JP2005309032A - Positive photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali developable positive photosensitive resin composition. <P>SOLUTION: The positive photosensitive resin composition contains: (a) polyamide having at least one group selected from a carboxyl group, phenolic hydroxyl group, sulfonic acid group and thiol group at the end of the polymer main chain; (b) a compound having a phenolic hydroxyl group; and (c) an esterified quinonediazide compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a positive photosensitive aromatic polyamide composition suitable for a surface protective film and interlayer insulating film of a semiconductor element, an insulating layer of an organic electroluminescent element, etc., wherein a portion exposed to ultraviolet rays is dissolved in an alkaline aqueous solution.

As positive-type photosensitive heat-resistant resin compositions in which exposed portions are dissolved by alkali development, those obtained by adding naphthoquinone diazide to polyamic acid and those obtained by adding naphthoquinone diazide to a soluble polyimide having a hydroxyl group have been known. However, in the case where naphthoquinone diazide is added to normal polyamic acid, the solubility of the carboxyl group of the polyamic acid is higher than the dissolution inhibiting effect of naphthoquinone diazide on alkali, so the desired pattern cannot be obtained in most cases. There was a point.
Therefore, in order to control the alkali solubility of the polyamic acid, a polyamic acid derivative in which the carboxyl group of the polyamic acid is protected with an ester group has been developed (for example, Patent Document 1). However, in the case where naphthoquinonediazide is added to this polyamic acid derivative, when finally obtaining a heat-resistant resin, it is necessary to perform heat treatment and imide ring closure reaction. In this case, deesterification accompanying imidization reaction is necessary. There was a problem that dehydration and the like occurred, and this caused a large film shrinkage. Therefore, it is necessary to design the composition in consideration of film shrinkage. In this case, although a desired pattern can be obtained by achieving a moderate dissolution inhibiting effect of naphthoquinonediazide on alkali, a large film can be obtained. Due to the shrinkage, in order to make the final film thickness after heat treatment 10 μm or more, it is impossible to develop in a short time (hereinafter referred to as low sensitivity) and the fine pattern is not resolved (hereinafter referred to as low resolution). was there. On the other hand, naphthoquinonediazide added to a soluble polyimide having a hydroxyl group does not require an imide ring-closing reaction, so film shrinkage can be reduced, but it is usually poor in solubility in polyimide itself and alkali developer. The alkali concentration developer used in the semiconductor industry has a problem of incurring low sensitivity and low resolution. As a method for improving such low sensitivity and low resolution, use of a resin other than polyimide has been studied. For example, Patent Document 2 has a technical disclosure under the name of “photosensitive polyamide and composition”, but the content is polyamideimide, and has not yet solved the drawbacks of low sensitivity and low resolution of polyimide. In addition, Patent Documents 3 and 4 have technical disclosures regarding polybenzoxazole, but these have excellent heat resistance and electrical characteristics, but have the disadvantages of low sensitivity and low resolution, and improvements are desired. It was.
JP 2002-221974 A JP 2003-26796 A JP 2004-37790 A JP 2004-18593 A

An object of the present invention is to improve the disadvantages of low sensitivity and low resolution of conventional positive photosensitive resins.

  The present invention for achieving the above object is a positive photosensitive resin composition containing the following components (a), (b) and (c).

(A) Polyamide having at least one group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group at the end of the polymer main chain (b) a compound having a phenolic hydroxyl group (c) esterified Quinonediazide compound

According to the present invention, as described below, it is possible to develop a positive photosensitive resin composition that can be developed with an alkaline aqueous solution and has excellent resolution, sensitivity, remaining film rate, and shrinkage rate. In particular, the product can be suitably used for a surface protective film and an interlayer insulating film of a semiconductor element.

  In the present invention, a resin composition obtained by adding a compound having a phenolic hydroxyl group and a naphthoquinonediazide compound to a polyamide synthesized using an end-capping agent having an alkali-soluble group is added to an alkali developer before exposure. Since it hardly dissolves and dissolves easily in an alkaline developer when exposed to light, it can be developed in a short time (hereinafter referred to as high sensitivity) with little film loss due to development, and further resolves fine patterns (hereinafter referred to as high sensitivity). It was found that the film shrinkage was small (hereinafter referred to as “low shrinkage”) even in the subsequent heat treatment, which led to the invention.

In particular, with respect to film shrinkage, polyimides and polyoxazoles conventionally used as positive photosensitive resin compositions are dehydrated rings that occur after photocuring by photosensitivity when the precursor polyamic acid or polyoxazole is used. The film shrinkage due to crystallization was an unavoidable problem. In contrast,
The polyamide in the present invention does not cause dehydration or cyclization reaction after photocuring by photosensitivity even when heated or using an appropriate catalyst, and therefore the shrinkage of the film by heat treatment is extremely small. In addition, since normal polyimide and polyoxazole are insoluble in solvents, it is necessary to convert them to solvent-soluble structures or use precursors thereof, but soluble polyimides have poor solubility in alkaline developers. However, the alkali concentration developer usually used in the semiconductor industry has a problem in that low sensitivity and low resolution are caused. On the other hand, since polyimide and polyoxazole precursors are very unstable polymers, it is necessary to convert them to polyimide or polyoxazoles that have undergone dehydration. Polyamide is a solvent-soluble but stable polymer. Therefore, there is a great advantage that it is not necessary to use a precursor.



The positive photosensitive resin composition of the present invention comprises: (a) a polyamide having at least one group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group at the polymer main chain end; A compound having a phenolic hydroxyl group, and (c) an esterified quinonediazide compound.

  In this case, it is preferable that the polyamide of the component (a) includes a structural unit represented by the following general formula (1) and / or general formula (2), and the general formula (3) and / or It is also preferable that the structural unit represented by General formula (4) is included.

(Wherein R ¹ is a divalent to tetravalent organic group, R ² is a divalent to tetravalent organic group, R ³ is a divalent organic group, X is a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, A divalent to octavalent organic group having at least one group selected from thiol groups, n is an integer from 3 to 100,000, m is an integer from 0 to 10, and p is an integer from 0 to 2. .)

(Wherein R ¹ is a divalent to tetravalent organic group, R ² is a divalent to tetravalent organic group, R ³ is a divalent organic group, X is a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, A divalent to octavalent organic group having at least one group selected from thiol groups, n is an integer from 3 to 100,000, m is an integer from 0 to 10, and p is an integer from 0 to 2. .)

R ^{1 in the} above general formulas (1) to (4) represents a structural component of an acid halide, and this acid component is a divalent to tetravalent organic group containing an aromatic ring or an aliphatic ring. However, it is preferably an organic group having 5 to 40 carbon atoms.
Examples of the acid halide include carboxylic acid dibromide and carboxylic acid dichloride.

Examples of the carboxylic acid dichloride include terephthalic acid dichloride, 2chloro-terephthalic acid dichloride, isophthalic acid dichloride, naphthalene dicarbonyl chloride, biphenyl dicarbonyl chloride, terphenyl dicarbonyl chloride, and the like. Most preferably, terephthalic acid dichloride, 2chloro. Terephthalic acid dichloride is used. These are used alone or in combination of two or more.




R ² in the above general formulas (1) to (4) represents a structural component of a diamine, and the diamine represents a divalent to tetravalent organic group containing an aromatic ring or an aliphatic ring. An organic group having 5 to 40 carbon atoms is preferred.

  Examples of the diamine include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, and 2,2′-ditrifluoromethyl-4,4. '-Diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2 ′ -Bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4'-diaminodiph Nyl sulfone, 3,3′-diaminodiphenyl sulfone, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino) -3-methylphenyl) fluorene, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenyl Sulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, P-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) Sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4 Aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2 '-Diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3 '-Tetramethyl-4,4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2-chloro-1,4-phenylenediamine, 2-fluoro-1 , 4-phenylenediamine, 2-bromo-1,4-phenylenediamine, 2-trifluoromethyl-1,4-phenylenediamine, 2-nitro-1,4-phenylenediamine 2,2'-dihydroxy-4,4'-diaminobiphenyl, compounds in which these aromatic rings are substituted with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and the like.

Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'- Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, m-phenylenediamine, P-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 4,4 '-Diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-Amino-3-methylphenyl) fluorene, 2-chloro-1,4-phenylenedi Min, 2-nitro-1,4-phenylenediamine, and the like are preferable. Particularly preferably, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene. 9,9-bis (4-amino-3-methylphenyl) fluorene, 2-chloro-1,4-phenylenediamine, 2-nitro-1,4-phenylenediamine. You may use these individually or in combination of 2 or more types.

-NH- (R ³ ) _m -X, which is a structural component of the general formulas (1) and (2), is preferably a component represented by the following general formula (8), and these are end-capping agents. It is a component derived from a primary monoamine. X is preferably a divalent to octavalent organic group having at least one group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group, and more preferably selected from a carboxyl group, a phenolic hydroxyl group, and a thiol group. A divalent to octavalent organic group having at least one group is preferred.

In addition, —CO— (R ³ ) _m —Y, which is a structural component of the general formulas (3) and (4), is preferably a component represented by the following general formula (9) or general formula (10). These are components derived from those selected from an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, and a monoactive ester compound, which are end-capping agents. Y is preferably a divalent to octavalent organic group having at least one group selected from a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group, more preferably a group selected from a carboxyl group, a phenolic hydroxyl group and a thiol group. A divalent to octavalent organic group having at least one is preferable. Moreover, Y which comprises General formula (3) and General formula (4) is only the terminal blocking group represented by General formula (9), Only the terminal blocking group represented by General formula (10), General formula ( 9) Any one including both of the general formula (10) may be used.

In general formula (8), general formula (9), and general formula (10), R ³ represents a divalent group selected from —CR ¹⁷ R ¹⁸ —, —CH ₂ O—, and —CH ₂ SO ₂ —. , R ¹⁷ and R ¹⁸ represent a monovalent group selected from a hydrogen atom, a hydroxyl group, and a hydrocarbon group having 1 to 10 carbon atoms. R ¹⁴ represents a hydrogen atom or a monovalent group selected from hydrocarbon groups having 1 to 10 carbon atoms. Of these, a hydrogen atom and a hydrocarbon group having 1 to 4 carbon atoms are preferable, and a hydrogen atom, a methyl group, and a t-butyl group are particularly preferable. R ¹⁵ and R ^{16 each} represent a hydrogen atom, a monovalent group selected from a hydrocarbon group having 1 to 4 carbon atoms, or a ring structure in which R ¹⁵ and R ¹⁶ are directly bonded (for example, a nadiimide ring). R ¹² and R ¹³ are selected from a hydrogen atom, a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, and a hydrocarbon group having 1 to 10 carbon atoms, at least one of which is a hydroxyl group, a carboxyl group, a sulfonic acid group, Indicates a thiol group. A, B, and E are carbon atoms or nitrogen atoms, and may be the same or different. m is an integer from 0 to 10, preferably an integer from 0 to 4. l is 0 or 1, preferably 0. p is 0 or 1, preferably 0. q is an integer from 1 to 3, preferably 1 and 2. r, s, and t are 0 or 1.

  Specific examples of the primary monoamine related to the general formula (8) include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7- Aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1- Amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-amino Naphthalene, 1-amino-2-hydroxynaphthalene, 1-carbo Ci-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-amino Naphthalene, 1-carboxy-2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy -4-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalic Tyric acid, 3-amino-o-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzene Sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto -8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene 1-mercapto-2-aminonaphthalene, 1-amino-7-me Lucaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1 -Amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like.

  Of these, 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-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- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2- Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable. These are used alone or in combination of two or more.

  Specific examples of the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound relating to the general formula (9) and the general formula (10) are phthalic anhydride, maleic anhydride, nadic acid, 5-norbornene-2 , 3-dicarboxylic anhydride, 4-phenylethynylphthalic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, etc., 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy- 5-carboxynaphthalene, 1-hydro Ci-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxy Naphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfone Acids, monocarboxylic acids such as 4-carboxybenzenesulfonic acid, monoacid chloride compounds in which these carboxyl groups are converted to acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3 Hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6 Monocarboxylic acids such as dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, 2,7-dicarboxynaphthalene A monoacid chloride compound in which only a carboxyl group is converted to an acid chloride, an active ester compound obtained by a reaction of a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide, Can be mentioned.

  Among these, phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 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 Monocarboxylic acids such as 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid, monoacid chloride compounds in which these carboxyl groups are converted to acid chloride, terephthalic acid, Only monocarboxylic groups of dicarboxylic acids such as phosphoric acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene Preferred are monoacid chloride compounds obtained by acid chloride, active ester compounds obtained by reaction of monoacid chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide, and the like. These are used alone or in combination of two or more.

  The introduction ratio of the components represented by the general formula (8) (the X components of the general formulas (1) and (2)) is calculated based on the primary monoamine component of the end-capping agent that is the original component. The range of 0.1 to 60 mol% is preferable, and 5 to 50 mol% is particularly preferable.

  The introduction ratio of the component represented by the general formula (9) or the general formula (10) (the Y component in the general formulas (3) and (4)) is determined based on the acid anhydride of the terminal blocking agent, which is the original component, When converted in terms of carboxylic acid, monoacid chloride compound, and monoactive ester compound component, the range of 0.1 to 60 mol% is preferable with respect to the diamine component, and particularly preferably 5 to 55 mol%.

  In the general formula (1) and the general formula (2) or the general formula (3) and the general formula (4), n represents the number of repeating structural units of the polymer of the present invention and is in the range of 3 to 100,000. It is preferable.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized in R ¹ and R ² as long as the heat resistance is not lowered. Specifically, examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

  The positive photosensitive resin composition of the present invention comprises only the structural unit represented by general formula (1) and / or general formula (2), or general formula (3) and / or general formula (4). It may be a copolymer or a blend with other structural units. In that case, it is preferable to contain 50 mol% or more of structural units represented by general formula (1) and / or general formula (2), or general formula (3) and / or general formula (4). The type and amount of structural units used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyamide polymer obtained by the final heat treatment.

  In the polyamide of the present invention, a part of the diamine is replaced with a terminal blocking agent that is a monoamine, or an acid component typified by an acid dihalide is used as a monocarboxylic acid, an acid anhydride, a monoacid chloride compound, or a monoactive ester compound. It can be synthesized by using various methods in place of the end capping agent. For example, a method of reacting acid dichloride with a diamine compound (partially replaced with a monoamine end-capping agent) at low temperature, acid dichloride (partially acid anhydride or monoacid chloride compound or monoactive ester at low temperature) The compound can be synthesized using a method such as a method of reacting a terminal blocking agent, which is a compound, and a diamine compound, a vapor deposition polymerization method, or the like.

Moreover, the terminal blocker used for this invention introduce | transduced in the polymer can be easily detected with the following method. For example, a polymer having an end-capping agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component that are constituent units of the polymer, and this is measured by gas chromatography (GC) or NMR measurement. The end-capping agent used in the present invention can be easily detected. Apart from this, the polymer component into which the end-capping agent is introduced can also be easily detected directly by pyrolysis gas chromatography (PGC), infrared spectrum and C ¹³ NMR spectrum measurement.

  Examples of the compound having a phenolic hydroxyl group used in the present invention 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, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, Bis CHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-BIOC-F, TEP-BIP -A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.).

  Moreover, it is preferable that the compound which has a phenolic hydroxyl group is a compound represented by General formula (5).

Here, R ⁴ to R ⁷ in the general formula (5) represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, and an alicyclic group having 4 to 20 carbon atoms. α represents an integer from 0 to 5. R ⁶ and R ⁷ are preferably represented by an alicyclic group having 4 to 20 carbon atoms.

  As represented by the general formula (5), BisPC-PCHP, BisRS-PEP, BisTBC-PC, Bis24X-PC, Bis35X-PC, methylenebis-p-CR, o, o′-BPF, oo-BisOC-F , Oo-Bis25X-F, MB-PIPP, BisMHQ-F, Bis24X-F (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIHQ-PC, BI2MR-PC, BI4MC-PC, BIR-34X, BIR -PAP, BIPC-PC, BIR-PC, BIR-PTBP, BIR-PCHP, 4PC, BIR-BIPC-F (trade name, manufactured by Asahi Organic Materials Co., Ltd.).

  Moreover, it is preferable that the compound which has a phenolic hydroxyl group is a heat-crosslinkable compound containing the organic group represented by General formula (6).

Here, in the general formula (6), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, or an R ⁹ CO group. R ⁹ represents an alkyl group having 1 to 20 carbon atoms. R ⁸ preferably represents an alkyl group having 1 to 20 carbon atoms and an alicyclic group having 4 to 20 carbon atoms.

  Examples of the thermally crosslinkable compound containing a group represented by the general formula (6) include ML-26X, ML-24X, ML-236TMP, 4-methylol 3M6C, ML- MC, ML-TBC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc., DM-BI25X-F (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC , Dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML-Bis25X-PCHP (trade name, Honshu Chemical) Kogyo Co., Ltd.).

  Moreover, it is preferable that the thermally crosslinkable compound containing the organic group represented by General formula (6) is a compound represented by General formula (7).

In the general formula (7), R ⁸ is the same as above, and R ¹⁰ and R ¹¹ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, or R ^12. COO group is shown. R ¹² represents an alkyl group having 1 to 20 carbon atoms.

  Examples of the compound represented by the general formula (7) include 46DMOC, 46DMOIPP, 46DMOEP, 46DMOCHP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-OC, DML-PFP, DML-PSBP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 2,6-dimethoxymethyl-4-t-butylphenol, 2 TriML-P, TriML-35XL, TriML-TrisCR-HAP (trade name, Honshu Chemical Industry Co., Ltd.), etc., which have three, such as 1,6-dimethoxymethyl-p-cresol and 2,6-diacetoxymethyl-p-cresol TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.) As ML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc., HML-TPPHBA, HML-TPHAP (trade name) , Honshu Chemical Industry Co., Ltd.).

  Of these, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X, represented by the general formula (5), BisPC-PCHP, BisTBC-PC, Bis35X-PC, methylenebis- p-CR, o, o'-BPF, MB-PIPP, BisMHQ-F, Bis24X-F (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BI2MR-PC, BI4MC-PC, BIR-PAP, BIPC -PC, BIR-PC, BIR-PTBP, BIR-PC P, 4PC, BIR-BIPC-F (trade name, manufactured by Asahi Organic Materials Co., Ltd.) and a thermally crosslinkable compound containing a group represented by the general formula (6) include the above organic groups. As two compounds, DML-MBPC, DML-MBOC, dimethylol-BisOC-P, DML-MTrisPC, and compounds represented by the general formula (7) include 46DMOC, 46DMOEP, 46DMOCHP, DML-OCHP, DML- PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP, DML-PFP, DML-PSBP, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl- TriM has three such as p-cresol and 2,6-diacetoxymethyl-p-cresol -P, TriML-35XL, etc. As four having TM-BIP-A, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, etc. As having six, HML-TPPHBA , HML-TPHAP.

  Of these, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, those represented by the general formula (5), BisPC-PCHP, BisTBC-PC, BI2MR-PC, BI4MC- PC, BIR-PAP, BIPC-PC, BIR-PC, BIR-PTBP, BIR-PCHP, 4PC, BIR-BIPC-F, and the thermally crosslinkable compound containing a group represented by the general formula (6) As those having two organic groups, DML-MBPC, DML-MBOC, and compounds represented by the general formula (7) include DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML. -POP, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p- Resole, 2,6-acetoxymethyl -p- cresol and the like.

  Among these, more preferably, as represented by the general formula (5), BisPC-PCHP, BIR-PCHP and the compound represented by the general formula (7) include DML-OCHP, DML-PC, DML-PCHP, DML-PTBP, DML-POP, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, etc. It is done.

  By adding this phenolic hydroxyl group-containing compound, the resulting resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. Development is easy in a short time.

  The addition amount of the compound having a phenolic hydroxyl group is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the polymer. These are used alone or in combination of two or more.

  The esterified quinonediazide compound (c) added to the present invention is preferably a compound in which a sulfonic acid of naphthoquinonediazide is bonded with an ester to a compound having a phenolic hydroxyl group. The compound having a phenolic hydroxyl group used here may be the same as or different from the compound (b) having a phenolic hydroxyl group. Such compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP. , BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X (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 (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), naphthol, tetrahydroxybenzophenone, gallic acid Methyl ester, bisphenol A, methylene bisphenol, Bis A compound obtained by introducing 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid into a compound such as -AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) with an ester bond is preferable. Other compounds can also be used. These are used alone or in combination of two or more.

  Further, when the molecular weight of the naphthoquinone diazide compound used in the present invention is larger than 1,000, the naphthoquinone diazide compound is not sufficiently thermally decomposed in the subsequent heat treatment, so that the heat resistance of the resulting film is lowered and the mechanical properties are lowered. There is a possibility that problems such as a decrease in adhesiveness may occur. From this point of view, the molecular weight of a preferred naphthoquinonediazide compound is 300 to 1,000. More preferably, it is 350 to 800. The addition amount of such a naphthoquinonediazide compound is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the polymer.

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

  Further, in order to improve the adhesion to a base substrate such as a silicon wafer, 0.5 to 10% by weight of a silane coupling agent, a titanium chelating agent or the like is added to the varnish of the photosensitive resin composition. It can also be pretreated with various chemicals.

  When added to the varnish, 0.5 to 10% by weight of a silane coupling agent such as methylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, titanium chelating agent, or aluminum chelating agent is added to the polymer in the varnish. Good.

  When processing a substrate, the coupling agent described above is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, and the like in an amount of 0.5 to 20. The surface solution may be subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. In some cases, the reaction between the substrate and the coupling agent is allowed to proceed by applying a temperature from 50 ° C. to 300 ° C.

  Next, a method for forming a pattern using the photosensitive resin composition of the present invention will be described.

  A photosensitive resin composition is applied onto a substrate. Examples of the substrate include inorganic substrates such as silicon wafers, ceramics, gallium arsenide, soda glass, and quartz glass, and organic substrates such as polyimide and aromatic polyamide, but are not limited thereto. Examples of the application method include spin coating using a spinner, spray coating, and roll coating. The coating film thickness varies depending on the coating method, 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 10 μm.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at a temperature of 50 ° C. to 180 ° C. for 1 minute to several hours.

  Next, the photosensitive resin composition 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-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) of a mercury lamp. .

  Formation of a pattern is achieved by removing the exposed portion using a developer after exposure. Developers include tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound showing alkalinity such as aminoethyl 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, dimethylsulfoxide, γ-butyrolaclone, 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. After development, 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 the development, it is heated at a temperature of 120 ° C. to 500 ° C. to convert it into a heat resistant resin film. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method of increasing the temperature linearly from room temperature to 250 ° C. over 2 hours or from 400 ° C. over 2 hours may be used.

  The heat-resistant resin film formed from the photosensitive resin composition according to the present invention is used for applications such as an insulating layer in a display device equipped with a semiconductor passivation film, a semiconductor element protective film, an organic electroluminescent element, and the like.

  Moreover, the insulating layer formed in a display apparatus using the composition of this invention is related with the display apparatus containing the 1st electrode formed on the board | substrate, and the 2nd electrode provided facing the said 1st electrode. Specifically, for example, LCDs, ECDs, ELDs, display devices using organic electroluminescent elements (organic electroluminescent devices), and the like are applicable. The organic electroluminescent device includes a first electrode formed on a substrate, a thin film layer including a light emitting layer made of at least an organic compound formed on the first electrode, and a second electrode formed on the thin film layer. It is a display apparatus which consists of an organic electroluminescent element containing.

  Hereinafter, the present invention will be described with reference to examples, 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.

(Production of photosensitive polyamide film)
A 6-inch silicon wafer was coated with a photosensitive resin composition (hereinafter referred to as varnish) so that the film thickness after pre-baking was 10.0 μm, and then a hot plate (SCW-manufactured by Dainippon Screen Mfg. Co., Ltd.). 636), a polyamide film was obtained by prebaking at 120 ° C. for 3 minutes.

(Measuring method of film thickness)
Measurement was performed at a refractive index of 1.64 using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd.

(exposure)
A contest pattern was set on an exposure machine (Canon, Inc. contact aligner PLA501F), and ultraviolet full-wavelength exposure was performed for a predetermined time at an ultraviolet intensity of 10 mW / cm ² (in terms of 365 nm).

(developing)
Immersion development was performed at 23 ° C. for 120 seconds using a developer composed of a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. Subsequently, it was rinsed with water for 20 seconds and then dried.

(Heat treatment)
The developed polyamide film was heat-treated at a predetermined temperature and time.

(Calculation of remaining film rate)
The remaining film rate was calculated according to the following formula.

Residual film ratio (%) = (film thickness after development / film thickness after pre-baking) × 100
(Sensitivity calculation)
After the exposure and development, an exposure amount (hereinafter referred to as an optimal exposure amount) for forming a 50 μm line and space pattern (1L / 1S) in a 1: 1 width was determined.

(Calculation of resolution)
After the exposure and development, the resolution was defined as the minimum pattern size at the optimum exposure amount for forming a 50 μm line-and-space pattern (1L / 1S) in a 1: 1 width.

(Calculation of shrinkage rate)
The shrinkage rate was calculated according to the following formula.
Shrinkage rate (%) = (film thickness after heat treatment / film thickness after development) × 100

Synthesis Example 1 Synthesis of Active Ester Compound (a) In a dry nitrogen stream, 18.5 g (0.1 mol) of 4-carboxybenzoic acid chloride and 13.5 g (0.1 mol) of hydroxybenzotriazole were added to tetrahydrofuran (THF). ) Dissolved in 100 g and cooled to -15 ° C. Here, 10.0 g (0.1 mol) of triethylamine dissolved in 50 g of THF was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of the dropwise addition, the mixture was reacted at 25 ° C. for 4 hours. This solution was concentrated by a rotary evaporator to obtain an active ester compound (a).

(Synthesis Example 2) Synthesis of quinonediazide compound (1) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.23 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 33 in a dry nitrogen stream .58 g (0.125 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g (0.125 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature inside 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 the following quinonediazide compound (1).

(Synthesis Example 3) Synthesis of quinonediazide compound (2) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride under a dry nitrogen stream 40.28 g (0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g (0.15 mol) of triethylamine mixed with 50 g of 1,4-dioxane was used, and the following quinonediazide compound (2) was obtained in the same manner as in Synthesis Example 2.

(Synthesis Example 4) Synthesis of quinonediazide compound (3) In a dry nitrogen stream, 6.81 g (0.05 mol) of 4-isopropylphenol and 13.43 g (0.05 mol) of 5-naphthoquinonediazidesulfonyl acid chloride were Dissolved in 450 g of 4-dioxane and brought to room temperature. Here, 5.06 g of triethylamine mixed with 50 g of 1,4-dioxane was used in the same manner as in Synthesis Example 2 to obtain the following quinonediazide compound (3).

(Synthesis Example 5) Synthesis of quinonediazide compound (4) Under a dry nitrogen stream, 11.41 g (0.05 mol) of bisphenol A and 26.86 g (0.1 mol) of 5-naphthoquinonediazidesulfonyl acid chloride were added to 1,4- Dissolved in 450 g of dioxane and brought to room temperature. The following quinonediazide compound (4) was obtained in the same manner as in Synthesis Example 2 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.

  Similarly, the compounds having a phenolic hydroxyl group, diamines, and acid chlorides used in Examples and Comparative Examples are shown below.

(Example 1)
Under a dry nitrogen stream, 17.28 g (0.054 mol) of 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 1.86 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane ( 0.007 mol), 2.05 g (0.019 mol) of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 120 g of N-methyl-2-pyrrolidone (NMP) as a terminal blocking agent. . To this, 15.23 g (0.075 mol) of isophthalic acid chloride was added together with 15 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. This was designated as Polymer Solution A.

  10 g of the obtained polymer solution A was weighed, 7 g of the naphthoquinone diazide compound (1) shown above, and 4 g of Bis-Z (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group were added to form a photosensitive fragrance. A varnish A of an aromatic polyamide composition was obtained. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 300 ° C. for 1 hour, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were obtained. Evaluation was performed.

(Example 2)
Under a dry nitrogen stream, 9.77 g (0.051 mol) of 9,9-bis (4-aminophenyl) fluorene, 1.86 g (0.075 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane ), As a terminal blocking agent, 6.31 g (0.034 mol) of 1-carboxy-5-aminonaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). It was. Here, 15.227 g (0.075 mol) of a terephthalic acid chloride solution was added dropwise so that the temperature inside the system would not be 10 ° C. or higher. After dropping, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours, and this was designated as polymer solid B.

  The polymer solid B thus obtained was weighed and 2.9 g of the naphthoquinonediazide compound (2) shown above, and BisRS-2P (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group. 4 g and 0.3 g of vinyltrimethoxysilane were dissolved in 70 g of gamma butyrolactone to obtain varnish B of a photosensitive aromatic polyamide composition. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 250 ° C. for 2 hours, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were obtained. Evaluation was performed.

(Example 3)
Under a dry nitrogen stream, 4,21 '(0.008 mol) of 4,4'-diaminodiphenylsulfone, 6,21 g (0.008 mol) of 3,3'-diaminodiphenylsulfone, 1,3-bis (3-amino) Propyl) tetramethyldisiloxane 1.39 g (0.0056 mol), terminal blocker 5.38 g (0.019 mol) active ester compound (a) and 7.03 g (0.089 mol) pyridine N -Methyl-2-pyrrolidone (NMP) was dissolved in 50 g and reacted at room temperature for 2 hours. Here, terephthalic acid chloride (0.044 mol) was added dropwise so that the temperature inside the system would not exceed 10 ° C. After dropping, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours, and this was designated as polymer solid C.

  The polymer solid C10 g thus obtained was weighed, 1.7 g of the naphthoquinonediazide compound (3) shown above, and TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group. 7 g was dissolved in 70 g of N, N-dimethylacetamide to obtain a varnish C of a photosensitive aromatic polyamide composition. Using the obtained varnish, as described above, a photosensitive aromatic polyamide film was produced on a silicon wafer, exposed, developed, and heat-treated at 180 ° C. for 1 hour, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were Evaluation was performed.

Example 4
2-Chloro-1,4-phenylenediamine (0.048 mol), 4,4′-diaminodiphenyl ether (0.008 mol) 1,3-bis (3-aminopropyl) tetramethyldisiloxane under a dry nitrogen stream 1.1.39 g (0.0056 mol) and 3.12 g (0.019 mol) of 3-hydroxyphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) as an end-capping agent were added to N-methyl-2- It was dissolved in 50 g of pyrrolidone (NMP). Here, 2-chloroterephthalic acid chloride (0.044 mol) was added together with 140 g of NMP, reacted at 20 ° C. for 1 hour, and then stirred at 50 ° C. for 3 hours. Subsequently, 125 g of NMP was added, and this was used as a polymer solution D.

8 g of the naphthoquinonediazide compound (4) shown above and 2.6 g of BIR-PC (trade name, manufactured by Asahi Organic Materials Co., Ltd.) as a compound having a phenolic hydroxyl group were dissolved in 10 g of the obtained polymer solution D. Varnish D of the photosensitive aromatic polyamide composition was obtained. Using the obtained varnish, as described above, a photosensitive aromatic polyamide film was produced on a silicon wafer, exposed, developed, and heat-treated at 250 ° C. for 30 minutes, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were Evaluation was performed.







(Example 5)
To the polymer solution A obtained in Example 1, 7 g of the naphthoquinonediazide compound (1) shown above and 6.2 g of BisPC-PCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group were added. Thus, varnish E of the photosensitive aromatic polyamide composition was obtained. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 280 ° C. for 3 hours, and the varnish sensitivity, residual film ratio, resolution, and shrinkage ratio were obtained. Evaluation was performed.

(Example 6)
2. 10 g of the polymer solid B obtained in Example 2 was weighed, 2.9 g of the naphthoquinone diazide compound (2) shown above, and 4PC (trade name, manufactured by Asahi Organic Materials Co., Ltd.) as a compound having a phenolic hydroxyl group. 5 g and 0.3 g of vinyltrimethoxysilane were dissolved in 70 g of gamma butyrolactone to obtain a varnish F of a photosensitive aromatic polyamide composition. Using the obtained varnish, as described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer, exposed, developed, and heat treated at 200 ° C. for 4 hours, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were Evaluation was performed.

(Example 7)
The polymer solid C10g obtained in Example 3 was weighed, 1.7 g of the naphthoquinonediazide compound (3) shown above, and BIR-PCHP (trade name, manufactured by Asahi Organic Materials Co., Ltd.) as a compound having a phenolic hydroxyl group. 1.7 g was dissolved in 70 g of N, N-dimethylformamide to obtain varnish G of a photosensitive aromatic polyamide composition. As described above, a photosensitive aromatic polyamide film was produced on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 160 ° C. for 3 hours, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were Evaluation was performed.

(Example 8)
To the polymer solution D obtained in Example 4, 8 g of the naphthoquinonediazide compound (4) shown above and 2.1 g of DML-MBPC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group were added. Dissolved to obtain varnish H of a photosensitive aromatic polyamide composition. Using the obtained varnish, as described above, a photosensitive aromatic polyamide film was produced on a silicon wafer, exposed, developed, and heat-treated at 250 ° C. for 30 minutes, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were Evaluation was performed.

Example 9
To the polymer solution A obtained in Example 1, 7 g of the naphthoquinonediazide compound (1) shown above and 2.5 g of DML-PC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group were added. Thus, a varnish I of a photosensitive aromatic polyamide composition was obtained. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 300 ° C. for 1 hour, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were obtained. Evaluation was performed.

(Example 10)
10 g of the polymer solid B obtained in Example 2 was weighed, 2.9 g of the naphthoquinonediazide compound (2) shown above, and DML-PTBP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 1 as a compound having a phenolic hydroxyl group. 0.6 g and 0.3 g of vinyltrimethoxysilane were dissolved in 70 g of gamma butyrolactone to obtain a varnish S of a photosensitive aromatic polyamide composition. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 250 ° C. for 2 hours, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were obtained. Evaluation was performed.

(Example 11)
The solid C10 g of the polymer obtained in Example 3 was weighed, 1.7 g of the naphthoquinonediazide compound (3) shown above, and 2,6-dimethoxymethyl-4-tert-butylphenol (Honshu Chemical Industry) as the compound having a phenolic hydroxyl group. Varnish K of photosensitive aromatic polyamide composition was obtained by dissolving 1.0 g in 70 g of N-methylpyrrolidone. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 280 ° C. for 30 minutes, and the sensitivity, remaining film rate, resolution, and shrinkage rate of the varnish Evaluation was performed.

(Example 12)
7 g of the naphthoquinonediazide compound (1) shown above and 3.8 g of 2,6-diacetoxymethyl-p-cresol as a compound having a phenolic hydroxyl group were added to the polymer solution A obtained in Example 1, and a photosensitive fragrance was added. The varnish L of the group polyamide composition was obtained. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 300 ° C. for 1 hour, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were obtained. Evaluation was performed.

(Example 13)
10 g of the polymer solid obtained in Example 2 was weighed, 2.9 g of the naphthoquinonediazide compound (2) shown above, and DML-PCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 1 as a compound having a phenolic hydroxyl group. .2 g, BisPC-PCHP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 1.2 g, and vinyltrimethoxysilane 0.3 g were dissolved in 70 g of gamma butyrolactone to obtain a varnish M of a photosensitive aromatic polyamide composition. It was. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 250 ° C. for 2 hours, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were obtained. Evaluation was performed.

(Example 14)
Under a dry nitrogen stream, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl 17.28 g (0.054 mol), 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) as a terminal blocking agent 2.05 g (0.019 mol) was dissolved in 120 g of N-methyl-2-pyrrolidone (NMP). To this, 15.23 g (0.075 mol) of isophthalic acid chloride was added together with 15 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. This was designated as Polymer Solution E.

  10 g of the obtained polymer solution E was weighed, 7 g of the naphthoquinonediazide compound (1) shown above, and 4 g of Bis-Z (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group were added to form a photosensitive fragrance. A varnish Y of an aromatic polyamide composition was obtained. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 300 ° C. for 1 hour, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were obtained. Evaluation was performed.

(Example 15)
Under a dry nitrogen stream, 4,21 '(0.008 mol) 4,4'-diaminodiphenylsulfone, 6,21 g (0.008 mol) 3,3'-diaminodiphenylsulfone, active ester compound as terminal blocker (A) 5.38 g (0.019 mol) and 7.03 g (0.089 mol) of pyridine were dissolved in 50 g of N-methyl-2-pyrrolidone (NMP) and reacted at room temperature for 2 hours. Here, terephthalic acid chloride (0.044 mol) was added dropwise so that the temperature inside the system would not exceed 10 ° C. After dropping, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the solution was poured into 2 liters of water, and the polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours, and this was designated as polymer solid F.

The polymer solid F10 g thus obtained was weighed, 1.7 g of the naphthoquinonediazide compound (3) shown above, and TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group. 7 g was dissolved in 70 g of N, N-dimethylacetamide to obtain a varnish Z of a photosensitive aromatic polyamide composition. Using the obtained varnish, as described above, a photosensitive aromatic polyamide film was produced on a silicon wafer, exposed, developed, and heat-treated at 180 ° C. for 1 hour, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were Evaluation was performed.

(Example 16)
A glass substrate on which an ITO transparent electrode film having a thickness of 130 nm was formed on a non-alkali glass surface having a thickness of 1.1 mm by a sputtering vapor deposition method was cut into a size of 120 × 100 mm. A photoresist was applied on the ITO substrate, and was patterned by exposure and development by a normal photolithography method. After removing unnecessary portions of the ITO by etching, the ITO film was patterned into a stripe shape by removing the photoresist. The striped first electrodes have a pitch of 100 μm.

  Next, the concentration of the varnish A obtained in Example 1 was adjusted using NMP, applied onto the substrate on which the first electrode was formed by spin coating, and prebaked at 120 ° C. for 3 minutes on a hot plate. This film was exposed to UV through a photomask, developed by dissolving only the exposed portion with a 2.38% TMAH aqueous solution, and rinsed with pure water. The obtained aromatic polyamide pattern was cured by heating at 170 ° C. for 30 minutes and further at 320 ° C. for 60 minutes in a nitrogen atmosphere in a clean oven to form an insulating layer so as to cover the edge of the first electrode. . The thickness of the insulating layer was about 1 μm.

  Next, an organic electroluminescent device was manufactured using the substrate on which the insulating layer was formed. The thin film layer including the light emitting layer was formed by a vacuum evaporation method using a resistance wire heating method. A hole transport layer was formed by vapor deposition over the entire substrate effective area, and a light emitting layer and aluminum for the second electrode were formed using a shadow mask.

  The obtained said board | substrate was taken out from the vapor deposition machine, and it sealed by bonding a board | substrate and the glass plate for sealing using curable epoxy resin. In this way, a simple matrix type color organic electroluminescence device in which a patterned light emitting layer was formed on the ITO striped first electrode and the striped second electrode was disposed so as to be orthogonal to the first electrode was produced. . When this display device was line-sequentially driven, good display characteristics could be obtained. The thin film layer and the second electrode at the boundary of the insulating layer were formed smoothly without any thinning or disconnection, so there was no uneven brightness in the light emitting region and stable light emission. was gotten. The cross section was still forward tapered.

(Example 17)
A simple matrix color organic electroluminescent device was produced in the same manner as in Example 14 except that the varnish E obtained in Example 5 was used and the curing condition was changed to 230 ° C. for 30 minutes. When this display device was driven line-sequentially, no uneven luminance was observed and good display characteristics could be obtained.

(Example 18)
A simple matrix color organic electroluminescent device was produced in the same manner as in Example 14 except that the varnish F obtained in Example 6 was used and the curing condition was changed to 250 ° C. for 30 minutes. When this display device was driven line-sequentially, no uneven luminance was observed and good display characteristics could be obtained.

(Example 19)


A simple matrix type color organic electroluminescent device was produced in the same manner as in Example 14 except that the varnish I obtained in Example 9 was used and the curing condition was changed to 230 ° C. for 30 minutes. When this display device was driven line-sequentially, no uneven luminance was observed and good display characteristics could be obtained.

(Example 20)
A simple matrix color organic electroluminescent device was produced in the same manner as in Example 14 except that the varnish L obtained in Example 12 was used and the curing condition was changed to 280 ° C. for 60 minutes. When this display device was driven line-sequentially, no uneven luminance was observed and good display characteristics could be obtained.

(Example 21)
A simple matrix color organic electroluminescent device was produced in the same manner as in Example 14 except that the varnish M obtained in Example 13 was used and the curing condition was changed to 250 ° C. for 60 minutes. When this display device was driven line-sequentially, no uneven luminance was observed and good display characteristics could be obtained.

(Comparative Example 1)
The 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl of Example 1 was changed from 17.28 g (0.054 mol) to 20.48 g (0.064 mol), and no end-capping agent was used. The others were carried out in the same manner as in Example 1 to obtain a varnish N of a photosensitive aromatic polyamide composition. Using the obtained varnish, as described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer, exposed, developed, and heat-treated at 300 ° C. for 1 hour, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were Evaluation was performed.

(Comparative Example 2)
Except not using the terminal blocker of Example 2, it carried out similarly to Example 2 and obtained the varnish P of the photosensitive aromatic polyamide composition. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 250 ° C. for 2 hours, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were obtained. Evaluation was performed.

(Comparative Example 3)
Varnish Q of the photosensitive aromatic polyamide composition was obtained in the same manner as in Example 3 except that the end capping agent of Example 3 and the compound TrisP-PA having a phenolic hydroxyl group were not used. Using the obtained varnish, as described above, a photosensitive aromatic polyamide film was produced on a silicon wafer, exposed, developed, and heat-treated at 180 ° C. for 1 hour, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were Evaluation was performed.

(Comparative Example 4)
Except not using the terminal blocker of Example 4, it carried out similarly to Example 4 and obtained the varnish R of the photosensitive aromatic polyamide composition. Using the obtained varnish, as described above, a photosensitive aromatic polyamide film was produced on a silicon wafer, exposed, developed, and heat treated at 250 ° C. for 3 hours, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were Evaluation was performed.

(Comparative Example 5)
Except not using the terminal blocker of Example 5, it carried out similarly to Example 5 and obtained the varnish S of the photosensitive aromatic polyamide composition. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 280 ° C. for 3 hours, and the varnish sensitivity, residual film ratio, resolution, and shrinkage ratio were obtained. Evaluation was performed.

(Comparative Example 6)
Except not using the terminal blocker of Example 9, it carried out similarly to Example 9 and obtained the varnish T of the photosensitive aromatic polyamide composition. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 300 ° C. for 1 hour, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were obtained. Evaluation was performed.

(Comparative Example 7)
Varnish U of the photosensitive aromatic polyamide composition was obtained in the same manner as in Example 1 except that Compound Bis-Z having a phenolic hydroxyl group of Example 1 was not used. As described above, a photosensitive aromatic polyamide film was prepared on a silicon wafer using the obtained varnish, exposed, developed, and heat-treated at 300 ° C. for 1 hour, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were obtained. Evaluation was performed.

(Comparative Example 8)
Varnish V of the photosensitive aromatic polyamide composition was obtained in the same manner as in Example 4 except that the compound BIR-PC having a phenolic hydroxyl group of Example 4 was not used. Using the obtained varnish, as described above, a photosensitive aromatic polyamide film was produced on a silicon wafer, exposed, developed, and heat-treated at 250 ° C. for 30 minutes, and the varnish sensitivity, remaining film rate, resolution, and shrinkage rate were Evaluation was performed.

(Comparative Example 9)
Under a dry nitrogen stream, 10.89 g (0.054 mol) of 4,4′-diaminodiphenyl ether, 1.86 g (0.007 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, end-capping As an agent, 2.05 g (0.019 mol) of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 20 g of N-methyl-2-pyrrolidone (NMP). To this, 23.27 g (0.075 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added together with 15 g of NMP, and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, a solution obtained by diluting 15.19 g (0.127 mol) of N, N-dimethylformamide dimethylacetal with 4 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. Subsequently, 123.9 g of NMP was added, and this was used as a polyimide precursor polymer solution W.

  7 g of the naphthoquinone diazide compound (1) shown above and 4 g of Bis-Z (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group were added to the obtained polymer solution W, and a photosensitive polyimide precursor was added. A varnish W of the composition was obtained. Using the obtained varnish, a photosensitive polyimide precursor film was prepared on a silicon wafer in the same manner as in the preparation of the photosensitive polyamide film, exposed to light, developed, and heat-treated at 300 ° C. for 1 hour. The film rate, resolution, and shrinkage rate were evaluated.

(Comparative Example 10)

Under a dry nitrogen stream, 6FDA 17.77 g (0.04 mol), 33DDS 8.65 g (0.02 mol), 3,5-diaminobenzoic acid (Dainippon Ink Co., Ltd. product, DABz) 3.04 g (0. 02 mol), 0.8 g of gamma butyrolactone and 1.2 g (0.016 mol) of pyridine, 112 g of N-methylpyrrolidone, and 40 g of toluene were charged. After stirring at room temperature for 0.5 hour, the temperature was raised to 180 ° C., and the reaction was stirred for 2.25 hours while removing the azeotrope of toluene-water during the reaction. Thereafter, the mixture was cooled to room temperature, added with 8.41 g (0.100 mol) of 3,4-dihydro-211-pyran and 20 g of toluene, stirred at room temperature for 25 minutes, and stirred at 160 ° C. for 3 hours. In this way, polyimide solution X was obtained. 2.9 g of the naphthoquinone diazide compound (2) shown above in the obtained polymer solution X, 2.4 g of BisRS-2P (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) as a compound having a phenolic hydroxyl group, vinyltrimethoxy Silane 0.3 g was dissolved in gamma butyrolactone 70 g to obtain a varnish X of a photosensitive polyimide composition. Using the obtained varnish, a photosensitive polyimide film was prepared on a silicon wafer in the same manner as in the preparation of the photosensitive polyamide film described above, exposed, developed, and heat-treated at 250 ° C. for 2 hours. The resolution and shrinkage rate were evaluated.

The evaluation results of Examples 1 to 13 and Comparative Examples 1 to 10 are shown in Tables 1 to 4.

Claims (7)

A positive photosensitive resin composition containing the following components (a), (b) and (c).
(A) Polyamide having at least one group selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group at the polymer main chain terminal (b) Compound (c) having a phenolic hydroxyl group Quinonediazide compound The positive photosensitive resin composition of Claim 1 in which the polyamide of a component (a) contains the structural unit represented by General formula (1) and / or General formula (2).

(Wherein R ¹ is a divalent to tetravalent organic group, R ² is a divalent to tetravalent organic group, R ³ is a divalent organic group, X is a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, A divalent to octavalent organic group having at least one group selected from thiol groups, n is an integer from 3 to 100,000, m is an integer from 0 to 10, and p is an integer from 0 to 2. .) The positive photosensitive resin composition of Claim 1 in which the polyamide of a component (a) contains the structural unit represented by General formula (3) and / or General formula (4).

(Wherein R ¹ is a divalent to tetravalent organic group, R ² is a divalent to tetravalent organic group, R ³ is a divalent organic group, X is a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, A divalent to octavalent organic group having at least one group selected from thiol groups, n is an integer from 3 to 100,000, m is an integer from 0 to 10, and p is an integer from 0 to 2. .)
The positive photosensitive resin composition according to claim 2 or 3, wherein m = 0. The positive photosensitive resin composition in any one of Claims 1-4 whose compound which has a phenolic hydroxyl group of a component (b) is a compound represented by General formula (5).

(Wherein R ⁴ to R ⁷ represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, and an alicyclic group having 4 to 20 carbon atoms, α represents an integer of 0 to 5) The positive photosensitive resin composition in any one of Claims 1-5 whose compound which has a phenolic hydroxyl group of a component (b) is a heat-crosslinkable compound containing the organic group represented by General formula (6). Stuff.

(In the formula, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, or an R ⁹ CO group. Also, R ⁹ has 1 to 20 carbon atoms. Represents an alkyl group of The positive photosensitive resin composition of Claim 6 whose heat-crosslinkable compound containing the organic group represented by General formula (6) is a compound represented by General formula (7).

(Wherein R ⁸ is the same as above, and R ¹⁰ and R ¹¹ represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alicyclic group having 4 to 20 carbon atoms, or an R ¹⁹ COO group. , R ¹⁹ represents an alkyl group having 1 to 20 carbon atoms.)