JP2008040324A - Resin composition and method for producing patterned resin film using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having both of excellent chemical resistance and high adhesiveness to a substrate. <P>SOLUTION: The resin composition comprises (a) a resin consisting mainly of a structural unit represented by formula (1), (b) a heat crosslinkable compound having a phenolic hydroxyl group and/or a heat crosslinkable compound having a urea-based organic group, and (c) an adhesion improver having a heterocyclic structure containing a nitrogen atom or a sulfur atom. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition and a method for producing a patterned resin film using the same. More specifically, surface protective films for semiconductor elements, interlayer insulating films, insulating layers such as organic electroluminescence (organic EL) displays, planarization films for thin film transistor (TFT) substrates for display devices, and overcoats for color filter substrates for display devices The present invention relates to a resin composition suitable for a film and the like, and a method for producing a patterned resin film using the same.

  In order to reduce the mounting area of an LSI package, a conventional method of connecting pins to a substrate, such as a QFP, which is connected to a substrate, forms a bump on the package and directly bonds the package to the substrate. It has come to be used. For this reason, it is necessary to form solder bumps or the like when forming a package, and an insulating material such as polyimide used for protecting an LSI chip is required to have heat resistance and chemical resistance. In particular, in forming solder bumps, high-temperature processing using an organic acid called flux processing is performed, so that chemical resistance higher than that of conventional methods is required.

  In the display field, various substrate cleaning processes are performed in the manufacturing process, and the interlayer insulating film, the surface protective film, and the planarization film of the TFT substrate are required to have resistance to these processes. Examples of the substrate cleaning treatment include dry processes such as oxygen plasma, excimer laser, and UV ozone treatment, and wet processes such as ultrasonic cleaning, cleaning with a surfactant and alkaline solution, and resist stripping solution treatment for removing the photoresist. It is done. Recently, with the high definition and high precision of pixels, these processes have been strengthened, and chemical resistance higher than conventional is required.

  Furthermore, particularly in an organic EL display, the light-emitting element is very weak to water and organic gas, and the material that insulates the light-emitting pixels is not hygroscopic, and does not degas due to gradual decomposition during light emission driving. It becomes important. For this reason, an insulating film having better chemical resistance than before has been demanded.

As a technique for enhancing such chemical resistance, a positive photosensitive resin composition containing a thermally crosslinkable compound (see, for example, Patent Document 1) and a negative resist composition containing a polyfunctional phenolic crosslinking agent. (See, for example, Patent Document 2). As such phenolic compounds, trimethylolated triphenols (for example, see Patent Document 3), compounds having 12 methylol groups (for example, see Patent Document 4), and the like are disclosed. . However, the resin composition containing these thermally crosslinkable compounds has a problem that the adhesion to the substrate is lowered. In particular, a reduction in adhesion to metal electrodes used in liquid crystal displays and organic EL displays, particularly indium tin oxide (ITO) films, has been a problem.
JP 2002-328472 A (Claims 1, 2) JP 2004-94025 A (Claims 1 and 3) JP 2003-3000922 A (Claim 1) JP 2000-290211 (Claims 1 and 2)

  Such a decrease in adhesion is due to the fact that the resin composition is accelerated by containing a thermally crosslinkable compound, the degree of freedom of polymer molecules on the surface of the resin film is reduced, and the physical properties at the interface between the substrate and the resin film are reduced.・ It is thought that this is because chemical interaction is reduced. An object of this invention is to provide the resin composition which has the outstanding chemical resistance and the high adhesiveness with respect to a board | substrate in view of the subject of this prior art.

  The present invention includes (a) a resin mainly composed of a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2), (b) (b1) a phenolic hydroxyl group, and Thermally crosslinkable compound having a group represented by formula (3) and / or (b2) Thermally crosslinkable compound having a urea organic group represented by general formula (4), and (c) a nitrogen atom or a sulfur atom It is a resin composition characterized by containing the adhesive improvement agent which has a heterocyclic structure containing.

(R ¹ and R ² represent a divalent to hexavalent organic group having 2 to 30 carbon atoms. A may be the same or different, and OR ³ , SO ₃ R ³ , CONR ³ R ⁴ , COOR ³ , SO ₂ selected from NR ³ R ^4. R ³ and R ⁴ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, m and p represent an integer of 0 to 4, provided that m + p> 0 .)

(R ⁵ represents a C 4-30 tetravalent organic group. R ⁶ represents a C 2-30 bivalent organic group. E may be the same or different, OR ⁷ , SO ₃ R ⁷ , CONR ⁷ R ⁸ , COOR ⁷ , SO ₂ NR ⁷ R ^8, R ⁷ and R ⁸ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. And Z is selected from CO, N, NH, O and S, and Y represents C or N. The bond between Z and Y is a single bond or a double bond, and r and s are integers of 0 to 4. Q represents an integer of 0 to 2, provided that r + s> 0.)

(R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.)

(R ¹⁰ may be the same or different and represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.)

  According to the present invention, a resin composition having both excellent chemical resistance and high adhesion to a substrate can be obtained. Moreover, the patterned resin film which has the outstanding chemical resistance and the high adhesiveness with respect to a board | substrate can be obtained using the resin composition of this invention.

  The resin composition of the present invention contains a resin mainly composed of a structural unit represented by the following general formula (1) and / or a structural unit represented by the general formula (2). Here, the main component means that 60% or more of the structural units represented by the following general formula (1) and / or general formula (2) are contained, and that 80% or more is contained. preferable.

R ¹ and R ² represent a divalent to hexavalent organic group having 2 to 30 carbon atoms. A may be the same or different and is selected from OR ³ , SO ₃ R ³ , CONR ³ R ⁴ , COOR ³ , and SO ₂ NR ³ R ⁴ . R ³ and R ⁴ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. m and p show the integer of 0-4. However, m + p> 0.

R ⁵ represents a C 4-30 tetravalent organic group. R ⁶ represents a divalent to hexavalent organic group having 2 to 30 carbon atoms. E may be the same or different and is selected from OR ⁷ , SO ₃ R ⁷ , CONR ⁷ R ⁸ , COOR ⁷ , SO ₂ NR ⁷ R ⁸ . R ⁷ and R ⁸ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. X and Z are selected from CO, N, NH, O, and S, and Y represents C or N. The bond between Z and Y is a single bond or a double bond. r and s are integers of 0 to 4, and q is an integer of 0 to 2. However, r + s> 0.

  Among the components (a) used in the present invention, the resin having the structural unit represented by the general formula (1) has an amide bond in the main chain, and is a polyimide precursor, polyamic acid, polyamic acid Examples thereof include polyhydroxyamides, polyaminoamides, polyamides, polyamideimides, and the like that can be esters and polybenzoxazole precursors, but any other compounds having the structural unit of the general formula (1) may be used. Among these, since the resin after heat treatment is excellent in heat resistance and mechanical properties, polyamic acid, polyamic acid ester, polyhydroxyamide, and the like are preferably used.

  Moreover, it can replace with the structural unit represented by General formula (1), or can use together and can use resin which has a structural unit represented by General formula (2). The resin having the structural unit represented by the general formula (2) is a resin having a cyclic structure such as an imide ring, an oxazole ring, an imidazole ring, and a thiazole ring in the main chain structure. Benzoxazole, polybenzimidazole, polybenzthiazole and the like can be mentioned.

  Each of the structural units represented by the general formula (1) or (2) may be used alone, or a plurality of structural units may be mixed or copolymerized. Moreover, the other structural unit may be included as needed.

  The weight average molecular weight of the resin having the structural unit represented by the general formula (1) and / or the structural unit represented by (2) as a main component is determined by gel permeation from the viewpoint of heat resistance after heat treatment and mechanical properties. It is preferably 1,000 or more and more preferably 5,000 or more in terms of polystyrene by chromatography. The upper limit is preferably 100,000 or less, and more preferably 50,000 or less from the viewpoint of solubility in a developer when a photosensitive resin composition is used.

  The polyimide preferably used in the present invention can be obtained by reacting tetracarboxylic acid, corresponding tetracarboxylic dianhydride, tetracarboxylic acid diester dichloride and the like with diamine, corresponding diisocyanate compound, and trimethylsilylated diamine. Polyimide can be obtained by dehydrating and ring-closing polyamic acid, which is one of polyimide precursors generally obtained by reacting tetracarboxylic dianhydride and diamine, by heating or chemical treatment with acid or base. In the present invention, not only polyamic acid and polyimide can be used, but also other polyimide precursors such as polyamic acid ester, polyamic acid amide, and polyisoimide can be used.

  The polybenzoxazole preferably used in the present invention can be obtained by reacting bisaminophenol with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, a dicarboxylic acid active ester and the like. In general, polyhydroxyamide, one of the polybenzoxazole precursors obtained by reacting bisaminophenol compounds with dicarboxylic acids, is subjected to dehydration and cyclization by heating or chemical treatment with phosphoric anhydride, base, carbodiimide compounds, etc. Polybenzoxazole can be obtained.

  Polybenzimidazole can be obtained by reacting tetraamine with dicarboxylic acid, the corresponding dicarboxylic acid chloride, dicarboxylic acid active ester and the like. In general, polyaminoamide, which is one of the polybenzimidazole precursors obtained by reacting bisaminophenol compounds with dicarboxylic acids, is subjected to dehydration and ring closure by heating or chemical treatment with phosphoric anhydride, base, carbodiimide compounds, etc. Benzimidazole can be obtained.

  Polybenzothiazole can be obtained by reacting bisaminothiophenol with dicarboxylic acid, the corresponding dicarboxylic acid chloride, dicarboxylic acid active ester and the like. In general, polythiohydroxyamide, which is one of the polybenzothiazole precursors obtained by reacting bisaminothiophenol compounds with dicarboxylic acids, is subjected to dehydration and ring closure by heating or chemical treatment with phosphoric anhydride, base, carbodiimide compounds, etc. Thus, polybenzothiazole can be obtained.

Examples of the acid component constituting —CO—R ¹ (A) _m —CO— in the general formula (1) include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, Examples of tricarboxylic acids such as biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid. Examples of tetracarboxylic acid include pyromellitic acid, 3 , 3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4 , 4'-Benzophenonetetracarboxylic acid, 2,2 ', 3,3'-benzophen Enone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3 4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis ( 3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2, Aromatic tetracarboxylic acids such as 3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, butanetetracarbo Acid, and aliphatic tetracarboxylic acids such as 1,2,3,4-cyclopentane tetracarboxylic acid. Among these, in tricarboxylic acid and tetracarboxylic acid, one or two carboxyl groups correspond to the A group in the general formula (1). Further, 1 to 4 dicarboxylic acids, tricarboxylic acids, and tetracarboxylic acids exemplified above are substituted with the A group in the general formula (1), preferably a hydroxyl group, a sulfonic acid group, a sulfonic acid amide group, or a sulfonic acid ester group. It is more preferable to use what was done. These acids can be used alone or in combination of two or more as an acid anhydride and an active ester.

Examples of the diamine component constituting —NH—R ² (A) _p —NH— in the general formula (1) include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino -4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3 -Amino-4-hydroxy) biphenyl, hydroxyl group-containing diamines such as bis (3-amino-4-hydroxyphenyl) fluorene, carboxyls such as 3,5-diaminobenzoic acid, 3-carboxy-4,4'-diaminodiphenyl ether Group-containing diamines, sulfones such as 3-sulfonic acid-4,4′-diaminodiphenyl ether Phosphate-containing diamines, such as dithio-hydroxy-phenylenediamine and the like.

  Furthermore, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl Sulfone, 3,4′-diaminodiphenyl sulfide, 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′-diamino Biphenyl, 3,3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4′-diaminobiphenyl, 3,3 ′, 4,4′-tetramethyl -4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, or compounds obtained by substituting these aromatic rings with alkyl groups or halogen atoms. . Moreover, you may use aliphatic cyclohexyl diamine, a methylene bis cyclohexyl amine, etc. 0-50 mol% of all the diamine components. Furthermore, these diamines are monovalent groups having 1 to 10 carbon atoms such as a methyl group and an ethyl group, fluoroalkyl groups having 1 to 10 carbon atoms such as a trifluoromethyl group, groups such as F, Cl, Br, and I. May be substituted. These diamines can be used alone or in combination of two or more as diamines or as corresponding diisocyanate compounds and trimethylsilylated diamines. In applications where heat resistance is required, it is preferable to use an aromatic diamine in an amount of 50 mol% or more of the total diamine.

In the general formula (1), A represents a group selected from OR ³ , SO ₃ R ³ , CONR ³ R ⁴ , COOR ³ , and SO ₂ NR ³ R ⁴ . R ³ and R ⁴ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. A particularly preferred example of A is a hydroxyl group.

In the present invention, the resin represented by the general formula (2) represents a resin having a cyclic structure such as polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole. Preferred as the structure of R ^5- (E) _{r in} the general formula (2) is the following structure, or a part of these is an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, Examples include a structure in which 1 to 4 groups are substituted with a nitro group, a cyano group, a fluorine atom, or a chlorine atom.

  Moreover, the structure shown next is also mentioned.

J is a direct bond, —COO—, —CONH—, —CH ₂ —, —C ₂ H ₄ —, —O—, —C ₃ H 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 general formula (2), E represents a group selected from OR ⁷ , SO ₃ R ⁷ , CONR ⁷ R ⁸ , COOR ⁷ , and SO ₂ NR ⁷ R ⁸ . R ⁷ and R ⁸ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Among these, E is preferably a hydroxyl group, a carboxyl group, an ester group, a sulfonic acid group, a sulfonic acid amide group, or a sulfonic acid ester group.

  X and Z in the general formula (2) are selected from CO, N, NH, O, and S. Y is N or C. When Y is C, one bond of XY or YZ is a double bond. q represents an integer of 0 to 2, and q = 0 is particularly preferable.

  In addition, by sealing the end of these resins with a monoamine having a functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group and a thiol group, the dissolution rate of the resin in an alkaline aqueous solution is adjusted to a preferred range. can do.

  Examples of such monoamines include 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-hydroxyquinoline having a phenolic hydroxyl group. 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- 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene having a carboxyl group, such as droxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, etc. 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 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-carboxynaphthale 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-o-toluic acid, amelide 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, etc., thiol such as 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid having a sulfonic acid group 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene having a group 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-me Lucapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-amino Naphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-amino Examples include thiophenol and 4-aminothiophenol.

  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 preferably used because they have a hydrophilic group. These monoamines can be used alone or in combination of two or more.

  Further, by sealing the end of the resin with an acid anhydride, acid chloride, or monocarboxylic acid, the dissolution rate with respect to the alkaline aqueous solution can be adjusted to a preferred range.

  Examples of such acid anhydrides, acid chlorides and monocarboxylic acids include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, 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-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8- Cal Xinaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1- Monocarboxylic acids such as mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and the like, monoacid chloride compounds in which these carboxyl groups are 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-dicarbo Sinaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene , Monoacid chloride compounds in which only the monocarboxyl group of dicarboxylic acids such as 2,7-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3- Examples include active ester compounds obtained by reaction with dicarboximide.

  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, and monoacid chloride compounds and terephthalic acid in which these carboxyl groups are converted to acid chloride Only monocarboxylic groups of dicarboxylic acids such as phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene Is preferably a monoacid chloride compound obtained by acid chloride, an active ester compound obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide. . These can be used alone or in combination of two or more.

  The content of the end-capping agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid is preferably in the range of 0.1 to 40 mol%, particularly preferably 5 to 20 mol% of the whole resin. . 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.

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

  The resin composition of the present invention contains (b) a thermally crosslinkable compound. The (b) thermally crosslinkable compound in the present invention is represented by (b1) a thermally crosslinkable compound having a phenolic hydroxyl group and a group represented by the general formula (3) and / or (b2) a general formula (4). It is a thermally crosslinkable compound having a urea organic group. When the component (b) in the present invention is mixed with an unsubstituted component or an increased component, the crosslinking reaction of the resin composition may not sufficiently proceed. For this reason, it is preferable that the purity of (b) component is 80 weight% or more, and it is more preferable in it being 95 weight% or more. If the purity is 80% by weight or more, the cross-linking reaction of the resin composition can be sufficiently performed to reduce the number of unreacted groups that become water-absorbing groups, so that the water absorption of the resin composition can be reduced. Examples of a method for obtaining a highly pure thermally crosslinkable compound include a method of collecting only the target product by performing recrystallization, distillation or the like. The purity of the thermally crosslinkable compound can be determined by a liquid chromatography method.

In general formula (3), R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. In particular, a methyl group and an ethyl group are preferable because they retain moderate reactivity and are chemically stable.

  Specific examples of the component (b1) are shown below, but are not limited thereto. Moreover, the component (b1) may be used alone or in combination.

  In addition, from the viewpoint of further improving chemical resistance, the component (b1) preferably contains 4 or more thermally crosslinkable groups represented by the general formula (3), more preferably 6 or more. It is. Specific examples of such thermally crosslinkable compounds are shown below, but are not limited thereto.

In General Formula (4), R ¹⁰ may be the same or different and represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Since it is highly soluble in a solvent, an alkyl group having 1 to 20 carbon atoms is preferable. Furthermore, it is more preferably a methyl group or an ethyl group because it retains moderate reactivity and is chemically stable.

  (B2) Specific examples of the thermally crosslinkable compound containing the urea-based organic group in the general formula (4) are shown below, but are not limited thereto. Moreover, the component (b2) may be used alone or in combination.

  (B) The content of the thermally crosslinkable compound is preferably 10 parts by weight or more, and more preferably 40 parts by weight or more with respect to 100 parts by weight of the resin of component (a). Moreover, 100 weight part or less is preferable and 80 weight part or less is more preferable. When the content of component (b) is within this range, the resin composition exhibits sufficient stability and low water absorption, and further exhibits chemical resistance and high mechanical properties (particularly elongation at break) of the film after heat treatment. Can be satisfied. In general, the chemical resistance is preferably 0.1 μm or less and the elongation at break is preferably 10% or more. In addition, the component (b1) and the component (b2) may be used either alone or in combination.

  The resin composition of the present invention contains (c) an adhesion improving agent having a heterocyclic structure containing a nitrogen atom or a sulfur atom. By containing (c) component, the adhesiveness with respect to metal electrodes, such as chromium and aluminum, especially an ITO electrode improves after heat processing. This is because the heterocyclic structure containing a nitrogen atom or sulfur atom contained in the component (c) forms a complex with various metals and exhibits an adhesive effect at the interface portion between the coating film of the resin composition and the metal electrode. it is conceivable that.

  Examples of the (c) adhesion improver preferably used in the present invention include (c1) an adhesion improver selected from the compounds represented by the following general formula (5) or (6). The component (c1) is a compound having both an imide ring structure and a silane or siloxane structure. Because it has a hydrophobic silane or siloxane structure, it effectively moves from the coating film to the interface between the resin composition and the metal electrode after coating, and the imide ring structure at the end interacts with the metal electrode. It is thought that the adhesive effect is expressed.

In the formula, R ¹¹ , R ¹² , R ¹⁷ and R ¹⁸ may be the same or different and are each a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, a nitro group, an amino group, a carboxyl group. Represents a group selected from a group, an ester group having 2 to 10 carbon atoms, and an alkoxyl group having 1 to 10 carbon atoms. R <^13> , R <^14> , R <^15> and R <^16> may be the same or different and are each an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, an alkenyl group, a phenyl group, a substituted phenyl group, or an alkoxyl group having 1 to 6 carbon atoms. It represents an organic group selected from the group. R ¹⁹ represents a group selected from a monovalent hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, a nitro group, an amino group, a carboxyl group, an ester group having 2 to 10 carbon atoms, and an alkoxyl group having 1 to 10 carbon atoms. To express. a and c are integers of 1 to 10, b is an integer of 0 to 10, and d is an integer of 0 to 2.

  The adhesion improver of the component (c1) can be obtained by a reaction between an amino group-containing silane or siloxane and an acid dianhydride. From the viewpoint of solubility in the resin composition, a longer alkyl chain portion is preferred, and in general formulas (5) and (6), a and c are preferably 2 or more and 10 or less. More preferably, it is 3 or more and 10 or less. Moreover, since the adhesive improvement agent represented by General formula (6) has two imide ring structures in 1 molecule, an adhesive improvement effect is higher and is preferable.

  Although the specific example of a compound represented by General formula (5) or (6) is shown below, it is not limited to these. These may be used alone or in combination.

  Other examples of the (c) adhesion improver preferably used in the present invention include (c2) a compound having a heterocyclic structure containing 3 or more nitrogen atoms. A heterocyclic structure having 3 or more nitrogen atoms is preferable because the effect of improving the adhesion to the substrate is higher. Moreover, when the photoacid generator mentioned later is contained in a resin composition, from a viewpoint of preventing decomposition | disassembly of a photoacid generator, a tertiary amine has a preferable tertiary amine. (C2) Although the specific example of the heterocyclic structure which has 3 or more of nitrogen atoms is shown below, it is not limited to these. These may be used alone or in combination.

  Among the components (c2), the compound represented by any one of the following general formulas (7) to (9) is particularly preferable because of its remarkable effect of improving the adhesion to the ITO film and high solubility in a solvent. Used. Moreover, when the photoacid generator mentioned later is contained in a resin composition, there exists an effect which prevents decomposition | disassembly of a photoacid generator.

In the formula, R ²⁰ and R ²¹ may be the same or different and are each an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a phenyl group, a substituted phenyl group, a hydroxyl group, a nitro group, an amino group, a carboxyl group, or carbon. It represents a group selected from an alkoxyl group having 1 to 10 carbon atoms, an epoxy group having 2 to 10 carbon atoms, and an ester group having 2 to 10 carbon atoms. R ^{22 to} R ²⁷ may be the same or different and are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a phenyl group, a substituted phenyl group, a hydroxyl group, a nitro group, an amino group, and a substituted amino group, carboxyl group, an alkoxyl group having 1 to 10 carbon atoms, an epoxy group having 2 to 10 carbon atoms, an ester group having 2 to 10 carbon _{atoms, CH 3 - (CH 2)} g -CH = CH-O-, CH 2 = CH - it represents a _{(CH 2)} g -O- from selected groups. e represents an integer of 0 to 4, f represents 0 or 1, and g represents an integer of 0 to 7.

  Although the specific example of a compound represented by either of General formula (7)-(9) is shown below, it is not limited to these. These may be used alone or in combination.

  In the present invention, the content of the (c) adhesion improving agent is preferably 0.1 parts by weight or more, more preferably 3 parts by weight or more with respect to 100 parts by weight of the resin of the component (a). Moreover, 100 weight part or less is preferable and 40 weight part or less is preferable. If the content of the component (c) is within this range, the adhesiveness (particularly, PCT 200 hours exposure) of the resin film after heat treatment and the mechanical properties (particularly elongation at break) can be compatible at a high level. As the component (c), the component (c1) or the component (c2) may be used alone, or both components may be used in combination.

  The resin composition of the present invention can contain (d) a photoacid generator. (D) By containing a photoacid generator, an acid is generated in the light irradiation part, and the solubility of the light irradiation part in the alkaline aqueous solution is increased, thereby obtaining a positive relief pattern in which the light irradiation part dissolves. be able to. (D) Photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like. In the present invention, a plurality of these may be used. By using two types of photoacid generators, the ratio of the dissolution rate between the exposed part and the unexposed part can be increased, and as a result, a highly sensitive photosensitive resin composition can be obtained.

  The quinonediazide compound is a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound with an ester, a sulfonic acid of quinonediazide bonded to a polyamino compound in a sulfonamide bond, and a sulfonic acid of quinonediazide is bonded to a polyhydroxypolyamino compound in an ester bond and / or sulfonamide bond And the like. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. In the case of 50 mol% or more, it has a solubility in an alkaline developer suitable for obtaining a contrast with an unexposed portion.

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

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

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

  In the present invention, as the quinonediazide compound, those having either a 5-naphthoquinonediazidosulfonyl group or a 4-naphthoquinonediazidesulfonyl group are preferably used. 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 in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound. Can also be used together.

  By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can. Such compounds may be used alone or in combination of two or more.

  Further, when the molecular weight of the quinonediazide compound is 5000 or less, the quinonediazide compound is sufficiently thermally decomposed in the subsequent heat treatment, and no residue remains in the film, so that the heat resistance and mechanical properties of the obtained film are well maintained. . More preferably, it is 3000 or less, More preferably, it is 1500 or less. In addition, the molecular weight of the quinonediazide compound is 300 or more, more preferably 350 or more, in order to sufficiently exhibit the effect of suppressing the dissolution rate of the unexposed area.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  In the resin composition of the present invention, the content of the (d) photoacid generator is preferably 1 part by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the resin of the component (a). Of these, the quinonediazide compound is preferably in the range of 3 to 70 parts by weight. The compound selected from sulfonium salts, phosphonium salts, and diazonium salts is preferably in the range of 0.05 to 40 parts by weight, and more preferably in the range of 3 to 30 parts by weight. By setting the content of the component (d) within this range, higher sensitivity can be achieved. A photo-acid generator may be used independently and may be used 2 or more types. Furthermore, it can also contain a sensitizer etc. as needed.

  Moreover, the compound which has a phenolic hydroxyl group can be contained in the range which does not reduce the shrinkage | contraction rate after hardening for the purpose of improving the sensitivity of the said photosensitive resin composition as needed.

  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-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26 -OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (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.).

  Among these, preferred compounds having a phenolic hydroxyl group used in the present invention include, for example, 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, BIP-PC, BIR-PC, BIR-PTBP, BIR- BIPC-F etc. are mentioned. Among these, particularly preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR- BIPC-F. By containing the compound having a phenolic hydroxyl group, the obtained resin composition is hardly dissolved in an alkali developer before exposure, and is easily dissolved in an alkali developer upon exposure. Development is easy in a short time.

  The content of such a compound having a phenolic hydroxyl group is preferably 1 part by weight or more and more preferably 3 parts by weight or more with respect to 100 parts by weight of the resin (a). Moreover, 50 weight part or less is preferable and 40 weight part or less is more preferable.

  Furthermore, the resin composition according to the present invention contains a silane coupling agent such as trimethoxyaminopropyl silane, trimethoxy epoxy silane, trimethoxy vinyl silane, trimethoxy thiol propyl silane, thereby further improving the adhesion to the substrate. , Resistance to oxygen plasma, UV ozone treatment, excimer laser, etc. used for cleaning can be enhanced. Alternatively, as the acid dianhydride component, a dianhydride of a silicon atom-containing tetracarboxylic acid such as dimethylsilanediphthalic acid or 1,3-bis (phthalic acid) tetramethyldisiloxane is used as 1 to 1 of the total acid dianhydride component. 30 mol% is copolymerized or all diamine components such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane and 1,3-bis (4-anilino) tetramethyldisiloxane are used as diamine components. By copolymerizing 1 to 30 mol% of the diamine component, it is possible to further enhance the adhesion to the substrate and to improve the resistance to oxygen plasma, UV ozone treatment, excimer laser, etc. used for cleaning.

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

  Furthermore, in order to further improve the adhesion to a base material such as an ITO film, the base material can be pretreated with the component (c) used in the present invention. In this case, the component (c) 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% by weight. The dissolved solution is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. Depending on the case, reaction of a board | substrate and said (c) component is advanced by applying temperature of 50 to 300 degreeC after that.

  The resin composition of the present invention may contain a solvent. As the solvent, polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, Ethers such as propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxy Esters such as butyl acetate, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, toluene, xylate The solvents such as aromatic hydrocarbons such as alone or may be used two or more.

  In the resin composition of the present invention, the content of the solvent is preferably 50 to 2000 parts by weight, particularly preferably 100 to 1500 parts by weight, with respect to 100 parts by weight of the resin (a). Moreover, it is preferable that the viscosity of the resin composition obtained by this invention shall be 3-100 mPa * s. What is necessary is just to adjust the viscosity of a resin composition with solvent content.

  In order to improve chemical resistance, heat resistance, etc., the resin composition of the present invention may contain inorganic fine particles such as silicon dioxide, titanium dioxide, zircon oxide and cerium oxide, and fine resin particles such as polyimide. .

  Next, a heat resistant resin film using the resin composition of the present invention will be described. The resin composition of the present invention is applied by a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, or the like, and dried if necessary to obtain a resin composition film. By heat-treating this resin composition film, the resin composition film can be cured to obtain a heat resistant resin film. Curing conditions are not limited to heat treatment at 230 ° C. for 60 minutes, and can be carried out in the range of 120 to 400 ° C. for 1 minute to 10 hours. A cured film can also be obtained by curing at a low temperature of about 0 ° C., a method of curing by ultrasonic wave or electromagnetic wave treatment, and the like.

  In addition, it is also possible to form a printed circuit board or the like by forming a wiring with copper, aluminum or the like on a film or substrate such as polyimide or ceramics, and applying the resin composition of the present invention as an insulating film or protective film of the wiring. it can. Furthermore, the resin composition of the present invention can be used as a protective film material for partially soldering the wiring.

  In addition, the resin composition of the present invention may contain 0.1 to 1000 parts by weight of fine particles of metal such as silver, copper and aluminum with respect to 100 parts by weight of the resin in order to provide conductivity. . By forming this conductive resin composition on a polyimide film or ceramic that is an insulating substrate, it is also possible to obtain a circuit pattern without warping.

  Furthermore, the resin composition of the present invention is preferably used as a surface protective film for semiconductor devices such as LSI, an interlayer insulating film, an adhesive or underfill agent for encapsulating a device in a package, a cap agent for preventing copper migration, and the like. Can do.

  Next, the manufacturing method of the patterned resin film of the photosensitive resin composition containing (d) photo-acid generator among the resin compositions of this invention is demonstrated.

A photosensitive resin composition is applied onto a substrate. Examples of the material of the substrate in the present invention include all materials that can be provided with the electrode metal on the surface, such as metal, glass, semiconductor, metal oxide insulating film, silicon nitride, and polymer film. Preferably glass is used. The material of the glass is not particularly limited, but alkali zinc borosilicate glass, sodium borosilicate glass, soda lime glass, low alkali borosilicate glass, barium borosilicate glass, borosilicate glass, aluminosilicate glass, molten Quartz glass, synthetic quartz glass, and the like are used, and soda-lime glass with a barrier coating such as non-alkali glass or SiO ₂ that usually has few ions eluted from the glass is used. As the material of the polymer film, polyethylene terephthalate, polyethersulfone, and materials having a similar chemical structure can be used. Also, since the thickness should be sufficient to maintain the mechanical strength, if the material is inorganic, it is 0.1 mm or more, preferably 0.5 mm or more, and if the material is organic, 0.05 mm or more, Preferably it is 0.1 mm or more. The size of the substrate is not particularly limited, but a rectangular or square rectangular substrate having a side of 150 mm or more and a round substrate can provide a good coating film on a substrate having a diameter of 6 inches or more. Examples of the coating method include a slit coating method, a spin coating method, a spray coating method, a roll coating method, a bar coating method, and an ink jet method, and these methods may be used in combination. 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 100 μm.

  If necessary, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. For drying, a hot plate, an oven, an infrared ray, a vacuum chamber or the like is used.

In the case of using a hot plate, the object to be heated is held and heated directly on the plate or on a jig such as a proxy pin installed on the plate. As a material of the proxy pin, there is a metal material such as aluminum or stellenless, or a synthetic resin such as polyimide resin or Teflon (registered trademark), and any proxy pin may be used. The height of the proxy pin varies depending on the size of the substrate, the type of the resin layer to be heated, the purpose of heating, etc. For example, a resin layer coated on a 400 × 500 × 0.7 mm ³ glass substrate is used. When heating, the height of the proxy pin is preferably about 2 to 12 mm.

  The heating temperature varies depending on the type and purpose of the object to be heated, and it is preferably performed in the range of room temperature 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. .

  In order to form the pattern of the heat resistant resin from the photosensitive resin composition film, the exposed portion may be removed using a developer after the exposure. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, 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 development, a temperature of 130 ° C. to 400 ° C. is applied to convert to 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 linearly raising the temperature from room temperature to 230 ° C. over 1 hour can be used.

  The patterned resin film formed by the photosensitive resin composition in the present invention is used for a semiconductor passivation film, a surface protective film for a semiconductor element, an interlayer insulating film for a multilayer wiring for high-density mounting, an insulating layer for an organic electroluminescent element, etc. Is preferably used.

Next, a method for manufacturing an organic EL display device using TFTs will be described with reference to FIG. A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ is formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.

  Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded. The planarizing film 4 is formed on the insulating film 3 by applying the resin composition of the present invention on a substrate (spin, slit, spray, dip, etc.) and pre-baking with a hot plate or oven. Next, exposure is performed by setting a reticle having a desired pattern cut in an exposure machine (a stepper or aligner is preferably used). Thereafter, heat treatment is performed at a temperature of 200 ° C. to 350 ° C.

  A bottom emission type organic EL element is formed on the obtained planarizing film 4. First, a lower electrode made of ITO is formed on the planarizing film 4 by being connected to the wiring 2 through the contact hole 7. Thereafter, the lower electrode is formed into a desired pattern by etching using a resist. This lower electrode corresponds to the anode of the organic EL element.

  Next, an insulating layer having a shape covering the periphery of the lower electrode is formed. The resin composition of the present invention was used for the insulating layer. By providing this insulating layer, it is possible to prevent a short circuit between the lower electrode and the upper electrode formed in the subsequent process. Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, an upper electrode made of Al, Mg / Ag, Au or the like is formed on the entire surface above the substrate.

  As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element is obtained. Light emission is obtained by applying a voltage through a drive circuit.

  Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples.

<Preparation of resin composition film>
A resin composition is applied onto an ITO substrate of 100 mm × 100 mm × 0.7 mm so that the film thickness after pre-baking is 3 μm, and then a hot plate (a coating and developing apparatus Mark-7 manufactured by Tokyo Electron Co., Ltd.) is used. A resin composition film was obtained by pre-baking at 120 ° C. for 3 minutes.

<Measuring method of film thickness>
A lambda ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. was used, and the film after pre-baking and development was measured at a refractive index of 1.63, and the cured film was measured at a refractive index of 1.65.

<Preparation of cure film>
The resin composition film prepared by the above method was heated from room temperature to 230 ° C. in 20 minutes using an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd. under a nitrogen stream (oxygen concentration of 100 ppm or less), Heat treatment was performed at 230 ° C. for 30 minutes to prepare a cured film.

<Chemical resistance test>
The cured film produced by the above method was immersed in a stripping solution 106 manufactured by Tokyo Ohka Kogyo Co., Ltd. at 70 ° C. for 10 minutes. About the cured film after a process, the presence or absence of a crack was evaluated under 20 times optical microscope. In addition, the film thickness before and after the treatment was measured to determine the amount of film reduction.

<Adhesion test>
The adhesion to the substrate was evaluated by a cross-cut tape test method. That is, cuts reaching the ITO substrate through the resin composition film produced by the above method are made in a grid pattern (gap spacing 2 mm), and a cellophane adhesive tape (JIS-Z-1522) is pasted on the grid pattern. The adhesion state of the resin composition film after peeling was visually observed. At this time, as an acceleration test, the resin composition film was exposed to conditions of 120 ° C., 100% RH and 2 atm for 100 hours and 200 hours to evaluate the adhesion state. In the test results, the ratio of the squares adhered to the substrate without peeling was described in 10 stages. That is, “0” was assigned when all the cells were adhered and “10” when all defects were peeled off.

<Measurement of elongation at break>
Evaluation was performed according to JIS-K-7113 (1995). In other words, the resin composition film prepared by the above method on a 6-inch silicon wafer (manufactured by Shin-Etsu Chemical Co., Ltd., Miller index <100>, dummy) is applied to hydrofluoric acid (manufactured by Wako Pure Chemical Industries, reagent special grade). After being immersed for 7 minutes, it was slowly peeled off from the edge of the wafer to obtain a resin composition film. The obtained film was cut into a 90 mm × 5 mm strip to obtain a measurement sample, which was evaluated using a tensile tester “Tensilon” manufactured by A & D. Measurement conditions are measurement temperature 23 ° C., measurement humidity 45.0% RH, tensile mode, initial sample length 50.00 mm, load full scale 24.5 N, crosshead speed 50.00 mm / min, break detection sensitivity 1.0%. It was.

Synthesis Example 1 Synthesis of hydroxyl-containing acid anhydride (A) 18.3 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF, manufactured by Central Glass Co., Ltd.) under a dry nitrogen stream 0.05 mol) and 34.2 g (0.3 mol) of allyl glycidyl ether were dissolved in 100 g of gamma butyrolactone and cooled to -15 ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of gamma butyrolactone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated with a rotary evaporator and charged into 1 liter of toluene to obtain a hydroxyl group-containing acid anhydride (A) represented by the following formula.

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (B) 18.3 g (0.05 mol) of BAHF was dissolved in 100 ml of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 ml of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the obtained solid was put in a 300 ml stainless steel autoclave, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, filtration was performed to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound (B) represented by the following formula. The resulting solid was used for the reaction.

Synthesis Example 3 Synthesis of Hydroxyl-Containing Diamine Compound (C) 15.4 g (0.1 mol) of 2-amino-4-nitrophenol was dissolved in 50 ml of acetone and 30 g (0.34 mol) of propylene oxide, and the temperature was reduced to −15 ° C. Cooled down. A solution prepared by dissolving 17.8 g (0.055 mol) of 2,2-bis (4-benzoyl chloride) propane in 60 ml of acetone was gradually added dropwise thereto. After completion of dropping, the reaction was carried out at -15 ° C for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration.

  This precipitate was dissolved in 200 ml of γ-butyrolactone, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon filled with hydrogen gas was attached thereto, and stirring was continued until the balloon of hydrogen gas did not contract any further at room temperature, and further stirred for 2 hours with the balloon of hydrogen gas attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to half by a rotary evaporator. Ethanol was added thereto and recrystallization was performed to obtain a hydroxyl group-containing diamine compound (C) crystal represented by the following formula.

Synthesis Example 4 Synthesis of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di n-butyl ester dichloride solution (D) 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride under a dry nitrogen stream 24.82 g (0.08 mol) of the product and 59.3 g (0.8 mol) of n-butyl alcohol were stirred and reacted at 95 ° C. for 6 hours. Excess n-butyl alcohol was distilled off under reduced pressure to obtain 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester. Next, 95.17 g (0.8 mol) of thionyl chloride and 70 g of tetrahydrofuran (THF) were added and reacted at 40 ° C. for 3 hours. Subsequently, 200 g of N-methylpyrrolidone was added, excess thionyl chloride and THF were removed under reduced pressure, and 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid di-n-butyl ester dichloride solution (D) 239 0.6 g (0.08 mol) was obtained.

Synthesis Example 5 Synthesis of quinonediazide compound (E) Under a dry nitrogen stream, BisP-RS (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 16.10 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 26.86 g (0.1 mol, NAC-5, manufactured by Toyo Gosei Co., Ltd.) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration 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 (E) represented by the following formula.

Synthesis Example 6 Synthesis of quinonediazide compound (F) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and NAC-5 26.86 g (0. 10 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was used, and in the same manner as in Synthesis Example 5, on average, two of Q were converted to 5-naphthoquinonediazide sulfonic acid ester, The quinonediazide compound (F) represented by these was obtained.

Synthesis Example 7 Synthesis of quinonediazide compound (G) Under a nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and NAC-5 13.43 g (0.05) Mol), 13.43 g (0.05 mol, NAC-4, manufactured by Toyo Gosei Co., Ltd.) of 4-naphthoquinonediazide sulfonyl chloride was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane was used, and in the same manner as in Synthesis Example 5, one of Q on average became 5-naphthoquinonediazide sulfonic acid ester, and one on average A quinonediazide compound (G) represented by the following formula, which was 4-naphthoquinonediazidesulfonic acid ester, was obtained.

Synthesis Example 8 Synthesis of Thermally Crosslinkable Compound (H) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 122.4 g (0.4 mol) and sodium hydroxide 80 g (2.0 mol) in pure water It was dissolved in a solution dissolved in 530 g. After complete dissolution, 686 g of 36-38% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Thereafter, stirring was continued at 20 ° C. to 25 ° C. for 17 hours. This was neutralized with 98 g of sulfuric acid and 552 g of water and allowed to stand for 2 days.

  Needle-like white crystals formed in the solution after standing were collected by filtration and washed with 100 mL of water. This crystal was vacuum-dried at 50 ° C. for 48 hours to obtain a thermally crosslinkable compound (H) represented by the following formula. This was analyzed by Shimadzu Corporation high performance liquid chromatography using ODS in the column and acetonitrile / water = 70: 30 as the developing solvent at 254 nm. The starting material was completely disappeared and the purity was 88%. I found out that Furthermore, when analyzed by NMR (GX-270 manufactured by JEOL Ltd.) using DMSO-d6 as a heavy solvent, it was found to be TrimethylP-HAP that was hexamethylolated.

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

  Other thermally crosslinkable compounds used in Examples and Comparative Examples are shown below.

Synthesis Example 9 Synthesis of Adhesion Improving Agent Solution (I) Under a dry nitrogen stream, 7.67 g (0.031 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was dissolved in 75 g of γ-butyrolactone, While stirring at room temperature, 10 g (0.056 mol) of methyl-5-norbornene-2,3-dicarboxylic acid anhydride was gradually added. The resulting white salt was stirred until dissolved. Then, it stirred at 115-125 degreeC for 2 hours, and obtained the solution (I) of the adhesive improvement agent represented by (c1) general formula (6) with a solid content concentration of 19.1%.

Synthesis Example 10 Synthesis of Adhesion Improving Agent Solution (J) Under a stream of dry nitrogen, 8.96 g (0.036 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was dissolved in 75 g of γ-butyrolactone, While stirring at room temperature, 10 g (0.066 mol) of 1,2,3,6-tetrahydrophthalic dianhydride was gradually added. The resulting white salt was stirred until dissolved. Then, it stirred at 115-125 degreeC for 2 hours, and obtained the solution (J) of the adhesive improvement agent represented by (c1) general formula (6) of 20.2% of solid content concentration.

Synthesis Example 11 Synthesis of Adhesion Improving Agent Solution (K) Under a stream of dry nitrogen, 8.96 g (0.033 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane was dissolved in 75 g of γ-butyrolactone, While stirring at room temperature, 10 g (0.061 mol) of 5-norbornene-2,3-dicarboxylic dianhydride was gradually added. The resulting white salt was stirred until dissolved. Then, it stirred at 115-125 degreeC for 2 hours, and obtained the solution (K) of the adhesive improvement agent represented by (c1) general formula (6) of solid content concentration 19.6%.

Synthesis Example 12 Synthesis of Adhesion Improving Agent Solution (L) 6.16 g (0.03 mol) of 1,1,1-trimethyl-3-aminopropyl-tetramethyldisiloxane was dissolved in 75 g of γ-butyrolactone under a dry nitrogen stream. While stirring at room temperature, 10 g (0.061 mol) of 5-norbornene-2,3-dicarboxylic dianhydride was gradually added. The resulting white salt was stirred until dissolved. Then, it stirred at 115-125 degreeC for 2 hours, and obtained the solution (L) of the adhesive improvement agent represented by (c1) general formula (5) with a solid content concentration of 19.6%.

  Moreover, the other (c) component used for each Example and the comparative example was shown below.

Synthesis Example 13 Synthesis of Polyimide Resin Precursor (M) Under a dry nitrogen stream, hydroxyl group-containing diamine compound (B) 9.67 (0.016 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 0 .50 g (0.002 mol) and 0.94 g (0.004 mol) of 4-ethynylaniline as an end-capping agent were dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added thereto together with 14 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, a solution prepared by diluting 4.77 g (0.04 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 70 ° C. for 60 hours to obtain a polyimide resin precursor (M).

Synthesis Example 14 Synthesis of Polyimide Resin Precursor (N) Hydroxyl-containing diamine compound (B) 9.67 (0.016 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 0 in a dry nitrogen stream .50 g (0.002 mol) and 3-aminophenol 0.44 g (0.004 mol) as an end-capping agent were dissolved in NMP 50 g. 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was added thereto together with 14 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 70 ° C. for 60 hours to obtain a polyimide resin precursor (N).

Synthesis Example 15 Synthesis of Polyimide Resin Precursor (O) 6.2 g (0.02 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was dissolved in 50 g of NMP under a dry nitrogen stream. 3-aminophenol 1.09g (0.01 mol) was added here as terminal blocker, and it was made to react at 40 degreeC for 1 hour. Subsequently, 6.04 g (0.01 mol) of the hydroxyl group-containing diamine compound (B) and 1.0 g (0.005 mol) of 4,4′-diaminodiphenyl ether were added with 10 g of NMP, and the mixture was further reacted at 40 ° C. for 2 hours. Thereafter, a solution obtained by diluting 5.96 g (0.05 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 70 ° C. for 60 hours to obtain a polyimide resin precursor (O).

Synthesis Example 16 Synthesis of Polyimide Resin Precursor (P) Under a dry nitrogen stream, 12.01 g (0.02 mol) of a hydroxyl group-containing acid anhydride (A) was dissolved in 100 g of NMP. To this, 9.68 g (0.016 mol) of the hydroxyl group-containing diamine compound (B) was added together with 25 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. Next, 0.94 g (0.008 mol) of 4-ethynylaniline was added and reacted at 50 ° C. for 2 hours. Thereafter, a solution prepared by diluting 4.77 g (0.04 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 40 hours to obtain a polyimide resin precursor (P).

Synthesis Example 17 Synthesis of Polyimide Resin Precursor (Q) Under a dry nitrogen stream, 9.61 g (0.016 mol) of a hydroxyl group-containing acid anhydride (A) was dissolved in 100 g of NMP. To this was added 12 g (0.02 mol) of a hydroxyl group-containing diamine compound (C) together with 25 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. Next, 0.78 g (0.008 mol) of maleic anhydride was added as a terminal blocking agent and reacted at 50 ° C. for 2 hours. Thereafter, a solution prepared by diluting 4.77 g (0.04 mol) of N, N-dimethylformamide dimethylacetal with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 1 liter of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with an 80 ° C. vacuum dryer for 40 hours to obtain a polyimide resin precursor (Q).

Synthesis Example 18 Synthesis of polybenzoxazole precursor (R) In a dry nitrogen stream, 18.5 g (0.10 mol) of 4-carboxybenzoic acid chloride and 13.5 g (0.10 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.

  Under a dry nitrogen stream, BAHF 18.68 g (0.051 mol), 1,3-bis (3-aminopropyl) tetramethyldisiloxane 1.86 g (0.0075 mol), obtained as above as end-capping agent The active ester compound (9.62 g (0.034 mol) and 11.93 g (0.151 mol) of pyridine were dissolved in 50 g of NMP. Here, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid din was added. -239.6 g (0.08 mol) of butyl ester dichloride solution (D) was added dropwise so that the reaction system did not exceed 10 ° C. After the addition, the mixture was stirred for 6 hours at room temperature. The polymer solid precipitate was collected by filtration, and the polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours to obtain a polybenzoxazole precursor (R).

Synthesis Example 19 Synthesis of Polyimide Resin Precursor (S) In dry nitrogen stream, 15.1 g (0.025 mol) of hydroxyl group-containing diamine (B) was dissolved in 50 g of NMP in Synthesis Example 2. 17.5 g (0.025 mol) of the hydroxy group-containing acid anhydride (A) obtained in Synthesis Example 1 was added thereto together with 30 g of pyridine, and reacted at 60 ° C. for 6 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain a polyimide resin precursor (S).

Synthesis Example 20 Synthesis of polyimide resin precursor (T) Under a dry nitrogen stream, 17 g (0.045 mol) of hydroxyl group-containing diamine compound (C) obtained in Synthesis Example 3 and 1,3-bis (3-aminopropyl) ) 1.24 g (0.005 mol) of tetramethyldisiloxane was dissolved in 50 g of NMP. To this, 12.4 g (0.04 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic anhydride was added together with 21 g of NMP, and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. . To this, 0.98 g (0.01 mol) of maleic anhydride was added, stirred for 2 hours at 50 ° C., and then a solution obtained by diluting 14.7 g (0.1 mol) of N, N-dimethylformamide diethyl acetal with 5 g of NMP was added. It was added dropwise over a period of minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain a polyimide resin precursor (T).

Synthesis Example 21 Synthesis of polyimide resin (U) Under a nitrogen stream, 32.9 g (0.09 mol) of BAHF was dissolved in 500 g of NMP. Here, 31.0 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (0.1 mol, manufactured by Manac Co., Ltd.) was added together with 50 g of NMP, and the mixture was stirred at 30 ° C. for 2 hours. Thereafter, 2.18 g of 3-aminophenol (0.02 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and stirring was continued at 40 ° C. for 2 hours. Furthermore, 5 g of pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) was diluted with 30 g of toluene (manufactured by Tokyo Chemical Industry Co., Ltd.), added to the solution, and a cooling tube was attached to remove the water azeotropically with toluene. The reaction was carried out at 120 ° C. for 2 hours and further at 180 ° C. for 2 hours. When the temperature of this solution dropped to room temperature, the solution was poured into 3 L of water to obtain a white solid. 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 a polyimide resin (U).

Example 1
10 g of polyimide resin precursor (M), 8.0 g (0.025 mol) of thermally crosslinkable compound Nicalac MX-270, 1.1 g (0.004 mol) of adhesion improver TAIC, 20 g of ethyl lactate (Musashino Chemical Laboratory ( EL) and 20 g of gamma butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd., GBL) were added to obtain a uniform solution to obtain a resin composition. When a chemical resistance test was performed using this resin composition, no cracks were observed, and the film reduction amount was as good as 0.1 μm. Furthermore, an adhesion test was conducted. As a result, “0” in which all the cells were adhered under the 100-hour exposure condition was good.

Examples 2-14
A resin composition was prepared in the same manner as in Example 1 except that the resin (a), the thermally crosslinkable compound (b), the adhesion improver (c), and the photoacid generator (d) were as shown in Tables 1 and 2. Obtained. Table 3 shows the results of a chemical resistance test and an adhesion test performed on the obtained resin composition.

Comparative Examples 1-13
A resin composition was obtained in the same manner as in Example 1 except that the resin (a), the thermally crosslinkable compound (b), the adhesion improver (c), and the photoacid generator (d) were as shown in Table 2. . Table 3 shows the results of a chemical resistance test and an adhesion test performed on the obtained resin composition.

Example 15
The resin composition obtained in Example 5 was subjected to UV exposure through a photomask having a shape covering the edge of the first electrode. After the exposure, development was performed by dissolving only the exposed portion with a 2.38% TMAH aqueous solution, followed by rinsing with pure water. Subsequently, the photosensitive polyimide resin film was cured by heating at 230 ° C. for 30 minutes under a nitrogen atmosphere in a clean oven to obtain a polyimide insulating layer. The thickness of the insulating layer was about 1 μm. The insulating layer is formed so as to cover the edge of the first electrode, and an opening having a width of 70 μm and a length of 250 μm is provided in the central portion so that the first electrode is exposed. The insulating layer had a gentle forward taper as shown in FIG. The taper angle was 20 °.

  Next, on the substrate on which the insulating layer was formed, a hole transport layer, a light emitting layer, and an aluminum layer serving as a second electrode were sequentially formed by a vacuum vapor deposition method using a resistance wire heating method. The hole transport layer was deposited on the entire substrate effective area. The light emitting layer was formed by patterning on the stripe-shaped first electrode using a shadow mask. The second electrode was formed by patterning in a stripe shape so as to be orthogonal to the first electrode.

  The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin. In this way, a simple matrix type color organic electroluminescent device 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.

Example 16
The organic EL display device shown in FIG. 1 was produced by the following procedure. A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si ₃ N ₄ was formed so as to cover the TFT 1. Next, a contact hole (not shown here) was formed in the insulating film 3, and then a wiring 2 (height 1 μm) connected to the TFT 1 through the contact hole was formed on the insulating film 3. Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the resin composition obtained in Example 7 on a substrate, and on a hot plate (coating and developing apparatus Mark-7 manufactured by Tokyo Electron Ltd.). And pre-baking (120 ° C. × 2 minutes). Next, a reticle from which a desired pattern was cut was set in an exposure machine (CGA i-line stepper DSW-8000), and exposure was performed at an exposure intensity of 365 nm of 150 mJ / cm ² . Thereafter, heat treatment was performed at 250 ° C. for 30 minutes under a nitrogen stream (oxygen concentration of 100 ppm or less).

  A bottom emission type organic EL element was formed on the obtained planarizing film 4. First, a lower electrode made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, the lower electrode was formed into a desired pattern by etching using a resist.

  Next, an insulating layer having a shape covering the periphery of the lower electrode was formed. The resin composition obtained in Example 7 was used for the insulating layer. Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, an upper electrode made of Al was formed on the entire surface above the substrate.

  As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When voltage was applied through the drive circuit, good light emission was exhibited.

Diagram showing the boundary of the insulating layer

Explanation of symbols

1 TFT
2 Wiring 3 Insulating film 4 Planarizing film 5 ITO electrode 6 Glass substrate 7 Contact hole

Claims (7)

(A) a resin mainly composed of a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2), (b) (b1) a phenolic hydroxyl group and the general formula (3) And / or (b2) a thermally crosslinkable compound having a urea organic group represented by the general formula (4), and (c) a complex containing a nitrogen atom or a sulfur atom. A resin composition comprising an adhesion improver having a ring structure.

(R ¹ and R ² represent a divalent to hexavalent organic group having 2 to 30 carbon atoms. A may be the same or different, and OR ³ , SO ₃ R ³ , CONR ³ R ⁴ , COOR ³ , SO ₂ selected from NR ³ R ^4. R ³ and R ⁴ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, m and p represent an integer of 0 to 4, provided that m + p> 0 .)

(R ⁵ represents a C 4-30 tetravalent organic group. R ⁶ represents a C 2-30 bivalent organic group. E may be the same or different, OR ⁷ , SO ₃ R ⁷ , CONR ⁷ R ⁸ , COOR ⁷ , SO ₂ NR ⁷ R ^8, R ⁷ and R ⁸ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. And Z is selected from CO, N, NH, O and S, and Y represents C or N. The bond between Z and Y is a single bond or a double bond, and r and s are integers of 0 to 4. Q represents an integer of 0 to 2, provided that r + s> 0.)

(R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.)

(R ¹⁰ may be the same or different and represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.) The resin composition according to claim 1, wherein the adhesion improver (c) is selected from the compounds represented by (c1) general formula (5) or (6).

(Wherein R ¹¹ , R ¹² , R ¹⁷ and R ¹⁸ may be the same or different and are each a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group, a nitro group, an amino group, Represents a group selected from a carboxyl group, an ester group having 2 to 10 carbon atoms, and an alkoxyl group having 1 to 10 carbon atoms, wherein R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be the same or different; An organic group selected from an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, an alkenyl group, a phenyl group, a substituted phenyl group, and an alkoxyl group having 1 to 6 carbon atoms, and R ¹⁹ is a monovalent having 1 to 10 carbon atoms. Represents a group selected from a hydrocarbon group, a hydroxyl group, a nitro group, an amino group, a carboxyl group, an ester group having 2 to 10 carbon atoms, and an alkoxyl group having 1 to 10 carbon atoms, a and c are integers of 1 to 10; b is 0-1 (An integer of 0 and d represents an integer of 0 to 2.) The resin composition according to claim 1, wherein the (c) adhesion improving agent has a heterocyclic structure (c2) having at least three nitrogen atoms. The (c2) adhesion improver having a heterocyclic structure having at least three nitrogen atoms is selected from compounds represented by any one of the following general formulas (7) to (9). The resin composition as described.

(In the formula, R ²⁰ and R ²¹ may be the same or different, and are each an alkyl group having 1 to 10 carbon atoms, an alkenyl group, a phenyl group, a substituted phenyl group, a hydroxyl group, a nitro group, an amino group, a carboxyl group, Represents a group selected from an alkoxyl group having 1 to 10 carbon atoms, an epoxy group having 2 to 10 carbon atoms, and an ester group having 2 to 10 carbon atoms, and R ^{22 to} R ²⁷ may be the same or different; Hydrogen atom, alkyl group having 1 to 10 carbon atoms, alkenyl group, phenyl group, substituted phenyl group, hydroxyl group, nitro group, amino group and substituted amino group, carboxyl group, alkoxyl group having 1 to 10 carbon atoms, and 2 to 2 carbon atoms 10 epoxy group, an ester group having 2 to 10 carbon _{atoms, CH 3 - (CH 2)} g -CH = CH-O-, CH 2 = CH- (CH 2) selected from g -O- Integer .e is 0-4 represents a group, f is 0 or 1, g is an integer of 0-7.) The resin composition according to claim 1, further comprising (d) a photoacid generator. A method for producing a patterned resin film, comprising a step of applying the resin composition according to claim 5 to a substrate, a step of exposing with ultraviolet light, a step of developing using an alkaline aqueous solution, and a step of heat treatment. The organic electroluminescent element which has a patterned resin film obtained by the method of Claim 6.

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