KR20160073711A

KR20160073711A - Positive-type photoresist composition, insulating film and OLED comprising the same

Info

Publication number: KR20160073711A
Application number: KR1020140182345A
Authority: KR
Inventors: 박세형; 김병기; 하지민
Original assignee: 코오롱인더스트리 주식회사
Priority date: 2014-12-17
Filing date: 2014-12-17
Publication date: 2016-06-27

Abstract

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.

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,

Recently, in the display field, it is in the trend to enlarge the existing small and medium-sized products through the construction of the large-area production line and the enlargement of the production panel area. Organic light emitting diodes (OLEDs), which have been developed following conventional liquid crystal displays (LCDs), have emerged as a new alternative in the large TV market based on their technological capabilities in the small handset market. In the organic light emitting device, an organic light emitting material is used to form a thin film between two electrodes. When current is applied to both electrodes, electrons and holes, which are carriers in the anode and the cathode, are injected into the organic thin film layer. Is emitted in the form of light. It utilizes the characteristic that organic matter emits light when voltage is applied, and it implements color tone by using red, green, and blue emitting characteristics according to organic matter. One example of a method of manufacturing an organic light emitting device includes forming a thin film transistor on a transparent substrate on which a transparent electrode such as ITO is deposited and applying a photoresist to the organic thin film transistor through a process such as coating, exposure, development, etching, An insulating film is formed and a barrier rib is formed on the insulating film pattern. After the above operation, 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 a metal electrode layer is deposited thereon. Finally, after sealing through the sealing material, the module is assembled to fabricate the organic light emitting device. In the organic insulating film patterning process as described above, a liquid positive photosensitive resin composition is generally dropped on a substrate, and the entire surface of the substrate is coated by spin coating or the like, followed by preliminary heat treatment and exposure to form a circuit. The insulating layer is formed to a thickness of 2000 to 2800 Å in order to prevent deterioration of the edge of the transparent electrode and to prevent a vertical short.

On the other hand, the key technology for the enlargement of organic light emitting devices is the ability to realize a thin film transistor (TFT), and a rapid decrease in yield is caused by the low temperature polycrystalline silicon (LTPS) used in the conventional small thin film transistor An oxide thin film transistor (oxide TFT) in which indium (In), gallium (Ga), and zinc (Zn) are combined has actively been developed. The oxide thin film transistor has a higher electron mobility than the amorphous silicon (a-Si) used as a thin film transistor material of an LCD, has a higher yield than the polycrystalline silicon, The existing amorphous silicon equipment can be utilized as it is, and the initial investment cost is relatively small. Most of the oxide thin film transistors are fabricated through 4 to 6 steps. First, a gate electrode is deposited and patterned. Then, a gate insulating film and amorphous silicon are deposited. Then, a source electrode and a drain electrode are deposited and patterned on the gate insulating film and the amorphous silicon. Thereafter, a protective film is applied and a hole forming operation is performed, and then a pixel electrode is deposited and patterned. And the organic insulating layer material is patterned to divide the boundary between the color elements when the organic light emitting device is deposited on the organic light emitting layer and to prevent a short circuit between the electrodes.

However, the oxide thin film transistor has a fatal weak point in that the threshold voltage variation due to light irradiation occurs and image quality is deteriorated, and development of a polyimide material as an organic insulating film material that blocks such light irradiation is required. The polyimide resin is excellent in heat resistance, chemical resistance, and thermal oxidation resistance, and can be used as an electrode protecting film for an ultra-thin liquid crystal display (TFT-LCD), an insulating film of an organic light emitting element, Have been used in a wide range of fields.

In the initial polyimide resin, a method of simply coating a photoresist on the upper surface to form a pattern and etching it is used, but a photoresist-based lithography process is omitted while using a photosensitive polyimide having a photosensitive function added to the polyimide itself, Simplify and improve productivity. The polyimide resin is generally prepared by polymerizing an aromatic diamine and an aromatic dianhydride to prepare a polyamic acid derivative, followed by cyclodehydration at a high temperature, followed by imidization. As the aromatic diamine component, oxydianiline (ODA), m-phenylenediamine (m-PDA), bisaminophenylhexafluoropropane (HFDA) and methylene dianiline (MDA) are mainly used for producing polyimide resin (PMDA), biphenyltetracarboxylic dianhydride (BPDA), and oxytocetallic dianhydride (ODPA) are mainly used as the aromatic dianhydride components.

The conventional oxide thin film transistor has a fatal weak point that a threshold voltage variation due to light irradiation occurs and image quality is deteriorated and development of a polyimide material as an organic insulating film material to block such light irradiation is required.

Accordingly, it is an object of the present invention to provide a positive photosensitive resin composition containing a specific compound and having excellent light blocking effect. Another object of the present invention is to provide a positive-working photosensitive resin composition having improved light-shielding ability in a short-wavelength region when a thin film is coated. In addition to this, it is an object of the present invention to provide a positive photosensitive resin composition which maintains a constant pattern development property.

In order to achieve the above object, the present invention provides a positive photosensitive resin composition comprising an alkali soluble polyimide resin, a diazide photosensitive compound, a sensitivity enhancer, a solvent, and a compound represented by the following general formula (1).

[Chemical Formula 1]

According to a preferred embodiment of the present invention, when the thickness of the coating film formed of the positive photosensitive resin composition is 2.0 to 2.8 μm, the light transmittance in the light wavelength region of 400 nm or less is 5 to 10% . The compound represented by Formula 1 may include 180 to 230 parts by weight based on 100 parts by weight of the alkali-soluble polyimide resin.

Another aspect of the present invention provides an insulating film formed from the positive photosensitive resin composition of the present invention. The present invention also provides an organic light emitting device including the insulating film of the present invention.

The present invention can provide a positive photosensitive resin composition.

The positive photosensitive resin composition provided in the present invention can exhibit excellent light diffusibility in a short wavelength region. In addition to this, it maintains high sensitivity in view of developability, and thus can be usefully used for forming insulating films and organic light emitting devices.

1 is a graph of light transmittance measured in Experimental Example 1-1.
2 is a SEM photograph of Experimental Example 1-2.

Hereinafter, the present invention will be described in detail. The following detailed description is merely an example of the present invention, and therefore, the present invention is not limited thereto.

Thus, the present inventors confirmed that the light blocking degree was remarkably improved by incorporating a specific compound into the positive photosensitive resin composition, and thus the present invention was completed.

That is, the present invention provides a positive photosensitive resin composition comprising an alkali soluble polyimide resin, a diazide photosensitive compound, a sensitivity enhancer, a solvent, and a compound represented by the following formula (1).

[Chemical Formula 1]

According to a preferred embodiment of the present invention, when the thickness of the coating film formed of the positive photosensitive resin composition is 2.0 to 2.8 μm, the light transmittance in the light wavelength region of 400 nm or less is 5 to 10% It can be possible.

Hereinafter, the positive photosensitive resin composition of the present invention will be described.

First, the alkali-soluble polyimide resin will be described.

In the present invention, the alkali-soluble polyimide resin is a binder resin constituting the skeleton of the coating film, and may be prepared by mixing an aromatic diamine and an aromatic dianhydride at a molar ratio of 1: 0.8 to 1: 0.9. That is, according to one preferred embodiment of the present invention, the alkali-soluble polyimide resin is prepared by a) mixing 5 to 50% by weight of a mixture of aromatic diamine and aromatic dianhydride in a molar ratio of 1: 0.8 to 0.9, To 95% by weight to prepare a polyamic acid solution; b) Imidizing the polyamic acid solution with a chemical curing agent and an imidization catalyst; And c) adding a second solvent having a lower polarity than the first solvent in an amount of 200 to 1000 parts by weight based on 100 parts by weight of the polyamic acid solution to the polyamic acid solution in step b), and drying.

Specifically, the reaction conditions are not particularly limited, but it is preferable to stir at a temperature of -20 to 80 ° C for 1 to 48 hours. Further, it is preferable that the reaction atmosphere is an inert atmosphere such as argon or nitrogen. The alkali-soluble polyimide resin is prepared by mixing an aromatic diamine and an aromatic dianhydride in a molar ratio of 1: 0.8 to 1: 0.9. If the molar ratio of the aromatic dianhydride is less than 0.8, the imidization degree is lowered to lower the dielectric constant and the leakage current characteristic. If the molar ratio exceeds 0.9, the imidization degree increases and the solution uniformity and resolution are lowered.

According to a preferred embodiment of the present invention, the aromatic diamine is 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (Bis-AP- -Bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-TFDB (2-aminophenoxy) ), 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (3,3'-TFDB), 4,4'-bis (3-aminophenoxy) diphenyl sulfone (DBSDA), bis (3-aminophenyl) sulfone (3DDS), bis (4-aminophenyl) sulfone (4DDS), 1,3- 3-aminophenoxy) benzene (APB-134), 2,2'-bis [3- (3-aminophenoxy) phenyl] hexafluoropropane (3-BDAF), oxydianiline (ODA) 4,4'-oxydianiline (the following formula 2), 3,4'-oxydianiline (the formula 3), 4,4'-diaminodiphenyl sulfone (the formula 4), 3,3'- (5) and 2,2'-bis [4 (4-aminophenoxy ) Phenyl] hexafluoropropane (4-BDAF, the following formula (6)), and may contain at least one selected from the group consisting of 2,2-bis (3-amino-4- -Hydroxyphenyl) -hexafluoropropane (Bis-AP-AF) is preferably used. The chemical structure of some of the above compounds is as follows:

According to a preferred embodiment of the present invention, the aromatic dianhydride is selected from the group consisting of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanediamine hydride (6FDA, , 5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA), 4,4 '- (4'-oxy dipyridyl dianhydride) (ODPA), 3,3 ', 4', 4'- 4'-diphenylsulfone tetracarboxylic dianhydride, 3,4,3 ', 4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydipthalic dianhydride (8), 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride (9) and 3,3', 4,4'-biphenyltetracarboxylic dianhydride ( (10) < / RTI > < RTI ID = 0.0 > (3,4-dicarboxyphenyl) hexafluoropropanediamine hydrate (6FDA) having excellent light transmittance and heat resistance is preferably used. The chemical structure of some of the above compounds is as follows:

In addition, in the step a), the first solvent is not particularly limited as long as it is a solvent dissolving the polyamic acid, but preferably N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide DMAc), dimethylsulfoxide (DMSO), acetone, diethyl acetate, tetrahydrofuran (THF), chloroform, and γ-butyrolactone. 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 30 to 100 cps, preferably 30 to 50 cps. When the viscosity is less than 30 cps, the polymerization reaction time through the chemical imidation method is slowed to decrease the resin yield and photosensitivity. When the viscosity exceeds 100 cps, the weight average molecular weight of the polyimide resin increases to over 40,000, making it difficult to realize a high sensitivity pattern.

In the step b), the polyimic acid solution is imidized using a chemical imidation 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. The step b) is preferably carried out at 60 to 80 ° C for 1 to 3 hours in order to achieve a uniform and stable reaction.

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 200 to 1,000 parts by weight based on 100 parts by weight of the polyamic acid solution in the step b). If the amount of the second solvent is less than 200 parts by weight, precipitation and purification may not be performed. If the amount of the second solvent is more than 1,000 parts by weight, it takes a long time for dewatering and drying after the precipitation.

In the step c), the polyimide resin prepared in step b) is filtered, and then the polyimide resin is filtered at a temperature of 80 to 100 ° C in consideration of the boiling point of the first solvent remaining in the second solvent and the solidified polyimide resin It is preferable to dry for 2 to 10 hours. If the temperature is lower than 80 ° C, the imidization degree is lowered to lower the dielectric constant and the leakage current characteristic. If the temperature exceeds 100 ° C, the imidization degree increases and the resolution and transmittance decrease.

Meanwhile, 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 polyimide resin prepared by steps a), b) and c) is 10,000 to 40,000 based on the GPC measurement method. When the weight-average molecular weight is within the above range, good resolution can be achieved during patterning.

Next, the compound represented by the above formula (1) will be described.

The compound represented by the formula (1) of the present invention plays a role of improving the light blocking rate and forming a pattern by exposure when a coating film is formed using the positive photosensitive resin composition of the present invention.

The compound represented by Formula 1 may be contained in an amount of 180 to 230 parts by weight based on 100 parts by weight of the alkali-soluble polyimide resin. If the content is less than 180 parts by weight, there is a problem that the light-blocking rate is lowered and the performance of the light emitting device is deteriorated. If the amount is more than 230 parts by weight, stability of the solution is deteriorated and pattern formation by the developer is not carried out. Therefore, the above range is preferable.

The following diazide-based photosensitive compounds will be described.

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.

The diazide-based photosensitive compound can be synthesized by an esterification reaction of a quinonediazide sulfonic acid compound and a polyhydroxy compound. 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.

Specifically, in the esterification reaction for obtaining the diazide-based photosensitive compound, the polyhydroxy compound and the quinonediazide sulfonic acid compound are reacted with a compound represented by the following formula: dioxane, acetone, tetrahydrofuran, methyl ethyl ketone, N-methylpyrrolidone, Followed by condensation by adding a basic catalyst such as ethylamine, N-methylmorpholine, N-methylpiperazine and 4-dimethylaminopyridine, and then washing, purifying and drying the obtained product. And the diazide-based photosensitive compound obtained from the quinone diazide sulfonic acid compound and the polyhydroxy compound in the method described above is 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide 5-sulfonate, and (1- [1- (4-hydroxyphenyl) isopropyl] -2-naphthoquinone diazide- And 4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene) -1,2-naphthoquinonediazide-5-sulfonate, and the like.

According to a preferred embodiment of the present invention, 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 polyimide resin. If the amount of the diazide-based photosensitive compound is less than 30 parts by weight, the resolution may be lowered and residues may be generated. On the other hand, if it exceeds 80 parts by weight, the solubility of the crude liquid deteriorates, which makes long-term storage difficult and lowers the transmittance. Therefore, the above range is preferable.

Next, the sensitivity enhancer will be described.

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. According to a preferred embodiment of the present invention, in the positive photosensitive resin composition, the sensitivity enhancer is included in an amount of 20 to 40 parts by weight based on 100 parts by weight of the alkali-soluble polyimide resin. And a high margin can be obtained in the window process.

Next, the solvent contained in the positive-working photosensitive resin composition may be any generally usable. Preferably, 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, methyl alcohol, And at least one selected from the group consisting of isopropyl alcohol, benzene, toluene, cyclopentanone, cyclohexanone, ethylene glycol, xylene, ethylene glycol monoethyl ether and diethylene glycol monoethyl ether. According to a preferred embodiment of the present invention, the solvent may include 70 to 90% by weight of a solvent based on the total weight percentage of the positive photosensitive resin composition.

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

Another aspect of the present invention provides an insulating film formed from the positive photosensitive resin composition of the present invention. The insulating film has excellent light barrier properties, pattern developability and high insulation resistance due to the improved alkali-soluble polyimide resin.

According to one preferred embodiment of the present invention, the positive photosensitive resin composition preferably has a The thickness may be between 2 and 2.8 mu m. It is preferable that the dielectric constant of the insulating film formed to the above thickness is 4 or less.

A method of manufacturing the insulating film is described below, for example.

The positive photosensitive resin composition of the present invention is applied to the surface of the substrate to a thickness of 2 to 2.8 mu m using a spin coater. Then, preliminary heat treatment is performed at 90 to 120 DEG 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 2.38% by weight of TMAH (Tetra methyl ammonium hydroxide) Containing aqueous TMAH solution is used. The development is carried out with the aqueous alkali solution for 60 to 180 seconds. Thereafter, the pattern is subjected to a post-heat treatment using a hot plate at 120 to 190 ° C for 4 to 60 minutes to form an insulating film.

Another aspect of the present invention provides an organic light emitting device including an insulating film of the present invention. Specifically, the organic light emitting device is patterned by patterning a photoresist on a transparent substrate having a transparent electrode deposited thereon through coating, exposure, development, etching, peeling, and the like, Thereby forming a barrier rib. 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.

On the other hand, if the light transmittance of the organic light emitting diode is higher than 10% at a wavelength of 400 nm, the performance of the oxide thin film transistor in the organic light emitting diode structure is degraded. If the light transmittance is lower than 5%, the sensitivity is lowered in the photolithography process However, there may arise a problem of deteriorating the insulating property.

Therefore, the organic light-emitting device of the present invention can solve the above-mentioned problem because the light transmittance is 5 to 10% in a short wavelength region (400 nm or less).

As a result, the positive photosensitive resin composition of the present invention exhibits insoluble or poorly soluble characteristics with respect to the alkali developer due to the dissolution-inhibiting action of the diazide-based photosensitive compound before exposure, and the diazide-based photosensitive compound is changed by exposure to change the alkali developer Which is a positive type which changes in characteristics to be dissolved with respect to the solution. 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 more detail with reference to examples. However, the embodiments of the present invention described below are illustrative only and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

Preparation Example : Alkali soluble polyimide resin polymerization

72.20 g of N, N-dimethylacetamide (DMAc) 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 nitrogen was passed through the reactor, 0.0 > 0 C. < / RTI > 9.16 g (0.25 mol) of 2,2-bis (3-amino-4-hydroxylphenyl) hexafluoropropane (hereinafter referred to as Bis-AP-AF) was dissolved as an aromatic diamine in the above solution, 0 < 0 > C. To this solution was added 8.89 g (0.2 mol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (hereinafter referred to as 6FDA) as an aromatic dianhydride and stirred for 1 hour To completely dissolve 6FDA. 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 curing agent and pyridine as an imidation catalyst were added in an amount of 2 equivalents to 90.25 g of the polyamic acid resin, and then the polyamic acid resin was imidated 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 DEG C for 6 hours to obtain a solution having a weight average molecular weight of about 20 g / mol. < / RTI >

Example 1: Preparation of positive photosensitive resin composition

Example 1-1

The diazide photosensitive compound ((1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4 (4-hydroxyphenyl) ethyl] benzene) -1,2-naphthoquinonediazide-5-sulfonate), 58 parts by weight of a sensitizer , 30 parts by weight of [1,1-bis (4-hydroxyphenyl) ethyl] benzene), 720 parts by weight of a solvent (propylene glycol monomethyl ether acetate), 180 parts by weight of a compound represented by the following formula And 2.5 parts by weight of a silicon additive used as a photopolymerization initiator were added and stirred for 2 hours to prepare a positive photosensitive resin composition.

[Chemical Formula 1]

Example 1-2

780 parts by weight of a solvent and 230 parts by weight of a compound represented by the general formula (1) were used in the same manner as in Example 1-1.

Example 1-3

710 parts by weight of a solvent, and 170 parts by weight of a compound represented by the formula (1) were used.

Example 1-4

Except that 810 parts by weight of a solvent and 240 parts by weight of a compound represented by the formula (1) were used.

Comparative Example 1-1

180 parts by weight of 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine was used instead of the compound represented by the above formula Was used in the same manner as in Example 1-1.

Comparative Example 1-2

The procedure of Example 1-1 was repeated except that the compound represented by Formula 1 was not used and 180 parts by weight of 2- (2-hydroxyphenyl) -benzotriazole was used.

Comparative Example 1-3

Was prepared in the same manner as in Example 1-1, except that the compound represented by Formula 1 was not used and 180 parts by weight of Black Mill base prepared by the following method was used.

- Black mill base manufacturing

10 parts by weight of red pigment particles (CI Pigment Red 254) in a black mill base stock solution, 10 parts by weight of blue pigment particles (CI Pigment Blue 15: 3) as a solvent were mixed with propylene glycol monoethyl ether acetate as a solvent to prepare a black mill base as a pigment mixing component. , 4 parts by weight of yellow pigment particles (CI Pigment Yellow 139), 4 parts by weight of a pigment dispersant (polyester resin, molecular weight 25,000) and 1 part by weight of a binder resin (polyacrylate resin, molecular weight 7,500) The covariance was mixed. The size of the pigment after dispersion was 100 nm or less.

Experimental Example 1-1 Resolution Measurement

Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-3 The positive photosensitive resin composition was spin-coated on the ITO substrate to a thickness of 4.0 탆. Thereafter, preliminary heat treatment was performed on a hot plate at 120 캜 for 100 seconds and dried to form a coating film having a thickness of 2.7 짹 0.5 탆. The coating film was irradiated with ultraviolet light of 200 mJ / cm ² using a photomask, developed with 2.38% TMAH alkali developer for 70 seconds, and rinsed for 40 seconds. And a circuit with a final thickness of 2.3 mu m was formed. The resolution at this time was observed with an electron microscope. 1 is shown.

Experimental Example 1-2. Residue Measure

Circuits were formed in the same manner as in Experimental Example 1-1 using the positive photosensitive resin compositions prepared in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-3. Then, whether or not development was possible without residue in a resolution pattern of 30 mu m was observed with an electron microscope. If there is no residue, 'X', if there is a partial residue, 'Δ', and if there is residue, 'O'. The results are shown in Table 1.

Example 1-1 Examples 1-2 Example 1-3 Examples 1-4 Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 Resolution (탆) 26 30 24 34 40 42 70 Residual occurrence X X X O O O O

As shown in Table 1, the coating films formed using the positive photosensitive resin compositions of the present invention in Examples 1-1 and 1-2 were able to develop without residue in a resolution pattern of 30 mu m level. This can be seen from the inclusion and content control of the compound represented by the formula (1) contained in the positive-type photosensitive resin composition. On the other hand, in Comparative Examples 1-1 to 1-3, as the residue was generated, the resolution deteriorated remarkably.

Example 2: Insulating film manufacturing

Example 2-1

First, a gate electrode is deposited and patterned on an ITO substrate to manufacture an oxide thin film transistor, and then a gate insulating film and amorphous silicon are deposited. A source electrode and a drain electrode are deposited and patterned on top of the gate electrode. After that, a protective film is applied and a hole forming operation is performed. Then, a pixel electrode is deposited and patterned. A positive photosensitive resin composition of Example 1-1 was spin-coated as an insulating film to a thickness of 4.0 mu m thereon and then subjected to preliminary heat treatment for 100 seconds on a hot plate at 120 DEG C to form a coating film having a thickness of 2.7 +/- 0.05 mu m. A photomask was placed on the substrate and irradiated with ultraviolet rays of 200 mJ / cm ² , and then a 2.38% by weight aqueous TMAH solution was developed with a developing solution for 70 seconds. The developed developer was rinsed for 40 seconds and then heated on a hot plate at 180 DEG C for 1 hour to form an insulating film having a final thickness of 2.3 mu m.

Example 2-2 to 2-4

Using the positive photosensitive resin compositions of Examples 1-2 to 1-4, insulating films of Examples 2-2 to 2-4 were prepared in the same manner as in Example 2-1.

Comparative Example 2-1 to 2-3

Using the positive photosensitive resin compositions of Comparative Examples 1-1 to 1-3, insulating films of Comparative Examples 2-1 to 2-3 were prepared in the same manner as in Example 2-1.

Experimental Example 2-1. Dielectric constant measurement

A metal electrode (Al) was deposited to a thickness of 2,000 Å on the insulating film prepared in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3 using a deposition apparatus (Thermal Evaporator Model E306) . The permittivity was measured using a Precision Impedance Analyzer (Model: 4294A, HP).

All of the dielectric constants of Examples 2-1 to 2-4 were found to be 4 or less, but Comparative Example 2-3 containing black mill base showed a dielectric constant of more than 4.

Example 3: Manufacture of organic light emitting device

Example 3-1

Barrier ribs were formed on the insulating film layer formed on the ITO substrate of Example 2-1. Forming an emission layer by applying an organic material to the barrier ribs, and laminating metal on the emission layer to form an electrode. An organic light emitting device was fabricated by sequentially depositing a thin film of an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, and a hole injection layer, and depositing a metal electrode (Al) layer thereon.

Example 3-2 ~ 3-4

Using the insulating films of Examples 2-2 to 2-4, the organic light emitting devices of Examples 3-2 to 3-4 were produced in the same manner as in Example 3-1.

Comparative Example 3-1 to 3-3

Using the insulating films of Comparative Examples 2-1 to 2-3, organic light emitting devices of Comparative Examples 3-1 to 3-3 were produced in the same manner as in Example 3-1.

Experimental Example 3-1. Light transmittance measurement

The light transmittance of the organic luminescent devices of Examples 3-2 to 3-4 and Comparative Examples 3-1 to 3-3 was measured using a magnetic spectrophotometer (shimadzu, Model UV-3101PC), and Table 2 Respectively.

Experimental Example 3-2. Leakage current measurement

The leakage currents of the organic light emitting devices of Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-3 were measured using a leakage current meter and are shown in Table 2.

Experimental Example 3-3. Luminance measurement

The luminance of the organic light emitting devices of Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-3 was measured using a luminance meter and is shown in Table 2.

Example 3-1 Example 3-2 Example 3-3 Example 3-4 Comparative Example 3-1 Comparative Example 3-2 Comparative Example 3-3 Light transmittance (%) 9.47 5.33 10.77 4.58 73.66 76.50 0.10 Leakage current (nA) 310.5 316.2 408.3 412.0 497.5 452.8 790.2 Brightness (cd / m ² ) 431.5 433.1 318.4 319.3 266.6 250.1 8.3

As shown in Table 2, in Examples 3-1 to 3-4 in which a circuit was formed using the positive photosensitive resin composition of the present invention, a low leakage current and a high luminance value It looked. Particularly, in Examples 3-1 and 3-2, a lower leakage current and a higher luminance value were exhibited due to a light blocking rate of 90% or more.

Claims

An alkali-soluble polyimide resin, a diazide-based photosensitive compound, a sensitivity enhancing agent, a solvent, and a compound represented by the following formula (1).
[Chemical Formula 1]

The method according to claim 1,
Wherein the positive photosensitive resin composition has a light transmittance of 5 to 10% in a light wavelength region of 400 nm or less when the thickness of the coating film formed of the positive photosensitive resin composition is 2.0 to 2.8 mu m.

The method according to claim 1,
Wherein the compound represented by Formula 1 is contained in an amount of 180 to 230 parts by weight based on 100 parts by weight of the alkali-soluble polyimide resin.

The method according to claim 1,
Wherein the diazide-based photosensitive compound is contained in an amount of 30 to 80 parts by weight based on 100 parts by weight of the alkali-soluble polyimide resin,
Wherein the sensitivity enhancer comprises 20 to 40 parts by weight,
Wherein the solvent comprises 70 to 90% by weight based on the total weight percentage of the positive photosensitive resin composition.

The method according to claim 1,
Wherein the alkali-soluble polyimide resin has a weight average molecular weight of 10,000 to 40,000, which is defined in terms of equivalent polystyrene equivalent.

The method according to claim 1,
The alkali-soluble polyimide resin
a) preparing a polyamic acid solution by dissolving 5 to 50% by weight of a mixture obtained by mixing aromatic diamine and aromatic dianhydride in a molar ratio of 1: 0.8 to 0.9 in 50 to 95% by weight of a first solvent;
b) Imidizing the polyamic acid solution with a chemical curing agent and an imidization catalyst; And
c) adding to the polyamic acid solution of step b) a second solvent having a lower polarity than 200 to 1000 parts by weight of the first solvent based on 100 parts by weight of the polyamic acid solution, and drying the polyamic acid solution. A positive photosensitive resin composition.

The method of claim 6,
The aromatic diamine may be selected from the group consisting of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (Bis-AP- ] Propane (6HMDA), 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2,2'-TFDB), 3,3'- ), 4,4'-diaminobiphenyl (3,3'-TFDB), 4,4'-bis (3-aminophenoxy) diphenylsulfone (DBSDA), bis ), Bis (4-aminophenyl) sulfone (4DDS), 1,3-bis (3-aminophenoxy) benzene (APB- ), Hexafluoropropane (3-BDAF), 2,2'-bis [4 (4-aminophenoxy) phenyl] hexafluoropropane (4-BDAF), oxydianiline (ODA), 4,4'-oxydianiline, 3,4'-oxydianiline, 4,4'-diaminodiphenylsulfone, 3,3'- Phenyl sulfone and 2,2'-bis [4 (4-aminophenoxy) phenyl] hexafluoropropane (4-BDAF) Select positive photosensitive resin composition characterized by comprising at least any one.

The method of claim 6,
The aromatic dianhydride may be at least one selected from the group consisting of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanediamine hydrate (6FDA), 4- (2,5-dioxotetrahydrofuran- , 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA), 4,4 '- (4,4'-isopropylidene diphenoxy) bis (phthalic anhydride (HBDA), 3,3 '- (4,4'-oxydiphthalic dianhydride) (ODPA), 3,3', 4,4'-diphenylsulfone tetracarboxylic dianhydride, 3 , 4,3 ', 4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxyl Wherein the positive photosensitive resin composition comprises at least one selected from the group consisting of ricin, anthraquinone, xanthan gum, xanthan gum, xanthan gum, xanthan gum, xanthan gum, xanthan gum, and xanthan gum.

The method of claim 6,
The first solvent is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), acetone, diethyl acetate, tetrahydrofuran ), Chloroform, and? -Butyrolactone,
Wherein the second solvent comprises at least one selected from the group consisting of water, alcohols, ethers, and ketones.

The method of claim 6,
Wherein the viscosity of the polyamic acid solution is 30 to 100 cps.

The method of claim 6,
Wherein the chemical curing agent includes at least one selected from the group consisting of acetic anhydride (AA), phthalic anhydride (PA), tetrahydrophthalic anhydride (THPA), and methyltetrahydrophthalic anhydride (MTHPA)
Wherein the imidization catalyst comprises at least one selected from the group consisting of isoquinoline,? -Picoline, pyridine, triethylamine and dimethylaniline.

The method according to claim 1,
The diazide-based photosensitive compound includes 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, 2,3,4-trihydroxybenzophenone-1 (2-naphthoquinone diazide-5-sulfonate) and (1- [1- (4-hydroxyphenyl) isopropyl] -4- [ -1,2-naphthoquinonediazide-5-sulfonate. The positive photosensitive resin composition according to any one of claims 1 to 5,

The method according to claim 1,
The sensitivity enhancer may be 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. The positive-working photosensitive resin composition according to claim 1,

The method according to claim 1,
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 at least one compound 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 By weight based on the total weight of the 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 15.