CN101038437A - Black photosensitive composition, shielding film and el device manufactured by the black photosensitive composition - Google Patents
Black photosensitive composition, shielding film and el device manufactured by the black photosensitive composition Download PDFInfo
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- CN101038437A CN101038437A CNA200710087762XA CN200710087762A CN101038437A CN 101038437 A CN101038437 A CN 101038437A CN A200710087762X A CNA200710087762X A CN A200710087762XA CN 200710087762 A CN200710087762 A CN 200710087762A CN 101038437 A CN101038437 A CN 101038437A
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- black photosensitive
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
- Electroluminescent Light Sources (AREA)
- Optical Filters (AREA)
Abstract
The invention provides black photosensitivity composition for formation of EL component lightproof membrane which can form lightproof membrane having high stability and low dielectric coefficient. The black photosensitivity composition contains photopolymerization property compound, photopolymerization initiator, black carbon, and organic colour.
Description
Technical field
The present invention relates to the EL element photomask forms with black photosensitive composition, by the photomask and the EL element of this black photosensitive composition preparation.
Background technology
In recent years, the exploitation of EL element is being carried out always.EL element is included in the laminated body that stacks gradually lower electrode, luminescent layer, upper electrode on its transparency carrier.This luminescent layer has R, G, B light-emitting zone.In this EL element,, carried out studying (referring to patent documentation 1,2) to forming photomask in order to improve the contrast of display degree.
[patent documentation 1] spy opens the 2001-092119 communique
[patent documentation 2] spy opens flat 11-273870 communique
Summary of the invention
Yet, used photomask in above-mentioned EL element, himself directly contacts and forms with electrode.Therefore, requiring the EL element photomask is low-k.
In view of above problem, the object of the present invention is to provide a kind of EL element black photosensitive composition that can form the low-k photomask.In addition, the present invention also aims to provide a kind of by formed photomask of this black photosensitive composition and EL element.
Discoveries such as the inventor contain organic pigment to scale in black photosensitive composition be effectively to the low-kization of photomask, and finished the present invention thus.
The invention provides a kind of EL element photomask formation that contains optical polymerism compound, Photoepolymerizationinitiater initiater and black pigment and use black photosensitive composition, and wherein also contain organic pigment.
In addition, the invention provides a kind of by formed photomask of above-mentioned black photosensitive composition and EL element with this photomask.
According to the present invention,, can form the photomask of low-k by in black photosensitive composition, adding organic pigment.
Embodiment
Below, embodiments of the present invention are described.EL element photomask of the present invention forms and contains optical polymerism compound, Photoepolymerizationinitiater initiater, black pigment and organic pigment with black photosensitive composition.
[optical polymerism compound]
So-called " optical polymerism compound " is meant illumination such as accepting ultraviolet ray and polymerization and solidified material.As the optical polymerism compound, preferably have the compound of the two keys of ethene, and more preferably acryl resin.
＜have a compound of the two keys of ethene 〉
As compound with the two keys of ethene, can enumerate acrylic acid, methacrylic acid, fumaric acid, maleic acid, monomethyl fumarate, monomethyl ester, acrylic acid-2-hydroxyl ethyl ester, 2-hydroxyethyl methacry-late, the glycol monoethyl ether acrylate, the glycol monoethyl ether methacrylate, the ethylene glycol monoethyl ether acrylate, the ethylene glycol monoethyl ether methacrylate, acrylic acid glyceride, glyceral methacrylate, acrylamide, Methacrylamide, vinyl cyanide, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, Jia Jibingxisuanyizhi, isobutyl acrylate, isobutyl methacrylate, acrylic acid-2-ethyl caproite, methacrylic acid-2-Octyl Nitrite, benzyl acrylate, benzyl methacrylate, glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butanediol dimethylacrylate, propylene glycol diacrylate, the propylene glycol dimethylacrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, tetra methylol propane tetraacrylate, tetra methylol propane tetramethyl acrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, 1, the 6-hexanediyl ester, 1, the 6-hexanediol dimethacrylate, monomers such as the epoxy diacrylate of curling, the oligomer class; Make (methyl) acrylic acid with the polyester prepolyer reaction that obtains by polyalcohols and monoacid or polyprotonic acid condensation polyester (methyl) acrylate, make polynary alcohol radical and have the compound reaction of two isocyanate group after, (methyl) acrylic acid is reacted and polycarbamate (methyl) acrylate that obtains with it; Epoxy (methyl) acrylate resins that make the reaction of following epoxy resin and (methyl) acrylic acid and obtain etc., described epoxy resin comprises bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol or cresols-linear phenol-aldehyde resin type epoxy resin, bakelite type epoxy resin, tris-phenol type epoxy resin, poly carboxylic acid poly glycidyl ester, polyvalent alcohol poly glycidyl ester, aliphatics or alicyclic epoxy resin, amine epoxy resin, dihydroxy benzenes type epoxy resin etc.The resin that can use the reaction of multi-anhydride and aforementioned epoxy (methyl) acrylate resin in addition and obtain.Owing in these compounds, imported acryloyl group or methacryl, therefore can improve cross-linking efficiency, and the photostability of filming, chemical proofing are good.
Wherein preferably use the resin that in molecule, has coiled structure.Because its thermotolerance of resin and chemical proofing height with coiled structure when therefore using as the optical polymerism compound, can improve the thermotolerance and the chemical proofing of black photosensitive composition.The concrete preferred represented resin of following general formula (1) that uses.
Change 1
In the formula, X is the represented group of following general formula (2), and (residue CO-O-CO-), Z are for to slough two residues after the anhydride group from the tetracarboxylic dianhydride, n is 1～20 integer in order to slough anhydride group from dicarboxylic anhydride for Y.
Change 2
As the instantiation of the dicarboxylic anhydride that derives aforementioned Y (sloughing anhydride group dicarboxylic anhydride before), can enumerate for example maleic anhydride, succinic anhydride, itaconic anhydride, phthalate anhydride, tetrahydrobenzene dicarboxylic acid anhydride, hexahydrobenzene dicarboxylic acid anhydride, methyl endo-methylene group tetrahydrobenzene dicarboxylic acid anhydride, chlorendic acid acid anhydride, methyltetrahydro phthalate anhydride, glutaric anhydride etc.
In addition, as the tetracarboxylic dianhydride's who derives aforementioned Z (slough two anhydride group before tetracarboxylic dianhydride) instantiation, for example can enumerate tetracarboxylic dianhydrides such as PMA, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride etc.
In addition, the preferred service property (quality) mean molecular weight of compound with the two keys of above-mentioned ethene is the material more than 1,000.By making the quality mean molecular weight is more than 1,000, can make to film evenly.In addition, the quality mean molecular weight is preferably below 100,000.By making the quality mean molecular weight is below 100,000, can make development good.Among the present invention, be that the compound with the two keys of ethene more than 1,000 is called the macromolecular compound with the two keys of ethene with the quality mean molecular weight.
In addition, preferably above-mentioned macromolecular compound and photopolymerization monomer with the two keys of ethene is used in combination.As this photopolymerization monomer, can enumerate methyl acrylate, methyl methacrylate, acrylic acid-2-hydroxyl ethyl ester, 2-hydroxyethyl methacry-late, methacrylic acid-2-hydroxypropyl acrylate, glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, propylene glycol diacrylate, the propylene glycol dimethylacrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, tetra methylol propane tetraacrylate, tetra methylol propane tetramethyl acrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, pentaerythrite tetramethyl acrylate, dipentaerythritol five acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol acrylate, dipentaerythritol hexamethyl acrylate, 1, the 6-hexanediyl ester, benzyl acrylate, benzyl methacrylate, curling epoxy diacrylate, acrylic acid, methacrylic acid etc., but be not limited to these.Wherein, preferred multi-functional photopolymerization monomer.By this macromolecular compound and photopolymerization monomer with the two keys of ethene combined, can improve curable, and make pattern formation become easy.
As above-mentioned optical polymerism compound, can enumerate the material that its molecule self can polymerization, in the present invention, the potpourri of polymer binder and photopolymerization monomer is also contained in the optical polymerism compound.
As polymer binder, consider the bonding agent that preferably can carry out alkaline development from the difficulty or ease of developing.
As polymer binder, specifically can enumerate acrylic acid, methacrylic acids etc. have the monomer and the methyl acrylate of carboxyl, methyl methacrylate, ethyl acrylate, Jia Jibingxisuanyizhi, acrylic acid-2-hydroxyl ethyl ester, 2-hydroxyethyl methacry-late, methacrylic acid-2-hydroxypropyl acrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylic acid phenoxy group ester, methacrylic acid phenoxy group ester, isobornyl acrylate, IBOMA, glycidyl methacrylate, styrene, acrylamide, the multipolymer of vinyl cyanide etc., and phenol linear phenol-aldehyde resin type epoxy acrylic ester polymer, phenol linear phenol-aldehyde resin type epoxy methacrylates polymkeric substance, cresols linear phenol-aldehyde resin type epoxy acrylic ester polymer, cresols linear phenol-aldehyde resin type epoxy methacrylates polymkeric substance, the bisphenol-a epoxy acrylate polymkeric substance, resins such as bisphenol S type epoxy acrylic ester polymer.The content that the acrylic acid, methacrylic acid etc. that constitute aforementioned resin have a monomer component of carboxyl is preferably the scope of 5～40mol%.
The preferable range of above-mentioned polymer binder quality mean molecular weight is 1,000～100,000.By making the quality mean molecular weight is more than 1,000, can make to film evenly.In addition, be below 100,000 by making the quality mean molecular weight, can make development good.
When containing polymer binder and photopolymerization monomer, with respect to the total amount of polymer binder and the photopolymerization monomer and the Photoepolymerizationinitiater initiater of 100 mass parts, preferably with the range fit polymer binder of 10～60 mass parts as the optical polymerism compound.By making use level is more than 10 mass parts, can form film at an easy rate in coating, when dry, and can fully improve after the curing by film strength.In addition, be below 60 mass parts by making use level, can make development good.
In addition, with respect to the total amount of polymer binder and the photopolymerization monomer and the Photoepolymerizationinitiater initiater of 100 mass parts, preferably with the range fit photopolymerization monomer of 15～50 mass parts.By making aforementioned use level is more than 15 mass parts, can prevent that photocuring is bad, and can access enough thermotolerances and chemical proofing.In addition, be below 50 mass parts by making use level, can make the formation ability of filming good.
[Photoepolymerizationinitiater initiater]
As Photoepolymerizationinitiater initiater; for example can enumerate; the 1-hydroxycyclohexylphenylketone; 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone; 1-[4-(2-hydroxyl-oxethyl) phenyl]-2-hydroxy-2-methyl-1-propane-1-ketone; 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl propane-1-ketone; 1-(4-dodecylphenyl)-2-hydroxy-2-methyl propane-1-ketone; 2; 2-dimethoxy-1; 2-diphenylethane-1-ketone; two (4-dimethylaminophenyl) ketone; 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino propane-1-ketone; 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone; ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl group oxime); 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; 4-benzoyl-4 '-methyl dimethoxy base sulfide; the 4-dimethylaminobenzoic acid; 4-dimethylaminobenzoic acid methyl esters; 4-dimethylaminobenzoic acid ethyl ester; 4-dimethylaminobenzoic acid butyl ester; 4-dimethylamino-2-ethylhexyl benzoic acid; 4-dimethylamino-2-isoamyl benzene formic acid; benzyl-'beta '-methoxy ethyl acetals; benzyl dimethyl ketal; 1-phenyl-1; 2-propanedione-2-(neighbour-ethoxy carbonyl) oxime; neighbour-benzoyl methyl benzoate; 2; the 4-diethyl thioxanthone; the 2-clopenthixal ketone; 2; 4-dimethyl thioxanthones; 1-chloro-4-propoxyl group thioxanthones; thioxanthene; 2-diuril ton; 2; 4-diethyl thioxanthene; 2-methyl thioxanthene; 2-isopropyl thioxanthene; the 2-EAQ; the prestox anthraquinone; 1; 2-benzo anthraquinone; 2; 3-diphenyl anthraquinone; azoisobutyronitrile; benzoyl peroxide; dicumyl peroxide; 2-mercaptobenzimidazole; the 2-mercaptobenzoxazole; 2-mercaptobenzothiazole; 2-(Chloro-O-Phenyl)-4; 5-two (m-methoxyphenyl)-imidazole radicals dipolymer; benzophenone; the 2-chlorobenzophenone; right; right '-two dimethylamino benzophenone; 4; 4 '-two lignocaine benzophenone; 4; 4 '-dichloro benzophenone; 3; 3-dimethyl-4-methoxy benzophenone; benzil; benzoin; benzoin methylether; benzoin ethyl ether; benzoin iso-propylether; benzoin n-butylether; the benzoin isobutyl ether; the benzoin butyl ether; acetophenone; 2; the 2-diethoxy acetophenone; to dimethyl acetophenone; to the dimethylamino propiophenone; dichloroacetophenone; trichloroacetophenone; p-tert.-butyl acetophenone; to the dimethylamino benzoylformaldoxime; to tert-butyl group trichloroacetophenone; to tert-butyl group dichloroacetophenone; α; α-Er Lv-4-Ben Yangjibenyitong; thioxanthones; 2-methyl thioxanthones; the 2-isopropyl thioxanthone; Dibenzosuberone; amyl group-4-dimethylaminobenzoic acid ester; the 9-phenylacridine; 1; 7-pair-(9-acridinyl) heptane; 1; 5-pair-(9-acridinyl) pentane; 1; 3-pair-(9-acridinyl) propane; to the methoxyl triazine; 2; 4; 6-three (trichloromethyl)-s-triazine; 2-methyl-4; two (the trichloromethyl)-s-triazines of 6-; 2-[2-(5-methylfuran-2-yl) vinyl]-4; two (the trichloromethyl)-s-triazines of 6-; 2-[2-(furans-2-yl) vinyl]-4; two (the trichloromethyl)-s-triazines of 6-; 2-[2-(4-diethylamino-2-aminomethyl phenyl) vinyl]-4; two (the trichloromethyl)-s-triazines of 6-; 2-[2-(3; the 4-Dimethoxyphenyl) vinyl]-4; two (the trichloromethyl)-s-triazines of 6-; 2-(4-methoxyphenyl)-4; two (the trichloromethyl)-s-triazines of 6-; 2-(4-ethoxybenzene vinyl)-4; two (the trichloromethyl)-s-triazines of 6-; 2-(4-n-butoxy phenyl)-4; two (the trichloromethyl)-s-triazines of 6-; 2; 4-pair-trichloromethyl-6-(3-bromo-4-methoxyl) phenyl-s-triazine; 2; 4-pair-trichloromethyl-6-(2-bromo-4-methoxyl) phenyl-s-triazine; 2; 4-pair-trichloromethyl-6-(3-bromo-4-methoxyl) styryl phenyl-s-triazine; 2,4-pair-trichloromethyl-6-(2-bromo-4-methoxyl) styryl phenyl-s-triazine etc.These Photoepolymerizationinitiater initiaters can independent or two or more being used in combination.
With respect to the total amount of above-mentioned optical polymerism compound of 100 mass parts and Photoepolymerizationinitiater initiater, the content of this Photoepolymerizationinitiater initiater is preferably 1～40 mass parts.
[black pigment]
As this black pigment, so long as have the pigment of light-proofness, just be not particularly limited, specifically can enumerate the inorganic pigments such as oxide, composite oxides, metal sulfide, metal sulfate or metal carbonate of metals such as carbon black, titanium are black, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver.In these black pigments, more preferably use cheap and have the carbon black of high light-proofness.
As carbon black, can use channel black, stove China ink, thermal black, known carbon black such as dim.In addition, preferably use the carbon black of coated with resins.By the carbon black of this coated with resins, can further reduce the specific inductive capacity of formed photomask.
In addition, as spreading agent, preferably use polyethyleneimine: amine, carbamate resins class, crylic acid resin macromolecule dispersing agent.
As these spreading agents, for example can enumerate the commodity ソ Le ス パ one ス S3000 of the commodity BYK-161,162,163,164,166,170,182 of BYK-ChemieJapan Co., Ltd. system, Zeneca Co., Ltd. system, S9000, S17000, S20000, S27000, S24000, S26000, S28000 etc.
[organic pigment]
Black photosensitive composition of the present invention contains organic pigment.By containing this organic pigment, can form the low photomask of specific inductive capacity.In addition, the shape stability of formed photomask can be improved, and the cone angle of photomask can also be adjusted by the amount of adjusting organic pigment.Further, owing to, can present the black identical, therefore can form the lower photomask of photomask that permittivity ratio only adds carbon black with carbon black by the multiple organic pigment of combination.
Particularly, though when using carbon black as above-mentioned black pigment, the specific inductive capacity ascendant trend height of formed photomask is by the combination organic pigment, can under the state of keeping desirable OD value (optical density (OD)), reduce the specific inductive capacity of formed photomask.
As this organic pigment, can enumerate color index (C.I.; The distribution of The Society of Dyers andColourists society) is categorized as the compound of pigment (pigment) in, is specially material shown in following color index (C.I.) numbering.
C.I. pigment yellow 1 (below, only record be the numbering of " C.I. pigment yellow " equally), 3,11,12,13,14,15,16,17,20,24,31,53,55,60,61,65,71,73,74,81,83,86,93,95,97,98,99,100,101,104,106,108,109,110,113,114,116,117,119,120,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,166,167,168,175,180,185;
C.I. pigment orange 1 (below, only record be the numbering of " C.I. pigment orange " equally), 5,13,14,16,17,24,34,36,38,40,43,46,49,51,55,59,61,63,64,71,73;
C.I. pigment violet 1 (below, only record be the numbering of " C.I. pigment violet " equally), 19,23,29,30,32,36,37,38,39,40,50;
C.I. paratonere 1 (below, only record be the numbering of " C.I. paratonere " equally), 2,3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,19,21,22,23,30,31,32,37,38,40,41,42,48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,53:1,57,57:1,57:2,58:2,58:4,60:1,63:1,63:2,64:1,81:1,83,88,90:1,97,101,102,104,105,106,108,112,113,114,122,123,144,146,149,150,151,155,166,168,170,171,172,174,175,176,177,178,179,180,185,187,188,190,192,193,194,202,206,207,208,209,215,216,217,220,223,224,226,227,228,240,242,243,245,254,255,264,265;
C.I. pigment blue 1 (below, only record be the numbering of " C.I. alizarol saphirol " equally), 2,15,15:3,15:4,15:6,16,22,60,64,66;
C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 37;
C.I. bistre 23, C.I. bistre 25, C.I. bistre 26, C.I. bistre 28;
C.I. pigment black 1, C.I. pigment black 7.
In addition, as mentioned above, organic pigment also is used as the auxiliary pigment of carbon black not only as the dimensionally stable agent.As auxiliary pigment, for example can enumerate phthalocyanine pigment, azo class pigment and basic-dyeable fibre mordant pigment etc.
The mass ratio of organic pigment and black pigment is preferably 10: 0.7～and 10: 10, and more preferably 10: 4～10: 7.
In addition, the total amount of aforementioned organic pigment and aforementioned black pigment is preferably 10～80 quality % with respect to the gross mass of optical polymerism compound and Photoepolymerizationinitiater initiater, and 20-50 quality % more preferably.By making its total amount is below the 80 quality %, can obtain appropriate sensitivity.In addition, be more than the 10 quality % by making its total amount, can improve light-proofness, and fully obtain function as photomask.
Preferred substance in the organic pigment can be enumerated the C.I. pigment blue 15: 6, C.I. paratonere 177, C.I. pigment yellow 13 9.These organic pigments can further improve light-proofness and shape stability.
Preferably the content of aforementioned organic pigment and aforementioned black pigment is adjusted so that by the specific inductive capacity of the formed photomask of black photosensitive composition of the present invention less than 10, more preferably making specific inductive capacity is to adjust below 6.Thus, even photomask contacts with electrode, also can prevent to produce inconvenience such as short circuit.
In addition, preferably the content of aforementioned organic pigment and aforementioned black pigment is adjusted so that be more than 1 by the OD value of the per 1 μ m thickness of the formed photomask of black photosensitive composition of the present invention.If be above-mentioned OD value, then can fully obtain in EL element function as photomask.
[other composition]
In black photosensitive composition of the present invention, can cooperate adjuvant as required.Specifically can enumerate sensitizer, curing accelerator, photocrosslinking agent, light sensitizer, spreading agent, dispersing aid, filling agent, adhesion promotor, antioxidant, ultraviolet light absorber, anti-agglomerating agent etc.
In addition, the solvent or the thermal polymerization that are used to dilute be can also add in the black photosensitive composition of the present invention and agent, defoamer, surfactant etc. forbidden.
Wherein, as the solvent that can be added in the black photosensitive composition, for example can enumerate glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diglycol monotertiary positive propyl ether, the diglycol monotertiary n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol list ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, the propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, the single ether of dipropylene glycol, the single positive propyl ether of dipropylene glycol, the dipropylene glycol mono-n-butyl ether, the tripropylene glycol monomethyl ether, (gathering) alkylene glycol monoalkyl ethers classes such as tripropylene glycol list ether; (gathering) alkylene glycol monoalkyl ethers acetate esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate; Other ethers such as diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; Ketones such as MEK, cyclohexanone, 2-heptanone, 3-heptanone; Lactic acid alkyl ester classes such as 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester; 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-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butylacetic acid ester, 3-methyl-3-methoxyl butyl propionic ester, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, the formic acid n-pentyl ester, 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; Toluene, dimethylbenzene etc. are aromatic hydrocarbon based; N-Methyl pyrrolidone, N, amide-types such as dinethylformamide, N,N-dimethylacetamide etc.These solvents can be used alone or mixed use of two or more.
Wherein, because propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethylmethyl ether, cyclohexanone, 3-methoxyl butylacetic acid ester, optical polymerism compound, Photoepolymerizationinitiater initiater are demonstrated good dissolubility, can make simultaneously the favorable dispersibility of insoluble composition such as black pigment, therefore be preferred, and especially preferably use propylene glycol methyl ether acetate, 3-methoxyl butylacetic acid ester.With respect to the total amount of 100 mass parts optical polymerism compounds, Photoepolymerizationinitiater initiater and colorant, solvent can use in the scope of 50～500 mass parts.
In addition, forbid agent, can use quinhydrones, quinhydrones list ether etc. as thermal polymerization.As defoamer, can use polysiloxane-based, fluoride compound, as surfactant, can use known various surfactants such as anionic species, cationic, nonionic class.
As the preparation method of black photosensitive composition of the present invention, can obtain by compositions such as above-mentioned optical polymerism compound, Photoepolymerizationinitiater initiater, black pigment and organic pigment are mixed in stirring machine fully.In addition, can also use filtrator to filter so that the gained potpourri becomes evenly.
In addition, as described below when using black photosensitive composition of the present invention to form photomask, coating black photosensitive composition of the present invention on substrate, and the dry film that forms.In order to improve coating at this moment and the rerum natura behind the photocuring, except that mentioned component, can also further contain polymer binder as bonding agent.According to improve compatibility, the purpose of film formation property, development, cohesive etc., suitably select to use bonding agent to get final product.
The thickness of formed photomask on substrate can be set in the scope of 0.5～10 μ m usually, is preferably 0.8～5 μ m, and 1～4 μ m more preferably.
The formation of＜photomask 〉
At first, use contact transfer printing type apparatus for coating or non-contact type apparatus for coating such as spinner (rotary apparatus for coating), showering curtain type spreader such as print roll coating device, counter-rotating spreader, bar type spreader, coating black photosensitive composition of the present invention on substrate.Substrate then is not particularly limited so long as have the substrate of photopermeability.For example can enumerate glass plate, quartz plate, transparent or semitransparent resin plate etc.In general EL element, on aforesaid substrate, be formed with transparency electrode.This transparency electrode forms lower electrode.This transparency electrode is formed by for example ITO (tin indium oxide).And this lower electrode is patterned as clause shape etc.
In addition, in order to improve the cohesive of substrate and black photosensitive composition, silane-coating coupling agent on substrate in advance.Perhaps can when the preparation black photosensitive composition, add silane coupling agent in advance.
After being coated with this black photosensitive composition, carry out drying, remove and desolvate.Drying means is not particularly limited, can use following any method, for example (1) is at 80～120 ℃, under preferred 90～100 ℃ temperature on hot plate the method in dry 60～120 seconds, (2) at room temperature place several hours to several days method, (3) put into storage heater or the infrared heater dozens of minutes was removed the method for desolvating by several hours.
Then, by the minus mask, irradiation ultraviolet radiation, excimer laser isoreactivity energy-ray carry out the part exposure.The energy-ray amount of irradiation changes according to the composition of black photosensitive composition, but preference is as 30～2000mJ/cm
2About.
Then, make film development after the exposure, be patterned as desirable shape thus by developer solution.Developing method is not particularly limited, and for example can use infusion process, spray-on process etc.As developer solution, can enumerate organic class materials such as monoethanolamine, diethanolamine, triethanolamine, or the aqueous solution of NaOH, potassium hydroxide, sodium carbonate, ammonia, quaternary ammonium salt etc.
Then, after under the temperature about 200 ℃ the pattern after developing being carried out, cure.In addition, preferably formed photomask pattern is carried out blanket exposure.Thus, can form photomask with regulation shape.
＜EL element 〉
Above-mentioned photomask can be used as the black matrix" in the EL element.Forming this photomask makes it surround for example above-mentioned transparency electrode (lower electrode).
Then, on transparency carrier, form luminescent layer.This luminescent layer is given R, G, B luminescent material of all kinds assigned address and is formed by for example using evaporation or ink-jetting style.
When forming luminescent layer by evaporation, the cross sectional shape of above-mentioned photomask is preferably turbination (base is than short trapezoidal in top).In addition, when the cross sectional shape of photomask is not turbination, preferably on this photomask, form obconic next door.This next door is formed by in the past photosensitive composite and gets final product.
Then, form upper electrode on luminescent layer top.This upper electrode by evaporation for example metal such as Al form.
In addition, when forming luminescent layer by ink-jetting style, it can be by being provided with opening portion on above-mentioned photomask, and give China ink and form on this opening portion.
In foregoing, the 3-tier architecture that has shown lower electrode, luminescent layer and upper electrode, but be not limited to this, it also can be 5 layers of structure of lower electrode, hole injection layer, luminescent layer, electron injecting layer and upper electrode and 7 layers of structures such as structure of lower electrode, hole injection layer, hole transporting layer, luminescent layer, electron supplying layer, electron injecting layer and upper electrode.
Embodiment
[synthesis example 1]
56 mass parts benzyl methacrylates, 36 mass parts methacrylic acid 2-hydroxyl ethyl esters, 78 mass parts glycidyl methacrylate are dissolved in the 250 mass parts ethylene glycol monomethyl ether acetates, and add 2 mass parts azoisobutyronitriles, carry out heated polymerizable.
Then, adding 40 mass parts has dissolved 2 mass parts and has forbidden the acrylic acid of the methylnaphthohydroquinone of agent and reaction as polymerization.Then, add 42 mass parts tetrahydrobenzene dicarboxylic acid anhydrides and reaction, obtain resin.The quality mean molecular weight of gained resin is 3000.
[embodiment 1～3, comparative example 1]
Mixture table 1 each composition, and adjust with propylene glycol methyl ether acetate, so that the concentration of the solid constituent outside desolventizing is 25 quality %, obtain black photosensitive composition thus.
Table 1
| The optical polymerism compound | Photoepolymerizationinitiater initiater | Dispersible pigment dispersion | |
| Embodiment 1 | Resin A: 30 mass parts DPHA:10 mass parts | The Irgacure369:10 mass parts | Blue dispersion liquid: 20 mass parts carbon dispersion liquids: 15 mass parts |
| Embodiment 2 | Resin A: 30 mass parts DPHA:10 mass parts | The Irgacure369:10 mass parts | Blue dispersion liquid: 30 mass parts carbon dispersion liquids: 5 mass parts |
| Embodiment 3 | Resin A: 30 mass parts DPHA:10 mass parts | The Irgacure369:10 mass parts | Blue dispersion liquid: the red dispersion liquid of 80 mass parts: 80 mass parts carbon dispersion liquids: 20 mass parts |
| Comparative example 1 | Resin A: 30 mass parts DPHA:10 mass parts | The Irgacure369:10 mass parts | Carbon dispersion liquid: 30 mass parts |
The corresponding relation of the abbreviation of each composition and formal title is as described below in the table.
DPHA: dipentaerythritol acrylate
Irgacure369:2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone (CibaSpecialty Chemicals corporate system)
Blue dispersion liquid: the blue UM of blue pigment dispersion liquid CF (contain 20 quality %C.I. pigment blue 15s: 6, Mikoku Pigment Co., Ltd.'s system)
Carbon dispersion liquid: " carbon dispersion liquid CF deceives EX-1455 " (containing 24 quality % high resistance carbon, Mikoku Pigment Co., Ltd.'s system)
Red dispersion liquid: " the red EX-109 of CF " (containing 20 quality %C.I. paratoneres 177, anthraquinone class red)
Yellow dispersion liquid: " the yellow HM of CF " (containing 20 quality %C.I. pigment yellow 13s 9, monoazo class yellow uitramarine)
(formation of photomask)
Use spinner that the black photosensitive composition of gained is coated on the glass substrate, drying is 2 minutes under 90 ℃, forms the black photosensitive composition layer.
Then, by minus mask irradiation ultraviolet radiation optionally on this black photosensitive composition layer.Then, develop in the tetramethylammonium hydroxide aqueous solution of 0.04 quality %, and cure 30 minutes after in 220 ℃ baking oven, forming thickness thus is the photomask pattern of 1.5 μ m.
(evaluation)
Estimate specific inductive capacity, the generation of wrinkle, the OD value of the photomask that forms as mentioned above.It the results are shown in table 2.
Use specific inductive capacity determinator " SSM495 " (trade name, Japanese SSM corporate system) to measure specific inductive capacity, use " Gretag MacbethD-200-2 " (trade name, Macbeth corporate system) to measure the OD value.
Table 2
| Specific inductive capacity | Have or not wrinkle | The OD value | |
| Embodiment 1 | 5.5 | Do not have | 2.5 |
| Embodiment 2 | 4.1 | Do not have | 1.2 |
| Embodiment 3 | 6.0 | Do not have | 3.0 |
| Comparative example 1 | 30 | Have | 3.8 |
Demonstrate the photomask that black photosensitive composition of the present invention can form the shape stability height and have low-k by above result.
Claims (8)
1. black photosensitive composition, described black photosensitive composition are that the EL element photomask that contains optical polymerism compound, Photoepolymerizationinitiater initiater and black pigment forms and uses black photosensitive composition, wherein also contain organic pigment.
2. black photosensitive composition as claimed in claim 1, wherein, the mass ratio of described organic pigment and described black pigment is 10: 0.7 to 10: 10.
3. black photosensitive composition as claimed in claim 1, wherein, described black pigment is a carbon black.
4. black photosensitive composition as claimed in claim 1, wherein, the total amount of described organic pigment and described black pigment is 10～80 quality % with respect to all solids composition outside desolventizing.
5. black photosensitive composition as claimed in claim 1, wherein, the specific inductive capacity of formed photomask is less than 10.
6. black photosensitive composition as claimed in claim 1, wherein, the OD value of formed photomask is more than 1.
7. one kind by the formed photomask of each described black photosensitive composition in the claim 1～6.
8. EL element with the described photomask of claim 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006075272A JP4745092B2 (en) | 2006-03-17 | 2006-03-17 | Black photosensitive composition, light-shielding film and EL device manufactured from this black photosensitive composition |
| JP2006075272 | 2006-03-17 |
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| Publication Number | Publication Date |
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| CN101038437A true CN101038437A (en) | 2007-09-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200710087762XA Pending CN101038437A (en) | 2006-03-17 | 2007-03-08 | Black photosensitive composition, shielding film and el device manufactured by the black photosensitive composition |
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| Country | Link |
|---|---|
| JP (1) | JP4745092B2 (en) |
| KR (1) | KR20070094459A (en) |
| CN (1) | CN101038437A (en) |
| TW (1) | TW200745746A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103293852A (en) * | 2012-03-01 | 2013-09-11 | 奇美实业股份有限公司 | Photosensitive resin composition, black matrix, color filter and liquid crystal display element thereof |
| CN106547168A (en) * | 2016-10-28 | 2017-03-29 | 深圳市华星光电技术有限公司 | A kind of black-matrix material compositionss and application |
| CN115466543A (en) * | 2022-10-19 | 2022-12-13 | 浙江福斯特新材料研究院有限公司 | Packaging composition for photocuring black ink-jet, packaging structure and application thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4745093B2 (en) * | 2006-03-17 | 2011-08-10 | 東京応化工業株式会社 | Black photosensitive composition |
| KR100937201B1 (en) * | 2007-11-30 | 2010-01-19 | 제일모직주식회사 | Black photosensitive resin composition |
| KR101858766B1 (en) * | 2013-07-31 | 2018-05-16 | 동우 화인켐 주식회사 | Black Photosensitive Resin Composition, Color Filter, and Liquid Crystal Display Device Having the Same |
| CN116107164B (en) * | 2022-12-30 | 2024-02-20 | 浙江鑫柔科技有限公司 | Photoresist composition, metal conductive pattern, preparation method of metal conductive pattern and touch screen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07100764B2 (en) * | 1990-07-03 | 1995-11-01 | 宇部興産株式会社 | Black photocurable polymer composition and method for forming black photocurable film |
| JP3346647B2 (en) * | 1993-05-12 | 2002-11-18 | 富士写真フイルム株式会社 | Light-shielding photosensitive resin composition and light-shielding image forming method |
| JP4302075B2 (en) * | 1997-02-28 | 2009-07-22 | 三菱化学株式会社 | Black resist composition for forming black matrix |
| JP4595374B2 (en) * | 2003-04-24 | 2010-12-08 | 住友化学株式会社 | Black photosensitive resin composition |
-
2006
- 2006-03-17 JP JP2006075272A patent/JP4745092B2/en active Active
-
2007
- 2007-02-06 KR KR1020070011945A patent/KR20070094459A/en not_active Application Discontinuation
- 2007-02-09 TW TW096104848A patent/TW200745746A/en unknown
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103293852A (en) * | 2012-03-01 | 2013-09-11 | 奇美实业股份有限公司 | Photosensitive resin composition, black matrix, color filter and liquid crystal display element thereof |
| CN103293852B (en) * | 2012-03-01 | 2015-07-15 | 奇美实业股份有限公司 | Photosensitive resin composition, black matrix, color filter and liquid crystal display element thereof |
| CN106547168A (en) * | 2016-10-28 | 2017-03-29 | 深圳市华星光电技术有限公司 | A kind of black-matrix material compositionss and application |
| CN115466543A (en) * | 2022-10-19 | 2022-12-13 | 浙江福斯特新材料研究院有限公司 | Packaging composition for photocuring black ink-jet, packaging structure and application thereof |
| CN115466543B (en) * | 2022-10-19 | 2024-02-27 | 福斯特(安吉)新材料有限公司 | Photocurable black inkjet packaging composition, packaging structure and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI377441B (en) | 2012-11-21 |
| JP4745092B2 (en) | 2011-08-10 |
| TW200745746A (en) | 2007-12-16 |
| JP2007249045A (en) | 2007-09-27 |
| KR20070094459A (en) | 2007-09-20 |
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