KR20140118622A - Positive-type photoresist composition, insulating film and OLED comprising the same - Google Patents

Abstract

The present invention relates to a positive-type photosensitive resin composition which is a positive-type photosensitive resin composition including an alkali-soluble polyamic acid-polyimide copolymer resin, a diazide-based photosensitive compound, a sensitivity enhancing agent, and a solvent, which improves the alkali-soluble polyamic acid-polyimide copolymer resin to have high resolution and an improved contacting force.

Description

[0001] The present invention relates to a positive-type photosensitive resin composition, an insulating film containing the same, and an organic light-emitting device including the positive-type photoresist composition,

The present invention relates to a positive photosensitive resin composition, an insulating film containing the positive photosensitive resin composition, and an organic light emitting device. More particularly, the present invention relates to a positive-working photosensitive resin composition containing an alkali-soluble polyamic acid-polyimide copolymer resin, a diazide-based photosensitive compound, and a sensitivity enhancer, and an insulating film and an organic light-

In the recent semiconductor field, due to the high density and high integration of devices, stable materials that are easy to process and able to withstand a baking process of 200 ° C or more are preferred. In particular, polyimide resins have excellent properties such as heat resistance, chemical resistance, And has been widely used from electronic materials such as TFT-LCD electrode protection films to heat resistant materials such as automobiles and airplanes.

As a conventional technique for a positive photosensitive polyimide resin, a chemical amplification method in which a photoacid generator that is a photosensitive agent is mixed with a polyamic acid, a method in which a polyamic acid and a dissolution inhibitor, a naphtoquinonediazide compound are mixed, A method in which a polyimide and a naphthoquinone diazide compound are mixed and used has been proposed. However, these conventional techniques have a problem that the reliability of the device is poor after curing, the patterning of a high resolution is difficult, and the physical properties are deteriorated due to a large amount of photosensitive agent.

In addition, the original polyimide resin has a yellow color due to its high aromatic ring density, and has a disadvantage in that it has a low transmittance in a visible light region and a high dielectric constant.

In the insulating layer patterning step, a liquid positive-working photosensitive resin composition is generally dropped on a substrate, and the resultant is uniformly coated on the entire surface of the substrate by spin / slit coating, followed by preliminary heat treatment and exposure to form a circuit. An insulating layer is formed with a thickness of 1000 to 2000 Å in order to prevent deterioration of the edge of the ITO and prevent vertical short-circuiting.

As the photosensitive resin composition for insulation, most of the organic insulating films such as imide polymers and acryl-based polymers are used, but the process margin is secured due to adhesion problems in the ITO and SiO ₂ protective film layers in the process And is effective in improving the adhesion problem in the SiO ₂ protective film layer by using a silane coupling agent as an additive on a stabilizing liquid containing a conventional polyimide obtained from diamine and acid anhydride However, depending on the content of silane coupling agent, there may be residue problems and long term storage safety problems in the phenomenon.

Korean Patent Publication No. 10-2010-0124905

The present invention improves the physical properties of the alkali-soluble polyamic acid-polyimide copolymer resin contained in the positive photosensitive resin composition, thereby improving the adhesion to the ITO layer, especially the SiO ₂ layer, And which can realize a circuit with high sensitivity and a low dielectric constant and a high sensitivity.

In order to achieve the above object, the present invention provides a positive photosensitive resin composition comprising an alkali soluble polyamic acid-polyimide copolymer resin, a diazide photosensitive compound, a sensitivity enhancer and a solvent, wherein the alkali soluble polyamic acid- The copolymer resin is prepared by mixing a diamine represented by the following general formula (1), a diamine represented by the general formula (2) and a dianhydride represented by the general formula (3) in a molar ratio of 1: 0.02-0.23: 0.8-1.2 A photosensitive resin composition is provided.

[Chemical Formula 1]

(2)

(3)

The present invention also provides an insulating film formed from the above positive photosensitive resin composition.

The present invention also provides an organic light emitting device including the insulating film.

INDUSTRIAL APPLICABILITY The positive photosensitive resin composition of the present invention has excellent adhesion to the ITO layer, particularly the SiO ₂ layer, does not generate residues during development, has a high light transmittance and a low dielectric constant. Therefore, the positive photosensitive resin composition can be effectively used in the field of flat panel displays requiring a high resolution pattern and in the formation of organic insulating films of organic light emitting devices.

1 is an SEM photograph of a 30 μm resolution pattern of the photosensitive resin composition of Example 5. FIG.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a positive photosensitive resin composition, which is a positive photosensitive resin composition comprising an alkali soluble polyamic acid-polyimide copolymer resin, a diazide photosensitive compound, a sensitivity enhancer and a solvent, wherein the alkali soluble polyamic acid- The copolymer resin is prepared by mixing a diamine represented by the following general formula (1), a diamine represented by the general formula (2) and a dianhydride represented by the general formula (3) in a molar ratio of 1: 0.02-0.23: 0.8-1.2 To a photosensitive resin composition.

[Chemical Formula 1]

(2)

(3)

The positive photosensitive resin composition contains the diazide photosensitive compound in an amount of 30 to 80 parts by weight based on 100 parts by weight of the alkali soluble polyamic acid-polyimide copolymer resin. When it is included in the above amount, it exhibits excellent developing property and solubility.

The sensitivity enhancer is contained in an amount of 3 to 15 parts by weight based on 100 parts by weight of the alkali-soluble polyamic acid-polyimide copolymer resin. When the content is included in the above amount, the sensitivity enhancing effect and a high margin in the window process can be obtained.

The solvent is used in an amount of 70 to 90% by weight.

The alkali-soluble polyamic acid-polyimide copolymer resin is prepared by mixing the diamine of the formula (1), the diamine of the formula (2) and the dianhydride of the formula (3) in a molar ratio of 1: 0.02-0.23: 0.8-1.2. When the contents of the formulas (1), (2) and (3) are included in the above amounts, the viscosity of the polyamic acid as the polymerization intermediate becomes 20 to 100 cps, preferably 30 to 60 cps when the solid content is 20%. When the polyamic acid solution is imidized, a polyamic acid-polyimide copolymer resin having a weight average molecular weight of 15,000 to 30,000 is prepared.

The alkali-soluble polyamic acid-polyimide copolymer resin

a) 5 to 50% by weight of a mixture of the diamine of the formula 1, the diamine of the formula 2 and the dianhydride of the formula 3 in a molar ratio of 1: 0.02 to 0.23: 0.8 to 1.2 is dissolved in 50 to 95% by weight of the first solvent Thereby producing a polyamic acid solution;

b) partially imidizing the polyamic acid solution with a chemical hardener and an imidization catalyst; And

c) adding a second solvent having a lower polarity than that of the first solvent to the polyamic acid solution of step b) in an amount of 5 to 20 parts by weight based on the weight of the polyamic acid solution, followed by drying.

The reaction conditions in step a) are not particularly limited, but it is preferable to stir at a temperature of 20 to 80 캜 for 0.5 to 10 hours. In addition, it is preferable that the reaction atmosphere is an inert atmosphere such as argon gas or nitrogen gas.

In the step a), the first solvent is not particularly limited as long as it is a solvent dissolving the polyamic acid. N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), N, N-dimethylacetamide ), Dimethylsulfoxide (DMSO), acetone, diethyl acetate, tetrahydrofuran (THF), chloroform and? -Butyrolactone, and the like.

Also, the content of the first solvent is 50 to 95% by weight, preferably 70 to 90% by weight. When the above content is included, the viscosity of the polyamic acid solution prepared by the method of step a) is 20 to 100 cps, preferably 30 to 60 cps. The viscosity of the polyamic acid solution is related to the molecular weight. When the viscosity is less than 20 cps, the molecular weight becomes small, so that the alkali developing speed occurs excessively rapidly at a constant exposure amount. When the viscosity exceeds 100 cps, the molecular weight increases and the developing speed becomes slow.

In the step b), the polyamic acid solution is partially imidized using a chemical imidization method. The chemical curing agent may include at least one selected from the group consisting of acetic anhydride (AA), phthalic anhydride (PA), tetrahydrophthalic anhydride (THPA), and methyltetrahydrophthalic anhydride (MTHPA).

The imidization catalyst may include at least one selected from the group consisting of isoquinoline, beta-picoline, pyridine, triethylamine, and dimethylaniline.

In the step c), the second solvent has a lower polarity than that of the first solvent. For example, the second solvent may include at least one selected from the group consisting of water, alcohols, ethers and ketones. The content of the second solvent is not particularly limited, but is preferably 5 to 20 parts by weight based on the weight of the polyamic acid solution in step a).

After filtering the polyimide resin prepared in the step b), the polyimide resin is filtered at a temperature of 50 to 150 캜 in consideration of the boiling points of the second solvent in the step c) and the first solvent remaining in the solidified polyimide resin, It is preferable to dry it for 24 hours.

The weight average molecular weight in the above and below is defined as a conversion of polystyrene equivalent determined by gel permeation chromatography (GPC). The weight average molecular weight of the alkali-soluble polyamic acid-polyimide copolymer resin prepared in steps a), b) and c) is 15,000 to 30,000 based on the GPC measurement method. When the weight average molecular weight is within the above range, / Development speed can be achieved.

The diazide-based photosensitive compound acts as a dissolution inhibitor that reduces the solubility of the alkali-soluble resin in alkali, and when irradiated with light, turns into an alkali-soluble material, thereby increasing the alkali solubility of the alkali-soluble resin. Therefore, the exposed portion of the photodegradable transfer material is developed by the change in solubility due to light irradiation.

Further, the above-mentioned diazide-based photosensitive compound can be synthesized by esterification reaction of a polyhydroxy compound with a quinone diazidesulfonic acid compound. The esterification reaction for obtaining the diazide-based photosensitive compound may be carried out by reacting a polyhydroxy compound and a quinonediazide sulfonic acid compound with a solvent such as dioxane, acetone, tetrahydrofuran, methyl ethyl ketone, N-methylpyrrolidone, chloroform, Followed by condensation by adding a basic catalyst such as N-methylmorpholine, N-methylpiperazine and 4-dimethylaminopyridine, and then washing, purifying and drying the obtained product.

The quinone diazide sulfonic acid compound functions as a dissolution inhibiting agent that lowers the solubility of the alkali-soluble resin. However, since it is alkali soluble at the time of exposure, it exhibits the property of promoting the dissolution of the alkali-soluble resin in the alkali. Examples of the quinonediazide sulfonic acid compound include 1,2-benzoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2- An o-quinonediazide sulfonic acid compound such as 2-naphthoquinonediazide-5-sulfonic acid, and a quinonediazide sulfonic acid derivative; and the like.

Examples of the polyhydroxy compound include trihydroxybenzophenone such as 2,3,4-trihydroxybenzophenone, 2,2 ', 3-trihydroxybenzophenone and 2,3,4'-trihydroxybenzophenone. N, N, N, N, N, N, N, or N, such as 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone and 2,3,4,5- Pentahydroxybenzophenones such as 2,2 ', 3,4,4'-pentahydroxybenzophenone, 2,2', 3,4,5-pentahydroxybenzophenone, 2, Hexahydroxybenzophenones such as 3,3 ', 4,4', 5'-hexahydroxybenzophenone, 2,2 ', 3,3', 4,5'-hexahydroxybenzophenone and the like, Esters, oxyflavones, and the like can be used.

The diazide-based photosensitive compound obtained from the quinone diazide sulfonic acid compound and the polyhydroxy compound is preferably 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 1,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and 1- [1- (4-hydroxyphenyl) isopropyl] -4- [ Bis (4-hydroxyphenyl) ethyl] benzene) -1,2-naphthoquinonediazide-5-sulfonate, and the like.

The sensitivity enhancer improves the sensitivity and is preferably selected from the group consisting of 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone and 1- [1- (4-hydroxyphenyl) isopropyl ] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, and the like.

The solvent may be ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, acetone, methyl ethyl ketone, ethyl alcohol, And may include one or more selected from the group consisting of propyl alcohol, isopropyl alcohol, benzene, toluene, cyclopentanone, cyclohexanone, ethylene glycol, xylene, ethylene glycol monoethyl ether and diethylene glycol monoethyl ether .

The positive photosensitive resin composition may contain other components such as leveling agents such as silicones, fillers, antioxidants and the like, and the additives may be selected from materials widely used in the field to which the present invention belongs.

The present invention also provides an insulating film formed from the above positive photosensitive resin composition. The insulating film has an excellent sensitivity pattern developing property, light transmittance and high insulation resistance due to the improved alkali-soluble polyamic acid-polyimide copolymer resin.

The method of manufacturing the insulating film is as follows.

The positive photosensitive resin composition is coated on the surface of the substrate to a thickness of 1 to 3 m using a spin coater. And preliminarily heat-treated at 90 to 120 ° C for 1 to 10 minutes. After the mask is placed on the coating film, ultraviolet rays are irradiated and then developed with an aqueous alkaline solution to remove unnecessary portions to form a pattern. The amount of exposure is determined depending on the resolution, and as the alkaline aqueous solution, it is preferable to use inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, and ammonia, more preferably TMAH (Tetra methyl ammonium hydroxide) do. After the alkali aqueous solution is applied for 60 to 180 seconds, the pattern may be post-heat treated at 150 to 260 ° C for 20 to 60 minutes using a hot plate to form an insulating film.

The thickness of a preferable coating film of the positive photosensitive resin composition is 1.0 to 2.0 占 퐉, and the dielectric constant of the insulating film made to the thickness is 5 or less, preferably 3 to 4.

Also, the present invention provides an organic light emitting device including the insulating film. In the organic light emitting device, a photoresist is patterned on a transparent substrate on which a transparent electrode is deposited through a process such as coating, exposure, development, etching, peeling and the like, and barrier ribs are formed on the insulating layer pattern formed by the above method. Thereafter, an organic thin film is deposited in the order of an electron injection layer, an electron transporting layer, a light emitting layer, a hole transporting layer, and a hole injecting layer, and then a metal electrode layer is deposited thereon. Finally, after sealing through the sealing material, the module can be assembled to manufacture an organic light emitting device.

The positive photosensitive resin composition exhibits insoluble or poorly soluble characteristics with respect to an alkali developer due to the dissolution inhibiting action of the diazide-based photosensitive compound before exposure, and is characterized in that the diazide-based photosensitive compound is changed by exposure to dissolve in an alkaline developer As shown in Fig.

Therefore, the organic light emitting device may be referred to as an active matrix organic light emitting device.

Hereinafter, the present invention will be described in detail with reference to examples.

However, the following examples are illustrative of the present invention, and the present invention is not limited to the following examples.

≪ Polymerization of alkali soluble polyamic acid-polyimide copolymer resin >

Example  One.

N, N-dimethylacetamide (DMAc) (76.61 g) was charged into a 100 ml 3-neck round bottom flask equipped with a nitrogen inlet, a dropping funnel, a temperature controller and a condenser while passing nitrogen through the flask. 8.88 g (0.2425 mol) of bis-AP-AF and 0.19 g (0.0075 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in the solution and kept at room temperature. 10.0 g (0.225 mol) of 6FDA was added to the solution to completely dissolve 6FDA for 10 minutes. The concentration of the solid was 20% by weight, and the solution was stirred at room temperature for 1 hour. To obtain a polyamic acid resin having a viscosity of 39 cps at 23 占 폚.

Acetic anhydride (AA) as a chemical hardener and 0.5 mol of pyridine as an imidation catalyst are added to the polyamic acid solution, and then the polyamic acid solution is imidized by stirring at 80 ° C for 1 hour. 30 g of the imidized mixture was added to 300 g of water and precipitated. The precipitated solid was filtered and pulverized to fine powder, and dried in a vacuum drying oven at 100 캜 for 18 hours to obtain a solution having a weight average molecular weight of 20,000 g / mol. < / RTI >

Example  2.

N, N-dimethylacetamide (DMAc) (76.61 g) was charged into a 100 ml 3-neck round bottom flask equipped with a nitrogen inlet, a dropping funnel, a temperature controller and a condenser while passing nitrogen through the flask. 8.70 g (0.2375 mol) of bis-AP-AF and 0.31 g (0.0125 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in the solution and kept at room temperature. 10.0 g (0.225 mol) of 6FDA was added to the solution to completely dissolve 6FDA for 10 minutes. The concentration of the solid was 20% by weight, and the solution was stirred at room temperature for 1 hour. To obtain a polyamic acid resin having a viscosity of 40 cps at 23 占 폚.

Acetic anhydride (AA) as a chemical hardener and 0.5 mol of pyridine as an imidation catalyst are added to the polyamic acid solution, and then the polyamic acid solution is imidized by stirring at 80 ° C for 1 hour. The imidized mixture (30 g) was added to 300 g of water and precipitated. The precipitated solid was filtered and pulverized to fine powder, which was then dried in a vacuum drying oven at 100 ° C. for 18 hours to give a weight average molecular weight of about 18 g / mol. < / RTI >

Example  3.

N, N-dimethylacetamide (DMAc) (76.61 g) was charged into a 100 ml 3-neck round bottom flask equipped with a nitrogen inlet, a dropping funnel, a temperature controller and a condenser while passing nitrogen through the flask. To this solution, 8.24 g (0.2250 mol) of bis-AP-AF and 0.62 g (0.025 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved and kept at room temperature. 10.0 g (0.225 mol) of 6FDA was added to the solution to completely dissolve 6FDA for 10 minutes. The concentration of the solid was 20% by weight, and the solution was then stirred at room temperature for 3 hours. A polyamic acid resin having a viscosity of 43 cps at 23 占 폚 was obtained.

Acetic anhydride (AA) as a chemical hardener and 0.5 mol of pyridine as an imidation catalyst are added to the polyamic acid solution, and then the polyamic acid solution is imidized by stirring at 80 ° C for 1 hour. 30 g of the imidized mixture was added to 300 g of water and precipitated. The precipitated solid was filtered and pulverized to fine powder, and dried in a vacuum drying oven at 100 캜 for 18 hours to obtain a solution having a weight average molecular weight of 20,000 g / mol. < / RTI >

Example  4.

N, N-dimethylacetamide (DMAc) (76.61 g) was charged into a 100 ml 3-neck round bottom flask equipped with a nitrogen inlet, a dropping funnel, a temperature controller and a condenser while passing nitrogen through the flask. 7.78 g (0.2125 mol) of bis-AP-AF and 0.93 g (0.0375 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in the solution and kept at room temperature. 10.0 g (0.225 mol) of 6FDA was added to the solution to completely dissolve 6FDA for 10 minutes. The concentration of the solid was 20% by weight, and the solution was then stirred at room temperature for 3 hours. To obtain a polyamic acid resin having a viscosity of 40 cps at 23 占 폚.

Acetic anhydride (AA) as a chemical hardener and 0.5 mol of pyridine as an imidation catalyst are added to the polyamic acid solution, and then the polyamic acid solution is imidized by stirring at 80 ° C for 1 hour. 30 g of the imidized mixture was added to 300 g of water and precipitated. The precipitated solid was filtered and pulverized to fine powder, and dried in a vacuum drying oven at 100 캜 for 18 hours to obtain a solution having a weight average molecular weight of 20,000 g / mol. < / RTI >

Comparative Example  One.

N, N-dimethylacetamide (DMAc) (76.61 g) was charged into a 100 ml 3-neck round bottom flask equipped with a nitrogen inlet, a dropping funnel, a temperature controller and a condenser while passing nitrogen through the flask. To this solution was dissolved 9.16 g (0.25 mol) of Bis-AP-AF. 10.0 g (0.225 mol) of 6FDA was added to the solution to completely dissolve 6FDA for 10 minutes. The concentration of the solid was 20% by weight, and the solution was then stirred at room temperature for 3 hours. A polyamic acid resin having a viscosity of 43 cps at 23 占 폚 was obtained.

Acetic anhydride (AA) as a chemical hardener and 0.5 mol of pyridine as an imidation catalyst are added to the polyamic acid solution, and then the polyamic acid solution is imidized by stirring at 80 ° C for 1 hour. The imidized mixture (30 g) was added to 300 g of water and precipitated. The precipitated solid was filtered and pulverized to fine powder and dried in a vacuum drying oven at 100 ° C. for 18 hours to obtain a solution having a weight average molecular weight of 22,000 g / mol. < / RTI >

Comparative Example  2.

N, N-dimethylacetamide (DMAc) (76.61 g) was charged into a 100 ml 3-neck round bottom flask equipped with a nitrogen inlet, a dropping funnel, a temperature controller and a condenser while passing nitrogen through the flask. 9.06 g (0.2475 mol) of bis-AP-AF and 0.06 g (0.0025 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in the solution and kept at room temperature. 10.0 g (0.225 mol) of 6FDA was added to the solution to completely dissolve 6FDA for 10 minutes. The concentration of the solid was 20% by weight, and the solution was then stirred at room temperature for 3 hours. To obtain a polyamic acid resin having a viscosity of 42 cps at 23 占 폚.

Acetic anhydride (AA) as a chemical hardener and 0.5 mol of pyridine as an imidation catalyst are added to the polyamic acid solution, and then the polyamic acid solution is imidized by stirring at 80 ° C for 1 hour. The imidized mixture (30 g) was added to 300 g of water and precipitated. The precipitated solid was filtered and pulverized to fine powder, which was then dried in a vacuum drying oven at 100 ° C. for 18 hours to give a weight average molecular weight of about 18 g / mol. < / RTI >

Comparative Example  3.

N, N-dimethylacetamide (DMAc) (76.61 g) was charged into a 100 ml 3-neck round bottom flask equipped with a nitrogen inlet, a dropping funnel, a temperature controller and a condenser while passing nitrogen through the flask. 7.36 g (0.2 mol) of bis-AP-AF and 1.24 g (0.05 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in the solution and kept at room temperature. 10.0 g (0.225 mol) of 6FDA was added to the solution to completely dissolve 6FDA for 10 minutes. The concentration of the solid was 20% by weight, and the solution was then stirred at room temperature for 3 hours. To obtain a polyamic acid resin having a viscosity of 42 cps at 23 占 폚.

Acetic anhydride (AA) as a chemical hardener and 0.5 mol of pyridine as an imidation catalyst are added to the polyamic acid solution, and then the polyamic acid solution is imidized by stirring at 80 ° C for 1 hour. The imidized mixture (30 g) was added to 300 g of water and precipitated. The precipitated solid was filtered and pulverized to fine powder, which was then dried in a vacuum drying oven at 100 ° C. for 18 hours to give a weight average molecular weight of about 18 g / mol. < / RTI >

≪ Preparation of Photosensitive Resin Composition &

Example  5.

12% by weight of the alkali-soluble polyamic acid-polyimide copolymer resin of Example 1, 0.1 part by weight of a diazide photosensitive compound ((1- [1- (4- hydroxyphenyl) isopropyl] -4- [ (4-hydroxyphenyl) ethyl] benzene) -1,2-naphthoquinonediazide-5-sulfonate), 6% 1.5 wt% of [1, 1 -bis (4-hydroxyphenyl) ethyl] benzene, 80 wt% of propylene glycol monomethyl ether acetate as a solvent, and 0.5 wt% of a silicon additive used as a leveling agent Lt; / RTI > for 1 hour to prepare a positive photosensitive resin composition.

Example  6-8.

Using the alkali-soluble polyamic acid-polyimide copolymer resins of Examples 2, 3 and 4, positive-working photosensitive resin compositions of Examples 6, 7 and 8 were prepared in the same manner as in Example 5.

Comparative Example  4-6.

The positive photosensitive resin compositions of Comparative Examples 4, 5 and 6 were prepared in the same manner as in Example 5 using the alkali soluble polyamic acid-polyimide copolymer resins of Comparative Examples 1, 2 and 3.

≪ Preparation of insulating film &

Example  9.

The positive photosensitive resin composition of Example 5 was spin-coated on a bare glass substrate and preliminarily heat-treated for 120 seconds on a hot plate at 120 ° C to form a coating film having a thickness of 2.7 ± 0.05 μm. The substrate was irradiated with G, H, and I mixed ultraviolet rays using a hole photomask having a CD 8 μm size, developed with a 2.38% TMAH alkali developer for 70 seconds, and rinsed for 40 seconds to leave only unexposed portions to form a circuit . When the electron microscope was used, the exposure amount at which the hole size was 8 mu m was determined based on the appropriate exposure amount. Thereafter, it was heated on a hot plate at 230 캜 for 1 hour to form an insulating film having a final thickness of 2.0 탆.

Example  10-12.

Using the positive photosensitive resin compositions of Examples 6, 7 and 8, insulating films of Examples 10, 11 and 12 having a final thickness of 2.0 占 퐉 were prepared in the same manner as in Example 9.

Comparative Example  7-9.

Using the positive photosensitive resin compositions of Comparative Examples 4, 5, and 6, insulating films of Comparative Examples 7, 8, and 9 having a final thickness of 2.0 탆 were prepared in the same manner as in Example 9.

≪ Preparation of organic light emitting device &

The manufacturing process of the organic light emitting device was performed according to a method commonly used in this field.

Example  13.

Barrier ribs were formed on the insulating film layer prepared in Example 9. [ An organic thin film was deposited on the barrier rib in the order of an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, and a hole injection layer. And a metal electrode (Al) layer was deposited thereon to prepare an organic light emitting device.

Example  14-16

Using the insulating films of Examples 10, 11, and 12, organic light emitting devices of Comparative Examples 14, 15, and 16 were produced in the same manner as in Example 13.

Comparative Example  10-12

Using the insulating films of Comparative Examples 7, 8, and 9, organic light emitting devices of Comparative Examples 10, 11, and 12 were produced in the same manner as in Example 13.

Experimental Example  One. Residue  evaluation

The positive photosensitive resin compositions prepared in Examples 5 to 8 and Comparative Examples 4 to 6 were spin-coated on a bare glass substrate, preliminarily heat-treated for 120 seconds on a hot plate at 120 ° C, To form a coating film. The above substrate was irradiated with G, H, I mixed optical ultraviolet rays using a stripe photomask having a CD 30 μm (Line: Space = 30: 30) size. It was then developed with 2.38% TMAH alkaline developer for 70 seconds and rinsed for 40 seconds. A circuit is formed by leaving only the unexposed portion. The circuit was observed with an SEM to determine the degree of residue on the developed portion. If there is no residue, it is indicated as 'X', and if residue is 'O'.

Experimental Example  2. Adhesion evaluation

The positive photosensitive resin compositions prepared in Examples 5 to 8 and Comparative Examples 4 to 6 were prepared as in Experimental Example 1. SEM observation was performed to confirm that the CD 30 μm line portion remained.

Example 5 Example 6 Example 7 Example 8 Comparative Example 4 Comparative Example 5 Comparative Example 6 Residual occurrence X X X X X X O Adhesion O O O O X X O

In Examples 5 to 8 using an alkali soluble polyamic acid-polyimide copolymer resin mixed at a molar ratio of 1: 0.02 to 0.23: 0.8 to 1.2 in the formulas 1, 2 and 3, a high-resolution pattern having excellent adhesion without residue on bare glass Respectively. In Comparative Examples 4 and 5, it was confirmed that the pattern of the CD 30 μm line b portion was lost on the bare glass. In Comparative Example 6, the pattern of the CD 30 μm line b portion was formed on the bare glass, Respectively.

Experimental Example  3. Sensitivity evaluation

The sensitivity of the insulating films of Examples 9 to 12 and Comparative Examples 7 to 9 was measured.

Experimental Example  4. Evaluation of dielectric constant

A metal electrode (Al) was deposited to a thickness of 2,000 Å on the insulating films prepared in Examples 9 to 12 and Comparative Examples 7 to 9 using a thermal evaporator Model E306. The permittivity was measured using a Precision Impedance Analyzer (Model: 4294A, HP).

Experimental Example  5. Evaluation of light transmittance

The light transmittance of the insulating films of Examples 9 to 12 and Comparative Examples 7 to 9 at a wavelength of 550 nm was measured using a magnetic spectrophotometer (shimadzu, Model UV-3101PC).

Example 9 Example 10 Example 11 Example 12 Comparative Example 7 Comparative Example 8 Comparative Example 9 Sensitivity
(mJ / cm ² ) 35 35 35 40 30 35 40 permittivity 3.5 3.4 3.5 3.5 3.4 3.4 3.6 Light transmittance (%) 96 96 97 97 96 96 95

Examples 9 to 12 using an alkali-soluble polyamic acid-polyimide copolymer resin in which the molar ratios of formulas 1, 2 and 3 were mixed in the range of 1: 0.02 to 0.23: 0.8 to 1.2 and the insulating films of Comparative Examples 7 to 9 Showed a high sensitivity and a dielectric constant of 3 or more and 4 or less and excellent light transmittance.

Experimental Example  6. Leakage current measurement

The amounts of leakage currents through the current flow of the organic light emitting devices of Examples 13 to 16 and Comparative Examples 10 to 12 were measured using a leakage current meter.

Experimental Example  7. Luminance evaluation

The luminance of the organic light emitting devices of Examples 13 to 16 and Comparative Examples 10 to 12 was measured using a luminance meter.

Example 13 Example 14 Example 15 Example 16 Comparative Example 10 Comparative Example 11 Comparative Example 12 Leakage current
(nA) 350.3 360.1 356.2 356.2 Not measurable Not measurable Not measurable Luminance
(cd / m ² ) 524.2 516.5 520.3 520.3 Not measurable Not measurable Not measurable

The organic luminescent devices of Examples 13 to 16 showed excellent values in both leakage current and luminance. On the other hand, the organic light emitting devices of Comparative Examples 10 to 12 were unable to measure leakage current and luminance.

Therefore, in the present invention, the positive photosensitive resin using the alkali soluble polyamic acid-polyimide copolymer resin mixed at the molar ratio of 1: 0.02-0.23: 0.8-1.2 of the formulas 1, 2 and 3 does not generate residue, And shows excellent leakage current values and luminance values.

Claims (14)

A positive photosensitive resin composition comprising an alkali soluble polyamic acid-polyimide copolymer resin, a diazide photosensitive compound, a sensitivity enhancer and a solvent, wherein the alkali soluble polyamic acid-polyimide copolymer resin comprises a diamine , The diamine represented by the general formula (2) and the dianhydride represented by the general formula (3) in a molar ratio of 1: 0.02 to 0.23: 0.8 to 1.2.
[Chemical Formula 1]

(2)

(3)

The positive photosensitive resin composition according to claim 1, wherein the positive photosensitive resin composition comprises 30 to 80 parts by weight of a diazide photosensitive compound and 3 to 15 parts by weight of a sensitivity enhancer based on 100 parts by weight of an alkali soluble polyamic acid-polyimide copolymer resin, Wherein the positive photosensitive resin composition comprises 70 to 90% by weight of a solvent based on the total weight of the photosensitive resin composition. The positive photosensitive resin composition according to claim 1, wherein the alkali-soluble polyamic acid-polyimide copolymer resin has a weight average molecular weight of 15,000 to 30,000, which is defined in terms of equivalent polystyrene equivalent. The polyamic acid-polyimide resin composition according to claim 1, wherein the polyamic acid-polyimide copolymer resin
a) preparing a polyamic acid solution by dissolving 5 to 50% by weight of a mixture of Formulas 1, 2 and 3 in a molar ratio of 1: 0.02 to 0.23: 0.8 to 1.2 in 50 to 95% by weight of a first solvent;
b) partially imidizing the polyamic acid solution with a chemical hardener and an imidization catalyst; And
c) adding a second solvent having a lower polarity than that of the first solvent to the polyamic acid solution of the step b) in an amount of 5 to 20 parts by weight based on the polyamic acid solution, and drying the resultant. The method of claim 4, wherein the first solvent is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), dimethylsulfoxide (DMSO) Diethylacetate, and at least one selected from the group consisting of tetrahydrofuran (THF), chloroform and? -Butyrolactone. The positive photosensitive resin composition according to claim 4, wherein the viscosity of the polyamic acid solution in step b) ranges from 20 to 100 cps. [4] The method of claim 4, wherein the chemical curing agent comprises at least one selected from the group consisting of acetic anhydride (AA), phthalic anhydride (PA), tetrahydrophthalic anhydride (THPA) and methyltetrahydrophthalic anhydride (MTHPA) By weight based on the total weight of the positive photosensitive resin composition. 5. The positive photosensitive resin composition according to claim 4, wherein the imidization catalyst comprises at least one selected from the group consisting of isoquinoline,? -Picoline, pyridine, triethylamine and dimethylaniline. [Claim 4] The positive photosensitive resin composition according to claim 4, wherein the second solvent comprises at least one selected from the group consisting of water, alcohols, ethers and ketones. The photosensitive resin composition according to claim 1, wherein the diazide photosensitive compound is 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4- Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate and (1- [1- (4-hydroxyphenyl) isopropyl] -4- [ ) Ethyl] benzene) -1,2-naphthoquinonediazide-5-sulfonate. The positive photosensitive resin composition according to claim 1, [2] The composition of claim 1, wherein the sensitivity enhancer is 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone and 1- [1- (4- ] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene. The method of claim 1, wherein the solvent is selected from the group consisting of ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, acetone, At least one compound selected from the group consisting of alcohols, methyl alcohol, propyl alcohol, isopropyl alcohol, benzene, toluene, cyclopentanone, cyclohexanone, ethylene glycol, xylene, ethylene glycol monoethyl ether and diethylene glycol monoethyl ether Wherein the positive photosensitive resin composition is a positive photosensitive resin composition. An insulating film formed from the positive photosensitive resin composition of claim 1. An organic light emitting device comprising the insulating film of claim 13.

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