JP5712658B2 - Positive photosensitive resin composition - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition. More specifically, a surface protective film or an interlayer insulating film of a semiconductor element, an insulating film of an organic electroluminescence (hereinafter referred to as EL) element, a driving thin film transistor (Thin Film Transistor: hereinafter referred to as a TFT) of a display device using the organic EL element. The present invention relates to a positive-type photosensitive resin composition suitable for applications such as a flattening film on a substrate, a wiring protective insulating film on a circuit board, an on-chip microlens for a solid-state image sensor, and a flattening film for various displays and solid-state image sensors. .

  A resin film made of polyimide or polybenzoxazole is widely used for a surface protective film, an interlayer insulating film, a planarizing film, or the like of a semiconductor element. Recently, for example, it is also used for an insulating film of an organic EL element and a planarizing film of a TFT substrate (see Patent Document 1).

  With the miniaturization of semiconductor elements and organic EL elements, a resolution of several μm has been required for surface protective films, interlayer insulating films, planarization films, and insulating films of organic EL elements. In such applications, finely processable positive photosensitive polyimide and positive photosensitive polybenzoxazole are used, and naphthoquinone diazide sulfonyl chloride (see Patent Document 2) and an ester of a polyhydroxy compound as a positive photosensitive agent. Compounds (see Patent Document 3) are widely used.

  When the polyamic acid which is a polyimide precursor and a polybenzoxazole precursor is allowed to stand at room temperature in a state of being dissolved in a solvent, the properties change due to the progress of imidization and oxazolation in the system. In addition, it is known that quinonediazide compounds used as positive photosensitive agents have poor storage stability when dissolved in a solvent, and decomposition proceeds and changes in properties when left at room temperature. Therefore, in order to stably store the positive photosensitive resin composition, it is common to keep the storage temperature at 4 ° C. or lower.

JP 2004-54254 A JP 2000-297073 A JP 2003-337413 A

  However, when a positive photosensitive resin composition containing polyimide, polybenzoxazole or a precursor thereof is stored for a long time at 4 ° C. or less, polyimide, polybenzoxazole or a precursor thereof is precipitated, and a semiconductor element or an organic EL There was a problem that became a defect of the element.

  An object of the present invention is to solve such problems and to provide a positive photosensitive resin composition having excellent storage stability at a storage temperature of 4 ° C. or lower.

The present invention comprises (a) polyimide, polybenzoxazole or a precursor thereof, (b) a quinonediazide compound and (c) a solvent, and the contents of benzene, toluene and xylene are all 5 ppm or less. A naphthoquinone diazide sulfonyl chloride isolated by a method in which (b) a quinone diazide compound is extracted and distilled with benzene, toluene and xylene and then recrystallized. It is a manufacturing method of positive photosensitive resin composition characterized by being manufactured using .

  According to the present invention, a positive photosensitive resin composition having excellent storage stability at a storage temperature of 4 ° C. or less can be obtained.

  The positive photosensitive resin composition of the present invention contains (a) polyimide, polybenzoxazole or a precursor thereof, (b) a quinonediazide compound and (c) a solvent, and any of benzene, toluene and xylene contents. Is a positive photosensitive resin composition characterized by being 5 ppm or less. Below, each component is demonstrated.

  The positive photosensitive resin composition of the present invention contains (a) polyimide, polybenzoxazole, or a precursor thereof. Two or more of these may be contained, or a copolymer having two or more of these repeating units may be contained.

  Polyimide and polybenzoxazole are resins having a cyclic structure of an imide ring or an oxazole ring in the main chain structure. The number of repeating structural units is preferably 10 to 100,000.

  Polyimide can be obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride, tetracarboxylic diester dichloride, etc. with diamine, corresponding diisocyanate compound, trimethylsilylated diamine, and tetracarboxylic acid residue. Has a diamine residue. For example, polyamic acid, which is one of polyimide precursors obtained by reacting tetracarboxylic dianhydride and diamine, can be obtained by dehydrating and ring-closing by heat treatment. Alternatively, it can also be obtained by adding a dehydration condensing agent such as carboxylic acid anhydride or dicyclohexylcarbodiimide or a base such as triethylamine as a ring closure catalyst and performing dehydration and ring closure by chemical heat treatment. Alternatively, it can also be obtained by adding a weakly acidic carboxylic acid compound and dehydrating and ring-closing by heat treatment at a low temperature of 100 ° C. or lower.

  Polybenzoxazole can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester, etc., and has a dicarboxylic acid residue and a bisaminophenol residue. For example, polyhydroxyamide, which is one of polybenzoxazole precursors obtained by reacting a bisaminophenol compound with a dicarboxylic acid, can be obtained by dehydration and ring closure by heat treatment. Alternatively, it can be obtained by adding phosphoric anhydride, a base, a carbodiimide compound, etc., and dehydrating and ring-closing by chemical treatment.

  A polyimide precursor and a polybenzoxazole precursor are resins having an amide bond in the main chain, and become the above-described polyimide and polybenzoxazole by dehydration and ring closure by heat treatment or chemical treatment. The number of repeating structural units is preferably 10 to 100,000. Examples of the polyimide precursor include polyamic acid, polyamic acid ester, polyamic acid amide, polyisoimide, and the like, and polyamic acid and polyamic acid ester are preferable. Examples of the polybenzoxazole precursor include polyhydroxyamide, polyaminoamide, polyamide, polyamideimide and the like, and polyhydroxyamide is preferable.

Polyimide, polybenzoxazole, and their precursors are OR ¹ , SO ₃ R ¹ , CONR ¹ R ² , COOR ¹ , SO ₂ NR ¹ R in the acid residue or diamine residue from the viewpoint of solubility in an alkaline aqueous solution. It preferably has an acidic group or acidic group derivative such as ^2, and more preferably has a hydroxyl group. R ¹ and R ² represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different. The acidic group refers to the case where all R ¹ or R ² are hydrogen atoms, and the acidic group derivative refers to the case where a monovalent organic group having 1 to 20 carbon atoms is contained in R ¹ or R ² . Examples of the organic group include an alkyl group, an alkoxyl group, and an ester group.

  In the present invention, as a preferable structure of polyimide, tetracarboxylic acid residue of polyimide precursor and polybenzoxazole, dicarboxylic acid residue of polybenzoxazole precursor, the following structure or a part of these hydrogen atoms Examples include a structure in which 1 to 4 carbon atoms are substituted with an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group, a cyano group, a fluorine atom, or a chlorine atom.

Where J is a direct bond, —COO—, —CONH—, —CH ₂ —, —C ₂ H ₄ —, —O—, —C ₃ H ₆ —, —C ₃ F ₆ —, —SO ₂ —, _{-S -, - Si (CH 3} ) 2 -, - O-Si (CH 3) 2 -O -, - C 6 H 4 -, - C 6 H 4 -O-C 6 H 4 -, - C 6 _{H 4 -C 3 H 6 -C 6} H 4 - or _{-C 6 H 4 -C 3 F 6} -C 6 H 4 - shows a.

  In the present invention, preferred structures of polyimide, diamine residue of polyimide precursor and polybenzoxazole, bisaminophenol residue of polybenzoxazole precursor are as follows, and some of these hydrogen atoms are carbon atoms. Examples thereof include a structure in which 1 to 4 alkyl groups, fluoroalkyl groups, alkoxyl groups, ester groups, nitro groups, cyano groups, fluorine atoms, and chlorine atoms are substituted with 1 to 20 alkyl groups.

Where J is a direct bond, —COO—, —CONH—, —CH ₂ —, —C ₂ H ₄ —, —O—, —C ₃ H ₆ —, —C ₃ F ₆ —, —SO ₂ —, _{-S -, - Si (CH 3} ) 2 -, - O-Si (CH 3) 2 -O -, - C 6 H 4 -, - C 6 H 4 -O-C 6 H 4 -, - C 6 _{H 4 -C 3 H 6 -C 6} H 4 - or _{-C 6 H 4 -C 3 F 6} -C 6 H 4 - shows a. R ³ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

  Moreover, it is preferable to seal the terminal of polyimide, polybenzoxazole, or a precursor thereof with a monoamine, acid anhydride, acid chloride, or monocarboxylic acid having a hydroxyl group, a carboxyl group, a sulfonic acid group, or a thiol group. Two or more of these may be used. By having the above-mentioned group at the terminal of the resin, the dissolution rate of the resin in the alkaline aqueous solution can be easily adjusted to a preferred range.

  Preferred examples of the monoamine include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-amino. Naphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy -6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3- Aminobenzoic acid, 4-aminobenzoic acid, 4-a Nosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, Examples include 3-aminophenol, 4-aminophenol, 2-amino-4-terbutylphenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol.

  Preferred examples of the acid anhydride, acid chloride, and monocarboxylic acid include phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride and other 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 Monocarboxylic acids such as carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, and Converted monoacid chloride compound, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-di A monoacid chloride compound in which only one carboxyl group of a dicarboxylic acid such as carboxynaphthalene is acid chloride, a monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide The active ester compound obtained by reaction etc. can be mentioned.

  The content of the end-capping agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid described above is preferably in the range of 0.1 to 60 mol% of the charged number of moles of acid component monomer or diamine component monomer. -50 mol% is more preferable. By setting it as such a range, the viscosity of the solution at the time of apply | coating a resin composition can be obtained, and the resin composition which had the outstanding film | membrane physical property can be obtained.

  Moreover, you may have a polymerizable functional group at the terminal of resin. Examples of the polymerizable functional group include an ethylenically unsaturated bond group, an acetylene group, a methylol group, and an alkoxymethyl group.

The end-capping agent introduced into the resin can be easily detected by the following method. For example, a resin into which an end-capping agent has been introduced is dissolved in an acidic solution and decomposed into a diamine component and an acid component, which are the structural units of the resin, and this is analyzed by gas chromatography (GC) or NMR measurement. The sealant can be easily detected. Apart from this, it is possible to detect the resin into which the end-capping agent has been introduced by directly measuring by pyrolysis gas chromatography (PGC), infrared spectrum and ¹³ C-NMR spectrum.

  In the present invention, the component (a) is preferably a polyimide precursor or a polybenzoxazole precursor, and more preferably a polyimide precursor. The polyimide precursor undergoes an imidization reaction in which the amidic acid moiety closes upon firing at about 200 ° C., and the polybenzoxazole precursor undergoes an oxazolation reaction in which the hydroxyamide moiety undergoes ring closure upon firing at about 300 ° C., resulting in volume shrinkage. It has the property to do. The photosensitive resin composition using these precursor resins can obtain a forward tapered pattern by firing after obtaining a fine pattern by an exposure / development process. This forward tapered pattern is excellent in the coverage of the upper electrode when used as an insulating film of an organic EL element, can prevent disconnection, and can increase the reliability of the element.

  Moreover, the photosensitive resin composition of this invention may contain other alkali-soluble resin in addition to (a) polyimide, polybenzoxazole, or those precursors. The alkali-soluble resin refers to a resin having an acidic group that is soluble in alkali, and specifically includes a radical polymerizable polymer having acrylic acid, a phenol-novolak resin, polyhydroxystyrene, polysiloxane, and the like. Moreover, you may protect the acidic group of these resin and adjust alkali solubility. Such a resin is soluble in an aqueous solution of alkali such as choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate in addition to tetramethylammonium hydroxide. . Two or more of these resins may be contained, but (a) the proportion of the total resin including polyimide, polybenzoxazole or their precursors is preferably 50% by weight or less.

  The photosensitive resin composition of the present invention contains (b) a quinonediazide compound. (B) As the quinonediazide compound, a quinonediazide sulfonic acid bonded to a polyhydroxy compound with an ester, a quinonediazide sulfonic acid bonded to a polyamino compound with a sulfonamide bond, a quinonediazide sulfonic acid with an ester bond and a polyhydroxypolyamino compound And / or sulfonamide-bonded ones. It is preferable that 50 mol% or more of the total functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In 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 to be exposed. Further, a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. You may contain both.

  As a method for producing a quinonediazide compound, a method of esterifying naphthoquinonediazidesulfonyl chloride with a polyhydroxy compound is common. In the process of producing naphthoquinone diazide sulfonyl chloride, a step of isolating naphthoquinone diazide sulfonyl chloride from the reaction solvent after completion of the naphthoquinone diazide sulfonyl chloride synthesis reaction is required. In this isolation process, after injecting a sparingly soluble solvent such as ice water to precipitate naphthoquinonediazidesulfonyl chloride, the precipitate is extracted with benzene, toluene or xylene and distilled to remove benzene, toluene or xylene. There is a case. It has been found that the storage stability of the positive photosensitive resin composition is remarkably lowered when benzene, toluene or xylene is mixed into the quinonediazide compound employing this isolation method.

  Naphthoquinone diazide sulfonyl chloride can be isolated by distillation under reduced pressure or atmospheric pressure, or precipitated with a poorly soluble solvent such as ice water and then extracted and distilled with an organic solvent such as methylene chloride other than benzene, toluene and xylene. The method is preferably a method in which benzene, toluene or xylene is removed by recrystallization after extraction and distillation with benzene, toluene or xylene.

The contents of benzene, toluene, and xylene contained in the positive photosensitive resin composition of the present invention are all 5 ppm or less, and preferably 1 ppm or less. Therefore, the content of benzene, toluene and xylene contained in the (b) quinonediazide compound is preferably 25 ppm or less, and more preferably 5 ppm or less .

  Moreover, you may use photoacid generators other than (b) quinonediazide compound, and may contain 2 or more types. Thereby, a highly sensitive photosensitive resin composition can be obtained. Of the photoacid generators, sulfonium salts, phosphonium salts, and diazonium salts are preferable because they moderately stabilize the acid component generated by exposure. Of these, sulfonium salts are preferred. Furthermore, it can also contain a sensitizer etc. as needed.

  In the present invention, the total content of the (b) quinonediazide compound and the photoacid generator other than the (b) quinonediazide compound is preferably 0.05 to 50 parts by weight with respect to 100 parts by weight of the resin (a). Among these, (b) 3-40 weight part of a quinonediazide compound is preferable. The total amount of the photoacid generator such as sulfonium salt, phosphonium salt, diazonium salt is preferably 0.5 to 20 parts by weight. Moreover, 20 weight% or less is preferable in a positive photosensitive resin composition.

  The photosensitive resin composition of the present invention contains (c) 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 (c) is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, and preferably 3000 parts by weight or less, more preferably 100 parts by weight or more with respect to 100 parts by weight of the resin of the component (a). Is 2500 parts by weight or less.

  The photosensitive resin composition of the present invention may contain a thermal crosslinking agent having a structure represented by the following general formula (1) or a thermal crosslinking agent having a group represented by the following general formula (2). These thermal crosslinking agents can crosslink (a) polyimide, polybenzoxazole, their precursors, or other additive components, and can improve the chemical resistance and hardness of the film after baking or curing.

In the general formula (1), R represents a divalent to tetravalent linking group. R ⁴ represents a monovalent organic group having 1 to 20 carbon atoms, Cl, Br, I or F. R ⁵ and R ⁶ represent CH ₂ OR ⁸ (R ⁸ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms). R ⁷ represents a hydrogen atom, a methyl group or an ethyl group. s represents an integer of 0 to 2, and u represents an integer of 2 to 4. The plurality of R ^{4 to} R ⁷ may be the same or different. Examples of the linking group R are shown below.

In the above formula, R ^{10 to} R ²⁸ represent a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms, Cl, Br, I or F.

^{_{-N (CH 2 OR 9) t}} (H) v (2)
In the general formula (2), R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. t represents 1 or 2, and v represents 0 or 1. However, t + v is 1 or 2.

In the general formula (1), R ⁵ and R ⁶ represent CH ₂ OR ⁸ (R ⁸ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms) which is a thermal crosslinking group. R ⁸ is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms because it retains moderate reactivity and is excellent in storage stability. Moreover, in the photosensitive resin composition containing a photoacid generator or a photopolymerization initiator, R ⁸ is more preferably a methyl group or an ethyl group.

  In the thermal crosslinking agent having a structure represented by the general formula (1), the purity of the compound is preferably 85% or more. If the purity is 85% or more, the storage stability is excellent and the number of unreacted groups that become water-absorbing groups can be reduced, so that the water-absorbing property of the photosensitive resin composition can be reduced. Examples of the method for obtaining a high-purity thermal crosslinking agent include recrystallization and distillation. The purity of the thermal crosslinking agent can be determined by a liquid chromatography method.

  Preferred examples of the thermal crosslinking agent having the structure represented by the general formula (1) are shown below.

In general formula (2), R ⁹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms. Further, from the viewpoint of the stability of the compound and the storage stability in the resin composition, in the photosensitive resin composition containing a photoacid generator or a photopolymerization initiator, R ⁹ is preferably a methyl group or an ethyl group, The number of (CH ₂ OR ⁹ ) groups contained therein is preferably 8 or less.

  Preferred examples of the thermal crosslinking agent having a group represented by the general formula (2) are shown below.

  The content of the thermal crosslinking agent is preferably 10 to 100 parts by weight with respect to 100 parts by weight of the resin (a). When the content of the thermal crosslinking agent is 10 parts by weight or more and 100 parts by weight or less, the strength of the film after baking or curing is high, and the storage stability of the photosensitive resin composition is also excellent.

  The resin composition of the present invention may further contain a thermal acid generator. The thermal acid generator generates an acid by heating after development, which will be described later, and promotes the crosslinking reaction between the resin of component (a) and the thermal crosslinking agent, as well as the ring of imide ring and oxazole ring of the resin of component (a). Promote For this reason, the chemical resistance of the film after firing is improved, and film loss can be reduced. The acid generated from the thermal acid generator is preferably a strong acid. For example, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, and alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid are preferable. In the present invention, the thermal acid generator is preferably an aliphatic sulfonic acid compound represented by the general formula (3) or (4), and may contain two or more of these.

In the general formulas (3) and (4), R ^{29 to} R ³¹ represent an alkyl group having 1 to 10 carbon atoms or a monovalent aromatic group having 7 to 12 carbon atoms. The alkyl group and the aromatic group may be substituted, and examples of the substituent include an alkyl group and a carbonyl group.

  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.

  The content of the thermal acid generator is preferably 0.5 parts by weight or more and more preferably 10 parts by weight or less with respect to 100 parts by weight of the resin of component (a) from the viewpoint of further promoting the crosslinking reaction.

  As needed, you may contain the compound which has a phenolic hydroxyl group in order to supplement the alkali developability of the photosensitive resin composition. Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ. Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisP-HAP, TrisP -PA, TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP, (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 (trade name, manufactured by Asahi Organic Materials Co., Ltd.), 1,4-dihydroxy Naphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline 2,6-dihydroxyquinoline, 2,3-dihi Loki Shiki tetrahydroquinoxaline, anthracene -1,2,10- triol, anthracene -1,8,9- triols, such as 8-quinolinol, and the like. By containing these compounds having a phenolic hydroxyl group, the resulting 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. Therefore, the sensitivity is easily improved.

  The content of such a compound having a phenolic hydroxyl group is preferably 3 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the component (a) resin.

  In the photosensitive resin composition of the present invention, a thermochromic compound that develops color when heated and exhibits an absorption maximum at 350 nm to 700 nm, or has an absorption maximum at 500 nm to 750 nm without an absorption maximum at 350 nm to less than 500 nm. Organic pigments or dyes can be included. The coloring temperature of the thermochromic compound is preferably 120 ° C. or higher, more preferably 150 ° C. or higher. The higher the color development temperature of the thermochromic compound, the better the heat resistance under high temperature conditions, and the better the light resistance without fading due to prolonged ultraviolet-visible light irradiation.

  Examples of thermochromic compounds include thermal dyes, pressure sensitive dyes, and hydroxyl group-containing compounds having a triarylmethane skeleton.

The photosensitive resin composition of the present invention may contain an adhesion improving agent. As adhesion improvers, vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, Examples include silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, and aluminum chelating agents. Two or more of these may be contained. By containing these adhesion improving agents, adhesion to an underlying substrate such as a silicon wafer, ITO, SiO ₂ , or silicon nitride can be enhanced when developing a photosensitive resin film. Further, resistance to oxygen plasma and UV ozone treatment used for cleaning or the like can be increased. The content of the adhesion improving agent is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin (a).

  The photosensitive resin composition of the present invention may contain an adhesion improver. Examples of the adhesion improving agent include an alkoxysilane-containing aromatic amine compound, an aromatic amide compound, or an aromatic non-containing silane compound. Two or more of these may be contained. By containing these compounds, the adhesion between the film after baking or curing and the substrate can be improved. Specific examples of the alkoxysilane-containing aromatic amine compound and aromatic amide compound are shown below. In addition, a compound obtained by reacting an aromatic amine compound and an alkoxyl group-containing silicon compound may be used. For example, an aromatic amine compound and a group that reacts with an amino group such as an epoxy group or a chloromethyl group may be used. The compound etc. which are obtained by making the alkoxysilane compound which has it react are mentioned.

  The total content of the adhesion improving agent is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the resin of component (a).

  The photosensitive resin composition of the present invention may contain a surfactant and can improve the wettability with the substrate.

  Surfactants such as Fluorard (trade name, manufactured by Sumitomo 3M Co., Ltd.), “Megafac (registered trademark)” (manufactured by DIC Corporation), Sulflon (trade name, manufactured by Asahi Glass Co., Ltd.), etc. Surfactant, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corp.), Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), BYK (BIC Chemie Corp.) ) And other organic siloxane surfactants, and acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

  Next, the manufacturing method of the photosensitive resin composition of this invention is demonstrated. For example, the components (a) to (c) and, if necessary, a thermal crosslinking agent, a thermal acid generator, a solubility regulator such as a compound having a phenolic hydroxyl group, a thermochromic compound, an organic pigment, a dye, an adhesion improver, A photosensitive resin composition can be obtained by dissolving an adhesion improver or a surfactant. Examples of the dissolution method include stirring and heating. In the case of heating, the heating temperature is preferably set in a range that does not impair the performance of the photosensitive resin composition, and is usually room temperature to 80 ° C. In addition, the dissolution order of each component is not particularly limited, and for example, there is a method of sequentially dissolving compounds having low solubility. In addition, for components that tend to generate bubbles when stirring and dissolving, such as surfactants and some adhesion improvers, by dissolving other components and adding them last, poor dissolution of other components due to the generation of bubbles Can be prevented.

  The obtained photosensitive resin composition is preferably filtered using a filtration filter to remove dust and particles. Examples of the filter pore diameter include, but are not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, and 0.05 μm. Examples of the material for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), and polyethylene and nylon are preferable.

  Next, the photosensitive resin film manufacturing method using the photosensitive resin composition of this invention is demonstrated. As the substrate, Si, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, ITO and the like are generally used, but are not limited thereto. Examples of the method for applying the photosensitive resin composition include spin coating, slit coating, dip coating, spray coating, and printing. Moreover, although a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is normally 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, a method for forming a pattern from the obtained photosensitive resin film will be described. Exposure is performed by irradiating actinic radiation on a photosensitive resin film 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. . When it has positive photosensitivity, the exposed portion is dissolved in the developer. When it has negative photosensitivity, the exposed area is cured and insolubilized in the developer.

  After exposure, a desired pattern is formed using a developer by removing an exposed portion in the case of a positive type and a non-exposed portion in the case of a negative type. As the developer, in both positive and negative types, an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, acetic acid An aqueous solution of an alkaline compound such as dimethylaminoethyl, dimethylaminoethanol, dimethylaminoethyl 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, 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 singly or in combination. Good. In the negative type, the above polar solvent not containing an alkaline aqueous solution, alcohols, esters, ketones and the like can be used singly or in combination. 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.

  The photosensitive resin film is baked by heat-treating the pattern of the obtained photosensitive resin film. For example, a method of heat treatment at 230 ° C. for 60 minutes, a method of heat treatment at 120 to 400 ° C. for 1 minute to 10 hours, a method of heat treatment at a low temperature of about room temperature to 100 ° C. with addition of a curing catalyst, ultrasonic waves or electromagnetic waves Examples of the method include a method of curing at a low temperature of about room temperature to 100 ° C. by the treatment.

  Films obtained by firing the photosensitive resin composition of the present invention include surface protection films and interlayer insulation films for semiconductor devices such as LSI, insulation films for organic EL elements, planarization films for TFT substrates for display elements, and circuit boards. It can be preferably used for applications such as a wiring protective film, an on-chip microlens for a solid-state imaging device, and a flattening film for various displays and solid-state imaging devices.

  Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. In addition, evaluation of the photosensitive resin composition in an Example was performed with the following method.

(1) Content of benzene, toluene and xylene The content of benzene, toluene and xylene in the varnish was measured using GC / MS (GCMS-QP2010, manufactured by Shimadzu Corporation). The analysis conditions are as follows.
Analysis condition Column: CBP-1 (25 m, inner diameter 0.33 mm)
Column Temp: 50 ° C. (5 min) −250 ° C. 5 ° C./min
Inj. Temp: 250 ° C
Det. Temp: 250 ° C
Carrier Gas: He 38cm / sec
The contents of benzene, toluene and xylene in the quinonediazide compound were measured under the above GC / MS analysis conditions by preparing a 10 wt% γ-butyrolactone solution by dissolving the quinonediazide compound in γ-butyrolactone.

(2) Production of photosensitive resin film Using a coating / developing apparatus “CLEAN TRACK ACT-12” manufactured by Tokyo Electron Co., Ltd., a positive photosensitive resin composition was applied on a 12-inch Si wafer, and the temperature was 120 ° C. Hot plate baking was performed for 3 minutes to obtain a polyimide precursor composition film having a thickness of 8 μm.

(3) Defect evaluation of photosensitive resin film The photosensitive resin film obtained by the method of (2) was subjected to defect inspection using a wafer surface inspection apparatus “WM-10” manufactured by Topcon Corporation. If more defect density 0.5μm is there at 0.1 / cm ² or less ○, if the defect density is 0.1 to 1.0 pieces / cm ² △, 1.0 pieces / cm ² or more If there was, it was set as x.

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound (HFHA) 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF) 18.3 g (0.05 mol) Was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.) and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and dried in vacuo 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 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 by a rotary evaporator to obtain a hydroxyl group-containing diamine compound (HFHA) represented by the following formula.

Synthesis Example 2 Synthesis of quinonediazide compound 1 60 ml (0.91 mol) of chlorosulfuric acid and 25 ml (0.34 mol) of thionyl chloride were charged and stirred under a dry nitrogen stream while 1,2-naphthoquinonediazide- 65.0 g (0.24 mol) of sodium 5-sulfonate was charged. While stirring under a dry nitrogen stream, the temperature was raised to 70 ° C. and reacted for 8 hours. After completion of the reaction, the reaction mixture containing the sulfonyl chloride is poured into ice water, the precipitate is extracted with methylene chloride, washed with water and separated, and then the methylene chloride is removed under reduced pressure to give a sulfonyl chloride represented by the following formula. I got a release.

  Next, under a dry nitrogen stream, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.3 g (0.05 mol) and 26.8 g (0.1 mol) of the sulfonyl chloride were added to 1,4- Dissolved in 450 g of dioxane and brought to room temperature. Here, 12.65 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. After dropping, the mixture was stirred at 40 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration and further washed with 1 L of 1% aqueous hydrochloric acid. Thereafter, it was further washed twice with 2 L of water. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound represented by the following formula. As a result of measuring the content of benzene, toluene and xylene of the quinonediazide compound by GC-MG, all were 1 ppm or less.

Synthesis Example 3 Synthesis of Quinone Diazide Compound 2 Regarding the isolation method of sulfonyl chloride of Synthesis Example 2, the reaction mixture was poured into ice water, the precipitate was extracted with methylene chloride, washed with water and separated, and then methylene chloride was reduced under reduced pressure. Instead of the method described above, the sample is poured into ice water, the precipitate is extracted with benzene, washed with water and separated, after which benzene is removed under reduced pressure, and the resulting crude product is recrystallized once with acetone. The compound was synthesized in the same procedure as in Synthesis Example 2 except that the method was changed. As a result of measuring the content of benzene, toluene and xylene in the quinonediazide compound by GC-MG, the benzene content was 24 ppm, and both toluene and xylene were 1 ppm or less.

Synthesis Example 4 Synthesis of Quinonediazide Compound 3 Regarding the isolation method of sulfonyl chloride of Synthesis Example 2, the reaction mixture was poured into ice water, the precipitate was extracted with methylene chloride, washed with water and separated, and then methylene chloride was reduced under reduced pressure. Instead of the method described above, the sample is poured into ice water, the precipitate is extracted with benzene, washed with water and separated, after which benzene is removed under reduced pressure, and the resulting crude product is recrystallized twice with acetone. The compound was synthesized in the same procedure as in Synthesis Example 2 except that the method was changed. As a result of measuring the benzene, toluene and xylene contents of the quinonediazide compound by GC-MG, the benzene content was 4 ppm, and both toluene and xylene were 1 ppm or less.

Synthesis Example 5 Synthesis of quinonediazide compound 4 Regarding the isolation method of sulfonyl chloride of Synthesis Example 2, the reaction mixture was poured into ice water, the precipitate was extracted with methylene chloride, washed with water and separated, and then methylene chloride was removed under reduced pressure. In the same manner as in Synthesis Example 2 except that the method was changed to a method in which the benzene was removed under reduced pressure after being poured into ice water, extracted with benzene, washed with water and separated, and then removed under reduced pressure. . As a result of measuring the benzene, toluene, and xylene contents of the quinonediazide compound by GC-MG, the benzene content was 196 ppm, and both toluene and xylene were 1 ppm or less.

Synthesis Example 6 Synthesis of quinonediazide compound 5 Regarding the isolation method of sulfonyl chloride of Synthesis Example 2, the reaction mixture was poured into ice water, the precipitate was extracted with methylene chloride, washed with water and separated, and then methylene chloride was reduced under reduced pressure. In the same manner as in Synthesis Example 2, except that the method was replaced with a method in which the toluene was removed under reduced pressure after being poured into ice water, extracted with toluene, washed with water and separated, and then the toluene was removed under reduced pressure. . As a result of measuring the content of benzene, toluene and xylene in the quinonediazide compound by GC-MG, the toluene content was 352 ppm, and both benzene and xylene were 1 ppm or less.

Synthesis Example 7 Synthesis of Quinone Diazide Compound 6 Regarding the isolation method of sulfonyl chloride of Synthesis Example 2, the reaction mixture was poured into ice water, the precipitate was extracted with methylene chloride, washed with water and separated, and then methylene chloride was reduced under reduced pressure. In the same manner as in Synthesis Example 2, except that the method was replaced with a method in which xylene was removed under reduced pressure after being poured into ice water, extracted with xylene, washed with water and separated, and then removed under reduced pressure. . As a result of measuring the content of benzene, toluene and xylene in the quinonediazide compound by GC-MG, the xylene content was 515 ppm, and both benzene and toluene were 1 ppm or less.

Synthesis Example 8 Synthesis of polyimide precursor 51.3 g (0.085 mol) of hydroxyl group-containing diamine obtained in Synthesis Example 1 and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (under a nitrogen stream) SiDA, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.24 g (0.005 mol), 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.18 g (0.02 mol) into 200 g of N-methylpyrrolidone (NMP) Dissolved. 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride (ODPA, Manac Co., Ltd.) 31.0g (0.1 mol) was added here, and it stirred at 40 degreeC for 2 hours. Thereafter, a solution obtained by diluting 7.14 g (0.06 mol) of dimethylformamide dimethyl acetal (manufactured by Mitsubishi Rayon Co., Ltd., DFA) with 5 g of NMP was added dropwise over 10 minutes. After dropping, stirring was continued at 40 ° C. for 2 hours. After completion of the stirring, the solution was poured into 2 L of water, and a precipitate of polymer solid was collected by filtration. Furthermore, it wash | cleaned 3 times with 2 L of water, and the collected polymer solid was dried with a 50 degreeC vacuum dryer for 72 hours, and the polyimide precursor was obtained.

Synthesis Example 9 Synthesis of Polybenzoxazole Precursor Under dry nitrogen flow, 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, and the temperature of the solution was −15 ° C. Until cooled. 7.4 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Agricultural Chemicals Co., Ltd.) and 5.1 g (0.025 mol) of isophthalic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to γ-butyrolactone (GBL). ) A solution dissolved in 25 g 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 containing 10% by weight of methanol to collect a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polybenzoxazole precursor.

Synthesis Example 10 Synthesis of Polyimide Under a dry nitrogen stream, 32.9 g (0.09 mol) of BAHF was dissolved in 500 g of NMP. ODPA 31.0g (0.1mol) was added here with NMP50g, and it stirred at 30 degreeC for 2 hours. Thereafter, 2.18 g (0.02 mol) of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirring was continued at 40 ° C. for 2 hours. Further, 5 g of pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution, and the temperature of the solution was increased to 120 ° C. for 2 hours while adding a cooling tube to remove water outside the system, and further reacted at 180 ° C. for 2 hours. The temperature of this solution was lowered to room temperature, and the solution was poured into 3 L of water to obtain a white powder. This powder was collected by filtration and further washed with water three times. After washing, the white powder was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain polyimide.

Example 1
100 g of the polyimide precursor obtained in Synthesis Example 8 and the quinonediazide compound 1 obtained in Synthesis Example 2 were added to 40 g of γ-butyrolactone and stirred to obtain a varnish of a positive photosensitive polyimide precursor composition. Further, the obtained varnish was filtered using a polyethylene filter having a pore size of 0.2 μm. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, all were 1 ppm or less.

Next, after storing at 4 ° C. immediately after filtration and 7 days after filtration (hereinafter, after 7 days of filtration), the photosensitive resin film is formed by the method described in (1) so that the film thickness after drying becomes 8 μm. A defect inspection was performed by the method described in (2) above. The defect inspection results were “◯” (0.03 / cm ² ) immediately after filtration, and “◯” (0.04 / cm ² ) after 7 days of filtration.

Example 2
The procedure was the same as in Example 1, except that the quinonediazide compound 1 in Example 1 was changed to the quinonediazide compound 2 obtained in Synthesis Example 3. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, the benzene content was 3 ppm, and both toluene and xylene were 1 ppm or less.

The defect inspection results were “◯” (0.02 / cm ² ) immediately after filtration and “Δ” (0.21 / cm ² ) after 7 days of filtration.

Example 3
The same procedure as in Example 1 was performed, except that the quinonediazide compound 1 of Example 1 was changed to the quinonediazide compound 3 obtained in Synthesis Example 4. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, all were 1 ppm or less.

The defect inspection results were “◯” (0.01 pieces / cm ² ) immediately after filtration, and “◯” (0.04 pieces / cm ² ) after 7 days of filtration.

Example 4
The same procedure as in Example 1 was performed, except that the polyimide precursor of Example 1 was changed to the polybenzoxazole precursor obtained in Synthesis Example 9. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, all were 1 ppm or less.

The defect inspection results were “◯” (0.03 / cm ² ) immediately after filtration, and “◯” (0.02 / cm ² ) after 7 days of filtration.

Example 5
The same procedure as in Example 1 was performed, except that the quinonediazide compound 1 of Example 4 was changed to the quinonediazide compound 2 obtained in Synthesis Example 3. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, the benzene content was 3 ppm, and both toluene and xylene were 1 ppm or less.

The defect inspection results were “◯” (0.04 / cm ² ) immediately after filtration and “Δ” (0.26 / cm ² ) after 7 days of filtration.

Example 6
The same procedure as in Example 1 was performed except that the quinonediazide compound 1 of Example 4 was changed to the quinonediazide compound 3 obtained in Synthesis Example 4. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, all were 1 ppm or less.

The defect inspection results were “◯” (0.02 pieces / cm ² ) immediately after filtration and “◯” (0.01 pieces / cm ² ) after 7 days of filtration.

Example 7
The procedure was the same as in Example 1 except that the polyimide precursor of Example 1 was changed to the polyimide obtained in Synthesis Example 10. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, all were 1 ppm or less.

The defect inspection results were “◯” (0.03 / cm ² ) immediately after filtration, and “◯” (0.02 / cm ² ) after 7 days of filtration.

Example 8
The procedure was the same as in Example 1, except that the quinonediazide compound 1 in Example 7 was changed to the quinonediazide compound 2 obtained in Synthesis Example 3. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, the benzene content was 3 ppm, and both toluene and xylene were 1 ppm or less.

The defect inspection results were “◯” (0.04 / cm ² ) immediately after filtration and “Δ” (0.19 / cm ² ) after 7 days of filtration.

Example 9
The same procedure as in Example 1 was performed, except that the quinonediazide compound 1 of Example 7 was changed to the quinonediazide compound 3 obtained in Synthesis Example 4. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, all were 1 ppm or less.

The defect inspection results were “◯” (0.02 pieces / cm ² ) immediately after filtration and “◯” (0.01 pieces / cm ² ) after 7 days of filtration.

Comparative Example 1
The same procedure as in Example 1 was performed, except that the quinonediazide compound 1 of Example 1 was changed to the quinonediazide compound 4 obtained in Synthesis Example 5. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, the benzene content was 16 ppm, and both toluene and xylene were 1 ppm or less.

The defect inspection results were “◯” (0.02 / cm ² ) immediately after filtration, and “x” (1.56 / cm ² ) after 7 days of filtration.

Comparative Example 2
The same procedure as in Example 1 was performed except that the quinonediazide compound 1 of Example 4 was changed to the quinonediazide compound 4 obtained in Synthesis Example 5. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, the benzene content was 16 ppm, and both toluene and xylene were 1 ppm or less.

The defect inspection results were “◯” (0.04 / cm ² ) immediately after filtration and “×” (1.43 / cm ² ) after 7 days of filtration.

Comparative Example 3
The same procedure as in Example 1 was performed, except that the quinonediazide compound 1 of Example 7 was changed to the quinonediazide compound 4 obtained in Synthesis Example 5. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, the benzene content was 17 ppm, and both toluene and xylene were 1 ppm or less.

The defect inspection results were “◯” (0.04 / cm ² ) immediately after filtration and “×” (2.22 / cm ² ) after 7 days of filtration.

Comparative Example 4
The same procedure as in Example 1 was performed, except that the quinonediazide compound 1 of Example 1 was changed to the quinonediazide compound 5 obtained in Synthesis Example 6. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, the toluene content was 33 ppm, and benzene and xylene were both 1 ppm or less.

The defect inspection results were “◯” (0.02 / cm ² ) immediately after filtration and “x” (2.69 / cm ² ) after 7 days of filtration.

Comparative Example 5
The same procedure as in Example 1 was performed, except that the quinonediazide compound 1 of Example 1 was changed to the quinonediazide compound 6 obtained in Synthesis Example 7. As a result of measuring the content of benzene, toluene and xylene in the varnish by GC-MG, the xylene content was 47 ppm, and benzene and toluene were both 1 ppm or less.

The defect inspection result was “◯” (0.02 / cm ² ) immediately after filtration, and “x” (3.88 / cm ² ) after 7 days of filtration.

  Table 1 shows the compositions of Examples 1 to 9 and Comparative Examples 1 to 5, and Table 2 shows the evaluation results.

Claims (1)

A positive type comprising (a) polyimide, polybenzoxazole or a precursor thereof, (b) a quinonediazide compound and (c) a solvent, wherein the contents of benzene, toluene and xylene are all 5 ppm or less. A method for producing a photosensitive resin composition , wherein (b) a quinonediazide compound is produced using naphthoquinonediazidesulfonyl chloride isolated by a method in which quinonediazide compound is extracted and distilled with benzene, toluene and xylene and then recrystallized. And a method for producing a positive photosensitive resin composition.