KR102260889B1 - Soluble polyimides and positive photosensitive resin composition containing the same - Google Patents

Abstract

The present invention relates to a soluble polyimide resin and uses thereof, and more particularly, to a diamine having 2 to tetravalent aromatic organic groups having 2 or more carbon atoms and 1 to 2 hydroxyl groups, diamines having divalent aromatic organic groups, and 2 Provided are a soluble polyimide copolymer resin prepared by condensation reaction of a diamine having a silicon-based substituent with an acid dianhydride in a predetermined ratio, and a positive photosensitive polyimide resin composition comprising the same.

Description

Soluble polyimide resin and positive photosensitive resin composition containing the same

The present invention relates to a polyimide resin, and more particularly, to a soluble polyimide resin having high solubility in an organic solvent and a positive photosensitive resin composition comprising the same.

In order for organic polymers to be used in semiconductor and display device fields, they must be thermally stable even at a temperature of 200° C. or higher in the device manufacturing process. First, polyimide compounds have excellent thermal stability and mechanical, electrical, and chemical properties. The use of the photosensitive insulating film including the photosensitive resin including the same is being expanded not only in the semiconductor field but also in the display field. Accordingly, there is a demand for a polyimide-based high molecular compound without film reduction or swelling in the formation of a fine pattern, which has not been required for conventional polyimide photosensitive resins.

The polyimide polymer is obtained by two-step polycondensation polymerization of a diamine component and a dianhydride component in a polar organic solvent such as N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) and dimethylformamide (DMF). It is generally manufactured by obtaining a polyimide precursor solution, coating it on a silicon wafer or glass, and curing it by heat treatment. Commercially available polyimide products for electronic materials are supplied in the form of polyimide precursor solution or polyimide film, and in the semiconductor device field, polyimide precursor solution is mainly supplied.

A polyimide resin is applied to a buffer coating film of a semiconductor device. In a large-scale integrated circuit (LSI), cracks occur in the passivation film of the chip due to thermal stress caused by volume shrinkage of the resin and the difference in thermal expansion coefficients between the chip and the resin after packaging of the device. Metal wiring may be damaged. To solve this problem, a buffer layer made of polyimide is formed between the chip and the encapsulant, and the thickness of the polyimide or more must be 10 μm or more to function properly. The thicker the buffer, the better the yield of semiconductor products. do.

The polyimide layer requires inter-electrode connection and formation of a fine pattern such as a wire bonding pad. In order to form a via hole in the polyimide layer, a conventional method of etching a non-photosensitive polyimide film by coating a photoresist is widely used, but recently, a photosensitive polyimide having a photosensitive function on the polyimide itself has been used. Many attempts have been made to apply This requires an etching process to process a hole using a separate photoresist for wire bonding and metal interconnection when using a conventional non-photosensitive polyimide, but when using a photosensitive polyimide, photoresist lithography (lithography) is required. ) process can be omitted, so the time taken for the buffer coating process is shortened by about 50%, thereby improving productivity and reducing manufacturing costs. In addition, there is an advantage in that it greatly contributes to the improvement of the production yield by shortening the process in the last stage of the semiconductor device assembly process.

In recent years, research on a positive photosensitive polyimide is being actively conducted rather than a negative photosensitive polyimide, because first, it has better resolution than a negative photosensitive polyimide; Second, since the light irradiation area is relatively smaller than the photosensitive polyimide of the negative method, the possibility of defects is low as much as that. Third, in the negative method, N-methyl-2-pyrrolidone (NMP) or dimethyl Because an organic solvent such as acetamide (DMAc) is used, there are problems in environmental aspects such as cost and wastewater treatment, whereas the positive method using an aqueous alkali solution as a developer reduces costs and is environmentally friendly.

As prior literatures on the positive photosensitive polyimide, there are the following. In Japanese Patent Application Laid-Open No. 52-013315 and Japanese Patent Application Laid-Open No. 62-135824, polyamic acid as a polyimide precursor and a naphtoquinonediazide compound as a dissolution inhibitor are mixed to form a pattern by the dissolution rate difference between the exposed and unexposed areas. However, there is a problem in that the difference in dissolution rate between the exposed portion and the non-exposed portion is not large enough to form a high-resolution pattern, respectively. In addition, Japanese Patent Application Laid-Open No. 64-060630 discloses a method of using a mixture of a soluble polyimide having a hydroxyl group and a naphthoquinonediazide compound, but the addition amount of the photosensitizer is large, the structure of the polyimide precursor is limited, and the physical properties This is a weak problem. In addition, Japanese Patent Application Laid-Open No. 60-037550 discloses a method of ester-bonding an o-nitrobenzylester group, which is a photosensitive group, to a precursor, but there is a problem in that it is difficult to improve the film thickness due to low strength. In addition, Japanese Patent Application Laid-Open No. 7-033874 and Japanese Patent Application Laid-Open No. 7-134414 disclose a chemically amplified composition prepared by mixing a resin obtained by replacing the carboxyl group of a polyamic acid with an acetal group that can be dissociated with an acid with a photoacid generator. have. However, although the remaining film ratio of the composition is excellent, there is a problem in that the film shrinkage rate after curing is high and the physical properties are weak.

Recently, as a method of increasing the sensitivity, a polyamic acid ester and/or a polyamic acid polymer containing a thermally crosslinkable compound containing a hydroxyl group is added (US Patent Application Publication No. US2003/0194631), a polyimide precursor or polyimide soluble in an aqueous alkali solution. In the molecule, a compound having two or more alkoxymethyl groups and phenolic hydroxyl groups is added (Japanese Patent Laid-Open Nos. 2003-121998 and 2001-312051), which have a plurality of methylol groups and phenolic hydroxyl groups Compound added (US Pat. No. 6,329,110), polyimide precursor or iodonium salt added as a dissolution inhibitor to polyimide (Japanese Patent Laid-Open No. 2001-042527), iodonium salt as dissolution inhibitor in polyamide (see Japanese Patent Application Laid-Open No. 2002-169283 (Claim 6, 7)), a polyamic acid ester with a photoacid generator and a vinyloxy group-containing compound added (Japanese Patent Application Laid-Open No. 2002-122993) Publication (refer to claim 1)), a polyamic acid ester having an acid dissociable group added with a photoacid generator (US Pat. No. 6,600,006) has been developed, but these are thick films whose film thickness after curing exceeds 10 μm. In this case, sufficient sensitivity could not be obtained, or even if obtained, distortion or collapse of the pattern occurred, so that a satisfactory pattern and sufficient sensitivity could not be achieved.

However, in the case of the prior art, although the positive photosensitive polyimide has many advantages, commercialization has not been made in earnest until now due to the technical problems to be overcome as described above. Therefore, there is an urgent need to develop a polyimide compound having excellent developability without film reduction or swelling in forming a fine pattern while having appropriate solubility in an alkali developer.

The present invention is to solve various problems, including the above problems, by solution polymerization of an acid dianhydride containing an aliphatic cyclic acid dianhydride in an appropriate ratio or more and a novel aromatic diamine monomer having a polar side chain group in an appropriate ratio in a solvent. An object of the present invention is to provide a soluble polyimide having excellent solubility, in particular, not requiring an imidization process at a high temperature and having excellent storage properties.

Another object of the present invention is to provide a positive photosensitive polyimide varnish composition using polyimide having the above characteristics as a binder resin.

In addition, another object of the present invention is to provide a photosensitive resin film obtained from the positive photosensitive polyimide varnish composition, a semiconductor protective film or an insulating film of LCD and OLED, and a flattening film or heat-resistant resin film including the same. However, these problems are exemplary, and the scope of the present invention is not limited thereto.

A polyimide resin comprising three kinds of repeating units represented by the following Chemical Formulas 1 to 3 is provided:

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3, A is the same as or different from each other and is a tetravalent aromatic or cyclic aliphatic organic group derived from an acid dianhydride, and B is a diamine having 2 or more carbon atoms and 1 to 2 hydroxyl groups. 2 to tetravalent aromatic organic group derived from, C represents a divalent aromatic organic group derived from diamine, D is a divalent silicone-based substituent derived from diamine, and x, y, and z are x+y+z= It is a rational number satisfying 1, O<y+z≤0.7, 0.3≤x+y<1.

According to another aspect of the present invention, there is provided a positive photosensitive polyimide varnish composition comprising the polyimide resin.

According to another aspect of the present invention, there is provided a film capable of realizing fine patterning and high resolution prepared by applying the positive photosensitive polyimide varnish composition on a substrate.

According to another aspect of the present invention, there is provided a semiconductor protective film including the photosensitive resin film.

According to another aspect of the present invention, an insulating film of LCD or OLED including the photosensitive resin film is provided.

According to another aspect of the present invention, there is provided a planarization film of a semiconductor TFT substrate including the photosensitive resin film.

According to another aspect of the present invention, there is provided a wiring protection insulating film of a circuit board including the photosensitive resin film.

The polyimide copolymer resin prepared according to an embodiment of the present invention and the positive photosensitive polyimide composition comprising the polyimide copolymer resin have excellent heat resistance, chemical resistance and mechanical properties, and excellent film properties, resulting in high sensitivity and high resolution. It can provide a pattern, can be applied as a semiconductor protective film or an insulating film material for OLEDs. In particular, it does not require an imidization process at a high temperature, has excellent storage stability, and easy control of solid content, so films of various thicknesses can be manufactured. has a However, these effects are exemplary, and the scope of the present invention is not limited thereto.

According to one aspect of the present invention, there is provided a polyimide resin comprising three kinds of repeating units represented by the following Chemical Formulas 1 to 3:

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3, A is the same as or different from each other and is a tetravalent aromatic or cyclic aliphatic organic group derived from an acid dianhydride, and B is a diamine having 2 or more carbon atoms and 1 to 2 hydroxyl groups. 2 to tetravalent aromatic organic group derived from, C represents an aromatic organic group derived from divalent diamine, D is a divalent silicone-based substituent derived from diamine, and x, y, and z are x+y+z= It is a rational number satisfying 1, O<y+z≤0.7, 0.3≤x+y<1.

In the soluble polyimide resin, the repeating unit of Formula 1 may be generated by a polycondensation reaction of a diamine monomer of Formula 4 or 5 and a dianhydride.

[Formula 4]

[Formula 5]

In Formula 4, R ₁ and R ₂ are each independently H, C1-C6 alkyl, C1-C6 alkoxy, fluorine, hydroxy or methyl trifluoride, and in Formula 5, R ₁ is H, C1-C6 alkyl, C1 ~C6 alkoxy, hydroxy, carboxy, fluorine, or methyl trifluoride, and R ₂ is hydrogen, methyl, or a hydroxy group.

In the soluble polyimide resin, the repeating unit of Chemical Formula 2 may be produced by polycondensation of an aromatic diamine monomer selected from the group consisting of Chemical Formulas 6 to 11 and a dianhydride:

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

.

.

(In Formula 6, R ₁ is hydrogen, C1-C6 alkyl, C1-C6 alkoxy, or a hydroxyl group, and in Formula 7, R ₁ is hydrogen, C1-C6 alkyl, C1-C6 alkoxy, fluorine, or methyl trifluoride; , R ₂ is hydrogen, a hydroxyl group, or C1 or C2 alcohol, R ₃ and R ₄ are each independently hydrogen, C1-C6 alkyl, C1-C6 alkoxy, hydroxyl, fluorine, or methyl trifluoride, and R in Formula 8 ₁ and R ₂ are each independently hydrogen, C1-C6 alkyl, C1-C6 alkoxy, hydroxyl group, fluorine, or methyl trifluoride, and R ₃ is hydrogen, C1-C6 alkyl, C1-C6 alkoxy, fluorine, or trifluoride methyl, and in Formula 9, R ₁ is C1-C6 alkyl or C1-C6 alkoxy, R ₂ and R ₃ are each independently hydrogen, C1-C6 alkyl, C1-C6 alkoxy, fluorine, or methyl trifluoride, R ₄ is hydrogen, methyl or a hydroxyl group, in Formulas 10 and 11, R ₁ and R ₂ are each independently hydrogen, C1-C6 alkyl, C1-C6 alkoxy, fluorine, or methyl trifluoride, and X is sulfur, oxygen or sulfonyl (SO ₂ ).)

In the soluble polyimide resin, A may be a tetravalent aromatic organic group selected from the group consisting of 1a to 1s of Formula 12:

[Formula 12]

In the soluble polyimide resin, B may be a divalent aromatic organic group selected from the group consisting of 2a to 2p of Formula 13:

[Formula 13]

In the soluble polyimide resin, C 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-triazin-1(2H)-yl)benzoic acid, 4,6-diamino-1,3-benzene Dicarboxylic 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) Consists of phenyl]sulfone, bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane and 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane It may be a divalent organic group derived from one or two or more diamines selected from the group.

In the soluble polyimide resin, C may be preferably a divalent aromatic organic group selected from the group consisting of 3a to 3e of the following Chemical Formula 14.

[Formula 14]

In the soluble polyimide resin, D may be a siloxane group selected from the group consisting of 4a to 4c of Formula 15 below.

[Formula 15]

In the soluble polyimide resin, 0.1 to 1 molar equivalent of monoamine may be used based on the molar equivalent of the acid dianhydride used in the reaction, and the monoamine 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-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, Bis(4-amino-3-carboxy phenyl)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'-dicarboxy biphenyl, 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-amino-3-carboxyphenoxy) phenyl] hexafluoropropane may be at least one selected from the group consisting of, more preferably 5a to 5s of the following formula 16 It may be selected from the group selected from the group consisting of.

[Formula 16]

In the soluble polyimide resin, 0.1 to 1 molar equivalent of an acid anhydride based on the total molar equivalent of all monoamines used in the reaction may be used for terminal sealing, and the acid anhydride is represented by 6a to 6i of the following Chemical Formula 17 It may be selected from the group selected from the group consisting of.

[Formula 17]

In the soluble polyimide resin, the diamine and the acid dianhydride may be mixed in a molar ratio of 1:1 to 5:4, and 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-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'-dicarboxy biphenyl, 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- It may be at least one selected from the group consisting of bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane, and the acid dianhydride is 1,2,3,4-cyclobutanetetracarboxyl Acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarp. Acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2, 3,4-tetrahydro-1-naphthalene succinic acid dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, 2, 3,5-tricarboxy-2-cyclopentane acetic acid 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 acet Acid dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, pyromellitic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4 ,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid It may be at least one selected from the group consisting of dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoroisopropylidene dianhydride.

In the preparation of the soluble polyimide resin, an imide conversion solution is used for chemical curing, and any material commonly used for causing chemical curing may be used as the imide conversion solution, and preferably, the The de-conversion solution may be a mixed solution of three types including a dehydrating agent, a catalyst and a solvent, and in this case, the reaction temperature may be 25 to 80°C.

In the soluble polyimide resin, the dehydrating agent may be acid anhydride, the acid anhydride may be acetic dianhydride, and the catalyst is one selected from the group consisting of triethylamine, pyridine, betapicoline and isoquinoline. It may be the above tertiary amine imidization catalyst, and the solvent may be a polar aprotic solvent, an ether-based solvent, a ketone-based solvent, an ester-based solvent, an aromatic hydrocarbon-based solvent, or a mixture thereof, wherein the polar aprotic solvent is It may be N-methyl-2-pyrrolidone, N,N-dimethyl formamide, N,N-dimethylacetamide, dimethyl sulfoxide, urea, or γ-butyrolactone, and the ether-based solvent is tetrahydro It may be furan, dioxane, or propylene glycol monomethyl ether, and the ketone-based solvent may be acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, or diacetone alcohol, and the ester-based solvent. The solvent may be ethyl acetate, propylene glycol monomethyl ether acetate, butyl acetate, or ethyl lactate, and the aromatic hydrocarbon-based solvent may be toluene or xylene.

The soluble polyimide resin prepared as described above may have an intrinsic viscosity of 0.1 to 3.0 dL/g, and a weight average molecular weight of 3,000 to 100,000 g/mol.

According to another aspect of the present invention, there is provided a positive photosensitive polyimide varnish composition comprising the polyimide resin.

The positive photosensitive polyimide varnish composition may include a photosensitizer and a solvent in addition to the soluble polyimide resin, and may additionally include a crosslinking agent, an adhesion promoter and/or a surfactant.

More specifically, based on 100 parts by weight of the polyimide resin, 1 to 50 parts by weight of a photosensitizer, and 200 to 650 parts by weight of a solvent, and 0.5 to 10 parts by weight of a crosslinking agent, 0.5 to 10 parts by weight of an adhesion promoter and / or 0.1 to 1 part by weight of a surfactant may be additionally included.

In the positive photosensitive polyimide varnish composition, the soluble polyimide resin may have an intrinsic viscosity of 0.1 to 3.0 dL/g, and a weight average molecular weight of 3,000 to 100,000 g/mol.

In the positive photosensitive polyimide varnish composition, the photosensitizer may include a photosensitive acid generator. The photosensitive acid generator may include at least one selected from the group consisting of 7a to 7g of the following Chemical Formula 18. have.

[Formula 18]

In the above formula, -OD may be a functional group represented by 7g or 7h of Formula 19 below.

[Formula 19]

In the positive photosensitive polyimide varnish composition, the photosensitive acid generator may be an ester-based compound having a 5-naphthoquinonediazidesulfonyl group and/or a 4-naphthoquinonediazidesulfonyl group. At this time, the 4-naphthoquinonediazidesulfonyl ester compound has absorption in the i-line region of the mercury lamp and is suitable for i-line exposure, and the 5-naphthoquinonediazidesulfonyl ester compound reaches the g-line region of the mercury lamp. It is suitable for g-ray exposure because it can be absorbed. In one embodiment of the present invention, it is possible to select from a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed, and 4-naphtho in the same molecule It is also possible to include both a quinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group. Alternatively, a mixture of a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be used.

In the positive photosensitive polyimide varnish composition, the photosensitizer may further include a thermal acid generator, the thermal acid generator may be an aliphatic sulfonic acid compound or an aromatic sulfonic acid compound, and the aromatic sulfonic acid is p-toluenesulfonic acid or benzenesulfonic acid. may be, and the aliphatic sulfonic acid may be methanesulfonic acid, ethanesulfonic acid, or butanesulfonic acid, and more preferably at least one selected from the group consisting of 8a to 8e of Formula 20 below.

[Formula 20]

In the positive photosensitive polyimide varnish composition, the crosslinking agent may be at least one selected from the group consisting of 9a to 9l of Formula 21 below.

[Formula 21]

In the positive photosensitive polyimide varnish composition, the adhesion promoter is trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltri It may be at least one selected from the group consisting of ethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

In the positive photosensitive polyimide varnish composition, the surfactant may be at least one selected from the group consisting of a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.

In the composition, the solvent is N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide , tetramethyl urea, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether acetate, 2-ethoxy ethanol, 2-methoxyethyl ether, ethyl It may be at least one selected from carbitol, butylcarbitol, ethylcarbitol acetate, butylcarbitol acetate, ethyl acetate, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, cyclohexanone, and cyclopentanone.

In the positive photosensitive polyimide varnish composition, the imidization temperature range of the polyimide resin may be 100 to 250 °C.

According to another aspect of the present invention, there is provided a photosensitive resin film formed using the positive photosensitive polyimide varnish composition.

According to another aspect of the present invention, there is provided a semiconductor protective film including the photosensitive resin film.

According to another aspect of the present invention, an insulating film of LCD or OLED including the photosensitive resin film is provided.

According to another aspect of the present invention, there is provided a planarization film of a semiconductor TFT substrate including the photosensitive resin film.

According to another aspect of the present invention, there is provided a wiring protection insulating film of a circuit board including the photosensitive resin film.

According to another aspect of the present invention, an on-chip microlens of a solid-state imaging device including the photosensitive resin film or a flattening or heat-resistant film for the solid-state imaging device is provided.

The present inventors solution polymerization of three or more diamine monomers including an acid dianhydride containing an aliphatic ring system or an aromatic acid dianhydride in an appropriate ratio or more and a novel aromatic diamine monomer of Formulas 5 and 6 having a polar side chain in an appropriate molar ratio, A soluble copolymerized polyimide resin having excellent solubility in solvents, not requiring an imidization process at a particularly high temperature, and easy to control storage and solid content, was prepared, and a polyimide having the above characteristics was used as a binder resin. A photosensitive polyimide resin composition could be produced. Since the positive photosensitive polyimide resin composition prepared as described above can properly control its solubility in an alkali developer, it can maximize its sensitivity to 365 nm ultraviolet light exposure, has high resolution and a high film remaining rate, and exhibits excellent adhesion to the substrate. The present invention was completed by confirming that new semiconductor, LCD, and OLED devices can be manufactured by using this as an insulating film.

Hereinafter, the present invention will be described in more detail through examples. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various different forms, and the following embodiments allow the disclosure of the present invention to be complete, and the scope of the invention to those of ordinary skill in the art It is provided to fully inform

Synthesis Example: Synthesis of a novel diamine monomer

Synthesis Example 1: Synthesis of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene

1-1: Synthesis of 4,4'-(9H-fluorene-9,9-diyl)bis(2-nitrophenol)

4,4'-(9H-fluorene-9,9-diyl)diphenol (34 g, 0.1 mol) was put in a 250ml round flask, 150ml of dichloromethane was added, stirred to dissolve completely, and then cooled to -5°C. Nitric acid (13 g, 0.21 mol) was slowly added dropwise, followed by stirring for 2 hours. After adding distilled water to separate the organic layer, it was washed once with a saturated aqueous sodium bicarbonate solution and then washed twice with distilled water. The organic layer was concentrated under reduced pressure and recrystallized from butanol/methanol. The resulting crystals were washed with methanol and then vacuum dried. ^{The yield was 74%, and 1} H NMR data of the synthesized 9,9-bis(3-nitro-4-hydroxyphenyl)fluorene were as follows.

¹ H NMR (DMSO- d ⁶ , 600 MHz): δ 11.0 (2H, s, -OH), 7.94 (2H, d, Ar-H), 7.50 (10H, m, Ar-H), 7.07 (2H, d, Ar-H).

1-2: Synthesis of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene

4,4'-(9H-fluorene-9,9-diyl)bis(2-nitrophenol) (26, 0.06 mol), 5% palladium/carbon (2.0g, 0.5 mmol) was placed in a 3L round flask Then, 800 ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. If the volume of the hydrogen balloon does not decrease after 3 hours of reaction by setting the stirring speed of the stirrer to 600 rpm, the catalyst is removed through silica/celite filtration and then concentrated under reduced pressure to completely remove the solvent. The resulting solid was washed with hexane and dried under vacuum. ^{The yield was 85%, and 1} H NMR data of the synthesized 9,9-bis(3-amino-4-hydroxyphenyl)fluorene were as follows.

¹ H NMR (DMSO- d ⁶ , 600 MHz): δ 8.77 (2H, s, -OH), 7.79 2H, d, Ar-H)), 7.24 (6H, m, Ar-H), 6.38 (4H, m, Ar-H), 6.02(2H, s, Ar-H), 4.35 4H, s, —NH ₂ ).

Synthesis Example 2: Synthesis of 5,5'-(1-(4-(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(2-aminophenol)

10 g of 4-trifluoromethylacetophenone, 12.7 g of 2-aminophenol, and 0.5 g of 2-aminophenol hydrochloride were placed in 80 ml of dimethylformamide, and the mixture was stirred under reflux at 120° C. for 12 hours. Upon completion of the reaction, after cooling to 80 °C, 150 ml of ethanol was added, followed by reflux stirring for 2 hours. After cooling to room temperature, the resulting solid was filtered, washed several times with water and ethanol, and dried under vacuum. The yield is 74%. ¹ H NMR data of the synthesized 5,5'-(1-(4-(trifluoromethyl)phenyl)ethane-1,1-diyl)bis(2-aminophenol) were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ(TMS, ppm): 2.28(3H, s, -CH ₃ ), 5.35(2H, s, -OH), 6.27(4H, s, -NH ₂ ) , 6.41 (2H, d, Ar-H), 6.60 (2H, d, Ar-H), 6.78 (2H, s, Ar-H), 7.22 (2H, d, Ar-H), 7.57 (2H, d , Ar-H).

Synthesis Example 3: Synthesis of 3,5-diamino-4-hydroxybenzoic acid

3-1: Synthesis of 3,5-dinitro-4-hydroxybenzoic acid

50 g of 4-hydroxybenzoic acid was added to 220 g of sulfuric acid, stirred, and then 70 g of nitric acid was slowly added dropwise at 0°C. Upon completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours and then poured into 2 L ice water with vigorous stirring. The resulting solid was filtered, washed with water several times, and then dried under vacuum. ^{The yield was 76%, and 1} H NMR data of the synthesized 3,5-dinitro-4-hydroxybenzoic acid were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ (TMS, ppm): 8.49 (2H, s, Ar-H), 12.86 (2H, b, —OH).

3-2: Synthesis of 3,5-diamino-4-hydroxybenzoic acid

After dissolving 2 g of dinitro-4-hydroxybenzoic acid synthesized in Synthesis Example 3-1 in 20 ml of 2-methoxyethanol, 0.1 g of 10% palladium-carbon was added. A hydrogen balloon was introduced here, stirred at room temperature for 6 hours, the catalyst was removed by filtration, and the solvent was removed by distillation under reduced pressure. The resulting solid was recrystallized from a mixed solution of methylene chloride/methanol. The resulting crystals were filtered, washed several times with methanol, and then dried under vacuum. ^{The yield was 91%, and 1} H NMR data of the synthesized 3,5-diamino-4-hydroxybenzoic acid were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ (TMS, ppm): 5.42(4H, s, -NH ₂ ), 7.32(2H, s, Ar-H), 12.74(2H, b, -OH) .

Synthesis Example 4: 4- (3,6-diamino-9 H -Synthesis of carbazol-9-yl)benzoic acid

4-1: 3,6-dinitro-9 H -Synthesis of carbazole

After stirring 17 g of copper nitrate in 100 ml of acetic anhydride and 100 ml of acetic acid, 10 g of carbazole was divided and slowly added at 0°C. After the addition was completed, the mixture was stirred at room temperature for two hours and then slowly added to the mixture while stirring in ice water. The resulting solid was filtered, washed several times with water, and then dried under vacuum. The yield was 84%, and ¹ H NMR data of the synthesized 3,6-dinitro-9 H -carbazole were as follows.

¹ H NMR (600 MHz, CDCl ₃ ) δ (TMS, ppm): 7.75 (2H, s, Ar-H), 8.67 (2H, d, Ar-H), 9.26 (2H, s, Ar-H), 10.2 (1H, s, -NH-).

4-2: Dynitro-9 H -carbazole-4-(3,6-dinitro-9 H -Synthesis of carbazol-9-yl)benzonitrile

With the 3,6-nitro synthesized in Synthesis Example 4-1 -9 H - carbazol-10 g, 4- fluoro-benzonitrile 9.4 g, copper iodide 15 g, 21.5 g of potassium carbonate and Dimethyl formamide 300 After dissolving in ml, the mixture was stirred under reflux under nitrogen. When the reaction was completed after 6 hours, the mixture was cooled to room temperature and stirred while adding excess water. After acidification with 3 N hydrochloric acid, it was extracted twice with methylene chloride. The organic layer was washed twice with water, and then the solvent was distilled under reduced pressure. The resulting solid was recrystallized from toluene/hexane. The yield was 87%, with the combined die nitro -9 H - and - (carbazol-9-one in 3,6-nitro -9 H) ¹ H NMR data of the benzonitrile to the carbazole-4 It was like

¹ H NMR (600 MHz, CDCl ₃ ) δ (TMS, ppm): 7.64 (2H, d, Ar-H), 7.92 (4H, m, Ar-H), 8.21 (2H, d, Ar-H), 9.26 (2H, s, Ar-H).

4-3: Synthesis of 4-(3,6-dinitro-9H-carbazol-9-yl)benzoic acid

10 g of 3,6-dinitro-9H-carbazole 4- (3,6-dinitro-9H-carbazol-9-yl) benzonitrile synthesized in Synthesis Example 4-2 was mixed with 30% It was put into 100 ml of potassium hydroxide aqueous solution, stirred under reflux for 16 hours, and then cooled. After acidification with 1 M aqueous hydrochloric acid solution, extraction was performed twice with methylene chloride. The extracted organic layer was concentrated and dried in vacuo. ^{The yield was 92%, and 1} H NMR data of the synthesized 4-(3,6-dinitro-9H-carbazol-9-yl)benzoic acid were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ (TMS, ppm): 7.83 (2H, d, Ar-H), 7.92 (4H, m, Ar-H), 8.21 (2H, d, Ar-H) ), 9.26 (2H, s, Ar-H), 11.4 (1H, s, COOH).

4-4: 4- (3,6-diamino-9 H -Synthesis of carbazol-9-yl)benzoic acid

Synthesized in the above Synthesis Example 4-3 4- (3,6-nitro -9 H-carbazole-9-yl) benzoic acid with 3 g of 2-methoxyethanol was dissolved in 30 ml of 10% palladium- 0.2 g of carbon was added. A hydrogen balloon was introduced here, stirred at room temperature for 6 hours, the catalyst was removed by filtration, and the solvent was removed by distillation under reduced pressure. The resulting solid was recrystallized from a mixed solution of methylene chloride/methanol. The resulting crystals were filtered, washed several times with methanol, and then dried under vacuum. ^{The yield was 94%, and 1} H NMR data of the synthesized 4-(3,6-diamino-9 H -carbazol-9-yl)benzoic acid were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ (TMS, ppm): 5.62(4H, s, -NH ₂ ), 6.77(4H, d, Ar-H), 7.62(2H, m, Ar-H ), 8.19 (2H, d, Ar-H), 9.31 (2H, s, Ar-H), 11.3 (1H, s, COOH).

Synthesis Example 5: Synthesis of 4-(1,1-bis(4-aminophenyl)ethyl)benzoic acid

5-1: Synthesis of 4-(1,1-bis(4-aminophenyl)ethyl)benzonitrile

10 g of 4-cyanoacetophenone and 0.9 g of aniline hydrochloride were added to 19.3 g of aniline and stirred under reflux at 120° C. for 12 hours. When the reaction was completed, after cooling to 80 °C, 100 ml of ethanol was added, and the mixture was stirred under reflux for 2 hours. After cooling to room temperature, the resulting solid was filtered and washed several times with water and ethanol. ^{The yield was 82%, and 1} H NMR data of the synthesized 4-(1,1-bis(4-aminophenyl)ethyl)benzonitrile were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ (TMS, ppm): 2.28(3H, s, -CH ₃ ), 6.27(4H, s, -NH ₂ ), 6.58(4H, d, Ar-H ), 7.04 (4H, d, Ar-H), 7.47 (2H, d, Ar-H), 7.59 (2H, d, Ar-H).

5-2: Synthesis of 4-(1,1-bis(4-aminophenyl)ethyl)benzoic acid

2 g of 4-(1,1-bis(4-aminophenyl)ethyl)benzonitrile synthesized in Synthesis Example 5-1 was placed in 30 ml of a 30% aqueous potassium hydroxide solution, stirred under reflux for 16 hours, and then cooled. After acidification with 3 M aqueous hydrochloric acid solution, extraction was performed twice with methylene chloride. The extracted organic layer was concentrated and vacuum dried. ^{The yield was 92%, and 1} H NMR data of the synthesized 4-(1,1-bis(4-aminophenyl)ethyl)benzoic acid were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ (TMS, ppm): 2.28 (3H, s, -CH ₃ ), 6.27 (4H, s, -NH2), 6.58 (4H, d, Ar-H) , 7.04 (4H, d, Ar-H), 7.50 (2H, d, Ar-H), 8.16 (2H, d, Ar-H), 11.5 (1H, s, COOH).

Synthesis Example 6: Synthesis of 4,4'-(1-(4-hydroxyphenyl)ethane-1,1-diyl)bis(2-aminophenol)

6-1: Synthesis of 4,4'-(1-(4-hydroxyphenyl)ethane-1,1-diyl)bis(2-nitrophenol)

1,1,1-tris(4-hydroxyphenyl)ethane (102g, 0.33 mol) was put in a 1L round flask, 500ml of dichloromethane was added, stirred to dissolve completely, and then cooled to -5°C. Nitric acid (62 g, 0.69 mol) was slowly added dropwise, followed by stirring for 2 hours. After adding distilled water to separate the organic layer, it was washed once with a saturated aqueous sodium bicarbonate solution and then washed twice with distilled water. The organic layer was concentrated under reduced pressure and purified by silica column with methylene chloride. ^{The yield was 82%, and 1} H NMR data of the synthesized 4,4'-(1-(4-hydroxyphenyl)ethane-1,1-diyl)bis(2-nitrophenol) were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ (TMS, ppm): 10.2 (1H, s, -OH), 8.91 (2H, s, -OH), 7.02 (2H, s, Ar-H), 6.82 (6H, m, Ar-H), 6.43 (2H, s, Ar-H), 1.88 ( s, -CH ₃ ).

6-2: Synthesis of 4,4'-(1-(4-hydroxyphenyl)ethane-1,1-diyl)bis(2-aminophenol)

In a 1 L round flask, 4,4'-(1-(4-hydroxyphenyl)ethane-1,1-diyl)bis(2-nitrophenol) (45 g, 0.11 mol), 5% palladium/carbon (3.0 g, 2 mmol), then 350 ml of 2-methoxyethanol was added, and the inside of the reactor was replaced with hydrogen using a hydrogen balloon. If the volume of the hydrogen balloon does not decrease after 3 hours of reaction by setting the stirring speed of the stirrer to 600 rpm, the catalyst is removed through silica/celite filtration and then concentrated under reduced pressure to completely remove the solvent. The resulting solid was washed with hexane and dried under vacuum. The yield was 89%. ¹ H NMR data of the synthesized 4,4'-(1-(4-hydroxyphenyl)ethane-1,1-diyl)bis(2-aminophenol) were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ (TMS, ppm): 9.08 (1H, s, -OH), 8.68 (2H, s, -OH), 6.75 (2H, s, Ar-H), 6.41(6H, m, Ar-H), 5.95(2H, s, Ar-H), 4.26(4H, s, -NH ₂ ), 1.81(s,-CH ₃ ).

Synthesis Example 7: 3,5-diamino-4-hydroxybenzoic acid

7-1: 3,5-dinitro-4-hydroxybenzoic acid

In a 3-liter reactor, 138 g of p-hydroxybenzoic acid was added to 588 g of sulfuric acid and stirred to dissolve it completely, and then the reactor was cooled to -5°C. Nitric acid (62 g, 0.69 mol) was slowly added dropwise, followed by stirring for 2 hours. While maintaining the same temperature, 1.5 L of ice water was poured and stirring was continued for 15 minutes, the solid was filtered and washed twice with distilled water with 500 ml of distilled water. The obtained product was washed with ethyl acetate and water, and crystallized with THF/MC to obtain 3,5-diamino-4-hydroxybenzoic acid. ^{The yield was 82%, and 1} H NMR data of the synthesized 4,4'-(1-(4-hydroxyphenyl)ethane-1,1-diyl)bis(2-nitrophenol) were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ (TMS, ppm): 12.7(1H, s, -COOH), 10.7(1H, s, -OH), 8.5(2H, s, Ar-H)

7-2: 3,5-diamino-4-hydroxy benzoic acid

3,5-dinitro-4-hydroxybenzoic acid (45 g, 0.11 mol) and 5% palladium/carbon (3.0 g, 2 mmol) were put in a 1 L round flask, and then 350 ml of 2-methoxyethanol was added. , the inside of the reactor was replaced with hydrogen using a hydrogen balloon. If the volume of the hydrogen balloon did not decrease after 3 hours of reaction by setting the stirring speed of the stirrer to 600 rpm, the catalyst was removed through silica/celite filtration and then concentrated under reduced pressure to completely remove the solvent. The resulting solid was washed with hexane and dried under vacuum. The yield was 86%. ¹ H NMR data of the synthesized 3,5-diamino-4-hydroxybenzoic acid were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ (TMS, ppm): 12.7(1H, s, -COOH), 9.5(1H, s, -OH), 6.6(2H, s, Ar-H), 3.1(2H, s, -NH ₂ )

Synthesis Example 8: N , N '-(5,5'-(9) H -fluorene-9,9-diyl)bis(2-hydroxy-5,1-phenylene))bis(3-aminobenzamide)

8-1: N , N '-(5,5'-(9) H Synthesis of -fluorene-9,9-diyl)bis(2-hydroxy-5,1-phenylene))bis(3-nitrobenzamide)

10 g of 9,9-bis(3-amino-4-hydroxyphenyl)fluorene and 9.2 g of propylene oxide were completely dissolved by stirring in 100 ml of acetone, and then cooled to -15°C. 10.8 g of 3-nitrobenzoyl chloride was dissolved in 100 ml of acetone and slowly added dropwise over 2 hours. Upon completion of the dropwise addition, the mixture was stirred at the same temperature for 6 hours and then raised to room temperature. Upon completion of the reaction, the precipitated solid was filtered and vacuum dried. The yield was 92%, the combined N, N '- (5,5' (9 H - fluorene-9,9-di-yl) bis (2-hydroxy -5,1- phenylene)) bis (3 ¹ H NMR data of -nitrobenzamide) were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ (TMS, ppm): 5.35 (2H, s, -OH), 6.88 (4H, dd, Ar-H), 7.38 (4H, m, Ar-H) , 7.57(4H, m, Ar-H), 7.87(4H, m, Ar-H), 8.42(4H, m, Ar-H), 8.98(2H, s, Ar-H), 9.15 (2H, s) , -NH-).

8-2: N , N '-(5,5'-(9) H Synthesis of -fluorene-9,9-diyl)bis(2-hydroxy-5,1-phenylene))bis(3-aminobenzamide)

Synthesized in the above Synthesis Example 6-1 N, N '- (5,5 ' - (9 H - fluorene-9,9-diyl) bis (2-hydroxy -5,1- phenylene)) bis ( 3-nitrobenzamide) 6 g was dissolved in 50 ml of dimethylformamide, and then 0.4 g of 10% palladium-carbon was added. A hydrogen balloon was introduced here, stirred at room temperature for 6 hours, the catalyst was removed by filtration, and water was added to the mixed solution to precipitate crystals. After filtration, the crystals were recrystallized from a tetrahydrofuran/methanol mixed solution. The resulting crystals were filtered, washed several times with methanol, and then dried under vacuum. The yield was 89%, the combined N, N '- (5,5' - (9 H - fluorene-9,9-diyl) bis (2-hydroxy -5,1- phenylene)) bis (3 -Aminobenzamide) ¹ H NMR data were as follows.

¹ H NMR (600 MHz, DMSO- d ₆ ) δ (TMS, ppm): 5.35 (2H, s, -OH), 6.27 (4H, s. -NH ₂ ), 6.83 (6H, m, Ar-H) , 7.09 (2H, s, Ar-H), 7.28-7.39 (8H, m, Ar-H), 7.55 (4H, m, Ar-H), 7.87 (2H, d, Ar-H), 9.15 (2H) , s, -NH-).

Example 1: Preparation of photosensitive polyimide copolymer resin (A-1)

1-1: Preparation of polyimide copolymer resin (A)

26.6 g (0.047 mol) of 4,4'-(9H-fluorene-9,9-diyl)bis(2-((3-aminophenyl)amino)phenol) under a dry nitrogen stream, Synthesis Example 3-2 2.3 g (0.013 mol) of 3,5-diamino-4-hydroxybenzoic acid synthesized in 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis (Propan-1-amine) 1.7 g (0.006 mol) was dissolved in 1.0 L of N-methylpyrrolidone. 30.0 g (0.067 mol) of 5,5'-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) was added thereto, stirred at 35°C for 5 hours, and then 3- 0.7 g (0.006 mol) of aminophenol was added and stirred at 25° C. for 5 hours. 16.7 g (0.167 mol) of acetic dianhydride and 13.7 g (0.174 mol) of pyridine were added dropwise together with 20 ml of N-methylpyrrolidone, followed by stirring at 60°C for 3 hours. After completion of the reaction, the solution was poured into 1.5 L of water, precipitated, filtered, and dried at 60° C. for 72 hours using a vacuum dryer to obtain a polyimide resin (A). In the infrared absorption spectrum, the synthesized polymer had ^{an NH absorption band of an amide group at 2,995 cm -1} , a C=O band of an imide group at 1,779 cm ^-1 and 1,725 cm ^-1 , a C=O absorption band of a carboxyl group at ^{1,709 cm -1 ,} At 1,652 cm ^-1 , the C=O absorption band of the amide group was observed, and the structure was analyzed by ¹ H NMR. Through gel permeation chromatography analysis, it was confirmed that the weight average molecular weight of the polymerized copolymer was 9,000 g/mol and the polydispersity index was 1.8.

1-2: Preparation of photosensitive polyimide resin composition (A-1)

To 10.0 g of the polyimide resin (A) obtained in Example 1-1, the quinonediazide compound 7a ((1-(4-(2-(4-(((6) -diazo-5-oxo-5,6-dihydronaphthalen-1-yl)sulfonyl)oxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1- After adding 3.0 g of phenylene)bis(6-diazo-5-oxo-5,6-dihydronaphthalene-1-sulfonate)) and 0.8 g of a crosslinking agent 9c represented by Formula 21, propylene glycol monoethyl ether acetate After diluting and dissolving the solid content of the composition to 30% by weight using a pore size 0.1 μm PTFE membrane filter to obtain a liquid resist composition (A-1).

Example 2: Preparation of photosensitive polyimide copolymer resin (B-1)

2-1: Preparation of polyimide copolymer resin (B)

26.6 g (0.047 mol) of 4,4'-(9H-fluorene-9,9-diyl)bis(2-((3-aminophenyl)amino)phenol) under a dry nitrogen stream, Synthesis Example 3-2 2.3 g (0.013 mol) of 3,5-diamino-4-hydroxybenzoic acid synthesized in 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis (Propan-1-amine) 1.7 g (0.006 mol) was dissolved in 1.0 L of N-methylpyrrolidone. 14.6 g (0.067 mol) of benzo[1,2-c: 4,5-c']difuran 1,3,5,7-tetraone) was added thereto, stirred at 35° C. for 5 hours, and then 3-amino 0.7 g (0.006 mol) of phenol was added and stirred at 25° C. for 5 hours. 16.7 g (0.167 mol) of acetic dianhydride and 13.7 g (0.174 mol) of pyridine were added dropwise together with 20 ml of N-methylpyrrolidone, followed by stirring at 60°C for 3 hours. After completion of the reaction, the solution was poured into 1.5 L of water, precipitated, filtered, and dried at 60° C. for 72 hours using a vacuum dryer to obtain a polyimide resin (A). In the infrared absorption spectrum, the synthesized polymer had ^{an NH absorption band of an amide group at 2,995 cm -1} , a C=O band of an imide group at 1,779 cm ^-1 and 1,725 cm ^-1 , a C=O absorption band of a carboxyl group at ^{1,709 cm -1 ,} At 1,652 cm ^-1 , the C=O absorption band of the amide group was observed, and the structure was analyzed by ¹ H NMR. Through gel permeation chromatography analysis, it was confirmed that the weight average molecular weight of the polymerized copolymer was 8,000 g/mol and the polydispersity index was 1.4.

2-2: Preparation of photosensitive polyimide resin composition (B-1)

In 10.0 g of the polyimide resin (B) obtained in Example 2-1, the quinonediazide compound 7a ((1-(4-(2-(4-(((6) -diazo-5-oxo-5,6-dihydronaphthalen-1-yl)sulfonyl)oxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1- After adding 3.0 g of phenylene)bis(6-diazo-5-oxo-5,6-dihydronaphthalene-1-sulfonate)) and 1.2 g of a crosslinking agent 9e represented by Formula 21, propylene glycol monoethyl ether A liquid resist composition (B-1) was obtained by diluting and dissolving the composition with a solid content of 30% by weight using acetate, followed by filtration with a pore size 0.1 μm PTFE membrane filter.

Example 3: Preparation of photosensitive polyimide copolymer resin (C-1)

3-1: Preparation of polyimide copolymer resin (C)

Under a stream of dry nitrogen, 20.2 g (0.06 mol) of 4,4'-(1-(4-hydroxyphenyl)ethane-1,1-diyl)bis(2-aminophenol) synthesized in Synthesis Example 6 was N- It was dissolved in 1.0 L of methylpyrrolidone. 30.0 g (0.067 mol) of 5,5'-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) was added thereto, 14.6 g (0.067 mol) After stirring for 5 hours, 0.5 g (0.006 mol) of aniline was added and stirred at 25° C. for 5 hours. 16.7 g (0.167 mol) of acetic dianhydride and 13.7 g (0.174 mol) of pyridine were added dropwise together with 20 ml of N-methylpyrrolidone, followed by stirring at 60°C for 3 hours. After completion of the reaction, the solution was poured into 1.5 L of water, precipitated, filtered, and dried at 60° C. for 72 hours using a vacuum dryer to obtain a polyimide resin (A). In the infrared absorption spectrum, the synthesized polymer had ^{an NH absorption band of an amide group at 2,995 cm -1} , a C=O band of an imide group at 1,779 cm ^-1 and 1,725 cm ^-1 , a C=O absorption band of a carboxyl group at ^{1,709 cm -1 ,} At 1,652 cm ^-1 , the C=O absorption band of the amide group was observed, and the structure was analyzed by ¹ H NMR. Through gel permeation chromatography analysis, it was confirmed that the weight average molecular weight of the polymerized copolymer was 11,000 g/mol and the polydispersity index was 2.0.

3-2: Preparation of photosensitive polyimide resin composition (C-1)

To 10.0 g of the polyimide resin (C) obtained in Example 3-1, 3.0 g of the quinonediazide compound 7b represented by Formula 18 and 1.2 g of the crosslinking agent 9e represented by Formula 21 were added as a photosensitive acid generator. After dissolving the composition by diluting and dissolving the solid content of the composition to 30% by weight using propylene glycol monoethyl ether acetate, it was filtered through a pore size 0.1 μm PTFE membrane filter to obtain a liquid resist composition (C-1).

Comparative Example 1: Preparation of photosensitive polyimide copolymer resin (D-1)

1-1: Preparation of polyimide copolymer resin (D)

26.6 g (0.047 mol) of 4,4'-(9H-fluorene-9,9-diyl)bis(2-((3-aminophenyl)amino)phenol) under a dry nitrogen stream, 4'4'-di 2.6 g (0.013 mol) of aminophenyl ether, 1.7 g (0.006 mol) of 3,3'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis(propan-1-amine) was dissolved in 1.0 L of N-methylpyrrolidone. 30.0 g (0.067 mol) of 5,5'-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) was added thereto, stirred at 35°C for 5 hours, and then 3- 0.7 g (0.006 mol) of aminophenol was added and stirred at 25° C. for 5 hours. 16.7 g (0.167 mol) of acetic dianhydride and 13.7 g (0.174 mol) of pyridine were added dropwise together with 20 ml of N-methylpyrrolidone, followed by stirring at 60°C for 3 hours. After completion of the reaction, the solution was poured into 1.5 L of water, precipitated, filtered, and dried at 60° C. for 72 hours using a vacuum dryer to obtain a polyimide resin (A). In the infrared absorption spectrum, the synthesized polymer shows the NH absorption band of the amide group at 2,995 cm -1 , the C=O absorption band of the imide group at 1,779 cm -1 and 1,725 cm -1 , and the C=O absorption band of the carboxyl group at 1,709 cm -1 . , a C=O absorption band of the amide group was observed at 1,652 cm -1 , and the structure was analyzed by ¹ H NMR. Through gel permeation chromatography analysis, it was confirmed that the weight average molecular weight of the polymerized copolymer was 7,000 g/mol and the polydispersity index was 1.5.

1-2: Preparation of photosensitive polyimide resin composition (D-1)

To 10.0 g of the polyimide resin (D) obtained in Comparative Example 1-1, the quinonediazide compound 7a ((1-(4-(2-(4-(((6) -diazo-5-oxo-5,6-dihydronaphthalen-1-yl)sulfonyl)oxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1- After adding 3.0 g of phenylene)bis(6-diazo-5-oxo-5,6-dihydronaphthalene-1-sulfonate)) and 0.8 g of a crosslinking agent 9c represented by Formula 21, propylene glycol monoethyl ether acetate After diluting and dissolving the solid content of the composition to 30% by weight using a pore size 0.1 μm PTFE membrane filter to obtain a liquid resist composition (D-1).

Comparative Example 2: Preparation of photosensitive polyimide copolymer resin (E-1)

2-1: Preparation of polyimide copolymer resin (E)

26.6 g (0.047 mol) of 4,4'-(9H-fluorene-9,9-diyl)bis(2-((3-aminophenyl)amino)phenol) under a dry nitrogen stream, 4,4'-di 2.8 g (0.013 mol) of amino[1,1'-biphenyl]3,3'-diol 1.7 g (0.006 mol) was dissolved in 1.0 L of N-methylpyrrolidone. 30.0 g (0.067 mol) of 5,5'-(perfluoropropane-2,2-diyl)bis(isobenzofuran-1,3-dione) was added thereto, stirred at 35°C for 5 hours, and then 3- 0.7 g (0.006 mol) of aminophenol was added and stirred at 25° C. for 5 hours. 16.7 g (0.167 mol) of acetic dianhydride and 13.7 g (0.174 mol) of pyridine were added dropwise together with 20 ml of N-methylpyrrolidone, followed by stirring at 60°C for 3 hours. After completion of the reaction, the solution was poured into 1.5 L of water, precipitated, filtered, and dried at 60° C. for 72 hours using a vacuum dryer to obtain a polyimide resin (A). In the infrared absorption spectrum, the synthesized polymer had ^{an NH absorption band of an amide group at 2,995 cm -1} , a C=O band of an imide group at 1,779 cm ^-1 and 1,725 cm ^-1 , a C=O absorption band of a carboxyl group at ^{1,709 cm -1 ,} At 1,652 cm ^-1 , the C=O absorption band of the amide group was observed, and the structure was analyzed by ¹ H NMR. Through gel permeation chromatography analysis, it was confirmed that the weight average molecular weight of the polymerized copolymer was 7,000 g/mol and the polydispersity index was 1.5.

2-2: Preparation of photosensitive polyimide resin composition (E-1)

In 10.0 g of the polyimide resin (E) obtained in Comparative Example 2-1, the quinonediazide compound 7a ((1-(4-(2-(4-(((6) -diazo-5-oxo-5,6-dihydronaphthalen-1-yl)sulfonyl)oxy)phenyl)propan-2-yl)phenyl)ethane-1,1-diyl)bis(4,1- After the addition of 3.0 g of phenylene)bis(6-diazo-5-oxo-5,6-dihydronaphthalene-1-sulfonate)) and 0.8 g of the crosslinking agent 9c represented by Formula 21, propylene glycol monoethyl ether A liquid resist composition (E-1) was obtained by diluting and dissolving the composition so that the solid content of the composition was 30% by weight using acetate, and then filtration with a pore size 0.1 μm PTFE membrane filter.

The resist compositions of Examples and Comparative Examples were subjected to physical property evaluation as described in Experimental Examples below, and the evaluation results are shown in Table 1 below.

Experimental Example 1: Evaluation of coating film formation

After forming a film by spin-coating the resist compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 at a speed of 1,000 rpm on a silicon wafer or a glass substrate, a soft bake process was performed on a hot plate at 100° C. for 120 seconds. and measuring the thickness of the coating film using an optical thickness measuring device (product name: K-Mac ST).

Experimental Example 2: Pattern evaluation

For the substrates coated with the resist compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2, a photomask of 3 μm to 300 μm line: interval = 1:1 and G, H, I-line UV lamps were mounted. ^{100 mJ/cm 2} (I-line, 365 nm standard) energy was irradiated using a mask aligner (product name: SUSS MA-6), developed in 2.38% TMAH diluted alkaline aqueous solution for 60 seconds, and washed with ultrapure water. The patterned substrate thus obtained was heated in an oven at 230° C. for 30 minutes.

The patterned silicon wafer or glass substrate was observed with an electron microscope, and a 3 μm pattern was formed without scum as “excellent”, and a sample that failed to form a 3 μm pattern or had severe scum was judged as “bad”.

Experimental Example 3: Remaining film rate evaluation

For the substrates coated with the resist compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2, the residual film ratio was calculated through Equation 1 below.

(Equation 1) Remaining film ratio (%) = (film thickness after development and curing process / initial film thickness) x 100

Experimental Example 4: Heat resistance evaluation

The resist compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were applied to a substrate and cured, followed by thermogravimetric analysis using a sample thermogravimetric analyzer (device name: TGA, Perkin elmer), from room temperature to 600° C. When the temperature was raised at a rate of ℃/min, the weight loss rate (loss wt%) according to the temperature was measured. At this time, the weight reduction rate at 400° C. was judged as “excellent” if less than 20%, “normal” between 20% and 40%, and “poor” if more than 40%.

Experimental Example 5: Evaluation of chemical resistance

The resist compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were applied to a substrate to form a coating film, and then subjected to a curing process, and then soaked in a PR stripper (trade name, LT-360) at a temperature of 40° C. for 10 minutes. After soaking, the rate of change in film thickness swelling was calculated. When it showed less than 5% of swelling change rate, it was judged as "excellent", and when it showed 5% or more of swelling change rate, it was judged as "poor".

Experimental Example 6: Evaluation of dielectric constant

A metal-insulator-metal (MIM) evaluation cell was manufactured by depositing an aluminum electrode with a diameter of 1.0 after the ITO substrate was formed and cured. To measure the dielectric constant, the capacitance (C) of the applied resist film was measured in the evaluation cell using an LCR-meter (Agilent 4284), and the dielectric constant was derived using Equation 2 below. In Equation 2 below, d is the thickness of the resist film, A is the area of the deposited electrode ^{, ε0 is the dielectric constant of vacuum (8.855×10 -12} F/m) as a constant, and ε is the dielectric constant of the resist film to be obtained .

(Equation 2) C=(ε0×εA)/d

Experimental Example 7: Evaluation of moisture absorption

Moisture absorption rate was analyzed by calculating the rate of change in film thickness swelling after immersion in distilled water at room temperature for 72 hours after the substrate was subjected to a coating film formation and curing process. When it showed a swelling change rate of less than 2%, it was judged as "excellent", and when it showed a swelling change rate of 2% or more, it was judged as "poor".

The results of Experimental Examples 1 to 7 are as shown in Table 1 below.

division pattern Remaining film rate (%) heat resistance
(Loss wt%) chemical resistance dielectric constant Moisture absorption (%) Example 1 Great 89 Great Great 3.31 Great Example 2 Great 85 Great Great 3.31 Great Example 3 Great 92 Great Great 3.30 Great Comparative Example 1 bad 75 bad bad 3.56 bad Comparative Example 2 bad 77 bad bad 3.72 bad

As can be seen from Table 1 above, the film finished with the soluble polyimide resin composition according to the present invention had a thickness of 10 μm, and the minimum line width of the pattern was 3 to 7 μm. It can be seen that not only exhibits heat resistance, but also has a high residual film rate and excellent chemical resistance.

Although the present invention has been described with reference to the above-described embodiments, these are merely exemplary, and those skilled in the art will understand that various modifications and equivalent other embodiments are possible therefrom. Therefore, the true technical protection scope of the present invention should be determined by the technical spirit of the appended claims.

Claims (27)

A soluble polyimide resin comprising three kinds of repeating units represented by the following formulas 1 to 3:
[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3, A is the same as or different from each other, and each is a tetravalent aromatic or cyclic aliphatic organic group, and B is a 2 to tetravalent aromatic oil having 2 or more carbon atoms and 1 to 2 hydroxyl groups. a device, wherein C represents a divalent aromatic organic group selected from the group consisting of 3b to 3e of the following formula 14, D is a divalent silicon-based substituent, and x, y, and z are x+y+z= It is a rational number satisfying 1, O<y+z≤0.7, 0.3≤x+y<1:
[Formula 14]

. According to claim 1,
The repeating unit of Formula 1 is a soluble polyimide resin produced by the polycondensation reaction of a diamine monomer of Formula 4 or 5 and an acid dianhydride:
[Formula 4]

[Formula 5]

In Formula 4, R ₁ and R ₂ are each independently H, C1-C6 alkyl, C1-C6 alkoxy, fluorine, hydroxy or methyl trifluoride, and in Formula 5, R ₁ is H, C1-C6 alkyl, C1 ~C6 alkoxy, hydroxy, carboxy, fluorine, or methyl trifluoride, and R ₂ is hydrogen, methyl, or a hydroxy group. delete According to claim 1,
Wherein A is a tetravalent aromatic organic group selected from the group consisting of 1a to 1s of the following formula 12, a soluble polyimide resin:
[Formula 12]

. According to claim 1,
Wherein B is a divalent aromatic organic group selected from the group consisting of 2a to 2p of the following Chemical Formula 13, a soluble polyimide resin:
[Formula 13]

. delete According to claim 1,
Wherein D is a siloxane group selected from the group consisting of 4a to 4c of Formula 15 below, a soluble polyimide resin.
[Formula 15]

. According to claim 1,
The terminal is sealed by 0.1 to 1 molar equivalent of monoamine with respect to the total molar equivalent of the repeating units of Formulas 1 to 3, wherein the monoamine is at least one selected from the group consisting of 5a to 5s of Formula 16, Soluble polyimide resin:
[Formula 16]

. According to claim 1,
The terminal is sealed by 0.1 to 1 molar equivalent of an acid anhydride based on the total molar equivalent of the repeating units of Formulas 1 to 3, wherein the acid anhydride is selected from the group consisting of 6a to 6i of Formula 17 At least one soluble polyimide resin:
[Formula 17]

. 3. The method of claim 2,
The diamine monomer and the acid dianhydride are mixed in a molar ratio of 1:1 to 5:4, a soluble polyimide resin. 3. The method of claim 2,
The acid dianhydride 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-cyclohexanetetra Carboxylic 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 dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, and 2,2- At least one selected from the group consisting of bis (3,4-dicarboxyphenyl) hexafluoroisopropylidene dianhydride, a soluble polyimide resin. According to claim 1,
A soluble polyimide resin that uses a mixed solution of a dehydrating agent, a catalyst and a solvent to cause chemical curing. 13. The method of claim 12,
The solvent is N-methyl-2-pyrrolidone, N,N-dimethyl formamide, N,N-dimethylacetamide, dimethylsulfoxide, urea, or γ-butyrolactone, tetrahydrofuran, dioxane, or propylene glycol monomethyl ether, acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, cyclopentanone, or diacetone alcohol, ethyl acetate, propylene glycol monomethyl ether acetate, butyl acetate, or ethyl lactate, toluene, or Xylene, soluble polyimide resin. According to claim 1,
A soluble polyimide resin having a weight average molecular weight of 3,000 to 100,000 g/mol. The soluble polyimide resin of any one of claims 1, 2, 4, 5, and 7 to 14;
at least one additional component selected from the group consisting of a crosslinking agent, an adhesion promoter and a surfactant;
photosensitizer; and
A positive photosensitive polyimide varnish composition comprising a solvent. 16. The method of claim 15,
A positive photosensitive polyimide varnish composition comprising 1 to 50 parts by weight of a photosensitizer and 200 to 650 parts by weight of a solvent based on 100 parts by weight of the soluble polyimide resin. 17. The method of claim 16,
Based on 100 parts by weight of the soluble polyimide resin, 1 to 50 parts by weight of a photosensitizer, 0.5 to 10 parts by weight of a crosslinking agent, 0.5 to 10 parts by weight of an adhesion promoter, 0.1 to 1 parts by weight of a surfactant, and 200 to 650 parts by weight of a solvent, A positive photosensitive polyimide varnish composition. 16. The method of claim 15,
The photosensitizer is a positive photosensitive polyimide varnish composition comprising at least one selected from the group consisting of 7a to 7g of the following Chemical Formula 18:
[Formula 18]

In the above formula, D may be a functional group represented by 7g or 7h of Formula 19 below:
[Formula 19]

. 16. The method of claim 15,
The photosensitizer further comprises a thermal acid generator, a positive photosensitive polyimide varnish composition. 20. The method of claim 19,
The thermal acid generator is at least one selected from the group consisting of methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid sulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, or 8a to 8e of the following Chemical Formula 20, Positive photosensitive polyimide varnish composition:
[Formula 20]

16. The method of claim 15,
The crosslinking agent is at least one selected from the group consisting of 9a to 9l of the following Chemical Formula 21, a positive photosensitive polyimide varnish composition:
[Formula 21]

. 16. The method of claim 15,
The adhesion promoter is trimethoxysilylbenzoic acid, γ-methacryloyloxy propyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidoxypropyl At least one selected from the group consisting of trimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, a positive photosensitive polyimide varnish composition. 16. The method of claim 15,
The surfactant is at least one selected from the group consisting of a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant, a positive photosensitive polyimide varnish composition. 16. The method of claim 15,
The solvent is N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethyl urea, Hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether acetate, 2-ethoxy ethanol, 2-methoxyethyl ether, ethyl carbitol, butyl carb Positive photosensitivity, comprising at least one selected from bitol, ethyl carbitol acetate, butyl carbitol acetate, ethyl acetate, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, cyclohexanone, and cyclopentanone A polyimide varnish composition. A photosensitive resin film formed using the positive photosensitive polyimide varnish composition of claim 15 . A semiconductor protective film comprising the photosensitive resin film of claim 25 . An insulating film of LCD or OLED comprising the photosensitive resin film of claim 25.