JP2010044143A - Method for manufacturing optical waveguide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition from which a cured film exhibiting excellent chemical resistance is formed by curing at a low temperature of ≤250°C. <P>SOLUTION: The positive photosensitive resin composition comprises (a) a resin consisting mainly of a structure represented by general formula (1), (b) a quinonediazide compound, (c) a specific alkoxymethyl group-containing compound, (d) an acid generator having a thermal decomposition initiation temperature of ≤250°C, and (e) a solvent (wherein R<SP>1</SP>and R<SP>2</SP>may be the same or different and each represents a ≥2C di- to octavalent organic group; and R<SP>3</SP>and R<SP>4</SP>may be the same or different and each represents H or a 1-20C monovalent organic group). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition. More specifically, the present invention relates to a positive photosensitive resin composition suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating film of an organic electroluminescent element, a planarizing film of a thin film transistor (hereinafter referred to as TFT) substrate, and the like. .

  In order to reduce the actual layer area of an LSI (Large Scale Integration Circuit) package, bumps are formed on the package directly from a conventional QFP (Quad Flat Package) method in which pins are taken out from the package and joined. The method of joining the packages to the above has come to be used. For this reason, it is necessary to form solder bumps or the like when forming a package, and heat resistance and chemical resistance are required for an insulating material such as polyimide for protecting an LSI chip. In particular, since the solder bump formation is performed at a high temperature using an organic acid called a flux treatment, chemical resistance higher than the conventional one is required.

  Recently, the demand for thin displays has been increasing, and among them, attention has been focused on organic electroluminescent element displays. Since this light-emitting element is very sensitive to organic gases, the material that insulates between the light-emitting elements and the flattening film of the TFT substrate do not absorb chemicals used in the cleaning process, etc. Excellent chemical resistance is required.

  Furthermore, some recent semiconductor devices and display devices cannot be processed at high temperatures. The protective film, insulating film, and planarizing film in such applications are required to be curable at a low temperature. However, when the curing temperature is lowered, there is a problem that the chemical resistance is lowered due to insufficient curing of the resin.

As a material that can be cured at a low temperature, photosensitive resin compositions containing a polybenzoxazole precursor, a photoacid generator, and a thermal acid generator have been proposed so far (for example, patents). References 1-4). Further, as a resin composition exhibiting excellent chemical resistance by low-temperature curing, a photosensitive resin composition containing 100 parts by weight of a resin and 10 to 100 parts by weight of a thermal crosslinking agent has been proposed (see, for example, Patent Document 5). ). However, in recent years when higher chemical resistance is required, the chemical resistance of resin films formed by low-temperature curing of these conventionally known resin compositions is still insufficient.
International Publication No. 2005/1090999 Pamphlet JP 2006-10781 A JP 2007-213032 A JP 2007-304125 A JP 2007-16214 A

  An object of this invention is to provide the positive photosensitive resin composition which can obtain the cured film which shows the outstanding chemical resistance by low temperature hardening of 250 degrees C or less.

  The present invention includes (a) a resin having a structure represented by general formula (1) as a main component, (b) a quinonediazide compound, (c) an alkoxymethyl group-containing compound represented by general formula (2), (d A positive photosensitive resin composition comprising an acid generator having a thermal decomposition starting temperature of 250 ° C. or less and (e) a solvent.

In the general formula (1), R ¹ and R ² may be the same or different and each represents a divalent to octavalent organic group having 2 or more carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. n is in the range of 10 to 10,000, m and l are integers of 0 to 2, and p and q are integers of 0 to 4. However, p + q> 0.

In the general formula (2), R ⁵ and R ⁶ may be the same or different and each represents CH ₂ OR ²⁰ (R ²⁰ represents a monovalent organic group having 1 to 6 carbon atoms). R ⁷ represents a hydrogen atom, a methyl group or an ethyl group. R ^{8 to} R ¹⁹ may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. u represents 3 or 4.

  According to the positive photosensitive resin composition of the present invention, a cured film exhibiting excellent chemical resistance can be obtained by low-temperature curing at 250 ° C. or lower.

  Hereinafter, the present invention will be described in detail.

(A) Resin whose main component is the structure represented by the general formula (1) The positive photosensitive resin composition of the present invention is (a) a resin whose main component is the structure represented by the general formula (1). Containing. Such a resin can be a resin having an imide ring, an oxazole ring, or other cyclic structure by heating or an appropriate catalyst. Preferable examples include polyamic acid and polyamic acid ester of a polyimide precursor, and polyhydroxyamide of a polybenzoxazole precursor. By having a cyclic structure, the cured film is imparted with excellent heat resistance and chemical resistance. Here, the main component means that the n structural units in the general formula (1) have 50 mol% or more in the structural units of the resin. 70 mol% or more is preferable and 90 mol% or more is more preferable.

In the general formula (1), R ¹ and R ² may be the same or different and each represents a divalent to octavalent organic group having 2 or more carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. n is in the range of 10 to 10,000, m and l are integers of 0 to 2, and p and q are integers of 0 to 4. However, p + q> 0.

In the general formula (1), R ¹ represents a divalent to octavalent organic group having 2 or more carbon atoms, and represents an acid structural component. Examples of acids in which R ¹ is divalent include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, and bis (carboxyphenyl) propane, and aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and adipic acid. And so on. The acid R ¹ is trivalent, as the acid, trimellitic acid, tricarboxylic acids such as trimesic acid, R ¹ is tetravalent, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic Examples thereof include aromatic tetracarboxylic acids such as acid and diphenylsulfonetetracarboxylic acid, and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid. Moreover, the acid which has hydroxyl groups, such as a hydroxyphthalic acid and a hydroxy trimellitic acid, can also be mentioned. These acid components are used as they are, or as acid anhydrides and active esters. Two or more acid components may be used.

In general formula (1), R ² represents a divalent to octavalent organic group having 2 or more carbon atoms and represents a structural component of diamine. R ² (COOR ⁴ ) _l (OH) _q in the general formula (1) preferably has an aromatic ring and a hydroxyl group or a carboxyl group from the viewpoint of heat resistance of the resulting cured film. Examples of diamines constituting such residues include diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, bis (aminohydroxyphenyl) hexa Fluoropropane, bis (aminohydroxyphenyl) propane, bis (aminohydroxyphenyl) sulfone, bis (aminohydroxyphenyl) fluorene, diaminohydroxydiphenyl ether, diaminodihydroxydiphenyl ether, diaminohydroxycyclohexane, diaminodihydroxycyclohexane, bis (hydroxyphenylene) diamine, Alternatively, at least a part of hydrogen atoms of these aromatic rings are substituted with alkyl groups. Mention may be made of the compound. Further, ^R 2 (COOR ⁴⁾ of the general formula (1) Preferred examples of _{l (OH) q,} may also be mentioned the following structures.

X represents a direct bond, —CH ₂ —, —C ₇ H ₁₀ —, —O—, —SO ₂ —, —C ₃ H ₆ — or —C ₃ F ₆ —.

  Furthermore, a diamine having no hydroxyl group can be used as long as the solubility in alkali, the photosensitive performance, and the heat resistance are not impaired. Specifically, phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, hexa Examples include methylenediamine, diaminocyclohexane, diaminoadamantane, bis (aminocyclohexyl) propane, and cyclohexanebis (methylamine).

  (A) The weight average molecular weight (hereinafter referred to as Mw) of the resin having the structure represented by the general formula (1) as a main component is preferably 100,000 or less from the viewpoint of solubility in an alkali developer, 1,000 or less is more preferable. Furthermore, 10,000 or more are preferable and 20,000 or more are more preferable from the surface of improving the elongation. Further, the number average molecular weight (hereinafter referred to as Mn) is preferably 50,000 or less, and more preferably 30,000 or less. Furthermore, 3,000 or more are preferable and 5,000 or more are more preferable.

  The weight average molecular weight Mw and the number average molecular weight Mn of the resin in the present invention are values calculated as values in terms of polystyrene by gel permeation chromatography (GPC) measurement. The number of repeating structural units n of the resin is n = Mw / M, where M is the molecular weight of the structural unit and Mw is the weight average molecular weight of the resin.

  In the resin of the present invention, a silicon atom-containing acid dianhydride and / or a silicon atom-containing diamine can be used for the purpose of improving the adhesion to the substrate. Specifically, dimethylsilanediphthalic acid, 1,3-bis (3-phthalic acid) tetramethyldisiloxane, etc. as acid dianhydride components, 1,3-bis (3-aminopropyl) as diamine components Examples thereof include tetramethyldisiloxane, 1,3-bis (4-anilino) tetramethyldisiloxane, and 1,3-bis (p-amino-phenyl) octamethylpentasiloxane.

  In addition, the resin mainly composed of the structural unit represented by the general formula (1) may be end-capped with a monoamino compound, a monoacid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. . By end-capping, the viscosity of the resulting positive photosensitive resin composition can be adjusted to an appropriate range, and hydrolysis at the acid end can be suppressed, so that storage stability is improved. The terminal group is preferably an organic group having 2 to 30 carbon atoms having an unsaturated hydrocarbon group and / or an electron donating group, and preferably has an aromatic ring from the heat resistance of the resulting resin. In the case where the terminal group has an unsaturated hydrocarbon group, the unsaturated hydrocarbon group in the terminal group reacts and crosslinks during heat curing, whereby good mechanical properties can be obtained. In addition, when the terminal group has an electron donating group, the crosslinking reaction with the alkoxymethyl group-containing compound (c) is promoted, and the chemical resistance of the cured film is further improved.

  Monoamino compounds used for the end-capping agent include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1- Hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-amino Naphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 4-aminosalicylic acid, 5-aminosalicylic acid, 6- Aminosalicylic acid, 2-aminobenzoic acid, 3 Aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-amino Phenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 3-ethynylaniline, 4-ethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline Etc. are preferable.

  Examples of the monoacid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used for the end-capping agent include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic acid. Anhydrides such as acid anhydrides, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1- Hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3 Monocarboxylic acids such as ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid and 3,5-diethynylbenzoic acid, and monoacid chloride compounds in which these carboxyl groups are acid chlorided, terephthalic acid, phthalic acid Only the monocarboxyl group of dicarboxylic acids such as cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, etc. Preference is given to monoacid chloride compounds, active ester compounds obtained by reaction of monoacid chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide.

The terminal component introduced into the resin is, for example, dissolving the resin in an acidic solution and decomposing it into an amine component and an acid anhydride component, which are constituent units of the resin, and measuring this by gas chromatography (GC) or NMR. Can be easily detected. It is also possible to detect a terminal component by directly measuring the resin by pyrolysis gas chromatography (PGC), infrared spectrum and ¹³ CNMR spectrum.

  (A) The resin having the structure represented by the general formula (1) as a main component can be produced in accordance with a known method for producing polyamic acid or polyamic acid ester and polyhydroxyamide, and the method is particularly limited. Not. For example, a method of reacting a tetracarboxylic dianhydride and a diamine compound and an end-capping agent at a low temperature, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then a diamine compound, an end-capping agent and a condensing agent Examples thereof include a method of reacting in the presence, a method of acidifying dicarboxylic acid and reacting with a diamine compound and a terminal blocking agent. Furthermore, it is desirable that the polymer obtained by the above method is poured into a large amount of water or a methanol / water mixture, precipitated, filtered, dried and isolated. By this precipitation operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and the film properties after thermosetting are improved.

  The solvent used in the polymerization reaction is not particularly limited as long as it can dissolve the acid anhydride and diamine which are raw material monomers, and a protic solvent is preferable. Specifically, N, N-dimethylformamide, N, N-dimethylacetamide, amides of N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε- Cyclic esters such as caprolactone and α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3 -Dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like. The amount of the polymerization solvent is preferably 100 to 1900 parts by weight, more preferably 150 to 950 parts by weight with respect to 100 parts by weight of the resin whose main component is the structure represented by (a) the general formula (1).

(B) Quinonediazide compound The positive photosensitive resin composition of the present invention contains (b) a quinonediazide compound. As quinonediazide compounds, quinonediazide sulfonic acid bonded to a polyhydroxy compound with an ester, quinonediazide sulfonic acid bonded to a polyamino compound with a sulfonamide bond, and a quinonediazide sulfonic acid bonded to a polyhydroxypolyamino compound with an ester bond and / or sulfone Examples include amide-bonded ones. From the viewpoint of the contrast between the exposed area and the unexposed area, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compound and polyamino compound are substituted with quinonediazide. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can.

  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 (above, trade name, 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 (above, trade name, Asahi Organic Materials Co., Ltd.) Manufactured), 2,6-dimethoxymethyl-4-t-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 (trade name) Honshu Chemical Industry like Ltd.), but is not limited thereto.

  Examples of polyamino compounds include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diamino. Examples thereof include, but are not limited to, diphenyl sulfide.

  Examples of the polyhydroxypolyamino compound include, but are not limited to, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 3,3'-dihydroxybenzidine and the like.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. Also, a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule can be used, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound are used in combination. You can also

  The content of the (b) quinonediazide compound is preferably 1 part by weight or more and more preferably 5 parts by weight or more with respect to 100 parts by weight of the resin whose main component is the structure represented by (a) the general formula (1). preferable. Moreover, 50 weight part or less is preferable and 35 weight part or less is more preferable.

  Examples of the synthesis method of the (b) quinonediazide compound used in the present invention include a method of reacting 5-naphthoquinonediazidesulfonyl chloride with a polyhydroxy compound in the presence of triethylamine.

(C) Alkoxymethyl group-containing compound represented by general formula (2) The positive photosensitive resin composition of the present invention contains (c) an alkoxymethyl group-containing compound represented by general formula (2). Two or more of these may be contained. Since the alkoxymethyl group causes a crosslinking reaction in a temperature range of 150 ° C. or higher, by containing the compound, it can be crosslinked by a post-development heat treatment described later to improve the chemical resistance of the cured film. Moreover, the temperature range of a crosslinking reaction is 150 degreeC or more, the crosslinking reaction in the prebaking process at the time of pattern processing can be prevented, and the photosensitive resin composition containing this compound has high sensitivity. Since the alkoxymethyl group-containing compound represented by the general formula (2) has 6 or more alkoxymethyl groups, the crosslink density of the cured film is increased and the chemical resistance is improved. Further, since the dispersion of alkoxymethyl groups in the thermal crosslinking agent molecule is larger than that of conventionally known thermal crosslinking agents, the crosslinking reactivity during curing is high, and the chemical resistance is improved.

In general formula (2), R ⁵ and R ⁶ may be the same or different and each represents CH ₂ OR ²⁰ . Here, R ²⁰ represents a monovalent organic group having 1 to 6 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is more preferable from the viewpoint of the solubility of the positive photosensitive resin composition. R ⁷ represents a hydrogen atom, a methyl group or an ethyl group. R ^{8 to} R ¹⁹ may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and an alkyl group is preferable. u represents 3 or 4.

  (C) Among the alkoxymethyl group-containing compounds represented by the general formula (2), preferred examples include the following compounds, but are not limited thereto.

  (C) The content of the alkoxymethyl group-containing compound represented by the general formula (2) is 10 parts by weight with respect to 100 parts by weight of the resin whose main component is the structure represented by the general formula (1). The above is preferable, 20 parts by weight or more is more preferable, and 25 parts by weight or more is more preferable. When it is 25 parts by weight or more, the crosslinking density is increased, and the chemical resistance is further improved. On the other hand, it is preferably 60 parts by weight or less, more preferably 50 parts by weight or less, and still more preferably 40 parts by weight or less from the viewpoints of storage stability and mechanical strength of the positive photosensitive resin composition.

(D) Acid generator having a thermal decomposition starting temperature of 250 ° C. or lower The positive photosensitive resin composition of the present invention contains (d) an acid generator having a thermal decomposition starting temperature of 250 ° C. or lower. The acid generator of component (d) used in the present invention generates an acid by heating after development, which will be described later, and serves as a catalyst for a crosslinking reaction between the resin of component (a) and the alkoxymethyl group-containing compound of component (c). In order to promote crosslinking, the crosslinking reaction proceeds sufficiently even in low-temperature curing, and the chemical resistance of the cured film can be dramatically improved. In addition, since the imide ring and oxazole ring of the component (a) resin are promoted, the cyclization reaction proceeds sufficiently even at low temperature curing, and the chemical resistance of the cured film is improved. In the present invention, it is important that the thermal decomposition starting temperature of the acid generator as the component (d) is 250 ° C. or lower. When the thermal decomposition starting temperature exceeds 250 ° C., sufficient acid is not generated in the low temperature curing, the crosslinking reaction and the cyclization reaction do not proceed sufficiently, and the chemical resistance of the cured film is lowered. An acid generator excellent in thermal stability such as a triarylsulfonium salt has a high decomposition initiation temperature and is not preferred. In addition, the thermal decomposition start temperature of the acid generator is preferably 150 ° C. or higher, and when it is 150 ° C. or higher, acid deactivation can be prevented in the pre-baking process during pattern processing. The acid generated from the acid generator is preferably a strong acid. For example, arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid are preferable. .

  The thermal decomposition start temperature of the acid generator in the present invention is determined from an exothermic peak when heated at a temperature increase rate of 10 ° C./min by differential scanning calorimetry.

  (D) Examples of the acid generator having a thermal decomposition starting temperature of 250 ° C. or lower include the following sulfonium salts and sulfonic acid esters. Two or more of these may be contained.

  Examples of the sulfonium salt include 4-hydroxyphenyldimethylsulfonium triflate, benzyl-4-hydroxyphenylmethylsulfonium triflate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium triflate, 4-methylbenzyl-4-hydroxyphenylmethylsulfonium. Examples include triflate, 4-hydroxyphenylmethyl-1-naphthylmethylsulfonium triflate, 4-methoxycarbonyloxyphenyldimethylsulfonium triflate, and the like.

  Examples of sulfonic acid esters include benzoin tosylate, p-nitrobenzyl-9,10-ethoxyanthracene-2-sulfonate, 2-nitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, and 2,4-dinitrobenzyl tosylate. Etc.

  In addition, 5-norbornene-2,3-dicarboxyimidyl triflate, 5-norbornene-2,3-dicarboxyimidyl tosylate, 4-methylphenylsulfonyloxyimino-α- (4-methoxyphenyl) acetonitrile, tri Fluoromethylsulfonyloxyimino-α- (4-methoxyphenyl) acetonitrile, 9-camphorsulfonyloxyimino-α- (4-methoxyphenyl) acetonitrile, 1,8-naphthalimidyl butanesulfonate, 1,8-naphthalimidyl tosylate, Examples include, but are not limited to, acid generators such as 1,8-naphthalimidyl triflate and 1,8-naphthalimidyl nonafluorobutanesulfonate.

  Moreover, the aliphatic sulfonic acid compound represented by General formula (3) or (4) is especially preferable.

R ²¹ in the general formula (3) and R ^{22 to} R ²³ in (4) may be the same or different, and represent an alkyl group having 1 to 10 carbon atoms or a monovalent aromatic group having 6 to 12 carbon atoms. Show.

  Specific examples of the compound represented by the general formula (3) include the following compounds.

  Specific examples of the compound represented by the general formula (4) include the following compounds.

  (D) The content of the acid generator having a thermal decomposition start temperature of 250 ° C. or lower is 1 part by weight or more with respect to 100 parts by weight of the resin whose main component is the structure represented by the general formula (1). Is preferably 3 parts by weight or more, more preferably 5 parts by weight or more. Within this range, the cyclization of the resin of component (a) and the crosslinking reaction with the alkoxymethyl group-containing compound of component (c) can be further promoted, and the chemical resistance of the cured film can be further improved. On the other hand, from the viewpoint of electrical insulation of the cured film, it is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less.

(E) Solvent The positive photosensitive resin composition of the present invention contains (e) a solvent. Solvents include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, etc. Ethers, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone and diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained. The content of the solvent is preferably (a) 50 parts by weight or more, more preferably 100 parts by weight or more, with respect to 100 parts by weight of the resin whose main component is the structure represented by the general formula (1). The amount is preferably 2000 parts by weight or less, more preferably 1500 parts by weight or less.

(F) Other additives The positive photosensitive resin composition of the present invention may contain a silane compound. By containing the silane compound, the adhesion to the base substrate can be improved. Specific examples of the silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltri Methoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltri Methoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and the following silane compounds are used: Door can be, but are not limited to these.

  The positive photosensitive resin composition of the present invention can contain a compound having a phenolic hydroxyl group. By containing a compound having a phenolic hydroxyl group, the obtained positive photosensitive resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. Less film loss and easy development in a short time.

  If necessary, for the purpose of improving the wettability between the positive photosensitive resin composition and the substrate, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone , Ketones such as methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane. Further, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.

  The manufacturing method of the positive photosensitive resin composition of this invention is illustrated. For example, (a) to (e), and if necessary, other components are placed in a glass flask or stainless steel container and stirred and dissolved with a mechanical stirrer, etc., ultrasonically dissolved, planetary stirring and defoaming The method of stirring and dissolving with an apparatus is mentioned. The viscosity of the composition is preferably 1 to 10,000 mPa · s. Moreover, you may filter with the filter of 0.1 micrometer-5 micrometers pore size in order to remove a foreign material.

  Next, a method for forming a heat resistant resin pattern (cured film) using the positive photosensitive resin composition of the present invention (hereinafter sometimes referred to as a photosensitive resin composition) will be described.

  A photosensitive resin composition is applied onto a substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, ITO, or the like is used, but not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and slit die coating. The coating film thickness varies depending on the coating technique, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 μm.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 ° C. to 150 ° C. for 1 minute to several hours.

  Next, the photosensitive resin film is exposed to actinic radiation through a mask having a desired pattern. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp. .

  In order to form a pattern on the photosensitive resin film, the exposed portion may be removed using a developer after exposure. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, One or more alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added. After development, it is common to rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, a temperature of 180 ° C. to 450 ° C. is applied to convert it into a heat resistant resin film (cured film). This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and increasing the temperature stepwise or by selecting a certain temperature range and continuously increasing the temperature. As a curing temperature, 200-300 degreeC is preferable and 220-280 degreeC is more preferable. It can also be cured by ultrasonic treatment or electromagnetic wave treatment.

  The heat-resistant resin film (cured film) formed by the positive photosensitive resin composition of the present invention includes a semiconductor passivation film, a protective film for a semiconductor element, an interlayer insulating film for multilayer wiring for high-density mounting, and an organic electroluminescent element. It is suitably used for applications such as an insulating film and a planarization film of a TFT substrate.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated in detail, this invention is not limited by these examples. In addition, preparation and evaluation of the cure film | membrane in an Example were performed with the following method.

Measurement Method of Thermal Decomposition Start Temperature of Acid Generator From the exothermic peak when heated to 400 ° C. at a rate of 10 ° C./min using a differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC-50) The decomposition start temperature was determined.

Production of photosensitive resin film A photosensitive resin composition (hereinafter referred to as varnish) was applied onto a 6-inch silicon wafer so that the film thickness after pre-baking was 3 μm, and then a hot plate (manufactured by Tokyo Electron Ltd., A photosensitive resin film was obtained by pre-baking at 120 ° C. for 2 minutes using a coating and developing apparatus Mark-7).

Film thickness measurement method Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the film after pre-baking and development is measured at a refractive index of 1.629, and the cured film is measured at a refractive index of 1.773. did.

Exposure The reticle from which the pattern was cut | disconnected was set to the exposure machine (The GCA company make, i line | wire stepper DSW-8570i), the exposure time was changed with the intensity | strength of 365 nm, and the photosensitive resin film was exposed with the i line | wire.

Development The film after the exposure was developed using a Mark-7 development apparatus manufactured by Tokyo Electron Ltd., and a 2.38% aqueous solution of tetramethylammonium hydroxide was used. The film thickness after development was 90% of the film thickness after pre-baking. Then, development was performed, followed by rinsing with pure water and drying by shaking.

Calculation of sensitivity After exposure and development, the exposure amount at which the exposed portion was not completely eluted was defined as sensitivity.

Production of heat-resistant resin film The photosensitive resin film produced by the above method was heat-treated at 230 ° C. for 1 hour in a nitrogen atmosphere (oxygen concentration of 20 ppm or less) using an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd. A cured film (heat resistant resin film) was obtained.

Evaluation of chemical resistance The cured film produced by the above method was immersed in a stripping solution TOK-106 manufactured by Tokyo Ohka Co., Ltd. at 60 ° C. for 10 minutes. About the film after a process, the presence or absence of the crack was evaluated using the optical microscope. In addition, the film thickness before and after the treatment was measured to determine the amount of film reduction.

<Synthesis Example 1> Synthesis of hydroxyl group-containing diamine compound (a) 9,9-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) 18.3 g (0.05 mol) in 100 mL of acetone and propylene It was dissolved in 17.4 g (0.3 mol) of oxide and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon 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 by confirming that the balloons did not squeeze any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration, and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (a) represented by the following formula.

<Synthesis Example 2> Synthesis of Heat Resistant Resin Precursor (Polymer A) 14.5 g (0.024 mol) of hydroxyl group-containing diamine compound (a) obtained in Synthesis Example 1 under a dry nitrogen stream, 1,3- Bis (3-aminopropyl) tetramethyldisiloxane (SiDA) 0.37 g (0.002 mol) was dissolved in N-methylpyrrolidone (NMP) 80 g. To this, 9.31 g (0.030 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (ODPA) was added together with 10 g of NMP, and reacted at 40 ° C. for 1 hour. Thereafter, 0.47 g (0.004 mol) of 4-ethynylaniline was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 1 hour. Thereafter, a solution prepared by diluting 5.95 g (0.05 mol) of N, N′-dimethylformamide dimethylacetal with 15 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 2 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain a heat-resistant resin precursor polymer A.

Synthesis Example 3 Synthesis of Heat Resistant Resin Precursor (Polymer B) As an end-capping agent, instead of 4-ethynylaniline 0.47 g (0.004 mol), 3-aminophenol 0.44 g (0.004 mol) ), And the amount of N, N′-dimethylformamide dimethyl acetal was changed from 5.95 g (0.05 mol) to 7.14 g (0.06 mol) in the same manner as in Synthesis Example 2, except that the heat resistant resin was changed. The precursor polymer B was obtained.

Synthesis Example 4 Synthesis of Heat Resistant Resin Precursor (Polymer C) Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether to obtain a solution. The temperature of was cooled to -15 ° C. A solution prepared by dissolving 14.7 g (0.05 mol) of diphenyl ether dicarboxylic acid chloride in 25 g of γ-butyrolactone was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C. After completion of the reaction, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried for 20 hours in a vacuum dryer at 80 ° C. to obtain polymer C as a heat resistant resin precursor.

<Synthesis Example 5> Synthesis of quinonediazide compound (b-1) 4,4 '-[1- [4- [1- (4-hydroxyphenyl-1) -1-methylethyl] phenyl] ethylidene under a dry nitrogen stream ] 21.22 g (0.05 mol) of bisphenol (Honshu Chemical Industry Co., Ltd., TrisP-PA), 26.86 g (0.10 mol) of 5-naphthoquinone diazide sulfonyl chloride, 4-naphthoquinone diazide sulfonyl chloride 13 .43 g (0.05 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (b-1) represented by the following formula.

<Synthesis Example 6> Synthesis of alkoxymethyl group-containing compound 169.6 g (0.4 mol) of TrisP-PA manufactured by Honshu Chemical Industry Co., Ltd., 80 g (2.0 mol) of sodium hydroxide dissolved in 800 g of pure water Dissolved in the solution. After complete dissolution, 686 g of 36-38% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Then, it stirred at 20-25 degreeC for 17 hours. This was neutralized by adding 98 g of sulfuric acid and 552 g of water, and allowed to stand for 2 days. Needle-like white crystals formed in the solution after standing were collected by filtration and washed with 100 mL of water. The white crystals were vacuum dried at 50 ° C. for 48 hours.

  When the obtained white crystals were analyzed at 254 nm by high performance liquid chromatography manufactured by Shimadzu Corporation using ODS as the column and acetonitrile / water = 70/30 as the developing solvent, the starting material was completely disappeared. It was found that the purity was 88%. Furthermore, when it analyzed by NMR (the JEOL Co., Ltd. product, GX-270) using DMSO-d6 for a heavy solvent, it turned out that it is a trimethyl P-PA hexahexylol-ized.

  Next, the compound thus obtained was dissolved in 300 mL of methanol, 2 g of sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours. To this solution, 15 g of an anionic ion exchange resin (Amberlyst IRA96SB, manufactured by Rohm and Haas) was added and stirred for 1 hour, and the ion exchange resin was removed by filtration. Thereafter, 500 mL of ethyl lactate was added, and methanol was removed by a rotary evaporator to obtain an ethyl lactate solution. When this solution was allowed to stand at room temperature for 2 days, white crystals were formed. When the obtained white crystal was examined by a liquid chromatography method, it was a 98% pure TrisP-PA hexamethoxymethylol compound (HMOM-TrisPPA).

<Synthesis Example 7> Synthesis of alkoxymethyl group-containing compound 1,1,1-tris (4-hydroxyphenyl) ethane (manufactured by Honshu Chemical Industry Co., Ltd., TrisP-HAP) (103.2 g, 0.4 mol) Sodium hydroxide 80 g (2.0 mol) was dissolved in a solution of 800 g of pure water. After complete dissolution, 686 g of 36-38% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Then, it stirred at 20-25 degreeC for 17 hours. This was neutralized by adding 98 g of sulfuric acid and 552 g of water, and allowed to stand for 2 days. Needle-like white crystals formed in the solution after standing were collected by filtration and washed with 100 mL of water. The white crystals were vacuum dried at 50 ° C. for 48 hours.

  When the obtained white crystals were analyzed at 254 nm by high performance liquid chromatography manufactured by Shimadzu Corporation using ODS as the column and acetonitrile / water = 70/30 as the developing solvent, the starting material was completely disappeared. The purity was found to be 92%. Furthermore, when it analyzed by NMR (the JEOL Co., Ltd. product, GX-270) using DMSO-d6 for a heavy solvent, it turned out that it is the trimethyl P-HAP hexamethylolated.

  Next, the compound thus obtained was dissolved in 300 mL of ethanol, 2 g of sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours. To this solution, 15 g of an anionic ion exchange resin (Amberlyst IRA96SB, manufactured by Rohm and Haas) was added and stirred for 1 hour, and the ion exchange resin was removed by filtration. Thereafter, 500 mL of ethyl lactate was added, and ethanol was removed by a rotary evaporator to obtain an ethyl lactate solution. When this solution was allowed to stand at room temperature for 2 days, white crystals were formed. When the obtained white crystal was examined by a liquid chromatography method, it was a 99% purity TrisP-HAP hexaethoxymethylol compound (HEOM-TPHAP).

  The alkoxymethyl group-containing compounds and methylol group-containing compounds used in Examples and Comparative Examples are as follows.

  The acid generators used in Examples and Comparative Examples are as follows.

<Example 1>
(A) 2.0 g of the quinonediazide compound [b-1] obtained in Synthesis Example 5 as the component (b) and HMOM-as the component (c) with respect to 10 g of the polymer A obtained in Synthesis Example 2 as the component. 15 g of TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd., 20% γ-butyrolactone solution, 3.0 g of crosslinking agent) and PAG-103 (trade name, Ciba Specialty Chemicals Co., Ltd.) as component (d) ), Thermal decomposition start temperature: 155 ° C.) 0.7 g was dissolved in 35 g of ethyl lactate as the component (e) to obtain a varnish of the photosensitive resin composition. When the chemical resistance of the cured film using this varnish was evaluated, the film reduction amount was 0.003 μm. No cracks were found on the film surface, indicating good chemical resistance. The sensitivity was 85 mJ / cm ² .

<Comparative Example 1>
A varnish was obtained in the same manner as in Example 1 except that PAG-103 as the component (d) was not added in Example 1. When the chemical resistance of the cured film using this varnish was evaluated, the amount of film reduction was 0.048 μm, and no crack was observed on the film surface. The sensitivity was 80 mJ / cm ² .

<Comparative example 2>
A varnish was obtained in the same manner as in Example 1 except that 12 g of γ-butyrolactone was added as a solvent without adding HMOM-TPHAP as the component (c) in Example 1. When the chemical resistance of the cured film using this varnish was evaluated, the film was completely dissolved. The sensitivity was 195 mJ / cm ² .

<Comparative Example 3>
A varnish was obtained in the same manner as in Example 1 except that 0.7 g of the component (d) was changed to WPAG-505 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., thermal decomposition start temperature: 371 ° C.) in Example 1. . When the chemical resistance of the cured film using this varnish was evaluated, the film loss was 0.019 μm, but cracks were found on the film surface. The sensitivity was 75 mJ / cm ² .

<Comparative example 4>
Example 1 except that the component (c) in Example 1 is 4.0 g of “Nicalac (registered trademark)” MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.), and 12 g of γ-butyrolactone is added as a solvent. In the same manner, a varnish was obtained. When the chemical resistance of the cured film using this varnish was evaluated, the film reduction amount was 0.280 μm, and cracks were observed on the film surface. The sensitivity was 100 mJ / cm ² .

<Comparative Example 5>
In Example 1, the component (c) was TML-BPAF-MF (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 3.0 g, and varnish was obtained in the same manner as in Example 1 except that 12 g of γ-butyrolactone was added as a solvent. Got. When the chemical resistance of the cured film using this varnish was evaluated, the film loss was 1.165 μm. No cracks were found on the film surface. The sensitivity was 95 mJ / cm ² .

<Example 2>
(A) 2.0 g of the quinonediazide compound [b-1] obtained in Synthesis Example 5 as the component (b), and HMOM-as the component (c) with respect to 10 g of the polymer B obtained in Synthesis Example 3 as the component (a). 15 g of TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd., 20% γ-butyrolactone solution, 3.0 g of crosslinking agent) and PAG-108 (trade name, Ciba Specialty Chemicals Co., Ltd.) as component (d) ), Thermal decomposition starting temperature: 152 ° C.) 1.0 g was dissolved in 35 g of ethyl lactate as the component (e) to obtain a varnish of the photosensitive resin composition. When the chemical resistance of the cured film using this varnish was evaluated, the amount of film reduction was 0.000 μm. No cracks were found on the film surface, indicating good chemical resistance. The sensitivity was 80 mJ / cm ² .

<Comparative Example 6>
A varnish was obtained in the same manner as in Example 2 except that PAG-108 as the component (d) was not added in Example 2. When the chemical resistance of the cured film using this varnish was evaluated, the film reduction amount was 0.040 μm. No cracks were found on the film surface. The sensitivity was 75 mJ / cm ² .

<Example 3>
(A) 2.0 g of quinonediazide compound [b-1] as component (b) and HMOM- obtained in Synthesis example 6 as component (c) with respect to 10 g of polymer A obtained in Synthesis example 2 as component (a) 3.0 g of TrisP-PA and 0.7 g of PAG-203 (trade name, manufactured by Ciba Specialty Chemicals, Inc., thermal decomposition start temperature: 204 ° C.) as component (d) and γ-butyrolactone as component (e) It melt | dissolved in 12g and ethyl lactate 35g, and the varnish of the photosensitive resin composition was obtained. When the chemical resistance of the cured film using the varnish was evaluated, the amount of film reduction was 0.009 μm. No cracks were found on the film surface. The sensitivity was 90 mJ / cm ² .

<Example 4>
(A) 2.0 g of the quinonediazide compound [b-1] as the component (b) and HEOM-obtained in the synthesis example 7 as the component (c) with respect to 10 g of the polymer C obtained in the synthesis example 4 as the component (a). Photosensitive by dissolving 3.0 g of TPHAP and 0.7 g of PAG-103 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.) as component (d) in 12 g of γ-butyrolactone and 35 g of ethyl lactate as component (e). The varnish of the functional resin composition was obtained. When the chemical resistance of the cured film using this varnish was evaluated, the film reduction amount was 0.001 μm. No cracks were found on the film surface. The sensitivity was 90 mJ / cm ² .

<Comparative Example 7>
A varnish was obtained in the same manner as in Example 4 except that PAG-103 as the component (d) was not added in Example 4. When the chemical resistance of the cured film using this varnish was evaluated, the film reduction amount was 0.062 μm. No cracks were found on the film surface. The sensitivity was 90 mJ / cm ² .

<Comparative Example 8>
A varnish was obtained in the same manner as in Example 4 except that HEOM-TPHAP as component (c) was not added. When the chemical resistance of the cured film using this varnish was evaluated, the film reduction amount was 0.444 μm, and cracks were observed on the film surface. The sensitivity was 110 mJ / cm ² .

  Table 1 shows the compositions and evaluation results of Examples 1 to 4 and Comparative Examples 1 to 8.

Claims (2)

(A) Resin having a structure represented by general formula (1) as a main component, (b) quinonediazide compound, (c) alkoxymethyl group-containing compound represented by general formula (2), (d) initiation of thermal decomposition A positive photosensitive resin composition comprising an acid generator having a temperature of 250 ° C. or less and (e) a solvent.

(In General Formula (1), R ¹ and R ² may be the same or different, and represent a divalent to octavalent organic group having 2 or more carbon atoms. R ³ and R ⁴ may be the same or different. , A hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, n is in the range of 10 to 10,000, m and l are integers of 0 to 2, and p and q are integers of 0 to 4, provided that p + q> 0.)

In (general formula (2), ^{R 5} and ^{R 6} may be the same or different _each, CH ² OR ^{20 (R} 20 represents a represents a monovalent organic group having 1 to 6 carbon atoms) .R ⁷ is R ^{8 to} R ¹⁹ may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and u represents 3 or 4. ) 2. The positive photosensitive resin composition according to claim 1, wherein the acid generator (d) having a thermal decomposition starting temperature of 250 ° C. or lower is a compound represented by the general formula (3) or (4). object.

(R ²¹ in the general formula (3) and R ^{22 to} R ²³ in (4) may be the same or different, and an alkyl group having 1 to 10 carbon atoms or a monovalent aromatic group having 6 to 12 carbon atoms. Is shown.)