KR101026954B1 - Photosensitive resin composition - Google Patents

Abstract

The present invention relates to a photosensitive resin composition comprising an alkali-soluble resin, a photosensitive agent having a quinonediazide group and a curing agent, wherein the alkali-soluble resin is an acrylic resin, the curing agent is a curing agent containing an epoxy group, and the photosensitive resin composition The present invention relates to a flat display panel or semiconductor device including a photosensitive resin composition containing a carboxylic acid and a planarization film or an interlayer insulating film formed by using the photosensitive resin composition. As said carboxylic acid, C ₁₂ -C ₁₈ saturated fatty acid and C ₁₂ -C ₂₄ unsaturated fatty acid are preferable.

Alkali-soluble resin, quinonediazide group, photosensitive agent, hardening | curing agent, photosensitive resin composition, acrylic resin, a flat display panel, and a semiconductor element.

Description

Photosensitive resin composition

This invention uses the photosensitive resin composition, More specifically, the photosensitive resin composition suitable for manufacture of a semiconductor device, a flat panel display (FPD), etc., especially the formation of an interlayer insulation film or planarization film, such as a semiconductor device and FPD, and the said photosensitive resin composition. And a method for forming a heat resistant thin film using the FPD and the semiconductor device formed by using the photosensitive resin composition.

BACKGROUND ART Photolithography techniques have conventionally been used to form or fabricate fine elements in a wide range of fields including semiconductor integrated circuits such as LSI, manufacturing of FPD display surfaces, and manufacturing circuit boards such as thermal heads. . And in photolithography technique, in order to form a resist pattern, the positive type or negative type photosensitive resin composition is used. In recent years, as a new use of such a photosensitive resin composition, the technique of forming an interlayer insulation film or planarization film, such as a semiconductor integrated circuit and FPD, attracts attention. In particular, the market demand for high precision of the FPD display surface is strong, and in order to achieve such high precision, an interlayer insulating film and a flattening film having high transparency and excellent insulating properties are known as essential materials. A lot of research is made about the photosensitive resin composition used for such a use, and the patent application is published and it is disclosed. -262709. However, the photosensitive resin composition proposed as suitable for use in conventional interlayer insulating films and the like requires a crosslinking (curing) agent in order to increase heat resistance. In comparison, special attention is paid to the preservation environment of the composition. In addition, in photolithography in the manufacturing process of the FPD display surface, a recycling developer using a developer repeatedly is used. In such a recycling developer, when a positive resist for TFT (thin film transistor) fabrication and a photosensitive resin composition containing the crosslinking agent are mixed, the crosslinking agent in the composition containing the positive resist and the crosslinking agent is insoluble in the developer. There is a problem that a large amount of phosphorus precipitate occurs.

On the other hand, by using 1,2-naphthoquinone diazide sulfonic acid ester of the polyhydroxy compound of the general formula (I) as a photosensitive agent, a photosensitive resin capable of forming a resist pattern having high resolution, high aspect ratio, heat resistance and cross-sectional shape Although the composition is known (see Japanese Patent Application Laid-Open No. 5-297582 (pages 1 to 5, 9 and 10)), acrylic resin is not used as alkali-soluble resin, and the time-lapse stability of the photosensitive resin composition There is no description of improvement.

Moreover, although the technique of preventing the clouding of the planarization film after heat processing by introducing the monomer which has an epoxy group in a polymer main chain is known, see Unexamined-Japanese-Patent No. 7-248629, Unexamined-Japanese-Patent No. (Ho) 8-262709] In this method, the stability of the polymer is inferior, and the storage stability of the photosensitive resin composition becomes very short. Moreover, when mixing and using a polymer and an epoxy resin without making it into a copolymer, although storage stability is very excellent, there exists a problem that the surface of the planarization film after heat processing becomes cloudy.

In view of the above circumstances, the present invention provides a photosensitive resin composition containing an alkali-soluble resin, a photosensitive agent containing a quinonediazide group, and a curing agent, which maintains the flatness of the film surface even after high temperature baking, A thin film having a low dielectric constant is obtained, and an object thereof is to provide a photosensitive resin composition having good stability over time.

Moreover, this invention provides the FPD or semiconductor device which has the planarization film or interlayer insulation film formed by the said photosensitive resin composition.

Moreover, this invention provides the method of forming a heat resistant thin film by patterning using the said photosensitive resin composition, performing whole surface exposure, and then post-baking.

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching and examining, in the photosensitive resin composition containing the photosensitive agent and hardening | curing agent containing alkali-soluble resin, a quinonediazide group, it uses the specific material as alkali-soluble resin and a hardening | curing agent, and the said photosensitive resin composition By containing carboxylic acid in the above, the above object can be achieved, that is, a thin film having a good light transmittance and low dielectric constant while maintaining the flatness of the film surface even after heat treatment at high temperature at 220 ° C. for 1 hour, for example. This was obtained, and it was found that a photosensitive resin composition having excellent stability over time was obtained, and completed the present invention.

That is, this invention provides the photosensitive resin composition of the following (1)-(12).

(1) A photosensitive resin composition comprising an alkali-soluble resin, a photosensitive agent having a quinonediazide group, and a curing agent, wherein the alkali-soluble resin is an acrylic resin, the curing agent contains an epoxy group, and the photosensitive resin composition contains a carboxylic acid. The photosensitive resin composition characterized by the above-mentioned.

(2) The photosensitive resin composition according to item (1), wherein the photosensitive agent having a quinone diazide group is a reaction product of a phenolic compound of formula (I) or formula (II) and a naphthoquinone diazide compound. .

In the above formulas (I) and (II),

R ¹ , R ² , R ³ and R ⁴ are each independently H or a C ₁ -C ₂ alkyl group,

R ⁵ and R ⁶ are each independently C ₁ -C ₂ alkyl group,

의 그룹이며, R¹⁴는 H 또는 C₁-C₄ 알킬 그룹이며,R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently H, C ₁ -C ₄ alkyl group or formula

Is a group of R ¹⁴ is H or a C ₁ -C ₄ alkyl group,

m and n are each independently an integer of 0 to 2,

a, b, c, d, e, f, g and h are integers of 0 to 5 satisfying a + b ≦ 5, c + d ≦ 5, e + f ≦ 5 and g + h ≦ 5 ,

i is an integer from 0 to 2.

(3) The photosensitive resin composition according to item (1) or (2), wherein the photosensitive resin composition further comprises a phenolic compound of the formula (I) or (II).

(4) The photosensitive resin composition according to any one of items (1) to (3), wherein the carboxylic acid is a C ₁₂ -C ₁₈ saturated fatty acid of the formula C _n H _{2n + 1} COOH, wherein n is 11 to 17 Photosensitive resin composition which is one or more types).

(5) The photosensitive resin composition according to any one of the items (1) to (3), wherein the carboxylic acid is at least one of C ₁₂ -C ₁₈ saturated fatty acids having 1 to 3 unsaturated double bonds in the molecule, Photosensitive resin composition.

(6) Photosensitive resin composition in any one of said item (1)-(5) WHEREIN: Acrylic resin contains the structural unit derived from the alkyl (meth) acrylate and the structural unit derived from (meth) acrylic acid Resin composition.

(7) The photosensitive resin composition as described in any one of said items (1)-(6) WHEREIN: The photosensitive resin composition in which acrylic resin contains 5-30 mol% of structural units derived from (meth) acrylic acid.

(8) The photosensitive resin composition as described in any one of said (1)-(7) whose polystyrene conversion weight average molecular weight of acrylic resin is 5,000-30,000.

(9) The photosensitive resin composition as described in any one of said (1)-(8) whose alkali-soluble resin is synthesize | combined using the cyano group-free azo polymerization initiator.

(10) The photosensitive resin composition according to any one of items (1) to (8), wherein the alkali-soluble resin is synthesized using a cyano group-containing azo polymerization initiator.

(11) The photosensitive resin composition according to any one of items (1) to (8), wherein the alkali-soluble resin is synthesized using a cyano group-free azo-based polymerization initiator and a cyano group-containing azo-based polymerization initiator in combination. The photosensitive resin composition whose molar ratio of the cyano group containing azo polymerization initiator and the cyano group containing azo polymerization initiator is 20: 80-80: 20.

Moreover, this invention provides the flat panel display or semiconductor device as described in the following item (12) or (13).

(12) An FPD having a flattening film or an interlayer insulating film formed of the photosensitive resin composition according to any one of the items (1) to (11).

(13) A semiconductor device characterized by having a planarization film or an interlayer insulation film formed of the photosensitive resin composition according to any one of the items (1) to (11).

The present invention also relates to the following thin film formation method.

(14) A method for forming a heat-resistant thin film, characterized in that after performing patterning using the photosensitive resin composition according to any one of the items (1) to (11), the surface is exposed and then postbaked.

Effects of the Invention

The photosensitive resin composition of this invention is excellent in time-lapse stability and application | coating characteristic, and the photosensitive resin composition of this invention is excellent in heat resistance, for example, after heat-processing for 1 hour at high temperature of 220 degreeC, It is possible to form a thin film which maintains flatness without causing, and has good light transmittance, low dielectric constant and also solvent resistance. For this reason, the photosensitive resin composition of this invention can be used suitably for planarization films, interlayer insulation films, etc., such as a semiconductor element, and the FPD and semiconductor device excellent in the characteristic can be obtained by using the photosensitive resin composition of this invention.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In the photosensitive resin composition of this invention, although acrylic resin is used as alkali-soluble resin, any alkali-soluble acrylic resin used by this invention is good if it is acrylic resin conventionally used as alkali-soluble resin of photosensitive resin. As the polymerization initiator, an alkali-soluble acrylic resin synthesized using a cyano group-containing azo polymerization initiator, an alkali-soluble acrylic resin synthesized using a cyano group-free azo polymerization initiator, or a cyano group ratio Any alkali-soluble acrylic resin synthesize | combined using the containing azo polymerization initiator and the cyano group containing azo polymerization initiator can be used preferably.

As a cyano group-free azo polymerization initiator used at the time of the synthesis | combination of the said alkali-soluble acrylic resin, For example, 1,1'- azobis (1-acetoxy-1- phenylethane), 1,1 ' Azobis (1-propionoxy-1-phenylethane), 1,1'-azobis (1-isobutyloxy-1-phenylethane), 1,1'-azobis (1-pivaloxy-1- Phenylethane), 1,1'-azobis (1-acetoxy-1-phenylpropane), 1,1'-azobis [1-acetoxy-1- (p-methylphenyl) ethane], 1,1 ' -Azobis [1-acetoxy-1- (p-chlorophenyl) ethane], 1,1'-azobis (1-acetoxy-1-phenylbutane), dimethyl-2,2'-azobis (2 -Methylpropionate), 1,1'-azobis (1-chloro-1-phenylethane), 1,1'-azobis (1-chloro-1-propane), 1,1'-azobis [ 1-chloro-1- (p-methylphenyl) ethane], 1,1'-azobis [1-chloro-1- (p-chlorophenyl) ethane], 1,1'-azobis (1-chloro-1 -Phenylbutane), 2,2'-azobis (2-acetoxy-3,3-dimethylbutane), 2,2'-azobis (2-acetoxy-4 -Methylpentane), 2,2'-azobis (2-propionoxy-3,3-dimethylbutane), 2,2'-azobis (2-propionoxy-4-methylpentane), 2,2'- Azobis (2-isobutoxy-3,3-dimethylbutane), 2,2'-azobis (2-isobutoxy-4-methylpentane), 2,2'-azobis (2-pivaloxy-3, 3-dimethylbutane), 2,2'-azobis (2-pivaloxy-4-methylpentane), 2,2'-azobis (2-benzoyloxy-3,3-dimethylbutane), 2,2 ' Azobis (2-benzoyloxy-4-methylpentane), 2,2'-azobis (2-acetoxypropane), 2,2'-azobis (2-acetoxybutane), 2,2'- Azobis (2-acetoxy-3-methylbutane), 2,2'-azobis (2-propionoxypropane), 2,2'-azobis (2-propionoxybutane), 2,2'-azo Bis (2-propionoxy-3-methylpropane), 2,2'-azobis (2-isobutyloxypropane), 2,2'-azobis (2-isobutyloxybutane), 2,2'- Azobis (2-isobutyloxy-3-methylbutane), 2,2'-azobis (2-pivaloxypropane), 2,2'-azobis (2-pivaloxybutane), 2,2'- Ah Bis (2-pivaloxy-3-methylbutane), 2,2'-azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), 1,1'- Azobis (1-methoxycyclohexane), 2,2'-azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-hydroxyphenyl ) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2'-azobis [N -(2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride , 2,2'-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] dihydrochloride, 2,2'-azobis [ 2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [N- (2-propyl) -2-methyl Propionamide], 2,2'-azo S [2- (2-imidazolin-2-yl) propane], 2,2'-azobis {2-methyl-N- [bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxy Methyl) propionamide], 2,2'-azobis (2-methylpropionamide) dihydrate, and the like.

Preferable cyano group-free azo polymerization initiators include 1,1'-azobis (1-acetoxy-1-phenylethane), 1,1'-azobis (1-propionoxy-1-phenylethane), 1,1'-azobis (1-isobutyloxy-1-phenylethane), 1,1'-azobis (1-pivaloxy-1-phenylethane), 1,1'-azobis (1-ace Methoxy-1-phenylpropane), 1,1'-azobis [1-acetoxy-1- (p-methylphenyl) ethane], 1,1'-azobis [1-acetoxy-1- (p-chloro Phenyl) ethane], 1,1'-azobis (1-acetoxy-1-phenylbutane), and dimethyl-2,2'-azobis (2-methylpropionate).

Further, as the cyano group-containing azo polymerization initiator, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2 ' Azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), and the like. A preferable cyano group containing azo polymerization initiator is 2,2'- azobisisobutyronitrile.

In the synthesis of the acrylic resin, when the acrylic resin is synthesized using a cyano group-free azo polymerization initiator as the polymerization initiator, and the resin is used as the acrylic resin of the photosensitive resin composition of the present invention, the light transmittance is very high. It is possible to form a film having good heat resistance and good solvent resistance. On the other hand, when the acrylic resin synthesize | combined using the cyano group containing azo polymerization initiator as a polymerization initiator is used, the photosensitive resin composition excellent in heat resistance and solvent resistance will be obtained. As the polymerization initiator, when acrylic resins synthesized by using a cyano group-free azo-based polymerization initiator and a cyano group-containing azo-based polymerization initiator in combination are used, various properties such as light transmittance, solvent resistance and heat resistance are excellent in balance. The photosensitive resin composition can be obtained. Moreover, also when using any, the time-lapse stability of the photosensitive resin composition of this invention is very excellent. When using a cyano group-free azo-type polymerization initiator and a cyano group-containing azo-type polymerization initiator together as a polymerization initiator, they are normally in the range of 20: 80-80: 20 in molar ratio, Preferably it is 30: 70-70 Used in the range of: 30.

As alkali-soluble acrylic resin used in the photosensitive resin composition of this invention, (a) alkali-soluble polyacrylic acid ester, (b) alkali-soluble polymethacrylic acid ester, and (c) 1 or more types of acrylic ester and 1 type Alkali-soluble poly (acrylic acid ester methacrylic acid ester) containing the above methacrylic acid ester as a structural unit is mentioned. Such acrylic resin may be used independently and 2 or more types may be used together. In addition, such an acrylic resin preferably contains an organic acid monomer as a copolymerization component in order to make the resin alkali-soluble. However, the copolymer unit for imparting alkali solubility to the resin is not limited to the organic acid monomer.

As a monomer component which comprises such alkali-soluble polyacrylic-type resin, acrylic acid ester, methacrylic acid ester, an organic acid monomer, and another copolymerizable monomer are mentioned. As a monomer component which comprises such a polymer, the acrylic acid ester, methacrylic acid ester, and organic acid monomer of the following illustration are preferable.

Acrylic esters:

Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-hexyl acrylate, isopropyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, benzyl acrylate 2-chloroethyl acrylate, methyl-α-chloracrylate, phenyl-α-acrylate and the like

Methacrylic acid esters:

Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate , Cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, 1-phenylethyl methacrylate, 2-phenylethyl methacrylate, furfuryl methacrylate, diphenylmethyl methacrylate, pentachlorphenyl methacrylate Acrylate, naphthyl methacrylate, isoboroyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, etc.

Organic Acid Monomers:

Monocarboxylic acids such as acrylic acid, methacrylic acid and clotonic acid, dicarboxylic acids such as itaconic acid, maleic acid, fumaric acid, citraconic acid and mesaconic acid, anhydrides of such dicarboxylic acids, 2-acryloylhydrogenphthalate, 2-acrylic acid Loyloxypropylhydrogenphthalate, etc.

Examples of the other copolymerizable monomers include maleic acid diesters, fumaric acid diesters, styrene and styrene derivatives, acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl chloride, vinylidene chloride, and the like. Such other copolymers may be used as necessary, and the amount thereof is also used in an amount within the range in which the acrylic resin can achieve the object of the present invention.

In this invention, what is preferable as acrylic resin is the copolymer containing the structural unit derived from alkyl (meth) acrylate and the structural unit derived from (meth) acrylic acid, More preferably, it contains 5-30 mol% of (meth) acrylic acid. It is. Moreover, it is preferable that the weight average molecular weights of polystyrene conversion weight average molecular weights of alkali-soluble acrylic resin used in this invention are 5,000-30,000. When the molecular weight of acrylic resin is less than 5,000, the problem of inferior solvent resistance and heat resistance may arise, and when it exceeds 30,000, the problem of developing residue may arise.

As a photosensitive agent which has a quinonediazide group used for the photosensitive resin composition of this invention, the reaction product of the said phenolic compound of Formula (I) or (II) and a naphthoquinone diazide compound is mentioned as a preferable thing. As a phenolic compound of general formula (I), the following compounds are mentioned, for example. The synthesis of these compounds can be suitably carried out by a conventionally known method, for example, the method described in JP-A-5-297582 (pages 1 to 5, 9, 10). .

In addition, as the phenolic compound of Formula (II), o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, bisphenol A, B, C, E, F and G, 4,4 ', 4 "-methylidritrisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4'-[1- [4- [2- (4-hydroxy Phenyl) -2-propyl] phenyl] ethylidene] bisphenol, 4,4 ', 4 "-ethylidinetrisphenol, 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol, 4,4 '-[(2-hydroxyphenyl) methylene] bis [2,3-dimethylphenol], 4,4'-[(3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 '-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2'-[(2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 '-[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4'-[(3,4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol ], 4-[ Bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) methyl] -1,2-benzenediol, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1, 2,3-benzenetriol, 4,4 '-[(2-hydroxyphenyl) methylene] bis [3-methylphenol], 4,4', 4 "-(3-methyl-1-propanyl-3 -Ilidine) trisphenol, 4,4 ', 4 ", 4' ''-(1,4-phenylenedimethylidine) tetrakisphenol, 2,4,6-tris [(3,5-dimethyl-4 -Hydroxyphenyl) methyl] -1,3-benzenediol, 2,4,6-tris [(3,5-dimethyl-2-hydroxyphenyl) methyl] -1,3-benzenediol, 4,4 ' -[1- [4- [1- [4-hydroxy-3,5-bis [hydroxy-3-methylphenyl) methyl] phenyl] -1-methylethyl] phenyl] ethylidene] bis [2,6- Bis (hydroxy-3-methylphenyl) methyl] phenol and the like. Further preferred compounds include 4,4 ', 4 "-methylidinetrisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol, 4,4'-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4 '-[1- [4- [2- (4-hydroxyphenyl) -2- Propyl] phenyl] ethylidene] bisphenol, 4,4 ', 4 "-ethylidine trisphenol, etc. are mentioned.

Among these phenolic compounds of formula (II), compounds of formula (III) or formula (IV) are particularly preferred.

On the other hand, the naphthoquinone diazide compound which is reacted with the phenolic compound of formula (I) or (II) is any compound containing a quinone diazide group capable of reacting with the phenolic compound of formula (I) or (II) to form an esterified product. It is also good. As such a quinone diazide compound, naphthoquinone diazide sulfonic acid chloride represented by 1,2-naphthoquinone diazide-5-sulfonyl chloride, 1,2-naphthoquinone diazide-4- sulfonyl chloride, etc. Or quinone diazide sulfonic acid halides such as benzoquinone diazide sulfonic acid chloride. The esterification reaction, for example, the phenolic compound of formula (I) or (II) and the quinonediazidesulfonic acid halide in the presence of a basic catalyst, for example, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, triethylamine and the like In general, the reaction is carried out at a temperature of about -20 to 60 ℃. The esterification may be a part of the hydroxyl groups of the phenolic compounds of the formula (I) or (II) or all hydroxyl groups. An esterification rate can be made suitable by adjusting the quantity of the phenolic compound of Formula (I) or (II), and the quantity of the compound which has a quinonediazide group. In this esterification reaction, mixtures having different esterification numbers and esterification positions are obtained. Thus, the esterification rate is expressed as the average of these mixtures. In addition, such a reaction product may be used individually by 1 type, and 2 or more types may be used together. In the present invention, by using the reaction product of the phenolic compound of formula (I) or (II) and the naphthoquinone diazide compound, excellent long-term storage stability and formation of a film excellent in light transmittance, solvent resistance, heat resistance and insulation can do. In this invention, the said reaction product is normally used in the quantity of 1-30 weight part with respect to 100 weight part of alkali-soluble resin components in the photosensitive resin composition. As the photosensitizer, other photosensitizers may be used together with the above reaction products within a range not impairing the object of the present invention.

Moreover, the photosensitive resin composition of this invention contains the hardening | curing agent which has an epoxy group as a hardening | curing agent. Examples of the curing agent having such an epoxy group include bisphenol type epoxy resins, cresol novolac type epoxy resins, cyclic aliphatic epoxy resins, glycidyl ether epoxy resins, glycidyl amine epoxy resins, heterocyclic epoxy resins, and the like. Can be mentioned. However, the curing agent which can be used in the present invention is not limited to such a high molecular weight epoxy resin, and may be a low molecular epoxy compound such as glycidyl ether of bisphenol A or bisphenol F. The curing agent having such an epoxy group is preferably used in an amount of 2 to 60 parts by weight, more preferably 10 to 40 parts by weight based on 100 parts by weight of the alkali-soluble resin.

In addition, carboxylic acid is used for the photosensitive resin composition of this invention. The carboxylic acid used in the present invention may be either a saturated carboxylic acid or an unsaturated carboxylic acid. Preferred saturated carboxylic acids include C ₁₂ -C ₁₈ fatty acids of the formula C _n H _{2n + 1} COOH, wherein n is an integer from 11 to 17. Although the aliphatic group of the saturated fatty acid of the said general formula may be linear or branched chain, a linear aliphatic group is preferable. As such saturated fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, etc. are mentioned, for example, stearic acid and lauric acid are preferable. Further, as a preferred unsaturated carboxylic acids, there may be mentioned C ₁₂ -C ₂₄ unsaturated fatty acid having 1 to 3 unsaturated double bonds in the molecule. Examples of the unsaturated fatty acid having one double bond include, for example, nerbonic acid [CH ₃ (CH ₂ ) ₇ CH = CH (CH ₂ ) ₁₃ COOH] and ercaic acid [CH ₃ (CH ₂ ) ₇ CH = CH (CH ₂ ) ₁₁ COOH], cis-11-eicosenoic acid [CH ₃ (CH ₂ ) ₇ CH = CH (CH ₂ ) ₉ COOH], oleic acid [CH ₃ (CH ₂ ) ₇ CH = CH (CH ₂ ) ₇ COOH] , Palmitic acid [CH ₃ (CH ₂ ) ₅ CH = CH (CH ₂ ) ₇ COOH], myristeric acid [CH ₃ (CH ₂ ) ₃ CH = CH (CH ₂ ) ₇ COOH], cis-5-dode Senic acid [CH ₃ (CH ₂ ) ₅ CH = CH (CH ₂ ) ₃ COOH] and the like, and examples of the unsaturated fatty acid having two double bonds include 11,14-eicosadienoic acid [CH ₃ (CH ₂ ) ₄ (CH = CHCH ₂ ) ₂ (CH ₂ ) ₈ COOH], linoleic acid [CH ₃ (CH ₂ ) ₄ (CH = CHCH ₂ ) ₂ (CH ₂ ) ₆ COOH], and the like. Examples of the unsaturated fatty acid having three double bonds include cis-8,11,14-eicosatriic acid [CH ₃ (CH ₂ ) ₃ (CH = CHCH ₂ ) ₃ (CH ₂ ) ₆ COOH], Linolenic acid [CH ₃ (CH = CHCH ₂ ) ₃ (CH ₂ ) ₇ COOH]. In such unsaturated fatty acids, the shortening of the alkyl chain tends to reduce the anti-clouding effect. On the other hand, when the alkyl chain is long, the anti-clouding effect is good, but developing residues may occur. In addition, when the alkyl chain is long, the melting point is higher than or equal to room temperature, and bumping may occur during the drying under reduced pressure. Therefore, it is preferable to select an unsaturated fatty acid that does not have such a problem. As unsaturated fatty acids, oleic acid is one of particularly preferred ones.

The photosensitive resin composition of the present invention is a phenol of formula (I) or (II) in addition to the alkali-soluble acrylic resin, a reaction product of the phenolic compound of formula (I) or (II) and a naphthoquinone diazide compound, and a curing agent containing an epoxy group. It is preferable to include a sex compound. In the photosensitive resin composition of this invention, the said phenolic compound of Formula (I) or (II) is normally used for adjusting a dissolution rate as a dissolution inhibitor, or for adjusting the residual film ratio of a photosensitive resin composition or adjustment of a sensitivity. As the phenolic compound of the formula (II), the phenolic compound of the formula (III) or (IV) is preferable. Such a phenolic compound is used in the quantity of 1-20 weight part with respect to 100 weight part of alkali-soluble resin.

In the photosensitive resin composition of this invention, as a solvent which melt | dissolves alkali-soluble resin, a photosensitizer, a hardening | curing agent, a carboxylic acid, a phenolic compound, etc. and forms a photosensitive resin composition solution, ethylene, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, Ethylene glycol monoalkyl ether acetates such as glycol monoalkyl ethers, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, etc. Propylene glycol monoalkyl ethers such as diethylene glycol dialkyl ethers, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Propylene glycol monoalkyl ether acetates such as acetates, lactic acid esters such as methyl lactate and ethyl lactate, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, 2-heptanone and cyclohexanone, N Amides such as N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ-butyrolactone. Such a solvent can be used individually or in mixture of 2 or more types.

An adhesive adjuvant, surfactant, etc. can be mix | blended with the photosensitive resin composition of this invention as needed. Examples of the adhesion assistant include alkyl imidazolines, butyric acids, alkyl acids, polyhydroxy styrenes, polyvinyl methyl ethers, t-butyl novolacs, epoxy silanes, epoxy polymers, silanes, and the like. Ionic surfactants such as polyglycols and derivatives thereof, ie polypropylene glycol or polyoxyethylene lauryl ether, fluorine-containing surfactants such as Fluorad (trade name, Sumitomos Reem) Kaisha), MEGAFAC (trade name, Dainippon Ink & Chemicals Co., Ltd.), sulfon (trade name, manufactured by Asahi Glass Co., Ltd.), or an organic siloxane surfactant, for example, KP341 (brand name, the Shin-Etsu Chemical Co., Ltd. product) is mentioned.

The photosensitive resin composition of this invention is adjusted by melt | dissolving each component in a predetermined amount solvent. At this time, each component may be previously separately dissolved in a solvent, and may be manufactured by mixing each component in a predetermined ratio immediately before use. Usually, the solution of the photosensitive resin composition is provided for use, after filtering using a 0.2 micrometer filter etc.

The photosensitive resin composition of this invention becomes a thin film which has high insulation, high transparency, high heat resistance, and solvent resistance by the following method, and is used suitably as a flat film, an interlayer insulation film, etc. That is, first, the solution of the photosensitive resin composition of this invention is apply | coated on a board | substrate, prebaking is performed, and the coating film (photosensitive resist) of the photosensitive resin composition is formed. At this time, the substrate on which the photosensitive resin composition is applied may be any known substrate such as a conventional FPD or a semiconductor device formation substrate such as glass or silicon. The substrate may be an exposed substrate, an oxide film, a nitride film, a metal film, or the like, or a substrate on which a circuit pattern or a semiconductor element is formed. Subsequently, after performing pattern exposure to a photosensitive resist through a predetermined mask, it develops using alkaline developing solution, and rinses as needed, and forms the thin film positive pattern of the photosensitive resin composition. The thin film positive pattern thus formed is post-baked after the entire surface is exposed, thereby forming a thin film having a high heat resistance temperature. The exposure amount at the time of full-surface exposure should just be 600 mJ / cm <2> or more normally. In addition, the postbaking temperature is usually 150 to 250 ° C, preferably 180 to 230 ° C, and the postbaking time is usually 30 to 90 minutes.

Although the reason why a thin film having a high heat resistance temperature is formed by the method of the present invention is not certain, the photosensitive agent is decomposed by full-surface exposure to form an acid, and crosslinking and curing by a curing agent having an epoxy group are promoted, and a high heat resistant film is formed. It is presumably because it is formed. The formed high heat resistance thin film positive pattern is used as a planarization film, an interlayer insulation film, etc. of FPD, such as a semiconductor element, a liquid crystal display device, and a plasma display. In addition, when forming a heat resistant and solvent resistant thin film on the whole surface, pattern exposure, image development, etc. may not be performed.

In formation of the said thin film, as a coating method of the photosensitive resin composition solution, it is good to use arbitrary methods, such as a spin coating method, a roll coating method, a land coating method, a spray method, the casting | coating method, the immersion coating method, and the like. . Moreover, as radiation used for exposure, ultraviolet rays, such as g-rays and i-rays, far ultraviolet rays, such as KrF excimer laser or ArF excimer laser light, X-ray, an electron beam, etc. are mentioned, for example.

Moreover, as a developing method, according to the method used when developing the conventional photosensitive resist, such as a paddle developing method, the immersion developing method, and the oscillation immersion developing method, it is favorable. As the developer, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and sodium silicate, organic amines such as ammonia, ethylamine, propylamine, diethylamine, diethylaminoethanol and triethylamine, tetramethylammonium hydroxide Quaternary amines, such as a side, etc. are mentioned.

Although an Example demonstrates this invention more concretely below, the aspect of this invention is not limited to this Example.

Synthesis Example 1 (Synthesis of Acrylic Copolymer 1)

In a 2000 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a nitrogen introduction tube, 700 g of propylene glycol monomethyl ether acetate, 171 g of methyl methacrylate, 90 g of methacrylic acid 2-hydroxypropyl, 39 g of methacrylic acid, dimethyl 2 12.6 g of, 2'-azobis (2-methylpropionate) was charged with stirring, heated with blowing nitrogen, and polymerized at 85 ° C for 8 hours to obtain an acrylic copolymer 1 having a weight average molecular weight of 11,000.

Synthesis Example 2 (Synthesis of Acrylic Copolymer 2)

In a 2000 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a nitrogen introduction tube, 700 g of propylene glycol monomethyl ether acetate, 171 g of methyl methacrylate, 90 g of methacrylic acid 2-hydroxypropyl, 39 g of methacrylic acid, dimethyl 2 6.3 g of 2,2'-azobis (2-methylpropionate) [molecular weight: 230.26] and 4.5 g of 2,2'-azobisisobutyronitrile [molecular weight: 164.21] were added and stirred, and the temperature was raised while blowing nitrogen. And polymerized at 85 ° C. for 8 hours to obtain acrylic copolymer 2 having a weight average molecular weight of 11,000.

Synthesis Example 3 (Synthesis of Acrylic Copolymer 3)

In a 2000 ml four-necked flask equipped with a stirrer, a cooling tube, a thermometer and a nitrogen introduction tube, 700 g of propylene glycol monomethyl ether acetate, 171 g of methyl methacrylate, 90 g of methacrylic acid 2-hydroxypropyl, 39 g of methacrylic acid, 2, 9 g of 2'-azobisisobutyronitrile was added and stirred, the temperature was raised while blowing in nitrogen, and the polymerization was carried out at 85 ° C. for 8 hours to obtain an acrylic copolymer 3 having a weight average molecular weight of 11,000.

Example 1

100 parts by weight of the acrylic copolymer 1 obtained in Synthesis Example 1, 25 parts by weight of an esterified product of the following general formula (V), and 5 parts by weight of the phenolic compound of the formula (III), an epoxy group-containing curing agent (TECHMORE) VG3101L (manufactured by Mitsui Chemical Co., Ltd.) 17 parts by weight and 1.0 part by weight of stearic acid are dissolved in propylene glycol monomethyl ether acetate / ethyl lactate (75/25), and photosensitive corrosion resistance during rotational coating. In order to prevent radiation wrinkles and so-called striations on the membrane, 300 ppm of a fluorine-based surfactant, MegaPac R-08 (see Dainippon Ink & Chemicals Co., Ltd.) was added and stirred, followed by stirring. The photosensitive resin composition 1 of this invention was manufactured by filtering by the micrometer filter.

<Formation of Thin Film Pattern>

The photosensitive resin composition 1 obtained above was spun on a 4 inch silicon wafer, baked at 100 ° C. for 90 seconds on a hot plate, and then a 3.0 μm thick photoresist was obtained. Canon + Co., Ltd. g + h + i line mask aligner (PLA-501F) was used to expose the test patterns of various line widths and contact holes having a 1: 1 line width and contact hole at an optimal exposure dose. The solution was developed at 23 ° C. for 60 seconds with an aqueous solution of wt% tetramethylammonium hydroxide to form patterns and contact holes having 1: 1 line and space widths.

Evaluation of Film Surface Properties

The pattern forming substrate obtained above was subjected to full exposure (600 mJ / cm 2) with a g + h + i line mask aligner (PLA-501F) manufactured by Canon Corporation, and then heated at 120 ° C. for 15 minutes on a hot plate. After treatment, heat treatment was performed at 220 ° C. for 60 minutes in a circulating clean oven. Then, the surface state of the film | membrane was observed with the optical microscope, and when white cloudiness was not observed, it evaluated as 0, (triangle | delta) when white cloudiness was observed, and x when white cloudiness was observed. The results are shown in Table 1.

<Evaluation of Stability Over Time>

Sample A was obtained by allowing the obtained photosensitive resin composition 1 to stand at 5 ° C. for 20 days, and Sample B was left standing at 23 ° C. for 20 days. Sample A and Sample B were each spin-coated onto a 4-inch silicon wafer and baked on a hot plate at 100 ° C. for 90 seconds to obtain a 3.0 μm thick photoresist. Canon + Co., Ltd. g + h + i line mask aligner (PLA-501F) was used to expose the test patterns of various line widths and contact holes having a 1: 1 line width and contact hole at an optimal exposure dose. The solution was developed at 23 ° C. for 60 seconds with an aqueous solution of wt% tetramethylammonium hydroxide to form patterns and contact holes having a 1: 1 line and space width. The residual film ratio is defined as a percentage of the value obtained by dividing the resist film thickness after development by the resist film thickness after application, and the difference between O and the residual film rate is different when the difference between the residual film rates of Sample A and Sample B is less than 3%. About 3% or more, it evaluated as x. The results are shown in Table 1.

Example 2

The photosensitive resin composition 2 was manufactured like Example 1 except having used the acrylic copolymer 2 obtained by the synthesis example 2 instead of the acrylic copolymer 1. Using the said photosensitive resin composition 2, formation of a thin film pattern, evaluation of a film surface characteristic, and evaluation of stability with time were performed like Example 1. The evaluation results are shown in Table 1.

Example 3

Photosensitive resin composition 3 was prepared in the same manner as in Example 1 except that the acrylic copolymer 3 obtained in Synthesis Example 3 was used instead of the acrylic copolymer 1. Using the said photosensitive resin composition 3, formation of a thin film pattern, evaluation of a film surface characteristic, and evaluation of stability with time were performed like Example 1. The evaluation results are shown in Table 1.

Example 4

Except for using the phenolic compound of formula III and 1,2-naphthoquinonediazide-5-sulfonyl chloride instead of the photosensitizer of formula (V) (esterification rate 50%) as in Example 1 Thus, the photosensitive resin composition 4 was manufactured. Using this photosensitive resin composition 4, formation of a thin film pattern, evaluation of a film surface characteristic, and evaluation of stability with time were performed like Example 1. The evaluation results are shown in Table 1.

Example 5

The photosensitive resin composition 5 was manufactured like Example 4 except having used the acrylic copolymer 2 obtained by the synthesis example 2 instead of the acrylic copolymer 1. Using this photosensitive resin composition 5, formation of a thin film pattern, evaluation of a film surface characteristic, and evaluation of stability with time were performed like Example 4. The evaluation results are shown in Table 1.

Example 6

A photosensitive resin composition 6 was prepared in the same manner as in Example 4 except that the acrylic copolymer 3 obtained in Synthesis Example 3 was used instead of the acrylic copolymer 1. Using this photosensitive resin composition 6, formation of a thin film pattern, evaluation of film surface characteristic, and evaluation of stability with time were performed like Example 4. The evaluation results are shown in Table 1.

Example 7

The photosensitive resin composition 7 was manufactured like Example 1 except having used lauric acid instead of stearic acid. Using this photosensitive resin composition 7, the formation of a thin film pattern, evaluation of film surface characteristics, and evaluation of stability over time were performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 8

The photosensitive resin composition 8 was manufactured like Example 2 except having used lauric acid instead of stearic acid. Using this photosensitive resin composition 8, formation of a thin film pattern, evaluation of the film surface characteristic, and evaluation of stability with time were performed like Example 2. The evaluation results are shown in Table 1.

Example 9

A photosensitive resin composition 9 was prepared in the same manner as in Example 3 except that lauric acid was used instead of stearic acid. Using this photosensitive resin composition 9, formation of a thin film pattern, evaluation of a film surface characteristic, and evaluation of stability with time were performed like Example 3. The evaluation results are shown in Table 1.

Example 10

The photosensitive resin composition 10 was manufactured like Example 4 except having used lauric acid instead of stearic acid. Using this photosensitive resin composition 10, formation of a thin film pattern, evaluation of the film surface characteristic, and evaluation of stability with time were performed like Example 4. The evaluation results are shown in Table 1.

Example 11

The photosensitive resin composition 11 was manufactured like Example 5 except having used lauric acid instead of stearic acid. Using this photosensitive resin composition 11, formation of a thin film pattern, evaluation of the film surface characteristic, and evaluation of stability with time were performed like Example 5. The evaluation results are shown in Table 1.

Example 12

Photosensitive resin composition 12 was prepared in the same manner as in Example 6 except that lauric acid was used instead of stearic acid. Using this photosensitive resin composition 12, formation of a thin film pattern, evaluation of film surface characteristic, and evaluation of stability with time were performed like Example 6. The evaluation results are shown in Table 1.

Example 13

100 parts by weight of the acrylic copolymer 1 obtained in Synthesis Example 1, 25 parts by weight of an esterified product of Formula V (esterification rate of 50%), 5 parts by weight of a phenolic compound of Formula III, and a techmoa which is an epoxy group-containing curing agent VG3101L (Ref .: Mitsui Chemical Co., Ltd.) 14 parts by weight and 5.0 parts by weight of oleic acid are dissolved in propylene glycol monomethyl ether acetate / ethyl lactate (75/25), and radiation generated on the photosensitive resist during rotational coating. In order to prevent wrinkling and so-called striation of the phase, 300 ppm of a fluorine-based surfactant, MegaPac R-08 (see Dainippon Ink & Chemicals Co., Ltd.) was further added and stirred, followed by a 0.2 µm filter. Filtration produced the photosensitive resin composition 13 of this invention.

Comparative Example 1

Except not using stearic acid, it carried out similarly to Example 1 and manufactured photosensitive resin composition 14. Using this photosensitive resin composition 14, formation of a thin film pattern, evaluation of film surface characteristics, and evaluation of stability with time were performed like Example 1. The evaluation results are shown in Table 1.

Comparative Example 2

Photosensitive resin composition 15 was produced in the same manner as in Example 1 except that 1.0 part by weight of U-CAT SA106 (manufactured by San Aflo Chemical Co., Ltd.), which was a curing accelerator, was further used. Using this photosensitive resin composition 15, formation of a thin film pattern, evaluation of the film surface characteristic, and evaluation of stability with time were performed like Example 1. The evaluation results are shown in Table 1.

Evaluation of Membrane Surface Properties Evaluation of stability over time Example 1 O O Example 2 O O Example 3 O O Example 4 O O Example 5 O O Example 6 O O Example 7 O O Example 8 O O Example 9 O O Example 10 O O Example 11 O O Example 12 O O Example 13 O O Comparative Example 1 × O Comparative Example 2 O ×

<Evaluation of low temperature preservation>

The said photosensitive resin compositions 13 and 15 were put in 180 cc each of 200 cc of clear glass bottles, and were left still at 5 degreeC for 10 hours. In the photosensitive resin composition 13 which concerns on this invention, precipitation of a crystal was not confirmed, but precipitation of a crystal occurred in the photosensitive resin composition 15 of a comparative.

<Dolby Evaluation>

Each of the photosensitive resin compositions was spin-coated on a 4-inch silicon wafer and baked at 90 ° C. for 90 seconds on a hot plate to obtain a 3.0 μm thick photoresist. This photosensitive resist was put into the pressure reduction apparatus, and it pressure-reduced to 10 Pa. Although the generation | occurrence | production of air bubble was not confirmed in the photosensitive resist surface which apply | coated the photosensitive resin composition 13 by this invention, the generation | occurrence | production of air bubble was confirmed in the photosensitive resist surface which apply | coated the comparative photosensitive resin composition 15, and that Dolby has arisen. Could know.

From these results, it turns out that the photosensitive resin composition of this invention is excellent in the balance of both a film surface characteristic and time-lapse stability. Moreover, all the photosensitive resin compositions of the Example were favorable for the insulation of the resist after heat processing. In addition, the heat resistance, solvent resistance, flatness, and electrical properties of the thin films formed by Examples 1 to 13 were all excellent, and no dolbi during drying under reduced pressure after application was observed.

On the other hand, the photosensitive resin composition of the comparative example 1 which does not contain a carboxylic acid was clouded by the heating after exposure, and the photosensitive resin composition of the comparative example 2 which contained the hardening accelerator for the prevention of cloudiness was inferior in stability with time.

Claims (14)

In the photosensitive resin composition containing alkali-soluble resin, the photosensitive agent which has a quinonediazide group, and a hardening | curing agent, The alkali-soluble resin is an acrylic resin, the curing agent comprises an epoxy group, and the photosensitive resin composition is C ₁₂ -C ₁₈ saturated of the formula C _n H _{2n + 1} COOH, where n is an integer from 11 to 17. A photosensitive resin composition, further comprising at least one carboxylic acid selected from the group consisting of C ₁₂ -C ₂₄ unsaturated fatty acids having 1 to 3 unsaturated double bonds in a fatty acid and a molecule. The photosensitive resin composition according to claim 1, wherein the photosensitive agent having a quinonediazide group is a reaction product of a phenolic compound of Formula I or Formula II and a naphthoquinonediazide compound. [Formula I]

&Lt; RTI ID = 0.0 &

In the above formulas (I) and (II), R ¹ , R ² , R ³ and R ⁴ are each independently H or a C ₁ -C ₂ alkyl group, R ⁵ and R ⁶ are each independently C ₁ -C ₂ alkyl group, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each independently H, C ₁ -C ₄ alkyl group or formula

Is a group of R ¹⁴ is H or a C ₁ -C ₄ alkyl group, m and n are each independently an integer of 0 to 2, a, b, c, d, e, f, g and h are integers of 0 to 5 satisfying a + b ≦ 5, c + d ≦ 5, e + f ≦ 5 and g + h ≦ 5 , i is an integer from 0 to 2. The photosensitive resin composition of Claim 2 which further contains the phenolic compound of said Formula (I) or Formula (II). delete delete Claim 6 was abandoned when the registration fee was paid. The photosensitive resin composition of Claim 1 or 2 in which the said acrylic resin contains the structural unit derived from the alkyl (meth) acrylate, and the structural unit derived from (meth) acrylic acid. Claim 7 was abandoned upon payment of a set-up fee. The photosensitive resin composition of Claim 1 or 2 in which the said acrylic resin contains 5-30 mol% of structural units derived from (meth) acrylic acid. Claim 8 was abandoned when the registration fee was paid. The photosensitive resin composition of Claim 1 or 2 whose polystyrene conversion weight average molecular weight of acrylic resin is 5,000-30,000. The photosensitive resin composition of Claim 1 or 2 in which the said alkali-soluble resin is synthesize | combined using the cyano group containing azo-type polymerization initiator. The photosensitive resin composition of Claim 1 or 2 in which the said alkali-soluble resin is synthesize | combined using the cyano group containing azo polymerization initiator. The said alkali-soluble resin is synthesize | combined using the cyano group containing azo polymerization initiator and the cyano group containing azo polymerization initiator together, The said cyano group containing azo polymerization initiator, The photosensitive resin composition whose molar ratio of the said cyano group containing azo-type polymerization initiator is 20: 80-80: 20. The flat panel display which has the planarization film or interlayer insulation film formed from the photosensitive resin composition of Claim 1 or 2 characterized by the above-mentioned. It has a planarization film or an interlayer insulation film formed from the photosensitive resin composition of Claim 1 or 2, The semiconductor device characterized by the above-mentioned. After patterning using the photosensitive resin composition of Claim 1 or 2, surface exposure is performed and post-bake is performed, The formation method of the heat resistant thin film characterized by the above-mentioned.