CN100434948C - Photosensitive resin composition for colour filter - Google Patents
Photosensitive resin composition for colour filter Download PDFInfo
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- CN100434948C CN100434948C CNB2004100925901A CN200410092590A CN100434948C CN 100434948 C CN100434948 C CN 100434948C CN B2004100925901 A CNB2004100925901 A CN B2004100925901A CN 200410092590 A CN200410092590 A CN 200410092590A CN 100434948 C CN100434948 C CN 100434948C
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Abstract
The present invention provides a photosensitive resin composition for color filters of a liquid crystal display, particularly a photosensitive resin composition for color filters, which has the advantages of good sensitivity during exposure, few residues on the unexposed part and a shading layer on a base plate after development, good side shape of picture element patterns after baking, good chroma and contrast grade of the formed color filters and high solubility of used optical initiators to solvents. The composition comprises alkali soluble resin, a compound containing an ethylene unsaturation base, the optical initiators, organic solvents and pigment, wherein the optical initiators contain a biimidazole compound indicated by undermentioned structural formula (1); the average particle diameter of primary particles of the pigment is between 10 and 200 nm; on the basis of every 100 parts by weight of alkali soluble resin, the consumption of the pigment is between 100 and 800 parts by weight; in the structural formula (1), R is alkyl of which the carbon number is from 1 to 4.
Description
Technical field
The present invention is the photosensitive resin composition for colour filter of relevant a kind of LCD.Sensitivity when a kind of the exposure particularly is provided is good, the level of residue of back on unexposed part and light shield layer on the substrate that develop is few, the shape of picture element pattern side, roasting back, back is good, the chroma and the contrast of formed colored filter are good, and the employed smooth initiator photosensitive resin composition for colour filter high to the solubleness of solvent.
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.
Usually, colored filter can by decoration method, print process, electricity methods such as method, pigment dispersing method, picture elements such as red, green, blue be formed on the transparent glass substrate and make.Generally speaking, for improving the contrast of colored filter, can between the picture element dyed layer, dispose light shield layer (or claiming black matrix") again.
In the processing procedure of decoration method, it is to mix earlier dichromate (dichromate is the usefulness as emulsion) to form photoresist in gel or polyvinyl alcohol (PVA), will dye behind this photoresist formation pattern more again.But when on same substrate, forming polychrome picture element dyed layer, must increase the resist printing engineering, so easily increase the complicacy of engineering to prevent that the picture element dyed layer from being polluted with decoration method; And, easily cause the weatherability variation of picture element dyed layer because of using dyestuff in the processing procedure; Again because of with dichromate as emulsion, the angle from public hazards prevent also has many problem points.
In the processing procedure of print process, it is in the mode of screen painting (Screen Printing) or flexure print process (flexo printing), and thermmohardening or photo-hardening printing ink are transferred on the glass substrate.This method has the advantage that need not form complex engineerings such as pattern and dyeing, but this method is difficult for making high meticulous picture element dyed layer, and has the not good problem of printing ink flatness.
Electricity in the processing procedure of method, it is that the glass substrate that will be provided with electrode infiltrates in the bath that contains pigment or dyestuff, the effect by electric swimming is attached to form and aspect on the substrate.This method has the good advantage of flatness of picture element dyed layer, but this method is provided with electrode in advance because of need on glass substrate, than complicated patterns its difficulty is arranged so desire forms.
In the processing procedure of pigment dispersing method, its be earlier with pigment dispersing in ray hardening resin and form colored photosensitive polymer combination, at last this resin combination is formed the picture element dyed layer.Advantages such as this method has high-fire resistance, need not dye, and, now become the main flow of making colored filter because of forming high-precision picture element dyed layer.
In the processing procedure of above-mentioned pigment dispersing method, usually system is earlier on transparent supports such as glass substrate, form light shield layer (black matrix) with metal photomasks such as chromium or chromium oxide, and then will disperse the photoresist (chromatic photoresist) of red pigment this photoresist to be coated on the transparent support by the rotary coating mode, expose by light shield, carry out after the exposure development treatment get final product red picture element; With same mode of operation, promptly repeat on support, to make three look picture elements such as red, green, blue respectively again by the mode of coating, exposure, development.
In the processing procedure of pigment dispersing method, the concrete example of employed photosensitive resin composition as: this photosensitive resin composition system is made up of pigment, alkali soluble resin, multi-functional monomer, light initiator and solvent, and wherein employed smooth initiator generally is as 2 with known smooth initiator, 2 '-two (neighbour-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2-bis (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenylbiimidazole] compound be main.(pertinent literature such as Japanese kokai publication hei 10-260309 communique, the spy open among the embodiment of flat 10-288837 communique put down in writing).
In recent years, the purposes of colour liquid crystal display device not only is confined on the personal computer, also is widely used in by (especially large-sized color liquid crystal TV) on color TV and the various supervision screen, and in this application, generally all is attended by the requirement of high chroma.For reaching this requirement, general corresponded manner is in photosensitive resin composition for colour filter, uses the pigment of high concentration or harmonic(-)mean particle diameter.
So in applying high densityization or the harmonic(-)mean particle footpath photosensitive resin composition that pigment disperseed, if when only using above-mentioned known smooth initiator, the sensitivity when then easily exposure taking place is poor, develop that the level of residue of back on unexposed part and light shield layer on the substrate is many, the back roasting after problem points such as the shapes of picture element pattern side are not good; And, more increase the difficulty of operation because of this known smooth initiator is low to the solubleness of solvent.
Summary of the invention
The object of the present invention is to provide a kind of photosensitive resin composition for colour filter of LCD.Sensitivity when a kind of the exposure particularly is provided is good, the level of residue of back on unexposed part and light shield layer on the substrate that develop is few, the shape of picture element pattern side, roasting back, back is good, the chroma and the contrast of formed colored filter are good, and the employed smooth initiator photosensitive resin composition for colour filter high to the solubleness of solvent.
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 light initiator (C) is to contain the represented diimidazole based compound (c-1) of note structural formula (1) down; And the averaged particles of the primary particle of pigment (E) footpath is between 10～200nm; And based on alkali soluble resin (A) 100 weight portions, the use amount of compound (B) that contains the ethene unsaturated group is between 10～500 weight portions, the use amount of organic solvent (D) is between 500～5,000 weight portion, and the use amount of pigment (E) is between 100～800 weight portions; And based on the compound that contains the ethene unsaturated group (B) 100 weight portions, the use amount of light initiator (c-1) is between 0.1～70 weight portion; This alkali soluble resin (A) is by the ethylene unsaturated monomer that contains one or more carboxylic acid group (a-1), and other copolymerizable ethylene unsaturated monomer (a-2) institute copolymerization forms.
In the structural formula (1), R is the alkyl of carbon element several 1～4.
Description of drawings
Aforementioned and other technology contents, characteristics and effect of the present invention in the explanation of following cooperation embodiment and comparative example, can clearly be understood, wherein:
Fig. 1 is the edge side surface state of photoresist pattern;
Fig. 2 is the edge side surface state of photoresist pattern;
Fig. 3 A is that the photo-sensitive resin contrast is measured view ();
Fig. 3 B is that the photo-sensitive resin contrast is measured view (two);
Embodiment
Below one by one each composition of the present invention is described in detail:
(A) alkali soluble resin
Alkali soluble resin of the present invention (A) is by the ethylene unsaturated monomer that contains one or more carboxylic acid group (a-1) 5～50 weight portions, and other copolymerizable ethylene unsaturated monomer (a-2) 95～50 weight portions institute copolymerization forms, more than (a-1), (a-2) add up to 100 weight portions.
The concrete example of the above-mentioned ethylene unsaturated monomer (a-1) that contains one or more carboxylic acid group is as the unsaturated monocarboxylic acid class of acrylic acid, methacrylic acid, butenoic acid, α-Lv Bingxisuan, ethylacrylic acid and cinnamic acid etc.; Unsaturated dicarboxylic acid (acid anhydride) class of maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride etc.; Unsaturated polyvalent carboxylic acid (acid anhydride) class that 3 valencys are above or the like.
Wherein cited is with acrylic acid, methacrylic acid is preferable.These ethylene unsaturated monomers that contain one or more carboxylic acid group can a kind of separately or mixing plural number kind use.
The concrete example of above-mentioned other copolymerizable ethylene unsaturated monomer (a-2) is as: styrene, α-Jia Jibenyixi, vinyltoluene, to the aromatic ethenyl compound of chlorostyrene, methoxy styrene etc.; Between N-phenyl Malaysia vinegar imines, N-neighbour-hydroxy phenyl Malaysia vinegar imines, N--hydroxy phenyl Malaysia vinegar imines, N-be right-hydroxy phenyl Malaysia vinegar imines, N-neighbour-aminomethyl phenyl Malaysia vinegar imines, N-between-aminomethyl phenyl Malaysia vinegar imines, N-be right-aminomethyl phenyl Malaysia vinegar imines, N-neighbour-methoxyphenyl Malaysia vinegar imines, N-between-methoxyphenyl Malaysia vinegar imines, N-be right-Malaysia vinegar imines class such as methoxyphenyl Malaysia vinegar imines, N-cyclohexyl Malaysia vinegar imines; 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, tert-butyl acrylate, the metering system tert-butyl acrylate, 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, the acrylic acid benzene methyl, the methacrylic acid benzene methyl, phenyl acrylate, phenyl methacrylate, acrylic acid triethylene glycol methoxyethoxy ester (methoxy triethyleneglycol acrylate), methacrylic acid triethylene glycol methoxyethoxy ester (methoxy triethyleneglycol methacrylate), lauryl methacrylate (lauryl methacrylate), methacrylic acid myristyl ester (tertadecyl methacrylate), methacrylic acid cetyl ester (cetyl methacrylate), methacrylic acid stearyl (octadecylmethacrylate), methacrylic acid eicosyl ester (eicosylmethacrylate), 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 vinegar amine of acrylamide, metering system vinegar amine, α-chloropropene vinegar amine, N-hydroxyethyl acrylamide, N-hydroxyethyl metering system vinegar amine etc.; The aliphatics conjugated diene of 1,3-butadiene, different propylene, chloropropene etc.
Wherein cited person is preferable with styrene, N-phenyl Malaysia vinegar imines, methyl acrylate, methyl methacrylate, acrylic acid 2-hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid benzene methyl, methacrylic acid benzene methyl.These other copolymerizable ethylene unsaturated monomer can be a kind of separately or be mixed plural number and plant and use.
The employed during fabrication solvent of alkali soluble resin of the present invention (A), general concrete example commonly used is as ethylene glycol monomethyl ether, 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 monomethyl ether), (gathering) alkylene glycol mono alkane ethers of tripropylene glycol ether (tripropylene glycol mono ethylether) etc.; (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, second vinegar methyl acetate, second vinegar ethyl acetate, other ester classes such as 2-oxygen base ethyl butyrate; Aromatic hydrocarbons such as toluene, dimethylbenzene class; N-Methyl pyrrolidone, N, N-dimethyl amide, N, carboxylic acid vinegar amines such as N-dimethyl ethanamide or the like.
Wherein cited person is preferable with 1-Methoxy-2-propyl acetate, 3-ethoxyl ethyl propionate.This equal solvent can a kind of separately or mixing plural number kind use.
Employed initiator when alkali soluble resin (A) is made, be generally free radical shape polymerization initiator, concrete example as: 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); Diphenyl peroxide first vinegar per-compound such as (benzoylperoxide).
(B) contain the compound of ethene unsaturated group
Based on alkali soluble resin (A) 100 weight portions, the use amount that contains the compound (B) of ethene unsaturated group of the present invention is generally 10～500 weight portions, is preferably 30～400 weight portions, is more preferred from 50～300 weight portions.
The above-mentioned compound (B) that contains the ethene unsaturated group is the compound that refers to have at least one ethene unsaturated group.
The concrete example of compound that wherein has ethene unsaturated group is as acrylamide, (methyl) propylene vinegar 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, uncle's octyl group (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, vinegar amine in vinyl is own, 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 compound with two or more ethene unsaturated groups is as 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.
The aforementioned cited compound that contains the ethene unsaturated group is with three acrylic acid trihydroxy methyl propyl ester, three acrylic acid trihydroxy methyl propyl ester of EO upgrading, three acrylic acid trihydroxy methyl propyl ester of PO upgrading, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, dipentaerythritol five acrylate, the dipentaerythritol tetraacrylate, the dipentaerythritol acrylate of caprolactone upgrading, tetrapropylene acid two trihydroxy methyl propyl ester, the glycerin tripropionate of PO upgrading is preferable.These compounds that contain the ethene unsaturated group can a kind of separately or mixing plural number kind use.
(C) light initiator
Initiator of the present invention (C) is to contain the represented diimidazole based compound (c-1) of note structural formula (1) down.
Structural formula (1)
(in the structural formula (1), R is the alkyl of carbon element several 1～4)
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-1) is generally 0.1～70 weight portion, is preferably 0.5～60 weight portion, is more preferred from 1～40 weight portion.
The concrete example of smooth initiator of the present invention (c-1) is as 2,2 '-two (neighbour-aminomethyl phenyl)-4,4 ', 5, and 5 '-tetraphenyl diimidazole [2,2 '-bis (o-methyl phenyl)-4,4 ', 5,5 '-tetraphenyl biimidazole], 2,2 '-two (neighbour-ethylphenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2,2 '-bis (o-ethyl phenyl)-4,4 ', 5,5 '-tetraphenyl biimidazole] or the like.
Wherein cited person is with 2,2 '-two (neighbour-aminomethyl phenyl)-4, and 4 ', 5,5 '-tetraphenyl diimidazole is preferable.These light initiators (c-1) can a kind of separately or mixing plural number kind use.
In the photosensitive resin composition of the present invention, note light initiator (c-1) light initiator (c-2) in addition before can further adding according to need.For example: the acetophenone based compound.
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-2) is generally 0～200 weight portion, is preferably 1～150 weight portion, is more preferred from 5～100 weight portions.
The concrete example of above-mentioned 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-morpholino propane-1-on), 2-benzyl-2-N, N dimethylamine-1-(4-morpholino phenyl)-1-butanone [2-benzyl-2-N, N-dimethylamino-1-(4-morphol inophenyl)-1-butanone].
Wherein cited person is with 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino-1-acetone, 2-benzyl-2-N, and (4-morpholino phenyl)-the 1-butanone is preferable for N dimethylamine-1-.These light initiators (c-2) can a kind of separately or mixing plural number kind use.
In the photosensitive resin composition of the present invention, under the situation that does not influence action effect of the present invention, note light initiator (c-1) and (c-2) in addition light initiator (c-3) before according to need can be more further adding as one feels fit.For example: in addition diimidazole (biimidazole) compounds of light initiator (c-1), benzophenone (benzophenone) compounds, α-diketone (α-diketone) compounds, keto-alcohol (acyloin) compounds, keto-alcohol ether (acyloin ether) compounds, vinegar phosphine oxide (acylphosphineoxide) compounds, quinone (quinone) compounds, halogen-containing compounds, superoxide etc.
Based on the compound that contains the ethene unsaturated group (B) 100 weight portions, the use amount of smooth initiator of the present invention (c-3) is generally 0～150 weight portion, is preferably 0～80 weight portion, is more preferred from 0～30 weight portion.
The concrete example of above-mentioned light initiator (c-1) diimidazole compounds in addition 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 '-tetraphenyl-biimidazole], 2,2 '-two (2, the 4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole [2, and 2 '-bis (2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-biimidazole], 2,2 '-two (neighbour-methoxyphenyl)-4,4 ', 5,5 '-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, [2,2 '-bis (2 for 5 '-tetraphenyl diimidazole, 2 ', 4,4 '-tetramethoxyphenyl)-4,4 ', 5,5 '-tetraphenyl-biimidazole] etc.; The concrete example of benzophenone compound is 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.; The concrete example of α-cyclohexadione compounds is as: benzene idol vinegar (benzil), acetyl group (acetyl) etc.; The concrete example of ketols compound is as diphenylhydroxyethanone (benzoin) etc.; The concrete example of keto-alcohol ether compound is as diphenylhydroxyethanone methyl ether (benzoin methylether), diphenylhydroxyethanone ether (benzoin ethylether), diphenylhydroxyethanone isopropyl ether (benzoin isopropyl ether) etc.; The concrete example of vinegar phosphine oxide compounds as: 2,4,6-trimethylbenzene vinegar diphenyl phosphine oxide (2,4,6-trimethyl-benzoyl diphenylphosphineoxide), two-(2,6-dimethoxy benzene vinegar)-2,4, and 4-trimethylphenyl phosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethylbenzyl phosphineoxide] etc.; The concrete example of quinones is as anthraquinone (anthraquinone), 1, and the 4-naphthoquinones (1,4-naphthoquinone) etc.; The concrete example of halogen-containing compounds is as benzene vinegar methyl chloride (phenacyl chloride), trisbromomethyl benzene sulfone (tribromomethyl phenylsulfone), three (trichloromethyl)-s-triazines [tris (trichloromethyl)-s-triazine] etc.; The concrete example of superoxide is as two-tert-butyl peroxide (di-tertbutylperoxide) etc.
Wherein cited person is preferable with benzophenone (benzophenone) compounds, especially with 4, and 4 '-two (diethylamine) benzophenone best results.These light initiators (c-3) can a kind of separately or mixing plural number kind use.
In the photosensitive resin composition for colour filter of the present invention, light initiator (C) can add proper amount of solvent in advance in order to be mixed with the solution of light initiator (C), and it can increase the dispersiveness of light initiator (C).
Above-mentioned preparation can be selected from employed solvent in aforementioned bases soluble resin (A) polymerization process with solvent, does not give unnecessary details at this.Wherein also preferable with 1-Methoxy-2-propyl acetate, 3-ethoxyl ethyl propionate.This equal solvent can a kind of separately or mixing plural number kind use.
(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 light initiator (C) and pigment described later (E) is neccessary composition, can add additive composition described later 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 solvent of photosensitive resin composition of the present invention (D) is generally 500～5, and 000 weight portion is preferably 800～4,500 weight portions, is more preferred from 1,000～4,000 weight portion.
Above-mentioned solvent (D) can be selected from employed solvent in aforementioned bases soluble resin (A) polymerization process, does not give unnecessary details at this.Wherein also preferable with 1-Methoxy-2-propyl acetate, 3-ethoxyl ethyl propionate.This equal solvent can a kind of separately or mixing plural number kind use.
(E) pigment
Based on alkali soluble resin (A) 100 weight portions, the use amount of pigment of the present invention (E) is generally 100～800 weight portions, is preferably 150～500 weight portions, is more preferred from 210～450 weight portions, and especially with 260～450 weight portion the bests.
Pigment of the present invention (E) can be inorganic pigment or organic pigment.There is the metallic compound of metal oxide, the wrong salt of metal etc. in inorganic pigment system, and concrete example is as the metal oxide of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, inferior lead, antimony etc., and the composite oxides of aforementioned metal.The concrete example of organic pigment as:
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 the primary particle of pigment (E) directly is preferably 10～200nm, is more preferred from 20～150nm, and the best is 30～100nm.
In the photosensitive resin composition for colour filter of the present invention, the concrete example of the miniaturization means of the mean grain size of pigment primary particle as: pigment is carried out dispersion and fining (abbreviation polishing) with mechanical lapping; Or with pigment dissolved in good solvent, drop into poor solvent again, in order to will separate out (abbreviation deposition method) than the pigment of fine particle size; Or in the pigment building-up process, produce pigment (being called for short synthetic deposition method) than fine particle size or the like.
In the photosensitive resin composition for colour filter of the present invention, meeting the present invention (1), (2), (3) under the condition, promptly (1) is based on the compound that contains the ethene unsaturated group (B) 100 weight portions, the use amount of light initiator (c-1) is between 0.1～70 weight portion, and (2) based on alkali soluble resin (A) 100 weight portions, the use amount of pigment (E) is between 100～800 weight portions, and (3) averaged particles of the primary particle of pigment (E) footpath is when 10～200nm, then this photosensitive resin composition is after coating, sensitivity during exposure is good, the level of residue of back on unexposed part and light shield layer on the substrate that develop is few, the shape of picture element pattern side, roasting back, back is good, and the chroma of formed colored filter and contrast are good.
If photosensitive resin composition for colour filter of the present invention can use the pigment in the averaged particles footpath of high concentrationization and low primary particle to reach when being applied in the range of application of LCD of high chroma in this photosensitive resin composition; The high chroma of indication of the present invention is meant this photosensitive resin composition especially with steps such as coating, drying under reduced pressure, pre-roasting and back are roasting, on substrate, form the photo-sensitive resin of one 2.0 μ m earlier, measure the chromaticity coordinate (x of this photo-sensitive resin again with colorimeter (illuminant-C), and the chromaticity coordinate of general high chroma need satisfy following scope y):
(1) red photo-sensitive resin
(0.55≤x) and (0.26≤y≤0.41)
(2) green photonasty resin bed
(0.11≤x≤0.32) and (0.50≤y)
(3) blue photo-sensitive resin
(0.10≤x≤0.21) and (y≤0.20)
The chromaticity coordinate of preferable high chroma need satisfy following scope again:
(1) red photo-sensitive resin
(0.61≤x) and (0.29≤y≤0.37)
(2) green photonasty resin bed
(0.12≤x≤0.29) and (0.56≤y)
(3) blue photo-sensitive resin
(0.11≤x≤0.19) and (y≤0.18)
For reaching purpose of the present invention, represented light initiator (c-1) the best of selected light initiator above note structural formula (1); Even use to go up the represented light initiator (c-1) of note structural formula (1) as high chroma during with the light initiator of the photosensitive resin composition for colour filter of LCD, because of the sensitivity of this light initiator itself high and also high to the solubleness of solvent, the sensitivity of the photosensitive resin composition that uses this light initiator and get when coating, exposure is preferable, and the shape of picture element pattern side was also preferable after the back was roasting.
Pigment of the present invention (E) according to desired person, also can be followed the use spreading agent.These spreading agents are for example: the interfacial agent of kation system, negative ion system, nonionic system, both sexes, polysiloxane series, fluorine system etc.
Wherein, the concrete example of interfacial agent is as the polyethylene oxide alkyl ethers class of: polyethylene oxide lauryl ether, the stearic vinegar ether of polyethylene oxide, 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 Kemu corporate system (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 (AsahiGuard), 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.
For improving coating, also can follow the use interfacial agent in the photosensitive resin composition of the present invention.Based on alkali soluble resin (A) 100 weight portions, the use amount of this interfacial agent is generally 0～6 weight portion, is preferably 0～4 weight portion, is more preferred from 0～3 weight portion, giving an example with employed interfacial agent in the aforementioned pigment (E) of above-mentioned interfacial agent do not given unnecessary details at this.
In addition, in the photosensitive resin composition of the present invention, 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.Wherein, based on alkali soluble resin (A) 100 weight portions, the use amount of additives such as in addition macromolecular compound of filling agent of the present invention, alkali soluble resin (A), adherence promoter, antioxidant, ultraviolet light absorber, anti-agglutinant is generally 0～10 weight portion, be preferably 0～6 weight portion, be more preferred from 0～3 weight portion.
The concrete example of these additives is as the filling agent of glass, aluminium; Alkali soluble resin (A) macromolecular compound in addition of polyvinyl alcohol (PVA), polyalkylene glycol monoalkyl ether, poly-perfluoroalkyl acrylate alkane ester etc.; Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxyethoxy) silane, N-(2-amino-ethyl)-3-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-tert butyl phenol), 2, the antioxidant of 6-two-tert-butyl phenol etc.; Ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorphenyl nitrine, alkoxy benzophenone; Reach anti-agglutinants such as sodium polyacrylate.
Photosensitive resin composition for colour filter of the present invention is that mentioned component (A)～(E) is uniformly mixed into solution state in stirrer, can add other adjuvants such as interfacial agent, adherence auxiliary agent in case of necessity.
The formation method of colored filter of the present invention is by coating methods such as revolution coating, curtain coating coating or print roll coatings, and above-mentioned colored filter is coated on the substrate with photosensitive compoistion.After the coating, in the mode of drying under reduced pressure, remove most solvent earlier, removal of solvents is formed pre-roasting filming in pre-roasting (pre-bake) mode again.Wherein, drying under reduced pressure and pre-roasting condition according to the kind of each composition, cooperate ratio and different, and usually, drying under reduced pressure is to carry out for 1 second～60 second under the pressure of 0～200mm-Hg, and pre-roasting be under 70～110 ℃ of temperature, to carry out 1 minute～15 minutes.After pre-roasting, this roasting in advance exposure between between specified light shield (mask) of filming, impregnated in developer solution under 23 ± 2C temperature developed in 15 seconds～5 minutes, and the part of not wanting is removed and is formed pattern.The light that exposure is used be good with the ultraviolet ray of g line, h line, i line etc., and UV-device can be (surpassing) high-pressure mercury-vapor lamp and metal halid lamp.
The concrete example of substrate of the present invention as: be used for 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 matrix" (blackmatrix) of isolating each picture element dyed layer earlier.
Moreover the concrete example of developer solution is 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, the croak pyridine, 1,8-diazabicylo-(5,4,0)-and the alkaline aqueous solutions that alkali compounds constituted such as 7-hendecene, its concentration is generally 0.001～10 weight %, is preferably 0.005～5 weight %, is more preferred from 0.01～1 weight %.
When using the developer solution that these alkaline aqueous solutions constitute, generally lie in after the development clean to wash, secondly pattern is air-dry again with pressurized air or compressed nitrogen.
Make last heat treated (post-bake) 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 15 minutes～150 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 ITO (tin indium oxide) 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, promptly can be used as the colored filter that LCD is used.
[synthesis example of alkali soluble resin (A)]
Synthesis example A-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: methacrylic acid monomer (hereinafter to be referred as MAA) 20 weight portions, methacrylic acid benzene methyl monomer (hereinafter to be referred as BzMA) 70 weight portions, styrene monomer (hereinafter to be referred as SM) 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 the content of four cervical vertebra bottles is 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 the solvent devolatilization.
Synthesis example A-2
With the method for operating of synthesis example A-1, difference system changes kind and the mixing consumption of polymerization with monomer, and its prescription and reaction conditions are stated from table one (after seeing instructions).
[formulation example of the solution of light initiator (C)]
Formulation example C-1
In the calibration cell of 23 ℃ of temperature, place 1000 milliliters beaker, according to injecting solvent 3-ethoxyl ethyl propionate (hereinafter to be referred as D-1) 750 weight portions shown in the table two, drop into the light initiator again, be respectively 2,2 '-two (neighbour-aminomethyl phenyl)-4,4 ', 5,5 '-tetraphenyl diimidazole (hereinafter to be referred as c-1-1), 10 weight portions, 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholino-1-acetone (hereinafter to be referred as c-2-1) 60 weight portions, 4,4 '-two (diethylamine) benzophenone (hereinafter to be referred as c-3-1), 10 weight portions, after stirring 10 minutes with swing-out stirrer, observe whether dissolved matter is arranged not as the metewand of light initiator to the dissolution with solvents degree with visual type.Its evaluation result is " zero ".
Formulation example C-2～C-4
With the method for operating of formulation example C-1, difference system changes the kind and the consumption of light initiator, and its prescription and evaluation result are stated from table two (after seeing instructions).
Formulation example C-5
With the method for operating of formulation example C-1, difference system changes the kind and the consumption of light initiator, and its prescription and evaluation result are stated from table two (after seeing instructions).This light initiator is " * " to the evaluation result of dissolution with solvents degree.
Formulation example C-6～C-7
With the method for operating of formulation example C-1, difference system changes the kind and the consumption of light initiator, and its prescription and evaluation result are stated from table two (after seeing instructions).
Formulation example C-8
With the method for operating of formulation example C-1, difference system changes the kind and the consumption of light initiator, and its prescription and evaluation result are stated from table two (after seeing instructions).This light initiator is " △ " to the evaluation result of dissolution with solvents degree.
[embodiment of photosensitive resin composition and comparative example]
Use alkali soluble resin (A-1) 100 weight portions (solid) of aforementioned synthesis example gained, dipentaerythritol acrylate shown in the table three (hereinafter to be referred as B-1) 150 weight portions, solution (C-1) 830 weight portions of the light initiator of formulation example gained and the red pigment shown in the table three are (hereinafter to be referred as E-1, consist of C.I.177/C.I.254 (30/70), the big day system of refining of Japan, trade name 9803, the averaged particles footpath 63nm of primary particle) potpourri of 300 weight portions, add solvent 3-ethoxyl ethyl propionate (hereinafter to be referred as D-1) 1, behind 250 weight portions and 1-Methoxy-2-propyl acetate (hereinafter to be referred as D-2) 500 weight portions, with swing-out stirrer, dissolved mixing, 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 is shown in table three (after seeing instructions).
[evaluation method]
(1)
Averaged particles footpath (the unit: nm) of the primary particle of pigment (E)
Earlier with pigment dispersing in solvent, take the pigment particles in the visual field with infiltration type electron microscope (model JEM-2010, Jeol Ltd. makes) again, appoint and get 50, record the diameter (major diameter) of the length direction of each particle respectively, try to achieve this mean value again and get.
(2)
The light initiator is to the solubleness of solvent
With the solution of the light initiator (C) after the preparation, observe with visual type whether not dissolved matter is arranged.
Zero: do not have not dissolved matter
△: dissolved matter not on a small quantity
*: volume is dissolved matter not
(3)
Sensitivity
With the mode of photosensitive resin composition with rotary coating, be coated on the glass substrate of 100mm * 100mm, carry out drying under reduced pressure earlier, pressure 100mmHg, 30 seconds of time, and then carry out baking in advance, 80 ℃ of temperature, 3 minutes time, pre-the baking that can form a thickness 2.5 μ m filmed.
Be adjacent to above-mentioned pre-roasting filming with optical concentration rank difference table (model T2115, the optical concentration rank difference is divided into 21 etc. for transparent step wedge, Stouffer corporate system), with the 20W high-pressure mercury-vapor lamp with 800mJ/cm
2Light quantity irradiation after, the developer solution that impregnated in 23 ℃ again developed in 2 minutes, cleaned with pure water, observed the situation (as the foundation of judging sensitivity, in this Evaluation Method, number of degrees multilist more shows that sensitivity is high more with number of degrees) of developing.
Zero: number of degrees 9～21
△: number of degrees 7～8
*: number of degrees 1～6
(4)
Residue
The pre-mask pattern (mask) of filming with appointment of baking of evaluation method (three) is adjacent to above-mentioned pre-roasting filming, after the light quantity irradiation of ultraviolet light (exposure machine Canon PLA-501F) with 300mJ/cm2, the developer solution that impregnated in 23 ℃ again developed in 2 minutes, unexposed part is removed on substrate, clean with pure water, after 200 ℃, baked 80 minutes again, can on glass substrate, form desired photoresist pattern, with microscopic examination, determine whether unexposed part has residue to exist.
Zero: no residue
△: a little residue
*: residue is a lot
(5)
Picture element pattern side
With the photoresist pattern of gained in the evaluation method (four), observe with sweep electron microscope (SEM), determine the shape of side, edge (edge profile).
Zero: as shown in Figure 1, the edge angle θ of photoresist pattern (12)
1(with respect to substrate (1
4) side wall angle) between 0～90 degree.
*: as shown in Figure 2, the edge angle θ of photoresist pattern (22)
2(with respect to the side wall angle of substrate (14)) is between 90 degree～180 degree.
(6)
Chroma
Pre-roasting filming with evaluation method (three) with ultraviolet light (exposure machine Canon PLA-501F) 300mJ/cm
2Light quantity irradiation should pre-roasting filming after, impregnated in 23 ℃ developer solution 2 minutes again, clean with pure water, again with after 200 ℃ roasting 80 minutes, can on glass substrate, form the photo-sensitive resin of a thickness 2.0 μ m.
Secondly, (big tomb electronics corporation system, model MCPD) measures chroma with colorimeter, and (x, y), its judgment standard as shown below for the chromaticity coordinate of measuring this photo-sensitive resin with illuminant-C for the mensuration mode.
(1) red photo-sensitive resin
Zero: [(0.61≤x) and (0.29≤y≤0.37)]
△: [(0.55≤x) and (0.26≤y≤0.41)], but need the scope of deduction [(0.61≤x) and (0.29≤y≤0.37)]
*: [(0.49≤x) and (0.23≤y≤0.44)], but need the scope of deduction [(0.55≤x) and (0.26≤y≤0.41)]
(2) green photonasty resin bed
Zero: [(0.12≤x≤0.29) and (0.56≤y)]
△: [(0.11≤x≤0.32) and (0.50≤y)], but need the scope of deduction [(0.12≤x≤0.29) and (0.56≤y)]
*: [(0.10≤x≤0.35) and (0.45≤y)], but need the scope of deduction [(0.11≤x≤0.32) and (0.50≤y)]
(3) blue photo-sensitive resin
Zero: [(0.11≤x≤0.19) and (y≤0.18)]
△: [(0.10≤x≤0.21) and (y≤0.20)], but need to deduct the scope of [(0.11≤x≤0.19) and (y≤0.18)]
*: [(0.09≤x≤0.23) and (y≤0.22)], but need to deduct the scope of [(0.10≤x≤0.21) and (y≤0.20)]
(7)
Contrast
Method determines contrast shown in Fig. 3 A and Fig. 3 B.The photo-sensitive resin (hereinafter referred to as photo-sensitive resin 1) that is about to gained in the evaluation method (six) places two pieces of Polarizer 2A, between the 2B, see through Polarizer 2A, photo-sensitive resin 1, Polarizer 2B in regular turn from the light that light source 3 shone out, and see through the light quantity (cd/cm of Polarizer 2B at last
2) measure with brightness photometer 4 (Japanese Topcon corporate system, model BM-5A) again.
As shown in Figure 3A, when the polarization direction of the polarization direction of Polarizer 2B and Polarizer 2A was parallel to each other, measured light quantity was A; Shown in Fig. 3 B, when the polarization direction of the polarization direction of Polarizer 2B and Polarizer 2A was orthogonal, measured light quantity was B; Then contrast can be calculated by the ratio (light quantity A/ light quantity B) of light quantity A and light quantity B and get.
Zero: ratio is more than 500
△: ratio is between 400～500
*: ratio is below 400
Embodiment 2
With the method for operating of embodiment 1, the kind and the consumption of the kind of difference system's change alkali soluble resin (A), the solution of light initiator (C), its prescription and evaluation result are stated from table three (after seeing instructions).
With the method for operating of embodiment 1, difference system changes the kind and the consumption of the solution of light initiator (C), and its prescription and evaluation result are stated from table three (after seeing instructions).
With the method for operating of embodiment 2, difference system changes the kind and the consumption of the solution of light initiator (C), and its prescription and evaluation result are stated from table three (after seeing instructions).
Embodiment 5
With the method for operating of embodiment 1, difference system changes kind, the kind of solvent (D) and the consumption of consumption and pigment (E) of alkali soluble resin (A), and its prescription and evaluation result are stated from table three (after seeing instructions).
Embodiment 6
With the method for operating of embodiment 2, difference system changes kind, the kind of solvent (D) and the consumption of consumption and pigment (E) of alkali soluble resin (A), and its prescription and evaluation result are stated from table three (after seeing instructions).
Embodiment 7
With the method for operating of embodiment 1, difference system changes the kind of pigment (E), and its prescription and evaluation result are stated from table three (after seeing instructions).
Embodiment 8
With the method for operating of embodiment 2, difference system changes the kind of pigment (E), and its prescription and evaluation result are stated from table three (after seeing instructions).
Comparative example 1
With the method for operating of embodiment 1, difference system changes the kind and the consumption of the solution of light initiator (C), and its prescription and evaluation result are stated from table three (after seeing instructions).
Comparative example 2
With the method for operating of embodiment 1, difference system changes the kind and the consumption of the solution of light initiator (C), and its prescription and evaluation result are stated from table three (after seeing instructions).
Comparative example 3
With the method for operating of embodiment 2, difference system changes the kind and the consumption of the solution of light initiator (C), and its prescription and evaluation result are stated from table three (after seeing instructions).
Comparative example 4
With the method for operating of embodiment 1, difference system changes the consumption of pigment (E), and its prescription and evaluation result are stated from table three (after seeing instructions).
Comparative example 5
With the method for operating of embodiment 2, difference system changes the kind and the consumption of pigment (E), and its prescription and evaluation result are stated from table three (after seeing instructions).Wherein, this photosensitive resin composition is too high because of viscosity, can't be coated with on substrate.
Comparative example 6
With the method for operating of embodiment 5, difference system changes the kind and the consumption of pigment (E), and its prescription and evaluation result are stated from table three (after seeing instructions).
Only above-described, it only is preferred embodiment of the present invention, when can not limiting scope of the invention process with this, promptly every simple equivalent of being done according to the present patent application claim and description of the invention content changes and modifies, and all should still belong in the scope that patent of the present invention contains.
Claims (2)
1. 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;
It is characterized in that this light initiator (C) is to contain the represented diimidazole based compound (c-1) of note structural formula (1) down; And the averaged particles of the primary particle of pigment (E) footpath is between 10～200nm; And based on alkali soluble resin (A) 100 weight portions, the use amount of compound (B) that contains the ethene unsaturated group is between 10～500 weight portions, the use amount of organic solvent (D) is between 500～5,000 weight portion, and the use amount of pigment (E) is between 100～800 weight portions; And based on the compound that contains the ethene unsaturated group (B) 100 weight portions, the use amount of light initiator (c-1) is between 0.1～70 weight portion; This alkali soluble resin (A) is by the ethylene unsaturated monomer that contains one or more carboxylic acid group (a-1), and other copolymerizable ethylene unsaturated monomer (a-2) institute copolymerization forms.
In the structural formula (1), R is the alkyl of carbon element several 1～4.
2, photosensitive resin composition for colour filter according to claim 1 is characterized in that, wherein the averaged particles of the primary particle of pigment (E) footpath is between 20～150nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100925901A CN100434948C (en) | 2004-11-16 | 2004-11-16 | Photosensitive resin composition for colour filter |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100925901A CN100434948C (en) | 2004-11-16 | 2004-11-16 | Photosensitive resin composition for colour filter |
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| Publication Number | Publication Date |
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| CN1776466A CN1776466A (en) | 2006-05-24 |
| CN100434948C true CN100434948C (en) | 2008-11-19 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61292136A (en) * | 1985-06-19 | 1986-12-22 | Daicel Chem Ind Ltd | Optical coloring curable composition |
| JPH09194546A (en) * | 1996-01-17 | 1997-07-29 | Mitsubishi Rayon Co Ltd | Curing resin composition and low hygroscopic optical member |
| WO2003073168A1 (en) * | 2002-02-28 | 2003-09-04 | Hitachi Chemical Co., Ltd. | Photosensitive resin composition, process for forming photosensitive elements or resist patterns with the same, and process for production of printed wiring boards |
| WO2003077035A1 (en) * | 2002-03-12 | 2003-09-18 | Asahi Kasei Kabushiki Kaisha | Photosensitive resin composition and use thereof |
| CN1126005C (en) * | 1999-12-30 | 2003-10-29 | 奇美实业股份有限公司 | Photosensitive resin composition |
-
2004
- 2004-11-16 CN CNB2004100925901A patent/CN100434948C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61292136A (en) * | 1985-06-19 | 1986-12-22 | Daicel Chem Ind Ltd | Optical coloring curable composition |
| JPH09194546A (en) * | 1996-01-17 | 1997-07-29 | Mitsubishi Rayon Co Ltd | Curing resin composition and low hygroscopic optical member |
| CN1126005C (en) * | 1999-12-30 | 2003-10-29 | 奇美实业股份有限公司 | Photosensitive resin composition |
| WO2003073168A1 (en) * | 2002-02-28 | 2003-09-04 | Hitachi Chemical Co., Ltd. | Photosensitive resin composition, process for forming photosensitive elements or resist patterns with the same, and process for production of printed wiring boards |
| WO2003077035A1 (en) * | 2002-03-12 | 2003-09-18 | Asahi Kasei Kabushiki Kaisha | Photosensitive resin composition and use thereof |
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| CN1776466A (en) | 2006-05-24 |
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