JP2008039961A - Positive photosensitive resin composition and organic electroluminescence device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition having good adhesiveness during development and after heat treatment even in the case of a film thickness of ≤0.5 μm after heat treatment, and capable of forming a resin film having satisfactory breakdown voltage after heat treatment. <P>SOLUTION: The positive photosensitive resin composition comprises (a) a precursor of a heat resistant resin such as a polyimide or polybenzoxazole and/or a resin having a structural unit formed by ring closure thereof, (b) a quinonediazide compound, (c) a compound selected from the group consisting of an anthraquinone compound, an acenaphthene compound, an indole compound, a merocyanine compound and a styryl compound having an amino group and (d) a solvent, wherein the compound (c) has an absorption maximum wavelength in a wavelength range of 350 to <450 nm and no absorption maximum wavelength in a wavelength range of 450-700 nm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin composition. More specifically, the surface protective film of the semiconductor element, the interlayer insulating film, the insulating layer of the organic electroluminescence (hereinafter referred to as organic EL) element, the planarization film of the thin film transistor (hereinafter referred to as TFT) substrate, the circuit board The present invention relates to a resin composition suitable for uses such as a wiring protective insulating film, an on-chip microlens for a solid-state imaging device, a flattening film for various displays and solid-state imaging devices, and a solder resist for a circuit board.

  As an insulating layer of a conventional general organic EL element, a resin film having a thickness of about 1 μm in the case of a low molecular light emitting element and a thickness of 2 to 4 μm in the case of a polymer light emitting element has been used. As a material for forming such a resin film, a positive photosensitive resin composition such as photosensitive polyimide or photosensitive polybenzoxazole, which can be used as a permanent film by performing a heat treatment after pattern processing, is preferably used. I came.

  On the other hand, organic EL displays, which are attracting attention as next-generation flat panel displays, can be made thinner than liquid crystal displays and are expected to be applied to flexible substrates such as electronic paper in the future. An insulating layer of 5 μm or less has been demanded.

However, when a resin film made of a positive photosensitive resin composition having a thickness of 0.5 μm or less is exposed, the resin film is excessively exposed by reflected light from the substrate, or halation is caused by unevenness on the substrate surface. Therefore, there has been a problem that the pattern of the unexposed portion is peeled off from the substrate during development. So far, as a resin composition for preventing halation and forming a pattern with excellent dimensional stability, a positive photosensitive resin composition containing an oil-based dye and an alkali-soluble dye in a resist has been proposed (for example, Patent References 1-2). However, the resin film obtained from this photosensitive resin composition has a problem that it has low adhesion to the substrate after heat treatment. Moreover, since the edge breakdown voltage was low, it could not be used for the insulating layer of the organic EL element. On the other hand, resin compositions containing light stabilizers such as ultraviolet absorbers and radical trapping agents in polyimide, polybenzoxazole and their precursors have been proposed as resin compositions with improved light resistance (for example, (See Patent Document 3). However, even if these methods were used, the effect of preventing pattern peeling in a thin film having a thickness of 0.5 μm or less was insufficient. Furthermore, as a resin composition having a light-shielding property, a positive photosensitive resin composition containing a pigment as used in a black matrix of an organic EL element has been proposed (for example, see Patent Documents 4 to 6). . However, there has been a problem that the pigment particles reduce the adhesion between the resin composition and the substrate during development.
JP-A-62-295044 (Claims 1 and 2) JP-A-63-73240 (Claims 1, 2) JP-A-2005-139433 JP 2004-145320 A (Claim 1) JP 2005-266189 A (Claims 1 and 2) JP 2003-119181 A (Claim 1)

  As described above, a conventionally known method could not obtain a photosensitive resin composition having sufficient adhesion at a thickness of 0.5 μm or less that has recently been required. In view of the above problems, the present invention forms a resin film having good adhesion during development and after heat treatment and having good dielectric breakdown voltage after heat treatment even if the film thickness after heat treatment is 0.5 μm or less. An object of the present invention is to provide a positive photosensitive resin composition that can be used.

  (A) a resin having a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2), (b) a quinonediazide compound, (c) an anthraquinone compound, an acenaphthene compound, an indole compound, A compound selected from the group consisting of a merocyanine compound and a styryl compound represented by the following general formula (3), having an absorption maximum wavelength at a wavelength of 350 nm or more and less than 450 nm, and an absorption maximum wavelength at a wavelength of 450 nm or more and 700 nm or less A positive photosensitive resin composition, comprising: a non-reactive compound; and (d) a solvent.

(In the general formula (1), R ¹ and R ² represent a 2 to 6-valent organic group having 2 to 30 carbon atoms. Each A may be the same or different, and 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, and m and p are each 0 to 4 Represents an integer, where m + p> 0.)

(In General Formula (2), R ⁵ represents a C 4-30 tetravalent organic group. R ⁶ represents a C 2-30 bivalent organic group. Each E is the same. But it may be _{^{different, oR 7, SO 3 R 7}} , CONR 7 R 8, COOR 7, selected from SO 2 ^{NR 7 R 8} .R 7 and ^{R 8} is a hydrogen atom or a monovalent C1-10 X and Z are selected from CO, N, NH, O and S, and Y is C or N. The bond between Z and Y is a single bond or a double bond. q may be the same or different and each represents an integer of 0 to 2. r and s each represent an integer of 0 to 4, provided that r + s> 0.

(In General Formula (3), each R ⁹ may be the same or different and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ¹⁰ and R ¹¹ are each a hydrogen atom or 1 to 20 carbon atoms. R ¹² and R ¹³ represent a hydrogen atom, CN, SO ₃ R ¹⁴ , CONR ¹⁴ R ¹⁵ , COOR ¹⁴ , SO ₂ NR ¹⁴ R ¹⁵ , monovalent aromatic having 2 to 30 carbon atoms R ¹⁴ and R ¹⁵ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 4.)

  According to the present invention, even when the film thickness after heat treatment is 0.5 μm or less, the resin film having good adhesion at the time of development and after heat treatment and having a good breakdown voltage after heat treatment is formed. A positive-type photosensitive resin composition that can be obtained can be obtained.

  The positive photosensitive resin composition of the present invention comprises (a) a resin having a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2), (b) a quinonediazide compound, (C) a compound selected from the group consisting of an anthraquinone compound, an acenaphthene compound, an indole compound, a merocyanine compound and a styryl compound represented by the following general formula (3), having an absorption maximum wavelength at a wavelength of 350 nm to less than 450 nm, And a compound having no absorption maximum wavelength at a wavelength of 450 nm to 700 nm and (d) a solvent.

In the general formula (1), R ¹ and R ² represent a 2 to 6-valent organic group having 2 to 30 carbon atoms. Each 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 each represents an integer of 0 to 4. However, m + p> 0.

In general formula (2), 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. Each 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. Each q may be the same or different and represents an integer of 0 to 2. r and s each represent an integer of 0 to 4. However, r + s> 0.

In General Formula (3), each R ⁹ may be the same or different and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ¹⁰ and R ¹¹ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ¹² and R ¹³ are selected from a hydrogen atom, CN, SO ₃ R ¹⁴ , CONR ¹⁴ R ¹⁵ , COOR ¹⁴ , SO ₂ NR ¹⁴ R ¹⁵ , and a monovalent aromatic group having 2 to 30 carbon atoms. R ¹⁴ and R ¹⁵ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. n shows the integer of 0-4.

  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, 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). Examples of the resin having the structural unit represented by the general formula (2) include resins having a cyclic structure such as an imide ring, an oxazole ring, an imidazole ring, and a thiazole ring in the main chain structure. Specific examples include polyimide, polybenzoxazole, polybenzimidazole, and polybenzothiazole.

  The resin obtained by ring-closing the resin having the structural unit represented by the general formula (1) and the resin having the structural unit represented by the general formula (2) have high heat resistance and are adhesive even after heat treatment. Excellent. 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. The resin of component (a) in the present invention preferably has 10 to 100,000 structural units represented by general formula (1) or (2).

  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 such as acid or base. In the present invention, not only polyamic acid 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, which is one of the polybenzoxazole precursors obtained by reacting bisaminophenol compounds with dicarboxylic acids, is subjected to dehydration and cyclization by heating or chemical treatment of 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 of 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 of phosphoric anhydride, base, carbodiimide compounds, etc. Thus, polybenzothiazole can be obtained.

R ^{1 in the} general formula (1) represents a divalent to hexavalent organic group having 2 to 30 carbon atoms. Examples of the acid component constituting —CO—R ¹ (A) _m —CO— of 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′-ben Phenonetetracarboxylic 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, 2,3 , 5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid and other aromatic tetracarboxylic acids, butanetetracar Examples thereof include aliphatic tetracarboxylic acids such as boronic acid and 1,2,3,4-cyclopentanetetracarboxylic 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 A group in 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 or an active ester.

R ^{2 in the} general formula (1) represents a divalent to hexavalent organic group having 2 to 30 carbon atoms. 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 Hydroxyl group-containing diamines such as -4-hydroxy) biphenyl and bis (3-amino-4-hydroxyphenyl) fluorene, carboxyl groups such as 3,5-diaminobenzoic acid and 3-carboxy-4,4′-diaminodiphenyl ether Containing sulfonic acid such as diamine, 3-sulfonic acid-4,4′-diaminodiphenyl ether 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-naphthalene Diamine, 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- Minophenoxy) 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, 2,2′-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 hydrocarbon groups having 1 to 20 carbon atoms such as methyl group and ethyl group, fluoroalkyl groups having 1 to 10 carbon atoms such as trifluoromethyl group, F, Cl, Br, I and the like. It may be substituted with a group. 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. Particularly preferred as 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. R ^{5 in the} general formula (2) represents a tetravalent to octavalent organic group having 2 to 30 carbon atoms, and preferably has 1 to 2 aromatic rings. More preferable as the structure of R ^{5 in} the general formula (2) is the following structure, or a part of them is an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group, a cyano group. Examples include a structure in which 1 to 4 groups are substituted with a group, a fluorine atom, or a chlorine atom.

R ^{6 in the} general formula (2) represents a divalent to hexavalent organic group having 2 to 30 carbon atoms, and preferably has 1 to 4 aromatic rings. What is preferable as the structure of R ^6- (E) _s of the general formula (2) is a structure shown below, or a part of these: 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.

E in the general formula (2) 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 hydrogen or a monovalent hydrocarbon group having 1 to 20 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 the integer of 0-2.

  Further, by sealing the ends of these resins with monoamine, the dissolution rate of the resins in the alkaline aqueous solution can be adjusted to a preferred range.

  Examples of such monoamines include 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol having a phenolic hydroxyl group such as aniline, naphthylamine, and aminopyridine. 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-aminonaphthalene, 1-amino-2-hydroxynaphthalene, etc., having a carboxyl group, 1-carboxy-8- Aminonaphthalene, 1-carboxy-7-aminonaphthalene, 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-amino Naphthalene, 2-carboxy-3-amino Phthalene, 1-amino-2-carboxynaphthalene, 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, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, etc. And 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-amino having a thiol group Naphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-amino Nonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 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-aminothio Phenol, 3-aminothiophenol, 4-aminothiophenol and the like can be mentioned.

  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 anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, -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 − Ruboxynaphthalene, 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 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-dica Boxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxy A monoacid chloride compound in which only one carboxyl group of dicarboxylic acids such as naphthalene and 2,7-dicarboxynaphthalene is acid chloride, or a monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2 An active ester compound obtained by reaction with 1,3-dicarboximide, and the like.

  Among these, phthalic anhydride, maleic anhydride, nadic anhydride, 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-carboxy Monocarboxylic acid compounds such as naphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and the like, and monoacid chloride compounds in which these carboxyl groups are acid chloride, terephthalic , One carboxyl of dicarboxylic acids such as phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene Preferred are monoacid chloride compounds in which only the group is acid chloride, or active ester compounds obtained by reaction of monoacid chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide. used. 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 described above is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, relative to the resin of component (a). And preferably 60 mol% or less, particularly preferably 50 mol% or less. 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 into which a terminal blocking agent has been introduced 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. Thus, the end sealant can be easily detected. Apart from this, it is possible to directly detect the resin into which the end-capping agent has been introduced by pyrolysis gas chromatography (PGC), infrared spectrum and ¹³ C NMR spectrum measurement.

  In addition, as an acid dianhydride component, dimethylsilanediphthalic acid, 1,3-bis (phthalate) is used for the purpose of improving the adhesion to the substrate and enhancing the resistance to oxygen plasma used for cleaning and UV ozone treatment. Acid) copolymerize silicon atom-containing tetracarboxylic dianhydride such as tetramethyldisiloxane, 1-30 mol% of total acid dianhydride component, or 1,3-bis (3-aminopropyl) as diamine component ) Silicon atom-containing diamines such as tetramethyldisiloxane and 1,3-bis (4-anilino) tetramethyldisiloxane can be copolymerized in an amount of 1 to 30 mol% of the total diamine components.

  The positive photosensitive resin composition of the present invention contains a quinonediazide compound as the component (b). 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 is bonded to a polyamino compound in a sulfonamide, and a sulfonic acid of quinonediazide is bonded to a polyhydroxypolyamino compound in an ester bond and / or sulfonamide. Examples include those that are combined. 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. By using a quinonediazide compound substituted by 50 mol% or more, the affinity of the quinonediazide compound with respect to the aqueous alkaline solution is reduced, and the solubility of the resin composition in the unexposed area in the aqueous alkaline solution is greatly reduced. The sulfonyl group is changed to indenecarboxylic acid, and a large dissolution rate of the resin composition of the exposed portion in the aqueous alkali solution can be obtained. As a result, the dissolution rate ratio of the exposed portion and the unexposed portion of the composition is increased to be high. Patterns can be obtained with resolution. 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. Two or more quinonediazide compounds can also be used as component (b).

  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, the sulfonic acid ester of quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinonediazide sulfonyl ester compound has absorption extending to the g-line region of a mercury lamp, and is suitable for g-line exposure and full-wavelength 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.

  In addition, the molecular weight of the quinonediazide compound is preferably 300 or more, more preferably 350 or more, preferably 3000 or less, more preferably 1500 or less, from the viewpoint of heat resistance, mechanical properties, and adhesiveness of the film obtained by heat treatment. is there. The content of the quinonediazide compound is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and preferably 50 parts by weight or less, more preferably 40 parts by weight with respect to 100 parts by weight of the component (a) resin. Less than parts by weight. If it is 1-50 weight part, photosensitivity can be provided, maintaining the heat resistance of the film | membrane after heat processing, chemical resistance, and a mechanical characteristic.

  The quinonediazide compound used in the present invention is synthesized, for example, by a method of reacting 5-naphthoquinonediazidesulfonyl chloride with 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.

  Further, if necessary, for the purpose of supplementing the alkali developability of the photosensitive resin composition, the polyhydroxy compound may be used as it is without being esterified with naphthoquinonediazide. When this polyhydroxy compound is contained, the photosensitive resin composition hardly dissolves in the alkali developer before exposure, and easily dissolves in the alkali developer upon exposure, so that the film loss due to development is small and development in a short time is possible. Becomes easier. In this case, the content of the polyhydroxy compound is preferably 1 part by weight or more, more preferably 3 parts by weight or more, preferably 50 parts by weight or less, more preferably 100 parts by weight of the resin of component (a). Is 40 parts by weight or less. If it is 1-40 weight part, it can raise sensitivity, suppressing the film loss of an unexposed part.

  The positive photosensitive resin composition of the present invention is a compound selected from the group consisting of an anthraquinone compound, an acenaphthene compound, an indole compound, a merocyanine compound and a styryl compound represented by the following general formula (3) as the component (c). And a compound having an absorption maximum wavelength at a wavelength of 350 nm to less than 450 nm and having no absorption maximum wavelength at a wavelength of 450 nm to 700 nm.

In General Formula (3), each R ⁹ may be the same or different and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ¹⁰ and R ¹¹ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ¹² and R ¹³ are selected from a hydrogen atom, CN, SO ₃ R ¹⁴ , CONR ¹⁴ R ¹⁵ , COOR ¹⁴ , SO ₂ NR ¹⁴ R ¹⁵ , and a monovalent aromatic group having 2 to 30 carbon atoms. R ¹⁴ and R ¹⁵ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. n shows the integer of 0-4.

  Component (c) has an absorption maximum wavelength at a wavelength of 350 nm or more and less than 450 nm, and when exposed to i-ray (365 nm), h-ray (405 nm), and g-ray (436 nm) of a mercury lamp, which is a general ultraviolet ray, Excessive exposure and halation due to the reflected light from the light can be prevented, so that the adhesion of the unexposed part during development can be improved. Further, by not having an absorption maximum wavelength at a wavelength of 450 nm or more and 700 nm or less, light absorption can be selectively performed in a wavelength range of 350 or more and less than 450 nm. The absorption maximum wavelength of the component (c) can be determined by dissolving in gamma-butyrolactone and measuring.

  Furthermore, component (c) is a compound selected from the group consisting of anthraquinone compounds, acenaphthene compounds, indole compounds, merocyanine compounds, and styryl compounds represented by the general formula (3) among the compounds having the absorption characteristics as described above. is there. By using such a compound, the effect of preventing excessive exposure and halation is further increased, and the adhesion of the unexposed part during development can be further increased.

  Component (c) is preferably soluble in an organic solvent. In the present invention, soluble in an organic solvent means N-methyl-2-pyrrolidone, gamma butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, 30 weights at 23 ° C. in one or more solvents selected from acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, 3-methyl-3-methoxybutanol, ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate, toluene, xylene % Or more. If it is soluble in an organic solvent, the component (c) is not aggregated in the photosensitive resin composition, the adhesion during development is further improved, and the dielectric breakdown voltage of the film after heat treatment is improved.

  Specific examples of such component (c) include 1-hydroxyanthraquinone, 2-hydroxyanthraquinone, 3-hydroxyanthraquinone, 1-hydroxy-2-methoxyanthraquinone, 1,2-dihydroxyanthraquinone, 1,3-dihydroxyanthraquinone. 1,4-dihydroxyanthraquinone, 1,5-dihydroxyanthraquinone, 1,8-dihydroxyanthraquinone, 1,3-dihydroxy-3-methylanthraquinone, 1,5-dihydroxy-3-methylanthraquinone, 1,6-dihydroxy- 3-methylanthraquinone, 1,7-dihydroxy-3-methylanthraquinone, 1,8-dihydroxy-3-methylanthraquinone, 1,8-dihydroxy-2-methylanthraquinone, 1,3-dihydroxy-2- Toxianthraquinone, 2,4-dihydroxy-1-methoxyanthraquinone, 2,5-dihydroxy-1-methoxyanthraquinone, 2,8-dihydroxy-1-methoxyanthraquinone, 1,8-dihydroxy-3-methoxy-6-methylanthraquinone 1,2,3-trihydroxyanthraquinone, 1,3,5-trihydroxyanthraquinone, 2-aminoanthraquinone, 2-amino-1-nitroanthraquinone, 2,6-diaminoanthraquinone, 1-methoxyanthraquinone, 2-methoxy Anthraquinone, 1,8-dimethoxyanthraquinone, 1-acetylaminoanthraquinone, 2-acetylaminoanthraquinone (above anthraquinone compound), 5-nitroacenaphthene (acenaphthene compound), BONASORB U A-3912 (trade name, manufactured by Orient Chemical Co., Ltd.), 4- (1H-indole) -3-ylmethylene-2-phenyloxazolin-5-one, 3- (β-cyano-β-benzoylvinyl) indole ( Indole compound), 1,3-dimethyl-5- [2- (3-methyloxazolidine-2-ylidene) ethylidene] pyrimidine-2,4,6-trione, 1,3-dimethyl-5- [2- ( 1-methylpyrrolidine-2-ylidene) ethylidene] pyrimidine-2,4,6-trione, 1,3-dimethyl-5- [2- (3-methylthiazolidine-2-ylidene) ethylidene] pyrimidine-2,4 6-trione, 3-ethyl-5- [2- (3-methyloxazolidine-2-ylidene) ethylidene] -2-thioxooxazolidin-4-one, 3-ethyl Til-5- [2- (1-methylpyrrolidin-2-ylidene) ethylidene] -2-thioxooxazolidin-4-one (above merocyanine compound), 2- (4-dimethylaminostyryl) benzoxazole, 2- [ 2- [4- (dimethylamino) phenyl] ethenyl] naphtho [1,2-d] thiazole, 2- (4-dimethylaminostyryl) benzothiazole, 4- (4-dimethylaminostyryl) quinoline, 4- (β -Nitrovinyl) -N, N-dimethylaniline, 4- (β-carbomethoxy-β-cyanovinyl) -N, N-dimethylaniline, 2- (β, β-dicyanovinyl) aniline, 4- (β, β- Dicyanovinyl) aniline, 4- (β, β-dicyanovinyl) -3-methyl-N, N-dimethylaniline (hereinafter referred to as styryl compound), and the like. It is, but is not limited thereto. Among them, 1-methoxyanthraquinone, 2-methoxyanthraquinone, 1,8-dimethoxyanthraquinone, 1-acetylaminoanthraquinone, 2-acetylaminoanthraquinone, 5-nitroacenaphthene, BONASORB UA-3912, 1,3-dimethyl- 5- [2- (3-Methyloxazolidine-2-ylidene) ethylidene] pyrimidine-2,4,6-trione, 1,3-dimethyl-5- [2- (1-methylpyrrolidin-2-ylidene) ethylidene] Pyrimidine-2,4,6-trione, 2- (4-dimethylaminostyryl) benzoxazole, 2- [2- [4- (dimethylamino) phenyl] ethenyl] naphtho [1,2-d] thiazole, 2- (4-Dimethylaminostyryl) benzothiazole, 4- (4-dimethyl) Minosuchiriru) quinoline are particularly preferred.

  The content of the component (c) is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin of the component (a). If it is 0.5 part by weight or more, higher adhesiveness can be obtained. When the amount is 10 parts by weight or less, exposure sensitivity can be maintained.

  The positive photosensitive resin composition of the present invention contains a solvent as component (d). Examples of the solvent used in the present invention include polar aprotic solvents such as N-methyl-2-pyrrolidone, gamma butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, and propylene. Ethers such as glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone and diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene Can be used alone or in combination of two or more.

  The content of the solvent used in the present invention is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, preferably 2000 parts by weight or less, more preferably 100 parts by weight of the resin of component (a). Is 1500 parts by weight or less.

In addition to the component (c), the positive photosensitive resin composition of the present invention further improves the adhesion to a base substrate such as a silicon wafer, ITO, SiO ₂ , oxygen plasma used for cleaning, etc., UV Silane coupling agents such as trimethoxyaminopropyl silane, trimethoxy epoxy silane, trimethoxy vinyl silane, trimethoxy thiol propyl silane, titanium chelating agent, aluminum chelating agent, aromatic amine compound and alkoxy to increase resistance to ozone treatment An adhesion improving agent such as a compound obtained by reacting a group-containing silicon compound can be contained. In addition, the base substrate can be pretreated with a chemical solution containing these.

  When the photosensitive resin composition contains an adhesion improver, the content is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin of component (a). When the substrate is treated with a chemical solution containing an adhesion improver, the adhesion improver is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. Surface treatment is performed by spin coating, slit die coating, bar coating, dip coating, spray coating, steam treatment, or the like for a solution in which 0.5 to 20% by weight is dissolved. In some cases, the reaction between the substrate and the adhesion improver is allowed to proceed by applying a temperature from 50 ° C. to 300 ° C.

  The positive photosensitive resin composition of the present invention may contain a thermally crosslinkable compound for the purpose of improving the heat resistance, chemical resistance, mechanical properties and the like of the film after heat treatment. When it contains, an alkoxymethyl group containing compound etc. are mentioned as a heat-crosslinkable compound, It is preferable that the content shall be 0.5-50 weight part with respect to 100 weight part of resin of a component (a). Furthermore, the photosensitive resin composition of this invention may contain 0.01-10 weight part of surfactant with respect to 100 weight part of resin of a component (a) in order to improve the wettability with a board | substrate.

  Next, a method for producing a heat-resistant resin pattern using the positive photosensitive resin composition of the present invention will be described.

  First, a photosensitive resin composition is applied on a substrate. Examples of the substrate include silicon wafers, ceramics, gallium arsenide, soda glass, and quartz glass, but are not limited thereto. Examples of the coating method include a slit die coating method, a spin coating method, a spray coating method, a roll coating method, and a bar coating method, and these methods may be used in combination.

  Next, 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. When a hot plate is used, the object to be heated is heated by holding it 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, the resin layer coated on a 300 mm × 350 mm × 0.7 mm glass substrate is heated. In this case, 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 rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp. .

  In order to form the pattern of the photosensitive resin, the exposed portion may be removed 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, polar aqueous solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, gamma butyrolaclone, dimethylacrylamide, methanol, ethanol Contains 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, alone or in combination. Also 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 it 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 increasing the temperature linearly from room temperature to 250 ° C. over 2 hours or from 400 ° C. over 2 hours may be used.

  The resin film formed from the photosensitive resin composition of the present invention is used for insulating layers of organic EL elements, planarizing films of TFT substrates, surface protective films of semiconductor devices such as LSI, interlayer insulating films, and encapsulating devices in packages. Adhesive and underfill agent, cap agent to prevent copper migration, interlayer insulation film for multilayer wiring for high-density mounting, wiring protection film for circuit boards, on-chip microlens for solid-state image sensor, flat for various displays and solid-state image sensors It can use preferably for uses, such as a chemical film.

  Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. In addition, the measuring method of the absorption maximum wavelength of the component (c) in an Example, adhesive evaluation, the measurement of a dielectric breakdown voltage, and the PCT test were done with the following method.

(1) Measurement of absorption maximum wavelength of component (c) The component (c) was dissolved in gamma butyrolactone and measured using a spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation).

(2) Adhesive Evaluation Preparation of Prebaked Film A positive photosensitive resin composition (hereinafter referred to as varnish) was applied on a 4-inch silicon wafer so that the film thickness after prebaking was 0.48 ± 0.02 μm. Then, using a hot plate D-SPIN (Dainippon Screen Mfg. Co., Ltd.), prebaking was performed at 120 ° C. for 2 minutes to obtain a prebaked film.

Measurement of film thickness The thickness was measured with Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.).

Exposure Using an exposure machine (PLA-501F, manufactured by Canon Inc.), a line and space pattern (pitch is 150, 100, 80, 60, 50, 40, 30, 20, 15, 10 in order from the widest one) 5 μm) cut mask was set, and ultraviolet rays with an exposure amount of 50 mJ / cm ² (i-line conversion) were irradiated at all wavelengths of the mercury lamp. However, only the exposure amount of Example 12 was set to 100 mJ / cm ² (i-line conversion).

Development Using an automatic developing device AD-2000 (manufactured by Takizawa Sangyo Co., Ltd.), paddle development was performed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 30 seconds and rinsed with pure water for 30 seconds.

Evaluation of adhesion After development, the narrowest pitch width was recorded among the line-and-space patterns adhered to the substrate.

(3) Measurement of dielectric breakdown voltage Preparation of cured film A prebaked film was prepared on an aluminum substrate in the same manner as the preparation of the prebaked film in (2) above, and an inert oven INH-21CD manufactured by Koyo Thermo Systems Co., Ltd. was used. The heat treatment was performed in an air atmosphere under the heating conditions described in the examples.

Measurement of dielectric breakdown voltage A cured film produced on an aluminum substrate was boosted with DCW at a boosting rate of 0.1 kV / 4 seconds using a withstand voltage / insulation resistance tester TOS9201 manufactured by Kikusui Electronics Co., Ltd. The voltage at which breakdown occurred was measured, and the obtained voltage was divided by the film thickness to determine the dielectric breakdown voltage per unit film thickness.

(4) PCT test Preparation of cured film A pre-baked film was prepared on a glass substrate corning 1737 (manufactured by Corning) so that the film thickness after heat treatment was 0.48 ± 0.02 μm, and Koyo Thermo System ( Heat treatment was performed in an air atmosphere at 230 ° C. for 30 minutes using an Inert Oven INH-21CD.

PCT treatment 10 rows and 10 columns (100 squares) grid cuts are cut into the cured film at intervals of 2 mm, and pressure is applied under a saturated condition of 121 ° C. and 2 atm using a hast chamber EHS-212MD (manufactured by ESPEC Corporation). Cooker test (PCT) treatment was performed. The PCT processing time in which one square or more out of 100 squares by peeling with cellophane tape (registered trademark) was measured.

Synthesis Example 1 Synthesis of hydroxyl-containing acid anhydride (a) In a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and allyl 34.2 g (0.3 mol) of glycidyl ether was 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) 2-Amino-4-nitrophenol (15.4 g, 0.1 mol) was dissolved in acetone (50 ml) and propylene oxide (30 g, 0.34 mol). Cooled down. A solution prepared by dissolving 17.8 g (0.055 mol) of 2,2bis- (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 gamma 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 (b) crystal represented by the following formula.

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine compound (c) 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 solid was placed in a 300 ml stainless steel autoclave, dispersed in 250 ml of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the catalyst was filtered 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 (c) represented by the following formula. The obtained solid was used for the reaction as it was.

Synthesis Example 4 Synthesis of Hydroxyl-Containing Diamine Compound (d) 2-Amino-4-nitrophenol (15.4 g, 0.1 mol) was dissolved in acetone (100 ml) and propylene oxide (17.4 g, 0.3 mol). Cooled to ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 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. Thereafter, in the same manner as in Synthesis Example 2, a crystal of a hydroxyl group-containing diamine compound (d) represented by the following formula was obtained.

Synthesis Example 5 Synthesis of quinonediazide compound (e) Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 21.23 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 40.30 g (0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g (0.15 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (e) represented by the following formula.

Synthesis Example 6 Synthesis of quinonediazide compound (f) Under a dry nitrogen stream, 15.41 g (0.05 mol) of TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 20.15 g of 5-naphthoquinonediazidesulfonyl acid chloride (0.075 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. A quinonediazide compound (f) was obtained in the same manner as in Synthesis Example 5 using 7.59 g (0.075 mol) of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 7 Synthesis of quinonediazide compound (g) Under a dry nitrogen stream, 11.41 g (0.05 mol) of bisphenol A and 26.87 g (0.1 mol) of 4-naphthoquinonediazidesulfonyl acid chloride were added to 450 g of 1,4-dioxane. And brought to room temperature. A quinonediazide compound (g) represented by the following formula was obtained in the same manner as in Synthesis Example 5 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 8 Synthesis of Adhesion Improving Agent (h) 36.6 g (0.1 mol) of BAHF was dissolved in 100 g of ethyl lactate. Next, 55.6 g (0.2 mol, KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.) of 3-glycidoxypropyltriethoxysilane was added to this solution, stirred at 50 ° C. for 6 hours, and represented by the following formula. An adhesion improver (h) was obtained.

Synthesis Example 9 Synthesis of 1-acetylaminoanthraquinone (i) In a dry nitrogen stream, 22.3 g (0.1 mol) of 1-aminoanthraquinone and 11.1 g (0.11 mol) of triethylamine were dissolved in 50 g of tetrahydrofuran (THF). did. Acetyl chloride 7.85g (0.1mol) was dripped there over 5 minutes, stirring at 0 degreeC with 10g of THF. Thereafter, the mixture was stirred at room temperature for 1 hour. The precipitate was removed by filtration, and the filtrate was poured into 200 g of water. The product was recovered by filtration and then dried in a vacuum dryer to obtain 1-acetylaminoanthraquinone (i).

Synthesis Example 10 Synthesis of Polymer (A) Under a dry nitrogen stream, 12.01 g (0.02 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was added to 100 g of N-methyl-2-pyrrolidone (NMP). Dissolved in. To this was added 9.6 g (0.016 mol) of the hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 together with 25 g of NMP, and the mixture was reacted at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. Next, 0.87 g (0.008 mol) of 4-aminophenol was added and reacted at 50 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.15 g (0.06 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 in a vacuum dryer at 80 ° C. for 40 hours. Thus, polymer (A) (polyamic acid ester) was obtained.

Synthesis Example 11 Synthesis of Polymer (B) Under a dry nitrogen stream, 12.01 g (0.02 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was dissolved in 100 g of NMP. Here, 4.84 g (0.008 mol) of the hydroxyl group-containing diamine (c) obtained in Synthesis Example 3 and 1.94 g (0.008 mol) of the hydroxyl group-containing diamine (d) obtained in Synthesis Example 4 together with 25 g of NMP. In addition, it was reacted at 20 ° C. for 1 hour and then 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 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 in a vacuum dryer at 80 ° C. for 40 hours. Thus, polymer (B) (polyamic acid ester) was obtained.

Synthesis Example 12 Synthesis of Polymer (C) Under a dry nitrogen stream, 10.89 g (0.054 mol) of 4,4′-diaminodiphenyl ether, 1.86 g of 1,3-bis (3-aminopropyl) tetramethyldisiloxane ( 0.0075 mol) was dissolved in 20 g of NMP. Here, 30.02 g (0.05 mol) of the hydroxyl group-containing acid dianhydride (a) obtained in Synthesis Example 1 was added together with 15 g of NMP, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. . After the reaction, 2.25 g (0.023 mol) of maleic anhydride was added as a terminal blocking agent, and the mixture was further reacted at 50 ° C. for 2 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. 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 in a vacuum dryer at 70 ° C. for 60 hours. Thus, polymer (C) (polyamic acid ester) was obtained.

Synthesis Example 13 Synthesis of Polymer (D) Under a dry nitrogen stream, 18.68 g (0.100 mol) of BAHF and 12.66 g (0.420 mol) of pyridine were dissolved in 50 g of NMP. Here, 22.32 (0.095 mol) of terephthalic acid chloride was added dropwise together with 10 g of NMP so that the inside of the system would not become 10 ° C. or higher. After dropping, the mixture was stirred at room temperature for 4 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 in a vacuum dryer at 80 ° C. for 20 hours. Thus, polymer (D) (polyhydroxyamide) was obtained.

Synthesis Example 14 Synthesis of Polymer (E) Under a nitrogen stream, 32.9 g (0.09 mol) of BAHF was dissolved in 500 g of NMP. Bis (3,4-dicarboxyphenyl) ether dianhydride 31.0 g (0.1 mol, Manac Co., Ltd.) was added thereto 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. Further, 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, a cooling tube was attached and water was removed azeotropically with toluene while azeotropically removing the solution. 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 powder. The 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. Thus, polymer (E) (polyimide) was obtained.

Synthesis Example 15 Synthesis of Polymer (F) In a dry nitrogen stream, 21.8 g (0.1 mol) of pyromellitic anhydride and 15.3 g (0.21 mol) of 2-nitrobenzyl alcohol were dissolved in 200 g of NMP and stirred. Then, 21.3 g (0.21 mol) of triethylamine was added dropwise over 30 minutes. After the completion of the dropwise addition, the mixture was reacted for 3 hours to obtain 34.2 g (0.1 mol) of 2,6- (4,4′-diaminodiphenyl) -benzo [1,2-d: 5,4-d ′] bisoxazole. added. Next, 70.4 g (0.21 mol) of diphenyl- [2-thioxo-1,3-benzoxazol-3 (2H) -yl] phosphonate was added in 5 portions and allowed to react for 5 hours. Separately, 19.6 g (0.2 mol) of maleic anhydride and 15.3 g (0.21 mol) of 2-nitrobenzyl alcohol were dissolved in 100 g of NMP under a dry nitrogen stream, and triethylamine 21. 3 g (0.21 mol) was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction was allowed to proceed for 3 hours, mixed with the previous reaction solution and stirred for 30 minutes. Next, 70.4 g (0.21 mol) of diphenyl- [2-thioxo-1,3-benzoxazol-3 (2H) -yl] phosphonate was added in 5 portions and allowed to react for 5 hours. After putting the reaction liquid into 2 L of methanol, the precipitate was collected by filtration and dried in a vacuum dryer at 50 ° C. for 72 hours. Thus, polymer (F) (polyamic acid ester) was obtained.

Example 1
6.48 g of polymer (A) synthesized in Synthesis Example 10, 1.85 g of quinonediazide compound (e), BONASORB UA-3912 (trade name, indole compound, manufactured by Orient Chemical Co., Ltd., absorption maximum wavelength 391 nm as component (c) ) 0.37 g, 1.30 g of TrisP-PA as a polyhydroxy compound was dissolved in 27.0 g of gamma butyrolactone, 27.0 g of ethyl lactate, and 36.0 g of propylene glycol monomethyl ether to obtain a varnish (A). Using the varnish (A), adhesion evaluation, measurement of dielectric breakdown voltage of the cured film, and PCT test were performed. The heat treatment conditions for the cured film used for measuring the dielectric breakdown voltage were set at 230 ° C. for 30 minutes.

Example 2
7.78 g of the polymer (B) synthesized in Synthesis Example 11, 1.78 g of the quinonediazide compound (f), 0.44 g of BONASORB UA-3912, 27.0 g of gamma butyrolactone, 27.0 g of ethyl lactate, 36.0 g of propylene glycol monomethyl ether To give varnish (B). Using the varnish (B), evaluation of adhesiveness, measurement of dielectric breakdown voltage and PCT test were conducted in the same manner as in Example 1.

Example 3
7.78 g of polymer (C) synthesized in Synthesis Example 12, 1.78 g of quinonediazide compound (g), 0.44 g of BONASORB UA-3912, 27.0 g of gamma butyrolactone, 27.0 g of ethyl lactate, 36.0 g of propylene glycol monomethyl ether To give varnish (C). Using the varnish (C), in the same manner as in Example 1, evaluation of adhesiveness, measurement of dielectric breakdown voltage, and PCT test were performed.

Example 4
6.86 g of polymer (D) synthesized in Synthesis Example 13, 1.57 g of quinonediazide compound (e), 0.20 g of BONASORB UA-3912, 1.37 g of TrisP-PA as a polyhydroxy compound, 27.0 g of gamma butyrolactone, ethyl lactate It was dissolved in 27.0 g and 36.0 g of propylene glycol monomethyl ether to obtain varnish (D). Using the varnish (D), adhesion evaluation, measurement of the dielectric breakdown voltage of the cured film, and PCT test were performed. In addition, the heat treatment conditions of the cured film used for the measurement of the dielectric breakdown voltage were set at 320 ° C. for 30 minutes.

Example 5
7.22 g of the polymer (E) synthesized in Synthesis Example 14, 1.24 g of the quinonediazide compound (e), 0.10 g of BONASORB UA-3912, 1.44 g of the polyhydroxy compound TrisP-PA, 27.0 g of gamma-butyrolactone, 27 of ethyl lactate Dissolved in 0.06 g and 36.0 g of propylene glycol monomethyl ether to give varnish (E). Evaluation of adhesiveness, measurement of dielectric breakdown voltage, and PCT test were performed in the same manner as in Example 1 using varnish (E).

Example 6
A varnish (F) was prepared in the same manner as in Example 1 except that 0.37 g of 5-nitroacenaphthene (manufactured by Tokyo Chemical Industry Co., Ltd., absorption maximum wavelength 371 nm) was used as the component (c). Evaluation, dielectric breakdown voltage measurement, and PCT test.

Example 7
A varnish (G) was produced in the same manner as in Example 1 except that 0.37 g of 1-acetylaminoanthraquinone (i) (absorption maximum wavelength 400 nm) synthesized in Synthesis Example 9 was used as the component (c). Evaluation of adhesion, measurement of dielectric breakdown voltage, and PCT test were performed.

Example 8
Implemented except that 0.19 g of NK-1342 (trade name, 2- (4-dimethylaminostyryl) benzoxazole, Hayashibara Biochemical Laboratories, Inc., absorption maximum wavelength 394 nm) was used as component (c). A varnish (H) was produced in the same manner as in Example 1, and adhesion evaluation, dielectric breakdown voltage measurement, and PCT test were performed.

Example 9
As component (c), NK-1886 (trade name, 2- [2- [4- (dimethylamino) phenyl] ethenyl] naphtho [1,2-d] thiazole, manufactured by Hayashibara Biochemical Laboratories, Inc., absorption maximum A varnish (I) was produced in the same manner as in Example 1 except that 0.19 g (wavelength 416 nm) was used, and an adhesion evaluation dielectric breakdown voltage measurement and a PCT test were performed.

Example 10
1,3-dimethyl-5- [2- (1-methylpyrrolidin-2-ylidene) ethylidene] pyrimidine-2,4,6-trione (merocyanine compound, manufactured by Nippon Siebel Hegner Co., Ltd.) as component (c), absorption maximum A varnish (J) was prepared in the same manner as in Example 1 except that 0.37 g (wavelength 404 nm) was used, and adhesion evaluation, dielectric breakdown voltage measurement, and PCT test were performed.

Example 11
A varnish (K) was prepared in the same manner as in Example 1 except that 0.74 g of 5-nitroacenaphthene was used as the component (c), and adhesion evaluation, dielectric breakdown voltage measurement, and PCT test were performed. It was.

Example 12
Except that the exposure dose was increased from 50 mJ / cm ² to 100 mJ / cm ² , evaluation of adhesiveness of varnish (K), measurement of dielectric breakdown voltage, and PCT test were performed in the same manner as in Example 10.

Example 13
A varnish (L) was prepared in the same manner as in Example 1 except that 0.04 g of 5-nitroacenaphthene was used as the component (c), and adhesion evaluation, dielectric breakdown voltage measurement, and PCT test were performed. It was.

Example 14
A varnish (M) was prepared in the same manner as in Example 10 except that 0.02 g of 5-nitroacenaphthene was used as the component (c), and adhesion evaluation, dielectric breakdown voltage measurement, and PCT test were performed. It was.

Example 15
To the varnish (F) produced in Example 6, 0.10 g of the adhesion improver (h) synthesized in Synthesis Example 8 was added to obtain a varnish (N). Evaluation of adhesiveness, measurement of dielectric breakdown voltage, and PCT test were performed in the same manner as in Example 1 using varnish (N).

Comparative Example 1
A varnish (A ′) was produced in the same manner as in Example 1 except that the component (c) was not used, and adhesion evaluation and dielectric breakdown voltage were measured.

Comparative Example 2
Except for using 0.37 g of an ultraviolet absorber CHIMASSORB 81 (trade name, manufactured by Ciba Chemicalty Specials, Inc., absorption maximum wavelength 288, 325 nm) instead of component (c), the same as in Example 1 Then, a varnish (B ′) was prepared, and adhesion evaluation and dielectric breakdown voltage were measured.

Comparative Example 3
Except for using 0.37 g of the ultraviolet absorber TINUVIN 1130 (trade name, manufactured by Ciba Chemicalty Specials Co., Ltd., absorption maximum wavelength 301, 340 nm) instead of the component (c), the same as in Example 1. Then, a varnish (C ′) was prepared, and adhesion evaluation and dielectric breakdown voltage were measured.

Comparative Example 4
Varnish (D ′) in the same manner as in Example 1 except that 0.37 g of the dye VALIFAST BLACK 3830 (trade name, manufactured by Orient Chemical Co., Ltd., absorption maximum wavelength 378,579 nm) was used instead of component (c). ), And evaluation of adhesion and measurement of dielectric breakdown voltage were performed.

Comparative Example 5
Varnish (E ′) in the same manner as in Example 1 except that 0.37 g of the dye VALIFAST BLUE 2620 (trade name, manufactured by Orient Chemical Co., Ltd., absorption maximum wavelength 346,673 nm) was used instead of the component (c). ), And evaluation of adhesion and measurement of dielectric breakdown voltage were performed.

Comparative Example 6
Varnish (F ′) was prepared in the same manner as in Example 1 except that 0.37 g of the dye VALIFAST RED 3320 (trade name, manufactured by Orient Chemical Co., Ltd., absorption maximum wavelength 504 nm) was used instead of component (c). It produced and evaluated adhesiveness and measured the dielectric breakdown voltage.

Comparative Example 7
Varnish (G ′) in the same manner as in Example 1 except that 0.37 g of the dye VALIFAST GREEN 2520 (trade name, manufactured by Orient Chemical Co., Ltd., absorption maximum wavelength 346, 673 nm) was used instead of component (c). ), And evaluation of adhesion and measurement of dielectric breakdown voltage were performed.

Comparative Example 8
6.48 g of polymer (A) synthesized in Synthesis Example 10, 1.85 g of quinonediazide compound (e), 0.37 g of Pigment Blue 15: 6 (manufactured by Toyo Ink Co., Ltd., absorption maximum wavelength 670 nm), TrisP as a polyhydroxy compound -Disperse 1.30 g of PA, 27.0 g of gamma butyrolactone, 27.0 g of ethyl lactate, 36.0 g of propylene glycol monomethyl ether together with 25 g of glass beads using a homogenizer at 7000 rpm for 30 minutes, and then remove the glass beads by filtration. A varnish (H ′) was obtained. Using the varnish (H ′), in the same manner as in Example 1, evaluation of adhesiveness and measurement of dielectric breakdown voltage were performed.

Comparative Example 9
6.48 g of polymer (A) synthesized in Synthesis Example 10, 1.85 g of quinonediazide compound (e), 0.37 g of titanium black 13M (trade name, manufactured by Gemco Co., Ltd.), 1.30 g of TrisP-PA as a polyhydroxy compound , 27.0 g of gamma butyrolactone, 27.0 g of ethyl lactate and 36.0 g of propylene glycol monomethyl ether were dispersed together with 25 g of glass beads using a homogenizer at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration, and varnish (I ′ ) Using the varnish (I ′), in the same manner as in Example 1, evaluation of adhesion and measurement of dielectric breakdown voltage were performed.

Comparative Example 10
6.48 g of polymer (A) synthesized in Synthesis Example 10, 1.85 g of quinonediazide compound (e), 0.37 g of carbon black MA100 (trade name, manufactured by Mitsubishi Materials Corporation), TrisP-PA 1. 30 g, 27.0 g of gamma butyrolactone, 27.0 g of ethyl lactate, and 36.0 g of propylene glycol monomethyl ether were dispersed together with glass beads 25 g together with a homogenizer at 7000 rpm for 30 minutes, and then the glass beads were removed by filtration, and varnish (J ') Got. Using the varnish (J ′), in the same manner as in Example 1, evaluation of adhesion and measurement of dielectric breakdown voltage were performed.

Comparative Example 11
NKX-1320 (trade name, 3- (2′-N-methylbenzimidazolyl) -7-diethylaminocoumarin, manufactured by Hayashibara Biochemical Laboratories, Inc., absorption maximum wavelength 413 nm) instead of component (c) 0.37 g A varnish (K ′) was prepared in the same manner as in Example 1 except that was used, and adhesion evaluation and dielectric breakdown voltage were measured.

Comparative Example 12
A varnish (L ′) was produced in the same manner as in Example 4 except that the component (c) was not used, and adhesion evaluation and dielectric breakdown voltage were measured.

Comparative Example 13
A varnish (M ′) was prepared in the same manner as in Example 5 except that the component (c) was not used, and adhesion evaluation and dielectric breakdown voltage were measured.

Comparative Example 14
8.54 g of the polymer (F) synthesized in Synthesis Example 15 and 1.46 g of 1-acetylaminoanthraquinone were dissolved in 90.0 g of NMP to obtain a varnish (N ′). Using the varnish (N ′), in the same manner as in Example 1, evaluation of adhesion and measurement of dielectric breakdown voltage were performed.

Comparative Example 15
6.48 g of novolak resin EP4020G (manufactured by Asahi Organic Materials Co., Ltd.), 1.85 g of quinonediazide compound (e), 0.37 g of BONASORB UA-3912, 27.0 g of gamma butyrolactone, 27.0 g of ethyl lactate, propylene glycol monomethyl ether 36 Dissolved in 0.0 g to obtain varnish (O ′). Evaluation of adhesiveness, measurement of dielectric breakdown voltage, and PCT test were performed in the same manner as in Example 1 using varnish (O ′).

  The adhesive evaluation results, the dielectric breakdown voltage measurement results, and the PCT test results of Examples 1-15 and Comparative Examples 1-15 are summarized in Tables 1-2.

Example 16
An organic EL display device was produced by the following method.

  A 300 mm × 350 mm glass substrate in which an ITO transparent electrode film having a thickness of 130 nm was formed on the surface of 300 mm × 350 mm × 0.7 mm non-alkali glass (Corning Japan Co., Ltd., # 1737) by a sputtering vapor deposition method was prepared. A photoresist was applied onto the ITO substrate by a spinner, and patterning was performed 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 having a length of 90 mm and a width of 80 μm by removing the photoresist. The striped first electrodes have a pitch of 100 μm.

Varnish (A) was applied on a glass substrate patterned with ITO using a slit die coating method so that the film thickness after soft baking was 0.7 μm. The coating speed was 3 m / min. When the spin coating method was used, the coating was performed by adjusting the rotation speed so that the film thickness after soft baking was 0.7 μm. Then, using a hot plate (EA-4331 manufactured by Chuo Riken Co., Ltd.), the glass substrate is held at a height of 5.0 mm from the hot plate with a proxy pin, and heated at 120 ° C. for 10 minutes, thereby positive-type photosensitive. An adhesive resin coating film was obtained. This coating film of varnish A is irradiated with ultraviolet rays having an exposure amount of 70 mJ / cm ² (i-line conversion) at all wavelengths of a mercury lamp through a photomask, and then only the exposed portion is dissolved with a 2.38% TMAH aqueous solution for 30 seconds. This was developed and rinsed with pure water. The obtained polyimide precursor resin pattern was cured by heating at 230 ° C. for 30 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 0.4 μm. In this way, a light-shielding insulating layer made of a photosensitive polyimide resin having a shape in which an opening having a width of 70 μm and a length of 250 μm exposes the center of the first electrode and covers the end of the first electrode. Formed.

Next, an organic electroluminescent display device was manufactured using a substrate on which an insulating layer was formed. First, a thin film layer including a light emitting layer was formed by a vacuum evaporation method using a resistance wire heating method. Next, 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 together a board | substrate and the glass plate for sealing using the ultraviolet curing epoxy resin. In this way, a simple matrix type color organic light emitting display device in which a patterned light emitting layer is formed on the ITO striped first electrode and the striped second electrode is arranged so as to be orthogonal to the first electrode is manufactured. did. 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 effective light emission area ratio S after the durability test was 100%, indicating high reliability.

Claims (4)

(A) a resin having a structural unit represented by the following general formula (1) and / or a structural unit represented by the general formula (2), (b) a quinonediazide compound, (c) an anthraquinone compound, an acenaphthene compound, an indole compound , A compound selected from the group consisting of a merocyanine compound and a styryl compound represented by the following general formula (3), having an absorption maximum wavelength at a wavelength of 350 nm or more and less than 450 nm, and an absorption maximum wavelength at a wavelength of 450 nm or more and 700 nm or less A positive photosensitive resin composition comprising a non-retaining compound and (d) a solvent.

(In the general formula (1), R ¹ and R ² represent a 2 to 6-valent organic group having 2 to 30 carbon atoms. Each A may be the same or different, and 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, and m and p are each 0 to 4 Represents an integer, where m + p> 0.)

(In General Formula (2), R ⁵ represents a C 4-30 tetravalent organic group. R ⁶ represents a C 2-30 bivalent organic group. Each E is the same. But it may be _{^{different, oR 7, SO 3 R 7}} , CONR 7 R 8, COOR 7, SO selected from 2 ^NR 7 ^{R 8} .R ⁷ and ^{R 8} are monovalent hydrogen atom or a C 1-20 X and Z are selected from CO, N, NH, O and S, and Y is C or N. The bond between Z and Y is a single bond or a double bond. q may be the same or different and each represents an integer of 0 to 2. r and s each represent an integer of 0 to 4, provided that r + s> 0.

(In General Formula (3), each R ⁹ may be the same or different and represents a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ¹⁰ and R ¹¹ are a hydrogen atom or 1 having 1 to 20 carbon atoms. R ¹² and R ¹³ represent a hydrogen atom, CN, SO ₃ R ¹⁴ , CONR ¹⁴ R ¹⁵ , COOR ¹⁴ , SO ₂ NR ¹⁴ R ¹⁵ , monovalent aromatic having 2 to 30 carbon atoms R ¹⁴ and R ¹⁵ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 4.) 2. The positive photosensitive resin composition according to claim 1, wherein 0.5 to 10 parts by weight of the compound of component (c) is contained with respect to 100 parts by weight of resin of component (a). (1) A pattern production method comprising at least a step of exposing the positive photosensitive resin composition according to claim 1 or 2 using light having a wavelength of 350 nm or more and less than 450 nm, and (2) a step of developing. . An organic electroluminescence device comprising an insulating layer formed from the positive photosensitive resin composition according to claim 1.