9-, 5-3,5-dimethylphenyl) fluorenes [9, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene], 9, two (4-hydroxyl-3 of 9-, 5-dichlorophenyl) fluorenes [9, 9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene], or 9, two (4-hydroxyl-3 of 9-, 5-dibromo phenyl) fluorenes [9, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene] etc.
This halogenation epoxypropane can be used alone or as a mixture, chloro-1 such as but not limited to: 3-, and 2-epoxypropane (epichlorohydrin) or 3-are bromo-1,2-epoxypropane (epibromohydrin) etc.
Should can be used alone or as a mixture containing the bisphenol fluorene type compound of epoxy radicals, such as but not limited to: (1). the commodity that Nippon Steel's chemistry is manufactured, for example: ESF-300 etc.; (2). the commodity that Osaka gas is manufactured, for example: PG-100, EG-210 etc.; (3) commodity that .S.M.S Technology Co. manufactures, for example: SMS-F9PhPG, SMS-F9CrG, SMS-F914PG etc.
In more detail, the epoxy compound with at least two epoxy radicals shown in this formula (II) such as but not limited to: the second reactant by compound, halogenation epoxypropane and the alkali metal hydroxide shown in contained (II-1) reacts obtained.In more detail, this reaction is under the existence of alkali metal hydroxide, uses the compound shown in excessive halogenation epoxypropane and this formula (II-1) to carry out de-hydrogen halide (dehydrohalogenation).
Compound shown in this formula (II-1):
R 5to R 18represent independently of one another hydrogen, halogen, C 1to C 8alkyl or C 6to C 15aromatic radical, n represents 0 to 10 integer.
More particularly, compound shown in this formula (II-1) be by the second reactant of the compound shown in contained (II-2), phenol (phenol) compounds and acid catalyst through condensation reaction obtained its, the compound shown in this formula (II-2):
R 19and R 20represent independently of one another hydrogen atom, halogen atom, C 1to C 8alkyl or C 6to C 15aromatic radical; X 1and X 2represent independently of one another halogen atom, C 1to C 6alkyl or C 1to C 6alkoxy.Preferably, this halogen atom is chlorine or bromine.This C 1to C 8alkyl and C 1to C 6alkyl be methyl, ethyl or the tert-butyl group.This C 1to C 6alkoxy be methoxy or ethoxy.
This phenolic compound can be used alone or as a mixture, such as but not limited to: phenol (phenol), cresols (cresol), diethylstilbestrol (ethylphenol), n-the 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), encircle penta phenol (cyclopentylphenol), cyclohexyl phenol (cyclohexylphenol) or cyclohexyl cresols (cyclohexylcresol) etc.
The total amount of the compound based on shown in this formula (II-2) is 1 mole, and the use amount scope of this phenolic compound is 0.5 mole to 20 moles.Preferably, the use amount scope of this phenolic compound is 2 moles to 15 moles.
This acid catalyst can be used alone or as a mixture, such as but not limited to: hydrochloric acid, sulfuric acid, p-toluenesulfonic acid (p-toluenesulfonic acid), oxalic acid (oxalic acid), boron trifluoride (boron trifluoride), anhydrous Aluminum chloride (aluminium chloride anhydrous) or zinc chloride (zinc chloride) etc.Preferably, this acid catalyst is selected from p-toluenesulfonic acid, sulfuric acid or hydrochloric acid.There is no particular restriction for the use amount of this acid catalyst.Preferably, the total amount of the compound based on shown in this formula (II-2) is 100wt%, and the use amount scope of this acid catalyst is 0.1 to 30wt%.
This condensation reaction can be carried out under solvent-free or existence at organic solvent.This organic solvent can be used alone or as a mixture, such as but not limited to: toluene (toluene), dimethylbenzene (xylene) or methyl isobutyl ketone (methyl isobutyl ketone) etc.Compound based on shown in this formula (II-2) and the total amount of phenolic compound are 100wt%, and the use amount scope of this organic solvent is 50 to 300wt%, and preferably, the use amount scope of this organic solvent is 100 to 250wt%.In addition, the operating temperature of this condensation reaction is 40 to 180 DEG C, and the running time is 1 hour to 8 hours.After this condensation reaction completes, again the solution that obtains after reaction is carried out to neutralisation treatment or washing is processed, then, by decompression heat treated, unreacted phenolic compound and solvent are heated up in a steamer and removed, concentrate again, obtain the compound shown in formula (II-1).Neutralisation treatment is that the pH value scope of reacted solution is adjusted into 3 to 7, and preferably, pH value scope is 5 to 7.Washing is processed is to use to carry out for the neutralizing agent of alkaline matter, and neutralizing agent is such as but not limited to alkali metal hydroxides such as NaOH (sodiumhydroxide), potassium hydroxide (potassium hydroxide); The alkaline-earth metal oxyhydroxide such as calcium hydroxide (calcium hydroxide), magnesium hydroxide (magnesium hydroxide); The organic amines such as two sub-second triamines (diethylene triamine), Sanya second tetramine (triethylenetetramine), aniline (aniline), phenylenediamine (phenylene diamine); And ammonia (ammonia), sodium dihydrogen phosphate (sodium dihydrogen phosphate) etc.
It is chloro-1 that this halogenation epoxypropane is selected from 3-, and 2-epoxypropane, 3-are bromo-1,2-epoxypropane, or their combination.Carrying out before de-hydrogen halide, can add in advance or in course of reaction, add the alkali metal hydroxide such as NaOH, potassium hydroxide, and operating temperature range is 20 to 120 DEG C, running time scope is 1 hour to 10 hours.
In the concrete example of photosensitive resin composition of the present invention, the alkali metal hydroxide using in de-hydrogen halide can be also alkali metal hydroxide aqueous solution, now, by alkali metal hydroxide aqueous solution continuous adding to reactor, meanwhile, can be under decompression or normal pressure, continuous still water outlet and halogenation epoxypropane, whereby water is removed, and the halogenation epoxypropane that distillation obtains can be back in reactor continuously.
Before above-mentioned de-hydrogen halide carries out, also can add the quaternary ammonium salt of tetramethyl-ammonium chloride (tetramethylammonium chloride), tetramethylammonium bromide (tetramethyl ammonium bromide) or trimethyl benzyl ammonia chloride (trimethyl benzyl ammonium chloride) etc. as catalyzer, and at 50 to 150 DEG C, react 1 hour to 5 hours, add again alkali metal hydroxide or alkali metal hydroxide aqueous solution, at the temperature of 20 DEG C to 120 DEG C, react 1 hour to 10 hours, to carry out de-hydrogen halide.
Hydroxyl total yield in compound based on shown in this formula (II-1) is 1 equivalent, and the use amount scope of this halogenation epoxypropane is 1 to 20 equivalent.Preferably, the use amount scope of this halogenation epoxypropane is 2 to 10 equivalents.Hydroxyl total yield in compound based on shown in this formula (II-1) is 1 equivalent, and the use amount scope of this alkali metal hydroxide is 0.8 to 15 equivalent.Preferably, the use amount scope of this alkali metal hydroxide is 0.9 to 11 equivalent.
In addition, for de-hydrogen halide is carried out smoothly, except also adding the alcohols such as methyl alcohol or ethanol, the polar solvent etc. that also can add the non-proton property (aprotic) such as dimethyl sulfone (dimethyl sulfone), dimethyl sulfoxide (dimethyl sulfoxide) reacts.Using in the example of alcohols, the total amount based on this halogenation epoxypropane is 100wt%, and the use amount scope of this alcohols is 2 to 20wt%.Preferably, the use amount scope of this alcohols is 4 to 15wt%.Using in the example of polar solvent of non-proton property, the total amount based on this halogenation epoxypropane is 100wt%, and the use amount scope of the polar solvent of this non-proton property is 5 to 100wt%.Preferably, the use amount scope of the polar solvent of this non-proton property is 10 to 90wt%.
After de-hydrogen halide completes, can optionally wash processing.Then, utilize the mode of heating decompression, for example: be that 110 to 250 DEG C and pressure are below 1.3kPa (10mmHg) in temperature, remove the polar solvent of halogenation epoxypropane, alcohols and non-proton property etc.
Affect physical property for fear of having unreacted initiation material as halogenation epoxypropane, solution after de-hydrogen halide can be added to toluene or methyl isobutyl ketone (methyl isobutyl ketone) 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, hydroxyl total yield in compound based on shown in this formula (II-1) is 1 equivalent, the use amount scope of this alkali metal hydroxide is 0.01 to 0.3 mole, and preferably, the use amount scope of this alkali metal hydroxide is 0.05 to 0.2 mole.In addition, the operating temperature range of de-hydrogen halide is 50 to 120 DEG C, and running time scope is 0.5 hour to 2 hours.
After de-hydrogen halide completes, then by filtering and the step such as washing is removed salt.And utilize the mode of heating decompression, by toluene, methyl isobutyl ketone equal solvent is heated up in a steamer removes, and obtains the epoxy compound with at least two epoxy radicals shown in this formula (II).The commercially available product of the epoxy compound with at least two epoxy radicals shown in this formula (II) is such as but not limited to NC-3000, NC-3000H, NC-3000S and the NC-3000P etc. of Japanese chemical drug system.
< has compound (ii) > of at least one carboxylic acid group and at least one ethene unsaturated group
This compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group can be used alone or as a mixture, such as but not limited to (1). acrylic acid, methacrylic acid, 2-methylacryoyloxyethyl succinic acid (2-methacryloyloxyethylbutanedioic acid), 2-methacryl oxygen-butyl succinic acid, 2-methylacryoyloxyethyl hexane diacid, 2-methacryl oxygen-butyl hexane diacid, 2-methylacryoyloxyethyl hexahydrophthalic acid, 2-methylacryoyloxyethyl maleic acid, 2-methacryloxypropyl maleic acid, 2-methacryl oxygen-butyl maleic acid, 2-methacryloxypropyl succinic acid, 2-methacryloxypropyl hexane diacid, 2-methacryloxypropyl tetrahydrophthalic acid, 2-methacryloxypropyl phthalic acid, 2-methacryl oxygen-butyl phthalic acid, or 2-methacryl oxygen-butyl hydrogen phthalic acid, or (2). by (methyl) acrylate of hydroxyl react with dicarboxylic acids compound and compound, this dicarboxylic acids compound is such as but not limited to hexane diacid, succinic acid, maleic acid or phthalic acid etc., or (3). by (methyl) acrylate of hydroxyl react with carboxylic acid anhydrides based compound (iii) and half ester compounds, (methyl) acrylate of this hydroxyl is such as but not limited to 2-hydroxyethylmethacry,ate [(2-hydroxyethyl) acrylate], 2-HEMA [(2-hydroxyethyl) methacrylate], 2-hydroxypropyl 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.
This compound carboxylic acid anhydride (iii) is selected from dicarboxylic acid anhydride compound, quaternary compound carboxylic acid anhydride, or their combination.This dicarboxylic acid anhydride compound can be used alone or as a mixture, such as but not limited to succinic anhydride (butanedioic anhydride), maleic anhydride (maleic anhydride), itaconic anhydride (Itaconicanhydride), phthalic anhydride (phthalic anhydride), tetrabydrophthalic anhydride (tetrahydrophthalic anhydride), hexahydrophthalic anhydride (hexahydrophthalicanhydride), methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl Nadic anhydride (methyl endo-methylene tetrahydro phthalic anhydride), chlorendic anhydride (chlorendic anhydride) or glutaric anhydride or inclined to one side three benzoyl oxides (1, 3-dioxoisobenzofuran-5-carboxylic anhydride) etc.This quaternary compound carboxylic acid anhydride can be used alone or as a mixture, such as but not limited to benzophenone tetracarboxylic acid dianhydride (benzophenonetetracarboxylic dianhydride is called for short BTDA), two pyromellitic dianhydride or two phenylate tetracarboxylic acid dianhydrides etc.
< carboxylic acid anhydrides based compound (iii) >
This carboxylic acid anhydrides based compound (iii) is as mentioned above, so repeat no more.
< has epoxy compound (iv) > of an epoxy radicals
This epoxy compound (iv) with an epoxy radicals is selected from glytidyl methacrylate, 3,4-epoxy radicals cyclohexyl methyl acrylate, containing the glycidyl ether compound of unsaturated group, containing the unsaturated compound of epoxy radicals, or their combination.Should be containing commercially available prod of the glycidyl ether compound of unsaturated group such as but not limited to long rapids Denacol EX-111, EX-121Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, DenacolEX-192 etc. that change into Industrial Co., Ltd's system.
This resin (A-1) with unsaturated group can carry out polyreaction (operating temperature range is 50 DEG C to 130 DEG C) by the epoxy compound with at least two epoxy radicals shown in 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, then add carboxylic acid anhydrides based compound (iii) and react obtained.Preferably, the hydroxyl total yield of the reaction product based on this hydroxyl is 1 equivalent, the anhydride group in this carboxylic acid anhydrides based compound (iii) when weight range be 0.4 to 1 equivalent.More preferably, the anhydride group in this carboxylic acid anhydrides based compound (iii) when weight range be 0.75 to 1 equivalent.In the time using more than one this carboxylic acid anhydrides based compound (iii), in reaction, sequentially add or add simultaneously.Preferably, when this carboxylic acid anhydrides based compound (iii) uses dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride, dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride's molar ratio scope is 1/99 to 90/10.More preferably, dicarboxylic acid anhydride compound and quaternary compound carboxylic acid anhydride's molar ratio scope is 5/95 to 80/20.
This resin (A-1) with unsaturated group can be reacted with the compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group by the epoxy compound with at least two epoxy radicals shown in formula (II), form the reaction product of a hydroxyl, then, then the epoxy compound (iv) that adds carboxylic acid anhydrides based compound (iii) and/or there is an epoxy radicals to carry out polyreaction obtained.Preferably, the epoxy radicals total yield of the epoxy compound with at least two epoxy radicals based on shown in formula (II) is 1 equivalent, and this acid value equivalent with the compound (ii) of at least one carboxylic acid group and at least one ethene unsaturated group is 0.8 to 1.5 equivalent.More preferably, be 0.9 to 1.1 equivalent.The hydroxyl total amount of the reaction product based on this hydroxyl is 100 % by mole, and the use amount scope of this carboxylic acid anhydrides based compound (iii) is 10 to 100 % by mole, preferably, is 20 to 100 % by mole, more preferably, is 30 to 100 % by mole.
When this has the resin (A-1) of unsaturated group in preparation, be accelerated reaction, conventionally can in reaction solution, add alkali compounds as catalysts.This catalysts can be used alone or as a mixture, such as but not limited to: triphenylphosphine (triphenyl phosphine), antimony triphenyl (triphenyl stibine), triethylamine (triethylamine), triethanolamine (triethanolamine), tetramethyl ammonium chloride (tetramethylammonium chloride) or benzyltriethylammonium chloride (benzyltriethylammoniumchloride) etc.Preferably, be 100 weight portions based on this epoxy compound (i) with at least two epoxy radicals with the total amount of the compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group, the use amount scope of this catalysts is 0.01 to 10 weight portion, more preferably, be 0.3 to 5 weight portion.
In addition,, in order to control the degree of polymerization, conventionally also can in reaction solution, add polymerization inhibitor.This polymerization inhibitor can be used alone or as a mixture, such as 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.Be 100 weight portions based on this epoxy compound (i) with at least two epoxy radicals with the total amount of the compound (ii) with at least one carboxylic acid group and at least one ethene unsaturated group, the use amount scope of this polymerization inhibitor is 0.01 to 10 weight portion, preferably, be 0.1 to 5 weight portion.
When this has the resin (A-1) of unsaturated group in preparation, can use if desired polymerization solvent.This polymerization solvent can be used alone or as a mixture, such as but not limited to: the 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; Cellosolve (cellosolve) compounds such as cellosolve or butyl cellosolve (butylcellosolve); Card must appropriate (carbitol) or butyl card must appropriate (butylcarbito) etc. card must appropriate (carbitol) compounds; The propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether; Many propylene glycol alkyls ether [poly (propylene glycol) alkyl ether] compounds such as dipropylene glycol monomethyl ether [di (propylene glycol) methyl ether]; The acetic ester compounds such as ethyl acetate, butyl acetate, ethylene glycol ether acetate (ethylene glycol monoethyl ether acetate) or 1-Methoxy-2-propyl acetate (propylene glycol methyl ether acetate); Lactic acid alkane ester (alkyl lactate) compounds such as ethyl lactate (ethyllactate) or butyl lactate (butyl lactate); Or dialkyl group glycol ethers.In addition, this acid value scope with the resin (A-1) of unsaturated group is 50mgKOH/g to 200mgKOH/g, preferably, is 60mgKOH/g to 150mgKOH/g.
Because this resin (A-1) with unsaturated group has good thermotolerance, and contain that unsaturated link also can carry out cross-linking reaction and the sensitivity that can promote this photosensitive resin composition, and the black matrix" being formed by this photosensitive resin composition has good resolution, therefore, when this photosensitive resin composition does not use this resin with unsaturated group (A-1), can make the sensitivity of photosensitive compoistion not good, and the black matrix" being formed by this photosensitive resin composition have the not good shortcoming of resolution.Preferably, the total amount based on this alkali soluble resin (A) component is 100 weight portions, and this content range with the resin (A-1) of unsaturated group is 50 to 100 weight portions, preferably, being 60 to 100 weight portions, more preferably, is 70 to 100 weight portions.
[other alkali soluble resins (A-2)]
This alkali soluble resin component (A) also comprises other alkali soluble resins (A-2).These other alkali soluble resins (A-2) are such as but not limited to the resin containing carboxylic acid group or hydroxyl, and concrete example is: this resin (A-1) with unsaturated group acrylic resin, polyurethane (urethane) is in addition resin or phenolic varnish type (novolac) resin etc.
Total amount based on this alkali soluble resin component (A) is 100 weight portions, and the content range of these other alkali soluble resins (A-2) is 0 to 50 weight portion, preferably, is 0 to 40 weight portion, more preferably, is 0 to 30 weight portion.
<< is containing compound (B) >> of ethene unsaturated group
Total amount based on this alkali soluble resin component (A) is 100 weight portions, should be 30 weight portion to 300 weight portions containing the use amount scope of the compound (B) of ethene unsaturated group.In the time that this use amount containing the compound (B) of ethene unsaturated group is less than 30 weight portion, this photosensitive resin composition crosslinking degree deficiency, and cannot form the black matrix" of predetermined pattern; In the time that this use amount containing the compound (B) of ethene unsaturated group is greater than 300 weight portion, the sensitivity of this photosensitive compoistion is too high, makes not irradiation place after developing, easily have residue to produce.Preferably, the total amount based on this alkali soluble resin component (A) is 100 weight portions, should be 40 weight portion to 280 weight portions containing the use amount scope of the compound (B) of ethene unsaturated group.More preferably, the total amount based on this alkali soluble resin component (A) is 100 weight portions, should be 50 weight portion to 260 weight portions containing the use amount scope of the compound (B) of ethene unsaturated group.
Should containing compound (B) of ethene unsaturated group be selected from have an ethene unsaturated group compound (B-1), there is the compounds (B-2) of two above (containing two) ethene unsaturated groups or their combination.
This compound (B-1) with an ethene unsaturated group can be used alone or as a mixture, Li as but Bu Xian Yu ︰ (methyl) acrylamide [(meth) acrylamide), (methyl) acryloyl morpholine, (methyl) acrylic acid-7-amino-3,7-dimethyl monooctyl ester, isobutoxy methyl (methyl) acrylamide, (methyl) acrylic acid isobornyl 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) acrylic acid dimethylamino ethyl ester, (methyl) dodecylacrylate, (methyl) acrylic acid two cyclopentene oxygen base ethyl esters, (methyl) acrylic acid two cyclopentene esters, 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) acrylic acid phenoxy ethyl, (methyl) Pentachlorophenyl Acrylate, (methyl) acrylic acid pentabromo-phenyl ester, poly-single (methyl) acrylic acid second diester, poly-single (methyl) acrylic acid propylene diester or (methyl) acrylic acid norbornene ester etc.
This compound (B-2) with two above (containing two) ethene unsaturated groups can be used alone or as a mixture, Li as but Bu Xian Yu ︰ ethylene glycol bisthioglycolate (methyl) acrylate, two (methyl) acrylic acid, two cyclopentene esters, 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, through 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 ethane via epoxyethane (being called for short EO) upgrading, through epoxypropane upgrading three (methyl) acrylic acid trihydroxy methyl propyl ester of (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, through dipentaerythritol six (methyl) acrylate of caprolactone upgrading, through 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 or novolaks polyglycidyl ether (methyl) acrylate etc.
Should be selected from three acrylic acid trihydroxy methyl propyl ester of three acrylic acid trihydroxy methyl propyl ester, ethane via epoxyethane upgrading, three acrylic acid trihydroxy methyl propyl ester through epoxypropane upgrading, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, dipentaerythritol five acrylate, dipentaerythritol tetraacrylate, dipentaerythritol acrylate through caprolactone upgrading, tetrapropylene acid two trihydroxy methyl propyl ester, glycerol tri-acrylate through epoxypropane upgrading containing compound (B) of ethene unsaturated group, or their combination.
<< light initiator (C) >>
This light initiator (C) can be used alone or as a mixture, such as but not limited to: O-acyl group oxime compound (C-1), triazine based compound, vinylbenzene ketone based compound, diimidazole based compound, benzophenone based compound, α-diketone based compound, keto-alcohol based compound, keto-alcohol ether based compound, acyl phosphine oxide based compound, quinone based compound, halogen-containing based compound, superoxide etc.
This O-acyl group oxime compound (C-1) can be used alone or as a mixture, such as but not limited to: 1-[4-(phenyl sulfo-) phenyl]-heptane-1, 2-diketone 2-(O-benzoyl group oxime), 1-[4-(phenyl sulfo-) phenyl]-octane-1, 2-diketone 2-(O-benzoyl group oxime) (for example OXE01 of Ciba Specialty Chemicals system), 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) (for example OXE02 of Ciba Specialty Chemicals system), 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-4-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-5-THP trtrahydropyranyl 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), or ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxa penta cyclic group) methoxybenzene acyl group }-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime) etc.
Preferably, this O-acyl group oxime compound (C-1) is selected from 1-[4-(phenyl sulfo-) phenyl]-octane-1, 2-diketone 2-(O-benzoyl group oxime) [OXE01, Ciba Specialty Chemicals system], 1-[9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-substituting group]-ethane ketone 1-(O-acetyl group oxime) [OXE02, CibaSpecialty Chemicals system], ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran methoxybenzene acyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime), or ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxa penta cyclic group) methoxybenzene acyl group }-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime).
This triazine based compound can be used alone or as a mixture, such as but not limited to: vinyl-halogenated methyl-s-triazine compound, 2-(naphtho--1-substituting group)-4,6-pair-halogenated methyl-s-triazine compound, or 4-(p-aminophenyl)-2,6-bis--halogenated methyl-s-triazine compound etc.
This vinyl-halogenated methyl-s-triazine compound can be used alone or as a mixture, such as but not limited to: 2, two (the trichloromethyl)-6-p-methoxystyrene base-s-triazines, 2 of 4-, two (the trichloromethyl)-3-of 4-(p-dimethylaminophenyl-1 of 1-, 3-butadienyl)-s-triazine, or 2-trichloromethyl-3-amino-6-p-methoxystyrene base-s-triazine etc.
This 2-(naphtho--1-substituting group)-4, 6-pair-halogenated methyl-s-triazine compound can be used alone or as a mixture, such as but not limited to: 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, or 2-(4, 5-dimethoxy-naphtho--1-substituting group)-4, 6-pair-trichloromethyl-s-triazine etc.
This 4-(p-aminophenyl)-2, 6-bis--halogenated methyl-s-triazine compound can be used alone or as a mixture, such as but not limited to: the p-N of 4-[, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the o-methyl of 4-[-p-N, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the p-N of 4-[, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the o-methyl of 4-[-p-N, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-(p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(p-N-ethoxy carbonyl methylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, the p-N of 4-[, N-bis-(phenyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-(p-N-chloroethyl carbonylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, the p-N-of 4-[(p-methoxyphenyl) carbonylamino phenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the m-N of 4-[, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the m-bromo-p-N of 4-[, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the m-chloro-p-N of 4-[, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the m-fluoro-p-N of 4-[, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the o-bromo-p-N of 4-[, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the o-chloro-p-N of 4-[, N-bis-(ethoxy carbonyl methyl) aminophenyl-2, 6-bis-(trichloromethyl)-s-triazine, the o-fluoro-p-N of 4-[, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the o-bromo-p-N of 4-[, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the o-chloro-p-N of 4-[, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the o-fluoro-p-N of 4-[, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the m-bromo-p-N of 4-[, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the m-chloro-p-N of 4-[, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, the m-fluoro-p-N of 4-[, N-bis-(chloroethyl) aminophenyl]-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-bromo-p-N-ethoxy carbonyl methylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-chloro-p-N-ethoxy carbonyl methylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-fluoro-p-N-ethoxy carbonyl methylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-bromo-p-N-ethoxy carbonyl methylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-chloro-p-N-ethoxy carbonyl methylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-ethoxy carbonyl methylamino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-bromo-p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-chloro-p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(m-fluoro-p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-bromo-p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-chloro-p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, 4-(o-fluoro-p-N-chloroethyl amino phenyl)-2, 6-bis-(trichloromethyl)-s-triazine, or 2, the two bromo-4-[N of (trichloromethyl)-6-[3-of 4-, two (ethoxy carbonyl methyl) amino of N-] phenyl]-1, 3, 5-triazine etc.
Preferably, this triazine based compound is selected from the m-bromo-p-N of 4-[, N-bis-(ethoxy carbonyl methyl) aminophenyl]-2, two (the trichloromethyl)-6-p-methoxystyrene base-s-triazines of 6-bis-(trichloromethyl)-s-triazine or 2,4-.
This vinylbenzene ketone based compound can be used alone or as a mixture, such as but not limited to: to dimethylamino vinylbenzene ketone, α, α '-dimethoxy azoxy vinylbenzene ketone, 2,2 '-dimethyl-2-phenyl vinylbenzene ketone, p-methoxybenzene ethane ketone, 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino-1-acetone, or 2-benzyl-2-N, N-dimethylamino-1-(4-morpholino phenyl)-1-butanone etc.Preferably, this vinylbenzene ketone based compound is selected from 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino-1-acetone, or 2-benzyl-2-N, N-dimethylamino-1-(4-morpholino phenyl)-1-butanone.
This diimidazole based compound can be used alone or as a mixture, such as but not limited to: 2, 2 '-bis-(o-chlorphenyls)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(ortho-fluorophenyl bases)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-aminomethyl phenyls)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-methoxyphenyls)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(o-ethylphenyls)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(p-methoxyphenyls)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(2, 2 ', 4, 4 '-tetramethoxy phenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, 2, 2 '-bis-(2-chlorphenyls)-4, 4 ', 5, 5 '-tetraphenyl diimidazole, or 2, 2 '-bis-(2, 4-dichlorophenyl)-4, 4 ', 5, 5 '-tetraphenyl diimidazole etc.Preferably, this diimidazole compounds is 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole.
This benzophenone based compound can be used alone or as a mixture, such as but not limited to: thioxanthones, 2,4-diethyl thioxanthone, thioxanthones-4-sulfone, benzophenone, 4,4 '-bis-(dimethylamino) benzophenone or 4,4 '-bis-(lignocaine) benzophenone etc.Preferably, this benzophenone based compound is 4,4 '-bis-(lignocaine) benzophenone.
This α-diketone based compound is such as but not limited to benzil or acetyl group etc.This keto-alcohol based compound is such as but not limited to diphenylhydroxyethanone.This keto-alcohol ether based compound is such as but not limited to diphenylhydroxyethanone methyl ether, diphenylhydroxyethanone ether or diphenylhydroxyethanone isopropyl ether etc.This acyl phosphine oxide based compound is such as but not limited to 2,4,6-trimethyl benzoyl diphenyl phosphine oxide or two-(2,6-dimethoxy benzoyl)-2,4,4-trimethylphenyl phosphine oxide etc.This quinone based compound is such as but not limited to anthraquinone, 1,4-naphthoquinone etc.This halogen-containing based compound is such as but not limited to chloroacetophenone, trisbromomethyl benzene sulfone or three (trichloromethyl)-s-triazine etc.This superoxide is such as but not limited to two-tert-butyl peroxide etc.Above-mentioned α-diketone based compound, keto-alcohol based compound, keto-alcohol ether based compound, acyl phosphine oxide based compound, quinone based compound, halogen-containing based compound, superoxide etc. can be used alone or as a mixture.
The use amount of this light initiator (C) can be allocated according to need, preferably, is 100 weight portions based on this total amount containing the compound (B) of second unsaturated group, and the use amount scope of this light initiator (C) is 10 to 60 weight portions.More preferably, the total amount of the compound (B) based on containing ethene unsaturated group is 100 weight portions, and the use amount scope of this light initiator (C) is 15 to 55 weight portions.Again more preferably, the total amount of the compound (B) based on containing ethene unsaturated group is 100 weight portions, and the use amount scope of this light initiator (C) is 20 to 50 weight portions.
<< pigment component (D) >>
The use amount scope of this pigment component (D) is 100 to 1000 weight portions.The use amount of this pigment component (D) is during lower than 100 weight portion, and the light-proofness of the black matrix" being formed by this photosensitive resin composition is not good.And the use amount of this pigment component (D) is during higher than 1000 weight portion, can make the viscosity of photosensitive resin composition too high, will coat on substrate so that follow-up time, be difficult for evenly scattering, and be unfavorable for forming film or cause formed uneven film thickness on this substrate.
Preferably, the total amount based on this alkali soluble resin component (A) is 100 weight portions, and the use amount scope of this black pigment (D-1) is 50 to 600 weight portions, is preferably 75 to 500 weight portions, is more preferred from 100 to 400 weight portions; The use amount scope of this blue pigment (D-2) is 50 to 400 weight portions, is preferably 60 to 350 weight portions, is more preferred from 70 to 300 weight portions.If do not use black pigment (D-1) completely, the light-proofness of the black matrix" being formed by this photosensitive resin composition is not good; If do not use blue pigment (D-2) completely, the sensitivity of this photosensitive resin composition is not good, and the resolution of the black matrix" forming is not good.
Pigment component (D) in this photosensitive resin composition is used this blue pigment (D-2) in the time of exposure, making wavelength coverage is that 325 to 380nm luminous energy marches to and the photosensitive resin composition of substrate contacts, cause the cross-linking reaction degree of the photosensitive resin composition at this place to promote, then promote the sensitivity of overall photosensitive resin composition, therefore after developing, can make the wire spoke that is less than 4 μ m stay on substrate, and improve the resolution of black matrix".
In the time that the weight ratio of this black pigment (D-1) use amount and blue pigment (D-2) use amount is less than 0.5, the light-proofness of the black matrix" being formed by this photosensitive resin composition is not good.In the time that the weight ratio of this black pigment (D-1) use amount and blue pigment (D-2) use amount is greater than 10, the sensitivity of this photosensitive resin composition is not good, and the resolution of the black matrix" being formed by this photosensitive resin composition is not good.Below will do more detailed description for this black pigment (D-1) and this blue pigment (D-2):
[black pigment (D-1)]
This black pigment (D-1) is to have thermotolerance, photostability and solvent resistance person as good.
This black pigment (D-1) can be used alone or as a mixture, such as but not limited to: (1). black organic pigment, for example: perylene black (perylene black), cyanine black (cyanine black) or nigrosine (anilineblack) etc.; (2). in the pigment such as red, blue, green, purple, yellow, cyanine (cyanine) or fuchsin (magenta), select two or more pigment to mix, make the colour mixture organic pigment of nearly black; (3). lightproof material, for example: carbon black (carbon black), chromium oxide, iron oxide, titanium black (titanium black) or graphite etc., carbon black such as but not limited to: C.I. pigment blacks 7 etc., concrete example is MA100, MA230, MA8, #970, #1000, #2350 and the #2650 of Mitsubishi Chemical's system.
[blue pigment (D-2)]
The selection of this blue pigment (D-2), the not absorbing wavelength scope that is preferably is the light source below 380nm.This blue pigment can be used alone or as a mixture, such as but not limited to blue pigment or indanthrone blue (indanthrone blue) blue pigment with copper phthalocyanine structure.This blue pigment with copper phthalocyanine structure is such as but not limited to C.I. pigment blue 15: 1 (C.I.PB15:1), C.I. pigment blue 15: 2 (C.I.PB15:2), C.I. pigment blue 15: 3 (C.I.PB15:3), C.I. pigment blue 15: 4 (C.I.PB15:4), C.I. pigment blue 15: 5 (C.I.PB15:5), or C.I. pigment blue 15: 6 (C.I.PB15:6) etc.
This pigment component also comprises violet pigment and/or red pigment.
The selection of this violet pigment, the not absorbing wavelength scope that is preferably is the light source below 380nm.This violet pigment can be used alone or as a mixture, such as but not limited to: C.I. pigment violet 14 (C.I.PV14), C.I. pigment violet 19 (C.I.PV19), C.I. pigment Violet 23 (C.I.PV23), C.I. pigment violet 29 (C.I.PV29), C.I. pigment violet 32 (C.I.PV32), C.I. pigment violet 33 (C.I.PV33), C.I. pigment violet 36 (C.I.PV36), C.I. pigment violet 37 (C.I.PV37), C.I. pigment violet 38 (C.I.PV38), C.I. pigment violet 40 (C.I.PV40), or C.I. pigment violet 50 (C.I.PV50) etc.
This red pigment be selected from there is the red pigment of azo condensation structure, the red pigment with anthraquinone ring, quinacridone red pigment, perylene be red pigment, pyrrole anthracene-8,16-diketone is red pigment, or their combination.This red pigment with azo condensation structure can be used alone or as a mixture, such as but not limited to: C.I. pigment Red 83 (C.I.Pigment red83), C.I. pigment Red 89 (C.I.Pigment red89), or C.I. paratonere 177 (C.I.Pigment red177) etc.Preferably, this red pigment with azo condensation structure is selected from C.I. pigment Red 89, C.I. paratonere 177, or their combination.This red pigment with green onion quinone structure can be used alone or as a mixture, such as but not limited to: C.I. paratonere 144 (C.I.Pigmentred144), C.I. paratonere 166 (C.I.Pigment red166), 214 (C.I.Pigment red214), C.I. paratonere 220 (C.I.Pigment red220), C.I. paratonere 221 (C.I.Pigment red221), C.I. paratonere 242 (C.I.Pigment red242), C.I. paratonere 248 (C.I.Pigment red248), or C.I. paratonere 262 (C.I.Pigment red262) etc.Preferably, this red pigment with green onion quinone structure is selected from C.I. paratonere 166, C.I. paratonere 242, or their combination.
<< solvent (E) >>
This solvent (E) is can dissolve this alkali soluble resin component (A), containing compound (B), light initiator (C) and the pigment component (D) of ethene unsaturated group, and do not react with mentioned component, and there is suitable volatility person for good.
This solvent (E) can be used alone or as a mixture, such as but not limited to: alkyl diol list alkane ether compound, alkyl diol list alkane ether acetate compounds, other ether compound, ketone compounds, lactic acid alkane ester type compound, other ester type compound, aromatic hydrocarbon compounds, amine carboxylic acid compounds.
This alkyl diol list alkane ether compound can be used alone or as a mixture, such as but not limited to: 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, or Tripropylene glycol monomethyl Ether or tripropylene glycol list ether etc.
This alkyl diol list alkane ether acetate compounds can be used alone or as a mixture, such as but not limited to: glycol methyl ether acetate, ethylene glycol ether acetate or 1-Methoxy-2-propyl acetate, or propylene-glycol ethyl ether acetate etc.
These other ether compound can be used alone or as a mixture, such as but not limited to: diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether or tetrahydrofuran etc.
This ketone compounds can be used alone or as a mixture, such as but not limited to: MEK, cyclohexanone, 2-HEPTANONE, 3-heptanone or diacetone alcohol etc.
This lactic acid alkane ester type compound can be used alone or as a mixture, such as but not limited to: methyl lactate or ethyl lactate etc.
These other ester type compound can be used alone or as a mixture, such as but not limited to: 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 3-methoxy methyl propionate, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxacetic acid ethyl ester, 2-hydroxy-3-methyl methyl butyrate, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butyl propionic ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-Amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate or 2-oxygen base ethyl butyrate etc.
This aromatic hydrocarbon compounds can be used alone or as a mixture, such as but not limited to: toluene or dimethylbenzene etc.
This amine carboxylic acid compounds can be used alone or as a mixture, such as but not limited to: 1-METHYLPYRROLIDONE, DMF or DMA etc.
Preferably, the total amount based on this alkali soluble resin (A) is 100 weight portions, and the use amount scope of this solvent (E) is 1000 weight portion to 5000 weight portions.More preferably, the total amount based on this alkali soluble resin (A) is 100 weight portions, and the use amount scope of this solvent (E) is 1200 weight portion to 4800 weight portions.Again more preferably, the total amount based on this alkali soluble resin (A) is 100 weight portions, and the use amount scope of this solvent (E) is 1500 weight portion to 4500 weight portions.
<< adjuvant (F) >>
Do not affecting under the prerequisite of effect of the present invention, photosensitive resin composition of the present invention also comprises adjuvant (F), such as but not limited to: surfactant, filling agent, adherence promoter, crosslinking chemical, antioxidant, anti-agglutinant, or alkali soluble resin component (A) polymkeric substance in addition and that can increase various character (as engineering properties) etc.
It is that surfactant, negative ion are that surfactant, nonionic are that surfactant, amphoteric surfactant, polysiloxane series surfactant, fluorine are surfactant that this surfactant is selected from kation, or their combination.More particularly, this surfactant is such as but not limited to: polyethoxy alkyl ether, polyethoxy alkyl phenyl ethers, polyethylene glycol di class, sorbitan fatty acid ester class, through the polyesters of fatty acid upgrading, or through the polyurethanes of tertiary amine upgrading.This polyethoxy alkyl ether is such as but not limited to: polyethoxy lauryl ether or polyethoxy hard ester acyl ether or polyethoxy oil ether etc.This polyethoxy alkyl phenyl ethers is such as but not limited to polyethoxy octyl phenyl ether or polyethoxy nonylplenyl ether etc.This polyethylene glycol di class is such as but not limited to polyethylene glycol dilaurate or polyglycol two hard acid esters etc.Above-mentioned surfactant can be used alone or as a mixture.
For example KP of the commercially available product of the surfactant using (SHIN-ETSU HANTOTAI's chemical industry system), SF-8427 (TorayDow Corning Silicon system), Polyflow (common prosperity society oil chemical industry system), F-Top (TochemProduct Co., Ltd. system), Megafac (large Japanese INK chemical industry system), Fluorade (Sumitomo 3M system), Asahi Guard, Surflon (Asahi Glass system) or SINOPOL E8008 (Sino-Japan synthetic chemistry system) etc.
This filling agent can be used alone or as a mixture, such as but not limited to glass or aluminium.
This adherence promoter can be used alone or as a mixture, such as but not limited to vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, 3-aminopropyl triethoxysilane, 3-epoxy prapanol propyl trimethoxy silicane, 3-epoxy prapanol propyl group methyldiethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methyl-prop acyloxy propyl trimethoxy silicane or 3-mercaptopropyl trimethoxysilane etc.
This antioxidant can be used alone or as a mixture, such as but not limited to 2,2-thiobis (4-methyl-6-tert-butylphenol) or 2,6-, bis--tert-butyl phenol etc.
This anti-agglutinant is such as but not limited to sodium polyacrylate.
This crosslinking chemical is such as but not limited to epoxy based compound or the resin etc. of 1031S, the 157S-70 etc. of japan epoxy resin company system.
Total amount based on this alkali soluble resin component (A) is 100 weight portions, the use amount scope of the arbitrary adjuvant in this filling agent, adherence promoter, antioxidant, anti-agglutinant or alkali soluble resin (A) polymkeric substance is in addition 0 weight portion to 10 weight portion, preferably, use amount scope is 0 weight portion to 6 weight portion.
Total amount based on this alkali soluble resin component (A) is 100 weight portions, and the use amount scope of this surfactant is 0 weight portion to 6 weight portion, and preferably, the use amount scope of this surfactant is 0 weight portion to 4 weight portion.
Total amount based on this alkali soluble resin component (A) is 100 weight portions, and the use amount scope of this crosslinking chemical is 0 weight portion to 100 weight portion, and preferably, the use amount scope of this crosslinking chemical is 0 weight portion to 80 weight portion.
There is no particular restriction for the method for making of photosensitive resin composition of the present invention, for example can adopt this alkali soluble resin component (A), be placed in stirrer containing compound (B), light initiator (C), pigment component (D) and the solvent (E) of ethene unsaturated group and stir and mix to form solution state, can add if desired adjuvant (F), evenly mix.Or, for example adopt first this alkali soluble resin component (A), be placed in stirrer containing compound (B), light initiator (C) and the solvent (E) of ethene unsaturated group and stir and mix to form solution, again this pigment component (D) is directly added in this solution and disperseed, obtain photosensitive resin composition of the present invention.Again or first a part of pigment component (D) is scattered in the alkali soluble resin component (A) of part and the solvent (E) of part, form after dispersible pigment dispersion, mix again compound (B), light initiator (C) and remaining alkali soluble resin component (A) and the solvent (E) containing ethene unsaturated group, make photosensitive resin composition of the present invention.
Black matrix" of the present invention is formed by above-mentioned photosensitive resin composition.
When black matrix" thickness of the present invention is 1 μ m, optical density (OD) (optical density is called for short O.D value) scope is more than 3.5; Preferably, when this black matrix" thickness is 1 μ m, optical density (OD) scope is 3.8 to 5.5.
This black matrix" can adopt following order to process and make: (1). photosensitive resin constituent of the present invention is coated on substrate with coating processes such as rotary coating or curtain coating coatings, with drying under reduced pressure (pressure: be less than 200mmHg, processing time: 1 second to 20 seconds), and pre-baked processing (temperature: 70 to 110 DEG C, processing time: 1 minute to 15 minutes) solvent in photosensitive resin constituent (E) is removed, to form pre-baked film on this substrate; (2). for example this pre-baked film is placed under the light shield of appointment, with ultraviolet ray [: g line, h line or i line, ultraviolet lamp is: (surpass) high-pressure mercury-vapor lamp and metal halid lamp] and irradiates and expose; (3). be dipped in development (treatment temperature: 23 ± 2 DEG C in developer, processing time: 15 seconds to 5 minutes), so that unexposed part is removed, then clean with pure water, to form the pattern of light shield of this appointment, then with pressurized air or compressed nitrogen, pattern is air-dry; (4.) for example, carry out rear roasting processing (treatment temperature: 150 to 250 DEG C with heating arrangement (: hot plate or baking oven), processing time: be 150 to 250 DEG C while using hot plate, while using baking oven, be 15 minutes to 150 minutes), on this substrate, form this black matrix".
This developer is such as but not limited to NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sal tartari, saleratus, sodium silicate, sodium methyl silicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethylphosphonihydroxide hydroxide amine, tetraethylamine hydroxide, choline, pyrroles, piperidines or 1,8-diazabicylo-(5,4,0)-7-hendecene etc.The concentration range of this developer solution is 0.001 to 10wt%, and preferably, the concentration range of this developer solution is 0.005 to 5wt%, and more preferably, the concentration range of this developer solution is 0.01 to 1wt%.
The base material applicable in black matrix" of the present invention is: for alkali-free glass, soda-lime glass, hard glass (Pai Lesi glass) and the quartz glass of liquid crystal indicator etc., and in the described person that adheres to nesa coating on glass; Or for example, for photo-electric conversion device substrate (: silicon substrate) of solid-state image sensor etc. etc.
Colored filter of the present invention comprises above-mentioned black matrix".
Colored filter of the present invention is to make according to the mode of general preparation, for example: prior to forming above-mentioned black matrix" on substrate, again (mainly comprising red, green and Lan Sanse) of all kinds is formed on this substrate with identical generation type, and then obtains the pixel dyed layer of colored filter.Then,, under the vacuum of 220 DEG C to 250 DEG C, on this pixel dyed layer, form tin indium oxide (being called for short ITO) vapor-deposited film, if desired, ITO vapor-deposited film is implemented after etching and wiring, then coating of liquid crystalline alignment film polyimide, make the colored filter that liquid crystal display is used.
Liquid crystal display cells of the present invention comprises above-mentioned colored filter.
Liquid crystal display cells of the present invention, by by above-mentioned colored filter be provided with thin film transistor (TFT) (thinfilm transistor; TFT) driving substrate toward each other, and between this colored filter and this driving substrate, get involved cell gap (cell gap) and do subtend configuration, and with sealant by the surrounding position laminating of this colored filter and this driving substrate, only leave Liquid crystal pour hole, then, in the gap that described substrate surface and sealant are distinguished, liquid crystal is injected in filling, then seals this Liquid crystal pour hole and form liquid crystal structure cell (cell).Then, at the outside surface of liquid crystal structure cell, that is to say on other sides of each substrate that forms liquid crystal structure cell, after laminating Polarizer, and make liquid crystal display cells.
The liquid crystal of aforementioned use and liquid crystal orienting film be also not particularly limited, be used in toward affiliated field and use, and non-be emphasis of the present invention, so separately do not repeat.
The present invention will be described further with regard to following examples, but will be appreciated that, this embodiment is the purposes for illustrating only, and should not be interpreted as restriction of the invention process.
< embodiment >
[synthesis example 1] has the preparation of the resin (A-1-1) of unsaturated group
By the fluorenes epoxy compound of 100 weight portions (model ESF-300, Nippon Steel's chemistry system; Epoxide equivalent 231), the benzyltriethylammonium chloride of the acrylic acid of 30 weight portions, 0.3 weight portion, 0.1 weight portion 2,6-BHT, and the 1-Methoxy-2-propyl acetate of 130 weight portions is added to continous way addition manner in the four-hole boiling flask of 500mL, and pan feeding speed be controlled at 25 weight portions/minute, the temperature of this course of reaction maintains 100 to 110 DEG C, react 15 hours, obtain faint yellow transparent mixed liquor (Gu constituent concentration is 50wt%).
Then, faint yellow transparent mixed liquor above-mentioned 100 weight portions is dissolved in the ethylene glycol ether acetate of 25 weight portions and forms mixed liquor, and add the tetrabydrophthalic anhydride of 6 weight portions and the benzophenone tetracarboxylic acid dianhydride of 13 weight portions in this mixed liquor simultaneously, heat again this mixed liquor to 110 DEG C to 115 DEG C, react 2 hours, must there is the resin (acid value: 98.0mgKOH/g of unsaturated group; Be designated hereinafter simply as A-1-1).
[synthesis example 2] has the preparation of the resin (A-1-2) of unsaturated group
100 weight portions are prepared in the ethylene glycol ether acetate that the faint yellow transparent mixed liquor of gained in synthesis example 1 is dissolved in 25 weight portions and formed mixed liquor, and the benzophenone tetracarboxylic acid dianhydride that adds 13 weight portions is in this mixed liquor, first this mixed liquor is reacted 2 hours at 90 to 95 DEG C, add again the tetrabydrophthalic anhydride of 6 weight portions in this mixed liquor, and react 4 hours in 90 to 95 DEG C, obtain having the resin (acid value: 99.0mgKOH/g of unsaturated group; Be designated hereinafter simply as A-1-2).
[synthesis example 3] has the preparation of the resin (A-1-3) of unsaturated group
By the epoxy compound of 400 weight portions [model NC-3000, Japanese chemical drug (strain) system; Epoxide equivalent 288], the acrylic acid of 102 weight portions, the methoxyl phenol (methoxyphenol) of 0.3 weight portion, the triphenylphosphine of 5 weight portions, and the 1-Methoxy-2-propyl acetate of 264 weight portions is added in reaction bulb, the temperature of this course of reaction maintains 95 DEG C, react 9 hours, obtain intermediate product (acid value: 2.2mgKOH/g).Then, the tetrabydrophthalic anhydride (tetrahydrophthalic anhydride) that adds 151 weight portions reacts 4 hours at 95 DEG C, obtains having the resin (acid value: 102mgKOH/g of unsaturated group, weight average molecular weight is 3,200; Be designated hereinafter simply as A-1-3).
The preparation of [synthesis example 4] other alkali soluble resins (A-2-1)
By 2 of 1 weight portion, 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 methacrylic acid benzene methyl of 35 weight portions, the glycerin monomethyl acrylic ester of 10 weight portions and the N-phenylmaleimide of 20 weight portions are added in the round-bottomed flask that stirrer and condenser are housed, and make this flask interior be full of nitrogen, then, slowly stir and be warming up to 80 DEG C, each composition evenly mixed and carry out polyreaction 4 hours.Be warming up to 100 DEG C again, and add 2 of 0.5 weight portion, 2 '-azoisobutyronitrile carries out after polymerization in 1 hour, obtains other alkali soluble resin (being designated hereinafter simply as A-2-1).
The preparation of [synthesis example 5] 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-hydroxy acrylic acid ethyl ester of 15 weight portions and the methacrylic acid benzene methyl of 70 weight portions are added in the round-bottomed flask that stirrer and condenser are housed, and make this flask interior be full of nitrogen, then, slowly stir and be warming up to 80 DEG C, each composition evenly mixed and carry out polyreaction 3 hours.Be warming up to 100 DEG C again, and add 2 of 0.5 weight portion, 2 '-azoisobutyronitrile carries out after polymerization in 1 hour, obtains other alkali soluble resins (being designated hereinafter simply as A-2-2).
The preparation of [embodiment 1] photosensitive resin composition and black matrix"
< photosensitive resin composition >
By the resin with unsaturated group (A-1-1) of the synthesis example of 100 weight portions 1, the dipentaerythritol acrylate (hereinafter to be referred as B-1) of 60 weight portions, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-substituting group of 30 weight portions]-ethane ketone 1-(O-acetyl group oxime) (hereinafter to be referred as C-1-1), the C.I. pigment black 7 (hereinafter to be referred as D-1-1) of 50 weight portions, the C.I. pigment blue 15 of 100 weight portions: 1 (hereinafter to be referred as D-2-1), the C.I. pigment Violet 23 (hereinafter to be referred as D-3-1) of 5 weight portions, and the 1-Methoxy-2-propyl acetate of 1000 weight portions (hereinafter to be referred as E-1) is placed in swing-out stirrer and stirs to form solution, be embodiment 1 photosensitive resin composition.The property detection result of embodiment 1 photosensitive resin composition as shown in Table 1.
< black matrix" >
The photosensitive resin composition of embodiment 1 is inserted to coating machine (new light trade system; Model is MS-A150), be coated in the mode of rotary coating on the glass substrate of 100mm × 100mm, then carry out drying under reduced pressure with 100mmHg, lasted for 5 seconds, in baking oven, carry out pre-baked processing 2 minutes with 100 DEG C again, be about the pre-baked film of 1.2 μ m to form thickness.
Then, this pre-baked film is placed under the light shield of appointment, with ultraviolet light (exposure machine model: AG500-4N; M & R Nano Technology system) 100mJ/cm 2irradiate this pre-baked film, then, this pre-baked film be impregnated in the developer (0.04% potassium hydroxide) of 23 DEG C to 2 minutes, to remove the part of this pre-baked film without UV-irradiation, after cleaning with pure water again, in baking oven, carry out rear roasting processing 60 minutes with 230 DEG C again, on this substrate, form the black matrix" that thickness is 1.0 μ m.The property detection result of the black matrix" of gained as shown in Table 1.
The preparation of [embodiment 2 to 7 and comparative example 1 to 5] photosensitive resin composition and black matrix"
Embodiment 2 to 7 and comparative example 1 to 5 are prepared photosensitive resin composition and black matrix" with the step identical with embodiment 1, and different places are: change kind and the use amount of each raw material, in table 1.The property detection result of the photosensitive resin composition of gained and black matrix" as shown in Table 1.
[property detection]
Describe for convenience measuring process, below describe with embodiment 1, all the other embodiment and comparative example are all measured according to which.
1. optical density (OD) value (Optical Density value is called for short O.D value):
Irradiate after the black matrix" of embodiment 1 with incident light, measure black matrix" from this embodiment 1 (thickness: the emergent light intensity that 1 μ m) penetrates out, then calculate the O.D value of embodiment 1 black matrix" by following formula:
O.D=－log(I/I 0)
I 0for incident light intensity, I is that incident light passes the outgoing light intensity after black matrix".
2. resolution:
Pre-baked film in embodiment 1 is placed under the light shield with different wire spokes, exposure with the wire spoke that can form 20 μ m is irradiated this pre-baked film, then, this pre-baked film be impregnated in the developer (0.04% potassium hydroxide) of 23 DEG C to 2 minutes, to remove the part of this pre-baked film without UV-irradiation, after cleaning with pure water again, then carry out rear roasting processing 60 minutes with 230 DEG C in baking oven.Then, observe evaluation method with microscope (Nikon system, model Eclipse50i) and sweep electron microscope (Hitachi system, model S-3000N):
Zero: minimum wire spoke≤4 μ m;
△: 4 μ m≤minimum wire spoke <10 μ m;
╳: minimum wire spoke >10 μ m.
3. the pre-baked film in embodiment 1 is placed under specified shadow tone light shield (percent of pass 50%), and utilizes respectively ultraviolet light (the exposure machine model AG500-4N of different exposures; M & R NanoTechnology system) irradiate to carry out weak exposure manufacture process, form test film.Then, take up an official post and get a measuring point and record thickness δ in this test film, then this test film is dipped in the developer solution (0.045%KOH) of 23 DEG C and is developed after 50 seconds, record thickness δ at identical measuring point d.Calculate and obtain residual film ratio via following formula again:
Residual film ratio (%)=[(δ d)/(δ)] × 100%
Evaluate according to following benchmark:
Zero: exposure≤80mJ/cm 2, represent that photosensitive resin composition is at 80mJ/cm 2when following exposure, just can make formed test film residual film ratio reach more than 90%, represent that the sensitivity of photosensitive resin composition is good;
╳: exposure >80mJ/cm 2, represent that photosensitive resin composition need be at 80mJ/cm 2when above exposure, just can make formed test film residual film ratio reach more than 90%, represent that the sensitivity of photosensitive resin composition is not good.
Table 1
Note: "--": represent not add; B-1: dipentaerythritol acrylate; B-2: dipentaerythritol tetraacrylate; C-1-1:1-[9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-substituting group]-ethane ketone 1-(O-acetyl group oxime) (trade name OXE02, Ciba Specialty Chemicals system); C-1-2:1-[4-(phenyl sulfo-) phenyl]-octane-1,2-diketone 2-(O-benzoyl group oxime) (trade name OXE01, Ciba SpecialtyChemicals system); C-1-3: ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzene acyl group)-9H-carbazole-3-substituting group]-1-(O-acetyl group oxime); C-2-1:2-benzyl-2-N, N-dimethylamino-1-(4-morpholino phenyl)-1-butanone (trade name IRGACURE369; Ciba Specialty Chemicals system); C-2-2:2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino-1-acetone (trade name IRGACURE907; Ciba Specialty Chemicals system); D-1-1: trade name MA100 (Mitsubishi Chemical's system); D-1-2: trade name MA230 (Mitsubishi Chemical's system); D-1-3: trade name MA8 (Mitsubishi Chemical's system); D-2-1:C.I. pigment blue 15: 1; D-2-2:C.I. pigment blue 15: 3; D-2-3:C.I. pigment blue 15: 6; D-3-1:C.I. pigment Violet 23; D-3-2:C.I. pigment Red 89; E-1: 1-Methoxy-2-propyl acetate; E-2:3-ethoxyl ethyl propionate.
Experimental data by table 1 shows, the photosensitive resin composition of embodiment 1 to 7 is because containing this resin with unsaturated group (A-1), black pigment (D-1) and blue pigment (D-2), and the weight ratio scope of black pigment (D-1) use amount and blue pigment (D-2) use amount is 0.5 to 10, this photosensitive resin composition has preferably sensitivity, and the black matrix" being formed by this photosensitive resin composition has high light-proofness (O.D value is 4.0 to 4.8) and high resolving power (minimum wire spoke is below 4 μ m).
The photosensitive resin composition of comparative example 1 is not good because not containing this resin with unsaturated group (A-1) sensitivity, and the resolution of the black matrix" being formed by photosensitive resin composition is not good, and (minimum wire spoke is greater than 10 μ m).
The photosensitive resin composition of comparative example 2 is not because containing black pigment (D-1), the O.D value of the black matrix" being formed by its photosensitive resin composition is only 2.0, therefore light-proofness is not good, and the resolution of the black matrix" being formed by photosensitive resin composition is not good.
The photosensitive resin composition of comparative example 3 is not because containing blue pigment (D-2), and the sensitivity of this photosensitive resin composition is not good, and the resolution of the black matrix" being formed by photosensitive resin composition is not good yet.
The photosensitive resin composition of comparative example 4 because of the weight ratio of black pigment (D-1) use amount and blue pigment (D-2) use amount be 0.4, the O.D value of the black matrix" being formed by photosensitive resin composition be only 3.3 and resolution not good.
The photosensitive resin composition of comparative example 5 because of the weight ratio of black pigment (D-1) use amount and blue pigment (D-2) use amount be 11.0, the sensitivity of this photosensitive resin composition is not good, and the resolution of the black matrix" being formed by photosensitive resin composition is not good.
In sum, photosensitive resin composition of the present invention is by using this resin with unsaturated group (A-1), black pigment (D-1) and blue pigment (D-2), and the weight ratio scope of black pigment (D-1) use amount and blue pigment (D-2) use amount is 0.5 to 10, make this photosensitive resin composition there is high sensitivity, and the black matrix" being formed by photosensitive resin composition have high light-proofness (O.D value is 4.0 to 4.8) and high resolving power.
Be the above, for preferred embodiment of the present invention, can not limit scope of the invention process with this, that is to say as long as the simple equivalence of doing according to the claims in the present invention scope and invention description content changes and modifies, all still remain within the scope of the patent.

Claims (10)

1. a photosensitive resin composition, is characterized in that it comprises:
Alkali soluble resin component (A), comprise the resin (A-1) with unsaturated group, this resin (A-1) with unsaturated group is obtained through polyreaction by potpourri, this potpourri comprises the epoxy compound (i) with at least two epoxy radicals, and has the compound (ii) of at least one carboxylic acid group and at least one ethene unsaturated group;
Containing the compound (B) of ethene unsaturated group;
Light initiator (C);
Pigment component (D); And
Solvent (E);
This pigment component (D) comprises black pigment (D-1) and blue pigment (D-2), and the weight ratio scope of this black pigment (D-1) use amount and blue pigment (D-2) use amount is 0.5 to 10.
2. photosensitive resin composition according to claim 1, it is characterized in that, this epoxy compound (i) with at least two epoxy radicals is selected from the epoxy compound with at least two epoxy radicals shown in the epoxy compound with at least two epoxy radicals shown in formula (I), formula (II), or their combination:
R 1, R 2, R 3and R 4represent independently of one another hydrogen, halogen, C 1to C 5alkyl, C 1to C 5alkoxy, C 6to C 12aromatic radical or C 7to C 12aralkyl,
R 5to R 18represent independently of one another hydrogen, halogen, C 1to C 8alkyl or C 6to C 15aromatic radical, n represents 0 to 10 integer.
3. photosensitive resin composition according to claim 1, is characterized in that, this epoxy compound (i) with at least two epoxy radicals is the epoxy compound with at least two epoxy radicals shown in formula (I):
R 1, R 2, R 3and R 4represent independently of one another hydrogen, halogen, C 1to C 5alkyl, C 1to C 5alkoxy, C 6to C 12aromatic radical or C 7to C 12aralkyl.
4. photosensitive resin composition according to claim 1, is characterized in that, this epoxy compound (i) with at least two epoxy radicals is the epoxy compound with at least two epoxy radicals shown in formula (II):
R 5to R 18represent independently of one another hydrogen, halogen, C 1to C 8alkyl or C 6to C 15aromatic radical, n represents 0 to 10 integer.
5. photosensitive resin composition according to claim 1, it is characterized in that, total amount based on this alkali soluble resin component (A) is 100 weight portions, this content range with the resin (A-1) of unsaturated group is 50 to 100 weight portions, should be 30 to 300 weight portions containing the use amount scope of the compound (B) of ethene unsaturated group, the use amount scope of this pigment component (D) is 100 to 1000 weight portions, and the use amount scope of this solvent (E) is 1000 to 5000 weight portions.
6. photosensitive resin composition according to claim 1, is characterized in that, is 100 weight portions based on this total amount containing the compound (B) of second unsaturated group, and the use amount scope of this light initiator (C) is 10 to 60 weight portions.
7. photosensitive resin composition according to claim 1, it is characterized in that, total amount based on this alkali soluble resin component (A) is 100 weight portions, the use amount scope of this black pigment (D-1) is 50 to 600 weight portions, and the use amount scope of this blue pigment (D-2) is 50 to 400 weight portions.
8. a black matrix", it is formed by the photosensitive resin composition described in any one in claim 1 to 7.
9. a colored filter, it comprises black matrix" claimed in claim 8.
10. a liquid crystal display cells, comprises colored filter claimed in claim 9.
CN201410076078.1A 2013-03-19 2014-03-04 Photosensitive resin composition, black matrix, color filter and liquid crystal display element Pending CN104062848A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TW102109647 2013-03-19
TW102109647A TWI484295B (en) 2013-03-19 2013-03-19 Photosensitive resin composition, black matrix, color filter and liquid crystal display element

Publications (1)

Publication Number Publication Date
CN104062848A true CN104062848A (en) 2014-09-24

Family

ID=51550627

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410076078.1A Pending CN104062848A (en) 2013-03-19 2014-03-04 Photosensitive resin composition, black matrix, color filter and liquid crystal display element

Country Status (2)

Country Link
CN (1) CN104062848A (en)
TW (1) TWI484295B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106200265A (en) * 2015-05-29 2016-12-07 奇美实业股份有限公司 Photosensitive resin composition, color filter and preparation method thereof, and liquid crystal display device
CN106233203A (en) * 2014-10-15 2016-12-14 奇美实业股份有限公司 Photosensitive resin composition, colored filter and liquid crystal display cells thereof
CN106406025A (en) * 2015-07-31 2017-02-15 奇美实业股份有限公司 Black photosensitive resin composition and application thereof
CN106959581A (en) * 2015-12-31 2017-07-18 奇美实业股份有限公司 Photosensitive resin composition and application thereof
CN107015435A (en) * 2015-11-05 2017-08-04 奇美实业股份有限公司 Photosensitive resin composition, color filter and manufacturing method and application thereof
CN107561859A (en) * 2016-06-30 2018-01-09 奇美实业股份有限公司 Black photosensitive resin composition and application thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI554567B (en) * 2014-11-18 2016-10-21 Chi Mei Corp Alkali soluble resin and its photosensitive resin composition and its application
TWI553410B (en) 2015-10-08 2016-10-11 新應材股份有限公司 Composition, infrared ray transmitting filter and fabricating method thereof, and infrared ray sensor

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1906536A (en) * 2004-08-09 2007-01-31 三菱化学株式会社 Photosensitive resin composition, color filter and liquid crystal display device
CN1928714A (en) * 2005-09-05 2007-03-14 东京应化工业株式会社 Black photosensitive resin composition
CN101281368A (en) * 2007-04-06 2008-10-08 太阳油墨制造株式会社 Black solder resist compound and cured product thereof
JP2008268854A (en) * 2007-03-28 2008-11-06 Nippon Steel Chem Co Ltd Photosensitive resin composition for black matrix, cured product using the same and color filter
CN101738857A (en) * 2008-11-07 2010-06-16 京东方科技集团股份有限公司 Black photo resist and preparation method and picture composition method thereof
CN102112923A (en) * 2008-08-01 2011-06-29 旭硝子株式会社 Negative working photosensitive composition, partition wall for optical element using nagative working photosensitive composition, and optical element comprising partition wall
CN103969954A (en) * 2013-01-25 2014-08-06 罗门哈斯电子材料韩国有限公司 Colored Photosensitive Resin Composition Suitable For Cylinderical Separator And Black Substrate

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1906536A (en) * 2004-08-09 2007-01-31 三菱化学株式会社 Photosensitive resin composition, color filter and liquid crystal display device
CN1928714A (en) * 2005-09-05 2007-03-14 东京应化工业株式会社 Black photosensitive resin composition
JP2008268854A (en) * 2007-03-28 2008-11-06 Nippon Steel Chem Co Ltd Photosensitive resin composition for black matrix, cured product using the same and color filter
CN101281368A (en) * 2007-04-06 2008-10-08 太阳油墨制造株式会社 Black solder resist compound and cured product thereof
CN102112923A (en) * 2008-08-01 2011-06-29 旭硝子株式会社 Negative working photosensitive composition, partition wall for optical element using nagative working photosensitive composition, and optical element comprising partition wall
CN101738857A (en) * 2008-11-07 2010-06-16 京东方科技集团股份有限公司 Black photo resist and preparation method and picture composition method thereof
CN103969954A (en) * 2013-01-25 2014-08-06 罗门哈斯电子材料韩国有限公司 Colored Photosensitive Resin Composition Suitable For Cylinderical Separator And Black Substrate

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106233203A (en) * 2014-10-15 2016-12-14 奇美实业股份有限公司 Photosensitive resin composition, colored filter and liquid crystal display cells thereof
CN106233203B (en) * 2014-10-15 2020-07-14 奇美实业股份有限公司 Photosensitive resin composition, color filter and liquid crystal display element thereof
CN106200265A (en) * 2015-05-29 2016-12-07 奇美实业股份有限公司 Photosensitive resin composition, color filter and preparation method thereof, and liquid crystal display device
CN106406025A (en) * 2015-07-31 2017-02-15 奇美实业股份有限公司 Black photosensitive resin composition and application thereof
CN107015435A (en) * 2015-11-05 2017-08-04 奇美实业股份有限公司 Photosensitive resin composition, color filter and manufacturing method and application thereof
CN107015435B (en) * 2015-11-05 2019-12-13 奇美实业股份有限公司 Photosensitive resin composition, color filter and manufacturing method and application thereof
CN106959581A (en) * 2015-12-31 2017-07-18 奇美实业股份有限公司 Photosensitive resin composition and application thereof
CN107561859A (en) * 2016-06-30 2018-01-09 奇美实业股份有限公司 Black photosensitive resin composition and application thereof

Also Published As

Publication number Publication date
TWI484295B (en) 2015-05-11
TW201437751A (en) 2014-10-01

Similar Documents

Publication Publication Date Title
CN104062848A (en) Photosensitive resin composition, black matrix, color filter and liquid crystal display element
CN103135344B (en) Photosensitive resin composition, black matrix, color filter and liquid crystal display element thereof
JP6005774B2 (en) Alkali-soluble resin, photosensitive resin composition, color filter and method for producing the same, and liquid crystal display device
CN103885289A (en) Photosensitive resin composition, color filter and liquid crystal display element thereof
CN103324031A (en) Photosensitive resin composition, color filter and liquid crystal display thereof
CN103838083A (en) Photosensitive resin composition, color filter formed by same and liquid crystal display element
CN103838081A (en) Photosensitive resin composition for color filter and application thereof
US20150153646A1 (en) Photosensitive resin composition, color filter and method for manufacturing the same, and liquid crystal display apparatus
TWI554567B (en) Alkali soluble resin and its photosensitive resin composition and its application
CN104423161A (en) Photosensitive resin composition for black matrix, optical filter and display
CN105425542A (en) Photosensitive resin composition for color filter and application thereof
TW201508010A (en) Alkali-solutable resin, photosensitive resin composition, color filter and method for manufacturing the same, liquid crystal display apparatus
TWI506369B (en) Photosensitive resin composition, color filter and method for manufacturing the same, liquid crystal display apparatus
CN105204292A (en) Photosensitive Resin Composition For Black Matrix And Application Thereof
CN104570598A (en) Photosensitive resin composition, color filter and liquid crystal display element thereof
CN102200688B (en) Photosensitive resin composition, black matrix prepared from the photosensitive resin composition, and application of the black matrix
CN105182686A (en) Photosensitive resin composition and application thereof
CN104698752B (en) Photosensitive resin composition, color filter and manufacturing method thereof, and liquid crystal display device
CN104570597A (en) Photosensitive resin composition, color filter and liquid crystal display element thereof
CN104570599A (en) Photosensitive resin composition and application thereof
JP2007094164A (en) Cured film for liquid crystal display apparatus
CN105425541A (en) Photosensitive resin composition for color filter and application thereof
US10495919B2 (en) Photosensitive resin composition and manufacturing method of the same, black matrix, pixel layer, protection film, color filter, and liquid crystal display apparatus
CN106933032A (en) Black photosensitive resin composition and application thereof
CN105278244A (en) Photosensitive resin composition for color filter and application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140924

WD01 Invention patent application deemed withdrawn after publication