KR101323201B1 - Preparing method for pattern of oled - Google Patents

Abstract

The present invention relates to a method of forming an OLED pattern, and in particular, it is possible to simultaneously form two types of patterns of insulator and separator with one photosensitive resin composition, which can shorten the process time and at the same time, the aperture ratio on the panel. The present invention relates to an OLED pattern forming method suitable for application to an OLED manufacturing process by remarkably improving.

Photosensitive resin, step polymerization, novolac resin, photoacid generator, insulator, separator, low dielectric constant, aperture ratio

Description

ODL pattern formation method {PREPARING METHOD FOR PATTERN OF OLED}

The present invention relates to a method of forming an OLED pattern, more specifically, excellent in various performances such as sensitivity and low dielectric properties, and in particular, it is possible to simultaneously form two types of patterns of insulator and separator with one photosensitive resin composition. In addition to shortening the process time, the present invention relates to an OLED pattern formation method suitable for application to an OLED manufacturing process by significantly improving the aperture ratio on a panel.

Recently, in the manufacturing process of Organic Light Emitting Diodes (OLED), LCD, PDP, etc., process time can be shortened, and photoresist and process development for excellent aperture ratio are required.

Conventionally, the insulator used in the OLED manufacturing process is composed of components such as PAC, binder, solvent, and the like. Acrylic or imide series have been mainly used as the binder, and separators include PAG, novolac resin, crosslinking agent, solvent, and the like. Negative photoresists of components have been used. However, in the conventional insulator and separator formation, a long process time due to the progress of the 2-step process became a problem, and there was a problem of decreasing the aperture ratio by securing the alignment margin when separating the separator on the insulator.

Therefore, there is a need for further research to shorten the process time and secure an excellent aperture ratio in the insulator and separator forming process applied to the OLED manufacturing process.

In order to solve the problems of the prior art as described above, the present invention can simultaneously form two types of patterns of insulator and separator with one photosensitive resin composition, which can shorten the process time and at the same time panel An object of the present invention is to provide a photosensitive resin composition for an OLED suitable for application to an OLED manufacturing process by remarkably improving the opening ratio of a phase, an OLED substrate comprising a cured product of the photosensitive resin composition, and a pattern forming method of an OLED substrate using the photosensitive resin composition. do.

Another object of the present invention is excellent in a variety of performance, such as sensitivity, low dielectric properties, can shorten the process time, improve the aperture ratio of the photosensitive resin composition for OLED, the cured product of the photosensitive resin composition suitable for use in the OLED manufacturing process To provide an OLED substrate comprising a, and a pattern forming method of the OLED substrate using the photosensitive resin composition.

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

a) a novolak resin prepared through step polymerization;

b) 1,2-quinonediazide compounds;

c) photoacid generator;

d) melamine-based crosslinking agents; And

e) solvent

It provides a photosensitive resin composition for OLED comprising a.

Preferably, the present invention

a) based on 100 parts by weight of a novolak resin prepared through step polymerization

b) 5 to 100 parts by weight of 1,2-quinonediazide compound;

c) 1 to 20 parts by weight of photoacid generator;

d) 1 to 30 parts by weight of the melamine crosslinking agent; And

e) The solvent is included so that the solid content in the photosensitive resin composition is 10 to 50% by weight.

Moreover, this invention provides the OLED substrate containing the hardened | cured material of the said photosensitive resin composition.

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

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition for OLED of the present invention is a) a novolak resin prepared through the step polymerization; b) 1,2-quinonediazide compounds; c) photoacid generator; d) melamine-based crosslinking agents; And e) a solvent.

The novolak resin prepared through the step polymerization of a) used in the present invention is insoluble in alkaline developer by forming a crosslink in the presence of a crosslinker, and becomes soluble in an alkaline developer before crosslinking to form a pattern. have.

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 the weight average molecular weight of the novolak resin prepared through the step polymerization is less than 3,000, there is a problem that developability, residual film ratio, etc. of the photosensitive resin composition is lowered, pattern development, heat resistance, etc. are lowered, and when it exceeds 30,000. There exists a problem that the sensitivity of the photosensitive resin composition falls, or a pattern phenomenon falls.

The 1,2-quinonediazide compound of b) used in the present invention is used as a photosensitive compound in the photosensitive resin composition.

As the 1,2-quinonediazide compound, 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, or 1,2-quinonediazide 6-sulfonic acid ester may be used. have.

The quinonediazide compound as described above may be prepared by reacting a naphthoquinonediazide sulfonic acid halogen compound and a phenol compound under a weak base.

Examples of the phenolic compounds include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2'-tetrahydroxybenzophenone, and 4,4'-tetrahydroxybenzophenone. , 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy 4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy 3'-methoxybenzophenone, 2,3,4,2'-pentahydroxybenzophenone, 2,3,4,6'-pentahydroxybenzophenone, 2,4,6,3'-hexahydroxybenzophenone, 2,4,6,4'-hexahydroxybenzophenone, 2,4,6,5'-hexahydroxybenzophenone, 3,4,5 , 3'-hexahydroxybenzophenone, 3,4,5,4'-hexahydroxybenzophenone, 3,4,5,5'-hexahydroxybenzophenone, bis (2,4-dihydroxyphenyl ) Methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxy Phenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimeth Methyl 4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, or bis ( 2,5-dimethyl 4-hydroxyphenyl) -2-hydroxyphenylmethane etc. can be used, The said compound can be used individually or in mixture of 2 or more types.

When synthesizing a quinone diazide compound with the phenolic compound and the naphthoquinone diazidesulfonic acid halogen compound as described above, the degree of esterification is preferably 50 to 90%. When the degree of esterification is less than 50%, the residual film ratio may be deteriorated, and when the esterification degree is greater than 90%, there is a problem in that scum is generated on the pattern.

The 1,2-quinonediazide compound is preferably included in an amount of 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the novolak resin prepared through the step polymerization of a). . If the content is less than 5 parts by weight, the difference in solubility between the exposed and non-exposed parts is small, making it difficult to form a pattern. If the content exceeds 100 parts by weight, the unreacted 1,2-quinonediazide compound is released when irradiated with light for a short time. There is a problem that the development is difficult due to the excessively low solubility in the alkaline aqueous solution which is a developer.

The photoacid generator of c) used in the present invention forms an acid and diffuses through exposure or post-exposure bake to cause a crosslinking reaction of the novolak resin prepared through the step polymerization of a) and the melamine-based crosslinking agent of d). It acts to form a pattern.

The photoacid generator may be any compound that can generate an acid by light, of course, preferably an ionic photoacid generator such as sulfonium salt, iodonium salt, sulfonydiazomethane, N-sulfonyl Oxyimide type, benzoin sulfonate type, nitrobenzyl sulfonate type, sulfone type, glyoxime type, triazine type, etc. 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, di Phenylmethylsulfonium, methyl-2oxopropylphenylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonium, or tribenzylsulfonium, and the like sulfonates include trifluoromethanesulfo Nate, nonafluorobutanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pendafluorobenzenesulfonate, 4-trifluorofluoromethylbenzenesulfonate, 4- Fluorobenzenesulfonate, 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. Methanesulfonate, 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- (perfluoro Octanesulfonyl) -α-dimethylglyoxime, bis-o- ( 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 as described above is preferably included in an amount of 1 to 20 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the novolak resin prepared through the step polymerization 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 melanin crosslinking agent of d) used in the present invention functions to form a crosslinked structure with the novolak resin prepared through the step polymerization of a).

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 partial 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 in all of methylol groups, and specific examples thereof include hexamethylol melamine hexamethyl ether and hexamethylol melamine 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, and more preferably 1 to 20 parts by weight, based on 100 parts by weight of the novolak resin prepared through the step polymerization 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 e) used in the present invention functions to form a uniform pattern profile by preventing flatness and coating stains of the insulator and the separator.

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.

The solvent is preferably included so that the solid content of the entire photosensitive resin composition is 10 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.

The photosensitive resin composition of this invention which consists of the above components can further contain f) surfactant as needed.

The surfactant has the function of improving the applicability and developability of the photosensitive composition.

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 novolak resin prepared through the step polymerization of a), and when the content is within the above range, the coating property or developability of the photosensitive composition is improved. Even better.

It is preferable that the solid content concentration of the photosensitive resin composition of this invention which consists of the above components is 10-50 weight part, and the composition which has a solid content of the said range is good to use after filtering with a 0.1-0.2 micrometer millipore filter etc. .

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

The pattern forming method of the OLED substrate of the present invention is characterized in that the photosensitive resin composition is used in the method of forming a pattern of the OLED substrate by simultaneously forming an insulator and a separator.

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

First, the photosensitive resin composition of the present invention is applied to the surface of a substrate by a spraying method, a roll-coating method, a spin coating method, or the like, and the solvent is removed by pre-baking to form a coating film. At this time, it is preferable to perform the said prebaking for 1 to 15 minutes at the temperature of 80-120 degreeC.

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, methyldiethanolamine and triethanolamine; Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. In this case, the developer is used by dissolving the alkaline compound at a concentration of 0.1 to 10% by weight, and may be added an appropriate amount of a water-soluble organic solvent and a surfactant such as methanol, ethanol and the like.

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

The photosensitive resin composition according to the present invention is excellent in various performances such as sensitivity and low dielectric properties, and in particular, a single photosensitive resin composition can simultaneously form two types of patterns, an insulator and a separator, which can shorten the process time. In addition, the aperture ratio on the panel is remarkably improved at the same time, making it suitable for application to OLED manufacturing processes.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example]

Example 1

(Novolak resin production)

45 g of metacresol, 55 g of paracresol, 65 g of formaldehyde, and 0.5 g of oxalic acid were added to an overhead stirrer and stirred to prepare a homogeneous mixture. The homogeneous mixture was heated to 95 ° C. and maintained at this temperature for 4 hours. The ring condenser was replaced with a distillation apparatus and the temperature of the homogeneous mixture was distilled at 110 ° C. for 2 hours. Vacuum distillation was carried out at 180 ° C. for 2 hours to distill off residual monomer and to cool the molten novolak resin to room temperature. Then, the weight average molecular weight was measured by GPC to obtain a novolak resin having a weight average molecular weight of 3500. Here, the weight average molecular weight is the polystyrene reduced average molecular weight measured by GPC.

(1,2-quinonediazide compound preparation)

1 mole of 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid [ Chloride] condensation reaction of 2 moles to give 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinonediazide -5-sulfonic acid ester was prepared.

(Preparation of photosensitive resin composition)

100 parts by weight of the novolak resin prepared through the step polymerization and 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 30 parts by weight of 1,2-naphthoquinonediazide-5-sulfonic acid ester, 3 parts by weight of triazine-based TME-Triazine as a photoacid generator, and 5 parts by weight of hexamethylol melamine as a melamine crosslinking agent were mixed. Then, the mixture was dissolved in dipropylene glycol dimethyl ether so that the solid content of the mixture was 20% by weight, and then filtered through a 0.2 μm millipore filter to prepare a photosensitive resin composition.

Example 2

The photosensitive composition was carried out in the same manner as in Example 1, except that 70 g of metacresol and 30 g of xylenol were used instead of 45 g of metacresol and 55 g of paracresol as monomers in the polymerization of the novolak resin. A resin composition was prepared.

Example 3

In Example 1, except that 35 g of metacresol, 40 g of paracresol, and 25 g of xylenol were used instead of 45 g of metacresol and 55 g of paracresol as monomers in the polymerization of the novolak resin. It carried out by the same method and manufactured the photosensitive resin composition.

Example 4

The same procedure as in Example 1 was repeated except that in the Example 1, nocreac resin polymerization was performed using methacresol 40, paracresol 40 g, and trimethylphenol 20 g instead of 45 g of metacresol and 55 g of paracresol. It carried out by the method and manufactured the photosensitive resin composition.

Example 5

Except for using sulfonium salt-based triphenolsulfonium and (4-tert-butoxyphenyl) diphenylsulfonium in place of the triazine-based TME-Triazine photoacid generator when preparing the photosensitive resin composition in Example 1 It carried out by the same method as Example 1, and manufactured the photosensitive resin composition.

Example 6

Except for using the iodide salt-based bis (4-tert- butylphenyl) iodonium in place of the triazine-based TME-Triazine photoacid generator when preparing the photosensitive resin composition in Example 1 in the same manner as in Example 1 To prepare a photosensitive resin composition.

Example 7

The photosensitive resin composition was prepared in the same manner as in Example 1, except that bis (ethylsulfonyl) diazomethane was used instead of the triazine-based TME-Triazine as a photoacid generator when preparing the photosensitive resin composition in Example 1. Prepared.

Example 8

Except for using the nitrobenzyl sulfonate-based 2,4-dinitrobenzyl sulfonate instead of the triazine-based TME-Triazine photoacid generator in Example 1 prepared in the same manner as in Example 1 To prepare a photosensitive resin composition.

Comparative Example 1

A photosensitive resin composition was prepared in the same manner as in Example 1, except that triazine-based TME-Triazine, which is a photoacid generator, was not used when preparing the photosensitive resin composition in Example 1.

Comparative Example 2

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 1,2-naphthoquinone at the time of preparing the photosensitive resin composition in Example 1 A photosensitive resin composition was prepared in the same manner as in Example 1, except that no diazide-5-sulfonic acid ester was used.

After evaluating the physical properties by the following method using the photosensitive resin composition prepared in Examples 1 to 8 and Comparative Examples 1 to 2, the results are shown in Table 1 below.

A) Positive Sensitivity-After applying the photosensitive resin composition prepared in Examples 1 to 8 and Comparative Examples 1 and 2 using a spin coater on a 370 mm × 470 mm glass substrate on which ITO was deposited, Prebaking was carried out at 110 ° C. on a hot plate for 2 minutes to form a film having a thickness of 2.0 μm. The formed film was irradiated with 50 µm Isolate Pattern CD-based Dose to Clear amount of ultraviolet light having a intensity of 20 mA / cm 2 at 435 nm using a predetermined pattern mask, followed by 2.38 weight of tetramethyl ammonium hydroxide. After developing for 90 seconds at 23 degreeC with the aqueous solution of%, it wash | cleaned for 1 minute with ultrapure water. Then, the developed pattern was cured by heating at 140 ° C. for 60 minutes in an oven to obtain a pattern film having a thickness of 1.5 μm.

B) Negative sensitivity-After applying the photosensitive resin composition prepared in Examples 1 to 8 and Comparative Examples 1 and 2 using a spin coater on a 370 mm × 470 mm glass substrate on which ITO is deposited, Prebaking was performed on a hot plate at 110 degreeC for 2 minutes, and the film | membrane of 5.0 micrometers in thickness was formed. After irradiating 25 µm Isolate Pattern CD-based Dose amount to ultraviolet light having an intensity of 20 mW / cm 2 at 435 nm using a predetermined pattern mask on the formed film, it is baked after exposure on a hot plate at 110 ° C. for 90 seconds. (PEB). After developing at 23 ° C. for 100 seconds with an aqueous solution of 2.38 wt% tetramethyl ammonium hydroxide, the mixture was washed with ultrapure water for 1 minute. The developed pattern was cured by heating at 140 ° C. for 60 minutes in an oven to obtain a pattern film having a thickness of 4.0 μm.

C) Angle of positive pattern-The case where the angle of the edge portion of the pattern formed in (a) above (θ ₁ in Fig. ₁ ) is 10 to 30 degrees is represented by ○, less than 10 degrees or more than 30 degrees. Generally, when the angle is low, leakage current may occur. When the angle is high, uniformity may be a problem when the organic film is deposited.

[Figure 1]

D) Angle of negative pattern-The case where the reversal taper angle (θ ₂ in Fig. 2 below) of the edge portion of the pattern formed in the above _b ) is 50 to 70 degrees is represented by ○, less than 50 degrees or 70 degrees or more. In general, when the angle is low, there may be a problem in adhesion. When the angle is high, there is a problem in separation when the organic film is deposited.

[Figure 2]

E) Aperture Ratio-Separator was evaluated on the 370 × 470 glass substrate on which ITO was deposited in the manufacture of OLED Pannel based on 25 μm and the remaining ITO area except for the Insulator and Separator was determined as the aperture ratio (%). .

First, in the case of 2-Step process, using the photosensitive resin composition prepared in Comparative Example 1 to form an Insulator by the method of (a), by using the photosensitive resin composition prepared in Comparative Example 2 by the method of b) Separator was formed. In the case of the 1-Step process, the photosensitive resin composition prepared in Examples 1 to 8 was applied, and then prebaked at 110 ° C. on a hot plate for 2 minutes to form a film having a thickness of 6.0 μm. After irradiating 50 µm Isolate Pattern CD-based Dose to Clear amount of ultraviolet ray having an intensity of 20 mA / cm 2 at 435 nm using a predetermined positive pattern mask on the formed film, tetramethyl ammonium hydroxide was 2.38 weights. After developing for 90 seconds at 23 degreeC with the aqueous solution of%, it wash | cleaned for 1 minute with ultrapure water, and formed the positive pattern. Then, after aglining the negative pattern mask, irradiating a 25 μm Isolate Pattern CD reference dose with ultraviolet light having an intensity of 20 mA / cm 2 at 435 nm, and then exposing the film at 110 ° C. for 90 seconds on a hot plate. Bake (PEB). After that, the mask was removed, the entire surface exposure was 100 mJ / sqcm, and developed at 23 ° C. for 100 seconds in an aqueous solution of 2.38% by weight of tetramethyl ammonium hydroxide, followed by washing with ultrapure water for 1 minute. The developed pattern was cured by heating at 140 ° C. for 60 minutes in an oven to form an insulator having a thickness of 1.5 μm and a separator of 4.0 μm at the same time.

F) Dielectric constant-The dielectric constant was measured through the pattern formed in a). The dielectric constant was obtained by measuring the capacitance of the capacitor and the following equation. First, the dielectric thin film was coated to a predetermined thickness, and then the capacitance was measured by an impedance analyzer. The dielectric constants were calculated by the following equation, and the cases where the dielectric constant was 3.8 or less exceeded ○ or 3.8. Represented by ×.

[Mathematical Expression]

In the above equation, epsilon 0 is the vacuum dielectric constant, epsilon r is the dielectric film relative dielectric constant, A is the effective area, d is the dielectric film thickness.

division Positive Sensitivity (mJ / ㎠) Negative Sensitivity (mJ / ㎠) Positive Pattern Angle Negative Pattern Angle Aperture ratio (%) Permittivity Example 1 250 27 ○ ○ 70 ○ Example 2 245 27 ○ ○ 72 ○ Example 3 255 26 ○ ○ 71 ○ Example 4 260 26 ○ ○ 70 ○ Example 5 255 28 ○ ○ 70 ○ Example 6 250 28 ○ ○ 71 ○ Example 7 260 29 ○ ○ 70 ○ Example 8 260 28 ○ ○ 72 ○ Comparative Example 1 255 Pattern not formed ○ × 55 ○ Comparative Example 2 Pattern not formed 28 × ○ 55 ○

As shown in Table 1, the photosensitive resin compositions of Examples 1 to 8 according to the present invention were excellent in sensitivity, low dielectric properties, and the like, and in particular, two types of patterns even using one photosensitive resin composition. It was confirmed that it can be formed, from this it can be seen that the process time can be shortened. In addition, the opening ratio was much better than Comparative Examples 1 to 2, it can be seen from the results that the photosensitive resin composition according to the present invention can obtain a better result when applied to the OLED manufacturing process.

On the other hand, in the case of Comparative Examples 1 to 2, only one type of pattern can be realized, and thus the process time is long, and the process margin is decreased when forming the separator. And it was found.

The photosensitive resin composition according to the present invention is excellent in various performances such as sensitivity and low dielectric properties, and in particular, a single photosensitive resin composition can simultaneously form two types of patterns, an insulator and a separator, which can shorten the process time. In addition, at the same time, the aperture ratio on the panel is remarkably improved to have an effect suitable for application to an OLED manufacturing process.

Claims (10)

After the photosensitive resin composition is applied to the surface of the OLED substrate and prebaked, the coating film is exposed and developed to form an insulator and separator of the OLED. An OLED insulator and separator are formed using the photosensitive resin composition having the same composition. , The photosensitive resin composition a) based on 100 parts by weight of a novolak resin prepared through step polymerization b) 5 to 100 parts by weight of 1,2-quinonediazide compound; c) 1 to 20 parts by weight of photoacid generator; d) 1 to 30 parts by weight of the melamine crosslinking agent; And e) A method of forming an OLED pattern comprising a solvent such that the solid content in the photosensitive resin composition is 10 to 50% by weight. delete The method of claim 1, The novolak resin prepared through the step polymerization of a) is formaldehyde and ortho-, meta-, para-cresol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3 And 5-pylenol, 2,3,5-trimethylphenol, and an OLED pattern forming method characterized by condensation of at least one selected from the group consisting of a mixture thereof. The method of claim 1, Polystyrene reduced weight average molecular weight of the novolak resin prepared by the step polymerization of a) characterized in that 3,000 to 30,000. The method of claim 1, The 1,2-quinonediazide compound of b) is used as 1,2-quinonediazide 4-sulfonic acid ester, 1,2-quinonediazide 5-sulfonic acid ester, and 1,2-quinonediazide 6-sulfonic acid ester OLED pattern forming method characterized in that at least one selected from the group consisting of. The method of claim 1, The photoacid generator of c) includes sulfonium salts, iodonium salts, sulfonydiazomethane photoacid generators, N-sulfonyloxyimide photoacid generators, benzoin sulfonate photoacid generators, nitrobenzylsulfonate photoacid generators And at least one member selected from the group consisting of a sulfone photoacid generator, a glyoxime photoacid generator, and a triazine photoacid generator. The method of claim 1, The melanin crosslinking agent of d) is selected from the group consisting of a condensation product of urea and formaldehyde, a condensation product of melamine and formaldehyde, methylol urea alkyl ethers, and methylol melamine alkyl ethers. OLED pattern formation method. The method of claim 1, The solvent of e) is methanol, ethanol, benzyl alcohol, hexyl alcohol, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether, ethylene Glycol ethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene Glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, pro Made of ethylene glycol butyl ether, dipropylene glycol dimethyl ether, diporoethylene glycol diethyl ether, butylene glycol monomethyl ether, butylene glycol monoethyl ether, dibutylene glycol dimethyl ether, and dibutylene glycol diethyl ether OLED pattern forming method characterized in that at least one selected from the group. delete delete