JP2009020246A - Photosensitive resin composition, and manufacturing method for insulating resin pattern and organic electroluminescence element using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition, exhibiting excellent insulation even in low-temperature burning at 150°C. <P>SOLUTION: This photosensitive resin composition includes: (a) polyamide resin, (b) acrylic resin, (c) a photoacid generator, and (d) heat cross-linking compound, wherein the weight average molecular weight of (b) the acrylic resin is 5,000-30,000. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition. More specifically, a surface protective film for a semiconductor element, an interlayer insulating film, an insulating layer for an organic electroluminescent (EL) element and a flexible organic EL element, a thin film transistor (hereinafter abbreviated as TFT) substrate for a display device, a planarizing film, an organic The present invention relates to a positive photosensitive resin composition suitable for a gate insulating film of a TFT, an overcoat film of a color filter substrate for a display device, and the like, in which a portion exposed to ultraviolet rays is dissolved in an alkaline developer.

  In recent years, surface protection films for semiconductor elements, interlayer insulating films, insulating layers for organic electroluminescent elements, TFT substrates for display devices, planarizing films for color filters, and gate insulating films for organic TFTs, organic materials such as plastics are used as substrates. Since the material is used, low-temperature heating and baking at 150 ° C. is required. Conventionally, a positive photosensitive resin composition in which quinonediazide is added to polyamic acid has been used, but the heat treatment at 200 ° C. or lower does not sufficiently advance the cyclic structure of the polymer, and dissolves polyamic acid. Since the boiling point of the solvent is 200 ° C. or higher, it tends to remain in the film, and there is a problem that sufficient insulation cannot be imparted to the film after the heat treatment.

  On the other hand, the photosensitive resin composition using the alkali-soluble polyimide in which the resin itself is already imidized can be fired at a low temperature and is suitable for semiconductor use and display element use. Until now, what contains alkali-soluble groups, such as a phenolic hydroxyl group and a carboxyl group, is disclosed in the amine component in a principal chain as alkali-soluble polyimide resin (for example, refer patent documents 1-3). However, the compositions disclosed therein have a very high basic solubility in an organic solvent, and there is a problem that the insulation resistance and chemical resistance of the resulting polyimide resin film cannot be sufficiently obtained.

On the other hand, as another alkali-soluble resin composition, a photosensitive resin composition containing a polymer of a radical polymerizable monomer having a phenolic hydroxyl group or a carboxyl group, a quinonediazide compound, a basic nitrogen-containing compound and melamines is disclosed. (For example, refer to Patent Document 4). In addition, a photosensitive composition excellent in dry etch resistance comprising an acid or hydrolyzable oligomer having an alicyclic skeleton or a conjugated polycondensed aromatic skeleton in the main chain, a photoacid generator and a crosslinking agent is disclosed ( For example, see Patent Document 5). However, these compositions have a problem that sufficient insulation resistance cannot be obtained for a film after heat treatment at 200 ° C. or lower.
Japanese Patent No. 2935994 Japanese Patent No. 2990637 JP-A-2005-196130 JP 2002-40644 A JP 10-171120 A

  An object of this invention is to provide the photosensitive resin composition which exhibits the outstanding insulating property also in the low temperature baking at 150 degreeC.

  That is, the present invention provides (a) a resin having a structure represented by any one of the general formulas (1) to (4), (b) an acrylic resin, (c) a photoacid generator, and (d) a thermal crosslinking agent. And (b) the acrylic resin has a weight average molecular weight of 5,000 to 30,000.

(In the general formulas (1) to (4), R ¹ represents a 4- to 14-valent organic group, R ² represents a ^2- to 12-valent organic group, and may be the same or different. R ³ and R ⁵ are A phenolic hydroxyl group, a sulfonic acid group or a thiol group, which may be the same or different, R ⁴ represents a divalent organic group, and may be the same or different, X and Y are a carboxyl group, a phenolic hydroxyl group, A monovalent organic group having at least one group selected from a sulfonic acid group and a thiol group, n is in the range of 3 to 200, and m, r, and s are integers of 0 to 10.)

  ADVANTAGE OF THE INVENTION According to this invention, the positive photosensitive resin composition which exhibits high insulation under low-temperature baking of 150 degrees C or less can be provided.

  The photosensitive resin composition of the present invention comprises (a) a resin having a structure represented by any one of the general formulas (1) to (4), (b) an acrylic resin, (c) a photoacid generator, and (d ) A photosensitive resin composition comprising a thermal crosslinking agent. When (a) and (b) are used in combination, and (d) a thermally crosslinkable compound is used, the resin of component (a) and (d) a thermally crosslinkable compound are included, or (b) an acrylic resin And (d) High insulation can be obtained in low-temperature firing as compared with the case containing a thermally crosslinkable compound.

R ^{1 in the} above general formulas (1) to (4) may be the same or different and is a tetravalent to 14-valent organic group. It preferably has an aromatic ring, and more preferably an organic group having 4 to 40 carbon atoms. R ³ may be the same or different and represents a phenolic hydroxyl group, a sulfonic acid group or a thiol group. R ^1- (R ³ ) _r represents a structural component of acid dianhydride. R ² may be the same or different and is a divalent to divalent organic group. It preferably has an aromatic ring, and more preferably an organic group having 4 to 40 carbon atoms. R ⁵ may be the same or different and represents a phenolic hydroxyl group, a sulfonic acid group or a thiol group. R ² — (R ⁵ ) _s represents a structural component of diamine. From the viewpoint of solubility in an organic solvent, at least one of R ¹ and R ² is 1,1,1,3,3,3-hexafluoropropyl group, ether group, thioether group, SO ₂ group, cyclobutane residue, It is preferable to contain at least one group selected from a cyclopropane residue and a cyclohexane residue. R ¹ and R ² are both groups selected from 1,1,1,3,3,3-hexafluoropropyl group, ether group, thioether group, SO ₂ group, cyclobutane residue, cyclopropane residue, cyclohexane residue It is more preferable to have at least one.

  (A) As an acid dianhydride used for the resin having a structure represented by any one of the general formulas (1) to (4), specifically, pyromellitic dianhydride, 3, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3 , 3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane Dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2, 3-Dicarboxyphenyl) ethane dianhydride, bis 3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6, Aromatic tetracarboxylic dianhydrides such as 7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride Bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane Examples of dianhydrides, or compounds having an aromatic ring substituted with an alkyl group or a halogen atom, and aromatic dianhydrides such as acid dianhydrides having a structure having an amide group shown below. Rukoto can. These are used alone or in combination of two or more.

In the above formula, R ⁷ is C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, cyclobutane residue, cyclopropane residue or cyclohexane residue, and R ⁸ and R ⁹ are hydrogen atoms. Represents a hydroxyl group or a thiol group.

  Among these, alkali solubility or chemical resistance can be improved by using an acid dianhydride having an alkali-soluble group or an amide group as a raw material.

  Moreover, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2 -Dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid Dianhydride, 2, 3 Cycloaliphatic tetracarboxylic dianhydrides such as 4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornaneacetic dianhydride, 1,2,3,4-butane Mention may be made of aliphatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydrides.

  Of these, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoro Propane dianhydride or a compound in which these aromatic rings are substituted with an alkyl group or a halogen atom, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Anhydrides, aliphatic tetracarboxylic dianhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and acid dianhydrides having a structure having an amide group shown below Any aromatic or aliphatic dianhydride is particularly preferred. These are used alone or in combination of two or more.

In the above formula, R ⁷ represents an oxygen atom, C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, a cyclobutane residue, a cyclopropane residue or a cyclohexane residue, and R ⁸ and R ⁹ Represents a hydrogen atom, a hydroxyl group or a thiol group.

  (A) Specific examples of the diamine used in the resin having the structure represented by any one of the general formulas (1) to (4) include 3,4'-diaminodiphenylmethane and 4,4'-diaminodiphenylmethane. , Benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4 , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-tetramethyl- 4,4′-diaminobiphenyl, 3,3 ′, 4,4′-tetramethyl-4,4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-di Minobiphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4 '-Diaminodiphenylsulfide, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 2, - bis (3-amino-4-hydroxyphenyl) hexafluoropropane, or compounds substituted with alkyl group or halogen atom in the aromatic ring, and a diamine of the structure having an amide group shown below. These are used alone or in combination of two or more.

In the above formula, R ⁷ is C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, cyclobutane residue, cyclopropane residue or cyclohexane residue, and R ^{8 to} R ¹¹ are hydrogen atoms. Represents a hydroxyl group or a thiol group.

  Among these, alkali solubility or chemical resistance can be improved by using a diamine having an alkali-soluble group or an amide group as a raw material.

  Among these, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4, 4'-diaminodiphenylsulfide, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 -Bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Scan (3-amino-4-hydroxyphenyl) hexafluoropropane or compounds substituted with alkyl group or halogen atom in the aromatic ring, and a diamine of structure having an amide group is more preferable as shown below. These are used alone or in combination of two or more.

In the above formula, R ⁷ is C (CF ₃ ) ₂ , C (CH ₃ ) ₂ , SO ₂ , S, O, cyclobutane residue, cyclopropane residue or cyclohexane residue, and R ^{8 to} R ⁹ are hydrogen atoms. Represents a hydroxyl group or a thiol group.

R ³ and R ^{5 in the} general formulas (1) to (4) represent a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. From the viewpoint of the dissolution rate into the alkaline aqueous solution, the number r and the number of R ⁵ s of R ³ is preferably 1 or more. In the present invention, a repeating unit in which r or s is 1 or more and a repeating unit in which r and s are 0 can be used in combination. It is preferable that 5% to 100% of the repeating units have a phenolic hydroxyl group, a sulfonic acid group, or a thiol group.

The structure X— (R ⁴ ) _m — in the general formulas (1) to (2) is a component derived from a primary monoamine that is a terminal blocking agent. Y- (R ⁴ ) _m-, which is a structural component of the general formulas (3) to (4), is added to an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound as a terminal blocking agent. It is a derived component.

  Specific examples of the primary monoamine used as a terminal blocking agent include aniline, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene and 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-hydroxynaphtha 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-aminonaphthalene, 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotine 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, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3 -Aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1 -Amino-7-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-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be mentioned.

  Among these, from the viewpoint of solubility in an aqueous alkali solution, 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, -Aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like are preferable. These are used alone or in combination of two or more.

  Specific examples of acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds used as end-capping agents include phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, 3-hydroxy Acid anhydrides such as phthalic anhydride, 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxy Naphthalene, 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-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, Monocarboxylic acids such as 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, and these carboxyl groups are acid. Chlorinated monoacid chloride compound, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2, Monoacid chloride compounds, monoacid chloride compounds and N-hydroxybenzotriazoles in which only the monocarboxyl group of dicarboxylic acids such as 3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, 2,7-dicarboxynaphthalene is converted to acid chloride And active ester compounds obtained by reaction with N-hydroxy-5-norbornene-2,3-dicarboximide.

  Among these, from the ease of introduction into the resin, acid anhydrides such as phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, 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- Monocarboxylic acids such as carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid are preferably used. These are used alone or in combination of two or more.

  The introduction ratio of the X component in the general formulas (1) and (2) is 0.1 to 60 mol% with respect to the total amine component, when converted with the primary monoamine component of the terminal blocker which is the original component. A range is preferable, and 5 to 50 mol% is particularly preferable.

  The introduction ratio of the Y component in the general formulas (3) and (4) is diamine when converted in terms of the acid anhydride, monocarboxylic acid, monoacid chloride compound, and monoactive ester compound component of the terminal blocker that is the original component. The range of 0.1-60 mol% is preferable with respect to a component, Most preferably, it is 5-50 mol%. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

  In the general formulas (1) to (4), n represents the number of repeating structural units and is in the range of 3 to 200. Preferably it is 8-150. When it says with a weight average molecular weight, 3000-80000 are preferable in polystyrene conversion by gel permeation chromatography, More preferably, it is 8000-50000.

  In the present invention, (a) the resin having a structure represented by any one of the general formulas (1) to (4) has an end group represented by X or Y as an essential component, and has a terminal group sealing effect. An increase in the molecular weight of the polymer can be suppressed. Therefore, the photosensitive resin composition which suppressed gelation and was excellent in storage stability can be obtained. Furthermore, the photosensitive resin composition of the present invention exhibits excellent coating properties when applied by spin coating or slit coating. That is, by using a resin having a structure represented by any one of the general formulas (1) to (4), the obtained photosensitive resin composition has a solid content as compared with the case of using a polyimide resin that is not end-capped. The concentration is high but the viscosity is low. Therefore, in the spin coating method, in order to obtain a coating film having a uniform film thickness, it can be achieved by a small amount of coating and not by high-speed rotation coating with danger but by safe low-speed rotation coating. Moreover, it is the slit coat method that the coating property with especially low viscosity and high density | concentration obtained using resin of this invention exhibits the outstanding coating property. Specifically, a coating film having a uniform film thickness can be formed on the entire surface of the substrate without causing liquid breakage. In addition, with the recent increase in size of the coated substrate, a uniform coated film is formed on the entire surface of the substrate without causing liquid breakage even when the slit nozzle is scanned (swept) at high speed from the viewpoint of productivity. be able to. In addition, since the solid content concentration is high, it can be formed without lowering the target film thickness.

  In the present invention, (a) an end-capped resin having a structure represented by any one of the general formulas (1) to (4) has a logarithmic viscosity of 0.05 to 0.45 dl / g in dimethylacetamide at 25 ° C. It is preferable. More preferably, it is 0.1-0.35 dl / g. In order to obtain a resin having such a logarithmic viscosity, for example, the polymerization ratio of the terminal blocking agent may be 1 to 70 mol% with respect to 100 mol of acid dianhydride and / or diamine. More preferably, it is 5-70 mol%, More preferably, it is 20-60 mol%.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized in R ¹ and R ² as long as the heat resistance is not lowered. Specifically, as the diamine component, bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-anilino) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, acid Examples of the dianhydride component include 1 to 10 mol% copolymerized 3,4-dicarboxyphenyltetramethyldisiloxane dianhydride.

  (A) In the resin having the structure represented by any one of the general formulas (1) to (4), a part of the diamine is replaced with a terminal blocking agent that is a monoamine, or the acid dianhydride is replaced with a monocarboxylic acid. It is synthesized using a known method in place of an end capping agent which is an acid, an acid anhydride, a monoacid chloride compound or a monoactive ester compound. For example, a method of reacting a tetracarboxylic dianhydride and a diamine compound (partially substituted with a terminal blocking agent that is a monoamine) at a low temperature, a tetracarboxylic dianhydride (a part of an acid anhydride or A method of reacting a diamine compound with a monoacid chloride compound or a mono-active ester compound, and a diamine compound, a diester is obtained by reaction of tetracarboxylic dianhydride and alcohol, and then a diamine (partially with a monoamine) A method of reacting with a certain end-capping agent and the presence of a condensing agent, a diester is obtained by reaction of tetracarboxylic dianhydride and alcohol, and then the remaining dicarboxylic acid is acid chlorided to obtain a diamine (partially Using a method such as a method of reacting with a monoamine end-capping agent), a polyimide precursor is obtained, and this is known in the art. Method of de reaction can be synthesized using.

Moreover, the terminal blocker introduced in the resin can be easily detected by the following method. For example, by dissolving the resin into which the end-capping agent has been introduced in an acidic solution and decomposing it into an amine component and an acid anhydride component that are the structural 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, the resin into which the end-capping agent has been introduced can be easily detected by directly measuring by pyrolysis gas chromatography (PGC), infrared spectrum or C ¹³ NMR spectrum.

(B) As an example of an acrylic resin, the polymer of unsaturated carboxylic acid is mentioned preferably. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and the like. These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Examples of copolymerizable ethylenically unsaturated compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, N-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, n-pentyl acrylate, N-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, p-methylstyrene, o-methyls Ren, m- methylstyrene, alpha-methyl styrene, tricyclo [5.2.1.0 ^2,6] decan-8-yl acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl And methacrylate.

  Among these, an acrylic resin having an ethylenically unsaturated group in the side chain is preferable. By having an ethylenically unsaturated group in the side chain, compatibility with the resin of component (a) is improved. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, an acrylic group, and a methacryl group. As a method for adding an ethylenically unsaturated group to the side chain of an acrylic resin, a compound containing a functional group such as a hydroxyl group, an amino group, or a glycidyl group and an ethylenically unsaturated group is used. The method of making it react with the carbonyl group in it is mentioned. Examples of the compound containing a functional group such as a hydroxyl group, an amino group, or a glycidyl group and an ethylenically unsaturated group include 2-hydroxylethyl acrylate, 2-hydroxyethyl methacrylate, 2-aminoethyl acrylate, methacrylic acid. Examples include 2-aminoethyl acid, glycidyl acrylate, and glycidyl methacrylate.

  (B) It is important that the weight average molecular weight (Mw) of the acrylic resin is 5000 to 30000 in terms of polystyrene measured by GPC. When Mw is smaller than 5000, the insulating property of the film after firing is lowered. Further, the shape of the photo pattern flows and deforms, and the resolution is lowered. Preferably it is 7000 or more, More preferably, it is 8000 or more. On the other hand, if Mw is larger than 30000, the resin of component (a) and the acrylic resin are phase-separated, the film becomes cloudy, and the insulating property of the fired film is lowered. Preferably it is 25000 or less, More preferably, it is 23000 or less.

  Moreover, it is preferable that (b) acrylic resin is alkali-soluble, and it is preferable that an acid value is 50 mg / KOH or more. On the other hand, the acid value is preferably 150 mgKOH / g or less, more preferably 130 mgKOH / g or less, from the viewpoint of reducing the film loss of the unexposed area during development.

  The acid value can be calculated by the following method. 1 g of acrylic resin is taken into a 100 ml Erlenmeyer flask and weighed. Thereto, 40 ml of a mixed solvent of ethanol: toluene = 1: 2 (volume ratio) is added and dissolved. Titrate with 0.5N aqueous KOH solution using phenolphthalein solution as an indicator. The acid value is calculated from the KOH dropping weight and the acrylic resin weighed value with the point where the faint red color disappears for 30 seconds or more as the end point.

  In the photosensitive resin composition of the present invention, (a) the ratio of the content of the resin having a structure represented by any one of the general formulas (1) to (4) and (b) the content of the acrylic resin ((a ) / (B)) is preferably 80/20 to 20/80 (weight ratio). More preferably, (a) / (b) = 70/30 to 30/70. By setting the content ratio of (a) and (b) within this range, the insulating properties of the fired film are further improved.

  The resin contained in the photosensitive resin composition of the present invention may be (a) a resin having a structure represented by any one of the general formulas (1) to (4) and (b) an acrylic resin alone. Even if it is a copolymer with other structural units, it may further contain other resins. At that time, (a) a resin having a structure represented by any one of the general formulas (1) to (4) and (b) a total amount of 100% by weight including an acrylic resin and another resin, The content of the resin having a structure represented by any one of formulas (1) to (4) and (b) the acrylic resin is preferably 50% by weight or more. The type and amount of the structural unit used for copolymerization are preferably selected within a range that does not impair the heat resistance of the resin composition obtained by the final heat treatment.

  Specific examples of the other resin include alkali-soluble polybenzoxazole resin, polyamic acid that is a polyimide precursor, polyhydroxyamide that is a polybenzoxazole precursor, novolak resin, and siloxane resin. Such a resin is soluble in an aqueous solution of alkali such as choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate in addition to tetramethylammonium hydroxide. . In addition to polyamic acid, polyamic acid ester, polyisoimide, polyamic acid sulfonamide, polyamic acid having advanced imidization of 5 to 50%, and the like can also be used. These resins may be used alone or in combination.

  The photosensitive resin composition of the present invention contains (c) a photoacid generator. (C) Examples of the photoacid generator include a quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, and an iodonium salt.

  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 such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can. Such compounds may be used alone or in combination of two or more. By using 2 or more types of photo-acid generators, the ratio of the dissolution rate of an exposed part and an unexposed part can be taken larger, and 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-S, BisP-AF, 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-35X , 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.), 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxy Benzophenone, gallic acid methyl ester, bisphenol A, bisphenol E, methylene bisphenol BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and the like, but is not limited to these.

  Polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Although sulfide etc. are mentioned, it is not limited to these.

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

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidosulfonyl 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 5000 or less, more preferably 3000 or less, and more preferably 1500 or less in order to sufficiently perform thermal decomposition by heat treatment. Moreover, 300 or more are preferable and 350 or more are more preferable.

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

  The photosensitive resin composition of the present invention preferably contains a sulfonium salt, a phosphonium salt or a diazonium salt as the photoacid generator (c) together with the quinonediazide compound. By containing these, the acid component generated by exposure can be appropriately stabilized. Since the resin composition obtained from the photosensitive resin composition of the present invention is used as a permanent film, it is environmentally undesirable for phosphorus or the like to remain, and it is necessary to consider the color tone of the film. In this case, a sulfonium salt is preferably used. Although the specific example of a sulfonium salt is shown below, it is not limited to these.

  Since the photosensitive resin composition of the present invention contains (c) a photoacid generator, an acid is generated in the light irradiation part, and the solubility of the light irradiation part in the alkaline aqueous solution is increased. A positive relief pattern that dissolves can be obtained.

  In the photosensitive resin composition of the present invention, the content of (c) the photoacid generator is (a) a resin having a structure represented by any one of the general formulas (1) to (4) and (b) acrylic. Preferably it is 0.01-50 weight part with respect to 100 weight part of total amounts of resin. Of these, the quinonediazide compound is preferably in the range of 3 to 40 parts by weight. In addition, the compound selected from sulfonium salt, phosphonium salt, and diazonium salt is preferably independently or in a total range of 0.05 to 40 parts by weight, and among them, each independently or in a total range of 3 to 30 parts by weight. preferable. (C) By making content of a photo-acid generator into this range, higher sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed.

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

  Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, BisP-S, BisP-AF, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA ), TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25 -OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP -PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.) Can be mentioned.

  Among these, particularly preferable compounds are, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, and BIR-BIPC-F. . By containing these compounds having a phenolic hydroxyl group, 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.

  The content of such a compound having a phenolic hydroxyl group is based on (a) a resin having a structure represented by any one of the general formulas (1) to (4) and (b) a total amount of 100 parts by weight of the acrylic resin. The amount is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight.

The photosensitive resin composition of the present invention contains (d) a thermally crosslinkable compound. (D) It is preferable that a thermally crosslinkable compound contains group represented by General formula (5).
—CH ₂ —OR ⁶ (5)
In General Formula (5), R ⁶ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a cyclic aliphatic group having 4 to 20 carbon atoms.

  Among these, it is preferable to have a phenolic hydroxyl group or a urea organic group represented by the general formula (13).

R ²⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms.

  Examples of the (d) thermally crosslinkable compound preferably used in the present invention include, but are not limited to, the following compounds.

  Specific examples of the thermally crosslinkable compound containing the urea organic group represented by the general formula (13) are shown below, but are not limited thereto.

  Furthermore, the compound which has the following melamine resin type structures is also mentioned.

  By containing these (d) thermally crosslinkable compounds, (a) a resin having a structure represented by any one of the general formulas (1) to (4) and (b) acrylic by a crosslinking reaction during firing The resin forms a network, and the insulation performance is improved even under low temperature firing. In addition, the resulting photosensitive resin composition has drastically improved chemical resistance of the film after baking, and hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. In addition, film loss due to development is small, and development can be performed in a short time.

  In particular, in the case of an alkoxymethyl group-containing heat-crosslinkable compound containing a urea-based organic group represented by the general formula (13) or a melamine resin-based heat-crosslinkable compound, an aromatic heat-crosslinkable compound having a phenolic hydroxyl group and In comparison, since a film having a high transmittance at 400 nm of the fired film can be obtained, it can be more preferably used. Further, since the absorption with respect to light of the exposure wavelength is extremely small, the exposure energy is efficiently transmitted to the photosensitizer, so that there are advantages of high sensitivity and excellent heat resistance.

  Furthermore, among the alkoxymethyl group-containing heat-crosslinkable compound and the melamine resin-based heat-crosslinkable compound, a heat-crosslinkable compound having four or more structures represented by the general formula (5) in the molecule is preferable. By having four or more structures represented by the general formula (5) in the molecule, (a) a resin having a structure represented by any one of the general formulas (1) to (4) and (b) an acrylic resin And the cross-linking proceeds sufficiently to further improve the insulating properties.

  In the present invention, the content of (d) the thermally crosslinkable compound is (a) a resin having a structure represented by any one of the general formulas (1) to (4) and (b) a total amount of 100 parts by weight of the acrylic resin. On the other hand, it is preferably 0.5 to 100 parts by weight, more preferably 3 to 80 parts by weight.

  The photosensitive resin composition of the present invention may contain a compound having a plurality of epoxy structures or oxetane structures in the molecule as a reactive crosslinking agent.

  Specific examples of the compound having two or more epoxy structures include “Epolite” (registered trademark) 40E, “Epolite” 100E, “Epolite” 200E, “Epolite” 400E, “Epolite” 70P, “Epolite” 200P, “Epolite” "400P", "Epolite" 1500NP, "Epolite" 80MF, "Epolite" 4000, "Epolite" 3002 (trade name, manufactured by Kyoeisha Chemical Industry Co., Ltd.), "Denacol" (registered trademark) EX-212L, "Denacol" EX-214L, "Denacol" EX-216L, "Denacol" EX-850L, "Denacol" EX-321L (above product names, manufactured by Nagase ChemteX Corporation), GAN, GOT, EPPN502H, NC3000, NC6000 (above products) Name, Nippon Kayaku Co., Ltd.), “ "Picoat" (registered trademark) 828, "Epicoat" 1002, "Epicoat" 1750, "Epicoat" 1007, YX8100-BH30, E1256, E4250, E4275 (above, trade name, manufactured by Japan Epoxy Resins Co., Ltd.), "Epicron" ( (Registered trademark) EXA-9583, “Epiclon” HP4032, “Epiclon” N695, “Epiclon” HP7200 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), “Tepic” (registered trademark) S, “Tepic” G “Tepic” P (trade name, manufactured by Nissan Chemical Industries, Ltd.), “Epototo” (registered trademark) YH-434L (trade name, manufactured by Toto Kasei Co., Ltd.), and the like.

  Specific examples of the compound having two or more oxetane structures include OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (above, trade name, manufactured by Toa Gosei Co., Ltd.), “Etanacor” (registered trademark) OXBP, “Etanacor” OXTP (trade name, manufactured by Ube Industries, Ltd.), and the like.

  The reactive crosslinking agent may be used alone or in combination of two or more. The content of the reactive crosslinking agent is 0.1 with respect to 100 parts by weight of the total amount of (a) the resin having the structure represented by any one of the general formulas (1) to (4) and (b) the acrylic resin. -10 parts by weight is preferred.

In the present invention, an adhesion improving agent may be contained for the purpose of improving the adhesion to the substrate during development. Adhesion improvers include silane coupling agents such as trimethoxyaminopropyl silane, trimethoxy epoxy silane, trimethoxy vinyl silane, trimethoxy thiol propyl silane, titanium chelating agent, aluminum chelating agent, aromatic amine compound and alkoxy group-containing silicon. Examples include compounds obtained by reacting compounds. When these compounds are contained, the adhesion to an underlying substrate such as a silicon wafer, ITO, SiO ₂ , or silicon nitride can be further enhanced, and resistance to oxygen plasma and UV ozone treatment used for cleaning can be increased. Alternatively, the base substrate can be pretreated with a chemical solution containing these compounds.

  The content of the adhesion improving agent is 0.5 to 10 with respect to 100 parts by weight of the total amount of (a) the resin having a structure represented by any one of the general formulas (1) to (4) and (b) the acrylic resin. It is preferable to use parts by weight. When treating the substrate with a chemical solution containing an adhesion improver, the adhesion improver is a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. It is desirable to perform surface treatment by spin coating, slit die coating, bar coating, dip coating, spray coating, steam treatment or the like in a solution in which 0.5 to 20% by weight is dissolved. As needed, reaction with a base material and the said adhesion improving agent can be advanced by applying temperature from 50 degreeC to 300 degreeC after that.

  Moreover, you may contain an alkoxysilane containing aromatic amine compound, an aromatic amide compound, or a vinylsilane compound for the purpose of raising adhesiveness with a base material after baking. Specific examples of the alkoxysilane-containing aromatic amine compound and aromatic amide compound are shown below, but are not limited thereto.

  Examples of the vinyl silane compound include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl trichloro silane, vinyl tris (β-methoxy ethoxy) silane, etc. In addition to this, 3-methacryloxypropyl trimethoxy silane, 3- Carbon-carbon unsaturated bond-containing silane compounds such as acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane can also be used. Vinyltrimethoxysilane and vinyltriethoxysilane are preferable.

  The alkoxysilane-containing aromatic amine compound, aromatic amide compound, or vinylsilane compound is (a) a resin having a structure represented by any one of the general formulas (1) to (4) and (b) a total amount of acrylic resin of 100. It is preferable to contain 0.001-30 weight part respectively with respect to a weight part. More preferably, it is 0.005-20 weight part, More preferably, it is 0.01-15 weight part.

  In the present invention, it is preferable to add the above-mentioned adhesion improving agent to the composition after completion of polymerization of the polymer. When a compound corresponding to the above-mentioned adhesion improving agent is added during polymer polymerization, it may be incorporated into the polymer main chain by a covalent bond in the polymer and the adhesion effect may be reduced. Further, when the polymer is reprecipitated, unreacted substances of the above compound are removed at the time of reprecipitation, and the adhesion effect may be reduced, or there may be problems such as gelation due to condensation of alkoxy groups. A preferred method of addition is to add the reprecipitated polymer at the time of re-dissolving in the solvent or after re-dissolution.

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

  Surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M Co., Ltd.), MegaFac (trade name, manufactured by Dainippon Ink and Chemicals), Sulflon (trade name, manufactured by Asahi Glass Co., Ltd.), etc. And surface active agents. In addition, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corporation), Polyflow, Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), BYK (Bic Chemie Corporation) )) And other organic siloxane surfactants. Furthermore, acrylic polymer surfactants such as polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) can be mentioned.

  The photosensitive resin composition of the present invention preferably contains a solvent. Solvents are polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl Esters such as acetate, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, toluene, xylene, etc. Can be used solvents such as aromatic hydrocarbons alone, or two or more. Since the photosensitive resin composition in the present invention can be used at a baking temperature of 200 ° C. or lower, a solvent having a boiling point not higher than the baking temperature can be appropriately used in accordance with the target baking temperature.

  The content of the solvent used in the present invention is based on (a) a resin having a structural unit represented by any one of the general formulas (1) to (4) and (b) a total amount of 100 parts by weight of the acrylic resin. 50 to 2000 parts by weight is preferable, and 100 to 1500 parts by weight is particularly preferable.

  3-100 mPa * s is preferable and the viscosity of the photosensitive resin composition obtained by this invention is a viscosity range. If the solid content concentration is adjusted so that the viscosity is lower than 3 m · Pas, the solid content concentration becomes too low, and it becomes difficult to obtain a desired film thickness. On the other hand, when the viscosity is greater than 100 mPa · s, it is difficult to obtain a highly uniform coating film.

  Next, a method for forming an insulating resin pattern using the photosensitive resin composition of the present invention will be described. In the present invention, (1) a step of applying the photosensitive resin composition to a substrate to obtain a photosensitive resin composition coating, (2) a step of exposing the photosensitive resin composition coating with ultraviolet rays, (3) An insulating resin pattern can be formed by the step of developing the exposed photosensitive resin composition film with an alkaline aqueous solution and the step of (4) heat-treating the developed photosensitive resin composition film. Hereinafter, each step will be described.

The photosensitive resin composition of this invention is apply | coated on a base material. Examples of the material of the base material include all materials that can provide a metal for an electrode on the surface, such as metal, glass, semiconductor, metal oxide insulating film, silicon nitride, and polymer film. Glass or polymer film is preferably used. The material of the glass is not particularly limited, but alkali zinc borosilicate glass, sodium borosilicate glass, soda lime glass, low alkali borosilicate glass, barium borosilicate glass, borosilicate glass, aluminosilicate glass, molten Quartz glass, synthetic quartz glass, and the like are used, and soda-lime glass with a barrier coating such as non-alkali glass or SiO ₂ that usually has few ions eluted from the glass is used. As the material of the polymer film, polyethylene terephthalate, polyethersulfone, and materials having a similar chemical structure can be used. Also, since the thickness should be sufficient to maintain the mechanical strength, if the material is inorganic, it is 0.1 mm or more, preferably 0.5 mm or more, and if the material is organic, 0.05 mm or more, Preferably it is 0.1 mm or more. The size of the substrate is not particularly limited, but a rectangular or square rectangular substrate having a side of 150 mm or more and a round substrate can provide a good coating film on a substrate having a diameter of 6 inches or more. The coating method includes a slit coating method, a spin coating method, a spray coating method, a roll coating method, a bar coating method, and the like, and these methods may be used in combination. Moreover, although a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is normally applied so that the film thickness after drying is 0.1 to 100 μm. If the material is a polymer film and one side is 300 mm or more and it is difficult to maintain the mechanical strength even if the thickness is adjusted, the polymer film is pasted on a glass substrate or the like to maintain the mechanical strength. The coating method can be used.

Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. For drying, a hot plate, an oven, an infrared ray, a vacuum chamber or the like is used. When a hot plate is used, the object to be heated is heated by holding it directly on the plate or on a jig such as a proxy pin installed on the plate. As a material of the proxy pin, there is a metal material such as aluminum or stellenless, or a synthetic resin such as polyimide resin or Teflon (registered trademark), and any proxy pin may be used. The height of the proxy pin varies depending on the size of the substrate, the type of the resin layer to be heated, the purpose of heating, etc. For example, a resin layer coated on a 400 × 500 × 0.7 mm ³ glass substrate is used. When heating, the height of the proxy pin is preferably about 2 to 12 mm. The heating temperature varies depending on the type and purpose of the object to be heated, and it is preferably performed in the range of room temperature to 180 ° C for 1 minute to several hours.

  Next, the photosensitive resin composition film is exposed to actinic radiation through a mask having a desired pattern. There are ultraviolet rays, visible rays, electron beams, X-rays and the like as actinic rays used for exposure. In the present invention, it is preferable to use ultraviolet rays, and in particular, i-line (365 nm), h-line (405 nm), g-line of a mercury lamp. (436 nm) is preferably used.

  Forming a heat-resistant resin pattern from the photosensitive resin composition film is accomplished by removing the exposed portion using a developer after exposure. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be used alone or in combination. After development, it is preferable to rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, heat treatment is performed to convert to an insulating resin film. This heat treatment is preferably 120 ° C. to 300 ° C., the temperature may be selected and the temperature may be raised stepwise, or may be carried out for 5 minutes to 5 hours while selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C., 150 ° C., 170 ° C., 200 ° C., and 250 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 160 ° C. over 30 minutes can be mentioned.

  The insulating resin film formed from the photosensitive heat-resistant composition according to the present invention is used for a semiconductor passivation film, a protective film for a semiconductor element, an interlayer insulating film for a multilayer wiring for high-density mounting, an insulating layer for an organic electroluminescent element, etc. Used for.

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

(1) Production of photosensitive resin film 400 × 500 × 0.7 mm ³ and 200 × 214 × 0.7 mm ³ non-alkali glass (Corning Japan Co., Ltd., # 1737) surface was deposited by sputtering deposition. 400 mm × 500 mm and 200 mm × 214 mm glass substrates on which a 125 nm ITO transparent electrode film was formed were prepared. A photoresist was applied onto the ITO film by a spinner, and patterning was performed by exposure and development by a normal photolithography method. After removing unnecessary portions of ITO by etching, the photoresist was removed to pattern the ITO film into a stripe shape having a length of 90 mm, a width of 80 μm, and a pitch of 100 μm. This striped ITO film becomes the first electrode when an organic electroluminescent device is formed.

  A photosensitive resin composition (hereinafter referred to as varnish) was applied onto a glass substrate patterned with ITO so that the film thickness after drying was 1.5 μm. Application onto a 200 mm × 214 mm substrate was performed by spin coating, the amount of varnish dropped onto the center of the substrate was 20 g, and the rotation speed was 800 rpm for 10 seconds. The application onto the 400 mm × 500 mm substrate was performed by slit coating, the nozzle scan speed was 4 m / min, and the nozzle-substrate gap was 150 μm. Then, using a hot plate (EA-4331 manufactured by Chuo Riken Co., Ltd.), the glass substrate is held at a height of 5.0 mm from the hot plate with a proxy pin, heated at 100 ° C. for 5 minutes, and dried. A photosensitive resin film was obtained.

(2) Viscosity measurement Using an Ubbelohde viscometer, the logarithmic viscosity of a 0.5 dl / g polyimide resin dilute solution in dimethylacetamide was measured. Moreover, the viscosity measurement of the varnish was performed using the E-type rotational viscometer (made by Toki Sangyo Co., Ltd.).

(3) Evaluation of applicability The surface of the photosensitive resin film formed by the spin coating method was visually observed for the applicability to the edge of the substrate under irradiation with a sodium lamp. Those with good covering properties were judged as good- ◯, and those with poor covering properties were judged as poor-x. Moreover, about the photosensitive resin film formed by the slit-coating method, the surface observation was performed visually about the presence or absence of liquid cutting | disconnection and a vertical stripe under sodium lamp irradiation. With respect to each of the liquid breakage and the vertical stripe, it was determined that the case where no occurrence occurred was good-.

(4) Compatibility evaluation after development A varnish was spin-coated on a 6-inch silicon wafer, then baked on a hot plate at 100 ° C. for 2 minutes (using Mark-7), finally having a thickness of 1.2 μm A pre-baked film was prepared. The film was exposed at 10 mJ / cm ² steps by the exposure amount of 0~400mJ / cm ² using an i-line stepper (GCA manufactured DSW-8000), after exposure, a 3% aqueous sodium carbonate (NA3-K, (Developed by Tokyo Ohka Co., Ltd.) for 60 seconds, followed by rinsing with pure water. After development, the surface of the film was visually checked for white turbidity or phase separation with an optical microscope. An example of a normal post-development film surface is shown in FIG. 1, and an example of a post-development film surface that has undergone phase separation is shown in FIG. When the microscope magnification was 50 times, the case where no roughness was observed on the film surface was marked with ◯, and when the roughness was observed, x was marked.

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

(6) Evaluation of insulating properties 0.5 μm and 1 μm thick insulating resin films produced on a silicon wafer by coating, developing, and heat treatment at 150 ° C. for 60 minutes were applied to Kikusui Electronics Co., Ltd. withstand voltage / insulation. Using a resistance tester TOS9201, the voltage was increased with DCW at a voltage increase rate of 0.1 kV / 4 seconds, the voltage when dielectric breakdown occurred was measured, and the obtained voltage was divided by the film thickness to obtain a unit film thickness. The dielectric breakdown voltage was obtained.

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

Synthesis Example 2 Synthesis of Amide Group-Containing Diamine Compound (b) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g of propylene oxide (0.3 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and −15 Cooled to ° C. A solution prepared by dissolving 20.4 g of 3-nitrobenzoyl chloride (0.11 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon (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, filtration was performed to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain an amide group-containing diamine compound (b) represented by the following formula.

Synthesis Example 3 Synthesis of quinonediazide compound (c) Under a dry nitrogen stream, BisP-RS (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 16.10 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 26.86 g (0.1 mol, NAC-5, manufactured by Toyo Gosei Co., Ltd.) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration and further washed with 1 L of 1% aqueous hydrochloric acid. Thereafter, it was further washed twice with 2 L of water. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (c) represented by the following formula.

Synthesis Example 4 Synthesis of quinonediazide compound (d) Under a dry nitrogen stream, TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and NAC-5 13.43 g (0. 05 mol), 13.43 g (0.05 mol, NAC-4, manufactured by Toyo Gosei Co., Ltd.) of 4-naphthoquinone diazide sulfonyl chloride was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane was used, and in the same manner as in Synthesis Example 3, on average, one of Q became 5-naphthoquinonediazide sulfonic acid ester, and one on average A quinonediazide compound (d) represented by the following formula, which was 4-naphthoquinonediazidesulfonic acid ester, was obtained.

Synthesis Example 5 Synthesis of acrylic resin solution (e) In a 500 ml flask, 5 g of 2,2′-azobis (isobutyronitrile), 5 g of t-dodecanethiol, propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) 150 g was charged. Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature. The mixture was stirred with heating at 5 ° C. for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain an acrylic resin solution (e). The obtained acrylic resin solution (e) had a solid content concentration of 43% by weight, the weight average molecular weight (Mw) of the obtained resin was 10600, and the acid value was 118 mgKOH / g.

Synthesis Example 6 Synthesis of Acrylic Resin Solution (f) A 500 ml flask was charged with 5 g of 2,2′-azobis (isobutyronitrile) and 150 g of PGMEA. Thereafter, 27 g of methacrylic acid, 38 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature. The mixture was stirred with heating at 5 ° C. for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain an acrylic resin solution (f). The obtained acrylic resin solution (f) had a solid content concentration of 43% by weight, the weight average molecular weight (Mw) of the obtained resin was 31400, and the acid value was 105 mgKOH / g.

Synthesis Example 7 Synthesis of Acrylic Resin Solution (g) A 500 ml flask was charged with 5 g of 2,2′-azobis (isobutyronitrile) and 150 g of PGMEA. Thereafter, 15 g of methacrylic acid, 45 g of methyl methacrylate and 40 g of styrene were charged, stirred for a while at room temperature, purged with nitrogen in the flask, and then heated and stirred at 70 ° C. for 5 hours to obtain an acrylic resin solution (g). . The obtained acrylic resin solution (g) had a solid content concentration of 43% by weight, the weight average molecular weight (Mw) of the obtained resin was 23000, and the acid value was 97 mgKOH / g.

Synthesis Example 8 Synthesis of Acrylic Resin Solution (h) A 500 ml flask was charged with 5 g of 2,2′-azobis (isobutyronitrile), 20 g of t-dodecanethiol, and 200 g of PGMEA. Thereafter, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and stirred for a while at room temperature. The mixture was stirred with heating at 5 ° C for 5 hours. Next, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine, and 0.2 g of p-methoxyphenol were added to the resulting solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain an acrylic resin solution (h). The obtained acrylic resin solution (h) had a solid content concentration of 43% by weight, the weight average molecular weight (Mw) of the obtained resin was 4500, and the acid value was 118 mgKOH / g.

Synthesis Example 9 Synthesis of acrylic resin solution (i) A 500 ml flask was charged with 5 g of 2,2′-azobis (isobutyronitrile) and 200 g of THF. Thereafter, 35 g of methyl methacrylate (MM), 30 g of tert-butyl methacrylate (t-BM) and 35 g of methacrylic acid (MA) were charged and stirred for a while at room temperature. After the atmosphere in the flask was replaced with nitrogen, the mixture was stirred at room temperature for 40 hours. An acrylic resin solution (i) was obtained. The obtained acrylic resin solution (i) had a solid content concentration of 35% by weight, the weight average molecular weight (Mw) of the obtained resin was 7000, and the acid value was 137 mgKOH / g.

  The structure of heat-crosslinkable compound Nicarak 100LM used in Examples and Comparative Examples is shown below.

Example 1
Under a dry nitrogen stream, 29.30 g (0.08 mol) of BAHF, 1.24 g (0.005 mol, SiDA) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 3.27 g (0.03 mol) of aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd., 3-APH) was dissolved in 80 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). Here, 31.2 g of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (manac Co., Ltd., 0.1 mol, ODPA) was added together with 20 g of NMP and reacted at 20 ° C. for 1 hour. Subsequently, it was made to react at 50 degreeC for 4 hours. Thereafter, 15 g of xylene was added, and the mixture was stirred at 150 ° C. for 5 hours while azeotropically distilling water with xylene. After stirring, the solution was poured into 3 liters of water to collect a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80 ° C. for 20 hours. The resulting polymer solids, was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The logarithmic viscosity at 25 ° C. of a dilute solution adjusted to a concentration of 0.5 g / dl in dimethylacetamide of this polyimide polymer was 0.15 dl / g.

  8.31 g of the polyimide polymer A thus obtained, 8.27 g of the acrylic resin solution (e) obtained in Synthesis Example 5, 2.71 g of the quinonediazide compound (d) obtained in Synthesis Example 4, and a thermally crosslinkable compound As a result, 3.39 g of Nicalac 100LM was added to 77.24 g of propylene glycol monomethyl ether (hereinafter referred to as PGME) to obtain a varnish A of a photosensitive resin composition. The viscosity of varnish A was 15 mPa · s. Using the obtained varnish A, applicability evaluation was performed as described above. As a result, in the coating by the spin coating method, the coverage to the substrate edge was good. Moreover, in the application | coating by a slit coating method, generation | occurrence | production of a liquid cut and a vertical stripe was not recognized. Next, when compatibility after development was evaluated, no phase separation was observed on the film surface after development. In the evaluation of insulation, the dielectric breakdown voltage per unit film thickness was 461 V / μm when the film thickness was 1.0 μm and 318 V / μm when the film thickness was 0.5 μm.

Example 2
Weighing 5.93 g of polyimide polymer A obtained in Example 1, 13.80 g of the acrylic resin solution (e) obtained in Synthesis Example 5, 2.71 g of the quinonediazide compound (d) obtained in Synthesis Example 4, and thermal crosslinking Varnish B of the photosensitive resin composition was obtained by adding 3.39 g of Nicalac 100LM as a functional compound to 74.13 g of PGME. The viscosity of varnish B was 13 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Example 3
Weighing 3.56 g of the polyimide polymer A obtained in Example 1, 19.31 g of the acrylic resin solution (e) obtained in Synthesis Example 5, 2.71 g of the quinonediazide compound (d) obtained in Synthesis Example 4, and thermal crosslinking The varnish C of the photosensitive resin composition was obtained by adding 3.39 g of Nicalac 100LM as a functional compound to 70.93 g of PGME. The viscosity of varnish C was 11 m · Pas. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Example 4
Under a dry nitrogen stream, the hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 (24.18 g, 0.04 mol), BAHF (10.99 g, 0.03 mol), SiDA (1.24 g, 0.005 mol), terminal As a sealant, 5.46 g (0.05 mol) of 3-APH was dissolved in 200 g of NMP. ODPA 31.02g (0.1mol) was added here, and it stirred at 40 degreeC for 4 hours. Then, it stirred at 180 degreeC for 5 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 polymer B. The resulting polymer solids, was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The logarithmic viscosity at 25 ° C. of a dilute solution prepared by adjusting the polyimide polymer in dimethylacetamide to a concentration of 0.5 g / dl was 0.13 dl / g.

  5.93 g of the polymer B solid thus obtained was weighed, 13.80 g of the acrylic resin solution (g) obtained in Synthesis Example 7, 2.71 g of the quinonediazide compound (c) obtained in Synthesis Example 3, and heat Varnish D of the photosensitive resin composition was obtained by adding 3.39 g of Nicalac 100LM as a crosslinkable compound to 74.13 g of PGME. The viscosity of varnish D was 12 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Example 5
Under a dry nitrogen stream, 8.01 g (0.04 mol, 3,4'-DAE) of 3,4'-diaminodiphenyl ether, 16.48 g (0.045 mol) of BAHF, 1.24 g (0.005 mol) of SiDA, terminal As a sealant, 2.18 g (0.02 mol) of 3-APH was dissolved in 200 g of NMP. Here, 35.7 g (0.05 mol) of the amide group-containing acid dianhydride (a) obtained in Synthesis Example 1 and 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride 22 .21 g (6FDA, 0.05 mol) was added and stirred at 50 ° C. for 6 hours. Then, it stirred at 180 degreeC for 5 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 polymer B. The resulting polymer solids, was measured by infrared absorption spectrum, 1780 cm around ^-1, absorption peaks of an imide structure caused by a polyimide near 1377 cm ^-1 was detected. The logarithmic viscosity at 25 ° C. of a dilute solution adjusted to a concentration of 0.5 g / dl in dimethylacetamide of this polyimide polymer was 0.25 dl / g.

  5.93 g of the polymer C solid thus obtained was weighed, 13.80 g of the acrylic resin solution (e) obtained in Synthesis Example 5, 2.71 g of the quinonediazide compound (d) obtained in Synthesis Example 4, and heat Varnish E of the photosensitive resin composition was obtained by adding 3.39 g of Nicalak 100LM as a crosslinkable compound to 74.13 g of PGME. The viscosity of varnish E was 18 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Example 6
Weighing 5.93 g of polyimide polymer A obtained in Example 1, 16.95 g of acrylic resin solution (i) obtained in Synthesis Example 9, 2.71 g of the quinonediazide compound (d) obtained in Synthesis Example 4, and thermal crosslinking As a functional compound, 3.39 g of Nicalac 100LM was added to 74.12 g of PGME to obtain a varnish F of a photosensitive resin composition. The viscosity of varnish F was 10 mPa · s. Table 1 shows the results of various evaluations using the obtained varnish as described above.

Example 7
The photosensitive resin composition varnish B obtained in Example 2 was UV-exposed through a photomask having a shape covering the edge of the first electrode. After the exposure, development was performed by dissolving only the exposed portion with a 0.1% TMAH aqueous solution, followed by rinsing with pure water. Subsequently, the photosensitive resin film was cured by heating at 230 ° C. for 30 minutes under a nitrogen atmosphere in a clean oven to obtain an insulating layer. The thickness of the insulating layer was about 1 μm. The insulating layer is formed so as to cover the edge of the first electrode, and an opening having a width of 70 μm and a length of 250 μm is provided in the central portion so that the first electrode is exposed. The insulating layer had a gentle forward taper as shown in FIG. The taper angle was 20 °.

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

  The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin. In this way, a simple matrix type color organic electroluminescent device was produced. When this display device was line-sequentially driven, good display characteristics could be obtained. The thin film layer and the second electrode at the boundary of the insulating layer were formed smoothly without any thinning or disconnection, so there was no uneven brightness in the light emitting region and stable light emission. was gotten.

Example 8
A thin film (thickness: 0.2 μm) of oxynitride composite chromium was formed on an alkali-free glass substrate by sputtering. A photosensitive resist is coated on the composite chrome thin film, mask exposure, development, and etching of the composite chrome thin film are sequentially performed, so that a rectangular opening of 80 μm × 280 μm has a pitch of 100 μm in the short side direction and a long side. A black matrix arranged on the matrix at a pitch of 300 μm in the direction was formed.

  Next, a photosensitive coating composition for forming color filter layers of red, green, and blue was prepared. As a red colorant, a condensed azo pigment (manufactured by Ciba Geigy, Chromophthalred BRN), as a green colorant, a phthalocyanine green pigment (manufactured by Toyo Ink Manufacturing Co., Ltd., Lionol Green 2Y-301), and as a blue colorant Each anthraquinone pigment (Ciba Geigy Co., Chromophthal Blue A3R) was used, polyvinyl alcohol (10% aqueous solution) was used as the binder resin, and one part of each colorant was added to 10 parts of the polyvinyl alcohol aqueous solution. Is also mixed and dispersed at a ratio of mass basis), and 100 parts of the resulting solution is mixed with 1 part of ammonium dichromate as a crosslinking agent to form a color coating layer for each color filter layer. A composition was obtained.

  The color filter layer of each color was formed using the above-mentioned photosensitive coating composition for forming each color filter layer in sequence. That is, a photosensitive coating composition for forming a red color filter layer was applied on the transparent base material on which the black matrix was formed by spin coating, and prebaked at 100 ° C. for 5 minutes. Then, it exposed using the photomask and developed with the developing solution (0.05% KOH aqueous solution). Next, post-baking is performed at a temperature of 230 ° C. for 60 minutes, and the black matrix pattern is tuned to the opening. A band-shaped red pattern having a width of 85 μm and a thickness of 1.5 μm is formed. It was formed to be in the short side direction. Thereafter, a green color filter layer forming photosensitive coating composition and a blue color filter layer forming photosensitive coating composition are sequentially used to form a green pattern and a blue pattern. A color filter layer in which patterns were repeatedly arranged in the width direction was formed.

  On this color filter, the photosensitive resin composition varnish E obtained in Example 5 was applied by spin coating, and prebaked at 100 ° C. for 2 minutes. Next, an area of 10 mm from the edge of the color filter substrate was exposed using a photomask and developed with a developer (0.5% KOH aqueous solution). Next, a transparent overcoat layer covering the entire color filter substrate was formed by baking at 230 ° C. for 30 minutes.

  Further, a 300 nm thick SiON thin film was formed on the formed protective layer by sputtering to form a transparent barrier layer. Subsequently, an ITO transparent electrode film having a thickness of 125 nm was formed on the transparent barrier layer by a sputtering vapor deposition method. A photoresist was applied onto the ITO film by a spinner, and patterning was performed by exposure and development by a normal photolithography method. After removing unnecessary portions of ITO by etching, the photoresist was removed to pattern the ITO film into a stripe shape having a length of 90 mm, a width of 80 μm, and a pitch of 100 μm.

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

  The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin. In this way, a simple matrix white color filter type organic electroluminescent device was produced. When this display device was line-sequentially driven, good display characteristics could be obtained. The thin film layer and the second electrode at the boundary of the insulating layer were formed smoothly without any thinning or disconnection, so there was no uneven brightness in the light emitting region and stable light emission. was gotten.

Example 9
On a 0.2 mm thick polymer film substrate made of polyethersulfone resin, a 0.1 μm thick barrier layer made of SiON was formed by a reactive sputtering apparatus. Subsequently, a transparent electrode made of ITO having a thickness of 0.1 mm was formed as a first electrode on the barrier layer by a sputtering method. A photoresist was applied onto the ITO film by a spinner, and patterning was performed by exposure and development by a normal photolithography method. After removing unnecessary portions of ITO by etching, the photoresist was removed to pattern the ITO film into a stripe shape having a length of 90 mm, a width of 80 μm, and a pitch of 100 μm.

  The photosensitive resin composition varnish C obtained in Example 3 was spin-coated on the substrate, and UV-exposed through a photomask having a shape covering the edge of the first electrode. After the exposure, development was carried out by dissolving only the exposed portion with a 3% aqueous sodium carbonate solution, followed by rinsing with pure water. Subsequently, the photosensitive resin film was cured by heating at 150 ° C. for 60 minutes under a nitrogen atmosphere in an oven to obtain an insulating layer. The thickness of the insulating layer was about 1 μm. The insulating layer is formed so as to cover the edge of the first electrode, and an opening having a width of 70 μm and a length of 250 μm is provided in the central portion so that the first electrode is exposed. The insulating layer had a gentle forward taper as shown in FIG. The taper angle was 30 °.

  An EL layer having a thickness of 1.5 μm made of a hole transport material and an organic light emitting material was formed on the first electrode on which the insulating pattern was formed by a printing method. After forming the EL layer, a metal electrode made of silver and having a thickness of 0.5 μm was formed as a second electrode by a vapor deposition method. On the second electrode, a sealant made of a two-component curable epoxy adhesive was formed by screen printing so as to have a thickness of about 50 μm. On the sealing agent, a sealing substrate provided with a barrier layer was provided. In addition, the sealing base material provided with the barrier layer is a barrier layer having a thickness of 0.1 μm made of SiON by a continuous vapor deposition apparatus on a sealing base material having a thickness of 100 μm obtained by extruding a polyethersulfone resin in advance. What formed was used.

  Thus, a simple matrix type flexible organic electroluminescent device was produced. When this display device was line-sequentially driven, good display characteristics could be obtained. The thin film layer and the second electrode at the boundary of the insulating layer were formed smoothly without any thinning or disconnection, so there was no uneven brightness in the light emitting region and stable light emission. was gotten.

Comparative Example 1
Into a 500 ml four-necked flask equipped with a thermometer, a condenser, a Dean-Stark trap, a mechanical stirrer and a nitrogen introduction tube, hexafluoro-2,2-bis (3-amino-4) was added under a nitrogen atmosphere. -Hydroxyphenyl) propane (6FDA) 7.32 g (0.02 mol) was charged along with 128 ml monochlorobenzene (MCB) and 32.0 ml NMP. The mixture was stirred until a clear solution was obtained and 6.2 g (0.02 mol) of ODPA was added. The contents of the flask were heated to 90 ° C. and 0.04 g of p-toluenesulfonic acid (PTSA) was added. The contents were then heated at reflux temperature (about 142 ° C.). In the first hour, about 100 ml of water-chlorobenzene azeotrope was separated into the Dean-Stark trap. 100 ml of chlorobenzene was newly added to the flask, and the contents were heated to reflux at 142-145 ° C. for 10 hours.

  100 ml of N-methylpyrrolidone was then added to the flask. Excess monochlorobenzene was distilled off at 160-165 ° C. The reaction mixture was cooled and a precipitate was slowly deposited in an ice-water-methanol mixture. The precipitated white precipitate was thoroughly washed with hot water, and the resulting polymer was dried overnight in a vacuum dryer at 125 ° C. The logarithmic viscosity number of this polymer was 0.50 dl / g in dimethylacetamide at 25 ° C.

  13 parts by weight of this hydroxypolyimide and 13 parts by weight of trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid mixed ester (Z-2000 photosensitizer) were mixed with the same weight of propylene glycol methyl ether and N-methylpyrrolidone. It melt | dissolved in 74 weight part of mixed solvent which becomes, and the varnish G of the photosensitive polyimide resin composition was obtained. The viscosity of varnish G was 500 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Comparative Example 2
As diamines, 3,5-diaminobenzoic acid (DBA) 2.28 g (0.015 mol), bis [4- (3-aminophenoxy) phenyl] sulfone (BAPS) 6.49 g (0.015 mol), acid 6FDA 13.3 g (0.03 mol) and NMP 125 g were used as a dianhydride and reacted at room temperature for 8 hours. After dilution with NMP to a solid content of 7% by weight, 24.7 g of acetic anhydride and 28.7 g of pyridine were added and reacted at 40 ° C. for 30 minutes. This solution was put into ethanol, filtered and dried to obtain about 22 g of a light brownish powder. As a result of measuring the infrared absorption spectrum of this powder, peaks of imide groups were confirmed near 1780 cm ⁻¹ and 800 cm ⁻¹ . As a result of NMR spectrum measurement of this powder, no peak of acetyl group was confirmed. The logarithmic viscosity at 25 ° C. of a dilute solution adjusted to a concentration of 0.5 g / dl in dimethylacetamide of this polyimide polymer was 0.55 dl / g.

  A 3-mol substituted compound of 1,2-naphthoquinonediazide-5-sulfonic acid of 2,3,4,4′-tetrahydroxybenzophenone with respect to 100 parts by weight of resin in an NMP solution of the organic solvent-soluble polyimide resin thus obtained Varnish H of the photosensitive polyimide resin composition was obtained by adding 50 parts by weight of (4NT-300). The viscosity of varnish H was 180 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Comparative Example 3
In a vessel equipped with a condenser tube with a ball equipped with a trap with a silicon cock in a 300 ml separable three-necked flask equipped with a stirrer, 17.77 g of 6FDA and 6.05 g of 3,3′-dihydroxybenzene (HOAB), 3 , 5′-diaminobenzoic acid (DAB) 1.82 g, 0.45 g of γ-caprolactone, 0.63 g of pyridine, 96.8 g of NMP, and 19.4 g of toluene were added, and the mixture was heated to 180 ° C. and reacted for 2 hours. The number of rotations was 250 rpm, and was appropriately reduced as the reaction decreased. The water produced during the reaction was removed from the silicon cock to obtain a reaction liquid (varnish). Thereafter, the reaction solution was put into methanol and stirred at a high speed, followed by filtration with a glass filter to obtain 16.0 g of a white polyimide resin powder. The logarithmic viscosity at 25 ° C. of a dilute solution adjusted to a concentration of 0.5 g / dl in dimethylacetamide of this polyimide resin was 0.50 dl / g.

  16.0 g of this polyimide powder was made into a 12% solution of propylene glycol-1-monomethyl ether, and 7.2 g of the quinonediazide compound (d) obtained in Synthesis Example 4 was added as a photosensitive agent to obtain a photosensitive polyimide varnish I. . The viscosity of varnish I was 80 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Comparative Example 4
11.86 g of the polyimide polymer A obtained in Example 1 was weighed, and 2.71 g of the quinonediazide compound (d) obtained in Synthesis Example 4 and 3.39 g of Nicalac 100LM as a heat-crosslinkable compound were added to 81.97 g of PGME to make it photosensitive A varnish J of the resin composition was obtained. The viscosity of varnish J was 20 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Comparative Example 5
Weighing 5.93 g of polyimide polymer A obtained in Example 1, 13.80 g of the acrylic resin solution (h) obtained in Synthesis Example 8, 2.71 g of the quinonediazide compound (d) obtained in Synthesis Example 4, and thermal crosslinking Varnish K of the photosensitive resin composition was obtained by adding 3.39 g of Nicalac 100LM as a functional compound to 74.13 g of PGME. The viscosity of varnish K was 10 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Comparative Example 6
Weighing 5.93 g of polyimide polymer C obtained in Example 5, 13.80 g of the acrylic resin solution (f) obtained in Synthesis Example 6, 2.71 g of the quinonediazide compound (d) obtained in Synthesis Example 4, and thermal crosslinking The varnish L of the photosensitive resin composition was obtained by adding 3.39 g of Nicalac 100LM as a functional compound to 74.13 g of PGME. The viscosity of the varnish L was 16 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Comparative Example 7
27.59 g of the acrylic resin solution (e) obtained in Synthesis Example 5; 2.71 g of the quinonediazide compound (d) obtained in Synthesis Example 4; and 3.39 g of Nicalac 100LM as a thermally crosslinkable compound were added to 66.99 g of PGME. The varnish M of the photosensitive resin composition was obtained. The viscosity of Varnish M was 10 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Comparative Example 8
0.1 mol of adamantane dicarboxylic acid (Aldrich reagent) was dissolved in 200 ml of tetrahydrofuran (THF), 0.3 mol of thionyl chloride was added, and the refluxing was performed for 3 hours. After the generation of the gas was completed, unreacted thionyl chloride was distilled off, and the pressure was reduced, and the solvent THF was distilled off to obtain adamantane dicarbonyl chloride. 0.05 mol of 2-methyl-2adamantanol was added to a solution obtained by dissolving 0.05 mol of the obtained adamantane dicarbonyl chloride in THF. While maintaining the temperature of this solution at 0 ° C., 0.1 mol of triethylamine THF solution was gradually added dropwise. After stirring for 2 hours, the reaction solution was further filtered by stirring at room temperature for 2 hours. The reaction solution was gradually dropped into water and the deposited precipitate was further reprecipitated with a water-acetone solvent to obtain oligomer Z.

  4.0 g of the oligomer Z, 16.86 g of the acrylic resin solution (i) obtained in Synthesis Example 9 and 0.1 g of the photoacid generator TPS105 (manufactured by Midori Chemical) were dissolved in 29 g of cyclohexanone to obtain varnish N of the photosensitive resin composition. Obtained. The viscosity of varnish N was 9 mPa · s. Table 2 shows the results of various evaluations using the obtained varnish as described above.

Example of normal post-development film surface in compatibility evaluation after development Example of film surface where phase separation is observed in compatibility evaluation after development Schematic showing the boundary of the insulating layer

Explanation of symbols

1 Substrate 2 First electrode 3 Insulating layer

Claims (5)

(A) a resin having a structure represented by any one of the general formulas (1) to (4), (b) an acrylic resin, (c) a photoacid generator, and (d) a thermally crosslinkable compound, b) The photosensitive resin composition characterized by the weight average molecular weights of an acrylic resin being 5000-30000.
(In the general formulas (1) to (4), R ¹ represents a 4- to 14-valent organic group, R ² represents a ^2- to 12-valent organic group, and may be the same or different. R ³ and R ⁵ are A phenolic hydroxyl group, a sulfonic acid group or a thiol group, which may be the same or different, R ⁴ represents a divalent organic group, and may be the same or different, X and Y are a carboxyl group, a phenolic hydroxyl group, A monovalent organic group having at least one group selected from a sulfonic acid group and a thiol group, n is in the range of 3 to 200, and m, r, and s are integers of 0 to 10.) The ratio ((a) / (b)) of the content of the resin having the structure represented by any one of (a) general formulas (1) to (4) and the content of the (b) acrylic resin is as follows: It is 80 / 20-20 / 80 (weight ratio), The photosensitive resin composition of Claim 1 characterized by the above-mentioned. The photosensitive resin composition according to claim 1, wherein the (d) thermally crosslinkable compound has a group represented by the general formula (5).
—CH ₂ —OR ⁶ (5)
(In General Formula (5), R ⁶ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a cyclic aliphatic group having 4 to 20 carbon atoms.) At least (1) a step of applying the photosensitive resin composition according to any one of claims 1 to 3 to a substrate to obtain a photosensitive resin composition coating; and (2) a step of exposing the photosensitive resin composition coating with ultraviolet rays. The manufacturing method of the insulating resin pattern including the process of developing (3) exposed photosensitive resin composition film | membrane using aqueous alkali solution, and (4) heat-processing the developed photosensitive resin composition film | membrane. The organic electroluminescent element which has the insulating resin pattern obtained by the method of Claim 4.