JP2019101440A - Positive photosensitive resin composition, cured film, semiconductor device and production method of relief pattern in cured film - Google Patents

Abstract

To provide a positive photosensitive resin composition showing high durability even under severe use conditions at low temperature or high temperature.SOLUTION: The positive photosensitive resin composition comprises: (A) at least one alkali-soluble resin selected from a polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor and a copolymer of at least two resins selected from the above compounds; (B) a polysiloxane having a carboxyl group and/or a phenolic hydroxyl group; (C) a photosensitive agent; and (D) a solvent. The composition contains the (B) polysiloxane by 1 to 100 pts.wt. with respect to 100 pts.wt. of the (A) alkali-soluble resin.SELECTED DRAWING: None

Description

  The present invention relates to a positive photosensitive resin composition, a resin sheet, a cured film, a surface protective film, an interlayer insulating film, a semiconductor protective film, a semiconductor electronic component, a semiconductor device, and a method of producing a relief pattern of a cured film. More specifically, a resin composition suitably used for a surface protective film of a semiconductor element or the like, an interlayer insulating film, an insulating layer of an organic electroluminescent element, a cured film using the same, a semiconductor device using the resin composition, The present invention relates to a method for producing a relief pattern of a cured film.

  Conventionally, polyimide resin and polybenzoxazole resin, which are excellent in heat resistance and electrical insulation, are widely used as surface protection films and interlayer insulation films of semiconductor devices, and insulation films of organic electrolytic devices and planarization films of TFT substrates. It is used. In recent years, in semiconductor devices, miniaturization of pattern processing, miniaturization and densification of packages, high speed, large capacity, high mechanical strength, adhesion, electrical reliability, and high in severe use conditions such as low temperature and high temperature There is a need for durable materials.

  Specifically, the material having high durability as described herein refers to a material in which the mechanical strength of the cured film does not easily decrease, and such a material causes a crack in the pattern or wiring in use at a low temperature and a high temperature. And problems such as peeling off from the substrate are unlikely to occur. Above all, when the elongation, which is an index of the flexibility of the cured film, is high, the cured film can withstand the stress change in the device, and so it is effective in suppressing the cracks and peeling. However, at low temperatures, the degree of freedom of the resin decreases and the cured film becomes hard. At high temperatures, the cured film is exposed to high temperature conditions for a long time to be thermally deteriorated and becomes brittle.

  For this reason, as a material having high durability, it is necessary that the material has a high elongation at low temperature and a decrease in elongation less even after holding at high temperature conditions.

  As a material exhibiting such high mechanical strength, a negative resin composition using a polyamic acid ester in which a specific acid dianhydride and a diamine are combined has been proposed (see, for example, Patent Document 1).

  In addition, as a positive resin composition capable of obtaining mechanical properties such as high elongation at room temperature, polyimide resin compositions having an alkyl chain structure in the main chain and polybenzoxazole precursor resin compositions (for example, patent documents 2, 3 etc.) are known.

  Furthermore, a material having a siloxane structure such as polysiloxane is an excellent material in terms of transparency and flexibility, and a high elongation positive resin composition has been proposed. Further, resins or the like which are mixed with the above-described polyimide or copolymerized as a component of the polyimide as a siloxane diamine have been proposed (see, for example, Patent Documents 4 and 5).

Patent No. 5602691 gazette JP 2012-208360 A JP, 2013-167743, A JP, 2010-211109, A JP 2014-191002 A

  However, the technology of Patent Document 1 is limited to the use in the negative type of organic development because the solubility and transparency of the resin are low, and it is difficult to miniaturize the pattern and use a large amount of organic solvent. There was a problem that the environmental load was high.

  Further, in the techniques of Patent Documents 2 and 3, the alkyl chain is easily decomposed under high temperature conditions, and since the decrease in elongation under low temperature conditions is remarkable, the pattern is cracked or peeled when used under high temperature and low temperature conditions. There was a problem that it was inferior to sex.

  The siloxane materials in the techniques of Patent Documents 4 and 5 generally have poor compatibility with components such as polyimide, so that phase separation occurs when mixed, or polymerization itself is difficult when copolymerized. It was difficult to produce a stable resin composition. In addition, when the compatibility is insufficient, the resin component in the cured film becomes nonuniform, and the elongation is lowered, and the mechanical characteristics are adversely affected, such as variation. Furthermore, there were problems with the photosensitive characteristics, such as the coating film becoming cloudy and development residues and development unevenness appearing.

  Therefore, the present invention solves the problems associated with the prior art as described above, and a positive photosensitive resin composition having high durability and a small decrease in elongation even under severe use conditions of low temperature and high temperature. Intended to be provided.

In order to solve the said subject, the positive photosensitive resin composition of this invention has the following structures. That is,
The positive photosensitive resin composition of the present invention is one type selected from (A) polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor and copolymer of two or more resins selected from these. A positive photosensitive resin composition comprising the above alkali-soluble resin, (B) a polysiloxane having a structure represented by the general formula (1), (C) a photosensitizer and (D) a solvent, A) 1 to 100 parts by weight of the polysiloxane containing the structure represented by (B) the general formula (1) with respect to 100 parts by weight of the alkali-soluble resin.

(In general formula (1), R ¹ represents a monovalent organic group having one or more carbon atoms, and R ² represents an organic group having a phenolic hydroxyl group or a carboxyl group or both in the structure p: q = 50: 50 to 0: 100. In the repeating units, each R ¹ and R ² may be the same or different.)
The positive photosensitive resin composition of the present invention preferably has a structural unit in which R ² in the general formula (1) is represented by the general formula (2).

(In the general formula (2), R ³ represents a group having a phenolic hydroxyl group or a carboxyl group or both of them. X represents an alkylene group having 1 or more carbon atoms.)
The positive photosensitive resin composition of the present invention preferably further contains a thermal crosslinking agent.
The positive photosensitive resin composition of the present invention preferably further contains an antioxidant.

The sheet of the present invention has the following constitution. That is,
It is a sheet formed using the above-mentioned positive photosensitive resin composition.

The cured film of the present invention has the following constitution. That is,
It is a cured film obtained by curing the positive photosensitive resin composition or a cured film obtained by curing a sheet formed using the positive photosensitive resin composition.

The method for producing a relief pattern of a cured film of the present invention has the following constitution. That is,
The process of apply | coating the said positive type photosensitive resin composition on a board | substrate or laminating the said resin sheet on a board | substrate, drying, and forming a resin film, the process of exposing through a mask, alkali of an irradiation part It is a manufacturing method of a relief pattern including the process of carrying out the process of eluting and removing with a solution or removing and heat-processing the resin film after development.

The electronic component or semiconductor device of the present invention has the following configuration. That is,
It is an electronic component or a semiconductor device in which the cured film is disposed as a surface protective film or an interlayer insulating film.

  The present invention provides a positive photosensitive resin composition having high durability even under severe conditions of low temperature and high temperature.

  The positive photosensitive resin composition of the present invention is one type selected from (A) polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor and copolymer of two or more resins selected from these. A positive photosensitive resin composition comprising the above alkali-soluble resin, (B) a polysiloxane having a structure represented by the general formula (1), (C) a photosensitizer and (D) a solvent, A) 1 to 100 parts by weight of the polysiloxane containing the structure represented by (B) the general formula (1) with respect to 100 parts by weight of the alkali-soluble resin.

(In general formula (1), R ¹ represents a monovalent organic group having one or more carbon atoms, and R ² represents an organic group having a phenolic hydroxyl group or a carboxyl group or both in the structure p: q = 50: 50 to 0: 100. In the repeating unit, each R ⁴ and R ⁵ may be the same or different.)
The positive photosensitive resin composition of the present invention is one selected from (A) polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor and copolymer of two or more kinds of polymers selected from these. It contains the above alkali-soluble resin.

  Here, the "alkali-soluble resin" is specifically a resin having a functional group which is dissolved in an alkaline aqueous solution such as phenolic hydroxyl group, carboxyl group and sulfonic acid group in a resin structure.

  Polyimides and polybenzoxazoles are resins having a cyclic structure of an imido ring or an oxazole ring in the main chain structure. Moreover, the polyimide precursor and polybenzoxazole precursor which are those precursors are resin which forms an imido ring and a benzoxazole ring structure, respectively, by dehydrating ring closure.

  A polyimide can be obtained by reacting a tetracarboxylic acid, corresponding tetracarboxylic acid dianhydride, tetracarboxylic acid diester dichloride or the like with a diamine, a corresponding diisocyanate compound, trimethylsilylated diamine or the like, and a tetracarboxylic acid residue And diamine residues. For example, a polyimide can be obtained by dehydration ring closure of a polyamide acid which is one of polyimide precursors obtained by reacting tetracarboxylic acid dianhydride with diamine, by heat treatment. At the time of the heat treatment, a solvent which azeotropes with water, such as m-xylene, can also be added. Alternatively, dehydration ring closure can be performed by chemical heat treatment by adding a ring closure catalyst such as a carboxylic acid anhydride or a dehydration condensation agent such as dicyclohexylcarbodiimide or a base such as triethylamine. Alternatively, it is possible to add a weakly acidic carboxylic acid compound and perform dehydration ring closure by heat treatment at a low temperature of 100 ° C. or lower.

  In addition, the reaction time can be adjusted in the process of dehydration ring closure, or a copolymer can be obtained by polymerizing a polyimide and subsequently polymerizing a polyamic acid.

  Examples of tetracarboxylic acid dianhydrides include butanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, pyromellitic acid dianhydride, bicyclohexanetetracarboxylic acid dianhydride, pentanetetracarboxylic acid dianhydride , Hexanetetracarboxylic acid dianhydride, cyclopropanetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, cyclohexanetetracarboxylic acid dianhydride, 3,3 ', 4 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride, 4,4'-oxydiphthalic acid anhydride, P-phenylene bis (trimellitate anhydride) , Ethylene glycol bisanhydro trimellitate, 4,4'- Such as hexafluoro isopropylidene) diphthalic anhydride. These compounds may be used alone or in combination of two or more. As the diamine, for example, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, benzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, o-tolidine, 4,4 "-diaminoter Phenyl, 1,5-diaminonaphthalene, 2,5-diaminopyridine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-bis (p-aminophenoxy) biphenyl, 2,2-bis [4- (p-Aminophenoxy) phenyl] propane, hexahydro-4, -. Meta the like Noin mite range methylene diamine is not particularly limited these compounds may be used alone or in combination of two or more.

  The polybenzoxazole can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester or the like, and has a dicarboxylic acid residue and a bisaminophenol residue. For example, polybenzoxazole can be obtained by dehydration ring closure of a polyhydroxyamide which is one of polybenzoxazole precursors obtained by reacting a bisaminophenol compound and a dicarboxylic acid by heat treatment. Alternatively, anhydrous ring closure can be carried out by chemical treatment with the addition of phosphoric anhydride, a base, a carbodiimide compound or the like.

  Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, etc. Examples of tricarboxylic acids include trimellitic acid, There may be mentioned trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid and the like. These compounds may be used alone or in combination of two or more.

  Examples of bisaminophenol compounds include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl and bis (3-amino-4-hydroxyphenyl) propane Bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino- 4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3- Although hexafluoro propane etc. are mentioned, it is not limited to these. These compounds may be used alone or in combination of two or more.

  In the positive photosensitive resin composition of the present invention, in order to improve the storage stability of the positive photosensitive resin composition, (A) the alkali-soluble resin has a main chain terminal of monoamine, acid anhydride, monocarboxylic acid, mono It is preferable to seal with an end capping agent such as an acid chloride compound or a monoactive ester compound. In addition, the resin dissolution rate of the resin in an alkaline solution and the obtained curing can be obtained by sealing the end of the resin with a terminal blocking agent having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group or an allyl group. The mechanical properties of the membrane can be easily adjusted to the preferred range. The introduction ratio of the end capping agent is preferably 0.1 mol% in order to prevent the molecular weight of the (A) alkali-soluble resin from increasing with respect to all the amine components and the decrease in solubility in the alkaline solution. Or more, particularly preferably 5 mol% or more, and the molecular weight of the (A) alkali-soluble resin is lowered to suppress a decrease in mechanical properties of the resulting cured film, preferably 60 mol% or less, particularly preferably 50 mol % Or less. Multiple different end groups may be introduced by reacting multiple end capping agents.

  As the monoamine, M-600, M-1000, M-2005, M-2070 (trade name, manufactured by HUNTSMAN Co., Ltd.), aniline, 2-ethynyl aniline, 3-ethynyl aniline, 4-ethynyl aniline, 5- Amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amino Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy -7-aminonaphthalene, 2-carboxy-6-a Nonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfone Acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Aminothiophenol, 4-aminothiophenol and the like are preferable. Two or more of these may be used.

  As acid anhydrides, monocarboxylic acids, mono acid chloride compounds, monoactive ester compounds, acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic acid anhydride, etc. , 3-Carboxyphenol, 4-Carboxyphenol, 3-Carboxythiophenol, 4-Carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene Monocarboxylic acids such as 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and the like; Mono-acid chloride compounds of which acid group is acid-chlorided, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene A monoacid chloride compound in which only one carboxyl group of a dicarboxylic acid such as 2,6-dicarboxynaphthalene is acid chlorided, a monoacid chloride compound and N-hydroxybenzotriazole or imidazole, N-hydroxy-5-norbornene-2 The active ester compound etc. which are obtained by reaction with 3, 3- dicarboximide are preferable. Two or more of these may be used.

  The molecular weight of the (A) alkali-soluble resin of the present invention is not particularly limited, but the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 3,000 or more, more preferably Is over 5000. Thereby, a cured film having high mechanical strength can be obtained. Moreover, it is preferable that it is 60,000 or less, More preferably, it is 25,000 or less. When the molecular weight is in this range, it is dissolved in an appropriate solvent to improve the coatability.

  The positive photosensitive resin composition of the present invention contains (B) a polysiloxane having a structure represented by the general formula (1).

(In general formula (1), R ¹ represents a monovalent organic group having one or more carbon atoms, and R ² represents an organic group having a phenolic hydroxyl group or a carboxyl group or both in the structure p: q = 50: 50 to 0: 100. In the repeating units, each R ¹ and R ² may be the same or different.)
Examples of R ¹ include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, aryl groups, aryl ether groups, carbonyl groups, allyl groups, vinyl groups, and combinations thereof. These groups may further have a substituent and, for example, those substituted with an aryl group or a heterocyclic compound are preferable.

  The alkyl group is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. The cycloalkyl group is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentoxy group are preferable. As an aryl group, a phenyl group and a naphthyl group are preferable.

Examples of R ² include the following structures.

By partially introducing an alkali-soluble functional group into the polysiloxane, it is possible to suppress the water repellency derived from the structure of the siloxane and to enhance the compatibility with the (A) alkali-soluble resin. As a result, the polysiloxane can be uniformly present without phase separation, and as a result, the resin composition as a whole exhibits flexibility and resistance at high temperatures derived from the siloxane skeleton at high temperatures and high durability. be able to. Further, by improving the compatibility, it is possible to prevent the clouding and the development unevenness of the coating film, and it is possible to obtain a photosensitive resin composition with high sensitivity and no development residue.
In general formula (1), p and q satisfy p: q = 50: 50 to 0: 100. By setting this range, sufficient alkali solubility is imparted to the polysiloxane, and the affinity with the (A) alkali-soluble resin is improved. As a result, the polysiloxane component can be uniformly present in the positive photosensitive resin composition, and flexibility at a low temperature derived from the siloxane skeleton and thermal stability at a high temperature are exhibited throughout the resin composition, so that high durability can be obtained. It can be set as the positive photosensitive resin composition which it has. It contains 1 to 100 parts by weight of the polysiloxane containing the structure represented by (B) the general formula (1) with respect to 100 parts by weight of the (A) alkali-soluble resin. Within this range, while having high mechanical properties and heat resistance as (A) alkali-soluble resin, flexibility at low temperature is also imparted by polysiloxane including the structure represented by (B) general formula (1) It is preferable because it can be done.
Among them, a structure in which R ² is represented by the general formula (2) is preferable because durability is improved.

(In the general formula (2), R ³ represents a group having a phenolic hydroxyl group or a carboxyl group or both of them. X represents an alkylene group having 1 or more carbon atoms.)
By making X into an alkylene group, the steric hindrance around Si is alleviated, so that the steric structure of the main chain is stabilized, the thermal decomposition of the side chain is suppressed, and a resin which is more excellent in durability particularly on the high temperature side Become. As the alkylene group, one having a linear structure such as a methylene group, an ethylene group or a propylene group is preferable.
R ³ is the same as described for R ² .

  A well-known method can be used as a synthesis method of polysiloxane. For example, there is a method of hydrolyzing and condensing commercially available dialkoxysilanes in which side chains have already been introduced to obtain a polysiloxane. Commercially available dialkoxysilanes include KBM-402, KBE-402, KBE-502, KBM-602, KBM-802, KBM-202SS, KBE-22 (brand names, all manufactured by Shin-Etsu Chemical Co., Ltd.), etc. It can be mentioned. Hydrolytic condensation is obtained by dissolving dialkoxysilane in a solvent such as gamma butyrolactone, adding water and heating. At this time, the reaction can be accelerated by adding a catalytic amount of an acid component such as phosphoric acid.

  Also, if the desired dialkoxysilane is not available, it can be synthesized utilizing a hydrosilylation reaction. Specifically, it is synthesized by reacting a dialkoxydihydrosilane with a compound such as an olefin having a desired functional group such as a phenolic hydroxyl group, a ketone, or an imine using a platinum catalyst. Thereafter, the same is subjected to hydrolysis and condensation to obtain a polysiloxane, but not limited thereto.

  The positive photosensitive resin composition of the present invention contains (C) a photosensitizer. By including a photosensitizer, it is possible to directly form a pattern, and the process of the resist can be omitted. In order to obtain a positive type, as the photosensitizer (C), a photoacid generator is contained.

  The photoacid generator contained in the positive photosensitive resin composition of the present invention is characterized in that an acid is generated by light irradiation, and the solubility of the light irradiated part in an alkaline aqueous solution is increased. The photoacid generator includes quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like.

  The quinone diazide compound is a polyhydroxy compound in which a sulfonic acid of quinone diazide is bound by an ester, a polyamino compound is a sulfonic acid of quinone diazide in a sulfonamide bond, a polyhydroxy polyamino compound is a sulfonic acid of quinone diazide in an ester bond and / or a sulfonamide And the like. Although all functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups be substituted with quinonediazide. When the substitution with quinonediazide is 50 mol% or more, the solubility in an alkali developer is not too high, and the contrast with the unexposed area can be obtained, and a desired pattern can be obtained. By containing such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition which is sensitive to i-line (365 nm), h-line (405 nm) and g-line (436 nm) of a general ultraviolet ray of a mercury lamp. Can. Such compounds may be contained singly or in combination of two or more. In addition, by containing two types of photoacid generators, the ratio of dissolution rate between exposed and unexposed parts can be further increased, and as a result, a highly sensitive positive photosensitive resin composition can be obtained. it can.

  The polyhydroxy compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ , TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR -PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade names, manufactured by Asahi Organic Materials Co., Ltd.) ), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (brand name, Honshu Chemical industry Co., Ltd. product) etc. is mentioned, However, It is not limited to these.

  The polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl Although a sulfide etc. are mentioned, it is not limited to these.

  In addition, polyhydroxy polyamino compounds include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3'-dihydroxybenzidine and the like.

  In the positive photosensitive resin composition of the present invention, the quinone diazide can preferably contain any of 5-naphthoquinone diazide sulfonyl group and 4-naphthoquinone diazide sulfonyl group. The 4-naphthoquinone diazide sulfonyl ester compound has an absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound extends its absorption to the g-line region of a mercury lamp and is suitable for g-line exposure.

  In the positive photosensitive resin composition of the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure. Also, it is possible to contain a naphthoquinone diazide sulfonyl ester compound in which a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in combination in the same molecule, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester It can also contain a compound.

  The molecular weight of the quinone diazide compound contained in the positive photosensitive resin composition of the present invention is preferably 3,000 or less. When the molecular weight of the quinonediazide compound is 3,000 or less, the quinonediazide compound is sufficiently thermally decomposed in the subsequent heat treatment, the amount of residual in the film can be reduced, and the heat resistance and mechanical properties of the obtained film are improved. Good adhesion is obtained.

  The quinone diazide compound contained in the positive photosensitive resin composition of the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method in which 5-naphthoquinone diazide sulfonyl chloride is reacted with a phenol compound in the presence of triethylamine. The synthesis method of a phenol compound includes a method of reacting an α- (hydroxyphenyl) styrene derivative with a polyhydric phenol compound under an acid catalyst.

  Among the photoacid generators contained in the positive photosensitive resin composition of the present invention, the photoacid generator appropriately stabilizing the acid component generated by exposure is a sulfonium salt, a phosphonium salt or a diazonium salt Is preferred. Among these, sulfonium salts can be preferably contained because they are less affected by color tone. Particularly preferred are triarylsulfonium salts, which can significantly improve the stability after exposure.

  In the positive photosensitive resin composition of the present invention, the content of the (C) photosensitizer is 100% by weight in total of (A) an alkali-soluble resin and (B) a polysiloxane represented by the general formula (1). 0.01 weight part or more is preferable with respect to a part, More preferably, it is 3 weight part or more. By setting this range, it is possible to suppress film thinning for the unexposed area while completely dissolving the exposed area within a desired development time, and it is possible to form a pattern with high contrast. Moreover, 50 parts by weight or less is preferable, and 40 parts by weight or less is more preferable. By setting this range, light can be transmitted to the bottom of the film, and a pattern can be obtained with high exposure sensitivity. For the same reason, the content of the compound selected from sulfonium salt, phosphonium salt and diazonium salt is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight with respect to 100 parts by weight of the (A) alkali-soluble resin. It is at least parts by weight. Moreover, 40 parts by weight or less is preferable, and more preferably 30 parts by weight or less. Furthermore, a sensitizer may be added as needed.

  The positive photosensitive resin composition of the present invention contains (D) a solvent. Thereby, the state of the varnish can be obtained, and the coatability can be improved.

  The (D) solvent is a polar aprotic solvent such as gamma butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n- Propyl ether, propylene glycol mono-n-butyl ether, Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, ethers such as tetrahydrofuran, dioxane, etc. , Acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, ketones such as diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate , Propylene glyco Esters such as ethyl monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate Ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-butyrate Propyl butyric acid i-pe Other esters such as ropir, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, aromatic hydrocarbons such as toluene and xylene And amides such as N, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like, which may be contained alone or in combination. Among these, N-methylpyrrolidone and gamma-butyrolactone are preferable because they can dissolve other components well and form a coating film with good flatness.

  The amount of the solvent (D) to be added is not particularly limited because it is changed depending on the required film thickness and the coating method to be employed, but the (A) alkali-soluble resin of the present invention and (B) the general formula (1) The amount is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, based on 100 parts by weight of the total amount of the polysiloxane including the structure to be expressed. Within this range, a uniform film can be produced by a coating method using a relatively high viscosity coating solution such as spin coating. Moreover, 2000 parts by weight or less is preferable, and more preferably 1500 parts by weight or less. By setting it as this range, a uniform film | membrane can be produced in the apply | coating method using low viscosity coating liquids, such as a slit coat.

The positive photosensitive resin composition of the present invention preferably contains (E) a thermal crosslinking agent which is crosslinked by heat. By containing the thermal crosslinking agent (E), the durability of the cured film on the high temperature side can be further improved.
Examples of the thermal crosslinking agent (E) include a compound having an epoxy structure and a compound having an alkoxymethyl structure.

  Preferred examples of the compound having an epoxy structure include, for example, Epiclon 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon EXA-4710, Epiclon HP-4770, Epiclon EXA -859 CRP, Epiclon EXA-4880, Epiclon EXA-4850, Epiclon EXA-4816, Epiclon EXA-4822 (trade names available from Dainippon Ink and Chemicals, Inc.), Rica resin BPO-20E, Rica resin BEO-60E The trade name, available from Shin Nippon Rika Co., Ltd., EP-4003S, EP-4000S (trade name, available from Adeka Co., Ltd.), etc. may be mentioned, but not limited thereto.

  Preferred examples of the compound having an alkoxymethyl structure include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35 XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMO -BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade names, available from Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX -280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (trade names, available from Sanwa Chemical Co., Ltd.).

  Among these compounds, NIKALAC MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX- from the viewpoint of the heat resistance of the cured film obtained after curing by heat. It is preferable from the viewpoint of storage stability that the compound is selected from any of 750 LM.

  The content of the thermal crosslinking agent (E) is 100 parts by weight of the total of (A) an alkali-soluble resin and (B) a structure represented by the general formula (1) in the positive photosensitive resin composition. When it is set as above, from the viewpoint of obtaining high chemical resistance of the cured film, 1.0 parts by weight or more is preferable, and 5 parts by weight or more is more preferable. Further, from the viewpoint of reducing the amount of degassing, 100 parts by weight or less is preferable, and 80 parts by weight or less is more preferable.

The positive photosensitive resin composition of the present invention preferably further comprises (F) an antioxidant. (F) Antioxidants are antioxidants added to suppress the oxidation of components.
(F) By having an antioxidant, hydrolysis of the alkali-soluble resin of (A) or polysiloxane including the structure represented by (B) general formula (1), water absorption, and diffusion of acid derived from a photosensitizer Since oxidation and decomposition of the resin can be suppressed, it is possible to suppress a decrease in elongation under low temperature and high temperature conditions.

  Examples of the (F) antioxidant contained in the positive photosensitive resin composition of the present invention include benzotriazole, organic phosphorus, and an antioxidant having a hindered phenol structure. Among them, an antioxidant having a hindered phenol structure is preferable because it is excellent in solubility and storage stability at the time of development, and a high-resolution positive photosensitive resin composition can be obtained.

  Specifically as the antioxidant having a benzotriazole structure, 1,2,3-benzotriazole (1H-benzotriazole), 1H-benzotriazole sodium salt, 4-methyl-1H-benzotriazole, 5-methyl -1H-benzotriazole, tolyltriazole (a mixture of 4-methyl-1H-benzotriazole and 5-methyl-1H-benzotriazole), 4-methyl-1H-benzotriazole potassium salt, 5-methyl-1H-benzotriazole potassium Salt, 4-methyl-1H-benzotriazole amine salt, 5-methyl-1H-benzotriazole salt, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2 -(3,5-di-t-amyl-2-hydroxypheny ) Benzotriazole, but not limited thereto.

  Specific examples of the antioxidant having organic phosphorus include tris (2,4-di-tert-butylphenyl) phosphite, 3,9-di (2,4-di-tert-butylphenoxy) -2, 4,8,10-Tetraoxa-3,9-diphosphaspiro [5.5] undecane, 3,9-di (2,4-dicumylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] Undecane, tris (p-nonylphenyl) phosphite, 2,2 ′, 2 ′ ′-nitrilo [triethyl-tris [3,3 ′, 5,5′-tetra-tert-butyl-1, 1′-biphenyl-2′-diyl] phosphite], 3,9-distearyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, dilaurylphos Yate, 3,9-di [2,6-di-tert-butyl-4-methylphenoxy] -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, tetrakis (2, 4-di-tert-butylphenyl) 4,4'-bis (diphenylene) phosphonite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, 2,4,6-tri-tert-butylphenyl-2- Butyl-2-ethyl-1,3-propanediol phosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylene diphosphonite, (2,4,6 -Tri-tert-butylphenyl) -2-butyl-2-ethyl-1,3-pro Emissions diol phosphite, tri - including but isodecyl phosphite, not limited to this.

  As an antioxidant having a hindered phenol structure, for example, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol; Mono-t-butyl-p-cresol, mono-t-butyl-m-cresol, 4-t-butyl catechol, 2,5-di-t-butyl hydroquinone, 2,5-di-t-amyl hydroquinone, propyl 4,4'-methylenebis (2,6-t-butylphenol), 4,4'-isopropylidenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis (3-methyl-) 6-t-butylphenol), butylhydroxyanisole, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butylphenol, 2,6- -Tert-Butyl-4-ethylphenol, 2,4,6-tri-tert-butylphenol, 4-hydroxymethyl-2,6-di-tert-butyl, octadecyl-3- (4-hydroxy-3 ', 5 '-Di-tert-butylphenyl) propionate, distearyl (4-hydroxy-3-methyl-5-tert-butyl) benzylmalonate, 6- (4-hydroxy-3,5-di-tert-butylanilino) 2 , 4-Bisoctylthio-1,3,5-triazine, 2,6-diphenyl-4-octadecanoxyphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2 '-Methylenebis (4-ethyl-6-t-butylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,2'-dihydroxy 3,3′-di- (α-methylcyclohexyl) -5,5′-dimethyldiphenylmethane, 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), tris [β- (3,5-di- t-Butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-t-butylbenzyl) isocyanurate, tris (3,5-) Di-t-butyl-4-hydroxyphenol) isocyanurate, 1,1,3′-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 2,6-bis (2′-hydroxy) -3'-t-Butyl-5'-methylbenzyl) 4-methylphenol, N, N'-hexamethylene bis (3,5-di-t-butyl- Hydroxyhydrocinnamate), hexamethylene glycol bis [β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2 ′, 3-bis [[3- [3,5-di-] tert-Butyl-4-hydroxyphenyl] propionyl]] propionohydrazide, triethylene glycol bis [β- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,3, 5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (3,5-di-tert-butyl) 4-hydroxybenzyl) -1,3,5-triazine -2,4,6 (1H, 3H, 5H) - trione and include but are structure illustrated below, but are not limited to.

  The antioxidant (F) can be contained singly or in combination of two or more. The content of the antioxidant is 100 parts by weight of the total amount of the (A) alkali-soluble resin of the positive photosensitive resin composition of the present invention and the (B) polysiloxane represented by the general formula (1). If it is added, the amount is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more. By using it in this range, it is possible to prevent the oxidative deterioration of the cured film and the oxidative deterioration of the metal surface when the substrate has a metal wiring. Moreover, 10 parts by weight or less is preferable, and more preferably 5 parts by weight or less. By using in this range, an antioxidant effect can be obtained without losing photosensitivity.

The resin sheet formed from the positive photosensitive resin composition of the present invention will be described.
The sheet of the present invention is a sheet which is coated on the support with the positive photosensitive resin composition of the present invention, dried at a temperature and for a time that can evaporate the solvent, and is not completely cured. Say something.

  The support is not particularly limited, but it is possible to use various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, polyimide film and the like. The bonding surface between the support and the resin composition may be subjected to surface treatment with silicone, a silane coupling agent, an aluminum chelating agent, polyurea or the like in order to improve adhesion and releasability. The thickness of the support is not particularly limited, but is preferably in the range of 10 to 100 μm from the viewpoint of workability. Furthermore, in order to protect the film surface of the composition obtained by application, a protective film may be provided on the film surface. Thereby, the surface of the resin composition can be protected from contaminants in the atmosphere such as dust and dirt.

The positive photosensitive resin composition of the present invention can be coated on a support by spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, Examples of the method include a roll coater, a comma roll coater, a gravure coater, a screen coater, and a slit die coater. The thickness of the applied film varies depending on the application method, the solid content concentration of the composition, the viscosity and the like, but the thickness after drying is preferably 0.5 μm to 100 μm.
An oven, a hot plate, infrared rays etc. can be used for drying.

  Next, a method of forming a relief pattern of a positive photosensitive resin composition on a substrate using the positive photosensitive resin composition of the present invention or a sheet formed using the same will be described.

  First, the positive photosensitive resin composition resin composition is applied onto a substrate. As the coating method, methods such as spin coating using a spinner, spray coating, roll coating, screen printing and the like can be mentioned. The thickness of the applied film varies depending on the application method, the solid content concentration and viscosity of the resin composition, and the like, but in general, the applied film is preferably 0.5 μm to 100 μm after drying. Next, the substrate coated with the positive photosensitive resin composition is dried to obtain a positive photosensitive resin composition film. Drying can use oven, a hotplate, infrared rays etc. The drying temperature and the drying time may be in the range in which the organic solvent can be volatilized, and it is preferable to appropriately set the range in which the positive photosensitive resin composition film is in the uncured or semi-cured state. Specifically, it is preferable to carry out in the range of 40 to 150 ° C. for one minute to several tens of minutes.

  On the other hand, when using a sheet, when it has a protective film, this is exfoliated, a sheet and a substrate are made to face, and it bonds together by thermocompression bonding, and obtains a positive type photosensitive resin composition film. The thermocompression bonding can be performed by a heat press process, a heat lamination process, a heat vacuum lamination process or the like. The bonding temperature is preferably 40 ° C. or more from the viewpoint of adhesion to a substrate and embeddability. In addition, the lamination temperature is preferably 150 ° C. or lower in order to prevent the sheet from being cured at the time of lamination due to the influence of the photosensitizer and the resolution of pattern formation in the exposure / development process becoming worse.

  In any case, the substrate to be used may be silicon wafer, ceramics, gallium arsenide, organic circuit board, inorganic circuit board, and those obtained by arranging circuit components on these boards, etc. It is not limited to. Examples of organic circuit boards include glass-clad copper-clad laminates such as glass cloth and epoxy copper-clad laminates, composite copper-clad laminates such as glass nonwoven and epoxy copper-clad laminates, polyetherimide resin substrates, and polyethers A heat-resistant thermoplastic substrate such as a ketone resin substrate or a polysulfone resin substrate, a flexible substrate such as a polyester copper-clad film substrate, or a polyimide copper-clad film substrate can be mentioned. Further, examples of the inorganic circuit board include a ceramic board such as an alumina board, an aluminum nitride board, and a silicon carbide board, and a metal board such as an aluminum base board or an iron base board. Examples of the constituent material of the circuit include a conductor containing a metal such as silver, gold and copper, a resistor containing an inorganic oxide, a low dielectric containing a glass material and / or a resin, a resin and a high Examples thereof include high dielectrics containing dielectric inorganic particles and the like, and insulators containing a glass-based material and the like.

  Next, a pattern is formed on the positive photosensitive resin composition film formed by the above method. If a photosensitive resin composition such as a photoresist is further applied onto the positive photosensitive resin composition film, or if the photosensitive resin composition contains a photosensitive agent, the desired pattern is directly obtained. The actinic radiation is irradiated and exposed through the mask. Examples of actinic radiation used for exposure include ultraviolet light, visible light, electron beam and X-ray. In the present invention, ultraviolet light such as i-line (365 nm), h-line (405 nm) and g-line (436 nm) of a mercury lamp is used. Is preferred. In the case of a sheet, in the case where the support is a material transparent to these light rays, exposure can be carried out without peeling the support from the sheet.

  To form a pattern, after exposure, the exposed portion is removed using a developer. As a developing solution, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamine An aqueous solution of a compound exhibiting alkalinity such as aminoethyl methacrylate, cyclohexylamine, ethylene diamine, hexamethylene diamine and the like is preferable. In some cases, polar aqueous solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, dimethylacrylamide, etc. in these alkaline aqueous solutions, methanol, ethanol, Even if alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone are used singly or in combination of several types. Good.

The development can be carried out by spraying the developer on the coated surface, immersing in the developer, applying ultrasonic waves while immersing, or spraying the developer while rotating the substrate. Various conditions such as the development time, the number of times of development, and the temperature of the developing solution are not particularly limited as long as they exhibit a desired pattern.
After development, it is preferable to rinse with water. Also in this case, ethanol, alcohols such as isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinse treatment.

After development, a temperature of 150 ° C. to 500 ° C. is added to advance the thermal crosslinking reaction to form a cured film. This heat treatment is carried out for 5 minutes to 5 hours while selecting a temperature and raising the temperature stepwise or selecting a certain temperature range while raising the temperature continuously. As an example, heat treatment is performed at 130 ° C. and 200 ° C. for 30 minutes each. Or the method of raising temperature linearly from room temperature to 400 degreeC over 2 hours is mentioned. As curing conditions in the present invention, 170 ° C. or more and 400 ° C. or less are preferable, and 180 ° C. or more and 300 ° C. or less are more preferable.
Although the film thickness of a cured film can be set arbitrarily, it is preferable that it is 0.5 micrometer or more and 100 micrometers or less, but it is not particularly limited.

  Next, a semiconductor device having a cured film formed using the positive photosensitive resin composition of the present invention will be described. In recent years, semiconductor devices having various structures have been proposed, and the application of the positive photosensitive resin composition of the present invention is not limited to the following.

  The cured film formed using the positive photosensitive resin composition of the present invention is formed through the above steps, and can be suitably used as a semiconductor protective film and an interlayer insulating film. In addition, the semiconductor device in the present invention is not limited to the semiconductor element itself, or the one in which the semiconductor element is connected to the substrate, or the one in which the semiconductor elements are connected to each other or the substrates, but can function by utilizing the characteristics of the semiconductor element. The device generally refers to an electro-optical device, a semiconductor circuit substrate, and an electronic component including them all included in the semiconductor device.

The relief pattern of a cured film or a cured film obtained by curing the positive photosensitive resin composition or resin sheet of the present invention can be used as follows.
That is, it can be used as an organic EL display device disposed on at least one of the planarizing layer on the drive circuit and the first electrode.
Further, it can be used as a semiconductor electronic component or a semiconductor device disposed as an interlayer insulating film between rewirings.
Further, it can be used as a semiconductor electronic component or a semiconductor device disposed as an interlayer insulating film between rewirings on a sealing resin substrate on which a silicon chip is disposed.
Furthermore, it can be used as a semiconductor electronic component or a semiconductor device disposed as an interlayer insulating film of an adjacent substrate composed of two or more types of materials.

  In using a cured film formed by curing the resin composition or resin sheet of the present invention or a relief pattern of the cured film for a semiconductor electronic component or semiconductor device, specifically, a passivation film of a semiconductor, a surface protective film of a semiconductor element It is suitably used for applications such as interlayer insulating films, interlayer insulating films of multilayer wiring for high density mounting, and insulating layers of organic electroluminescent elements. Of course, it is not limited to this, and can take various structures.

  Hereinafter, the present invention will be specifically described based on examples.

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited by these examples. First, evaluation methods in the respective examples and comparative examples will be described. The following evaluation was carried out using a positive photosensitive resin composition (hereinafter referred to as a varnish) filtered in advance by a polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 1 μm.

(1) Evaluation of film physical properties (1) -1 Preparation of cured film for evaluation Varnish was coated on an 8-inch silicon wafer so that the film thickness after prebaking at 120 ° C. for 3 minutes was 11 μm. ACT-8 After coating and prebaking by spin coating using Tokyo Electron Co., Ltd., and using an inert oven CLH-21CD-S (Kokoyo Thermo System Co., Ltd.), the oxygen concentration is 20 ppm or less in a nitrogen atmosphere. The temperature was raised to 110 ° C. at 3.5 ° C./min and held for 30 minutes, and then the temperature was raised to 250 ° C. at 3.5 ° C./min, and heat treatment was performed for 1 hour. When the temperature became 50 ° C. or less, the wafer was taken out to prepare a cured film (a).

  Further, this cured film (a) was held for 200 hours in a hot air oven at 175 ° C. in a nitrogen stream, and a high temperature holding test was conducted to produce a cured film (b).

(1) -2 Measurement of film physical properties The cured film (a) and the cured film (b) prepared in (1) -1 are cured from the wafer by immersing in 45 wt% of hydrofluoric acid for 5 minutes The membrane was peeled off. This film was cut into strips 1.5 cm wide and 2 cm long to prepare samples for elongation measurement.
A sample produced from the cured films (a) and (b) was subjected to a tensile speed of 50 mm / min at a room temperature of 23.0 ° C. and a humidity of 45.0% RH using Tensilon RTM-100 (manufactured by ORIENTEC Co., Ltd.) And the elongation at break at room temperature 23.0 ° C. was measured.

In addition, for the cured film (a), using Instron 5582 (manufactured by Instron Co., Ltd.), the film is pulled at a tensile speed of 5.0 mm / min at -55 ° C., and the elongation at break at low temperature is The measurement was also performed.
The measurement was performed on 10 strips per sample under each temperature condition, and the average value of the top 5 points in each result was determined. In contrast to the case where the elongation at break (a-1) at room temperature of the cured film (a) is 100%, the elongation at break (b-1) of the cured film (b) and the cured film (a) The value of elongation at break (a-2) at a low temperature of 70% or more is very good (A), 50% or more and less than 70% is good (B), 40% or more and less than 50% (C) and less than 40% were insufficient (D). In this evaluation, it can be said that the higher the evaluation material is, the less the deterioration in the use conditions at high temperature and low temperature, and the higher the durability.

(2) Evaluation of sensitivity <Preparation of developed film>
The varnish is spin-coated on an 8-inch silicon wafer and then baked for 3 minutes on a hot plate at 120 ° C. (using a coating and developing apparatus Act-8 manufactured by Tokyo Electron Ltd.) to obtain a pre-baked film with an average thickness of 10 μm. Made. The membrane was exposed at 10 mJ / cm ² steps by the exposure amount of 0~1000mJ / cm ² using an exposure system i-line stepper. After exposure, development was carried out with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) (ELM-D, manufactured by Mitsubishi Gas Chemical Co., Ltd.) for 90 seconds, and then rinsed with pure water to obtain a developed film. .

<Calculation of sensitivity>
The pattern of the developed film obtained by the above method is observed at a magnification of × 20 using an FDP microscope MX61 (manufactured by Olympus Corporation), and the minimum necessary exposure Eth for opening a line pattern having a mask size of 200 μm is determined. It asked and this was made into sensitivity. Eth very good of less than ^{350mJ / cm 2 (A),} Eth is 350 mJ / cm ² or more 500 mJ / cm ² less than good ones (B), not openings remain 500 mJ / cm ² or more and the residue The product is considered bad (C).

Synthesis Example 1 Synthesis of Alkali-Soluble Resin (A-1) Under dry nitrogen gas flow, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by JFE Chemical Co., Ltd., hereinafter BAHF) 32 .9 g (0.09 mol), and 2.18 g (0.02 mol) of 4-aminophenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as an end capping agent with N-methyl-2-pyrrolidone (Mitsubishi Chemical Co., Ltd.) (Hereinafter, NMP) was dissolved in 239 g. To this was added 31.02 g (0.1 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride (manufactured by Manac Corporation, hereinafter referred to as ODPA) together with 20 g of NMP, and allowed to react at 20 ° C. for 1 hour, and then The reaction was carried out at 50 ° C. for 4 hours. Then, it stirred at 190 degreeC for 2 hours. After completion of the stirring, the mixture was allowed to cool, and the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried with a vacuum dryer at 80 ° C. for 20 hours to obtain a powder of an alkali-soluble polyimide resin (A-1).

Synthesis Example 2 Synthesis of Alkali-Soluble Resin (A-2) Under dry nitrogen gas flow, 31.02 g (0.1 mol) of ODPA was dissolved in 195 g of NMP. To this, 11.01 g (0.06 mol) of 4,4'-diaminodiphenyl ether (Wakayama Seika Co., Ltd. product, hereinafter, 4,4'-DAE) and 7.3 g (0.02 mol) of BAHF are added together with 15 g of NMP, The reaction was carried out for 1 hour at ° C and then for 2 hours at 50 ° C. Next, 4.37 g (0.04 mol) of 4-aminophenol as an end capping agent was added together with 10 g of NMP, and reacted at 50 ° C. for 2 hours. Thereafter, a solution of 21.45 g (0.18 mol) of N, N-dimethylformamide dimethylacetal (manufactured by Mitsubishi Rayon Co., Ltd.) diluted with 20 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After the stirring was over, the solution was cooled to room temperature and then poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried with a vacuum dryer at 50 ° C. for 20 hours to obtain a powder of polyamic acid ester (polyimide precursor) (A-2).

Synthesis Example 3 Synthesis of Alkali-Soluble Resin (A-3) Under dry nitrogen gas flow, 18.3 g (0.05 mol) of BAHF, 50 g NMP, and 26.4 g (0. 8 g) of glycidyl methyl ether (manufactured by Wako Pure Chemical Industries, Ltd.). It was dissolved in 3 mol) and the temperature of the solution was cooled to -15 ° C. A solution of 14.7 g (0.050 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Japan Pesticide Co., Ltd.) dissolved in 25 g of γ-butyrolactone was added dropwise so that the temperature in the reaction system did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued at -15 ° C for 6 hours. After completion of the reaction, the solution was poured into 3 liters of water containing 10% by weight of methanol to precipitate a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain an alkali-soluble polybenzoxazole precursor (A-3).

Synthesis Example 4 Synthesis of Alkali-Soluble Resin (A-4) A polyimide, polyamic acid copolymer resin (A-4) was prepared in the same manner as in Synthesis Example (1) except that the heating time at 190 ° C. was 1 hour. Of the powder. In IR measurement, the peak intensity at 1360 cm ⁻¹ , which is the C—N stretching vibration of imide, was compared with the peak intensity of the alkali-soluble polyimide resin (A-1), and the imidation ratio was calculated to be 75% Met.

Synthesis Example 5 Synthesis of Hydroxyl Group-Containing Diamine Compound 18.3 g (0.05 mol) of BAHF is dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Kasei Kogyo Co., Ltd.), It cooled. A solution of 20.4 g (0.1 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) dissolved in 100 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the mixture was stirred at -15 ° C for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and vacuum dried at 50 ° C.

  30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated after confirming that the balloon did not deflate any further. After completion of the reaction, the reaction product was filtered to remove the catalyst palladium compound, and concentrated by a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

Synthesis Example 6 Synthesis of Alkali-Soluble Resin (A-5) Under a stream of dry nitrogen, 15.1 g (0.025 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 5, 3.66 g (0.01 mol) of BAHF, SiDA0 0.62 g (0.0025 mol) was dissolved in 200 g of NMP. 15.5 g (0.05 mol) of ODPA was added here, and it stirred at 40 degreeC for 1 hour. Thereafter, 2.73 g (0.025 mol) of 3-aminophenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added, and the mixture was stirred for 1 hour at 40 ° C. Furthermore, 11.9 g (0.1 mol) of dimethyl formamide dimethyl acetal was added to 5 g of NMP. The solution diluted with was added dropwise over 10 minutes, and after dropwise addition, stirring was continued for 2 hours at 40 ° C. After the stirring was over, the solution was poured into 2 L of water, and the precipitate of the polymer solid was collected by filtration. The obtained polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain an alkali-soluble resin (A-5) which is a polyamic acid ester.
Synthesis Example 7 Synthesis of Closed Ring Polybenzoxazole Resin (PBO-1) 20 g of the alkali-soluble polybenzoxazole precursor (A-3) obtained in Synthesis Example 3 is dissolved in 50 g of NMP and dried under nitrogen stream It heat-stirred at 190 degreeC for 2 hours. After the stirring was over, the solution was cooled to room temperature and then poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 50 ° C. for 20 hours to obtain a powder of a closed-ring polybenzoxazole resin (PBO-1). The ring closure rate of PBO-1 is 100%.

Synthesis Example 8 Synthesis of Alkali-Soluble Resin (A-6) In the same manner as in Synthesis Example 7 except that the heating time at 190 ° C. was 1 hour, a copolymer resin of polybenzoxazole and polybenzoxazole precursor ( The powder of A-5) was obtained. In IR measurement, the peak intensity near 1050 cm ⁻¹ , which is the C—O stretching vibration of oxazole, is compared with the peak intensity of a closed-ring polybenzoxazole resin (PBO-1), and the oxazolization ratio is calculated. The rate was 60%.

  Synthesis Example 9 Synthesis of Polysiloxane (B-1)

  In a stream of dry nitrogen, 14.8 g (0.1 mol) of phthalic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 100 ml of dichloromethane (manufactured by Wako Pure Chemical Industries, Ltd.), and cooled to 10 ° C. To this was added dropwise 19.1 g (0.1 mol) of 3-aminopropyldiethoxymethylsilane (Shin-Etsu Chemical Co., Ltd. product name, KBE-902) dissolved in 100 ml of dichloromethane, and the solution was added at 10 ° C. for 1.5 hours. Then, it returned to room temperature and stirred for 4 hours. The solvent was distilled off with a rotary evaporator to obtain 33.4 g of a transparent oil (Intermediate (1)).

  Intermediate (1) 13.6 g (40 mmol) was dissolved in 15 g of gamma-butyrolactone (hereinafter GBL), and the temperature was raised to 40 ° C. Thereto, 2.1 g of distilled water was added, and the temperature was raised to 70 ° C. and stirred for 30 minutes, and then the temperature was raised to 110 ° C. and stirred for 2 hours. The reaction solution was cooled to room temperature, and the low-boiling separated components were distilled off with a rotary evaporator to obtain a GBL solution of polysiloxane (B-1).

  Synthesis Example 10 Synthesis of Polysiloxane (B-2)

  In a stream of dry nitrogen, 4-hydroxybenzoic acid (manufactured by Wako Pure Chemical Industries, Ltd. 15.1 g 80.11 mol) and KBE-902 19.1 g (0.1 mol) were dissolved in 50 g of dichloromethane and cooled to 10 ° C. . To this was added dropwise 21.1 g (0.11 mol) of 1-ethyl-3- (3 dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 10 g of dichloromethane. The reaction solution was stirred at 10 ° C. for 1 hour and further at room temperature for 2 hours. The reaction solution was separated and washed with distilled water, the organic solvent was dried over anhydrous magnesium sulfate, and the solvent was distilled off with a rotary evaporator to obtain 30.5 g of an intermediate (2).

  Intermediate (2) 4.6 g (15 mmol) was dissolved in 8 g of GBL and the temperature was raised to 40.degree. Thereto, 0.8 g of distilled water was added, and the temperature was raised to 70 ° C. and stirred for 30 minutes, and then the temperature was raised to 110 ° C. and stirred for 2 hours. The reaction solution was cooled to room temperature, and the low-boiling separated component was distilled off with a rotary evaporator to obtain a GBL solution of polysiloxane (B-2).

Synthesis Example 11 Synthetic Intermediate (2) of Polysiloxane (B-3) 9.2 g (30 mmol) of dimethyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 2.9 g (20 mmol) of dimethyldiethoxysilane dissolved in 35 g of gamma-butyrolactone And heated to 40.degree. Thereto, 0.8 g of distilled water was added, and the temperature was raised to 70 ° C. and stirred for 30 minutes, and then the temperature was raised to 110 ° C. and stirred for 2 hours. The reaction solution was cooled to room temperature, and the low-boiling separated components were distilled off with a rotary evaporator to obtain a GBL solution of polysiloxane (B-3). It was 55 mol%: 45 mol% when the content rate of the residue derived from the intermediate (2) in this resin, and the residue derived from dimethyldiethoxysilane in ¹ H-NMR was computed.

  Synthesis Example 12 Synthesis of Polysiloxane (B-4)

  Under a nitrogen stream of dry nitrogen, 5.1 g (0.21 mol) of magnesium (Wako Pure Chemical Industries, Ltd.) and dry tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) in a four-necked flask equipped with a stirrer, a reflux condenser, and a dropping wax. After the addition of 200 mL of THF Co., Ltd., THF), the temperature was raised to 40 ° C. Then, 2 drops of 1,2-dibromoethane (manufactured by Wako Pure Chemical Industries, Ltd.) are added as an initiator, and then 45.6 g of 1-bromo-4-tert-butoxybenzene (manufactured by Wako Pure Chemical Industries, Ltd.) 0.2 mol) was dripped in the range of 40-45 degreeC, and also it stirred for 1 hour, and obtained the THF suspension of 4-tert butoxy phenyl magnesium bromide.

  In a nitrogen stream, 71.2 g (0.4 mol) of triethoxy (methyl) silane (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 200 ml of dry THF, and the solution was cooled to 0 ° C. The whole THF suspension of 4-tert butoxyphenyl magnesium bromide was added dropwise over 45 minutes here. After completion of the dropwise addition, the mixture was further stirred overnight. After removing the formed magnesium salt, THF is distilled off with a rotary evaporator, and then unreacted triethoxy (methyl) silane and 1-bromo-4-tert-butoxybenzene are removed by vacuum distillation, 4-tert. 45 g of butoxyphenyldiethoxymethylsilane were obtained.

  Furthermore, formic acid is added to 4-tert-butoxyphenyldiethoxymethylsilane under nitrogen stream and stirred for 3 hours, and then the formic acid is distilled off by a rotary evaporator to obtain 35.5 g of 4-((diethoxymethyl) silyl) phenol Obtained.

  9.1 g (40 mmol) of 4-((diethoxy (methyl)) silyl) phenol was dissolved in 15 g of GBL, and the temperature was raised to 40 ° C. Thereto, 2.1 g of distilled water was added, and the temperature was raised to 70 ° C. and stirred for 30 minutes, and then the temperature was raised to 110 ° C. and stirred for 2 hours. The reaction solution was cooled to room temperature, and the low-boiling separated component was distilled off with a rotary evaporator to obtain a GBL solution of polysiloxane (B-4).

Synthesis Example 13 The procedure of Synthesis Example 7 was repeated except that 7.3 g (24 mmol) of synthetic intermediate (2) of the polysiloxane (B-5) and 3.8 g (26 mmol) of dimethyldiethoxysilane were used. The GBL solution of polysiloxane (B-5) was obtained. It was 46 mol%: 54 mol% when the content rate of the residue derived from the intermediate (2) in this resin, and the residue derived from dimethyldiethoxysilane in ¹ H-NMR was computed.

Synthesis Example 14 Synthesis of Naphthoquinone Diazide Compound (C-1) 21.23 g (0.05 mol) of Tris P-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 5-naphthoquinone diazide sulfonyl acid in a dry nitrogen stream 37.62 g (0.14 mol) of chloride were dissolved in 450 g of 1,4-dioxane and brought to room temperature. To this, 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was dropped so that the temperature in the system did not exceed 35 ° C. After dropping, the mixture was stirred at 30 ° C. for 2 hours. The triethylamine salt was filtered off and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. The precipitate was dried by a vacuum drier to obtain a naphthoquinone diazide compound (C-1) having the following structure.

Examples 1 to 13 and Comparative Examples 1 to 8
Each component was melt | dissolved in GBL10g by the quantity shown in the following Table 1, the varnish was prepared, and these characteristics were measured by the said evaluation method. The obtained results are shown in Table 1.

In Table 1, a crosslinking agent (E-1) and an antioxidant (F-1) are compounds respectively shown to the following chemical formula.

[Examples 1 to 3, Comparative Examples 1 to 3]
Improvement of initial elongation and low temperature, high temperature as compared with Comparative Example 1 by mixing an alkali-soluble resin (A-1) which is a closed ring polyimide resin with a polysiloxane (B-4) having an alkali-soluble group The result of improving the elongation retention rate at In addition, the elongation was further improved by the addition of the crosslinking agent (D-1), and a good result of the elongation retention after holding at a high temperature was obtained by the addition of the antioxidant (E-1).
[Examples 4 to 5]
The use of the polysiloxanes (B-1) and (B-2) resulted in an improvement in initial elongation and an improvement in elongation retention at low temperatures and high temperatures, as compared with Comparative Example 3. . Moreover, compared with Example 3, from the effect which the thermal stability of a siloxane unit improves, the result of elongation retention after high temperature holding became a more favorable result.
[Examples 6 to 7, Comparative Example 4]
Evaluation was performed by changing the mixing amount of the polysiloxane (B-1) to the alkali-soluble resin (A). In Example 6, since the amount of (B) polysiloxane is 1 part by weight or more with respect to 100 parts by weight of (A) alkali-soluble resin, the elongation retention at low temperature is sufficiently high as in Example 3. In addition to the above, the elongation retention rate after high temperature holding was also high. In Example 7, the content of the polysiloxane (B-1) is 100 parts by weight or less with respect to 100 parts by weight of the (A) alkali-soluble resin, and as in Example 3, the elongation after holding at high temperature In addition to the high retention, the result is obtained that the elongation retention at lower temperatures is higher and the sensitivity is better. On the other hand, in Comparative Example 4, the ratio of the polysiloxane (B-4) is more than 100 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A), and the cured film becomes cloudy after holding at high temperature and can be peeled off It was not.
[Example 8, Comparative Example 5]
(B) As polysiloxane, it evaluated using resin from which the amount of alkali-soluble groups differs. When (B-3), in which the amount of alkali-soluble groups in the polysiloxane is 55 mol%, results comparable to those of Example 4 were obtained. On the other hand, when (B-5) having an alkali-soluble group content of 46% is used, film unevenness occurs after coating and development, suggesting that the compatibility of the resin is insufficient, and residues remain after development. The
[Examples 9 to 13, Comparative Examples 6 to 8]
As an alkali-soluble resin (A), a polyamic acid is used as a main chain (A-2), a polybenzoxazole precursor is used as a main chain (A-3), and a copolymer of polyamic acid and polyimide is used as a main chain Evaluation was carried out using (A-4), a polyamic acid ester as the main chain (A-5), and a copolymer of polybenzoxazole and its precursor as the main chain (A-6). On the other hand, it was found that results comparable to those of Example 4 were obtained, and high properties were obtained even when using a polyamic acid, a polybenzoxazole precursor, or a copolymer thereof. On the other hand, when evaluation was performed without mixing (B) polysiloxane with these resins, the elongation retention after holding at low temperature and high temperature was extremely low, resulting in low durability.

Claims (9)

(A) at least one alkali-soluble resin selected from polyimide, polybenzoxazole, polyimide precursor, polybenzoxazole precursor, and a copolymer of two or more resins selected therefrom
(B) A positive photosensitive resin composition comprising a polysiloxane having a structure represented by the general formula (1), (C) a photosensitizer and (D) a solvent, wherein 100% by weight of the (A) alkali-soluble resin A positive photosensitive resin composition comprising: (B) 1 to 100 parts by weight of a polysiloxane having a structure represented by the general formula (1) with respect to part thereof.

(In general formula (1), R ¹ represents a monovalent organic group having one or more carbon atoms, and R ² represents an organic group having a phenolic hydroxyl group or a carboxyl group or both in the structure p: q = 50: 50 to 0: 100. In the repeating units, each R ¹ and R ² may be the same or different.) The positive photosensitive resin composition according to claim 1, wherein R ² is represented by the general formula (2) in the general formula (1).

(In the general formula (2), R ³ represents a group having a phenolic hydroxyl group or a carboxyl group or both of them. X represents an alkylene group having 1 or more carbon atoms.) The positive photosensitive resin composition according to claim 1 or 2, further comprising (E) a thermal crosslinking agent. Furthermore, the positive photosensitive resin composition in any one of the Claims 1-3 containing (F) antioxidant. The resin sheet formed from the positive type photosensitive resin composition in any one of Claims 1-4. The cured film which hardened | cured the positive type photosensitive resin composition in any one of Claims 1-4. A cured film obtained by curing the resin sheet according to claim 5. Applying the positive photosensitive resin composition according to any one of claims 1 to 4 on a substrate, or laminating the resin sheet according to claim 5 on a substrate and drying to form a resin film; A method for producing a relief pattern of a cured film, comprising: a step of exposing through a mask; a step of eluting or removing an irradiated part with an alkaline solution for development; and a step of heat-treating a resin film after development. An electronic component or a semiconductor device, wherein the cured film according to claim 6 or 7 is disposed as a surface protective film or an interlayer insulating film.