WO2013058506A2

WO2013058506A2 - Polyimide light-sensitive resin composition for oled

Info

Publication number: WO2013058506A2
Application number: PCT/KR2012/008362
Authority: WO
Inventors: 김동명; 김병욱; 윤혁민; 김진우; 황치용
Original assignee: 주식회사 동진쎄미켐
Priority date: 2011-10-18
Filing date: 2012-10-15
Publication date: 2013-04-25
Also published as: KR20130042212A; TW201331707A; CN103917916B; KR101882217B1; TWI585525B; WO2013058506A3; CN103917916A

Abstract

The present invention relates to a polyimide light-sensitive resin composition for an OLED, and, more particularly, relates to a polyimide light-sensitive resin composition for an OLED, comprising: a) a resin comprising i) a polyamide precursor and ii) poly(hydroxy styrene) (poly hydroxy styrene); b) a 1,2-quinone diazide compound; c) a crosslinking agent; and d) a solvent. The polyimide light-sensitive resin composition according to the present invention is suitable for forming an organic insulating film of an OLED through the use of a polyimide precursor of which the molecular weight and solubility are easily adjusted.

Description

Polyimide photosensitive resin composition for ODL

The present invention relates to a polyimide photosensitive resin composition for OLED, and more particularly, to a polyimide photosensitive resin, which is suitable for forming an organic insulating film of an OLED by using a polyimide precursor that is easy to control molecular weight and solubility, and particularly a sensitivity is remarkably improved. To a composition.

In recent years, organic light emitting diodes (OLEDs), especially AMOLEDs (active matrix OLEDs), have been in the spotlight for various reasons among display devices.

Typically, an OLED element includes an organic insulating film, and a polyimide photosensitive resin composition is generally used for forming the organic insulating film.

The polyimide precursor used in the conventional polyimide photosensitive resin composition was applied with GMA protecting technology, but the polyimide precursor protected with GMA was difficult to control the molecular weight and solubility, and the yield reduction due to gelation was a problem. Because of the low level, there was an urgent need for improvement.

In order to solve the problems of the prior art as described above, the present invention is suitable for forming an organic insulating film of the OLED using a polyimide precursor that is easy to control the molecular weight and solubility, in particular a polyimide photosensitive resin composition that can significantly improve the sensitivity, It is an object of the present invention to provide an OLED substrate including a pattern forming method of an OLED using the same and a cured product of the polyimide photosensitive resin composition.

In order to achieve the above object, the present invention in the photosensitive resin composition for OLED,

a) a resin comprising i) a polyimide precursor represented by Formula 1 below, and ii) poly hydroxy styrene;

b) 1,2-quinonediazide compounds;

c) crosslinking agents;

d) solvent

It provides a polyimide photosensitive resin composition for OLED, comprising:

[Formula 1]

In Chemical Formula 1,

X is a tetravalent organic group, Y is a divalent organic group, R is independently epoxy cyclohexyl methyl methacrylate (ECMMA) or methylglycidyl methacrylate (MGMA), and n is an integer of 3-100000.

Preferably, the present invention

a) 100 parts by weight of a resin comprising i) 40-90% by weight of polyimide precursor represented by Formula 1, ii) 10-60% by weight of poly hydroxy styrene;

b) 5-50 parts by weight of 1,2-quinonediazide compound;

c) 1-30 parts by weight of a crosslinking agent;

d) The polyimide photosensitive resin composition for OLED containing the solvent so that solid content of the whole polyimide photosensitive resin composition may be 5 to 50 weight%.

The present invention also provides an OLED substrate comprising a cured product of the polyimide photosensitive resin composition for OLED.

In another aspect, the present invention provides a pattern forming method of an OLED substrate using the polyimide photosensitive resin composition for OLED.

The polyimide photosensitive resin composition for OLEDs according to the present invention is suitable for forming an organic insulating film of an OLED by using a polyimide precursor that is easy to control molecular weight and solubility, and in particular, can significantly improve sensitivity.

Hereinafter, the present invention will be described in detail.

Polyimide photosensitive resin composition for an OLED of the present invention is a resin comprising a) i) a polyimide precursor represented by the general formula (1), ii) polyhydroxy styrene; b) 1,2-quinonediazide compounds; c) crosslinking agents; And d) a solvent.

Formula 1

In Chemical Formula 1,

A) i) The polyimide precursor represented by Chemical Formula 1 used in the present invention may be prepared through the process of Scheme 1 below. More preferably, in Scheme 1, X is 2,2-bis (3,4-anhydrodicarboxyphenyl) Hexafluoropropane (6FDA, Formula 2), 5- (2,5-Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, A tetravalent organic group derived from 2-dicarboxylic Anhydride (DOCDA, Formula 3), or 2,3,3 ', 4'-Biphenyl tetracarboxylic dianhydride (a-BPDA, Formula 4), Y is a 4,4'-diamino -3,3'-dimethyl-diphenylmethane (DADM, formula 5), 2,2-Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (Bis-APAF, formula 6), or 1,3-Bis (3- A divalent organic group derived from aminopropyl) tetramethyldisiloxane (SiDA (PAM-E), formula (7)), R is epoxy cyclohexyl methyl methacrylate (ECMMA).

Scheme 1

Formula 2

Formula 3

Formula 4

Formula 5

Formula 6

Formula 7

The polyimide precursor converts the protecting portion from conventional GMA to epoxy cyclohexyl methyl methacrylate (ECMMA) or methylglycidyl methacrylate (MGMA) to facilitate the control of molecular weight and solubility, and to reduce the yield decrease due to gelation, It improves the sensitivity of the mid photosensitive resin composition. In the present invention, the molecular weight of the polyimide precursor is preferably 3000-10000, preferably 3500-7000. If it is in the above range, solubility control, yield and sensitivity can be further enhanced.

The content of the polyimide precursor is preferably used in 40-90% by weight of a) resin used in the present invention. When in the above range, it is possible to further improve the developability, heat resistance and sensitivity.

In addition, ii) polyhydroxystyrene used as the resin of the present invention is preferably used with a molecular weight of 4000 to 20000, the content is preferably used in 10-60% by weight of the resin used in the present invention. When in the above range, it is possible to further improve the developability, heat resistance and sensitivity.

In addition, a) resin of the present invention may further include a novolak resin in addition to the polyimide precursor and polyhydroxy styrene. It is preferable to use a novolak resin prepared through the step polymerization.

The novolak resin prepared through the step polymerization may be prepared by condensing an aldehyde and a substituted phenol. The aldehyde is formaldehyde, etc., and substituted phenols are ortho-, meta-, para-cresol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5- Xylenol, 2,3,5-trimethylphenol, or mixtures thereof.

The polystyrene reduced weight average molecular weight of the novolak resin prepared through the step polymerization is preferably 3,000 to 30,000, more preferably 3,000 to 20,000.

When a) resin of the present invention comprises a novolak resin, it is preferable that the a) resin contains 40-85 wt% of polyimide precursor, 10-55 wt% of polyhydroxystyrene, and 1-20 wt% of novolak resin. good.

The 1,2-quinonediazide compound of b) used in the present invention is used as a photosensitive compound. B) The 1,2-quinonediazide compound may be used as long as it can be applied to a photosensitive composition used for forming an organic insulating film of a known OLED, and is obtained by, for example, reacting a phenol compound with a naphthoquinone diazide sulfonic acid halogen compound. Can be used.

Preferably, the 1,2-quinonediazide compound is 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, 1,2-quinonediazide 6-sulfonic acid ester, or the like. Can be used.

The b) 1,2-quinonediazide compound is preferably included 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 of the exposed and non-exposed parts may be difficult to form. If the content exceeds 50 parts by weight, unreacted 1,2-quinonediazide compound may be used when irradiated with light for a short time. It may be difficult to develop due to the excessively low solubility in the aqueous alkali solution being a developer.

The crosslinking agent of c) used in the present invention functions to form a crosslinked structure with the resin of a), and preferably, the crosslinking agent is a melanin crosslinking agent.

As the melanin-based crosslinking agent, condensation products of urea and formaldehyde, condensation products of melamine and formaldehyde, methylol urea alkyl ethers and methylol melamine alkyl ethers obtained from alcohols, and the like can be used.

Specifically, monomethylol urea, dimethylol urea, or the like may be used as a condensation product of the urea and formaldehyde. Hexamethylol melamine may be used as the condensation product of melamine and formaldehyde, and other condensation products of melamine and formaldehyde may be used.

In addition, the methylol urea alkyl ethers are obtained by reacting a condensation product of urea with formaldehyde with alcohols in part or all of the methylol groups, and specific examples thereof include monomethyl urea methyl ether, dimethyl urea methyl ether, and the like. Can be used. The methylol melamine alkyl ethers are obtained by reacting a condensation product of melamine and formaldehyde with alcohols in part or all of methylol groups, and specific examples thereof include hexamethylolmelamine hexamethyl ether and hexamethylolmelamine hexabutyl ether. Etc. can be used. Moreover, the compound of the structure where the hydrogen atom of the amino group of melamine was substituted by the hydroxy methyl group and the methoxy methyl group, the compound of the structure where the hydrogen atom of the amino group of melamine was substituted by the butoxy methyl group and the methoxy methyl group, etc. can also be used, Especially methylol Preference is given to using melamine alkyl ethers.

The melamine-based crosslinking agent is preferably included 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 part by weight, there is a problem that the photospeed is lowered, and if it exceeds 30 parts by weight, there is a problem that the storage stability is lowered.

The solvent of d) used in the present invention serves to form a uniform pattern profile by preventing the flatness and coating stain of the polyimide photosensitive resin composition.

The solvent may be alcohol such as methanol, ethanol, benzyl alcohol, hexyl alcohol; Ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; Ethylene glycol alkyl ether propionates such as ethylene glycol methyl ether propionate and ethylene glycol ethyl ether propionate; Ethylene glycol monoalkyl ethers such as ethylene glycol methyl ether and ethylene glycol ethyl ether; Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol propyl ether acetate; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate and propylene glycol propyl ether propionate; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; Dipropylene glycol alkyl ethers such as dipropylene glycol dimethyl ether and diporoethylene glycol diethyl ether; Butylene glycol monomethyl ether, such as butylene glycol monomethyl ether and butylene glycol monoethyl ether; Or dibutylene glycol alkyl ethers such as dibutylene glycol dimethyl ether and dibutylene glycol diethyl ether; Gamma butyrolactone etc. can be used. Preferably, the solvent is a solvent in which gamma butyrolactone and propylene glycol methyl ether acetate (PGMEA) are mixed in a weight ratio of 10-90: 10-90, respectively. In this case, the solubility and flatness of the resin are better.

The solvent is preferably included so that the solid content of the entire photosensitive resin composition is 5 to 50% by weight, more preferably 15 to 40% by weight. If the solid content of the total composition is less than 10% by weight, there is a problem that the coating thickness is thin, coating flatness is lowered, and when the content of the solid content exceeds 50% by weight, the coating thickness becomes thick, and the coating equipment is impaired during coating. There is a problem that can be.

Moreover, the photosensitive resin composition of this invention can also be applied also as a negative photosensitive resin composition which contains a positive photosensitive resin composition and a photo-acid generator fundamentally. The photoacid generator is not particularly limited as long as it is a photoacid generator used in the conventional photosensitive resin composition, and preferably, an ionic photoacid generator such as a sulfonium salt and an iodonium salt, a sulfonydiazomethane series, and an N-sulfonyloxyimide series , Benzoin sulfonate type, nitrobenzyl sulfonate type, sulfone type, glyoxime type, triazine type or the like can be used.

Specifically, the sulfonium salt is a salt of a sulfonium cation and a sulfonate (sulfoic acid anion), and the sulfonium cation includes triphenolsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, and bis (4 -tert-butoxyphenyl) phenylsulfonium, 4-methylphenyldiphenylsulfonium, tris (4-methylphenylsulfonium), 4-tert-butylphenyldiphenylsulfonium, tris (4-tert-butylphenyl) sulfonium , Tris (4-tert-butoxyphenyl) sulfonium, (3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxy Phenyl) sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis (3,4-ditert-butoxyphenyl) phenylsulfonium, tris (3,4-ditert-butoxy Phenyl) sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxyphenyl ) Sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tri (4-dimethylaminophenyl) sulfonium, -2-naphthyldiphenylsulfonium, dimethyl-2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium, 40methoxyphenyldimethylsulfonium, trimethylsulfonium, diphenyl Methylsulfonium, methyl-2oxopropylphenylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, or tribenzylsulfonium. The sulfonate is trifluoromethanesulfonate. , Nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pendafluorobenzenesulfonate, 4-trifluorofluoromethylbenzenesulfonate, 4-fluoro Robenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, or methanesulfonate.

The iodonium salt is a salt of an iodonium cation and a sulfonate (sulfoic acid anion), and the iodonium cation is diphenyl iodonium, bis (4-tert-butylphenyl) iodonium, and 4-tert-butoxyphenylphenyl. Iodonium or 4-methoxyphenylphenyl iodonium and the like, and the sulfonate is trifluoromethanesulfonate nonafluorobutasulfonate heptadecafluorooctanesulfonate, 2,2,2-trifluoro Roethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dode Silbenzenesulfonate, butanesulfonate, or methanesulfonate.

Examples of the sulfonyl diazomethane-based photoacid generators include bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropofylsulfonyl) diazomethane and bis (1). , 1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (perfluroloisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4 -Methylphenylsulfonyl) diazo methane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2-naphthylsulfonyl) diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcar Bonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthoyldiazomethane, methylsulfonylbenzoyldiazomethane, or tert-butoxycarbonyl Bissulfonyl diazomethane and sulfonylcarbonyl diazomethane, such as 4-methylphenyl sulfonyl diazomethane.

Examples of the N-sulfonyloxyimide-based photoacid generator include succinic acid imide, naphthalenedicarboxylic acid imide, phthalic acid imide, cyclohexyldicarboxylic acid imide, 5-norbornene-2,3-dicarboxyl Imide skeletons such as acid imides or 7-oxabicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid imides, trifluoromethanesulfonate, and nonafluorobutanesulfo Nate, Heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluorofluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluene Sulfonates, benzenesulfonates, naphthalenesulfonates, camphorsulfonates, octanesulfonates, dodecylbenzenesulfonates. Butanesulfonate or methanesulfonate.

Examples of the benzoin sulfonate-based photoacid generator include benzointosylate, benzoin mesylate, or benzoin butanesulfonate.

The nitrobenzylsulfonate-based photoacid generator includes 2,4-dinitrobenzylsulfonate, 2-nitrobenzylsulfonate, or 2,6-dinitrobenzylsulfonate, and the like. Sulfonate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4- Fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, or methanesulfonate. Moreover, the compound which substituted the nitro group of the benzyl side by the trifluoromethyl group can also be used.

The sulfone-based photoacid generators include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, 2,2-bis (phenylsulfonyl) propane, 2,2 -Bis (4-methylphenylsulfonyl) propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl) propiononeone, 2- (cyclohexylcarbonyl) -2- (p-toluenesulfonyl) propane or 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one and the like.

Examples of the glyoxime-based photoacid generators include bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime and bis-o- (p -Toluenesulfonyl) -α-disotlohexylglyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedioneglyoxime, bis-o- (p-toluenesulfonyl) -2- Methyl-3,4-pentanedioneglyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o -(n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-o- (n-butanesulfonyl) -2,3-pentanedioneglyoxime, bis-o- (n-butanesulfonyl)- 2-methyl-3,4-pentanedioneglyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis- o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctane Sulfonyl) -α-dimethylglyoxime, bis-o- (cy Clohexylsulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis- o- (p-tert-butylbenzenesulfonyl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, or bis-o- (cambosulfonyl) -α-dimethylgly Oxime.

The triazine-based photoacid generator includes PDM-Triazine, WS-Triazine, PDM-Triazine, Dimethoxy-Triazine, MP-Triazine, TFE-Triazine, or TME-Triazine (Sam Chemical).

The photoacid generator is preferably included in 1 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 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 reduced, and if it exceeds 20 parts by weight, outgassing and storage stability may be reduced.

The photosensitive resin composition of this invention which consists of such components can further contain surfactant as needed.

The said surfactant functions to improve the adhesiveness, applicability | paintability, and developability of the polyimide photosensitive composition of this invention.

The surfactant may be polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, F171, F172, F173 (trade name: Japan Nippon Ink Company), FC430, FC431 (trade name: Sumitomo Triem, Inc.), or KP341 (trade name: Shinwol) Chemical industry) and the like.

The surfactant is preferably included in an amount of 0.0001 to 2 parts by weight based on 100 parts by weight of the resin of a), and when the content is in the above range, it is more preferable in improving the coating property and developability of the photosensitive composition.

The solid content concentration of the polyimide photosensitive resin composition for OLEDs of the present invention comprising the above components is preferably 10 to 50 parts by weight, and the composition having a solid content in the above range is filtered through a 0.1-0.2 μm Millipore filter or the like. It is good to use.

The present invention also provides an OLED substrate comprising a cured product of the polyimide photosensitive resin composition for OLED and a pattern forming method of the OLED substrate using the polyimide photosensitive resin composition for OLED.

The pattern formation method of the OLED substrate of this invention is a method of forming the pattern of an OLED substrate using the photosensitive resin composition, It is characterized by using the said polyimide photosensitive resin composition for OLED. Preferably, the substrate is an AMOLED substrate.

As a specific example, a method of forming a pattern of an OLED substrate using the polyimide photosensitive resin composition for OLED is as follows.

First, the polyimide photosensitive resin composition for OLED of this invention is apply | coated to the surface of a board | substrate by the spray method, the roll coater method, the rotary coating method, etc., A solvent is removed by prebaking, and a coating film is formed. At this time, the prebaking is preferably carried out for 1-15 minutes at a temperature of 80-120 ℃.

Then, visible light, ultraviolet light, far ultraviolet rays, electron beams, X-rays, or the like are irradiated to the formed coating film according to a pre-prepared pattern, and then subjected to post-exposure bake (PEB) and flood exposure as necessary. It develops and removes an unnecessary part, and a predetermined pattern is formed.

The developer is preferably an aqueous alkali solution, specifically, inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethylethanolamine, methyl diethanolamine and triethanolamine; Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide can be used. In this case, the developer is used by dissolving the alkaline compound at a concentration of 0.1-10% by weight, and an appropriate amount of a water-soluble organic solvent such as methanol and ethanol and a surfactant may be added.

In addition, after developing with the developer as described above, it is washed with ultrapure water for 30-90 seconds to remove unnecessary parts and dried to form a pattern, the pattern is 30-90 minutes at a temperature of 130-250 ℃ by a heating apparatus such as an oven The heat treatment can give a final pattern.

The polyimide photosensitive resin composition for OLEDs according to the present invention is suitable for forming an organic insulating film of an OLED by using a polyimide precursor having easy solubility control, and is particularly suitable for application to an OLED manufacturing process by remarkably improving sensitivity.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

(Production of Polyimide Precursor)

In a 300 ml four-necked reaction vessel, 4 g of diamine DADM (Formula 5), 7 g of Bis-APAF (Formula 6), and 1 g of SiDA (Formula 7) were dissolved in 70 g of gamma butyrolactone. In addition, 5 g of 6-FDA (Chemical Formula 2), 3 g of DOCDA (Chemical Formula 3), and 3 g of a-BPDA (Chemical Formula 4) were added to the reaction vessel and reacted with stirring for 1 hour. In order to terminate the terminal reaction, 2 g of PA was added thereto, and then further reacted at 20 ° C. for 1 hour to prepare a polyimide precursor having a solid content of 30%. A total of 10 g of ECMMA and MGMA, which are protective materials, were added thereto, and the total temperature was raised to 70 ° C., followed by 24 hours of addition of TEA as a catalyst to prepare a new polyimide precursor.

(Manufacture of polyimide photosensitive resin composition for OLED)

30 parts by weight of the prepared polyimide precursor, 20 parts by weight of polyhydroxystyrene, 20 parts by weight of 1,2-quinonediazide compound and 5 parts by weight of hexamethylolmelamine were mixed with a melamine crosslinking agent. Next, the mixture was dissolved in a solvent in which gamma butyrolactone and PGMEA were mixed at a weight ratio of 50:50 so that the solid content of the mixture was 20% by weight, and then filtered through a 0.2 μm millipore filter for polyimide photosensitive resin for OLED. The composition was prepared.

Example 2

The polyimide photosensitive resin composition for OLED was prepared in the same manner as in Example 1, except that 10 g of ECMMA was used to prepare the polyimide precursor in Example 1.

Example 3

Except for using MGMA 10 g instead of ECMMA in Example 1 was prepared in the same manner as in Example 1 polyimide photosensitive resin composition for OLED.

Example 4

The polyimide photosensitive resin composition for OLED was manufactured in the same manner as in Example 1, except that 3 parts by weight of triazine-based TME-Triazine was further used as a photoacid generator in Example 1.

Comparative Example 1

The polyimide photosensitive resin composition for OLED was manufactured in the same manner as in Example 1, except that 8 g of GMA was used instead of ECMMA in Example 1.

Comparative Example 2

The polyimide photosensitive resin composition for OLED was manufactured in the same manner as in Example 1, except that 10 g of GMA was used instead of ECMMA in Example 1.

After evaluating physical properties by the following method using the polyimide photosensitive resin composition for OLED prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the results are shown in Table 1 below.

A) Sensitivity- The polyimide photosensitive resin composition for OLEDs prepared in Examples 1 to 4 and Comparative Examples 1 to 2 was coated on a 10 mm × 10 mm glass substrate on which ITO was deposited using a spin coater. Thereafter, the film was prebaked at 110 ° C. on a hot plate for 2 minutes to form a film having a thickness of 3.0 μm. 2.38% by weight of an aqueous solution of tetramethyl ammonium hydroxide after irradiating 20 µm Isolate Pattern CD-based Dose amount to ultraviolet rays having an intensity of 10 mW / cm 2 at 365 nm using a predetermined pattern mask on the formed film. After developing at 23 degreeC for 100 second, it wash | cleaned for 1 minute with ultrapure water. The developed pattern was cured by heating at 230 ° C. for 60 minutes in an oven to obtain a pattern film having a thickness of 2.5 μm.

B) Solubility-After the preparation of the precursor confirmed the presence of precipitation and after the preparation of the photosensitive resin composition after stirring for 3 hours to confirm the presence of precipitates and undissolved, it was confirmed after stirring for an additional 3 hours. No precipitates and undissolved products after stirring for 3 hours (◎), Precipitations and undissolved products after 3 hours of stirring but not after 3 hours of stirring (○), Precipitates and undissolved products after 6 hours of stirring (×).

Table 1

division	Solubility	Positive Sensitivity (mJ / ㎠)
Example 1	◎	95
Example 2	◎	90
Example 3	○	93
Example 4	○	90
Comparative Example 1	○	130
Comparative Example 2	×	Not rated for beauty

As shown in Table 1, the polyimide photosensitive resin composition for OLED of Examples 1 to 4 prepared according to the present invention was excellent in both solubility and sensitivity at the same time, from the above results, polyimide photosensitive for OLED according to the present invention It was found that the resin composition can obtain more excellent results when applied to the OLED manufacturing process, especially the AMOLED manufacturing process.

On the contrary, in the case of Comparative Example 1, the solubility was low and the sensitivity was difficult to be applied to the OLED process.In the case of Comparative Example 2, precipitates were generated due to gelation during the preparation of the precursor, and precipitates still remained after the photosensitive resin composition was prepared. It was difficult to evaluate because it was impossible to evaluate.

Claims

In the photosensitive resin composition for OLED,

a) a resin comprising i) a polyimide precursor represented by Formula 1 below, and ii) poly hydroxy styrene;

b) 1,2-quinonediazide compounds;

c) crosslinking agents;

d) solvent

Polyimide photosensitive resin composition for OLED, comprising:

[Formula 1]

In Chemical Formula 1,

X is a tetravalent organic group, Y is a divalent organic group, R is independently epoxy cyclohexyl methyl methacrylate (ECMMA) or methylglycidyl methacrylate (MGMA), and n is an integer of 3-100000.
The method of claim 1,

a) 100 parts by weight of a resin containing i) 40-90 wt% of the polyimide precursor represented by Formula 1, ii) 10-60 wt% of poly hydroxy styrene;

b) 5-50 parts by weight of 1,2-quinonediazide compound;

c) 1-30 parts by weight of a crosslinking agent;

d) The polyimide photosensitive resin composition for OLED containing the solvent so that solid content of the whole polyimide photosensitive resin composition may be 5 to 50 weight%.
The method of claim 1,

X in Formula 1 is 2,2-bis (3,4-anhydrodicarboxyphenyl) Hexafluoropropane (6FDA), 5- (2,5-Dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic Anhydride (DOCDA) Or a tetravalent organic group derived from 2,3,3 ', 4'-Biphenyl tetracarboxylic dianhydride (a-BPDA).
The method of claim 1,

Y in Formula 1 is 4,4'-diamino-3,3'-dimethyl-diphenylmethane (DADM), 2,2-Bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (Bis-APAF), or 1, A photosensitive resin composition for OLED, which is a divalent organic group derived from 3-Bis (3-aminopropyl) tetramethyldisiloxane (SiDA (PAM-E)).
The method of claim 1,

The resin of a) further comprises a novolak resin, the photosensitive resin composition for OLED.
The method of claim 1,

The melanin crosslinking agent of c) is selected from the group consisting of condensation products of urea and formaldehyde, condensation products of melamine and formaldehyde, methylol urea alkyl ethers, and methylol melamine alkyl ethers. Photosensitive resin composition for OLED.
The method of claim 1,

The solvent of e) is a photosensitive resin composition for OLED, wherein gamma butyrolactone and propylene glycol methyl ether acetate (PGMEA) are each mixed in a weight ratio of 10-90: 10-90.
The method of claim 1,

The photosensitive resin composition for OLED, wherein the photosensitive resin composition further includes a photoacid generator.
The OLED substrate containing the hardened | cured material of the photosensitive resin composition of any one of Claims 1-8.
The pattern formation method of the OLED substrate using the photosensitive resin composition of any one of Claims 1-8.