CN1277132C - Light sensitive resin composition for color filter - Google Patents
Light sensitive resin composition for color filter Download PDFInfo
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- CN1277132C CN1277132C CN 200310124450 CN200310124450A CN1277132C CN 1277132 C CN1277132 C CN 1277132C CN 200310124450 CN200310124450 CN 200310124450 CN 200310124450 A CN200310124450 A CN 200310124450A CN 1277132 C CN1277132 C CN 1277132C
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Abstract
The present invention relates to a photosensitive resin composition for a color optical filter, which comprises alkali soluble resin (A), a compound (B) containing an ethylene unsaturation base, optical initiators (C), organic solvents (D) and pigment (E), wherein the alkali soluble resin (A) is composed of alkali soluble resin (A-1) and soluble resin (A-2) selected according to need, wherein the soluble resin (A-1) and (A-2) are respectively copolymerized from maleic anhydride monomers, unsaturated monomers containing carboxyl and other copolymerizable monomers. After the composition is processed by coating, exposing and developing, the unexposed part on a base plate and the residue quantity on a shading layer are little, the composition has the advantages of good heat resistance of a picture element tinting layer and alkali resistance and no pigment agglutination particle after baking.
Description
Technical field
The present invention is the photosensitive resin composition for colour filter of relevant a kind of LCD.Particularly provide a kind of via after coating, exposure, developing, part and light shield layer (black matrix) level of residue upward unexposed on substrate are few; After the back was roasting, the thermotolerance of picture element dyed layer, alkali resistance was good and do not have the photosensitive resin composition for colour filter of pigment agglutination particle.
Background technology
At present, colored filter has been widely used in applications such as colour liquid crystal display device, colour facsimile apparatus, colour camera.Along with the market demand of office equipments such as colour liquid crystal display device day by day enlarges, on the manufacturing technology of colored filter, also trend variation.As decoration method, print process, methods such as electrochemical plating and dispersion method are all developed successively and are finished, and wherein, are main flow with the decoration method.
The processing procedure of decoration method, generally system will have photosensitive water-soluble photoresist (as acryl resin, gelatin etc.), and elder generation forms specific pattern on glass substrate, and then through after dyeing, fixing engineerings such as reaching anti-pollution processing, can make colored pattern.This processing procedure is operated through triplicate, the pattern that gets final product redly (R), green (G) and blue picture element dyed layers such as (B), and on the pattern of this picture element dyed layer, need apply diaphragm.Though decoration method has its superiority at aspects such as tractability and dichroisms, its processing procedure complexity, and the not good shortcoming of permanance is arranged.
Therefore, recently, dispersion method is gazed at gradually.The processing procedure of dispersion method is earlier coloring pigment to be scattered in the photoresist, this photoresist is coated on the glass substrate again, through steps such as overexposure, video pictures, can make specific pattern.This engineering is operated through triplicate, can make redness (R), the pattern of the picture element dyed layer of green (G) and blue (B), after optionally can on the pattern of picture element dyed layer, apply diaphragm.Therefore, do not need dyeing, numerous and diverse engineering such as fixing in the dispersion method, so productivity can improve relatively, and diaphragm can optionally make, and also can reduce the waste of material and engineering.
In the processing procedure of dispersion method, the concrete example of employed photoresist as: be multipolymer that monomer component was polymerized cementing agent with the methacrylic acid as photoresist.The special fair 6-95211 communique of the pertinent literature of this photoresist such as Japan, the spy opens flat 8-183819 communique, and the spy opens flat 9-311210 communique etc.
Yet, in the manufacture process of colored filter, need experience the step of repeatedly thermal treatment, as red (R), green (G) and blue dyed layer such as (B) picture element pattern form the formation step of afterwards roasting (post-bake) step in back and nesa coating (ITO film) etc., all require as this step 1 under the high temperature more than 200, to finish, but if above-mentioned known photoresist is in 180, heat under the condition about 1 hour, problem such as generation of pigment agglutination particle (the particle footpath of general pigment agglutination particle is between 1～10 μ m) and thermotolerance are not good but easily takes place in the picture element dyed layer.
Generally, in the processing procedure of dispersion method, in the employed photosensitive resin composition, can also contain the unsaturated monomer of carboxyl and other copolymerizable vinyl monomer institute's polymerization and polymkeric substance as the cementing agent of photoresist; For example Japanese kokai publication hei 4-122934, spy open among the flat 10-260309 and mention, this unsaturated monomer that contains carboxyl can be (methyl) acrylic monomers or anhydrous maleic acid anhydride monomer or both and usefulness.
But in the above-mentioned known photosensitive resin composition, all do not make any teaching for pigment agglutination particle and thermotolerance etc. in the special ratios of the specific use amount of (methyl) acrylic monomers and anhydrous maleic acid anhydride monomer and the usage rate of the two, anhydrous maleic acid anhydride monomer polymerized unit content and pigment content and the picture element dyed layer.
Again, in the processing procedure of dispersion method, another concrete example of the photoresist that is used as: in the polymkeric substance that anhydrous maleic acid anhydride monomer and other copolymerizable monomer are formed, what add polyglycol (methyl) esters of acrylic acid contains ethene unsaturated group monomer, after the half ester reaction, the multipolymer that contains the ethene unsaturated group of formation is as the cementing agent of photoresist.Relevant patent of this photoresist such as Japanese kokai publication hei 6-228239, spy open flat 9-15858.
Above-mentioned known photoresist through coating, exposure, develop and after the back baked, the thermotolerance of picture element dyed layer was not good, easily produce shortcoming such as pigment agglutination particle and still can't be improved.
Summary of the invention
The bright purpose of this Hair is at the photosensitive resin composition for colour filter of what Ti Gong Yi Seed LCD.Particularly provide a kind of via after coating, exposure, developing, part and light shield layer (black matrix) level of residue upward unexposed on substrate are few; After the back was roasting, the thermotolerance of picture element dyed layer, alkali resistance was good and do not have the photosensitive resin composition for colour filter of pigment agglutination particle.
Technical scheme of the present invention is that this constituent comprises: alkali soluble resin (A), the compound (B) that contains the ethene unsaturated group, light initiator (C), organic solvent (D) and pigment (E); Wherein, this alkali soluble resin (A) is by alkali soluble resin (A-1) 0.1～100 weight portion and optionally is selected from a kind of alkali soluble resin (A-2) 99.9～0 weight portions and combined, more than (A-1), (A-2) add up to 100 weight portions; Wherein, this alkali soluble resin (A-1) is to be formed by maleic anhydride monomer (a-1) 0.2～30 weight portion, unsaturated monomer (a-2) 3～40 weight portions that contain carboxyl, monomer (a-1), (a-2) other copolymerizable vinyl monomer (a-3) 30～96.8 weight portions institute copolymerization in addition, more than (a-1), (a-2), (a-3) add up to 100 weight portions; Alkali soluble resin (A-2) is to be formed by maleic anhydride monomer (a '-1) 0.2 weight portion following (not containing 0.2 weight portion), unsaturated monomer (a '-2) 5～50 weight portions that contain carboxyl, monomer (a '-1), (a '-2) other copolymerizable vinyl monomer (a '-3) 49.8～95 weight portions institute copolymerization in addition, more than (a '-1), (a '-2), (a '-3) add up to 100 weight portions; And in the above-mentioned photosensitive resin composition, the polymerized unit of the maleic anhydride monomer (a-1) of alkali soluble resin (A) and (a '-1) adds up to the ratio of content and pigment (E) content between 0.001～0.015.
Beneficial effect of the present invention is that this photosensitive resin composition for colour filter is via after coating, exposure, developing, level of residue on unexposed part and light shield layer on the substrate (black matrix) is few, after the back was roasting, the thermotolerance of picture element dyed layer, alkali resistance was good and do not have the pigment agglutination particle.
Embodiment
Below one by one each composition of the present invention is described in detail:
(A) alkali soluble resin
The present invention's alkali soluble resin (A) is by alkali soluble resin (A-1) 0.1～100 weight portion and optionally is selected from a kind of alkali soluble resin (A-2) 99.9～0 weight portions and combined, more than (A-1), (A-2) add up to 100 weight portions; Wherein, this alkali soluble resin (A-1) is to be formed by maleic anhydride monomer (a-1) 0.2～30 weight portion, unsaturated monomer (a-2) 3～40 weight portions that contain carboxyl, monomer (a-1), (a-2) other copolymerizable vinyl monomer (a-3) 30～96.8 weight portions institute copolymerization in addition, more than (a-1), (a-2), (a-3) add up to 100 weight portions; Alkali soluble resin (A-2) is to be formed by maleic anhydride monomer (a '-1) 0.2 weight portion following (not containing 0.2 weight portion), unsaturated monomer (a '-2) 5～50 weight portions that contain carboxyl, monomer (a '-1), (a '-2) other copolymerizable vinyl monomer (a '-3) 49.8～95 weight portions institute copolymerization in addition, more than (a '-1), (a '-2), (a '-3) add up to 100 weight portions.
The above-mentioned unsaturated monomer that contains carboxyl (a-2) is for example: unsaturated monocarboxylic acid classes such as acrylic acid, methacrylic acid, butenoic acid, α-Lv Bingxisuan, ethylacrylic acid and cinnamic acid; Unsaturated dicarboxylic acid (acid anhydride) classes such as fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride; Unsaturated polyvalent carboxylic acid (acid anhydride) class that 3 valencys are above or the like.
Wherein cited person is preferable with acrylic acid, methacrylic acid.These unsaturated monomers that contain carboxyl can a kind of separately or mixing plural number kind use.
The kind of the above-mentioned unsaturated monomer that contains carboxyl (a '-2) is identical with enumerating of the above-mentioned unsaturated monomer that contains carboxyl (a-2), does not give unnecessary details at this.
Above-mentioned monomer (a-1), (a-2) other copolymerizable vinyl monomer (a-3) in addition is for example: contain aromatic series functional group's copolymerizable vinyl monomer (a-3-1), as: the aromatic ethenyl compound of styrene, α-Jia Jibenyixi, vinyltoluene, vinyl chloride, methoxy styrene etc.; The unsaturated carboxylate type of acrylic acid benzene methyl, methacrylic acid benzene methyl, phenyl acrylate, phenyl methacrylate etc.; N-phenylmaleimide, N-neighbour-hydroxy phenyl maleimide, between N--the hydroxy phenyl maleimide, N-is right-the hydroxy phenyl maleimide, and N-neighbour-aminomethyl phenyl maleimide, between N--the aminomethyl phenyl maleimide, N-is right-the aminomethyl phenyl maleimide, N-neighbour-methoxyphenyl maleimide, between N--the methoxyphenyl maleimide, N-is right-maleimides such as methoxyphenyl maleimide; Reach the copolymerizable vinyl monomer (a-3-2) that does not contain the aromatic series functional group, as: methyl acrylate, methyl methacrylate, ethyl acrylate, Jia Jibingxisuanyizhi, the acrylic acid n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, isobutyl methacrylate, acrylic acid second butyl ester, methacrylic acid second butyl ester, the acrylic acid tributyl, the methacrylic acid tributyl, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2-hydroxy propyl ester, methacrylic acid 2-hydroxy propyl ester, acrylic acid 3-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester, acrylic acid 2-hydroxyl butyl ester, methacrylic acid 2-hydroxyl butyl ester, acrylic acid 3-hydroxyl butyl ester, methacrylic acid 3-hydroxyl butyl ester, acrylic acid 4-hydroxyl butyl ester, methacrylic acid 4-hydroxyl butyl ester, allyl acrylate, allyl methacrylate, acrylic acid triethylene glycol methoxyethoxy ester (methoxy triethylene glycol acrylate), methacrylic acid triethylene glycol methoxyethoxy ester (methoxy triethylene glycolmethacrylate), lauryl methacrylate (lauryl methacrylate), methacrylic acid myristyl ester (tertadecylmethacrylate), methacrylic acid cetyl ester (cetyl methacrylate), methacrylic acid stearyl (octadecylmethacrylate), methacrylic acid eicosyl ester (eicosyl methacrylate), the unsaturated carboxylate type of methacrylic acid docosyl ester (docosyl methacrylate) etc.; Unsaturated carboxylic acid ammonia alkane ester classes such as acrylic acid 2-ammonia ethyl ester, methacrylic acid 2-ammonia ethyl ester, acrylic acid 2-ammonia propyl ester, methacrylic acid 2-ammonia propyl ester, acrylic acid 3-ammonia propyl ester, methacrylic acid 3-ammonia propyl ester; Unsaturated carboxylic acid glycidyl ester classes such as acrylic acid epoxy propyl diester, methacrylic acid glycidyl ester; The vinyl carboxylates class of vinyl acetate, propionate, vinyl butyrate etc.; Unsaturated ethers such as methoxy ethylene, ethyl vinyl ether, allyl glycidyl ethers, methylallyl glycidyl ethers; The vinyl cyanide based compound of vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, the inferior ethene of cyaniding etc.; The unsaturated amides of acrylamide, Methacrylamide, α-chloropropene acid amides, N-hydroxyethyl acrylamide, N-hydroxyethyl methacrylamide etc.; The aliphatics conjugated diene of 1,3-butadiene, different propylene, chloropropene etc.
Wherein cited person is preferable with styrene, acrylic acid benzene methyl, methacrylic acid benzene methyl, N-phenylmaleimide, methyl acrylate, methyl methacrylate, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate.These monomers (a-1), (a-2) other copolymerizable vinyl monomer in addition can a kind of separately or mixing plural number kind use.
Above-mentioned monomer (a '-1), (a '-2) other copolymerizable vinyl monomer (a '-3) in addition is for example: contain the aromatic series functional group copolymerizable vinyl monomer (a '-3-1) and do not contain the aromatic series functional group copolymerizable vinyl monomer (a '-3-2).
The above-mentioned copolymerizable vinyl monomer that contains the aromatic series functional group (a '-3-1) and do not contain the aromatic series functional group copolymerizable vinyl monomer (a '-3-2) kind respectively with the above-mentioned copolymerizable vinyl monomer (a-3-1) that contains the aromatic series functional group and do not contain the aromatic series functional group copolymerizable vinyl monomer (a-3-2) enumerate identically, do not give unnecessary details at this.
Alkali soluble resin of the present invention (A) is by alkali soluble resin (A-1) and optionally is selected from a kind of alkali soluble resin (A-2) and is combined.Wherein, the content of alkali soluble resin (A-1) is preferably 0.1～100 weight portion, is more preferred from 1～90 weight portion, and the best is 2～80 weight portions; And the content of alkali soluble resin (A-2) is preferably 99.9～0 weight portions, is more preferred from 99～10 weight portions, and the best is 98～20 weight portions.If the content of alkali soluble resin (A-1) is lower than 0.1 weight portion, or the content of alkali soluble resin (A-2) is when being higher than 99.9 weight portions, then photosensitive resin composition through develop, after the back bakes, the thermotolerance of picture element dyed layer is not good, and easily produces the pigment agglutination particle.
The present invention's alkali soluble resin (A-1), its copolymerization is measured 100 weight portions based on its copolymerization with the total of monomer with the use amount of monomer, as shown below:
The use amount of maleic anhydride monomer (a-1) is preferably 0.2～30 weight portion, is more preferred from 0.5～25 weight portion, and the best is 1.0～20 weight portions.
The use amount that contains the unsaturated monomer (a-2) of carboxyl is preferably 3～40 weight portions, is more preferred from 5～35 weight portions, and the best is 8～30 weight portions.
The use amount of monomer (a-1), (a-2) other copolymerizable vinyl monomer (a-3) in addition is preferably 30～96.8 weight portions, is more preferred from 40～94.5 weight portions, and the best is 50～91 weight portions.
In addition, the use amount of the aforementioned copolymerizable vinyl monomer (a-3-1) that contains the aromatic series functional group is preferably more than 45 weight portions, is more preferred from more than 55 weight portions, and the best is more than 70 weight portions.
The copolymerization of alkali soluble resin of the present invention (A-1) is with in the monomer, the use amount of maleic anhydride monomer (a-1) is if be lower than 0.2 weight portion, then photosensitive resin composition through develop, after the back bakes, the thermotolerance of picture element dyed layer is not good, and easily produces the pigment agglutination particle; Use amount is if be higher than 30 weight portions, and then photosensitive resin composition is after developing, and unexposed part and light shield layer (black matrix) are gone up and easily produced residue on the substrate, and after the back baked, the alkali resistance of picture element dyed layer was not good.
The copolymerization of alkali soluble resin of the present invention (A-1) is with in the monomer, the use amount of unsaturated monomer (a-2) that contains carboxyl is if be lower than 3 weight portions, then photosensitive resin composition is after developing, and part and light shield layer (black matrix) unexposed on the substrate are gone up easily generation residue; Use amount is if be higher than 40 weight portions, then photosensitive resin composition through develop, after the back bakes, the alkali resistance of picture element dyed layer is not good.
The copolymerization of alkali soluble resin of the present invention (A-1) is with in the monomer, if the use amount of monomer (a-1), (a-2) other copolymerizable vinyl monomer (a-3) in addition is between 30～96.8 weight portions, then photosensitive resin composition is after developing, part and light shield layer (black matrix) unexposed on the substrate are gone up the difficult residue that produces, and after the back was roasting, the thermotolerance of picture element dyed layer was preferable.
The copolymerization of alkali soluble resin of the present invention (A-1) is with in the monomer, the use amount of copolymerizable vinyl monomer (a-3-1) that contains the aromatic series functional group is if be higher than 45 weight portions, then photosensitive resin composition through develop, after the back bakes, the thermotolerance and the alkali resistance of picture element dyed layer are preferable.
The copolymerization of alkali soluble resin of the present invention (A-1) is with in the monomer, and the ratio of the use amount of the use amount of monomer (a-1) and monomer (a-2) is preferable between 0.01～3.0, better between 0.03～2.8, and is best between 0.05～2.5; If the ratio of the use amount of the use amount/monomer (a-2) of monomer (a-1) is between 0.01～3.0, then photosensitive resin composition is after developing, part and light shield layer (black matrix) unexposed on the substrate are gone up the difficult residue that produces, and after the back is roasting, alkali resistance, the thermotolerance of picture element dyed layer are preferable, and are difficult for producing the pigment agglutination particle.
Alkali soluble resin of the present invention (A-1) can be the alkali soluble resin of independent a kind of composition, 10/15/75) and usefulness also can be the alkali soluble resin and the usefulness of two or more different composition, for example: the multipolymer of anhydrous maleic acid anhydride monomer/acrylic monomers/methacrylic acid benzene methyl monomer (monomer use amount: 5/15/80) with the multipolymer of anhydrous maleic acid anhydride monomer/methacrylic acid monomer/methacrylic acid benzene methyl monomer (monomer use amount:.
The present invention's alkali soluble resin (A-2), its copolymerization is measured 100 weight portions based on its copolymerization with the total of monomer with the use amount of monomer, as shown below:
The use amount of maleic anhydride monomer (a '-1) is preferably 0.2 weight portion following (not containing 0.2 weight portion), is more preferred from 0～0.15 weight portion, and the best is 0～0.1 weight portion.
The use amount that contains the unsaturated monomer (a '-2) of carboxyl is preferably 5～50 weight portions, is more preferred from 8～45 weight portions, and the best is 10～40 weight portions.
The use amount of monomer (a '-1), (a '-2) other copolymerizable vinyl monomer (a '-3) in addition is preferably 49.8～95 weight portions, is more preferred from 54.85～92 weight portions, and the best is 59.9～90 weight portions.
In addition, the aforementioned copolymerizable vinyl monomer that contains the aromatic series functional group (a '-3-1) use amount is preferably more than 45 weight portions, is more preferred from more than 55 weight portions, and the best is more than 70 weight portions.
The copolymerization of alkali soluble resin of the present invention (A-2) is with in the monomer, the use amount of maleic anhydride monomer (a '-1) is if be lower than 0.2 weight portion (not containing 0.2 weight portion), then photosensitive resin composition is after developing, and part and light shield layer (blackmatrix) unexposed on the substrate are gone up the difficult residue that produces.
The copolymerization of alkali soluble resin of the present invention (A-2) is with in the monomer, the use amount of unsaturated monomer (a '-2) that contains carboxyl is if be lower than 5 weight portions, then photosensitive resin composition is after developing, and part and light shield layer (black matrix) unexposed on the substrate are gone up easily generation residue; Use amount is if be higher than 50 weight portions, then photosensitive resin composition through develop, after the back bakes, the alkali resistance of picture element dyed layer is not good.
The copolymerization of alkali soluble resin of the present invention (A-2) is with in the monomer, if the use amount of monomer (a '-1), (a '-2) other copolymerizable vinyl monomer (a '-3) in addition is between 49.8～95 weight portions, then photosensitive resin composition is after developing, part and light shield layer (black matrix) unexposed on the substrate are gone up the difficult residue that produces, and through develop, after the back bakes, the thermotolerance of picture element dyed layer is preferable.
The copolymerization of alkali soluble resin of the present invention (A-2) is with in the monomer, contain the aromatic series functional group copolymerizable vinyl monomer (a '-3-1) use amount is if be higher than 45 weight portions, then photosensitive resin composition through develop, after the back bakes, the thermotolerance and the alkali resistance of picture element dyed layer are preferable.
The present invention's alkali soluble resin (A-1) reaches (A-2) employed during fabrication solvent, is ethylene glycol monomethyl ether than the dust head generally, ethylene glycol ethyl ether, diethylene glycol methyl ether, DGDE, the diglycol positive propyl ether, the diglycol n-butyl ether, the triethylene glycol methyl ether, the triethylene glycol ether, propylene glycol monomethyl ether, propylene-glycol ethyl ether, the dipropylene glycol methyl ether, the dipropylene glycol ether, the dipropylene glycol positive propyl ether, the dipropylene glycol n-butyl ether, tripropylene glycol methyl ether (tripropylene glycol mono methyl ether), tripropylene glycol ether (tripropylene glycol mono ethyl ether) waits its (gathering) alkylene glycol mono alkane ethers; (gathering) alkylene glycol mono alkane ether acetate classes such as glycol methyl ether acetate, ethylene glycol ether acetate, 1-Methoxy-2-propyl acetate, propylene-glycol ethyl ether acetate; Other ethers such as diethylene glycol dimethyl ether, diglycol ethyl methyl ether, diethyl carbitol, tetrahydrofuran; Ketones such as MEK, cyclohexanone, 2-heptanone, 3-heptanone; Lactic acid alkane ester classes such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester; 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butyl propionic ester, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, the butyric acid n-propyl, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, the pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, other ester classes such as 2-oxygen base ethyl butyrate; Aromatic hydrocarbons such as toluene, dimethylbenzene class; N-Methyl pyrrolidone, N, carboxylic acyloxy amines such as dinethylformamide, N,N-dimethylacetamide or the like.This equal solvent can independent a kind of use, also can mix two or more use.Be preferable in the aforementioned solvents with 1-Methoxy-2-propyl acetate, 3-ethoxyl ethyl propionate.
Alkali soluble resin (A-1) reaches the initiator that is used when (A-2) making, be generally free radical shape polymerization initiator, for example 2,2 '-azobis isobutyronitrile (2,2 '-azobisisobutyronitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile) [2,2 '-azobis-(2,4-dimethylvaleronitrile)], 2, two (the 4-methoxyls-2 of 2 '-azo, the 4-methyl pentane nitrile) [2,2 '-azobis-(4-methoxy-2,4-dimethylvaleronitrile)], 2,2 '-azo is two-2-methylbutyronitrile azo (azo) compounds such as (2,2 '-azobis-2-methyl butyronitrile); The per-compound of dibenzoyl peroxide (benzoylperoxide) etc.
(B) contain the compound of ethene unsaturated group
Based on alkali soluble resin (A) 100 weight portions, the use amount that the present invention contains the compound (B) of ethene unsaturated group is preferably the 5-220 weight portion, is more preferred from the 50-160 weight portion.
The above-mentioned compound (B) that contains the ethene unsaturated group is the ethene unsaturated compound with at least one ethene unsaturated group.
The concrete example that wherein has the compound of an ethene unsaturated group has 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 diglycol (methyl) acrylate, trioctylphosphine (methyl) acrylamide, two acetone (methyl) acrylamide, (methyl) acrylic acid dimethylamino ester, (methyl) dodecylacrylate, (methyl) acrylic acid two cyclopentene 2-ethoxyethyl acetates, (methyl) acrylic acid two cyclopentene esters, N, N-dimethyl (methyl) acrylamide, (methyl) acrylic acid tetrachloro phenyl ester, (methyl) acrylic acid-2-tetrachloro phenoxy ethyl, (methyl) tetrahydrofurfuryl acrylate, (methyl) tetrabromophenyl acrylate, (methyl) acrylic acid-2-tetrabromo phenoxy ethyl, (methyl) acrylic acid-2-Trichlorophenoxy ethyl ester, (methyl) acrylic acid tribromophenyl, (methyl) acrylic acid-2-tribromophenoxy ethyl ester, (methyl) acrylic acid-2-hydroxyl ethyl ester, (methyl) acrylic acid-2-hydroxypropyl acrylate, caprolactam, N-vinyl skin junket alkane ketone, (methyl) acrylic acid phenoxy ethyl, (methyl) acrylic acid pentachlorophenyl ester, (methyl) acrylic acid pentabromo-phenyl ester, poly-single (methyl) acrylic acid glycol ester, poly-single (methyl) acrylic acid propylene glycol ester, (methyl) acrylic acid norbornene ester.
The concrete example of ethene unsaturated compound with 2 or 2 above ethene unsaturated groups is as follows: ethylene glycol bisthioglycolate (methyl) acrylate, two (methyl) acrylic acid, two cyclopentene esters, triethylene glycol diacrylate, tetraethylene glycol two (methyl) acrylate, three (2-hydroxyethyl) isocyanates two (methyl) acrylate, three (2-hydroxyethyl) isocyanates three (methyl) acrylate, three (2-hydroxyethyl) isocyanates three (methyl) acrylate of caprolactone upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester, three (methyl) acrylic acid trihydroxy methyl propyl ester of oxirane (hereinafter to be referred as EO) upgrading, three (methyl) acrylic acid trihydroxy methyl propyl ester of epoxypropane (hereinafter to be referred as PO) upgrading, triethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,4-butylene glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, polyester two (methyl) acrylate, polyglycol two (methyl) acrylate, dipentaerythritol six (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol four (methyl) acrylate, dipentaerythritol six (methyl) acrylate of caprolactone upgrading, dipentaerythritol five (methyl) acrylate of caprolactone upgrading, four (methyl) acrylic acid, two trihydroxy methyl propyl ester, bisphenol-A two (methyl) acrylate of EO upgrading, bisphenol-A two (methyl) acrylate of PO upgrading, hydrogenated bisphenol A two (methyl) acrylate of EO upgrading, hydrogenated bisphenol A two (methyl) acrylate of PO upgrading, the glycerin tripropionate of PO upgrading, Bisphenol F two (methyl) acrylate of EO upgrading, phenolic aldehyde polyglycidyl ether (methyl) acrylate or the like.
In the aforementioned ethene unsaturated compound, the preferably is dipentaerythritol acrylate, the tetrapropylene acid two trihydroxy methyl propyl ester of three acrylic acid trihydroxy methyl propyl ester, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, dipentaerythritol five acrylate, dipentaerythritol tetraacrylate, the caprolactone upgrading of three acrylic acid trihydroxy methyl propyl ester, the PO upgrading of three acrylic acid trihydroxy methyl propyl ester, EO upgrading, the glycerin tripropionate of PO upgrading.
(C) light initiator
Based on the compound that contains the ethene unsaturated group (B) 100 weight portions, the use amount of light initiator of the present invention (C) is preferably the 20-120 weight portion, is more preferred from the 30-100 weight portion.
Above-mentioned smooth initiator (C) can be selected from: acetophenone based compound (acetophenone) or diimidazole based compound (biimidazole).
Wherein, the acetophenone based compound as: to dimethylamine acetophenone (p-dimethylamino-acetophenone), α, α '-dimethoxy azoxy acetophenone (α, α '-dimethoxyazoxyacetophenone), 2,2 '-dimethyl-2-phenyl acetophenone (2,2 '-dimethyl-2-phenylacetophenone), acetanisole (p-methoxyacetophenone), 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino-1-acetone (2-methyl-1-(4-methylthio phenyl)-2-morpholinopropane-1-on), 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone [2-benzyl-2-N, N-dimethylamino-1-(4-morpholinophenyl)-1-butanone].
And diimidazole based compound (biimidazole) is as 2,2 '-two (neighbour-chlorphenyl)-4,4 ', 5, and 5 '-tetraphenyl diimidazole [2,2 '-bis (o-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-two (ortho-fluorophenyl base)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (o-fluorophenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole], 2,2 '-two (neighbour-aminomethyl phenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (o-methyl phenyl)-4,4 ', 5,5 '-tetraphenyl biimidazole], 2,2 '-two (neighbour-methoxyphenyl)-4,4 ', 5, and 5 '-tetraphenyl diimidazole [2,2 '-bis (o-methoxyphenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole], 2,2 '-two (p-methoxyphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (p-methoxyphenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole], 2,2 '-two (2,2 ', 4,4 '-tetramethoxy phenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (2,2 ', 4,4 '-tetramethoxyphenyl)-4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole], 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole] etc.
Wherein with 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone, 2,2 '-two (neighbour-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole and the light initiator effect of using are preferable.
In the present invention's the photosensitive resin composition for colour filter, can further add benzophenone (benzophenone) based compound is the light initiator, as thioxanthones (thioxanthone), 2,4-diethyl thioxanthone (2,4-diethylthioxanthanone), thioxanthones-4-sulfone (thioxanthone-4-sulfone), benzophenone (benzophenone), 4,4 '-two (dimethylamine) benzophenone [4,4 '-bis (dimethylamino) benzophenone], 4,4 '-two (diethylamine) benzophenone [4,4 '-bis (diethylamino) benzophenone] etc.
Other still has α-diketone (class of α-diketone), keto-alcohol (acyloin) class of diphenylhydroxyethanone (benzoin) etc. of benzil (benzil), acetyl group (acetyl) etc.; Keto-alcohol ether (acyloin ether) class of diphenylhydroxyethanone methyl ether (benzoin methylether), diphenylhydroxyethanone ether (benzoinethylether), diphenylhydroxyethanone isopropyl ether (benzoin isopropyl ether) etc.; 2,4,6-trimethyl benzoyl diphenyl phosphine oxide (2,4,6-trimethyl-benzoyl diphenylphosphineoxide), two-(2,6-dimethoxy benzoyl)-2,4, and 4-trimethylphenyl phosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethylbenzylphosphineoxide] etc. acyl phosphine oxide (acylphosphineoxide) class; Anthraquinone (anthraquinone), 1, and the 4-naphthoquinones (1, the 4-naphthoquinone) quinone of grade (quinone) class; The halogenide of chloroacetophenone (phenacyl chloride), trisbromomethyl benzene sulfone (tribromomethyl phenylsulfone), three (trichloromethyl)-s-triazines [tris (trichloromethyl)-s-triazine] etc.; The superoxide of two-Di tributyl superoxide (di-tertbutylperoxide) etc.
Wherein with benzophenone (benzophenone) based compound the best, especially with 4,4 '-two (diethylamine) benzophenone best results.
(D) organic solvent
Photosensitive resin composition for colour filter of the present invention system with aforementioned alkali soluble resin (A), contain the compound (B) of ethene unsaturated group, and the pigment (E) of light initiator (C) and aftermentioned is neccessary composition, can add the additive composition of aftermentioned in case of necessity.
Usually, be that pigment (E) each composition in addition is dissolved in the suitable organic solvent (D), be modulated into aqueous constituent.In the selection of aforementioned solvents (D), need are selected solubilized alkali soluble resin (A), are contained the compound (B) of ethene unsaturated group, and light initiator (C), and do not react to each other with these compositions, and have suitable volatility person.
Based on alkali soluble resin (A) 100 weight portions, the use amount of the present invention's organic solvent (D) is preferably the 300-2500 weight portion, is more preferred from the 500-2000 weight portion.
Above-mentioned solvent (D) can be selected from the solvent that is used in aforementioned bases soluble resin (A) polymerization process, does not give unnecessary details at this.Above-mentioned solvent can independent a kind of use, or two or more is mixed use.
In the aforementioned solvents (D), also preferable with 1-Methoxy-2-propyl acetate, 3-ethoxyl ethyl propionate.
(E) pigment
Based on alkali soluble resin (A) 100 weight portions, the use amount of the present invention's pigment (E) is preferably 20～500 weight portions, and the best is 50～400 weight portions.
The present invention's pigment (E) is to use known so far various inorganic pigments or organic pigment.There is the metallic compound of metal oxide, the wrong salt of metal etc. in inorganic pigment system, particularly can lift the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, inferior lead, antimony etc., and the composite oxides of aforementioned metal is example.
Organic pigment can be exemplified below:
C.I. pigment yellow 1,3, and 11,12,13,14,15,16,17,20,24,31,53,55,60,61,65,71,73,74,81,83,93,95,97,98,99,100,101,104,106,108,109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,155,156,166,167,168,175.
C.I. pigment orange 1,5, and 13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71,73.
C.I. paratonere 1,2, and 3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,19,21,22,23,30,31,32,37,38,40,41,42,48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,53:1,57,57:1,57:2,58:2,58:4,60:1,63:1,63:2,64:1,81:1,83,88,90:1,97,101,102,104,105,106,108,112,113,114,122,123,144,146,149,150,151,155,166,168,170,171,172,174,175,176,177,178,179,180,185,187,188,190,193,194,202,206,207,208,209,215,216,220,224,226,242,243,245,254,255,264,265.
C.I. pigment violet 1,19,23,29,32,36,38,39.
C.I. pigment blue 1,2,15,15:3,15:4,15:6,16,22,60,66.
C.I. pigment Green 7,36,37.
C.I. pigment brown 23,25, and 28.
C.I. pigment black 1,7.
Aforementioned pigment can be a kind of separately or be mixed two or more use.
In the photosensitive resin composition for colour filter of the present invention, the averaged particles of aforementioned organic pigment directly is preferably 0.03～0.5 μ m, is more preferred from 0.04～0.4 μ m, and the best is 0.05～0.3 μ m.
In the photosensitive resin composition for colour filter of the present invention, the polymerized unit of the maleic anhydride monomer (a-1) of alkali soluble resin (A) and (a '-1) adds up to the ratio of content and pigment (E) content to be preferably between 0.001～0.015, be more preferred between 0.002～0.012, the best is between 0.003～0.010.If this ratio is lower than 0.001, then photosensitive resin composition through develop, after the back bakes, the thermotolerance of picture element dyed layer is not good, and easily produces the pigment agglutination particle; If this ratio is higher than 0.015, then photosensitive resin composition is after developing, and unexposed part and light shield layer (black_matrix) are gone up and easily produced residue on the substrate, and after the back baked, the alkali resistance of picture element dyed layer was not good.
Colorant in the present invention (E) according to desired person, also can be followed the use spreading agent.The interfacial agent that these spreading agents can be lifted kation system, negative ion system, nonionic system, both sexes, polysiloxane series, fluorine system etc. is an example.
Wherein, interfacial agent for example has: the polyethylene oxide alkyl ethers class of polyethylene oxide lauryl ether, polyethylene oxide stearoyl ether, polyethylene oxide oil ether etc.; The polyethylene oxide alkyl benzene ethers of polyethylene oxide octyl group phenylate, polyethylene oxide nonyl phenylate etc.; The polyethylene glycol di class of polyethylene glycol dilaurate, polyglycol distearate etc.; The sorbitan fatty acid ester class; The polyesters of fatty acid upgrading; The polyurethane class of 3 grades of amine upgradings; Below be trade name: KP (SHIN-ETSU HANTOTAI's chemical industry system), SF-8427 (Toray Dow Corning Silicon system), Puli's furlong (Polyflow, common prosperity society oil chemistry industry system), Ai Fuduopu [F-Top, De Kemupuluo is big make now in the storehouse (Tochem Products Co., Ltd.)], Mei Kafuke (Megafac, the black chemical industry system of big Japan's seal), Fu Luoduo (Fluorade, Sumitomo 3M system), asafoetide card many (Asahi Guard), Sa Fulong (Surflon, Asahi Glass system) or the like.These interfacial agents can a kind of separately or above use of mixing plural number kind.
Be the raising coating in the photosensitive resin composition of the present invention, and can follow the use interfacial agent.Based on alkali soluble resin (A) 100 weight portions, the use amount of interfacial agent of the present invention generally is between 0～6 weight portion, being good between 0～3 weight portion, above-mentioned interfacial agent for example with the interfacial agent that is used in the aforementioned pigment.
In addition, in the present invention's the photosensitive resin composition, can concoct various additives in case of necessity, for example in addition macromolecular compound of filling agent, alkali soluble resin (A), adherence promoter, antioxidant, ultraviolet light absorber, anti-agglutinant etc.With respect to the alkali soluble resin (A) of 100 weight portions, the use amount of additive of the present invention generally is 0～10 weight portion, and is preferable with 0～6 weight portion, and is the best with 0～3 weight portion.
The concrete example of these additives has: the filling agent of glass, aluminium; Alkali soluble resin (A) macromolecular compound in addition of polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, poly-perfluoroalkyl acrylate alkane ester etc.; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxyethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 3-epoxy prapanol propyl trimethoxy silicane, 3-epoxy prapanol propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, the 3-chloropropylmethyldimethoxysilane, the 3-r-chloropropyl trimethoxyl silane, 3-metacryloxy propyl trimethoxy silicane, adherence promoter such as 3-mercapto propyl trimethoxy silicane; 2,2-thiobis (4-methyl-6-tributyl phenol), 2, the antioxidant of 6-two-Di tributyl phenol etc.; Ultraviolet light absorbers such as 2-(3-the tributyl-5-methyl-2-hydroxy phenyl)-5-chlorphenyl nitrine, alkoxy benzophenone; Reach anti-agglutinants such as sodium polyacrylate.
The present invention's photosensitive resin composition for colour filter system is uniformly mixed into solution state with mentioned component (A)-(E) in stirrer, can add other adjuvants such as interfacial agent, adherence auxiliary agent in case of necessity.
The present invention's photosensitive resin composition is by coating methods such as revolution coating, curtain coating coating or print roll coatings constituent to be coated on the substrate.After the coating, removal of solvents is formed the photosensitive resin composition layer in pre-roasting (prebake) mode.
Substrate of the present invention, for example be useful on the alkali-free glass, soda-lime glass, hard glass (Pai Lesi glass), quartz glass of liquid crystal indicator etc. and in these persons that adheres to the nesa coating on glass, or be used for photo-electric conversion device substrate (as silicon substrate) of solid-state image sensor etc. or the like.These substrates generally are to form the black demoulding of isolating each picture element.
Pre-roasting condition becomes kind, cooperation ratio of branchs and different according to each, carries out under 70～90 ℃ of temperature 1 minute～15 minutes usually.After pre-roasting, this photosensitive resin composition layer exposes between between specified light shield (mask), impregnated in developer solution to develop in 30 seconds～5 minutes under 23 ± 2 ℃ of temperature, and that does not want partly removes and form pattern.The light of exposure use be good with the ultraviolet ray of g line, h line, i line etc., and UV-device can be (surpassing) high mercury vapor lamp and metal halid lamp.
Moreover, developer solution system uses as NaOH, potassium hydroxide, sodium carbonate, sodium bicarbonate, sal tartari, saleratus, sodium silicate, sodium methyl silicate, ammoniacal liquor, ethamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrroles, piperidines, 1,8-diazabicylo-(5,4,0)-alkali compounds such as 7-hendecene, the concentration of developer solution is preferably 0.001～10wt%, the alkaline aqueous solution that the best is constituted by 0.01～1wt%.
When using the developer solution that these alkaline aqueous solutions constitute, generally lie in after the video picture clean to wash again.Secondly with pressurized air or compressed nitrogen that pattern is air-dry.
Make last heat treated with heating arrangements such as hot plate or baking ovens more afterwards.To decide heating-up temperature be 150～250 ℃, be 5 minutes～60 minutes heat time heating time when using hot plate, be 30 minutes～90 minutes the heat time heating time when using baking oven for heating.
(mainly comprising red, green, blue three looks) of all kinds repeats above-mentioned steps, just can make the picture element dyed layer of colored filter.Secondly, to the vacuum of 250 ℃ of temperature, forming the ITO vapor-deposited film with 220 ℃ on the picture element dyed layer, in case of necessity, after execution etching of ITO film and wiring, coating of liquid crystalline alignment film polyimide again, and then burn till it, promptly can be used as the colored filter that LCD is used.
State and other technology contents, characteristics and effect before the present invention,, can know and understand in the explanation of following cooperation embodiment and comparative example.
[synthesis example of alkali soluble resin (A-1)]
Synthesis example A-1-1
On four cervical vertebra bottles of 1000 milliliters of volumes, nitrogen inlet, stirrer, well heater, condenser pipe and thermometer are set, and import nitrogen and add the feed composition thing according to consumption shown in the table one, above-mentioned feed composition thing comprises: maleic anhydride monomer (hereinafter to be referred as MAn) 1 weight portion, methacrylic acid monomer (hereinafter to be referred as MAA) 14 weight portions, methacrylic acid benzene methyl monomer (hereinafter to be referred as BzMA) 75 weight portions, methacrylate monomer (hereinafter to be referred as MA) 10 weight portions, and solvent 3-ethoxyl ethyl propionate (hereinafter to be referred as EEP) 200 weight portions.Wherein, the enter material way of monomer mixture is for once all adding.
When within the four cervical vertebra bottles during tolerant being stirred, the temperature of oil bath is promoted to 100 ℃, then according to shown in the table one with polymerization with initiator 2,2 '-azo is two-and 2-methylbutyronitrile (hereinafter to be referred as AMBN) 4 weight portions are dissolved among the organic solvent EEP, and are added in the four cervical vertebra bottles at interval at one hour with the amount of five equal portions.
The temperature of reaction of polymerization process is kept 100 ℃, polymerization time 6 hours.After polymerization is finished, polymerizate is taken out in four cervical vertebra bottles,, can get alkali soluble resin A-1-1 the solvent devolatilization.
Synthesis example A-1-2～A-1-8
With the method for operating of synthesis example A-1-1, difference system changes kind and the mixing consumption of polymerization with monomer, and its prescription and reaction conditions are stated from table one.
Synthesis example A-1-9
Under the normal temperature, (copolymerization was than 1: 1, molecular weight 10 with styrene-maleic anhydride copolymer, 000) 500 weight portions are dissolved in ethoxyethyl acetate(EA) 1300 weight portions, add triethylamine 10 weight portions, hydroquinone monomethyl ether 2 weight portions, and NOF Corp's system polyethylene glycol monomethacrylate (trade name Blemmer-PE-350) 109 weight portions, reaction is 3 hours under 90～95 ℃ of temperature.Again above-mentioned reactant liquor is cooled to 80 ℃, adds Hydroxyethyl Acrylate 250 weight portions, reaction is 3 hours under 90～95 ℃ temperature.After polymerization is finished, polymerizate is taken out in four cervical vertebra bottles,, can get alkali soluble resin A-1-9 the solvent devolatilization.
Synthesis example A-1-10
On four cervical vertebra bottles of 1000 milliliters of volumes, nitrogen inlet, stirrer, well heater, condenser pipe and thermometer are set, and import nitrogen.With MAn monomer 50 weight portions, styrene monomer (hereinafter to be referred as SM) 50 weight portions, solvent methyl isobutyl ketone (hereinafter to be referred as MIBK) 200 weight portions, and initiator dicumyl peroxide (hereinafter to be referred as DCP) 2 weight portions add simultaneously in the four cervical vertebra bottles.
The temperature of reaction of polymerization process is kept 130 ℃, polymerization time 4 hours.After polymerization is finished, polymerizate is taken out in four cervical vertebra bottles,, can get alkali soluble resin A-1-10 the solvent devolatilization.
[synthesis example of alkali soluble resin (A-2)]
Synthesis example A-2-1
On four cervical vertebra bottles of 1000 milliliters of volumes, nitrogen inlet, stirrer, well heater, condenser pipe and thermometer are set, and import nitrogen and add the feed composition thing according to consumption shown in the table one, above-mentioned feed composition thing comprises: acrylic monomers (hereinafter to be referred as AA) 5 weight portions, MAA monomer 15 weight portions, SM monomer 60 weight portions, MA monomer 10 weight portions, and solvent EEP200 weight portion.Wherein, the enter material way of monomer mixture is for once all adding.
When within the four cervical vertebra bottles during tolerant being stirred, the temperature of oil bath is promoted to 100 ℃, then according to shown in the table one polymerization being dissolved among the organic solvent EEP with initiator AMBN 4 weight portions, and is added in the four cervical vertebra bottles at interval at one hour with the amount of five equal portions.
The temperature of reaction of polymerization process is kept 100 ℃, polymerization time 6 hours.After polymerization is finished, polymerizate is taken out in four cervical vertebra bottles,, can get alkali soluble resin A-2-1 the solvent devolatilization.
Synthesis example A-2-2～A-2-4
With the method for operating of synthesis example A-2-1, difference system changes kind and the mixing consumption of polymerization with monomer, and its prescription and reaction conditions are stated from table two.
[embodiment of photosensitive resin composition and comparative example]
Embodiment 1
Use alkali soluble resin (A-1-1) 100 weight portions (solid) of aforementioned synthesis example gained, with the dipentaerythritol acrylate shown in the table three (hereinafter to be referred as B-1) 120 weight portions, 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone (hereinafter to be referred as C-1) 22 weight portions, 4,4 '-two (diethylamine) benzophenone (hereinafter to be referred as C-2), 22 weight portions, 2,2 '-two (2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl diimidazole (hereinafter to be referred as C-3), 22 weight portions, the potpourri of pigment CI254 (hereinafter to be referred as E-1) 130 weight portions, after adding solvent 3-ethoxyl ethyl propionate (hereinafter to be referred as D-1) 830 weight portions and 1-Methoxy-2-propyl acetate (hereinafter to be referred as D-2) 170 weight portions, with swing-out stirrer, dissolved mixed, can modulate and photosensitive resin composition for colour filter, each evaluation of measuring mode of the following note of this photosensitive resin composition is estimated, and the gained result as shown in Table 3.
[evaluation method]
(1) polymerized unit of the maleic anhydride monomer (a-1) of alkali soluble resin (A) and (a '-1) total content (unit: weight %) can following calculating formula try to achieve by this content.
The polymerized unit of maleic anhydride monomer (a-1) and (a '-1) adds up to the whole content * 100 weight % of content/photosensitive resin composition.
Wherein, the polymerized unit content of maleic anhydride monomer (a-1) and (a '-1) can be respectively calculated and is got by the raw material feeding in alkali soluble resin (A-1) and the polyreaction (A-2), each monomer conversion and volatile component that each reclaims.
(2) pigment (E) content (unit: weight %)
This content can following calculating formula be tried to achieve.
Whole content of the use amount/photosensitive resin composition of pigment * 100 weight %
(3) polymerized unit of the maleic anhydride monomer (a-1) of alkali soluble resin (A) and (a '-1) adds up to the ratio of content and pigment (E) content
This ratio can following calculating formula be tried to achieve.
The polymerized unit of the maleic anhydride monomer (a-1) of alkali soluble resin (A) and (a '-1) adds up to content/pigment (E) content
(4) thermotolerance
Obtained photosensitive resin composition in the rotary coating mode, is coated on 10 centimeters * 10 centimeters glass substrates, can obtains filming of about 8 μ m, 85 ℃ of pre-down baking 5 minutes.Then this is filmed with ultraviolet light (exposure machine CanonPLA-501F) 200mJ/cm
2Irradiation, the developer solution that impregnated in 23 ℃ afterwards developed in 2 minutes, cleaned with pure water, baked 40 minutes after 200 ℃ again, can form photo-sensitive resin on glass substrate.
With the photo-sensitive resin on the obtained glass substrate, its light transmission rate of light measurement with 400～700nm wavelength changes, place in 250 ℃ then after 60 minutes, its transmitance of light measurement with 400～700nm wavelength changes again, and according to its variation ratio with following benchmark evaluation.
Zero: transmitance changes below 5%
△: transmitance changes 5～10%
*: transmitance changes more than 10%
(5) alkali resistance
With the photo-sensitive resin on the obtained glass substrate, its light transmission rate of light measurement with 400～700nm wavelength changes, place in 2%NaOH then after 10 minutes, its transmitance of light measurement with 400～700nm wavelength changes again, and according to its variation ratio with following benchmark evaluation.
Zero: transmitance changes below 5%
△: transmitance changes 5～10%
*: transmitance changes more than 10%
(6) pigment agglutination particle
With the photo-sensitive resin on the obtained glass substrate, have or not the pigment agglutination particle (particle diameter of general pigment agglutination particle is between 1～10 μ m) to occur with microscopic examination, with following benchmark evaluation.
Zero: no pigment agglutination particle
△: a little pigment agglutination particle
*: many pigment agglutination particle
(7) residue
Aforementioned obtained photosensitive resin composition to change coating method, is coated on 10 centimeters * 10 centimeters glass substrates, can obtains filming of about 8 μ m, 85 ℃ of pre-down baking 5 minutes.Then this is filmed between between specified mask pattern with ultraviolet light (exposure machine Canon PLA-501F) 300mJ/cm
2Irradiation, the developer solution that impregnated in 23 ℃ afterwards developed unexposed partly removing on substrate in 2 minutes, clean with pure water, after 200 ℃, baked 40 minutes again, can on glass substrate, form the photoresist pattern of being wanted, with microscopic examination, determine whether unexposed part has residue to exist.
Zero: no residue
△: a little residue
*: residue is a lot
Embodiment 2～4
With the method for operating of embodiment 1, difference system changes the kind and the consumption of alkali soluble resin (A), and its prescription and evaluation result are stated from table three.
Embodiment 5～7
With the method for operating of embodiment 1, difference system changes the kind and the consumption of alkali soluble resin (A) and pigment (E), and its prescription and evaluation result are stated from table three.
Comparative example 1～9
With the method for operating of embodiment 1, difference system changes the kind and the consumption of alkali soluble resin (A), and its prescription and evaluation result are stated from table three.
Comparative example 10
With the method for operating of embodiment 1, difference system changes the consumption of alkali soluble resin (A) and pigment (E), and its prescription and evaluation result are stated from table three.
The above person of thought, only for the present invention's preferred embodiment, when the scope that can not limit the invention process with this, promptly the simple equivalent of being done according to the present patent application claim and description of the invention content generally changes and modifies, and all should still belong in the scope that patent of the present invention contains.
The subordinate list explanation
Table one: the proportion of composing of each synthesis example of alkali soluble resin of the present invention (A-1).
Table two: the proportion of composing of each synthesis example of alkali soluble resin of the present invention (A-2).
Table three: the proportion of composing and the evaluation result of each embodiment of resin combination of the present invention and comparative example.
The synthesis example of table one, alkali soluble resin (A-1)
| Synthesis example | Constituent (weight portion) | ||||||||
| The copolymerization monomer | Initiator | Solvent | |||||||
| (a-1) | (a-2) | (a-3) | AMBN | EEP | |||||
| (a-3-1) | (a-3-2) | ||||||||
| MAn | AA | MAA | BzMA | SM | HEMA | MA | |||
| A-1-1 | 1 | 14 | 75 | 10 | 4 | 200 | |||
| A-1-2 | 5 | 5 | 10 | 65 | 10 | 5 | 4 | 200 | |
| A-1-3 | 10 | 20 | 70 | 4 | 200 | ||||
| A-1-4 | 20 | 10 | 65 | 5 | 4 | 200 | |||
| A-1-5 | 0 | 15 | 75 | 10 | 4 | 200 | |||
| A-1-6 | 35 | 15 | 50 | 4 | 200 | ||||
| A-1-7 | 10 | 2 | 75 | 13 | 4 | 200 | |||
| A-1-8 | 10 | 45 | 40 | 5 | 4 | 200 | |||
| Be called for short | Chinese | English name |
| MAn AA MAA BzMA SM HEMA MA AMBN EEP | Maleic anhydride monomer acrylic monomers methacrylic acid monomer methacrylic acid benzene methyl monomer styrene monomer 2-hydroxyethyl methacrylate methacrylate monomer 2,2 '-azo is two-2-methylbutyronitrile 3-ethoxyl ethyl propionate | maleic anhydride acrylic acid methacrylic acid benzyl methacrylate styrene monomer 2-hydroxyethyl(meth)acrylate methyl acrylate 2，2’-azobis-2-methyl butyronitrile ethyl 3-ethoxypropionate |
The synthesis example of table two, alkali soluble resin (A-2)
| Synthesis example | Constituent (weight portion) | |||||||
| The copolymerization monomer | Initiator | Solvent | ||||||
| (a’-1) | (a’-2) | (a’-3) | AMBN | EEP | ||||
| (a’-3-1) | (a’-3-2) | |||||||
| MAn | AA | MAA | BzMA | SM | MA | |||
| A-2-1 | 0 | 5 | 15 | 60 | 20 | 4 | 200 | |
| A-2-2 | 0.1 | 20 | 75 | 4.9 | 4 | 200 | ||
| A-2-3 | 0 | 3 | 75 | 22 | 4 | 200 | ||
| A-2-4 | 0 | 55 | 40 | 5 | 4 | 200 | ||
| Be called for short | Chinese | English name |
| MAn AA MAA BzMA SM MA AMBN EEP | Maleic anhydride monomer acrylic monomers methacrylic acid monomer methacrylic acid benzene methyl monomer styrene monomer methacrylate monomer 2,2 '-azo is two-2-methylbutyronitrile 3-ethoxyl ethyl propionate | maleic anhydride acrylic acid methacrylic acid benzyl methacrylate styrene monomer methyl acrylate 2，2’-azobis-2-methyl butyronitrile ethyl 3-ethoxypropionate |
Table three, photosensitive resin composition embodiment and comparative example
| Composition | Embodiment | Comparative example | ||||||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | ||||
| Alkali soluble resin (A) (weight portion) | Alkali soluble resin (A-1) (weight portion) | A-1-1 | 100 | 70 | 40 | 15 | ||||||||||||||
| A-1-2 | 10 | 15 | 20 | 20 | ||||||||||||||||
| A-1-3 | 5 | |||||||||||||||||||
| A-1-4 | 2 | |||||||||||||||||||
| A-1-5 | 20 | |||||||||||||||||||
| A-1-6 | 5 | |||||||||||||||||||
| A-1-7 | 20 | |||||||||||||||||||
| A-1-8 | 20 | |||||||||||||||||||
| A-1-9 | 100 | |||||||||||||||||||
| A-1-10 | 2 | |||||||||||||||||||
| Alkali soluble resin (A-1) (weight portion) | A-2-1 | 30 | 60 | 90 | 95 | 85 | 100 | 80 | 95 | 80 | 80 | 98 | 85 | |||||||
| A-2-2 | 98 | |||||||||||||||||||
| A-2-3 | 80 | |||||||||||||||||||
| A-2-4 | 80 | |||||||||||||||||||
| The compound (B) (weight portion) that contains the ethene unsaturated group | B-1 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | 120 | ||
| Light initiator (C) (weight portion) | C-1 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | ||
| C-2 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | |||
| C-3 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | 22 | |||
| Solvent (D) (weight portion) | D-1 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | 830 | ||
| D-2 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | 170 | |||
| Pigment (E) (weight portion) | E-1 E-2 E-3 | 130 | 130 | 130 | 130 | 220 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 130 | 220 | ||||
| 130 | ||||||||||||||||||||
| 100 | ||||||||||||||||||||
| The alkali-soluble tree refers to maleic anhydride monomer (a-1) and the polymerized unit total content of (a '-1) and the ratio of pigment (E) content of (A) | 0.0077 | 0.0054 | 0.0031 | 0.0038 | 0.0038 | 0.0050 | 0.0034 | 0.0000 | 0.0000 | 0.0135 | 0.0154 | 0.0154 | - | 0.0077 | 0.0077 | 0.0077 | 0.0007 | |||
| Evaluation result | Thermotolerance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | × | ○ | ○ | △ | × | × | ○ | △ | × | ||
| Alkali resistance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | △ | × | ○ | ○ | ○ | × | ○ | |||
| The pigment agglutination particle | ○ | ○ | ○ | ○ | ○ | ○ | ○ | × | × | ○ | ○ | ○ | × | × | ○ | ○ | × | |||
| Residue | △ | ○ | ○ | ○ | ○ | △ | ○ | ○ | ○ | × | × | △ | ○ | ○ | × | ○ | ○ | |||
| B-1 C-1 C-2 C-3 D-1 D-2 E-1 E-2 E-3 | Dipentaerythritol acrylate 2 benzyls-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone 4,4 '-two (diethylamine) benzophenone 2,2 '-two (neighbour-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole 3-ethoxyl ethyl propionate 1-Methoxy-2-propyl acetate pigment CI254 pigment G36 pigment B15:6 | dipentaerythritol hexaacrylate 2-benzyl-2-N，N-dimethylamino-1-(4-morpholinophenyl)-1-butanone 4，4’-bis(diethylamino)benzophenone 2，2’-bis(o-chlorophenyl)-4，4’，5，5’-tetraphenylbiimidazole Ethyl 3-ethoxypropionate propylene glycol methyl ether acetate |
Claims (1)
1, a kind of photosensitive resin composition for colour filter, its constituent comprises:
(A) alkali soluble resin;
(B) contain the compound of ethene unsaturated group;
(C) light initiator;
(D) organic solvent; And
(E) pigment;
Wherein, this alkali soluble resin (A) is by alkali soluble resin (A-1) 0.1～100 weight portion and optionally is selected from a kind of alkali soluble resin (A-2) 99.9～0 weight portions and combined, more than (A-1), (A-2) add up to 100 weight portions; Wherein, this alkali soluble resin (A-1) is to be formed by maleic anhydride monomer (a-1) 0.2～30 weight portion, unsaturated monomer (a-2) 3～40 weight portions that contain carboxyl, monomer (a-1), (a-2) other copolymerizable vinyl monomer (a-3) 30～96.8 weight portions institute copolymerization in addition, more than (a-1), (a-2), (a-3) add up to 100 weight portions; And the ratio of the use amount of the use amount of monomer (a-1) and monomer (a-2) is between 0.01～3.0; Alkali soluble resin (A-2) is by maleic anhydride monomer (a '-1) below 0.2 weight portion, but unsaturated monomer (a '-2) 5～50 weight portions, monomer (a '-1), (a '-2) other copolymerizable vinyl monomer (a '-3), copolymerization of 49.8～95 weight portions institute in addition of do not contain 0.2 weight portion, containing carboxyl form, more than (a '-1), (a '-2), (a '-3) add up to 100 weight portions; And in the above-mentioned photosensitive resin composition, the polymerized unit of the maleic anhydride monomer (a-1) of alkali soluble resin (A) and (a '-1) adds up to the ratio of content and pigment (E) content between 0.001～0.015; And based on alkali soluble resin (A) 100 weight portions, the use amount of compound (B) that contains the ethene unsaturated group is between 5～220 weight portions, and the use amount of organic solvent (D) is the 20-500 weight portion between the use amount of 300～2500 weight portions, pigment (E); And based on the compound that contains the ethene unsaturated group (B) 100 weight portions, the use amount of light initiator (C) is between 20～120 weight portions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310124450 CN1277132C (en) | 2003-12-26 | 2003-12-26 | Light sensitive resin composition for color filter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310124450 CN1277132C (en) | 2003-12-26 | 2003-12-26 | Light sensitive resin composition for color filter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1554959A CN1554959A (en) | 2004-12-15 |
| CN1277132C true CN1277132C (en) | 2006-09-27 |
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|---|---|---|---|
| CN 200310124450 Expired - Fee Related CN1277132C (en) | 2003-12-26 | 2003-12-26 | Light sensitive resin composition for color filter |
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| CN (1) | CN1277132C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100409073C (en) * | 2004-12-30 | 2008-08-06 | 财团法人工业技术研究院 | Alkali soluble resin, and composition containing the resin and capable of sensing optical activity |
| JP5723699B2 (en) * | 2011-02-25 | 2015-05-27 | 富士フイルム株式会社 | Light-shielding composition, method for producing light-shielding composition, solder resist, pattern forming method, and solid-state imaging device |
| TWI484299B (en) * | 2013-02-04 | 2015-05-11 | Everlight Chem Ind Corp | Use of positive-tone photoresist composition |
| TWI490238B (en) * | 2013-05-22 | 2015-07-01 | Daxin Materials Corp | An acrylic resin composition, an alignment film formed, and a three-dimensional liquid Crystal display |
| CN104865794A (en) * | 2014-02-20 | 2015-08-26 | 上海飞凯光电材料股份有限公司 | Photoresist |
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