KR101102256B1 - Polyimide polymer and Positive polyimide photosensitive resin composition comprising the same - Google Patents

Abstract

The present invention relates to a polyimide-based high molecular compound, and a positive polyimide photosensitive resin composition comprising the same, and in the present invention, solubility in an alkaline developer is satisfied by satisfying a specific repeating unit value during the preparation of the polyimide high-molecular compound. When it is appropriately controlled and included in the photosensitive resin composition, it can maximize sensitivity to 365nm ultraviolet exposure, has high resolution and residual film ratio, and has excellent adhesion to a substrate, and thus is applied to an insulating film of a semiconductor protective film or OLED. It is possible.

Polyimide * Photosensitive * Composition * Developer * Solubility

Description

Polyimide polymer compound and positive polyimide photosensitive resin composition comprising the same {Polyimide polymer and Positive polyimide photosensitive resin composition comprising the same}

The present invention relates to a polyimide polymer compound, a positive photosensitive resin composition containing the same, and a semiconductor protective film and an OLED insulating film made of a polyimide film using the resin composition.

Since polyimide compounds are excellent in thermal stability and excellent in mechanical, electrical, and chemical properties, in recent years, the use of photosensitive insulating films including photosensitive resins including the same has been extended to not only semiconductors but also display fields. Therefore, there is a demand for a polyimide polymer compound having no film reduction or swelling in the formation of fine patterns, which was not required in conventional polyimide photosensitive resins.

On the other hand, as a method of providing photosensitivity to a polyimide resin so that it can be used for the photosensitive resin composition, chemically bonding a crosslinkable functional group to a polyimide precursor, or mixing a crosslinkable monomer has been used.

For example, the polyamic acid, the polyamic acid ester which has an acidic group in a side chain, or the polyimide added the quinonediazide compound, etc. are mentioned.

However, since the polyamic acid has solubility in an alkaline developer is too good, there is a big problem in film reduction during development, it is necessary to add an amine or the like.

In addition, the polyimide or polyamic acid ester having an acid group in the side chain is excellent in terms of resolution and the like, but there is a problem that the acid group remains in the polymer even after curing, resulting in high water absorption of the final cured film or lower alkali resistance.

Therefore, there is an urgent need to develop a polyimide compound having an excellent solubility in an alkaline developer and having excellent developability without film reduction or swelling in forming a fine pattern.

Accordingly, the present invention is to solve the problems that the conventional polyimide has a photosensitive resin composition, an object of the present invention is to provide a polyimide-based polymer compound having high solubility in alkaline developing solution and excellent developability.

Another object of the present invention is to provide a polyimide photosensitive resin composition containing a polyimide polymer compound having the above characteristics.

Further, another object of the present invention is to provide an insulating film or a semiconductor protective film of an OLED containing a photosensitive film obtained from the polyimide photosensitive resin composition.

In the present invention, solubility in an alkaline developer can be properly adjusted by satisfying a specific repeating unit value in preparing a polyimide polymer compound.

The present invention can maximize the sensitivity to 365nm ultraviolet exposure because it is possible to appropriately control the solubility in the alkaline developer by preparing a polyimide-based polymer compound that satisfies a specific repeat unit value, and by including it in the photosensitive resin composition Its high resolution, high residual film ratio and excellent adhesion to the substrate make it applicable to semiconductor protective films and insulating films of OLEDs.

The polyimide polymer compound of the present invention for achieving the above object includes a repeating unit represented by the following formula (1), where m + n is 100, m is 60 to 90, n is 10 to It is characterized by satisfying 40.

Wherein X is the same or different from each other and is a tetravalent aromatic or aliphatic organic group, and Y ₁ and Y ₂ are a divalent aromatic or aliphatic organic group.

In addition, the positive polyimide photosensitive resin composition of the present invention is characterized in that it comprises a polyimide polymer compound represented by the formula (1).

Furthermore, this invention provides the insulating film or semiconductor protective film containing the photosensitive film manufactured from the said positive polyimide photosensitive resin composition.

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

1. Polyimide Polymer Compound

The polyimide polymer compound according to the present invention is represented by the following formula (1).

Formula 1

Wherein X is the same or different from each other and is a tetravalent aromatic or aliphatic organic group, Y ₁ and Y ₂ are a divalent aromatic or aliphatic organic group, and m is 60 to 90 assuming that m + n is 100. And n satisfies 10 to 40.

In the above formula, X is preferably one or more selected from the following substituents.

In the above formula, Y ₁ is a divalent aromatic or aliphatic organic group derived from diamine, and particularly preferably contains a carboxyl group. Examples of the diamine having such a carboxyl group include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,5-bis (4-aminophenoxy) benzoic acid, 4 -(4,6-diamino-2,2-dimethyl-1,3,5-triazin-1 (2H) -yl) benzoic acid , 4,6-diamino-1,3-benzenedicarboxylic acid , 2,5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4 -Amino-3-carboxyphenyl) sulfone, bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-dia Mino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis (4-amino-3-carboxyphenoxy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, Bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane, and 2,2-ratio [4- (4-amino-3-carboxy) phenyl] to one or two or more selected from the group consisting of hexafluoropropane.

In particular, in the present invention, it is more preferable to use one or more selected from the following substituents as Y ₁ .

In the above formula, Y ₂ is a divalent aromatic or aliphatic organic group derived from diamine, and at least one selected from the following substituents is preferable.

Particularly, in the polyimide polymer compound represented by Chemical Formula 1 of the present invention, since the values of m and n have an important meaning, the solubility in the alkaline developer can be adjusted according to the values of the repeating units m and n. That is, when the polyimide polymer compound of the present invention assumes that m + n is 100 as the polyimide copolymer, m is 60 to 90, and n is preferably 10 to 40.

If the value of m exceeds 90, there is a problem in that the solubility in the alkaline developer is too high and the desired pattern does not remain.In addition, when the value of m is less than 60, the solubility in the alkaline developer is too low to form a pattern. There is no problem.

The manufacturing method of the said polyimide high polymer compound of this invention is based on the polymerization method of a normal polyimide type polymer, and is not specifically limited.

Typically, an acid anhydride and a diamine are reacted and polymerized to prepare a polyamic acid as a polyimide precursor, which is then dehydrated and closed to prepare a polyimide polymer.

The acid anhydride is pyromellitic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl Aromatic tetracarboxylic anhydrides, such as the hexafluoro isopropylidene dianhydride, etc. are mentioned. From the viewpoint of solubility, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-hexafluoro And isopropylidene diphthalic anhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic dianhydride and the like are preferable.

Further, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4- Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclo Hexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentane acetic dianhydride, bicyclo [2.2.2] octo-7-ene-2,3,5,6 -Alicyclic tetracarboxylics such as tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornane acetic dianhydride Aliphatic tetracarboxylic dianhydrides such as acid dianhydrides, 1,2,3,4-butanetetracarboxylic dianhydrides It may be water.

The reaction temperature of the acid anhydride and diamine can be selected from -20 to 150 ℃, preferably -5 to 100 ℃.

In the preparation of the polyimide polymer compound of the present invention, the reaction molar ratio of the acid anhydride and diamine is preferably 1: 1 to 5: 4.

In addition, polar solvents used in the reaction of the diamine and the acid anhydride include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, and N-methyl. Caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone and the like are used alone or in combination.

The polyamic acid, which is a precursor of the polyimide thus obtained, is precipitated and separated from a solvent such as methanol or ethanol and recovered.

The obtained polyimide polymer compound preferably has a weight average molecular weight of 15,000 to 80,000.

In addition, its intrinsic viscosity is 0.05 to 0.4 dl / g, preferably 0.1 to 0.35 dl / g, the glass transition temperature is preferably 250 to 350 ℃.

2. Polyimide Photosensitive Resin Composition

The positive polyimide photosensitive resin composition of the present invention includes a polyimide polymer compound represented by Chemical Formula 1, and includes a photosensitive acid generator, an adhesion promoter, a surfactant, and a solvent.

The photosensitive resin composition of the present invention is 1 to 50 parts by weight of a photosensitive acid generator, 0.5 to 10 parts by weight of adhesion promoter, 0.1 to 1 part by weight of surfactant, and 200 to 650 weight of solvent based on 100 parts by weight of the polyimide polymer compound. We include with wealth.

In addition, the polyimide polymer compound of the present invention may contain another polyimide polymer in addition to the polyimide compound represented by the formula (1).

The photosensitive acid generator included in the photosensitive resin composition of the present invention is not particularly limited as long as it is included in a common photosensitive resin composition, and is preferably selected from the following chemical formulas.

In addition, the adhesion promoter is a component having an effect of improving the adhesion to the substrate, for example, a silane coupling agent having a reactive functional group such as a carboxyl group, a metachloroyl group, a vinyl group, an isocyanate group, an epoxy group is preferable. Specifically, trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltri It is at least one selected from the group consisting of methoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, but is not limited thereto.

In addition, the surfactant is a component having the effect of improving the coating property and coating property, uniformity and stain removal on the substrate, and is at least one selected from the group consisting of fluorine-based surfactants, silicone-based surfactants and non-ionic surfactants, It is not limited to this.

In addition, the solvent is not particularly limited as long as it can dissolve the polyimide polymer compound, and examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and N-. Vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl cellosolve, butyl cellosolve, ethyl Carbitol, butylcarbitol, ethylcarbitol acetate, butylcarbitol acetate, ethylene glycol, ethyl lactate, butyl lactate, cyclohexanone, and cyclopentanone.

The positive photosensitive polyimide resin composition of the present invention having the specific composition as described above is applied onto a substrate such as a silicon wafer substrate by using a conventional method such as spin coating, slit spin coating, roll coating, die coating, curtain coating, or the like. It forms through the exposure, and image development process. Exposure and development processes also use the method used at the time of forming the photosensitive layer using a normal photosensitive resin composition, and are not specifically limited.

There is no restriction | limiting in particular as light irradiated from the said light irradiation means in the said exposure process, According to the objective, it can select suitably, Visible light, an electron beam, an X-ray, a laser beam etc. are mentioned from electromagnetic waves and an ultraviolet-ray.

There is no restriction | limiting in particular as a irradiation method of the light by the said light irradiation means, According to the objective, it can select suitably, For example, well-known, such as a high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a cold cathode tube for copiers, an LED, a semiconductor laser, etc. The method of irradiating with the light source of this is mentioned.

The said developing process is a process of exposing the said photosensitive layer by the said exposure process, hardening the exposed area | region of the said photosensitive layer, and developing by removing a non-hardened area | region, and forming a pattern.

There is no restriction | limiting in particular as said developing solution, According to the objective, it can select suitably, For example, the aqueous solution of the hydroxide or carbonate, hydrogencarbonate, ammonia water, a quaternary ammonium salt of alkali metal or alkaline-earth metal, etc. are mentioned preferably. Among these, 0.38-2.39 weight% of tetramethylammonium hydroxide aqueous solution is especially preferable.

The overall process is spin coating the photosensitive composition onto a silicon wafer substrate and prebake at about 120 ° C. for 2 minutes to form a film. The film is exposed to light using a single mask of the i, g, or h lines using a photomask or an ultraviolet light of mixed light, and the exposure amount depends on the thickness of the coated film, but is typically exposed at an energy of 500 to 1000 mJ / cm 2. Let's do it. After the exposure is completed, the pattern is developed using 0.38 to 2.39 wt% aqueous tetramethylammonium hydroxide solution. The development usually proceeds for 30 to 120 seconds, and after the development, it is immersed in deionized water for 10 to 30 seconds and washed. Thereafter, a postbake is performed at 230 ° C. for about 30 to 60 minutes to obtain a desired pattern. Through this process, it can be seen that a positive pattern is formed along a pattern of a photomask on a desired portion.

The thickness of the photosensitive layer of the present invention thus obtained may vary depending on the purpose, but is preferably 0.7 to 10 ㎛, but is not limited thereto.

The positive photosensitive polyimide resin composition of the present invention is not only an interlayer insulating film, a passivation film, a buffer coat film, an insulating film for multilayer printed circuit boards, an insulating film for OLEDs, but also a protective film for thin film transistors for liquid crystal display devices, and electrodes for organic EL devices. It is preferable to use for a protective film, a semiconductor protective film, etc.

Hereinafter, the present invention will be described in more detail with reference to the following Examples, but the present invention is not limited thereto.

Synthetic example  1: Preparation of polyimide polymer compound

3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride as the acid anhydride component, 8.28 g (0.0267 mol), 2.71 g (0.0178 mol) of 3,5-diaminobenzoic acid as the diamine component and 4 0.89 g (0.0045 mole) of 4'-oxydianiline was dissolved in 110 g of NMP and reacted at −10 ° C. for 2 hours.

8.18 g (0.0801 mole) of acetic anhydride and 10.56 g (0.1335 mole) of pyridine were added to the reaction solution, followed by dehydration ring-closure reaction at 120 ° C for 3 hours. Then, the mixture was poured into distilled water, filtered and dried to obtain a weight average molecular weight of 15,500, an intrinsic viscosity of 0.12 dl / g, and a glass transition temperature of 250 ° C. 11 g of a polyimide polymer compound having the same structure and repeating unit as in Chemical Formula 2 was obtained.

Synthetic example  2: Preparation of Polyimide Polymer Compound

8.28 g (0.0267 mol) of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride as an acid anhydride component, 2.03 g (0.0134 mol) of 3,5-diaminobenzoic acid as a diamine component, 4, 1.78 g (0.0089 mol) of 4'-oxydianiline was dissolved in 110 g of NMP and reacted at -10 ° C for 2 hours.

8.18 g (0.0801 mole) of acetic anhydride and 10.56 g (0.1335 mole) of pyridine were added to the reaction solution, followed by dehydration ring-closure reaction at 120 ° C for 3 hours. Then, the mixture was poured into distilled water, filtered and dried to obtain a weight average molecular weight of 16,800, and an intrinsic viscosity of 0.13.

㎗ / g, glass transition temperature is 254 ℃, 11.2 g of a polyimide polymer compound having the same structure and repeating unit as in Formula 3 was obtained.

Synthetic example  3: Preparation of Polyimide Polymer Compound

8.28 g (0.0267 mol) of 3,3 ', 4,4'- diphenyl ether tetracarboxylic dianhydride as an acid anhydride component, 4.51 g of 3,5-bis (4-aminophenoxy) benzoic acid as a diamine component ( 0.0134 mol) and 1.78 g (0.0089 mol) of 4,4'-oxydianiline were dissolved in 110 g of NMP and reacted at -10 ° C for 2 hours.

8.18 g (0.0801 mole) of acetic anhydride and 10.56 g (0.1335 mole) of pyridine were added to the reaction solution, followed by dehydration ring-closure reaction at 120 ° C. for 3 hours. Then, the mixture was poured into distilled water, filtered and dried to obtain a weight average molecular weight of 23,900, an intrinsic viscosity of 0.18 dl / g, a glass transition temperature of 263 ° C, Next, 14 g of a polyimide-based polymer compound satisfying the structure and repeating unit of Formula 4 was obtained.

Synthetic example  4: Preparation of Polyimide Polymer Compound

8.28 g (0.0267 mol) of 3,3 ', 4,4'- diphenyl ether tetracarboxylic dianhydride as an acid anhydride component, 4- (4,6-diamino-2,2-dimethyl-1 as a diamine component 3.50 g (0.0134 mole) and 1.78 g (4.89 mole) of 4,4'-oxydianiline were dissolved in 110 g of NMP and dissolved at -10 ° C. to 2,3,5-triazine-1 (2H) -yl) benzoic acid. The reaction was carried out for a time.

8.18 g (0.0801 mole) of acetic anhydride and 10.56 g (0.1335 mole) of pyridine were added to the reaction solution, followed by dehydration ring-closure reaction at 120 ° C. for 3 hours. Then, the mixture was poured into distilled water, filtered and dried to obtain a weight average molecular weight of 18,700, an intrinsic viscosity of 0.15 dl / g, and a glass transition temperature of 259 ° C., 12.2 g of a polyimide polymer compound having the same structure and repeating unit as Formula 5 was obtained.

Comparative Synthesis Example  One

8.28 g (0.0267 mol) of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride as an acid anhydride component, 0.68 g (0.0045 mol) of 3,5-diaminobenzoic acid as a diamine component, 4, 3.56 g (0.0178 mol) of 4′-oxydianiline was dissolved in 110 g of NMP and reacted at −10 ° C. for 2 hours.

8.18 g (0.0801 mole) of acetic anhydride and 10.56 g (0.1335 mole) of pyridine were added to the reaction solution, followed by dehydration ring-closure reaction at 120 ° C. for 3 hours. Then, the mixture was poured into distilled water, filtered and dried to obtain a weight average molecular weight of 16,700, an intrinsic viscosity of 0.14 dl / g, a glass transition temperature of 257 ° C, 11.7 g of a polyimide-based polymer compound satisfying the structure and repeating unit of Formula 6 was obtained.

Comparative Synthesis Example  2

8.28 g (0.0267 mol) of 3,3 ', 4,4'- diphenyl ether tetracarboxylic dianhydride as an acid anhydride component, 2.99 g (3,5-bis (4-aminophenoxy) benzoic acid as a diamine component 0.0089 mol) and 2.67 g (0.0134 mol) of 4,4'-oxydianiline were dissolved in 110 g of NMP and reacted at -10 ° C for 2 hours.

8.18 g (0.0801 mole) of acetic anhydride and 10.56 g (0.1335 mole) of pyridine were added to the reaction solution, followed by dehydration ring-closure reaction at 120 ° C. for 3 hours. Then, the mixture was poured into distilled water, filtered and dried to obtain a weight average molecular weight of 20,900, an intrinsic viscosity of 0.18 dl / g, a glass transition temperature of 254 ° C, To obtain a polyimide polymer compound 13g satisfying the structure and repeating unit shown in the following formula (7).

Comparative Synthesis Example  3

8.28 g (0.0267 mol) of 3,3 ', 4,4'- diphenyl ether tetracarboxylic dianhydride as an acid anhydride component, 4- (4,6-diamino-2,2-dimethyl-1 as a diamine component 5.46 g (0.0209 mol) of, 3,5-triazine-1 (2H) -yl) benzoic acid and 0.27 g (0.0013 mol) of 4,4'-oxydianiline were dissolved in 110 g of NMP, followed by 2 hours at -10 ° C. Reacted for a while.

8.18 g (0.0801 mole) of acetic anhydride, 10.56 g (0.1335 mole) of pyridine were added to the reaction solution, followed by dehydration ring-closure reaction at 120 ° C. for 3 hours. Then, the mixture was poured into distilled water, filtered and dried to obtain a weight average molecular weight of 19,200, an intrinsic viscosity of 0.17 dl / g, and a glass transition temperature of 256 ° C., To obtain a polyimide polymer compound 13g satisfying the structure and repeating unit shown in the following formula (8).

Example  One

To 8.27 g (100 parts by weight) of the polyimide polymer compound prepared in Synthesis Example 1, 15 parts by weight of a diazonaptoquinone ester compound (hereinafter, TPPA 320) represented by Formula 9 as a photosensitive acid generator, an adhesion promoter 1 part by weight of γ-isocyanatepropyltriethoxysilane, 0.5 part by weight of BYK-306 as a surfactant, and 450 parts by weight of solvent NMP were added thereto, stirred at room temperature for 1 hour, and filtered through a 0.2 µm filter to form a positive photosensitive polyimide. Resin composition A was prepared.

Wherein OD is optionally given in OH or OD according to the ratio of OD / (OD + OH) = 2/3.

Example  2 to 4

A positive photosensitive polyimide resin composition was prepared in the same manner as in Example 1, except that the polyimide polymer compounds obtained in Synthesis Examples 2 to 4 were used, respectively.

Comparative example  1 to 3

A positive type photosensitive polyimide resin composition was prepared in the same manner as in Example 1, except that the polyimide polymer compounds obtained in Comparative Synthesis Examples 1 to 3 were used, respectively.

Solubility in alkaline developer, optimum Exposure energy  , Residual film ratio Evaluation of physical properties such as adhesion

The photosensitive resin composition solutions prepared in Examples and Comparative Examples were spin coated on a 4 "wafer, and prebakeed at 120 ° C. for 120 seconds on a hot plate to form a 1.2 μm thick film. . heat treatment was completed, the wafer the G-line stepper Nikon NSR brought from 20mJ / cm ² to 1505 G4 to 600mJ / cm ² to 5mJ / cm ² exposure interval in order, the mask used at this time is from 1㎛ to 10㎛ 1 The line / space pattern and the circular pattern are repeated at 占 퐉 intervals, and developed in a 2.38wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 60 seconds, followed by washing and drying with ultrapure water for 60 seconds to form a pattern. The optimum exposure energy for transferring the same pattern as the pattern of 10 μm and the residual film ratio of the film in the non-exposed part after development were measured, and the adhesion was developed when exposed using a line & space mask. Remaining was determined using the minimum pixel size.

Optimal Exposure Energy (mJ / cm ² ) Residual rate
(%) Adhesiveness
(Μm) Example 1 80 95 5 Example 2 135 99 2 Example 3 120 98 2 Example 4 124 97 One Comparative Example 1 Not developing 100 - Comparative Example 2 Not developing 100 - Comparative Example 3 Film 0 -

As shown in the results of Table 1, when the polyimide polymer compound is satisfied to satisfy a specific repeating unit value, the solubility in an alkaline developer can be properly adjusted as in the example, and when it is included in the photosensitive resin composition, 365 nm ultraviolet light exposure is performed. It can be applied to the semiconductor protective film or the insulating film of the OLED because it can maximize the sensitivity to, high resolution and high residual film ratio, and excellent adhesion to the substrate.

Claims (17)

A polyimide polymer compound including a repeating unit represented by the following Chemical Formula 1, wherein m is 60 to 90 and n is 10 to 40, assuming that m + n is 100. Formula 1

Wherein X is the same as or different from each other and is a tetravalent aromatic or aliphatic organic group, and Y ₁ is at least one selected from

Y ₂ is a divalent aromatic or aliphatic organic group. The polyimide-based polymer compound according to claim 1, wherein X is at least one selected from the following.

delete delete The polyimide polymer compound of claim 1, wherein Y ₂ is at least one selected from the following.

The polyimide polymer compound of claim 1, wherein the polyimide polymer compound has an intrinsic viscosity of 0.05 to 0.4 dl / g, a glass transition temperature of 250 to 350 ° C., and a weight average molecular weight of 15,000 to 80,000. The polyimide polymer compound according to claim 1, wherein the polyimide polymer compound is obtained by reacting an acid anhydride with a diamine in a molar ratio of 1: 1 to 5: 4. The method of claim 7, wherein the acid anhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentane acetic dianhydride, bicyclo [2.2.2] octo-7-ene -2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornane Acetic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, pyromellitic anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid Dianhydrides, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 3,3 ', 4,4 '-Diphenylsulfontetracarboxylic dianhydride, and 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride Polymer compounds. The method of claim 7, wherein the diamine is 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,5-bis (4-aminophenoxy) benzoic acid , 4- (4,6-diamino-2,2-dimethyl-1,3,5-triazine-1 (2H) -yl) benzoic acid, 4,6-diamino-1,3-benzenedicar Acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, bis (4-amino-3-carboxyphenyl) sulfone, bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4 ' -Diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4 -Bis (4-amino-3-carboxyphenoxy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] Sulfone, bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane, and 2,2-bis [4- (4-a No 3-carboxy) phenyl; polyimide-based high molecular weight compound, characterized in that the at least one selected from the group consisting of hexafluoropropane. The positive type polyimide photosensitive resin composition containing the polyimide-type high molecular compound of any one of Claims 1, 2, 5-9. The method of claim 10, wherein the composition is 1 to 50 parts by weight of a photosensitive acid generator, 0.5 to 10 parts by weight of adhesion promoter, 0.1 to 1 part by weight of surfactant, and 200 to solvent based on 100 parts by weight of the polyimide polymer compound. A positive polyimide photosensitive resin composition, comprising 650 parts by weight. 12. The positive type polyimide photosensitive resin composition according to claim 11, wherein the photosensitive acid generator is selected from the following chemical formulas.

The method of claim 11, wherein the adhesion promoter is trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, A positive polyimide photosensitive resin composition, characterized in that at least one member selected from the group consisting of γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. 12. The positive type polyimide photosensitive resin composition according to claim 11, wherein the surfactant is at least one selected from the group consisting of a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. The method of claim 11, wherein the solvent is N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetra Methyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate And at least one member selected from the group consisting of ethylene glycol, ethyl lactate, butyl lactate, cyclohexanone, and cyclopentanone. An insulating film comprising a photosensitive film prepared from the positive polyimide photosensitive resin composition according to claim 10. A semiconductor protective film comprising a photosensitive film prepared from the positive polyimide photosensitive resin composition according to claim 10.