JP5211438B2 - Resin composition and display device using the same - Google Patents

Description

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

  In order to reduce the mounting area of an LSI package, there is a method in which pins are provided outside a conventional package such as QFP and bonded to the substrate, and bumps are formed on the package and the package is directly bonded 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 heat resistance and chemical resistance are required for an insulating material such as polyimide used for protecting an LSI chip. In particular, since the solder bump formation is performed at a high temperature using an organic acid called a flux treatment, chemical resistance higher than the conventional one is required.

  In addition, organic EL displays are receiving attention as portable displays. This light-emitting element is very weak to water, organic gas, etc., the material that insulates between the light-emitting elements and the flattening film of the TFT substrate are not hygroscopic, and the insulating material and flattening are affected by the light-emitting element. It is important to have excellent chemical resistance, etc., so that the membrane does not decompose. For this reason, there is a need for an insulating layer and a planarizing film that have better chemical resistance than ever before. Further, in such applications, having an appropriate taper angle after curing is important in forming a wiring such as a metal after forming an insulating layer or a planarizing film.

So far, photosensitive resin compositions to which thermally crosslinkable compounds have been added have been proposed (see, for example, Patent Document 1). This photosensitive resin composition has been known to be effective in suppressing film loss during development, improving developability, and suppressing shrinkage during curing by the addition of a thermally crosslinkable compound. However, this method did not exhibit sufficient chemical resistance especially when fired at a low temperature of 250 ° C. or lower. In addition, polyfunctional methylol compounds, alkyl ether compounds thereof, and negative resist compositions using the same have been proposed (see, for example, Patent Documents 2 and 3). As polyfunctional methylol compounds, trimethylolated triphenols (for example, see Patent Document 4), compounds having 12 methylol groups (for example, see Patent Document 5), and the like have been proposed. . However, the negative resist using such a compound has insufficient chemical resistance. In particular, even when cured at a temperature of 200 ° C. to 250 ° C., sufficient chemical resistance could not be obtained. Furthermore, in negative resists using these compounds having methylol groups, an acid is generated from the photoacid generator, and the methylol groups are crosslinked by the acid, so that baking is performed at a temperature of 100 ° C. to 150 ° C. after exposure. Problems such as the necessity of treatment and weakness to amine-based gas in the atmosphere have been pointed out.
JP 2002-328472 A (Claims 1, 2) JP 2004-94025 A (Claims 1 and 3) JP 2001-51417 A (Claims 1 and 2) JP 2003-3000922 A (Claim 1) JP 2000-290211 (Claims 1 and 2)

  An object of this invention is to provide the resin composition which shows the chemical resistance which was excellent even if low temperature hardening was performed.

That is, the present invention provides (a) a structural unit represented by the general formula (1) selected from polyamic acid, polyamic acid ester, polyhydroxyamide, polyaminoamide, polyamide, and polyamideimide, and / or polyimide, polybenzoxazole, poly Contains 100 parts by weight of a resin having a structural unit represented by the general formula (2) selected from benzimidazole and polybenzthiazole and (b) 10 to 100 parts by weight of a thermal crosslinking agent represented by the general formula (3) It is a resin composition characterized by this.

(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 , Selected from 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 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 ⁸ , 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 0 to 4 And q represents an integer of 0 to 2, provided that r + s> 0.)

(R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ¹⁰ may be the same or different and represents CH ₂ OR ³⁰ (R ³⁰ is a hydrocarbon group having 1 to 4 carbon atoms). R ¹¹ represents a hydrogen atom, a methyl group or an ethyl group R ¹⁴ and R ^{19 to} R ²⁹ are a hydrogen atom, an organic group having 1 to 20 carbon atoms, Cl, Br, I, F or a carbon number of 1 to 20 And u represents 3 or 4.)

  According to the present invention, a resin composition exhibiting sufficiently excellent chemical resistance can be obtained even when cured at a low temperature of 250 ° C. or lower.

The resin composition of the present invention comprises (a) a structural unit represented by the general formula (1) selected from polyamic acid, polyamic acid ester, polyhydroxyamide, polyaminoamide, polyamide, and polyamideimide, and / or polyimide, polybenzo 100 parts by weight of a resin having a structural unit represented by the general formula (2) selected from oxazole, polybenzimidazole, and polybenzthiazole, and (b) 10 to 100 parts by weight of a thermal crosslinking agent represented by the general formula (3) It is characterized by 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 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 + q> 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 ⁸ , 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. 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.

R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ¹⁰ may be the same or different and represents CH ₂ OR ³⁰ (R ³⁰ is a hydrocarbon group having 1 to 4 carbon atoms). R ¹¹ represents a hydrogen atom, a methyl group or an ethyl group. R < ¹⁴ > , R < ¹⁹ > -R < ²⁹ > shows a hydrogen atom, a C1-C20 organic group, Cl, Br, I, F, or a C1-C20 fluoro substituted organic group. u represents 3 or 4.

(A) component used in the present invention is represented by the general formula (1) are those having an amide bond in the main chain, a polyamide acid which is a polyimide precursor, polyamic acid ester, polybenzoxazole precursor Is selected from polyhydroxyamides, polyaminoamides, polyamides, and polyamideimides . Among these, from the viewpoint of alkali developability, polyamic acid, polyamic acid ester, polyhydroxyamide and the like are preferably used. More preferably used are polyamic acid and polyamic acid ester. In these resins, an imide ring is sufficiently formed even in low-temperature baking at 250 ° C. or lower, so that chemical resistance in low-temperature baking is further improved.

A resin selected from polyimide, polybenzoxazole, polybenzimidazole, and polybenzthiazole having a structural unit represented by the general formula (2) in place of or in combination with the structural unit represented by the general formula (1) Can also be used. These resins having a structural unit represented by the general formula (2) is an imide ring in the main chain structure, an oxazole ring, an imidazole ring, having a cyclic structure such as a thiazole ring.

  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 as the component (a) in the present invention preferably has 10 to 100,000 structural units represented by the 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. Well polyamic acid, a polyimide can be used in the present invention, it is possible to use a polyamic acid ester which is another polyimide precursor.

  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.

  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.

  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.

R ^{1 in the} general formula (1) represents a divalent to hexavalent organic group having 2 to 30 carbon atoms, and preferably has an aromatic ring and / or an aliphatic ring.

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'-benzophen Non-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, 2,3 , 5,6-pyridinetetracarboxylic acid, aromatic tetracarboxylic acid such as 3,4,9,10-perylenetetracarboxylic acid, and butanetetracarboxylic acid And an aliphatic tetracarboxylic acid such as 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 the A group in the general formula (1), preferably a hydroxyl group, a sulfonic acid group, a sulfonic acid amide group, a sulfonic acid ester group, or the like. 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.

R ^{2 in the} general formula (1) represents a C 2-30 bivalent organic group, and preferably has an aromatic ring and / or an aliphatic ring.

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 -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. It may be replaced with. 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.

In the general formula (2), E represents a group selected from OR ⁷ , SO ₃ R ⁷ , CONR ⁷ R ⁸ , COOR ⁸ , and SO ₂ NR ⁷ R ⁸ . R ⁷ and R ⁸ represent hydrogen 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 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 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 acid compounds such as mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid and the like, and monoacid chloride compounds in which these carboxyl groups are converted to acid chloride, and 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 Monoacid chloride compounds in which only the monocarboxyl group of dicarboxylic acids such as naphthalene and 2,7-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole and N-hydroxy-5-norbornene-2,3 -The active ester compound obtained by reaction with dicarboximide, etc. are mentioned.

  Among these, phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene Monocarboxylic acids such as 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid and 4-carboxybenzenesulfonic acid, 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 described above is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 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, by dissolving a resin into which an end-capping agent has been introduced in an acidic solution and decomposing it into an amine component and an acid anhydride component, which are constituent units of the resin, this is measured by gas chromatography (GC) or NMR measurement. 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.

  Silane cups such as trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, and trimethoxythiolpropylsilane are added to the resin having the structural unit represented by the general formula (1) or (2) used in the present invention. By mixing the ring agent, the adhesion to the substrate can be improved, and the resistance to oxygen plasma and UV ozone treatment used for cleaning and the like can be increased. 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 enhance the adhesion to the substrate and the resistance to oxygen plasma and UV ozone treatment used for cleaning and the like.

  The resin composition of the present invention contains (b) a thermal crosslinking agent represented by the general formula (3). Such a thermal cross-linking agent has a higher cross-linking reaction temperature and higher cross-linking reactivity than conventionally known urea / melamine-based heat cross-linking agents, and thus can prevent the cross-linking reaction in the pre-bake process during pattern processing, and The chemical resistance of the cured film obtained can be improved. In particular, even when baked at a low temperature of 250 ° C. or lower, a cured film having sufficient chemical resistance can be obtained. Moreover, since the crosslinking reaction in a prebaking process can be prevented, when it is set as the photosensitive resin composition, it has a high sensitivity at the time of pattern processing. In the present invention, when the thermal cross-linking agent represented by the general formula (3) is mixed with an unsubstituted one or a large amount thereof, the cross-linking reaction of the resin composition may not sufficiently proceed. For this reason, the purity of the compound represented by the general formula (3) is preferably 80% or more, and more preferably 95% or more. If the purity is 80% or more, the crosslinking 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. In order to obtain a high-purity thermal crosslinking agent, there are methods such as recrystallization and distillation to collect only the desired product. The purity of the thermal crosslinking agent can be determined by a liquid chromatography method.

In General Formula (3), R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and R ¹⁰ represents CH ₂ OR ³⁰ (R ³⁰ is a hydrocarbon group having 1 to 4 carbon atoms). R ³⁰ is a hydrocarbon group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group, because it retains moderate reactivity and is stable. R ¹¹ is a hydrogen atom, a methyl group or an ethyl group, R ¹⁴ and R ^{19 to} R ²⁹ are a hydrogen atom, an organic group having 1 to 20 carbon atoms, Cl, Br, I, F, or a fluoro substitution having 1 to 20 carbon atoms. An organic group is shown. u represents 3 or 4. When u is 3 or more, the crosslink density of the cured film is increased and chemical resistance is improved.

  An example of the compound preferably used in the present invention as the thermal crosslinking agent represented by the general formula (3) is shown below.

  (B) Content of the thermal crosslinking agent represented by General formula (3) is 10-100 weight part with respect to 100 weight part of resin of (a) component. When the content of component (b) is less than 10 parts by weight, sufficient chemical resistance cannot be obtained. On the other hand, when the amount is more than 100 parts by weight, the film becomes fragile, the water absorption increases, and the stability of the composition deteriorates, which is not preferable. Preferably it is 15 weight part or more, More preferably, it is 40 weight part or more, Preferably it is 90 weight part or less, More preferably, it is 80 weight part or less.

  A photoacid generator or a photopolymerization initiator can be added to the resin composition of the present invention to make a photosensitive resin composition.

  A photoacid generator can also be used as the component (c) in the resin composition of the present invention. Photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like.

  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 indene carboxylic acid, and a large dissolution rate of the resin composition in the exposed portion with respect to the aqueous alkali solution can be obtained. A pattern can be obtained. By using such a quinonediazide compound, a positive photosensitive resin precursor composition sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, which is a general ultraviolet ray, is obtained. be able to. (C) Two or more photoacid generators are preferably used. By using two or more photoacid generators, the ratio of the dissolution rate between the exposed area and the unexposed area can be increased, and as a result, a highly sensitive photosensitive resin composition can be obtained.

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

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

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

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. 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. In addition, 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.

  The molecular weight of the quinonediazide compound is preferably 300 to 3000, more preferably 350 to 1500, from the viewpoints of heat resistance, mechanical properties, and adhesiveness of the film obtained by heat treatment.

  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.

  Moreover, you may use the said polyhydroxy compound or polyhydroxy polyamino compound as it is, without esterifying with a naphthoquinone diazide for the purpose of supplementing the alkali developability of the photosensitive resin composition as needed. By containing this polyhydroxy compound and polyhydroxypolyamino compound, the resulting resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. And development is easy in a short time. In this case, the content of the polyhydroxy compound or polyhydroxypolyamino compound is preferably 1 part by weight or more, more preferably 3 parts by weight or more, and preferably 50 parts by weight with respect to 100 parts by weight of the resin of component (a). Part or less, more preferably 40 parts by weight or less.

  Of the photoacid generators used as the component (c) of the present invention, sulfonium salts, phosphonium salts, and diazonium salts are preferable as the photoacid generator that appropriately stabilizes the acid components generated by exposure. It is not preferable from the environment that phosphorus or the like remains in the resin composition of the present invention, and since it is necessary to consider the color tone of the film, a sulfonium salt is preferably used among them. Of the sulfonium salts, the structures represented by the general formulas (4) to (6) are preferably used.

In general formulas (4) to (6), R ^{31 to} R ³³ may be the same as or different from each other, and represent a monovalent organic group having 1 to 20 carbon atoms. R ³⁴ and R ³⁵ represent a single bond or a divalent organic group having 1 to 20 carbon atoms. AA ⁻ represents an anion moiety selected from R ³⁶ SO ₃ ⁻ , R ³⁶ COO ⁻ and SbF ₆ ^— . R ³⁶ represents an organic group having 1 to 20 carbon atoms.

  Although the specific example of the sulfonium salt represented by General formula (4) is shown below, it is not limited to these.

  Although the specific example of the sulfonium salt represented by General formula (5) is shown below, it is not limited to these.

  Although the specific example of the sulfonium salt represented by General formula (6) is shown below, it is not limited to these.

  By adding a photoacid generator as the component (c) to the resin composition of the present invention, an acid is generated in the light irradiation part, and the solubility of the light irradiation part in an alkaline aqueous solution is increased, so that the light irradiation part is dissolved. Thus, a positive relief pattern can be obtained. Further, by adding a photoacid generator and an epoxy compound, a negative relief pattern in which the acid generated in the light irradiation part accelerates the reaction of the epoxy compound and the light irradiation part becomes insoluble can be obtained.

  In the present invention, the content of the photoacid generator used as the component (c) is preferably 0.01 to 50 parts by weight 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 40 parts by weight. The total amount of compounds selected from sulfonium salts, phosphonium salts and diazonium salts is preferably in the range of 0.05 to 40 parts by weight, more preferably in the range of 0.5 to 20 parts by weight. By setting the content of the component (c) within this range, higher sensitivity can be achieved. Furthermore, it can also contain a sensitizer etc. as needed.

  In the photosensitive resin composition of the present invention, (d) 0.1 to 20 parts by weight of a photopolymerization initiator and (e) 1 to 100 parts by weight of a compound having two or more ethylene-bonded unsaturated bonds, more preferably 5 It can also contain -50 weight part.

  As the photopolymerization initiator (d) preferably used in the present invention, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl)- 2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, bis (diethylaminophenyl) ketone, 1 -Phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butanone-1, benzoin Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl -Diphenyl sulfide, alkylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2 -Propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-tri Tyl-1-propenaminium chloride monohydrate, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl -9-oxo-9H-thioxanthene-2-yloxy) -N, N, N-trimethyl-1-propanaminium chloride, 2,4,6-trimethylbenzoylphenylphosphine oxide, 2,2′-bis (o -Chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone , Camphorquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6- Menyl-iron (1 +)-hexafluorophosphate (1-), diphenyl sulfide derivative, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole) -1-yl) -phenyl) titanium, 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methyl Phenylketone, dibenzylketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone , Benzylmethoxyethyl aceta , Anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberon, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o -Ethoxycarbonyl) oxime, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl -1,2-propanedione -2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, bis (α-isonitrosopropiophenone oxime) isophthal, 1,2-octanedione -1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4-azobisisobutyronitrile, benzthiazole disulfide , Triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide and eosin, a combination of a photoreducing dye such as methylene blue and a reducing agent such as ascorbic acid or triethanolamine. In the present invention, one or more of these can be used.

  Examples of the compound (e) having two or more ethylenically unsaturated bonds preferably used in the present invention include acrylic monomers.

  Such acrylic monomers include ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, ethoxylated bisphenol A dimethacrylate, glycerin dimethacrylate, tripropylene glycol dimethacrylate, butanediol dimethacrylate, Although compounds such as glycerin triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, and ethoxylated isocyanuric acid triacrylate can be mentioned, other compounds can also be used.

  Moreover, you may add 1-50 weight part of compounds which have only one ethylenically unsaturated bond for 100 weight part of resin for adjustment of solubility. Examples of such compounds are acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dimethylacrylamide, dimethylaminoethyl methacrylate, acryloyl morphophore, 1-hydroxyethyl. α-chloroacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl α-chloroacrylate, 1-hydroxypropyl methacrylate, 1-hydroxypropyl acrylate, 1-hydroxypropyl α-chloroacrylate, 2-hydroxy Propyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl α-chloroacrylate, 3-hydroxy Propyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl α-chloroacrylate, 1-hydroxy-1-methylethyl methacrylate, 1-hydroxy-1-methylethyl acrylate, 1-hydroxy-1-methylethyl α-chloroacrylate 2-hydroxy-1-methylethyl methacrylate, 2-hydroxy-1-methylethyl acrylate, 2-hydroxy-1-methylethyl α-chloroacrylate, 1-hydroxybutyl methacrylate, 1-hydroxybutyl acrylate, 1-hydroxybutyl α-chloroacrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl α-chloroacrylate, 3-hydroxybutyl methacrylate 3-hydroxybutyl acrylate, 3-hydroxybutyl α-chloroacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl α-chloroacrylate, 1-hydroxy-1-methylpropyl methacrylate, 1-hydroxy- 1-methylpropyl acrylate, 1-hydroxy-1-methylpropyl α-chloroacrylate, 2-hydroxy-1-methylpropyl methacrylate, 2-hydroxy-1-methylpropyl acrylate, 2-hydroxy-1-methylpropyl α-chloro Acrylate, 1-hydroxy-2-methylpropyl methacrylate, 1-hydroxy-2-methylpropyl acrylate, 1-hydroxy-2-methylpropyl α-chloroacrylate, 2-hydride Xyl-2-methylpropyl methacrylate, 2-hydroxy-2-methylpropyl acrylate, 2-hydroxy-2-methylpropyl α-chloroacrylate, 2-hydroxy-1,1-dimethylethyl methacrylate, 2-hydroxy-1,1 -Dimethylethyl acrylate, 2-hydroxy-1,1-dimethylethyl α-chloroacrylate, 1,2-dihydroxypropyl methacrylate, 1,2-dihydroxypropyl acrylate, 1,2-dihydroxypropyl α-chloroacrylate, 2,3 -Dihydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl α-chloroacrylate, 2,3-dihydroxybutyl methacrylate, 2,3-dihydroxybutyl acrylate 2,3-dihydroxybutyl α-chloroacrylate, p-hydroxystyrene, p-isopropenylphenol, phenethyl methacrylate, phenethyl acrylate, phenethyl α-chloroacrylate, N-methylol acrylamide, N-methylol methacrylamide, α-chloroacryl Acid, crotonic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonanoic acid, 9-decanoic acid, 10-undecylene acid, brassic acid, ricinoleic acid, 2- (methacrylic acid) Examples include leuoxy) ethyl isocyanate, 2- (acryloyloxy) ethyl isocyanate, 2- (α-chloroacryloyloxy) ethyl isocyanate, and others.

  The resin composition of the present invention preferably contains (f) a filler. (F) By containing a filler, there exists an effect | action which improves the chemical resistance of a cured film more. In particular, in the use of a solder resist for circuit boards, there is an effect of developing thixotropy in a coating / drying process by screen printing and maintaining a pattern shape. Furthermore, the effect which suppresses the shrinkage | contraction at the time of thermosetting is also show | played.

  Examples of the filler (f) used in the present invention include, for example, calcium carbonate, silica, alumina, aluminum nitride, titanium oxide, silica-titanium oxide composite particles as examples of the insulating filler, and examples of the conductive filler. Gold, silver, copper, nickel, aluminum, carbon, etc. are mentioned. A plurality of these may be contained depending on the use, but from the viewpoint of reliability and cost, in the case of an insulating filler, silica, titanium oxide, silica-titanium oxide composite particles are preferable, and in the case of a conductive filler, silver is preferable. . The content is preferably 2 parts by weight or more and more preferably 5 parts by weight or more with respect to 100 parts by weight of component (a). Moisture resistance can be improved by setting it as 2 parts weight or more. Moreover, 1000 weight part or less is preferable and 500 weight part or less is more preferable. By setting it to 1000 parts by weight or less, an excessive increase in product viscosity can be prevented, and good workability can be obtained. The filler preferably has a number average particle size of 10 μm or less, and more preferably 2 μm or less. By setting the number average particle diameter to 10 μm or less, fluidity can be maintained and coating can be facilitated. It is also preferable to use two or more kinds of fillers having different number average particle diameters from the viewpoint of imparting thixotropy and stress relaxation.

  In addition, it is preferable to use particles having a number average particle diameter of 100 nm or less, that is, so-called nanoparticles, as the filler because it is possible to control physical properties such as refractive index while maintaining light transmittance. In particular, by using high refractive index nanoparticles, high transmittance and high refractive index can be expressed simultaneously. Such a resin composition containing nanoparticles can be suitably used as a low-temperature curable optical thin film such as an on-chip microlens for a solid-state imaging device or a flattening film for various displays / solid-state imaging devices. Silica particles, aluminum oxide particles, tin oxide-aluminum oxide composite particles, silicon oxide-aluminum oxide composite particles, zirconium oxide-aluminum oxide composite particles, tin oxide-silicon oxide composite particles, zirconium oxide- Silicon oxide composite particles, tin oxide particles, zirconium oxide-tin oxide composite particles, titanium oxide particles, tin oxide-titanium oxide composite particles, silicon oxide-titanium oxide composite particles, zirconium oxide-titanium oxide composite particles, zirconium complex, zirconium oxide Particles and the like. Among these, tin oxide-aluminum oxide composite particles, zirconium oxide-aluminum oxide composite particles, zirconium oxide-silicon oxide composite particles, tin oxide particles, zirconium oxide-tin oxide composite particles, titanium oxide particles, tin oxide are more preferable. -Titanium oxide composite particles, silicon oxide-titanium oxide composite particles, zirconium oxide-titanium oxide composite particles, zirconium oxide particles, and the like. In particular, for titanium oxide particles, the photocatalytic reaction can be reduced by covering the surface with another substance, and the stability of the film can be improved. The particles may be in the form of a powder or a sol, but is more preferably a sol from the viewpoint of ease of dispersion. In the case of using nanoparticles as the filler, the number average particle diameter is preferably 50 nm or less, more preferably 30 nm or less from the viewpoint of transmittance.

  The average particle size of the filler and nanoparticles can be measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a scanning electron microscope, a method of directly measuring the particle size using a transmission electron microscope, or the like. . The particle diameter obtained by these measurement methods may be a volume average or a mass average, but can be converted to a number average molecular weight by assuming that the particle shape is spherical.

  The content of these nanoparticles is preferably 1000 parts by weight or less and more preferably 500 parts by weight or less with respect to 100 parts by weight of component (a). As the commercially available nanoparticles, “Optlake TR-502” and “Optlake TR-504”, which are tin oxide-titanium oxide composite sols, “Optlake TR-, which is a silicon oxide-titanium oxide composite sol,” 503 ”,“ Optlake TR-513 ”,“ Optlake TR-520 ”,“ Optlake TR-505 ”which is a titanium oxide particle sol (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.), zirconium oxide Particle sol (manufactured by Kojundo Chemical Laboratory Co., Ltd.), tin oxide-zirconium oxide composite particle sol (manufactured by Catalyst Chemical Industry Co., Ltd.), tin oxide particle sol (manufactured by Kojundo Chemical Laboratory Co., Ltd.), etc. It is done.

  The resin composition of the present invention preferably contains (g) a compound containing a secondary aromatic amine and a silicon atom having an alkoxy group. A photosensitive resin composition containing 0.01 to 100 parts by weight of such a compound with respect to 100 parts by weight of the resin of component (a) is a silicon substrate without adversely affecting the photoacid generator that is a photosensitive component. In addition to improving the adhesion to a substrate such as ceramic or metal, there is an effect of improving the adhesion to the substrate after development. Examples of such a compound include compounds obtained by reacting an aromatic amine compound and an alkoxy group-containing silicon compound. The compound of component (g) may be any compound as long as it contains a secondary aromatic amine and a silicon atom having an alkoxy group, but more preferably, the following general formulas (7) to (9) The compound shown in either of these is mentioned. The compound represented by any one of the general formulas (7) to (9) is obtained by reacting an alkoxysilane compound having an epoxy group, a chloromethyl group, or the like, which is a group that reacts with an amino group of an aromatic amine, The resin composition having adhesiveness to the substrate can be obtained without reducing the activity of the aromatic amine and promoting the decomposition of the naphthoquinonediazide compound. The silanol group on the silicon substrate surface and the secondary amino group in the compound represented by any one of the general formulas (7) to (9) act at a low temperature of 50 to 200 ° C. The alkoxy group in the compound represented by any one of (9) to (9) can form a siloxane bond with a silanol group on the surface of the silicon substrate, but the bond is promoted by the catalytic action of the secondary amino group. . With the above configuration, the adhesive force with the silicon substrate is further increased. In addition, since silicon nitride, silicon oxide, ceramics and the like similarly act on the surface silanol groups as the silicon-based substrate surface, the same effect can be obtained. Further, even on a metal surface such as iron, nickel, copper, ITO, etc., it acts with OH groups (hydroxyl groups) formed in a thin layer of metal oxide formed on the surface, so that good adhesion can be obtained. Further, in the compound represented by any one of the general formulas (7) to (9), since a large substituent is bonded to the secondary amino group, naphthoquinone diazide sulfone which is a photosensitive component weak to the amino group. Does not adversely affect the acid ester. Therefore, excellent storage stability can be exhibited.

In the above formula, R ³⁷ , R ⁴³ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ each represent a group selected from an organic group having 1 to 10 carbon atoms, a hydroxyl group, a nitro group, an amino group, and a carboxyl group. R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁵³ , R ⁵⁴ and R ⁵⁵ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, a phenyl group, and substituted phenyl. Represents a group selected from the group; Among these, R ³⁸ and R ⁴⁰ , R ⁴⁴ and R ⁴⁶ , or R ⁵³ and R ⁵⁵ may be bonded to each other to form an aliphatic cyclic structure.

R ⁴¹ , R ⁴² , R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵⁶ are each selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, a phenyl group, a substituted phenyl group, and an alkoxy group having 1 to 6 carbon atoms. And at least one of R ⁴¹ , R ⁴² and R ⁵⁶ and at least one of R ⁵⁰ , R ⁵¹ and R ⁵² is an alkoxy group having 1 to 6 carbon atoms. E ¹ represents a group selected from an alkyl group having 1 to 10 carbon atoms, an alkylene group, a nitro group, a hydroxyl group, an alkoxy group, a carboxyl group, an ester group having 2 to 10 carbon atoms, and an amide group having 2 to 10 carbon atoms. . E ² represents a group selected from a single bond, a phenyl group, and a —CH ₂ O— group.

E ¹ E ¹ , E ² E ² is a single bond, the following formula

Represents a group selected from R ⁵⁷ and R ⁵⁸ each represents a group selected from hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, a fluorinated alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. i, j, f, h and v are each an integer from 1 to 4, b is an integer from 1 to 3, d is an integer from 0 to 2, a, c, y and w are each an integer from 0 to 10, e is An integer of 1 to 4, g and h each represent an integer of 1 to 100. x represents an integer of 1 to 3.

The compound represented by the general formula (7) is obtained by reacting an aromatic amino compound having one amino group with a silane coupling agent having a group that reacts with the amino group of the aromatic amino compound. Can be obtained. R ³⁷ and R ⁴³ are alkyl groups such as methyl group, ethyl group, propyl group and butyl group, fluorinated alkyl groups such as trifluoromethyl group, pentafluoroethyl group, perfluoropropyl group and perfluorobutyl group, hydroxyl group Nitro group, carboxyl group, amino group, ester group having 2 or more and less than 10 carbon atoms, amide group having 2 to 10 carbon atoms, and the like. Among these, an alkyl group, a fluorinated alkyl group, and a hydroxyl group are preferable.

R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵³ , R ⁵⁴ and R ⁵⁵ are preferably a methyl group, an ethyl group, a propyl group, a phenyl group or the like. R ⁴¹ , R ⁴² and R ⁵⁶ are preferably a methyl group, an ethyl group, a propyl group, a phenyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group, and one of them is necessarily a methoxy group, an ethoxy group, a propoxy group or a butoxy group. An alkoxy group such as a group. E ¹ is preferably a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an alkoxy group such as a butoxy group, or a nitro group.

  The aromatic amine compound preferably used in the present invention has a pKa (dissociation constant in an aqueous solution) in the range of 3-9. When the pKa is 3 or more, the adhesion to the substrate is improved, and when the pKa is 9 or less, the stability of the photosensitive component is improved. More preferably, the pKa is in the range of 4-8. Aromatic amines with pKa in the range of 3-9 include aniline, cyanoaniline, hydroxylaniline, nitroaniline, chloroaniline, ethyl aminobenzoate, trifluoromethylaniline, methylaniline, dimethylaniline, methylhydroxylaniline, amino Aromatic amines such as pyridine, methylaminopyridine, dihydroxyaniline and hydroxyaminopyridine, or aromatic polyamines such as diaminobenzene, triaminobenzene, diaminopyridine, triaminopyridine, hydroxydiaminobenzene and dihydroxydiaminobenzene Mention may be made of polyvalent amines.

  By reacting these aromatic amines with an alkoxysilane compound having a group that reacts with an amino group, the compound of component (g) can be obtained. Preferred examples of the group that reacts with these amino groups include an epoxy group and a chloromethyl group. Examples of such alkoxysilane compounds include trimethoxy-1-dimethylene chloride, trimethoxyepoxysilane, triethoxyepoxysilane, carboxylpropyltrimethoxysilane, bis (epoxy) tetramethoxydisiloxane, tris (epoxy) trimethoxy. Examples thereof include silane compounds having a group that reacts with an amino group such as an epoxy group such as disiloxane and tris (epoxy) penta (methoxy) trisiloxane, and a chloromethyl group.

  The compound represented by the general formula (8) is obtained by reacting an aromatic amino compound having two or more amino groups with an alkoxysilane compound having a group that reacts with the amino group of the aromatic amino compound. Can be obtained.

  The aromatic amino compound having two or more amino groups includes an aromatic diamine compound having two amino groups, an aromatic triamino compound having three amino groups, and an aromatic tetra compound having four amino groups. Examples include amino compounds. The pKa is preferably in the range of 3-9. Examples of such aromatic diamine compounds include phenylenediamine, methylphenylenediamine, cyanophenylenediamine, hydroxyphenylenediamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminobiphenyl, dimethyldiaminobiphenyl, dimethoxydiaminobiphenyl, bis (trifluoromethyl). ) Diaminobiphenyl, bis (aminophenoxy) benzene, bis (aminohydroxyphenyl) propane, bis (aminophenyl) dipropylbenzene, bis (aminophenoxy) diphenyl ether, bis (aminophenoxy) diphenylsulfone, bis (aminophenoxy) diphenylpropane Bis (aminohydroxyphenyl) hexafluoropropane, bis (aminohydroxypheny ) Propane, bis (amino-hydroxyphenyl) sulfone, bis (such aminophenoxy phenyl) ether, and substituted or unsubstituted aromatic diamine. In particular, it is preferable to use a diamine having a phenolic hydroxyl group.

  Moreover, as an aromatic amino compound having three or more amino groups, tri (aminophenyl) methane, tri (aminophenyl) ethane, tri (aminophenyl) propane, tetra (aminophenyl) methane, tri (aminophenyl) Examples thereof include trifluoroethane, triamino compounds having a substituent such as a nitro group, an ester group, and an alkyl group attached thereto, and tetraamino compounds such as tetra (aminophenyl) methane.

  The compound represented by the general formula (9) is obtained by reacting an aromatic diamine, a triamine, or a triamine or higher polyamine with a silane coupling agent having a group that reacts with an amino group having these amine compounds. Can be obtained.

  As the alkoxysilane compound that can be used to obtain the compound represented by the general formula (8) or (9), the same compounds as those used in the general formula (7) can be preferably used.

  Preferable specific examples of the compound represented by any one of the general formulas (7) to (9) include, but are not limited to, compounds represented by the following.

  The compound (g) (hereinafter referred to as an adhesion improving agent) is an aromatic amine and an alkoxysilane compound as they are or mixed in a solvent, and reacted in the range of −20 ° C. to 150 ° C. for 1 minute to 1 week. Can be obtained. At this time, the compounding ratio of the aromatic amine and the alkoxysilane compound is preferably in the range of 10 to 400 mol%, more preferably 50 to 200 mol% with respect to the total amino group amount of 100 mol%. is there. More preferably, it is the range of 60-150 mol%. When the alkoxysilane compound is 10 mol% to 400 mol% with respect to 100 mol% of the aromatic amine, the adhesion improving effect can be stably obtained without adversely affecting the storage stability. Moreover, it is preferable to make it react as a 1-90% solution by adding a solvent.

  Also, organic acids having 1 to 10 carbon atoms such as formic acid, acetic acid and oxalic acid, acid compounds such as sulfuric acid, hydrochloric acid and phosphoric acid, or amines having 1 to 10 carbon atoms such as triethylamine and pyridine, sodium hydroxide, hydroxylated Bases such as potassium and sodium carbonate may be added as a catalyst. These catalysts are preferably 0.0001 to 10 parts by weight with respect to 100 parts by weight as the total weight of the aromatic amine and the silane compound.

  From the solubility and stability of the obtained adhesion improver, alcohols having 1 to 7 carbon atoms, esters having 2 to 20 carbon atoms, ketones having 3 to 20 carbon atoms, amides having 3 to 20 carbon atoms, It is preferable to dilute using at least one selected from sulfur-containing solvents having 3 to 20 carbon atoms. By diluting with these solvents, the stability of the solution can be enhanced. The content of such a solvent is preferably 1 to 10,000 parts by weight with respect to 100 parts by weight of the adhesion improver. More preferably, it is 10 to 1000 parts by weight. When the content of the solvent is 1 to 10,000 parts by weight, the storage stability of the adhesion improver alone is good, and the adhesion improvement effect is stably obtained without adversely affecting the storage stability of the composition. It is done. Specific examples of the solvent include alcohols such as ethanol, propanol, butanol and methoxymethylbutanol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate and propylene carbonate, ethers such as propylene glycol monomethyl ether and tetrahydrofuran. And N-methyl-2-pyrrolidone, dimethylacetamide, dimethylimidazoline, dimethyl sulfoxide and the like.

  The resin composition of the present invention can be applied by spin coating, slit coating, dip coating, spray coating, printing, or the like. The photosensitive resin composition of the present invention is applied by spin coating, slit coating, dip coating, spray coating, printing, etc., and then partially irradiated with actinic rays such as ultraviolet rays. When the development process is performed, a negative or positive relief pattern can be obtained.

  The final cured film can be obtained by heat-treating the resin composition and the photosensitive resin composition of the present invention. 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.

  An active matrix type display device having a TFT for driving a display element of a liquid crystal or an organic EL display is provided with a planarization film covering a TFT and a wiring provided on a substrate, and the display element is provided on the planarization film. Is provided. Further, the display element and the wiring are connected through a contact hole formed in the planarization film. The resin composition of the present invention can be suitably used as this planarizing film.

  FIG. 1 shows a cross-sectional view of a TFT substrate on which a planarizing film and an insulating layer are formed.

  A bottom gate type or top gate type TFT 1 is provided in a matrix on the substrate 6, and an insulating film 3 is formed so as to cover the TFT 1. A wiring 2 connected to the TFT 1 is provided on the insulating film 3. Further, a planarizing film 4 is provided on the insulating film 3 so as to bury the wiring 2. A contact hole 7 reaching the wiring 2 is provided in the planarizing film 4. A display element (for example, an organic EL element) is provided on the planarizing film 4 in a state of being connected to the wiring 2 through the contact hole 7. In the organic EL display element, the first electrode 5 is formed so as to be connected to the wiring 2, and the insulating layer 8 is formed so as to cover the contact hole 7 and the end face of the first electrode, and then on the first electrode opening. A hole transport layer, a light-emitting layer, and a second electrode are formed in order to produce. This organic EL element may be a top emission type that emits light from the side opposite to the substrate 6 or a bottom emission type that extracts light from the substrate 6 side. In this manner, an active matrix organic EL display device in which each organic EL element is connected with the TFT 1 for driving the organic EL element is obtained.

  Furthermore, the resin film formed from the resin composition of the present invention includes a surface protective film for semiconductor devices such as LSI, an interlayer insulating film, an adhesive or an underfill agent for encapsulating a device in a package, and a cap agent for preventing copper migration It can be preferably used for applications such as interlayer insulating films for multilayer wiring for high-density mounting, wiring protective films for circuit boards, on-chip microlenses for solid-state image sensors, and flat films for various displays and solid-state image sensors.

  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, preparation and evaluation of the cure film | membrane in an Example were performed with the following method.

Preparation of Resin Film A 6-inch silicon wafer was coated with a resin composition (hereinafter referred to as varnish) so that the film thickness after pre-baking was 5 μm, and then a hot plate (a coating and developing apparatus Mark manufactured by Tokyo Electron Ltd.). -7) was used for pre-baking at 120 ° C. for 2 minutes to obtain a resin film.

Measurement of film thickness Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the film after pre-baking and after development was measured with a refractive index of 1.629, and the cured film was measured with a refractive index of 1.773.

Exposure The reticle from which the pattern was cut was set in an exposure machine (i-line stepper DSW-8000 manufactured by GCA), and the photosensitive resin film was exposed to i-line by changing the exposure time at an exposure intensity of 365 nm.

Preparation of Cure Film The resin film prepared by the above method was heat-treated at 140 ° C. for 30 minutes under a nitrogen stream (oxygen concentration of 20 ppm or less) using an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd., and then 230 ° C. The temperature was raised in 30 minutes and heat treated at 230 ° C. for 1 hour to produce a cured film (heat resistant resin film).

Evaluation of Photosensitive Properties Varnish was spin-coated on a 6-inch silicon wafer and then baked on a hot plate (Mark-7) at 120 ° C. for 3 minutes to finally produce a pre-baked film having a thickness of 10 μm. The film was exposed at 25 mJ / cm ² steps by the exposure amount of 0~800mJ / cm ² using an i-line stepper (GCA manufactured DSW-8000), after exposure, 2.38% tetramethylammonium (TMAH) The film was developed with an aqueous solution (ELM-D, manufactured by Mitsubishi Gas Chemical Co., Ltd.) for 60 seconds and then rinsed with pure water to obtain a developed film. In the case of a positive type photosensitive resin composition, the sensitivity was the exposure amount at which the exposed portion was completely eluted by development and disappeared. In the case of a negative photosensitive resin composition, the sensitivity was the exposure amount that 90% of the film thickness before development remained after development.

Appearance Evaluation of Cure Film The developed film obtained by the above method was heat-treated by the above method to produce a cure film, and the presence or absence of wrinkles around a 100 μm pattern was observed using an optical microscope.

Evaluation of chemical resistance 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 with the optical microscope of 20 time. In addition, the film thickness before and after the treatment was measured to determine the amount of film reduction.

Measurement of transmittance For a cured film having a thickness of 1.0 μm produced on a 5 cm square glass substrate, a transmittance at a wavelength of 400 nm is measured using an ultraviolet-visible spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation). did.

Measurement of Refractive Index For a cured film prepared on a 5 cm square glass substrate, a prism coupler MODEL2010 (manufactured by Metricon Co., Ltd.) was used to measure the film surface at 633 nm (using a He—Ne laser) at a room temperature of 22 ° C. The refractive index (TE) in the vertical direction was measured.

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., BAHF) in 100 mL of acetone , 17.4 g (0.3 mol) of propylene oxide (Tokyo Kasei Co., Ltd.), and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the 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 represented by the following formula.

Synthesis Example 2 Synthesis of quinonediazide compound TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and 5-naphthoquinonediazidesulfonic acid chloride (Toyo Gosei Co., Ltd.) under a dry nitrogen stream ), NAC-5) 26.8 g (0.1 mol) 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 added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 40 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 represented by the following formula.

Synthesis example 3
A 20% ethyl lactate solution of thermal crosslinking agent HMOM-TPHAP (Honshu Chemical Industry Co., Ltd., purity 80%) was concentrated with an evaporator to make a 50% ethyl lactate solution. This solution was allowed to stand for 2 days to obtain white crystals. The purity of the obtained HMOM-TPHAP was analyzed at 254 nm by high performance liquid chromatography manufactured by Shimadzu Corporation using ODS as a column and acetonitrile / water = 70: 30 as a developing solvent. It turned out that. Its structure is shown below.

Synthesis example 4
169.6 g of 4,4 ′-[1- [4- [1- (4-hydroxyphenyl-1) -1-methylethyl] phenyl] ethylidene] bisphenol (manufactured by Honshu Chemical Industry Co., Ltd., TrisP-PA) 0.4 mol) was dissolved in a solution obtained by dissolving 80 g (2.0 mol) of sodium hydroxide in 800 g of pure water. After complete dissolution, 686 g of 36-38% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Thereafter, the mixture was stirred at 20 to 25 ° C. for 17 hours. This was neutralized by adding 98 g of sulfuric acid and 552 g of water, and left as it was for 2 days. Needle-like white crystals formed in the solution after standing were collected by filtration and washed with 100 mL of water. The white crystals were vacuum dried at 50 ° C. for 48 hours. This was analyzed by high performance liquid chromatography manufactured by Shimadzu Corporation using ODS as the column and acetonitrile / water = 70: 30 as the developing solvent at 254 nm. As a result, the starting material disappeared completely and the purity was 88. %. Furthermore, when it analyzed by NMR (JEOL Co., Ltd. GX-270) using DMSO-d6 as a heavy solvent, it turned out that it is the trimethyl P-PA formed into hexamethylol.

  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, it was a 99% purity TrisP-PA hexamethoxymethylol compound. Its structure is shown below.

Synthesis example 5
1,1,1-tris (4-hydroxyphenyl) ethane (manufactured by Honshu Chemical Industry Co., Ltd., TrisP-HAP) 103.2 g (0.4 mol), sodium hydroxide 80 g (2.0 mol) was purified. It was dissolved in a solution dissolved in 800 g of water. After complete dissolution, 686 g of 36-38% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Thereafter, the mixture was stirred at 20 to 25 ° C. for 17 hours. This was neutralized by adding 98 g of sulfuric acid and 552 g of water, and left as it was for 2 days. Needle-like white crystals formed in the solution after standing were collected by filtration and washed with 100 mL of water. The white crystals were vacuum dried at 50 ° C. for 48 hours. This was analyzed by high performance liquid chromatography manufactured by Shimadzu Corporation using ODS as the column and acetonitrile / water = 70: 30 as the developing solvent at 254 nm. As a result, the starting material disappeared completely and the purity was 92 %. Furthermore, when it analyzed by NMR (JEOL Co., Ltd. GX-270) using DMSO-d6 as a heavy solvent, it turned out that it is the trimethyl P-PA formed into hexamethylol.

  Next, the compound thus obtained was dissolved in 300 mL of ethanol, 2 g of sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours. To this solution, 15 g of an anionic ion exchange resin (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 ethanol was removed by a rotary evaporator to obtain an ethyl lactate solution. When this solution was allowed to stand at room temperature for 2 days, white crystals were formed. When the obtained white crystal was examined by a liquid chromatography method, it was a 99% purity TrisP-HAP ethoxymethylol compound. Its structure is shown below.

Synthesis Example 6
Dissolve 85.6 g (0.4 mol) of 4,4′-ethylidenebisphenol (BPE, manufactured by Honshu Chemical Industry Co., Ltd.) in a solution of 80 g (2.0 mol) of sodium hydroxide in 800 g of pure water. I let you. After complete dissolution, 686 g of 36-38% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Thereafter, the mixture was stirred at 20 to 25 ° C. for 17 hours. This was neutralized by adding 98 g of sulfuric acid and 552 g of water, and left as it was for 2 days. Needle-like white crystals formed in the solution after standing were collected by filtration and washed with 100 mL of water. The white crystals were vacuum dried at 50 ° C. for 48 hours. This was analyzed by high performance liquid chromatography manufactured by Shimadzu Corporation using ODS as the column and acetonitrile / water = 70: 30 as the developing solvent at 254 nm. As a result, the starting material disappeared completely, and the purity was 90 %. Furthermore, when analyzed by NMR (GX-270 manufactured by JEOL Ltd.) using DMSO-d6 as a heavy solvent, it was found to be tetramethylolated BPE.

  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, it was a 98% pure BPE methoxymethylol compound. Its structure is shown below.

  The crosslinking agents used in the comparative examples are as follows.

Example 1
Under a dry nitrogen stream, 32.9 g (0.09 mol) of BAHF was dissolved in 500 g of NMP. 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride 31.0g (0.1 mol, Manac Co., Ltd. product, ODPA) was added with NMP50g here, and it stirred at 30 degreeC 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, a polyimide polymer powder was obtained.

  To 10 g of this powder, 40 g of thermal crosslinking agent HMOM-TPHAP (20% ethyl lactate solution, Honshu Chemical Industry Co., Ltd., amount of crosslinking agent 8 g), ethyl lactate 20 g (Musashino Chemical Laboratory Co., Ltd., EL) and A uniform solution was obtained by adding 20 g of gamma butyrolactone (manufactured by Mitsubishi Chemical Corporation, GBL). When the chemical resistance of the cured film using this solution was evaluated, the amount of film reduction was very good at 0.1 μm or less.

Comparative Example 1
When the same evaluation was performed except that the thermal crosslinking agent was not added in Example 1, the film was completely dissolved and there was no chemical resistance.

Example 2
Under a dry nitrogen stream, 57.4 g (0.095 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of SiDA were dissolved in 200 g of NMP. ODPA 31.0g (manac Co., Ltd., 0.1 mol) was added here, and it stirred at 40 degreeC for 2 hours. Thereafter, a solution obtained by diluting 7.14 g (0.06 mol) of dimethylformamide dimethyl acetal (manufactured by Mitsubishi Rayon Co., Ltd., DFA) with 5 g of NMP was added dropwise over 10 minutes. After dropping, stirring was continued at 40 ° C. for 2 hours. After completion of the stirring, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. Further, it was washed with 2 L of water three times, and the collected polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain a polyamic acid polymer.

10 g of the polyamic acid polymer thus obtained was measured, and 2 g of the quinonediazide compound obtained in Synthesis Example 2 and 30 g of the solution of the compound used in Example 1 as a thermal crosslinking agent (6 g of crosslinking agent) were dissolved in 15 g of GBL. The varnish of the photosensitive polyimide precursor composition was obtained. Using the obtained varnish, the photosensitive characteristics, the appearance of the cured film and the chemical resistance were evaluated as described above. The thickness reduction of the cured film made from this varnish was excellent at 0.15 μm. Further, the cured film was not observed to be wrinkled, and the appearance was good. The sensitivity was 200 mJ / cm ² .

Comparative Example 2
A varnish was obtained in the same manner as in Example 2 except that the thermal crosslinking agent was not added in Example 2. When the chemical resistance of the cured film produced from this varnish was evaluated, it was completely dissolved.

Comparative Example 3
A varnish was obtained in the same manner as in Example 2 except that 8 g of Nicalac MW30HM (manufactured by Sanwa Chemical Co., Ltd.) was used as the thermal crosslinking agent in Example 2. The reduction amount of the cured film made from this varnish was 0.5 μm. Wrinkles were observed at the corners of the cured film pattern. The sensitivity was 1000 mJ / cm ² .

Comparative Example 4
A varnish was obtained in the same manner as in Example 2 except that 8 g of Nicalac N2702 (manufactured by Sanwa Chemical Co., Ltd.) was used as the thermal crosslinking agent in Example 2. The reduction amount of the cured film produced from this varnish was 0.6 μm. Wrinkles were observed at the corners of the cured film pattern. The sensitivity was 500 mJ / cm ² .

Comparative Example 5
In Example 2, a varnish was obtained in the same manner as in Example 2 except that the thermal crosslinking agent solution was changed to 4 g (amount of crosslinking agent: 0.8 g). When the chemical resistance of the cured film produced from this varnish was examined, the film loss was 1.2 μm. The sensitivity was 600 mJ / cm ² . The cured film was not observed to be wrinkled, and the appearance was good.

Example 3
A varnish was obtained in the same manner as in Example 2 except that 8 g of the compound obtained in Synthesis Example 4 was used as the thermal crosslinking agent in Example 2. The reduction amount of the cured film produced from this varnish was 0.1 μm. No wrinkle-like pattern was observed in the cured film pattern, and the appearance was good. The sensitivity was 300 mJ / cm ² .

Reference example 1
A varnish was obtained in the same manner as in Example 2 except that 8 g of the compound obtained in Synthesis Example 6 was used as the thermal crosslinking agent in Example 2. The amount of reduction of the cured film made from this varnish was 0.25 μm. No wrinkle-like pattern was observed in the cured film pattern, and the appearance was good. The sensitivity was 300 mJ / cm ² .

Comparative Example 6
1.05 g of novolak resin (m-cresol: p-cresol = 45/55 (molar ratio)), 0.07 g of the quinonediazide compound of Synthesis Example 2 as a photoacid generator, and compound 0 synthesized in Synthesis Example 4 as a thermal crosslinking agent .3 g of ethyl lactate and 2 g of gamma butyrolactone were added to 28 g to prepare a negative photosensitive resin composition. The cured film made from this varnish completely dissolved in the chemical resistance test and was not chemically resistant.

Example 4
Under a dry nitrogen stream, 18.3 g (0.05 mol) of BAHF was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether, and the temperature of the solution was cooled to −15 ° C. A solution prepared by dissolving 14.7 g of diphenyl ether dicarboxylic acid dichloride (manufactured by Nippon Agricultural Chemicals Co., Ltd., 0.050 mol) in 25 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C. After completion of the reaction, the solution was poured into 3 L of water containing 10% by weight of methanol to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 50 ° C. for 72 hours to obtain a polyhydroxyamide polymer.

To 30 g of GBL, 10 g of the obtained polymer solid, 2 g of the quinonediazide compound of Synthesis Example 2 as a photoacid generator, and WPAG-314 (trade name, Wako Pure Chemical Industries, Ltd.) which is a sulfonium salt represented by the general formula (4) Co., Ltd.) 0.7 g and 6 g of the compound of Synthesis Example 3 were dissolved as a thermal crosslinking agent to obtain a varnish of a positive photosensitive polybenzoxazole precursor composition. When the chemical resistance of the cured film prepared from this varnish was evaluated, the film loss was 0.25 μm, the sensitivity was 150 mJ / cm ² , and no wrinkles were observed in the cured film.

Example 5
Under a dry nitrogen stream, 19.2 g (0.1 mol) of trimellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 17.4 g (0.1 mol) of 2,4-tolylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) ), 0.2 g of diazabicyclo [5.4.0] undecene-7 (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 250 g of NMP, the temperature was raised to 100 ° C. under a nitrogen stream, and the mixture was reacted at 100 ° C. for 2 hours. Subsequently, after making it react at 150 degreeC for 1 hour, NMP79.4g was added (solid content 10%), and it cooled to room temperature.

  50 g of this solution was taken, and 2.3 g of the thermal crosslinking agent of Synthesis Example 3 was added thereto to obtain a composition containing a polyamideimide polymer. When the chemical resistance of the cured film produced from this composition was evaluated, the film loss was 0.1 μm or less.

Example 6
Under a dry nitrogen stream, BAHF 3.66 g (0.01 mol), 4,4′-diaminodiphenyl ether (manufactured by Wakayama Seika Co., Ltd.) 10.1 g (0.05 mol), 3,3′-diaminodiphenyl sulfone ( 9.92 g (0.04 mol) manufactured by Konishi Chemical Co., Ltd. was dissolved in 80 g of NMP and 20.2 g (0.2 mol) of triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.), and cooled to -10 ° C. Here, a solution prepared by dissolving 20.3 g (0.1 mol) of isophthalic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 80 g of cyclohexanone (manufactured by Tokyo Chemical Industry Co., Ltd.) is gradually added so that the internal temperature does not exceed 0 ° C. It was dripped in. After completion of the dropwise addition, the temperature was returned to room temperature at −10 ° C. for 3 hours and then for 1 hour, and stirring was continued for another hour. After the stirring, the precipitated hydrochloride of triethylamine was removed by filtration, and the filtrate was poured into 3 L of water. The precipitated white polymer precipitate was collected by filtration and further washed with water. Then, it dried for 72 hours with the 50 degreeC vacuum dryer.

  10 g of this dried polyamide polymer was weighed, and 5 g of the crosslinking agent synthesized in Synthesis Example 5 was added thereto and dissolved in 40 g of GBL. When the chemical resistance of this cured film was evaluated, the film loss was 0.2 μm.

Example 7
To 10 g of the polymer obtained in Example 1, 20 g of a thermal crosslinking agent HMOM-TPHAP (20% ethyl lactate solution, manufactured by Honshu Chemical Industry Co., Ltd., 4 g of crosslinking agent), 2 g of ethoxylated bisphenol A dimethacrylate (Shin Nakamura Chemical) Industrial Co., Ltd., NK ester BPE-100), trimethylolpropane triacrylate 0.5 g, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime) 1 g was dissolved in 20 g EL and 20 g GBL.

When the chemical resistance of the cured film was evaluated, the film reduction amount was 0.3 μm. The presence or absence of wrinkles was observed, but no wrinkles were observed. The sensitivity was 150 mJ / cm ² .

Example 8
To 10 g of the polymer obtained in Example 1, 20 g of thermal crosslinking agent HMOM-TPHAP (20% ethyl lactate solution, manufactured by Honshu Chemical Industry Co., Ltd., 4 g of crosslinking agent), 2 g of ethoxylated bisphenol A dimethacrylate (Shin Nakamura) Chemical Industry Co., Ltd., NK ester BPE-100), trimethylolpropane triacrylate 0.5 g, bis (diethylaminophenyl) ketone 0.1 g (Hodogaya Chemical Co., Ltd.), silicon oxide-titanium oxide composite particles A uniform solution was obtained by adding 30 g of TR-513 (trade name, γ-butyrolactone dispersion, number average particle size 15 nm, particle content 30% by weight, manufactured by Catalyst Kasei Kogyo Co., Ltd.) and 20 g of ethyl lactate. When the chemical resistance of the cured film using this solution was evaluated, the amount of film reduction was 0.1 μm. The presence or absence of wrinkles was observed, but no wrinkles were observed. The sensitivity was 200 mJ / cm ² . The refractive index was 1.72, and the transmittance was 96%.

Example 9
10 g of the polymer obtained in Example 1 was added with 10 g of a thermal crosslinking agent HMOM-TPHAP (as a 20% ethyl lactate solution, manufactured by Honshu Chemical Industry Co., Ltd., 2 g of crosslinking agent), and 2.5 g of the quinonediazide compound of Synthesis Example 2 was lactic acid. 20 g of ethyl and 20 g of gamma butyrolactone were added to obtain a uniform solution. When the chemical resistance of the cured film using this solution was evaluated, the amount of film reduction was 0.35 μm. The presence or absence of wrinkles was observed, but no wrinkles were observed. The sensitivity was 300 mJ / cm ² .

Example 10
To 10 g of the polymer obtained in Example 1, 10 g of thermal crosslinking agent HMOM-TPHAP (20% ethyl lactate solution, Honshu Chemical Industry Co., Ltd., amount of crosslinking agent 2 g), 2.5 g of quinonediazide compound of Synthesis Example 2, oxidation TR-520 (trade name, γ-butyrolactone dispersion, number average particle size 15 nm, particle content 30 wt%, manufactured by Catalyst Kasei Kogyo Co., Ltd.) and 20 g of ethyl lactate are added as silicon-titanium oxide composite particles. A homogeneous solution was obtained. When the chemical resistance of the cured film using this solution was evaluated, the amount of film reduction was 0.1 μm. The presence or absence of wrinkles was observed, but no wrinkles were observed. The sensitivity was 350 mJ / cm ² . The refractive index was 1.76 and the transmittance was 94%.

Example 11
10 g of the polymer obtained in Example 4 was added with 10 g of thermal crosslinking agent HMOM-TPHAP (20% ethyl lactate solution, Honshu Chemical Industry Co., Ltd., amount of crosslinking agent 2 g), 2.5 g of the quinonediazide compound of Synthesis Example 2, and oxidation. TR-520 (trade name, γ-butyrolactone dispersion, number average particle size 15 nm, particle content 30 wt%, manufactured by Catalyst Kasei Kogyo Co., Ltd.) and 20 g of ethyl lactate are added as silicon-titanium oxide composite particles. A homogeneous solution was obtained. When the chemical resistance of the cured film using this solution was evaluated, the amount of film reduction was 0.3 μm. The presence or absence of wrinkles was observed, but no wrinkles were observed. The sensitivity was 350 mJ / cm ² . The refractive index was 1.77 and the transmittance was 95%.

The compositions and evaluation results of Examples 1 to 11 , Reference Example 1 and Comparative Examples 1 to 6 are shown in Tables 1 and 2.

Example 12
An organic EL display device using TFT was produced by the following method (see FIG. 1).

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) is formed in the insulating film 3, and then a wiring 2 (height 1.0 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 flattening layer 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 after the photosensitive polyimide precursor composition obtained in Example 2 is spin-coated on a substrate and prebaked (120 ° C. × 3 minutes) on a hot plate. Then, heat treatment was performed at 300 ° C. for 60 minutes under an air flow. The applicability when applying the resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average level difference of the wiring 2 was 500 nm, and the thickness of the prepared planarization film was 2000 nm.

  Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 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, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and DMSO). The first electrode thus obtained corresponds to the anode of the organic EL element.

  Next, an insulating layer 8 having a shape covering the periphery of the first electrode was formed. The photosensitive polyimide precursor composition obtained in the same manner as in Example 2 was used for the insulating layer. By providing this insulating layer, it is possible to prevent a short circuit between the first electrode and the second electrode formed in the subsequent process.

  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, a second electrode made of Al was formed on the entire surface above the substrate. 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.

  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.

Cross-sectional view of a TFT substrate with a planarization film and insulating layer formed

Explanation of symbols

1 TFT
2 Wiring 3 Insulating film 4 Planarizing film 5 First electrode 6 Substrate 7 Contact hole 8 Insulating layer

Claims (7)

(A) Structural unit represented by general formula (1) selected from polyamic acid, polyamic acid ester, polyhydroxyamide, polyaminoamide, polyamide, and polyamideimide and / or polyimide, polybenzoxazole, polybenzimidazole, polybenz It contains 100 parts by weight of a resin having a structural unit represented by the general formula (2) selected from thiazole and (b) 10 to 100 parts by weight of a thermal crosslinking agent represented by the general formula (3). Resin composition.

(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 ⁸ , 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 0 to 4 And q represents an integer of 0 to 2, provided that r + s> 0.)

(R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ¹⁰ may be the same or different and represents CH ₂ OR ³⁰ (R ³⁰ is a hydrocarbon group having 1 to 4 carbon atoms). R ¹¹ represents a hydrogen atom, a methyl group or an ethyl group R ¹⁴ and R ^{19 to} R ²⁹ are a hydrogen atom, an organic group having 1 to 20 carbon atoms, Cl, Br, I, F or a carbon number of 1 to 20 And u represents 3 or 4.) The positive photosensitive resin composition, wherein the resin composition according to claim 1 further comprises (c) 0.01 to 50 parts by weight of a photoacid generator. (A) The resin composition according to claim 1 further includes (d) 0.1 to 20 parts by weight of a photopolymerization initiator and (e) 1 to 100 parts by weight of a compound having two or more ethylenically unsaturated bonds. A negative photosensitive resin composition characterized by comprising: (F) Filler is contained, The resin composition of Claim 1 characterized by the above-mentioned. (F) The resin composition according to claim 4, wherein the filler is a particle having a number average particle diameter of 100 nm or less. A display device having a planarization film and a display element in this order on a substrate on which a thin film transistor (TFT) is formed, the planarization film using the resin composition according to any one of claims 1 to 5. A display device characterized by being formed. The display device according to claim 6, wherein the display element is an organic electroluminescence element.

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