TWI585525B - Polyimide photosensitive resin composition for organic light emitting diodes - Google Patents

Description

Polyimine photosensitive resin composition for organic light-emitting diode Field of invention

The present invention relates to a polyfluorene imide photosensitive resin composition of an organic light-emitting diode, and more particularly to an organic insulating film formation of an OLED which is suitable for using a polyimine precursor which easily adjusts molecular weight and solubility. In particular, a polyimide-based photosensitive resin composition having a marked improvement in sensitivity.

Background of the invention

Recently, in the display devices of the market, there are various reasons for surrounding the optical rings of Organic Light Emitting Diodes (OLEDs) and, in particular, AMOLEDs (Active Matrix OLEDs, Active Matrix Organic Light Emitting Diodes).

Usually, the OLED element contains an organic insulating film, and when the above-mentioned organic insulating film is formed, a polyimide polyimide photosensitive resin composition is generally used.

The polyimine precursors used in the composition of the polyimine photosensitive resin are protected by GMA, and the GMA-protected polyimine precursors are difficult to adjust the molecular weight and solubility, and may be gelled. (gelation) leads to a problem of reduced yield, because the sensitivity is low, and therefore, an improvement strategy for this problem is indeed desired.

Summary of invention

In order to solve the conventional technical problems as described above, the present invention aims to Provided: a polyimine precursor which is easy to adjust molecular weight and solubility, and an organic insulating film formation of an OLED, in particular, a polyimide polyimide photosensitive resin composition having a marked improvement in sensitivity, and an OLED using the same The pattern forming method and the OLED substrate containing the hardened body of the polyimine photosensitive resin composition.

In order to achieve the above object, a polyimide composition photosensitive resin composition for an organic light-emitting diode according to the present invention is characterized in that the photosensitive resin composition for OLED contains: a) containing i) the following chemical formula 1 a polyimine precursor, and ii) a polyhydroxy styrene resin; b) a 1,2-quinonediazide compound; c) a crosslinking agent; and d) a solvent.

In the above Chemical Formula 1, X is a tetravalent organic group; Y is a divalent organic group; and R is an independent epoxy cyclohexyl methyl methacrylate (ECMMA) or methyl methacrylate Propyl ester (methylglycidyl methacrylate, MGMA); n series 3~100000 Integer.

Preferably, the polyimine photosensitive resin composition for an organic light-emitting diode of the present invention comprises: a) comprising i) 40 to 90% by weight of the polyimine precursor of the above Chemical Formula 1 And ii) 100 parts by weight of polyhydroxy styrene 10 to 60% by weight of the resin; b) 5 to 50 parts by weight of the 1,2-quinonediazide compound; c) 1 to 30 parts by weight of the crosslinking agent And d) the solvent accounts for 5 to 50% by weight of the solid content of the entire polyimideimide photosensitive resin composition.

Furthermore, the OLED substrate provided by the present invention contains the above-mentioned hardened body of a polyimide polyimide photosensitive resin composition for an organic light-emitting diode.

Furthermore, the pattern forming method of the OLED substrate provided by the present invention uses the above-mentioned polyimide polyimide photosensitive resin composition for an organic light-emitting diode.

The polyamidimide photosensitive resin composition for an organic light-emitting diode of the present invention is suitable for forming an organic insulating film of an OLED by using a polyimine precursor which is easy to adjust molecular weight and solubility, in particular, the sensitivity is obtained. Significant improvement.

Form for implementing the invention

Hereinafter, the present invention will be described in detail.

The polyimine photosensitive resin composition of the organic light-emitting diode of the present invention is characterized by comprising: a) a resin containing i) a polyimide precursor of the following Chemical Formula 1, and ii) polyhydroxystyrene; b) 1,2-quinonediazide compound; c) crosslinker; and d) solvent.

In the above Chemical Formula 1, X is a tetravalent organic group; Y is a divalent organic group; and R is an independent epoxy cyclohexyl methyl methacrylate (ECMMA) or methyl methacrylate Methyl ester (methylglycidyl methacrylate, MGMA); n is an integer from 3 to 100,000.

The i-imine precursor of the above formula (1) in the above a) used in the present invention is preferably produced by the following reaction scheme 1. More preferably, in the following Reaction Scheme 1, X is derived from 2,2-bis(3,4-anhydrodicarboxyphenyl) Hexafluoropropane, 6FDA, chemical formula 2) 5-(2,5-Dioxytetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (5-(2,5-Dioxotetrahydrofuryl)-3-methyl-3 -cyclohexene-1,2-dicarboxylicAnhydride, DOCDA, chemical 4 derived from the formula 3), or 2,3,3',4'-biphenyltetracarboxylic dianhydride (2,3,3',4'-Biphenyl tetra carboxylichydride, a-BPDA, chemical formula 4) Valence organic group; Y series from 4,4'-diamino-3,3'-dimethyl-diphenyl-3 (3,4'-diamino-3,3'-dimethyl-diphenylmethane, DADM, chemical formula 5 , 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (Bis-APAF, Chemical Formula 6), or Divalent organic group derived from 1,3-bis(3-aminopropyl)tetramethyldisiloxane, SiDA(PAM-E), Chemical Formula 7 ; R is epoxy cyclohexyl methyl methacrylate (ECMMA).

The aforementioned polybendylene precursor system converts the protective moiety from the conventional GMA to epoxy cyclohexyl methyl methacrylate (ECMMA) or methylglycidyl methacrylate (MGMA). ), to make the adjustment of molecular weight and solubility easier, and reduce the yield reduction due to gelation from the source In rare cases, and promotes the sensitivity of the polyimide pigment photosensitive resin composition. In the present invention, the molecular weight of the polyimine precursor is preferably from 3,000 to 10,000, more preferably from 3,500 to 7,000. If within the above range, solubility adjustment, yield and sensitivity can be further enhanced.

The content of the polyimine precursor is preferably set to 40 to 90% by weight of the resin used in the present invention. If it is within the above range, the developability, heat resistance and sensitivity can be further improved.

Further, in the present invention, ii) polyhydroxystyrene used as the above resin is preferably used in a molecular weight of 4,000 to 20,000, and the content is set to 10 to 60% by weight based on the resin used in the present invention. If it is within the above range, the developability, heat resistance and sensitivity can be further improved.

Further, the resin of a) of the present invention may further contain a phenol resin in addition to the polybenzamine precursor and polyhydroxystyrene. It is preferred to use a phenol resin which can be produced by the above-mentioned stage polymerization.

The phenol resin produced by the above-described stage polymerization can be produced by condensing an aldehyde with a substituted phenol. The aldehyde may be, for example, formaldehyde or the like; the substituted phenol may be, for example, o-, m-, p-cresol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol. , 3,5-xylenol, 2,3,5-trimethyl phenol, or a mixture of these, and the like.

The polystyrene-equivalent weight average molecular weight of the phenol resin produced by the above-described stage polymerization is preferably 3,000 to 30,000, more preferably 3,000 to 20,000.

When the resin of a) of the present invention contains a phenol resin, the a) resin preferably contains: 40 to 85% by weight of polybenzazole precursor, polyhydroxystyrene 10 to 55% by weight, and 1 to 20% by weight of the phenolic resin.

The 1,2-quinonediazide compound of the above b) used in the present invention is used as a photosensitive compound. The b) 1,2-quinonediazide compound can be used as the photosensitive composition used in the formation of an organic insulating film of a known OLED, and one of the examples is a phenol compound and naphthoquinonediazide. The acid halide compound is obtained by a reaction.

Preferably, the above-mentioned 1,2-quinonediazide compound may be, for example, 1,2-quinonediazide 4-sulfonate, 1,2-quinonediazide 5-sulfonate, or 1,2 - quinone diazide 6-sulfonate and the like.

The b) 1,2-quinonediazide compound is preferably contained in an amount of 5 to 50 parts by weight based on 100 parts by weight of the resin of a). If the content is less than 5 parts by weight, the difference in solubility between the exposed portion and the non-exposed portion may be reduced, resulting in difficulty in pattern formation; on the other hand, if it exceeds 50 parts by weight, there will be a large amount of light when irradiated in a short time. The remaining unreacted 1,2-quinonediazide compound causes an excessive decrease in the solubility of the aqueous alkali solution belonging to the developer, which also causes difficulty in development.

The crosslinking agent of the above c) used in the present invention has a function of forming a crosslinked structure with the resin of a), and the crosslinking agent is preferably a melamine-based crosslinking agent.

As the melamine-based crosslinking agent, for example, a condensation product of urea and formaldehyde, a condensation product of melamine and formaldehyde, or a methylol urea alkyl ether obtained from an alcohol, or a methylol melamine alkyl ether can be used. Wait.

Specifically, as the condensation product of urea and formaldehyde, monomethylol urea, dimethylol urea or the like can be used. The condensation product of melamine and formaldehyde may be hexamethylol melamine, and other melamine may be used. A partial condensation product of an amine and formaldehyde.

Further, the hydroxymethyl urea alkyl ether is a condensation product of urea and formaldehyde, and a part or all of the methylol group is reacted with an alcohol, and specific examples thereof may be monomethyl urea methyl ether. , dimethyl urea methyl ether and the like. The methylol melamine alkyl ether is a condensation product of melamine and formaldehyde, and a part or all of a methylol group is obtained by reacting an alcohol with an alcohol. Specific examples thereof may be hexamethylol melamine hexamethyl ether or six. Hydroxymethyl melamine hexabutyl ether and the like. Further, a hydrogen atom of an amine group of melamine may be used, and a compound having a structure of a methylol group and a methoxymethyl group; a hydrogen atom of an amine group of melamine may be substituted with a butoxymethyl group and a methoxy group. A compound having a methyl group structure or the like is particularly preferably a methylol melamine alkyl ether.

The melamine-based crosslinking agent is preferably contained in an amount of 1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the resin of a). If the content is less than 1 by weight, there is a problem that the photosensitive speed is lowered; if it exceeds 30 parts by weight, there is a problem that the storage stability is lowered.

The solvent of the above-mentioned d) used in the present invention has a function of forming a uniform pattern profile in accordance with the flatness of the composition of the polyimideimide photosensitive resin and the infiltration of the coating.

As the solvent, an alcohol such as methanol, ethanol, benzyl alcohol or hexanol; an ethylene glycol alkyl ether acetate such as ethylene glycol methyl ether acetate or ethylene glycol ethyl ether acetate; and ethylene glycol methyl ether acetate can be used. Ethylene glycol alkyl ether propionates such as acid esters, ethylene glycol ether propionates; ethylene glycol monoalkyl ethers such as ethylene glycol methyl ether and ethylene glycol ether; diethylene glycol monomethyl ether; Diethylene glycol alkyl ethers such as diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ether; propylene glycol alkyl ether; propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc. Ethyl ether acetates; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and other propylene glycol alkyl ether propionates; propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc. Propylene glycol monoalkyl ethers; dipropylene glycol alkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether; butanediol monomethyl ether such as butanediol monomethyl ether, butanediol monoethyl ether; or dibutyl Dibutylene glycol alkyl ethers such as glyceryl ether, dibutyl glycol diethyl ether; γ -butyrolactone and the like. Preferably, the solvent is a solvent obtained by mixing γ -butyrolactone and propylene glycol methyl ether acetate (PGMEA) in a weight ratio of 10 to 90:10 to 90, respectively. In this case, the resin has better solubility and flatness.

The solvent is contained in the solid content of the entire photosensitive resin composition, and preferably contains 5 to 50% by weight, more preferably 15 to 40% by weight. If the content of the solid content of the entire composition is less than 10% by weight, the coating thickness may become thin, resulting in a problem of lowering the flatness of the coating; if it exceeds 50% by weight, the coating thickness may become thicker and may be coated. The problem of excessive load on the coating equipment during the cloth.

Further, the photosensitive resin composition of the present invention is basically a positive photosensitive resin composition, and a negative photosensitive resin composition can also be used by further containing a photoacid generator. The photoacid generator is added before the photoacid generator used in the conventional photosensitive resin composition, and the rest is not particularly limited. Preferably, an ionic photoacid such as a phosphonium salt or an iodonium salt can be used. a generator, a sulfonyldiazomethane, an N-sulfonyloxyimine, a benzoin sulfonate, a nitrated benzylsulfonate, a sulfonate, a glyoxime, Or three Department and so on.

Specifically, the above-mentioned phosphonium salt is a salt of a phosphonium cation and a sulfonate (sulfonate anion); and the above phosphonium cation is, for example, triphenylsulfonium, (4-t-butoxyphenyl)diphenylphosphonium, or a double (4-tert-butoxyphenyl)phenylhydrazine, 4-methylphenyldiphenylphosphonium, tris(4-methylphenylphosphonium), 4-tert-butylphenyldiphenylphosphonium, Tris(4-t-butylphenyl)anthracene, tris(4-t-butoxyphenyl)anthracene, (3-t-butoxyphenyl)diphenylanthracene, bis(3-third-butyl) Oxyphenyl) phenyl hydrazine, tris(3-tert-butoxyphenyl) fluorene, (3,4-di-t-butoxyphenyl)diphenyl fluorene, bis(3,4-di Tributyloxyphenyl)phenylhydrazine, tris(3,4-di-t-butoxyphenyl)anthracene, diphenyl(4-thiophenoxyphenyl)anthracene, (4-tert-butoxy Carbomethoxymethoxyphenyl)diphenylphosphonium, tris(4-tert-butoxycarbonylmethoxyphenyl)anthracene, (4-tert-butoxyphenyl)bis(4-dimethylamino) Phenyl) anthracene, tris(4-dimethylaminophenyl)anthracene, 2-naphthyldiphenylanthracene, dimethyl-2-naphthyl anthracene, 4-hydroxyphenyldimethylhydrazine, 4-methyl Oxyphenyl dimethyl hydrazine, trimethyl hydrazine, diphenylmethyl hydrazine, methyl-2-oxypropyl phenyl hydrazine, 2- Oxycyclohexylcyclohexylmethyl hydrazine, trinaphthyl anthracene, or tribenzyl hydrazine, etc.; the aforementioned sulfonic acid esters are, for example, trifluoromethanesulfonate, nonafluorobutane sulfonate, heptafluorooctane sulfonate Ester, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, tosylate, benzenesulfonic acid Ester, naphthalene sulfonate, oxime sulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, or methane sulfonate.

The iodonium salt is a salt of an iodonium cation and a sulfonate (sulfonate anion), and the iodonium cation is diphenyl iodonium, bis(4-t-butylphenyl) iodonium, and 4-third butyl. Oxyphenyl phenyl iodonium or 4-methoxyphenyl phenyl iodine The above sulfonic acid esters are, for example, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluoro Benzene sulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, tosylate, benzenesulfonate, naphthalenesulfonate, oxime sulfonate, octane sulfonate, Dodecylbenzenesulfonate, butanesulfonate, or methanesulfonate.

The aforementioned sulfonyldiazomethane photoacid generator is, for example, bis(ethylsulfonyl) 10-2004-0029289 diazomethane, bis(1-methylpropanesulfonyl)diazomethane, double (2) -methylpropanesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(perfluoroisopropylsulfonate) Dimethylmethane, bis(phenylsulfonyl)diazomethane, bis(4-methylphenylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane , bis(2-naphthalenesulfonyl)diazomethane, 4-methylbenzenesulfonyl benzhydryl diazomethane, tert-butylcarbonyl-4-methylbenzenesulfonyldiazomethane, 2- Naphthosulfonyl benzhydryl diazomethane, 4-methylbenzenesulfonyl-2-naphthylcarbenyldiazomethane, methylsulfonyl benzhydryldiazomethane, or tert-butoxy A bis-sulfonyldiazomethane such as carbonyl-4-methylbenzenesulfonyldiazomethane or a sulfonylcarbonyldiazomethane.

The above-mentioned N-sulfodeoxyquinone imine photoacid generator may be, for example, succinimide succinate, quinone dialkyl naphthalate, ruthenium ruthenate, ruthenium cycline dicarboxylate, 5- drop Alkene-2,3-dicarboxylic acid quinone imine, or 7- a quinone imine skeleton such as a bicyclo[2,2,1]-5-heptene-2,3-dicarboxylate imine, and for example: trifluoromethanesulfonate, nonafluorobutane sulfonate, seventeen Fluorane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonic acid A compound such as an ester, a besylate, a naphthalenesulfonate, an oxime sulfonate, an octane sulfonate, a dodecylbenzenesulfonate, a butane sulfonate, or a methanesulfonate.

The benzoin sulfonate-based photoacid generator may be, for example, benzoin tosylate, benzoin mesylate, or benzoin butanesulfonate.

The nitration benzyl sulfonate-based photoacid generator may be, for example, sulfonic acid-2,4-dinitrated benzyl ester, sulfonic acid-2-nitrated benzyl ester, or sulfonic acid-2,6-dinitrated benzyl ester. The aforementioned sulfonate may be, for example, trifluoromethanesulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzene. Sulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, tosylate, benzenesulfonate, naphthalenesulfonate, oxime sulfonate, octane sulfonate, ten Dialkylbenzenesulfonate, butanesulfonate, or methanesulfonate, and the like. Further, a compound in which a nitro group on the benzyl group is substituted with a trifluoromethyl group can also be used.

The sulfonic acid photoacid generator may be, for example, bis(phenylsulfonyl)methane, bis(4-methylphenylsulfonyl)methane, bis(2-naphthalenesulfonyl)methane, 2,2-dual ( Phenylsulfonyl)propane, 2,2-bis(4-methylphenylsulfonyl)propane, 2,2-bis(2-naphthalenesulfonyl)propane, 2-methyl-2-(p-toluene) Mercaptopropionate, 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, or 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one Wait.

The above-mentioned ethylenediamine photoacid generator may be, for example, bis-o-(p-toluenesulfonyl)-α-diketoxime, bis-o-(p-toluenesulfonyl)-α-diketidoxime , bis-o-(p-toluenesulfonyl)-α-dicyclohexylethylenediazine, bis-o-(p-toluenesulfonyl)-2,3-pentanedione ethanedioxime, bis-o-( p-Toluenesulfonyl)-2-methyl-3,4-pentanedione ethanedioxane, bis-o-(n-butanesulfonyl)-α-diethanol oxime, bis-o-(n-butyl) Alkylsulfonyl)-α-diethanol oxime, bis-o-(n-butanesulfonyl)-α- Dicyclohexylethylenediazine, bis-o-(n-butanesulfonyl)-2,3-pentanedione ethanedioxime, bis-o-(n-butanesulfonyl)-2-methyl-3 , 4-pentanedione, ethylenedioxime, bis-o-(methanesulfonyl)-α-diacetone oxime, bis-o-(trifluoromethanesulfonyl)-α-diacetone oxime, double- O-(1,1,1-trifluoroethanesulfonyl)-α-diacetone oxime, bis-o-(t-butanesulfonyl)-α-diacetone oxime, double-o- (Perfluorooctanesulfonyl)-α-diacetone oxime, bis-o-(cyclohexylsulfonyl)-α-diacetone oxime, bis-o-(phenylsulfonyl)-α-double Ethyl ketone oxime, bis-o-(p-fluorophenylsulfonyl)-α-diacetone oxime, bis-o-(p-tert-butylphenylsulfonyl)-α-diacetone oxime, double-o - (xylsulfonyl)-α-diacetone oxime, or bis-o-(nonylsulfonyl)-α-diketoloxime or the like.

The aforementioned three The photoacid generator can be, for example, PDM-three WS-three , PDM-three Dimethoxy-three (Dimethoxy-Triazine), MP-three , TFE-three Or TME-three (Sanhe Chemical) and so on.

The photoacid generator is preferably contained in an amount of 1 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the resin of a). If the content is less than 1 part by weight, there is a problem that the photospeed is lowered. When it exceeds 20 parts by weight, there is a problem that the outgassing and the storage stability are lowered.

The photosensitive resin composition of the present invention comprising the above-mentioned components may optionally contain a surfactant.

The above surfactant has an effect of improving the adhesion, coatability, and developability of the polyimideimide photosensitive composition of the present invention.

For the aforementioned surfactant, for example, polyoxyethylene octylbenzene can be used. Ether, polyoxyethylene nonylphenyl ether, F171, F172, F173 (trade name: Dainippon Ink Co., Ltd.); FC430, FC431 (trade name: Sumitomo 3M); or KP341 (trade name: Shin-Etsu Chemical Co., Ltd.).

The surfactant is preferably contained in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the resin of the above a). When the content is within the above range, the coating property and developability of the photosensitive composition can be further improved.

The polyamidimide photosensitive resin composition of the organic light-emitting diode of the present invention comprising the above-mentioned components preferably has a solid content concentration of 10 to 50 parts by weight, and a composition having a solid content of the above range can be It is used only after filtering with a 0.1~0.2μm precision filter.

Furthermore, the pattern forming method of the OLED substrate provided by the present invention uses an OLED substrate containing a hardened body of the polyimine photosensitive resin composition of the organic light-emitting diode, and the above-mentioned organic light-emitting diode. A quinone imine photosensitive resin composition.

The pattern forming method of the OLED substrate of the present invention is a method of forming a pattern of an OLED substrate using a photosensitive resin composition, characterized in that a polyimide polyimide photosensitive resin composition of the above organic light-emitting diode is used. Preferably, the substrate is an AMOLED substrate.

Specifically, a method of forming a pattern of an OLED substrate using the polyimine photosensitive resin composition of the above organic light-emitting diode is as follows.

First, the polyimine photosensitive resin composition of the organic light-emitting diode of the present invention is applied onto the surface of the substrate by a spray coating method, a roll coating method, a spin coating method, or the like, and the solvent is removed by prebaking. A coating film is formed. at this time, The prebaking is preferably carried out at a temperature of 80 to 120 ° C for 1 to 15 minutes.

Then, visible light rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like are irradiated onto the formed coating film by using a pattern prepared in advance, and post-exposure bake (PEB) and full exposure (Flood Exposure) are performed as needed. After that, development is performed by the developer to remove unnecessary portions to form a predetermined pattern.

The developing solution is preferably an aqueous alkali solution, and specific examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, and sodium carbonate; primary amines such as ethylamine and n-propylamine; and secondary amines such as diethylamine and n-propylamine. a tertiary amine such as trimethylamine, methyldiethylamine, dimethylethylamine or triethylamine; an alcohol amine such as dimethylethanolamine, methyldiethanolamine or triethanolamine; or tetramethylammonium hydroxide; An aqueous solution of a quaternary ammonium salt such as tetraethylammonium hydroxide or the like. In this case, the developing solution is used after dissolving the basic compound in a concentration of 0.1 to 10% by weight, and a water-soluble organic solvent such as methanol or ethanol or the like may be added in an appropriate amount.

Furthermore, after performing development by the developer as described above, it is washed with ultrapure water for 30 to 90 seconds to remove unnecessary portions, and after drying, a pattern is formed, and the pattern is heated by a heating device such as an oven. The final pattern can be obtained by heating at °C for 30 to 90 minutes.

The polyimine photosensitive resin composition of the organic light-emitting diode of the present invention is suitable for forming an organic insulating film of an OLED by using a polyimide precursor which is easy to adjust solubility, in particular, by significantly improving Sensitivity is suitable for OLED manufacturing steps.

In the following, preferred embodiments are presented for the understanding of the present invention, but The following examples are merely illustrative of the invention, and the scope of the invention is not limited to the following examples.

[Examples] Example 1 (Manufacture of poly-imine precursors)

In a four-neck reaction vessel of 300 ml, 70 g of DADM (chemical formula 5), 7 g of Bis-APAF (chemical formula 6), and 1 g of SiDA (chemical formula 7) belonging to a diamine were dissolved by 70 g of γ -butyrolactone. Further, 6-FDA (Chemical Formula 2) 5 g, DOCDA (Chemical Formula 3) 3 g, and a-BPDA (Chemical Formula 4) 3 g, which are dianhydrides, were put into a reaction container, and the reaction was carried out while stirring for 1 hour. After PA2g was added to the reaction at the terminal end, an additional reaction was carried out at 20 ° C for 1 hour to obtain a polyimide intermediate having a solid content of 30%. After adding 10 g of 5 g of each of ECMMA and MGMA belonging to the protective substance, the temperature was raised to 70° C., and TEA belonging to the catalyst was added, and the reaction was carried out for 24 hours to obtain a novel polyimine precursor.

(Manufacture of polyfluorene imamine photosensitive resin composition of organic light-emitting diode)

30 parts by weight of the obtained polyimine precursor, 20 parts by weight of polyhydroxystyrene, 20 parts by weight of 1,2-quinonediazide compound, and hexamethylol melamine used as a melamine crosslinking agent 5 parts by weight were mixed. Then, using a solvent in which γ -butyrolactone and PGMEA were mixed at a weight ratio of 50:50, the solid content of the mixture was 20% by weight, and then filtered by a 0.2 μm precision filter to obtain an organic light-emitting layer. A polypolarimide photosensitive resin composition of a diode.

Example 2

In the foregoing Embodiment 1, except for the production of the polyimide precursor The polyimine photosensitive resin composition of the organic light-emitting diode was produced in the same manner as in the above Example 1 except for using ECMMA (10 g).

Example 3

In the first embodiment, the same procedure as in the above-mentioned Example 1 was carried out except that the substituted ECMMA was changed to MGMA10g, and a polyfluorene imamine photosensitive resin composition of an organic light-emitting diode was produced.

Example 4

In the foregoing Embodiment 1, the photoacid generator is further used in the third TME-three The polyimine photosensitive resin composition of the organic light-emitting diode was produced in the same manner as in the above Example 1 except for 3 parts by weight.

Comparative example 1

In the above-mentioned Example 1, except that the substituted ECMMA was replaced with GMA8g, the same method as in the above Example 1 was carried out to produce a polyfluorene imamine photosensitive resin composition of an organic light-emitting diode.

Comparative example 2

In the above-mentioned Example 1, except that the substituted ECMMA was changed to GMA10g, the same method as in the above Example 1 was carried out to produce a polyfluorene imamine photosensitive resin composition of an organic light-emitting diode.

Using the polyimine photosensitive resin composition of the organic light-emitting diodes manufactured in the above Examples 1 to 4 and Comparative Examples 1 to 2, the physical properties were evaluated according to the following method, and the results were recorded in the following table. 1.

1) Sensitivity: On the 10 mm × 10 mm glass substrate on which ITO was vapor-deposited, the polymerization of the organic light-emitting diodes manufactured by the foregoing Examples 1 to 4 and Comparative Examples 1 to 2 was applied using a spin coater. After the composition of the quinoneimide photosensitive resin, prebaking was performed on a hot plate at 110 ° C for 2 minutes to form a film having a thickness of 3.0 μm. Using a predetermined pattern mask, using a predetermined pattern mask, using an ultraviolet ray having a intensity of 10 mW/cm ² at 365 nm, and irradiating a 20 μm insulating pattern CD dose amount (Dose), A 2.3% by weight aqueous solution of methylammonium was developed at 23 ° C for 100 seconds, and then washed with ultrapure water for 1 minute. The pattern developed as described above was hardened by heating in an oven at 230 ° C for 60 minutes to obtain a pattern film having a thickness of 2.5 μm.

2) Solubility: It was confirmed whether or not the precipitate was precipitated after the production of the precursor, and it was confirmed that the precipitated product and the undissolved product were stirred after the photosensitive resin composition was produced for 3 hours, and it was confirmed after stirring for 3 hours. After stirring for 3 hours, there was no precipitated or undissolved material (?); after stirring for 3 hours, there were precipitates and undissolved matter, but after stirring for 3 hours, there was no (○); even after stirring for 6 hours There are precipitates and undissolved matter (x).

As shown in Table 1 above, Example 1 manufactured in accordance with the present invention The polyimine photosensitive resin composition of the organic light-emitting diode of 4 is excellent in solubility and sensitivity at the same time. From the results, the photosensitive polyimide of the organic light-emitting diode according to the present invention is photosensitive. The resin composition is more suitable when it is applied to an OLED manufacturing step (particularly, an AMOLED manufacturing step).

On the contrary, in the case of Comparative Example 1, since the solubility was low and the sensitivity was low, it was difficult to apply to the OLED step; in the case of Comparative Example 2, precipitates appeared due to gelation during the production of the precursor. Even after the photosensitive resin composition was produced, precipitates remained, which made it impossible to evaluate the sensitivity, and it was found to be difficult to apply.

Claims (10)

A composition of a polyimide resin photosensitive resin for an organic light-emitting diode, characterized in that the photosensitive resin composition for OLED contains: a) a polyimide-containing precursor of the following formula 1; And ii) 100 parts by weight of a polyhydroxy styrene resin; b) 5 to 50 parts by weight of a 1,2-quinonediazide compound; c) 1 to 30 parts by weight of a crosslinking agent; and d) a solvent 5 to 50% by weight of the solid content of the entire polyimine photosensitive resin composition; In the above Chemical Formula 1, the X-based tetravalent organic group; the Y-based divalent organic group; and the R-series are each independently a monovalent organic group derived from epoxy cyclohexyl methyl methacrylate (ECMMA), Or a monovalent organic group derived from methylglycidyl methacrylate (MGMA); n is an integer of 3 to 100,000. The polyimine photosensitive resin composition for an organic light-emitting diode according to the first aspect of the invention, wherein the resin: a) contains i) the polyimine precursor 40 to 90 of the above Chemical Formula 1 % by weight, and ii) polyhydroxy styrene 10~60% by weight Resin. The polyamidimide photosensitive resin composition for an organic light-emitting diode according to the first aspect of the invention, wherein the X system of the above Chemical Formula 1 is derived from 2,2-bis(3,4-anhydrodicarboxyphenyl) Hexafluoropropane, 6FDA, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-di Carboxylic anhydride (5-(2,5-Dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylicAnhydride, DOCDA), or 2,3,3',4'-biphenyltetracarboxylic dianhydride (2 , 4,3', 4'-Biphenyl tetra carboxylic dianhydride, a-BPDA) derived tetravalent organic group. The polyamidimide photosensitive resin composition for an organic light-emitting diode according to the first aspect of the invention, wherein the Y system of the above Chemical Formula 1 is from 4,4'-diamino-3,3'-dimethyl 2,4'-diamino-3,3'-dimethyl-diphenylmethane, DADM, 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane (2, 2-Bis(3-amino-4-hydroxyphenyl)-hexafluoropropane, Bis-APAF), or 1,3-bis(3-aminopropyl)tetramethyldioxane (1,3-Bis(3- Aminopropyl) a tetravalent organic group derived from tetramethyldisiloxane or SiDA (PAM-E). The polyimine photosensitive resin composition for an organic light-emitting diode according to the first aspect of the invention, wherein the resin of the above a) further contains a phenol resin. The polyamidimide photosensitive resin composition for an organic light-emitting diode according to the first aspect of the invention, wherein the crosslinking agent of the above c) is selected from the group consisting of One or more groups of the group consisting of a condensation product of urea and formaldehyde, a condensation product of melamine and formaldehyde, a methylol urea alkyl ether, and a methylol melamine alkyl ether. The polyamidimide photosensitive resin composition for an organic light-emitting diode according to the first aspect of the invention, wherein the solvent of the above d) is γ-butyrolactone and propylene glycol methyl ether acetate (PGMEA) respectively 10~90: 10~90 by weight of mixed solvent. The polyamidimide photosensitive resin composition for an organic light-emitting diode according to the first aspect of the invention, wherein the photosensitive resin composition further contains a photoacid generator. An organic light-emitting diode substrate is a hardened body containing the photosensitive resin composition according to any one of claims 1 to 8. A method of forming a pattern of an organic light-emitting diode substrate using the photosensitive resin composition according to any one of claims 1 to 8.