TWI377441B - - Google Patents

Description

[Technical Field] The present invention relates to a black photosensitive composition for forming an el element light-shielding film, a light-shielding film obtained from the black photosensitive composition, and an EL element. [Prior Art]

In recent years, the development of E L components has continued. The E L element has a laminate in which a lower electrode, a light-emitting layer, and an upper electrode are laminated in this order on a transparent substrate. The light-emitting layer has light-emitting regions of R, G, and B. Such an E L element is being studied to form a light shielding film for improving display contrast (see Patent Documents 1 and 2). [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei.

However, the light-shielding film used in the above-described EL element is formed such that the light-shielding film itself is in direct contact with the electrode. Therefore, a light shielding film for an EL element is required to have a low dielectric constant. In view of the above problems, an object of the present invention is to provide a black photosensitive composition for an EL element which can form a light-shielding film having a low dielectric constant. Further, an object of the present invention is to provide a light shielding film and an EL element formed of the black photosensitive composition. [Means for Solving the Problem] 5 1*377441 The present inventors have found that the black photosensitive composition contains a predetermined ratio of the organic pigment, and is effective for the low dielectric constant of the light-shielding film, and completed the present invention. The present invention provides a black photosensitive composition for forming an EL element light-shielding film containing a photopolymerizable compound, a photopolymerization initiator, and a black pigment, and further contains an organic pigment. Moreover, the present invention provides a light shielding film formed of the above black photosensitive composition and an EL element including the light shielding film.

[Effect of the Invention] According to the present invention, a light-shielding film having a low dielectric constant can be formed by adding an organic pigment to a black photosensitive composition. [Embodiment] Hereinafter, embodiments of the present invention will be described. The black photosensitive composition for forming an EL element light-shielding film of the present invention contains a photopolymerizable compound, a photopolymerization initiator, a black pigment, and an organic pigment.

[Photopolymerizable compound] [Photopolymerizable compound] A substance which is polymerized and hardened when it is irradiated with light such as ultraviolet rays. As the photopolymerizable compound, a compound having an ethylenic double bond is preferred, and an acrylic resin is more preferred. <Compound having an ethylenic double bond> Examples of the compound having an ethylenic double bond include acrylic acid, methacrylic acid, fumaric acid, maleic acid, and fumaric acid. Ester, monoethyl fumarate, 2-hydroxyethyl acrylate, mercapto propyl 6 1.377441

Ethylenic acid 2-hydroxyethyl from I, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether sulfhydryl Acrylate, glycerin acrylate, glyceryl methacrylate, acrylamide, methacrylamide, acrylonitrile, mercapto acrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate 'Isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethylene glycol diacrylate, ethylene Alcohol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimercapto acrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimercapto acrylate, butanediol II Mercapto acrylate, propylene glycol diacrylate, propylene glycol dimercapto acrylate 'trimethylolpropane triacrylate, trimethylolpropane trimethyl acrylate 6|, tetramethyl methacrylate tetrapropyl acid , four thiol-propylated tetradecyl acrylate, neopentyl Tetraol triacrylate, neopentyl alcohol trimethacrylate, neopentyl alcohol tetraacrylate, neopentyl alcohol tetradecyl acrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaquinone Acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethylene acrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimercapto acrylate, Caldo a monomer or oligomer such as car doepoxy diacrylate; a polyester prepolymer obtained by condensing a polyhydric alcohol with a unit acid or a polybasic acid and (mercapto)acrylic acid Poly(meth)acrylate, a poly(meth)acrylic acid urethane obtained by reacting a polyol group with a compound having two isononate groups and reacting with (mercapto)acrylic acid; Bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol or hydrazine 7 1377441

Cres novolac type epoxy resin, resol no vo lac type epoxy resin, trisphenol methane type epoxy resin, polycarboxylate polyglycidyl ester, polyglycol polyglycidyl ester An aliphatic or alicyclic epoxy resin, an amine epoxy resin, an epoxy (meth) acrylate resin obtained by reacting an epoxy resin such as a dihydroxybenzene type epoxy resin with (meth)acrylic acid, or the like. Further, a resin obtained by reacting the above-mentioned epoxy (fluorenyl) acrylate resin with a polybasic acid anhydride can also be used. Since the acrylonitrile group or the methacrylium group is introduced into these compounds, the crosslinking efficiency can be improved, and the coating film is excellent in light resistance and drug resistance. Among them, a resin having a cardo structure in a molecule is preferred. Since the resin having a structure of Caldo has high heat resistance and chemical resistance, it can improve the heat resistance and chemical resistance of the black photosensitive composition by using the photopolymerizable compound. Specifically, it is preferred to use a resin represented by the following formula (1). [Chemical Formula 1]

COOH HOOC-Y-CO——Ο X-0——C0——Z-C0-0——xo-co-y-cooh COOH J η (1) where X is the following formula ( 2) The group shown, Y is the residue after the removal of the carboxylic anhydride group (-C0-0-C0-) from the dicarboxylic anhydride, and the residue of the Z system after removing the two tarenic acid groups from the tetracarboxylic dianhydride The base, η is an integer from 1 to 20. · [Chemical Formula 2] 8 01377441

Oc-c=ch2 Η The specific example of the derivatization of the γ-carboxylic acid anhydride (the removal of the carboxylic anhydride group #) may, for example, be maleic anhydride, tonic anhydride, phthalic anhydride, tetrahydrophthalic anhydride or hexahydroanthracene. Specific examples of the acid anhydride-based tetrahydrophthalic anhydride, chloro-bromic anhydride, methyltetrahydrophthalic anhydride, and the above-mentioned tetracarboxylic dianhydride (two tetracarboxylic dianhydrides) are exemplified, for example, a tetracarboxylic dianhydride such as pyrophenyl ketone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride or biphenyl anhydride; and the polymerized weight average molecular weight having the above ethylenic double bond is 1, 〇〇〇 The above is preferable. The molecular weight is 1 or more, and the coating degree can be made uniform. The molecular weight is preferably 100,000 or less, and when the weight is 4 or less, better development performance can be obtained. The amount of the above-mentioned average molecular weight is 1, and the above-mentioned ethylene double is a polymer compound having an ethylenic double bond. It is preferable to use the above-mentioned polymerizable monomer having an ethylenic double bond. The monomer may be an oxime ester, decyl methacrylate or 2-hydroxy acrylate. No. Ethyl ... (2) 5r of the dicarboxylic anhydride) ίό acid needles, Iraq, methyl endomethylene methyl glutaric anhydride. a carboxylic anhydride group-based presorcinic acid anhydride or a dibasic ether tetracarboxylic acid dimer, which is obtained by using a weight averaged weight average amount of 100,000 Acrylic acid, methacrylic acid 9 1377441

2-hydroxyethyl ester, 2-hydroxypropyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol Diacrylate, tetraethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, trishydroxypropyl propane triacrylate, trimethylolpropane trimethacrylate, tetramethylol Hyun four acrylic acid vinegar, tetramethyl methacrylic acid tetramethyl propylene acid cool, neopentyl alcohol triacrylate, neopentyl alcohol trimethacrylate, neopentyl alcohol tetraacrylate, new pentylene Alcohol tetradecyl acrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentadecyl acrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethylene acrylate, 1,6 - hexanediol diacrylate, benzyl acrylate, benzyl methacrylate, cardo epoxy diacrylate, acrylic acid, methacrylic acid, etc., but are not limited by these. Among them, a multifunctional photopolymerizable monomer is preferred. By combining the polymer compound having an ethylenic double bond and the photopolymerizable monomer in this manner, the curability can be improved and pattern formation can be facilitated.

The photopolymerizable compound may be one in which the molecule itself is polymerizable. However, in the present invention, the photopolymerizable compound also contains a mixture of a polymer binder and a photopolymerizable monomer. From the viewpoint of easy development, the polymer binder is preferably an alkali-developable binder. Specific examples of the polymer binder include a carboxyl group-containing monomer such as acrylic acid or mercaptoacrylic acid, methyl propionate, methyl mercaptopropionate, ethyl propionate, and methyl propionic acid. Ethyl acetate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, acrylic acid 10 1377441

N-butyl acrylate, n-butyl methacrylate 'isobutyl acrylate, isobutyl methacrylate, benzyl acrylate, benzyl methacrylate, oxy acrylate, phenoxy methacrylate, acrylate a copolymer of an oxime ester, an isodecyl methacrylate, a glycidyl methacrylate, a stupid ethylene, an acrylamide, an acrylonitrile, or the like, and a phenol novolac type epoxy acrylate polymer. Phenol f-type phenolic epoxy methacrylate polymer, cresol novolac type epoxy acrylate polymer, acetal chain epoxy acrylate polymer, bisphenol A type A resin such as an epoxy acrylate polymer or a bisphenol S-type epoxy acrylate polymer. The content of the monomer component having a carboxyl group such as acrylic acid methacrylic acid constituting the above resin is preferably in the range of 5 mol% to 40 mol%. The weight average molecular weight of the above polymer binder is preferably in the range of 1,100 to 100,000. By having a weight average molecular weight of 1,000 or more, the coating degree can be made uniform. Further, when the weight average molecular weight is 100 or less, it is possible to obtain more excellent developability.

When the photopolymerizable compound contains a polymer binder and a photopolymerizable monomer, the polymer binder is blended in an amount of 10 to 60 per 100 parts by weight of the polymer binder, the photopolymerizable monomer, and the photopolymerizable initiator. The parts by weight are preferred. By setting the amount to be 10 parts by weight or more, the film can be easily formed during coating and drying, and the coating strength after curing can be sufficiently enhanced. Moreover, the developing property can be improved by setting the blending amount to 60 parts by weight or less. In addition, the polymerizable monomer component is preferably blended in an amount of from 15 to 50 parts by weight per 100 parts by weight of the polymer binder, the photopolymerizable monomer, and the photopolymerization initiator. By setting the compounding amount to 15 parts by weight or more, 11 1377441 can prevent photohardening failure and obtain sufficient heat resistance and chemical resistance. In addition, the coating film forming ability can be improved by setting the blending amount to 50 parts by weight or less. [Photopolymerization initiator]

The photopolymerization initiator may, for example, be 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-mercapto-1-phenylpropan-1-one, 1-[4-(2-hydroxyethyl) Oxy)phenyl]-2-carbyl-2-mercapto-1-propan-1-yl, 1-(4-isopropylphenyl)-2-yl-2-ylpropanone- 1- Ming, 1-(4-dodecylphenyl)-2-transyl-2-mercaptopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane 1-ketone, bis(4-dimethylaminophenyl)one, 2-methyl-1_[4-(methylthio)phenyl]-2-carboline (morpholino)-propan-1-ene, 2-benzyl-2-didecylamino-1-(4-indolyl)-butan-1-one, ethyl ketone-l-[9-ethyl-6-(2-methyl Benzomethanyl)-9H-carbazol-3-yl]-1-(0-acetamidine), 2,4,6-trimethylbenzhydryldiphenylphosphine, 4-benzoquinone Base 4'-mercaptodithiol sulfide, 4-didecylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4 - butyl dimethylaminobenzoate, 4-dimethylamino-2-ethylhexyl benzoic acid, 4-didecylamino-2-isopentyl succinic acid, benzyl-β-oxime Oxyethyl acetal, benzyl dimethyl ketal, 1- Base-1,2-propanedione-2-(0-ethoxycarbonyl)anthracene, 0-benzhydryl benzoyl decanoate, 2,4-diethyl thioxanthone, 2-air gust Ketone, 2,4-dimethylpyridone, 1-chloro-4-propoxy sultone, ·4 ta, 2-gas thioxanthene, 2,4-diethyl thioxanthene, 2- fluorenyl Thiophene, 2-isopropylthioxanthene, 2-ethylhydrazine, octamethylguanidine, 1,2-phenylpyrazine, 2,3-diphenylfluorene, diazobutyronitrile, peroxidation Stupid hyperthyroidism, cumene peroxide, 2-hydrosulfanyl stupid and dimethicone, 2-hydrothiol stupid domain oxazole, 2-hydrosulfanyl stupid 0 sitting, 2-(neighboring 12 1377441

Phenyl)-4,5-di(m-decyloxyphenyl)-imidazolyl dimer, diphenyl ketone, 2-chlorodiphenyl ketone, p,p,-bisdimethylamino 2 Phenyl ketone, 4,4'-bisdiethylaminodiphenyl ketone, 4,4'-dioxadiphenyl hydrazine, 3,3-dimethyl-4-methoxydiphenyl ketone, benzene Occasionally, stupid, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, stupid isobutyl ether, benzoin butyl Ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-didecylaminopropiophenone, diacetophenone, trichloroacetophenone, pair 3 Butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrisaceacetophenone, p-butylidene dichloroacetophenone, α,α-dioxa-4-phenoxy Stupid brewing], thioxanthone, 2-mercaptopurine, 2-isopropylthioxanthone, di-p-cycloheptanone, pentyl-4-didecylaminobenzoate , 9-phenyl acridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinyl)pentane, 1,3-bis(9-acridinyl) Propane, p-oxygen three <nitrogen> tillage, 2, 4,6-parade (trioxanyl)-s-three <nitrogen> triazine, 2-mercapto-4,6-bis(trichloromethyl)-s-three <nitrogen> Mouth, 2-[2-(5-fluorenylfuran-2-yl)vinyl]-4,6-bis(trichloroindenyl)-3-tris[nitrogen] tillage, 2-[2- (furan-2-yl)vinyl]-4,6-bis(trimethylsulfonyl)-s-triple <nitrogen> tillage, 2-[2-(4-diethylamino-2-) Phenyl phenyl)vinyl l·4,6-bis(trichloromethyl)-s-triple <nitrogen> well, 2-[2-(3,4-dimethoxyphenyl)vinyl ]-4,6-bis(trichloroindenyl)-3-tris<nitrogen> tillage, 2-(4-decyloxyphenyl)-4,6-bis(trimethylmethyl)-3- Three <nitrogen> tillage, 2-(4-ethoxy stupid vinyl)-4,6-bis(trichloroindolyl)-3-tris<nitrogen> tillage, 2-(4-n-butyl) Oxyphenyl)-4,6-bis(trimethylsulfonyl)-s-triple <nitrogen> tillage, 2,4-bis-triseodecyl-6-(3-bromo-4-oxo) Phenyl-s-triple <nitrogen> tillage, 2,4-bis-tris-methylmethyl-6-(2-bromo-4-methoxy)phenyl-s-triple <nitrogen> Plowing, 2,4-bis-three 13 1377441 gas methyl-6-(3-bromo-4-methoxy)styryl stupyl 24 bis-tris-methyl-6-(2-bromo-4- Methoxy) stupid vinyl _S three-yl < N > coffee and the like. These photopolymerization initiators may be used alone or in combination of two or more. The photopolymerization initiator is preferably contained in an amount of from 1 part by weight to 40 parts by weight per 100 parts by weight of the total of the photopolymerizable compound and the photopolymerization initiator. [black pigment]

When the black pigment is a light-shielding pigment, it is not particularly limited, and specific examples thereof include metal oxides of carbon black, titanium black 'copper, iron, manganese, magnet, chromium, nickel, rhodium, calcium, silver, and the like. An inorganic pigment such as a composite oxide, a metal sulfide, a metal sulfuric acid or a metal carbonate. Among these mist-colored pigments, carbon black which is inexpensive and has high light-shielding property is more preferable. As the carbon black, well-known carbon black such as channel black, furnace black, hot black, and lamp black can be used. Further, it is preferable to use a resin to cover the black. The dielectric black of the formed light-shielding film can be further reduced by coating the carbon black with the resin. Further, the dispersing agent is preferably a polymer dispersing agent which is a polyamidide-based, urethane-based resin or acrylic resin-based polymer.

Such dispersing agents include, for example, BYK-Chemie, manufactured by the company, BYK-161, 162, 163, 164, 166, 170, 182, and the trade name Solsperse S3000, S9000' manufactured by ZENECA AG. S17000, S20000' S27000' S24000' S26000, S28000 [Organic Pigment] The black photosensitive composition of the present invention contains the organic pigment β. By containing the organic pigment, a light-shielding film having a low dielectric constant can be formed. Further, by increasing the shape stability of the light-shielding film formed by 14 1377441 and adjusting the amount of the organic pigment, the dog can adjust the taper angle of the light-shielding film. Further, since a plurality of kinds of organic pigments are combined to exhibit the same black color as that of carbon black, it is possible to form a light-shielding film having a lower dielectric constant than a light-shielding film to which only carbon black is added.

In particular, when carbon black is used as the black pigment, the dielectric layer of the formed light-shielding film tends to increase. However, by constituting the organic pigment, the desired 0D value (optical density) can be maintained while reducing the formation. The dielectric ratio of the light-shielding film. Such an organic pigment may, for example, be a compound classified as a pigment in a colorimetric index (CI; issued by The Society of Dyers and Colourists), and specifically, may be exemplified The color index (CI) number below.

c · I. Pigment Yellow 1 (hereinafter, Γ CI Pigment Yellow J is the same, only the number is recorded), 3, 1 1 , 1 2 ' 13 , 1 4 , 1 5 , 1 6 , 1 7 , 20 ' 24 ' 3 1 ' 53 > 55, 60, 6 1 , 65 ' 71 , 73 , 74 , 8 1 , 83 ' 8 6 ' 93 , 95 , 97 , 98 , 99 , 1 〇〇 , 1 〇 1, 1 〇 4 , 106 ' 108 , 109 ^ 11 0, 1 13 , 114 , 116 , 117 , 119 , 120 ' 125 , 126 , 127 , 128 , 129 , 137 ' 138 ^ 139 , 147 > 148 ' 150 丨 ' 151 , 152 , 153 '154' 155 ' 156, 166' 167 * 168 ' 175 , 180 , 185 ; e · I · Pigment Orange 1 (hereinafter, Γ CI Pigment Orange j is the same, only the record number is Ma), 5 ' 13 ' 14 , 16, 1 7, 24, 34 • 36 ' 38 ' 40 ' 43 , 4 6 , 49 > ί 51 , 55 , 59 , 61 ' 63 , 64 , 71 , 73 ; C'I. Pigment Violet 1 (below, Γ CI Pigment violet j is the same, only record number 23, 29, 30, 32, 36, 37, 38, 39' 40, 50: 15 1377441 CI Yankehong 1 (below, "CI Pigment Red" is the same » only record number), 2, 3, 4 ' 5, 6, 7, 8, 9, 1 0 '11 '12' 1 4,1 5,1 6,17,18,19 ' 21 , 22 , 23 , 30 , 3 1 , 32 , 37 , 3 8 , 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 , 1 02 ' 1 04 , 105 , 10 6 , 108 ' 112 ' 113 , 1 14 , 122 , 123 , 144 ' 1 4 6 , 149 '150' 15 1 , 155 , 166 , 168 170 , 171 , 172 ' 1 74 , 175 , 176 , 177 , 178 , 179 , 180 185 , 187 , 188 ' 1 90 ' 192 , 193, 194 '202 ' 206 ' 207 208 ' 209, 2 15 , 2 16 , 217 , 220 , 223 , 224 , 226 , 227 228 , 240 ' 242 , 243 , 245 , 254 , 255 , 264 ' 265 » CI pigment Below blue U, "丨C · I · Pigment Blue" is the same as the number only), 2 '15, 1 5 : 3 ' 15 : 4 , 15 : 6 , 16 , 22 , 60 , 64 , 66 ; CI 颜ί 14 Green 7, CI Pigment Green 3 6 , C. I. Pigment Green 37;

C.I. Pigment Brown 23, C.I. Pigment Brown 25, C.I. Pigment Brown 26, C.I. Pigment Brown 2 8; C. I. Pigment Black 1, C. I. Pigment Black 7. Further, the organic pigment as described above is not only a shape stabilizer but also a function as a carbon black auxiliary pigment. Examples of the auxiliary pigment include, for example, a phthalocyanine pigment, an azo pigment, and a basic dye lake pigment. The weight ratio of the organic pigment to the black pigment is preferably from 1 〇 ·· 〇. 7 to 1 0 ··1 0 , and more preferably from 10:4 to 10:7. Further, the total amount of the organic pigment and the black pigment is preferably from 1% by weight to 8% by weight, based on the total weight of the photopolymerizable compound and the photopolymerization initiator, of 16 丄 '3 77441%, and is 20% by weight. More preferably, it is 50% by weight. ^ 〜& The error is 80% by weight or less, and appropriate sensitivity can be obtained. In addition, when the total amount is 10% by weight or more, the light-shielding property can be improved, and the function as a light-shielding film is sufficiently eliminated.

Among the organic pigments, 'preferably, rT 1·Ι. Pigment Blue 6, C.I. Pigment Red 177, C.I. Pigment Yellow 139 are mentioned. These are the machine pigments

It can improve the shading and shape stability. The content of the above-mentioned organic pigment and the above-mentioned black pigment, preferably β _ && 疋 is adjusted so that the dielectric layer of the eight-blade blade in the light-shielding film formed by the black photosensitive composition of the present invention is less than 10, more preferably adjusted It is 6 or less. Thereby, even if the film is in contact with the electrode, it is possible to prevent a problem such as a short circuit. The content of the organic pigment and the black pigment is preferably & stomach. The thickness of the light-shielding film formed by the black photosensitive composition of the present invention has an OD value of 1 or more. When it is the above OD value, the function as a light shielding film in the EL element can be achieved.

[Other components] The black photosensitive composition of the present invention can be blended with a force π as necessary. Specifically, there are sensitizers, hardening accelerators, and photocrosslinking _. • No sensitizer, dispersant , dispersing aids, fillers, adhesion promoters, agents, UV absorbers, anti-agglomerates, etc. Further, the black photosensitive composition of the present invention may be added with a solvent for dilution, a thermal polymerization inhibitor, an antifoaming agent, or a surfactant. Here as a solvent that can be added to the black photosensitive composition, 17 1377441

For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monodecyl ether, diethylene glycol Monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, di- propylene glycol monomethyl ether, di- propylene glycol monoethyl ether, di- propylene glycol mono-n-propyl ether, diexetane (poly)alkylene glycol monoalkyl ethers such as alcohol mono-n-butyl ether, tri-n-propylglycol monomethyl ether, tri-n-ethylene glycol monoethyl ether; ethylene glycol monodecyl ether Acid ester, ethylene glycol monoethyl ether acetate, diethylene glycol monodecyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monodecyl ether acetate, propylene glycol monoethyl ether (poly)alkylene glycol monoalkyl ether ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc. Ethers; methyl ethyl ketone, ring a ketone such as a ketone, a 2-heptanone or a 3-heptanone; an alkyl lactate such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; and 2-hydroxy-2-methylpropanoic acid ester,

3 - decyloxypropionate, ethyl 3-methoxyoxypropionate - methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, glycolic acid Ester, decyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl butyl acetate, 3-mercapto-3-methoxybutyl acetate, 3-methyl-3-anthracene Oxybutyl butyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate 'isobutyl acetate, n-pentyl phthalate 'isoamyl acetate, n-butyl propionate, butyl Acid ethyl ester, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, Other esters such as 2-oxoethyl butyrate; aromatic 18 1377441 hydrocarbons such as toluene and xylene; N-mercaptopyrrolidone, N,N-dimethylformamide, N , guanamines such as N-dimethylacetamide. These solvents may be used alone or in combination of two or more.

Among them, because propylene glycol monomethyl ether, ethylene glycol monodecyl ether acetate, propylene glycol monodecyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol didecyl ether, diethylene glycol Ethyl ethyl ether, cyclohexanone, and 3-methoxybutyl butyl acetate exhibit excellent solubility to a photopolymerizable compound and a photopolymerization initiator, and can also change the dispersibility of insoluble components such as black pigment. It is preferred to be good, and it is particularly preferable to use propylene glycol monomethyl ether acetate or 3-methoxybutyl acetic acid. The solvent may be used in the range of 50 parts by weight to 500 parts by weight based on 1 part by weight of the total of the photopolymerizable compound, the photopolymerization initiator, and the coloring agent. Further, as the thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether or the like can be used. Further, as the antifoaming agent, a lanthanoid-based or fluorine-based compound can be used, and various surfactants such as an anionic, cationic or nonionic surfactant can be used as the surfactant.

The method for producing a black photosensitive composition of the present invention can be obtained by mixing all of the components such as the photopolymerizable compound, the photopolymerization initiator, the black pigment, and the organic pigment by a stirrer. Alternatively, it may be filtered using a filter to homogenize the resulting mixture. Further, when the light-shielding film is formed by using the black photosensitive composition of the present invention, the black photosensitive composition of the present invention is applied onto a substrate and dried to form a film. In order to improve the coating property at this time and to improve the physical properties after photocuring, a polymer binder may be further contained as a binder in addition to the above components. The binder can be appropriately selected and used for the purpose of improving compatibility such as compatibility, film formability, developability, and adhesion. The thickness of the light-shielding film formed on the substrate can be usually set in the range of 〇5 μm to ίο μm, preferably 〇 8 μm to 5 μm, preferably 1 μm to 4 μm. <Formation of Light-Shielding Film> First, a contact-type coating device such as a roll coater or a reverse coater or a coating bar or the like is used for the black photosensitive composition of the present invention, or a rotating transfer coating device or the like A non-contact type coating device such as an applicator or a curtain coater is coated on a substrate. When the substrate has light transparency, it is not particularly limited. For example, a glass plate, a quartz plate, a transparent or translucent resin plate, or the like can be given. A typical EL element ' is a transparent electrode formed on the above substrate. This transparent electrode is a lower electrode. The transparent electrode is formed, for example, of ITO (indium tin oxide). The lower electrode is patterned into a stripe shape or the like. Further, in order to improve the adhesion between the substrate and the black photosensitive composition, a decane coupling agent may be applied to the substrate in advance. Alternatively, a decane coupling agent may be added in advance when modulating the black photosensitive composition. After the black photosensitive composition was applied, it was dried to remove the solvent. The drying method is not particularly limited. For example, any of the following methods can be used. (1) On a hot plate at 80 ° C to 120 ° C, preferably from 1 to 10 ° (temperature of rc, drying for 60 seconds to 120 seconds) The method, (2) a method of leaving at room temperature for several hours to several days, and (3) a method of removing the solvent by placing it in a warm air heater or an infrared heater for several ten minutes to several hours. The cover is interposed and irradiated with an active energy ray such as ultraviolet light or excimer light 20 1-377441 to emit light. The amount of energy ray to be irradiated varies depending on the composition of the black photosensitive composition, for example, at 30 mJ/cm 2 . It is better to be around 2000 mJ/cm2.

Next, the exposed film is developed by a developing liquid to be patterned into a desired shape. The development method is not particularly limited, and for example, a dipping method, a spraying method, or the like can be used. Examples of the developing solution include an organic substance such as ethanolamine, diethanolamine or triethanolamine; or an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or a quaternary ammonium salt. Subsequently, the developed pattern was post-baked at about 200 °C. Moreover, it is preferred to expose the pattern of the formed light-shielding film to the entire surface. Thereby, a light shielding film having a predetermined shape can be formed. <EL Element> The light shielding film described above can be a black matrix of the EL element. The light shielding film can be formed, for example, so as to surround the transparent electrode (lower electrode).

Next, a light-emitting layer is formed on the transparent substrate. The light-emitting layer can be formed, for example, by vapor deposition or ink jetting, by applying light-emitting materials of respective colors of R, G, and B at predetermined positions. When the light-emitting layer is formed by vapor deposition, the cross-sectional shape of the light-shielding film is preferably a cone shape (a trapezoidal shape in which the bottom side is shorter than the upper side). Further, when the cross-sectional shape of the light-shielding film is not an inverted tapered shape, it is preferable to form an inverted tapered wall on the light-shielding film. This partition wall can be formed using a conventional photosensitive composition. Subsequently, an upper electrode is formed on the light-emitting layer. The upper electrode can be formed, for example, by vapor-depositing a metal such as A1. Further, when the light-emitting layer is formed by the ink-jet method, it is possible to form an opening by providing an opening in the 21 Γ 377 441 light-shielding film and then applying ink from the opening. Although the structure of the lower electrode, the light-emitting layer, and the upper electrode is shown above, the present invention is not limited thereto, and may be a five-layer structure of a lower electrode, a hole injection light-emitting layer, an electron injection layer, and an upper electrode, or may be a lower portion. Three-layer structure, such as an electrode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron layer, an electron injection layer, and a seven-layer structure of an upper electrode,

[Examples] [Synthesis Example 1] 56 parts by weight of methyl methacrylate, 36 parts by weight of methyl propyl 2-hydroxyethyl ester, 78 parts by weight of glycidyl methacrylate, dissolved in parts by weight Alcohol monomethyl ether acetate was added and 2 parts by weight of azonitrile was added to carry out heating polymerization. Subsequently, 40 parts by weight of an acid in which 2 parts by weight of methylhydroquinone was dissolved was added as a polymerization inhibitor and allowed to react. Next, 42 parts by weight of phthalic anhydride was added and reacted to obtain a resin. The resulting weight average is 3000. Acetate 250 Isobutylpropylene tetrahydrogen amount [Examples 1-3, Comparative Example 1] Each component of Table 1 was mixed, and propylene glycol monomethyl ether acetate was adjusted so that the solid content other than the solvent was 0.05% by weight. The ester is a color sensitive composition. 25 to black 22 Γ 377441 [Table i] Photopolymerizable compound Photopolymerization initiator Pigment dispersion Example 1 Resin A: 30 parts by weight DPHA: 10 parts by weight IRGACURE 369: 10 parts by weight of blue dispersion: 20 parts by weight of carbon dispersion : 15 parts by weight Example 2 Tree deer A: 30 parts by weight DPHA: 10 parts by weight IRGACURE 369: 10 parts by weight of blue dispersion: 30 parts by weight of carbon dispersion: 5 parts by weight Example 3 Resin A: 30 parts by weight DPHA : 10 Parts by weight IRGACURE 369: 10 parts by weight of blue dispersion: 80 parts by weight of red dispersion: 80 parts by weight of carbon dispersion: 20 parts by weight of Comparative Example 1 Resin A: 30 parts by weight of DPHA: 10 parts by weight of iRGACURE 369: 10 parts by weight of carbon dispersion The correspondence between the abbreviations and the official names of the components in the 30 parts by weight is as follows. DPHA: dipentaerythritol hexaacrylate IRGACURE3 69 : 2-benzyl-2-dimethylamino-1-(4-indolyl)-butanone-1 (manufactured by CIBA SPECIALTYCHEMICALS) Blue dispersion: Blue dispersion CF Blue UM (CI Pigment Blue 15: 6, containing 20% by weight, manufactured by Royal Color Co., Ltd.)

Carbon dispersion: "Carbon dispersion CF black EX-1 455" (containing 24% by weight of high-resistance carbon, manufactured by Yuko Co., Ltd.) Red dispersion: "CF red EX-109" (containing 20% by weight of CI pigment red) 1 7 7. 蒽 red pigment) Yellow dispersion: "CF yellow HM" (containing 20% by weight (: 1. pigment yellow 139, monoazo yellow pigment) (formation of light-shielding film) The photosensitive composition was coated on a glass substrate using a spin coater, and dried at 90 ° C for 2 minutes to form a black photosensitive composition of 23 Γ 377 441. Next, the negative reticle was interposed between the black photosensitive The composition was selectively irradiated with ultraviolet rays. Subsequently, development was carried out using a 0.04% by weight aqueous solution of tetramethylammonium hydroxide, and post-baking was performed in an oven at 220 ° C for 30 minutes to form a light-shielding film pattern having a thickness of 1.5 μm. )

The light-shielding film formed as described above was evaluated for dielectric constant, presence or absence of wrinkles, and OD value. The results are shown in Table 2. The dielectric constant was measured using a dielectric constant measuring device "SSM495" (trade name: manufactured by Sakamoto SSM Co., Ltd.), and the OD value was measured using "Gretag Macbeth D-200-2" (trade name: manufactured by Macbeth Co., Ltd.). . [Table 2] Dielectric ratio Wrinkle-free OD value Example 1 5.5 No 2.5 Example 2 4.1 None 1.2 Example 3 6.0 None 3.0 Comparative Example 1 30 Yes 3.8

From the above results, it was revealed that the black photosensitive composition of the present invention has high shape stability and can form a light-shielding film having a low dielectric constant. [Simple description of the diagram] None [Key component symbol description] None 24

Claims (1)

1377441 view ift 14 Patent Application No. 1 is a black photosensitive composition for forming an EL element light-shielding film, which is a black photosensitive composition for forming an EL element light-shielding film containing a photopolymerizable compound, a photopolymerization initiator, and a black pigment. Containing an organic pigment, the photopolymerizable compound is a compound represented by the following formula (1), COOH XO-CO-Y-COOH HOOC-Y-CO-OXO-CO-Z-CO-0' COOH η (formula In the above, X is a group represented by the following formula (2), and the residue of the carboxylic acid anhydride group (-C0-0-C0-) is removed from the dicarboxylic acid anhydride, and the lanthanide is removed from the tetracarboxylic dianhydride. Except two The weight ratio of the organic pigment to the black pigment is from 10:0.7 to 10:10; the total amount of the organic pigment and the black pigment relative to the total weight of the photopolymerizable compound and the photopolymerization initiator It is 20% by weight to 50% by weight; and the photopolymerization initiator contains 1 part by weight to 40 parts by weight based on 100 parts by weight of the photopolymerizable compound and the photopolymerization initiator. 25 Γ377441 2. The black photosensitive composition forming EL as described in claim 1, wherein the black pigment is carbon 3. The black photosensitive composition forming EL as described in claim 1 of the patent application, wherein The light-shielding film formed is 10. 4. The black photosensitive composition forming EL as described in claim 1 above, wherein the light-shielding film is formed or more. A light-shielding film which is formed by a black photosensitive film for forming an EL element light-shielding film as described in the first aspect of the invention, wherein the light-shielding film has a thickness of from 0.5 μm to 10 μm. For the light-shielding film, the dielectric value of the light-shielding film is small, and the OD value is one of the components of the light-shielding film. 26