Resin composition, resin sheet, cured film

Abstract

To provide a resin composition showing high development adhesiveness and storage stability.SOLUTION: The resin composition of the present invention comprises an alkali-soluble resin (a), a β-alkoxy propionamide (b) and an amide group-containing tertiary amine compound (c), in which the content of the amide group-containing tertiary amine compound (c) with respect to the alkali soluble resin (a) is 1 to 90 ppm.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resin composition containing an alkali-soluble resin, a β-alkoxypropionamide, and an amide group-containing tertiary amine compound. [Background technology]

[0002] Heat-resistant resins such as polyimide, polybenzoxazole, and polyamideimide have excellent heat resistance and electrical insulation properties. Therefore, photosensitive resin compositions containing these heat-resistant resins are used in applications such as surface protection layers for semiconductor devices such as LSIs, interlayer insulating layers, insulating layers for organic electroluminescent devices and organic electroluminescent display devices, and planarizing layers for TFT substrates for display devices. As electronic devices have become lighter, thinner, and smaller in recent years, display devices have become more highly precise, and semiconductor devices have become more compact and highly integrated. This has led to various technical problems with the materials used for these insulating films, protective films, and other such materials. One particularly problematic issue is adhesion upon development. When adhesion between a photosensitive resin composition used for fine pattern formation and a substrate is poor upon development, peeling often occurs. To address this issue, a method of adding an aminosilane-based coupling agent to a photosensitive resin composition to improve adhesion upon development is known (see Non-Patent Document 1).

[0003] However, if the amount of the aminosilane coupling agent is large, when the resin composition containing an o-quinonediazide compound, which is currently widely used as a photosensitizer in photoresists, is stored, the amino group of the aminosilane coupling agent reacts with the o-quinonediazide compound, resulting in a gradual decrease in sensitivity. To solve this problem, a method has been proposed in which an aminosilane coupling agent is reacted with an isocyanate compound or a carbonate ester derivative to produce a resin composition containing a polyimide precursor and an o-quinonediazide compound (Patent Document 1). However, the resin composition obtained by this method has a problem in that the amino group is modified, and therefore sufficient adhesion to the substrate cannot be obtained. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2017-37129 A [Non-Patent Document 1] J.Greenblatt et al. Aminosilane―Polyimide Interactions and Their Implications in Adhesion. “POLYIMIDES” Synthesis, Characterization, and Applications, 1984, Volume 1, p.573 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a resin composition having high development adhesion and storage stability. [Means for solving the problem]

[0006] The present invention relates to a resin composition comprising an alkali-soluble resin (a), a β-alkoxypropionamide (b), and an amide group-containing tertiary amine compound (c), wherein the content of the amide group-containing tertiary amine compound (c) relative to the alkali-soluble resin (a) is 1 to 90 ppm. [Effects of the Invention]

[0007] The resin composition of the present invention can provide a resin composition having high development adhesion and storage stability. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a cross-sectional view of an example of a TFT substrate. [Figure 2] 1 is an enlarged cross-sectional view of an example of a pad portion of a semiconductor device having bumps. [Figure 3] 1A to 1C are schematic diagrams showing an example of a method for manufacturing a semiconductor device having bumps. DETAILED DESCRIPTION OF THE INVENTION

[0009] An embodiment of the present invention will now be described in detail.

[0010] <Alkali-soluble resin (a)> The resin composition of the present invention contains an alkali-soluble resin (a). In the present invention, alkali-soluble refers to a dissolution rate of 50 nm / min or more, as determined from the film thickness reduction when a solution of the resin dissolved in γ-butyrolactone is applied to a silicon wafer and prebaked at 120°C for 4 minutes to form a prebaked film having a film thickness of 10 μm±0.5 μm, the prebaked film is immersed in a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 23±1°C for 1 minute, and then rinsed with pure water.

[0011] The alkali-soluble resin (a) in the present invention preferably has an acidic group in the structural unit of the resin and / or at the end of its main chain to impart alkali solubility. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group. In addition, the alkali-soluble resin (a) preferably has a fluorine atom to impart water repellency.

[0012] Examples of the alkali-soluble resin (a) in the present invention include, but are not limited to, polyimide, polyimide precursor, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, polyamide, polymer of a radically polymerizable monomer having an alkali-soluble group, and phenolic resin. Two or more of these resins may be used. Among these alkali-soluble resins, polyimide, polybenzoxazole, polyamideimide, precursors thereof, or copolymers selected from two or more thereof are preferred because of their high development adhesion, excellent heat resistance, and low outgassing at high temperatures. Polyimide, polyimide precursor, polybenzoxazole precursor, or copolymers selected from two or more thereof are more preferred. Furthermore, from the viewpoint of further improving sensitivity, polyimide precursors or polybenzoxazole precursors are even more preferred. Furthermore, from the viewpoint of ease of synthesis, polyimide precursors are particularly preferred. Here, the term "polyimide precursor" refers to a resin that can be converted to polyimide by heat treatment or chemical treatment. Examples include polyamic acid and polyamic acid esters. Polyamic acid esters are preferred because of improved storage stability when used as a resin composition. From the viewpoint of improving storage stability, the esterification rate of the polyamic acid ester is preferably 60% or more, more preferably 75% or more. 1 The polybenzoxazole precursor can be calculated by measuring the area of the peak derived from the aromatic protons of the resin and the peak derived from the methyl protons of the carboxylic acid alkyl ester by H-NMR spectroscopy. The polybenzoxazole precursor refers to a resin that can be converted into polybenzoxazole by heat treatment or chemical treatment, and examples thereof include polyhydroxyamide.

[0013] The polyimide precursor and polybenzoxazole precursor described above have a structural unit represented by the following general formula (1), and the polyimide has a structural unit represented by the following general formula (2). Two or more of these may be contained, or a resin obtained by copolymerizing the structural unit represented by general formula (1) and the structural unit represented by general formula (2) may be contained.

[0014] [ka]

[0015] In general formula (1), X represents a divalent to octavalent organic group, and Y represents a divalent to eleven-valent organic group. 5 and R 7 represents a hydroxyl group or a sulfonic acid group, and each may be a single group or a mixture of different groups. 6 and R 8 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. r, s, and u represent integers of 0 to 3, and t represents an integer of 0 to 6, provided that r+s+t+u>0.

[0016] [ka]

[0017] In the general formula (2), E represents a tetravalent to decavalent organic group, and G represents a divalent to octavalent organic group. 9 and R 10 represents a carboxyl group, a sulfonic acid group, or a hydroxyl group. 9 and R 10 may be the same or different. p and q each independently represent an integer of 0 to 6.

[0018] The polyimide, polyimide precursor, polybenzoxazole precursor, or copolymer selected from two or more thereof preferably has 5 to 100,000 structural units represented by general formula (1) or (2). Furthermore, in addition to the structural units represented by general formula (1) or (2), other structural units may be contained. In this case, it is preferable that the structural units represented by general formula (1) or (2) account for 50 mol % or more of the total structural units.

[0019] In the general formula (1), X(R 5 ) r (COOR 6 ) srepresents an acid residue. X is a divalent to octavalent organic group, and among these, an organic group having 5 to 40 carbon atoms and containing an aromatic ring or a cycloaliphatic group is preferred.

[0020] Examples of acids include dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid, tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl tricarboxylic acid, pyromellitic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 2,3,3',4'-biphenyl tetracarboxylic acid, 2,2',3,3'-biphenyl tetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and 2,2-bis(2,3-dicarboxyl) Examples of suitable tetracarboxylic acids include 1,1-bis(3,4-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, and aromatic tetracarboxylic acids having the structures shown below, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, and aliphatic tetracarboxylic acids containing a cyclic aliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic acid. Two or more of these may be used.

[0021] [ka]

[0022] R 20 represents an oxygen atom, C(CF3)2 or C(CH3)2. 21and R 22 each independently represents a hydrogen atom or a hydroxyl group.

[0023] Among the above acids, in the case of tricarboxylic acids and tetracarboxylic acids, one or two carboxy groups are (COOR 6 ) is equivalent to

[0024] These acids may be used as they are, or as acid anhydrides, activated esters, or activated amides. Examples of activated esters include N-hydroxysuccinimide ester compounds obtained by reacting the carboxyl group of an acid with N-hydroxysuccinimide, and examples of activated amides include N-acylimidazole compounds obtained by reacting the carboxyl group of an acid with N,N'-carbonyldiimidazole.

[0025] In the above general formula (2), E(R 9 ) p represents a residue of an acid dianhydride. E is a tetravalent to decavalent organic group, and among these, an organic group having 5 to 40 carbon atoms and containing an aromatic ring or a cycloaliphatic group is preferred.

[0026] Specific examples of the acid dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic 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, bis(3,4-dicarboxyphenyl)methane dianhydride, and bis(3,4-dicarboxyphenyl)methane dianhydride. Examples of suitable dianhydrides include aromatic tetracarboxylic dianhydrides such as ether dianhydrides, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and dianhydrides having the structures shown below; aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride; and aliphatic tetracarboxylic dianhydrides containing alicyclic groups such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride. Two or more of these may be used.

[0027] [ka]

[0028] R 20 represents an oxygen atom, C(CF3)2 or C(CH3)2. 21 and R 22 each independently represents a hydrogen atom or a hydroxyl group.

[0029] Y(R 7 ) t (COOR 8 ) u and G(R 10 ) q represents a residue of a diamine. Y is a divalent to eleven-valent organic group, G is a divalent to octavalent organic group, and among these, an organic group having 5 to 40 carbon atoms and containing an aromatic ring or a cycloaliphatic group is preferred.

[0030] Specific examples of diamines include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, and 3,3'-diethyl-4,4'-diaminobiphenyl. Examples of suitable diamines include aromatic diamines such as aminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, and compounds in which at least some of the hydrogen atoms in these aromatic rings have been substituted with alkyl groups or halogen atoms, aliphatic diamines containing alicyclic groups such as cyclohexyldiamine and methylenebiscyclohexylamine, and diamines with the structures shown below. Two or more of these may be used.

[0031] [ka]

[0032] R 20 represents an oxygen atom, C(CF3)2 or C(CH3)2. 21 ~R 24 each independently represents a hydrogen atom or a hydroxyl group.

[0033] These diamines may be used as they are, or may be used as, for example, a diisocyanate compound obtained by reacting the amino group of the diamine with phosgene, or as a trimethylsilylated diamine obtained by reacting the amino group of the diamine with chlorotrimethylsilane.

[0034] Furthermore, by capping the terminals of these resins with monoamines, acid anhydrides, acid chlorides, monocarboxylic acids, or active ester compounds having acidic groups, resins having acidic groups at the terminals of the main chain can be obtained.

[0035] Preferred examples of monoamines having an acidic group include 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, and 1-carboxy-5-aminonaphthalene. Examples of such amino acids include phthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used.

[0036] Preferred examples of the acid anhydride include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, etc. Two or more of these may be used.

[0037] Preferred examples of monocarboxylic acids include 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, etc. Two or more of these may be used.

[0038] Preferred examples of acid chlorides include monoacid chloride compounds in which the carboxy group of the above-mentioned monocarboxylic acid is converted to an acid chloride, and monoacid chloride compounds in which only one carboxy group of dicarboxylic acids such as terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and 2,6-dicarboxynaphthalene is converted to an acid chloride. Two or more of these may be used.

[0039] Preferred examples of the active ester compound include reaction products of the monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide, etc. Two or more of these may be used.

[0040] The end-capping agent introduced into the resin can be easily detected by the following method. For example, the resin into which the end-capping agent has been introduced is dissolved in an acidic solution and decomposed into the amine component and the acid component, which are the structural units of the resin. The end-capping agent can be easily detected by measuring this using gas chromatography (GC) or NMR. The resin into which the end-capping agent has been introduced can also be measured using pyrolysis gas chromatography (PGC), infrared spectroscopy, and 13It can also be detected by measuring C-NMR spectrum.

[0041] To further enhance the effect of improving development adhesion, the resin composition of the present invention may contain the alkali-soluble resin (a) containing a β-alkoxypropionamide (b) and an amide group-containing tertiary amine compound (c). Such an alkali-soluble resin (a) can be obtained by using the β-alkoxypropionamide (b) containing the amide group-containing tertiary amine compound (c) as a polymerization solvent for the alkali-soluble resin (a) in the method for producing the alkali-soluble resin (a) described below.

[0042] <Method for producing alkali-soluble resin (a)> The alkali-soluble resin (a) in the present invention is synthesized by a known method. As a method for producing polyamic acid, which is a polyimide precursor, for example, there is a method in which a tetracarboxylic dianhydride and a diamine compound are reacted in a solvent at low temperature.

[0043] In addition to the aforementioned method of reacting a polyamic acid with an esterifying agent, methods for producing a polyamic acid ester, which is also a polyimide precursor, include a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, followed by reaction with an amine in a solvent in the presence of a condensing agent. Other methods include a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, followed by conversion of the remaining dicarboxylic acid into an acid chloride and reaction with an amine in a solvent. From the perspective of ease of synthesis, it is preferable to include a step of reacting a polyamic acid with an esterifying agent. The esterifying agent is not particularly limited, and known methods can be used, but N,N-dimethylformamide dialkyl acetal is preferred because it allows for easy purification of the resulting resin.

[0044] Examples of methods for producing polyhydroxyamide, a polybenzoxazole precursor, include a method of condensing a bisaminophenol compound with a dicarboxylic acid in a solvent. Specifically, examples include a method of reacting a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding a bisaminophenol compound to the reaction mixture. Examples include a method of adding a dicarboxylic acid dichloride solution dropwise to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine has been added.

[0045] Examples of methods for producing polyimides include a method in which the polyamic acid or polyamic acid ester obtained by the above-mentioned method is subjected to dehydration ring closure in a solvent, such as chemical treatment with an acid or base, or heat treatment.

[0046] Examples of methods for producing polybenzoxazole include a method in which the polyhydroxyamide obtained by the above-mentioned method is subjected to dehydration and ring-closure in a solvent, such as a chemical treatment with an acid or a base, or a heat treatment.

[0047] Examples of the polyamide-imide precursor include a polymer of a tricarboxylic acid, a corresponding tricarboxylic acid anhydride, a tricarboxylic acid anhydride halide, and a diamine compound, and a polymer of trimellitic acid chloride anhydride and an aromatic diamine compound is preferred. Examples of a method for producing the polyamide-imide precursor include a method of reacting a tricarboxylic acid, a corresponding tricarboxylic acid anhydride, a tricarboxylic acid anhydride halide, or the like with a diamine compound in a solvent at low temperature.

[0048] Examples of methods for producing polyamideimide include a method of reacting trimellitic anhydride with an aromatic diisocyanate in a solvent, and a method of dehydrating and cyclizing the polyamideimide precursor obtained by the above method in a solvent. Examples of methods for dehydrating and cyclizing include chemical treatment with an acid or a base, and heat treatment.

[0049] The method for producing the alkali-soluble resin (a) of the present invention preferably contains a β-alkoxypropionamide (b) as a polymerization solvent. β-Alkoxypropionamides have high solubility for the alkali-soluble resin (a), and can dissolve the alkali-soluble resin (a) without using NMP, which may be harmful to living organisms. From the viewpoint of ease of solvent production, the β-alkoxypropionamide (b) is preferably 3-methoxy-N,N-dimethylpropionamide or 3-butoxy-N,N-dimethylpropionamide.

[0050] The method for producing the alkali-soluble resin (a) of the present invention may contain a solvent other than the β-alkoxypropionamide (b) as a polymerization solvent. Examples of the solvent other than the β-alkoxypropionamide (b) include alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether (boiling point 124°C, SP value 10.8, calculated value) and propylene glycol monomethyl ether (boiling point 120°C, SP value 10.2, calculated value), and alkyl acetates such as propyl acetate (boiling point 102°C, SP value 8.7, calculated value), butyl acetate (boiling point 125°C, SP value 8.5, literature value), and isobutyl acetate (boiling point 118°C, SP value 8.4, literature value). Ketones such as methyl isobutyl ketone (boiling point 116°C, SP value 8.6, literature value), methyl propyl ketone (boiling point 102°C, SP value 8.9, calculated value), alcohols such as butyl alcohol (boiling point 117°C, SP value 11.3, literature value), isobutyl alcohol (boiling point 108°C, SP value 11.1, literature value), ethyl lactate (boiling point 154°C, SP value 10.6, literature value), butyl lactate (boiling point 186°C, SP value 9.7, literature value), dipropylene glycol dimethyl ether (boiling point 171°C, SP value 9.7, literature value), diethyl Ethylene glycol dimethyl ether (boiling point 162°C, SP value 8.1, calculated value), diethylene glycol ethyl methyl ether (boiling point 176°C, SP value 8.1, calculated value), diethylene glycol diethyl ether (boiling point 189°C, SP value 8.2, calculated value), 3-methoxybutyl acetate (boiling point 171°C, SP value 8.7, calculated value), ethylene glycol monoethyl ether acetate (boiling point 160°C, SP value 9.0, calculated value), gamma-butyrolactone (boiling point 203°C, SP value 12.8, literature value), N-methyl-2-pyronitrile N-cyclohexyl-2-pyrrolidone (boiling point 204°C, SP value 11.2, literature value), diacetone alcohol (boiling point 166°C, SP value 10.2, literature value), N-cyclohexyl-2-pyrrolidone (boiling point 154°C, SP value 10.8, literature value), N,N-dimethylformamide (boiling point 153°C, SP value 12.1, literature value), N,N-dimethylacetamide (boiling point 165°C, SP value 11.1, literature value), dimethyl sulfoxide (boiling point 189°C, SP value 12.9, literature value), propylene glycol monomethyl ether acetate (boiling point 146°C, SP value 8.7, calculated value), N,N-dimethylisobutyric acid amide (boiling point 175°C, SP value 9.9, calculated value), 1,3-dimethyl-2-imidazolidinone (boiling point 220°C, SP value 11.4, calculated value), N,N-dimethylpropylene urea (boiling point 246°C, SP value 11.1, calculated value), delta valerolactone (boiling point 230°C, SP value 9.7, calculated value), 2-phenoxyethanol (boiling point 245°C, SP value 12.4, calculated value), 2-pyrrolidone (boiling point 245°C, SP value 12.6, calculated value), 2-methyl-1,3-propanediol (boiling point 213°C, SP value 14.8, calculated value), triacetin (boiling point 260°C, SP value 10.2, calculated value), Examples of solubility parameters include butyl benzoate (boiling point 250°C, SP value 9.8, calculated value), cyclohexylbenzene (boiling point 236°C, SP value 12.2, calculated value), bicyclohexyl (boiling point 239°C, SP value 8.5, calculated value), o-nitroanisole (boiling point 273°C, SP value 10.4, calculated value), diethylene glycol monobutyl ether (boiling point 230°C, SP value 10.5, calculated value), triethylene glycol monomethyl ether (boiling point 248°C, SP value 10.8, calculated value), and N-(2-hydroxyethyl)-2-pyrrolidone (boiling point: 175°C / 10 mmHg, converted to normal pressure boiling point: 313°C, SP value 14.3, calculated value). The solubility parameters (SP values) used in the present invention were those listed in "Coating Basic Science" (page 65, Yuji Harasaki, Maki Shoten). For those without SP values, the values calculated from the evaporation energy and molar volume of atoms and atomic groups by Fedors in "Basic Science of Coatings" (page 55, Yuji Harasaki, Maki Shoten) were used.

[0051] The solvent other than the β-alkoxypropionamide (b) and the amide group-containing tertiary amine compound (c) preferably includes an organic solvent (d) having a solubility parameter of 10.4 to 13.0. The inclusion of an organic solvent with a higher solubility parameter than the β-alkoxypropionamide (b), such as 3-methoxy-N,N-dimethylpropionamide (SP value: 10.3, calculated value) or 3-butoxy-N,N-dimethylpropionamide (SP value: 10.0, calculated value), or the amide group-containing tertiary amine compound (c), such as 3-dimethylamino-N,N-dimethylpropionamide (SP value: 10.0, calculated value), increases the reaction efficiency of the aforementioned polyamic acid esterification step and improves the esterification rate of the resulting polyamic acid ester. Solvents containing urea bonds are particularly preferred from the perspective of improving the esterification efficiency of polyamic acid. Examples of solvents having a urea bond include 1,3-dimethyl-2-imidazolidinone (SP value 11.4, calculated value) and N,N-dimethylpropyleneurea (SP value 11.1, calculated value).

[0052] When an organic solvent (d) having a solubility parameter of 10.4 to 13.0 is used in combination with a β-alkoxypropionamide (b), the content of the organic solvent (d) having a solubility parameter of 10.4 to 13.0 is preferably 1% or more, more preferably 10% or more, based on 100% of the polymerization solvent. By adjusting the content within this range, a polyamic acid ester with a high esterification rate can be obtained. On the other hand, when the resulting alkali-soluble resin is made into a photosensitive resin composition (described below), the content is preferably 50% or less, more preferably 40% or less, from the viewpoint of suppressing the organic solvent from remaining in the film after baking.

[0053] The resin composition of the present invention may contain an amide group-containing tertiary amine compound (c) in the β-alkoxypropionamide (b). The amide group-containing tertiary amine compound (c) has a structure represented by the following general formula (3):

[0054] [ka]

[0055] In general formula (3), R 1 and R 2 are each independently a monovalent organic group having an alkyl group having 1 to 5 carbon atoms, R 3 and R 4 each independently represents a monovalent organic group having a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0056] From the viewpoint of ease of production of β-alkoxypropionamide (b), R 1 ~R 4 is preferably a methyl group.

[0057] When a β-alkoxypropionamide (b) containing an amide group-containing tertiary amine compound (c) is used as a polymerization solvent for an alkali-soluble resin (a), after the polymerization reaction is completed, the β-alkoxypropionamide (b) is reprecipitated in a poor solvent such as pure water, washed, purified, and dried. This allows the alkali-soluble resin (a) of the present invention to contain a specified amount of β-alkoxypropionamide (b) and amide group-containing tertiary amine compound (c). The content can be adjusted by appropriately selecting a poor solvent for reprecipitation, adjusting the flow rate during reprecipitation, and the number of washes. From the perspective of further enhancing the effect of improving development adhesion, it is preferable to incorporate the β-alkoxypropionamide (b) and amide group-containing tertiary amine compound (c) into the alkali-soluble resin (a) by using them as a polymerization solvent for the alkali-soluble resin (a) as described above, rather than adding them to the resin composition.

[0058] <β-alkoxypropionamide (b)> The resin composition of the present invention contains a β-alkoxypropionamide (b). By containing the β-alkoxypropionamide (b) and the amide group-containing tertiary amine compound (c), the adhesion of the resin composition of the present invention after development can be improved.

[0059] The β-alkoxypropionamide (b) may be contained in the alkali-soluble resin (a) by using it as a polymerization solvent for the alkali-soluble resin (a). From the viewpoint of further enhancing the effect of improving development adhesion, it is preferable to use the β-alkoxypropionamide (b) as a polymerization solvent for the alkali-soluble resin (a) as described above and thereby incorporate it into the alkali-soluble resin (a), rather than adding it to the resin composition.

[0060] From the viewpoint of versatility, the β-alkoxypropionamide (b) is preferably 3-methoxy-N,N-dimethylpropionamide or 3-butoxy-N,N-dimethylpropionamide.

[0061] In the present invention, the content of the β-alkoxypropionamide (b) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the alkali-soluble resin (a) from the viewpoint of improving development adhesion, while it is preferably 15 parts by mass or less, more preferably 7 parts by mass or less, from the viewpoint of forming a desired patterned film when made into a developed film. The development adhesion refers to the adhesion between the film and the substrate after development; when a coating film of the resin composition of the present invention is dried, exposed to light, and developed by the method described below, the smaller the minimum size of the convex pattern that adheres to the substrate without peeling, the higher the development adhesion.

[0062] <Amide group-containing tertiary amine compound (c)> The resin composition of the present invention contains an amide group-containing tertiary amine compound (c). By containing the β-alkoxypropionamide (b) and the amide group-containing tertiary amine compound (c), the adhesion of the resin composition of the present invention after development can be improved.

[0063] The amide group-containing tertiary amine compound (c) may be contained in the alkali-soluble resin (a) by being used as part of the polymerization solvent for the alkali-soluble resin (a) as described above. From the viewpoint of further enhancing the effect of improving development adhesion, it is preferable to use a β-alkoxypropionamide (b) containing the amide group-containing tertiary amine compound (c) as a polymerization solvent for the alkali-soluble resin (a) as described above and include a specified amount of the amide group-containing tertiary amine compound (c) therein, rather than adding the amide group-containing tertiary amine compound (c) to the resin composition.

[0064] From the viewpoint of improving the storage stability when the obtained alkali-soluble resin (a) is made into a photosensitive resin composition, the amide group-containing tertiary amine compound (c) preferably has a structure represented by the following general formula (3):

[0065] [ka]

[0066] In general formula (3), R 1 and R 2 are each independently a monovalent organic group having an alkyl group having 1 to 5 carbon atoms, R 3 and R 4 each independently represents a monovalent organic group having a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0067] In the present invention, the content of the amide group-containing tertiary amine compound (c) is 1 ppm or more, more preferably 10 ppm or more, relative to the alkali-soluble resin (a) from the viewpoint of improving development adhesion, while it is 90 ppm or less, more preferably 50 ppm or less from the viewpoint of improving storage stability of the resin composition.

[0068] <Photosensitive compound (d)> The resin composition of the present invention preferably contains a photosensitive compound (d), and can be made into a photosensitive resin composition. Examples of the photosensitive compound (d) include a photoacid generator (d1) and a photopolymerization initiator (d2). The photoacid generator (d1) is a compound that generates an acid upon exposure to light, and the photopolymerization initiator (d2) is a compound that undergoes bond cleavage and / or reaction upon exposure to generate radicals.

[0069] By including a photoacid generator (d1), acid is generated in the irradiated areas, increasing the solubility of the irradiated areas in an alkaline aqueous solution, thereby obtaining a positive-tone relief pattern in which the irradiated areas are dissolved. Furthermore, by including a photoacid generator (d1) and an epoxy compound or a thermal crosslinking agent (described below), the acid generated in the irradiated areas promotes the crosslinking reaction of the epoxy compound or thermal crosslinking agent, thereby obtaining a negative-tone relief pattern in which the irradiated areas are insolubilized. On the other hand, by including a photopolymerization initiator and a radically polymerizable compound (described below), radical polymerization proceeds in the irradiated areas, thereby obtaining a negative-tone relief pattern in which the irradiated areas are insolubilized.

[0070] Examples of the photoacid generator (d1) include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, etc. It is preferable to contain two or more types of photoacid generators, which allows for the production of a highly sensitive photosensitive resin composition.

[0071] Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxy compound via an ester bond, those in which the sulfonic acid of quinone diazide is bonded to a polyamino compound via a sulfonamide bond, and those in which the sulfonic acid of quinone diazide is bonded to a polyhydroxypolyamino compound via an ester bond and / or a sulfonamide bond. It is preferable that 50 mol % or more of the total functional groups of these polyhydroxy compounds or polyamino compounds are substituted with the sulfonic acid of quinone diazide.

[0072] As the quinone diazide structure, either a 5-naphthoquinone diazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group is preferably used. 4-naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure. 5-naphthoquinone diazide sulfonyl ester compounds have absorption extending to the g-line region of a mercury lamp and are 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 of exposure. Furthermore, naphthoquinone diazide sulfonyl ester compounds having both a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be contained.

[0073] The quinone diazide compound can be synthesized by any esterification reaction of a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound. The use of such a quinone diazide compound further improves resolution, sensitivity, and film retention.

[0074] Among the photoacid generators (d1), sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts are preferred because they appropriately stabilize the acid component generated by exposure. Of these, sulfonium salts are preferred. Furthermore, a sensitizer or the like can be contained as needed.

[0075] In the present invention, the content of the photoacid generator (d1) is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the alkali-soluble resin (a) from the viewpoint of increasing sensitivity. Among these, the content of the quinone diazide compound is preferably 3 to 40 parts by mass. Furthermore, the total amount of the sulfonium salt, phosphonium salt, diazonium salt, and iodonium salt is preferably 0.5 to 20 parts by mass.

[0076] Examples of the photopolymerization initiator (d2) include benzyl ketal-based photopolymerization initiators, α-hydroxyketone-based photopolymerization initiators, α-aminoketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, acridine-based photopolymerization initiators, titanocene-based photopolymerization initiators, benzophenone-based photopolymerization initiators, acetophenone-based photopolymerization initiators, aromatic ketoester-based photopolymerization initiators, and benzoic acid ester-based photopolymerization initiators. Two or more types of photopolymerization initiators (d2) may be contained. From the viewpoint of further improving sensitivity, α-aminoketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and oxime ester-based photopolymerization initiators are more preferred.

[0077] Examples of the α-aminoketone photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octyl-9H-carbazole.

[0078] Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide.

[0079] Examples of the oxime ester photopolymerization initiator include 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1- [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, or 1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-1-[2-methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime.

[0080] In the present invention, the content of the photopolymerization initiator (d2) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of the alkali-soluble resin (a) and the radically polymerizable compound described below, from the viewpoint of further improving sensitivity, while being preferably 25 parts by mass or less, more preferably 15 parts by mass or less, from the viewpoint of further improving resolution and reducing the taper angle.

[0081] <Radical polymerizable compound> The resin composition of the present invention may further contain a radically polymerizable compound. A radically polymerizable compound refers to a compound having multiple ethylenically unsaturated double bonds in its molecule. During exposure, radicals generated from the photopolymerization initiator (d2) cause radical polymerization of the radically polymerizable compound, resulting in insolubilization of the irradiated area, resulting in a negative pattern. Furthermore, the inclusion of a radically polymerizable compound promotes photocuring of the irradiated area, further improving sensitivity. In addition, the crosslink density after thermal curing is improved, thereby improving the hardness of the cured film.

[0082] The radical polymerizable compound is preferably a compound having a (meth)acrylic group, which facilitates radical polymerization. From the viewpoint of improving sensitivity during exposure and hardness of the cured film, a compound having two or more (meth)acrylic groups in the molecule is more preferred. From the viewpoint of improving sensitivity during exposure and hardness of the cured film, the double bond equivalent of the radical polymerizable compound is preferably 80 to 400 g / mol.

[0083] Examples of the radical polymerizable compound include trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, 2,2-bis[ Examples of suitable acrylic acid-modified acrylic acid compounds include 4-(3-(meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloxyethyl)isocyanuric acid, 1,3-bis((meth)acryloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloxypropoxy)phenyl]fluorene, 9,9-bis(4-(meth)acryloxyphenyl)fluorene, and acid-modified, ethylene oxide-modified, and propylene oxide-modified acrylic acid-modified acrylic acid compounds.

[0084] In the resin composition of the present invention, the content of the radical polymerizable compound is preferably 15 parts by mass or more, more preferably 30 parts by mass or more, per 100 parts by mass of the total of the alkali-soluble resin (a) and the radical polymerizable compound, from the viewpoints of further improving the sensitivity and reducing the taper angle, while it is preferably 65 parts by mass or less, more preferably 50 parts by mass or less, from the viewpoints of further improving the heat resistance of the cured film and reducing the taper angle.

[0085] <Thermal crosslinking agent> The resin composition of the present invention may further contain a thermal crosslinking agent. A thermal crosslinking agent refers to a compound having at least two thermally reactive functional groups, such as an alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group, in the molecule. The inclusion of a thermal crosslinking agent can crosslink the alkali-soluble resin (a) or other additive components, thereby improving the heat resistance, chemical resistance, and hardness of the film after thermal curing. In addition, the amount of outgassing from the cured film can be further reduced, thereby improving the long-term reliability of the organic EL display device.

[0086] Preferred examples of the compound having at least two alkoxymethyl groups or methylol groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp- Examples of suitable acrylic acid esters include BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, and HMOM-TPHAP (all trade names, manufactured by Honshu Chemical Industry Co., Ltd.), "NIKALAC" (registered trademark) MX-290, "NIKALAC" MX-280, "NIKALAC" MX-270, "NIKALAC" MX-279, "NIKALAC" MW-100LM, and "NIKALAC" MX-750LM (all trade names, manufactured by Sanwa Chemical Co., Ltd.).

[0087] Preferred examples of compounds having at least two epoxy groups include "Epolite" (registered trademark) 40E, "Epolite" 100E, "Epolite" 200E, "Epolite" 400E, "Epolite" 70P, "Epolite" 200P, "Epolite" 400P, "Epolite" 1500NP, and "Epolite" 80MF. , "Epolight" 4000, "Epolight" 3002 (all manufactured by Kyoeisha Chemical Co., Ltd.), "Denacol" (registered trademark) EX-212L, "Denacol" EX-214L, "Denacol" EX-216L, "Denacol" EX-850L (all manufactured by Nagase ChemteX Corporation), GAN, GOT (all manufactured by Nippon Kayaku Co., Ltd.), "Epicoat" (registered trademark) 828, "Epicoat" 1002, "Epicoat" 1750, "Epicoat" 1007, YX8100-BH30, E1256, E4250, E4275 (all manufactured by Japan Epoxy Resins Co., Ltd.), "E Examples of the anti-corrosive agent include "Piclon" (registered trademark) EXA-9583 and HP4032 (all manufactured by DIC Corporation), VG3101 (manufactured by Mitsui Chemicals, Inc.), "Tepic" (registered trademark) S, "Tepic" G and "Tepic" P (all manufactured by Nissan Chemical Industries, Ltd.), "Denacol" EX-321L (manufactured by Nagase ChemteX Corporation), NC6000 (manufactured by Nippon Kayaku Co., Ltd.), "Epototo" (registered trademark) YH-434L (manufactured by Tohto Kasei Co., Ltd.), EPPN502H and NC3000 (manufactured by Nippon Kayaku Co., Ltd.), "Epiclon" (registered trademark) N695 and HP7200 (all manufactured by DIC Corporation).

[0088] Preferred examples of the compound having at least two oxetanyl groups include Ethanacol EHO, Ethanacol OXBP, Ethanacol OXTP, Ethanacol OXMA (all manufactured by Ube Industries, Ltd.), oxetanized phenol novolak, and the like.

[0089] Two or more types of thermal crosslinking agents may be used in combination. The content of the thermal crosslinking agent is preferably 1 part by mass or more and 30 parts by mass or less, based on 100 parts by mass of the total amount of the resin composition excluding the solvent. When the content of the thermal crosslinking agent is 1 part by mass or more, the chemical resistance and hardness of the cured film can be further improved. Furthermore, when the content of the thermal crosslinking agent is 30 parts by mass or less, the amount of outgassing from the cured film can be further reduced, the long-term reliability of the organic EL display device can be further improved, and the storage stability of the resin composition can also be excellent.

[0090] <Solvent> The resin composition of the present invention may further contain a solvent. By containing a solvent, the resin composition can be made into a varnish state, and the coatability can be improved.

[0091] Examples of the solvent include polar aprotic solvents such as γ-butyrolactone, ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, and dioxane, acetone, methyl ethyl Ketones such as diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and diacetone alcohol, esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethyl lactate, 2-hydroxy-2-methylpropionate, 3-methoxypropionate, and methylpropionate. Methyl pionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate,Examples of the ester include n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; and amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. Two or more of these may be contained.

[0092] The content of the solvent is not particularly limited, but is preferably 100 to 3,000 parts by mass, and more preferably 150 to 2,000 parts by mass, relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent. Furthermore, the proportion of the solvent with a boiling point of 180°C or higher relative to the total amount of solvent is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less. By keeping the proportion of the solvent with a boiling point of 180°C or higher to 20 parts by mass or less, the amount of outgassing after thermal curing can be further reduced, and the long-term reliability of the organic EL device can be further improved.

[0093] <Adhesion improver> The resin composition of the present invention may further contain an adhesion improver. Examples of adhesion improvers include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; titanium chelating agents; aluminum chelating agents; and compounds obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound. Two or more of these may be contained. The inclusion of these adhesion improvers can improve development adhesion with underlying substrates such as silicon wafers, ITO, SiO2, and silicon nitride when developing a resin film. Furthermore, it can improve resistance to oxygen plasma and UV ozone treatments used for cleaning. The content of the adhesion improver is preferably 0.1 to 10 parts by mass per 100 parts by mass of the total amount of the resin composition excluding the solvent.

[0094] <Surfactant> The resin composition of the present invention may further contain a surfactant, if necessary, to improve wettability with the substrate. Examples of surfactants include fluorine-based surfactants such as the SH series, SD series, and ST series from Dow Corning Toray Co., Ltd., the BYK series from BYK Japan K.K., the KP series from Shin-Etsu Chemical Co., Ltd., the Disfoam series from NOF Corporation, the Megafac® series from DIC Corporation, the Fluorad series from Sumitomo 3M Limited, the Surflon® series and AsahiGuard® series from Asahi Glass Co., Ltd., and the Polyfox series from Omnova Solutions, as well as acrylic and / or methacrylic surfactants such as the Polyflow series from Kyoeisha Chemical Co., Ltd. and the Disparlon® series from Kusumoto Chemical Co., Ltd.

[0095] The content of the surfactant is preferably 0.001 to 1 part by mass relative to 100 parts by mass of the total amount of the resin composition excluding the solvent.

[0096] <Compounds containing a phenolic hydroxyl group> In order to improve the alkaline developability of the resin composition of the present invention, the resin composition may contain a compound having a phenolic hydroxyl group. Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, and BisOTBP. -CP, TekP-4HBPA (tetrakis P-DO-BPA), TrisPHAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS -2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, Cilentris-FR-CR, BisRS-26X, BisRS-OCHP (all trade names available from Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PCBIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (all trade names available from Asahi Organic Materials Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene Examples of suitable compounds include quinoxaline, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, and 8-quinolinol. By incorporating these compounds having a phenolic hydroxyl group, the resulting photosensitive resin composition is virtually insoluble in an alkaline developer before exposure, but readily dissolves in an alkaline developer after exposure. This reduces film loss during development and facilitates development in a short time. This facilitates improved sensitivity.

[0097] The content of such a compound having a phenolic hydroxyl group is preferably 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of (a) the alkali-soluble resin. By setting the content within the above range, it is possible to improve the alkali developability of the photosensitive resin composition while maintaining high heat resistance.

[0098] <Inorganic particles> The resin composition of the present invention may further contain inorganic particles. Specific examples of preferred inorganic particles include silicon oxide, titanium oxide, barium titanate, alumina, and talc. The primary particle size of the inorganic particles is preferably 100 nm or less, and more preferably 60 nm or less.

[0099] The content of the inorganic particles is preferably 5 to 90 parts by mass relative to 100 parts by mass of the total amount of the resin composition excluding the solvent.

[0100] <Thermal acid generator> The resin composition of the present invention may further contain a thermal acid generator within a range that does not impair the long-term reliability of the organic EL display device. The thermal acid generator generates an acid upon heating and promotes the crosslinking reaction of the thermal crosslinking agent. In addition, if the resin of component (a) has an unclosed imide ring structure or oxazole ring structure, it promotes cyclization of these structures, thereby further improving the mechanical properties of the cured film.

[0101] The thermal decomposition starting temperature of the thermal acid generator used in the present invention is preferably 50° C. to 270° C., more preferably not higher than 250° C. In addition, it is preferable to select a thermal acid generator that does not generate acid during drying (pre-baking: about 70 to 140° C.) after applying the resin composition of the present invention to a substrate, but generates acid during final heating (curing: about 100 to 400° C.) after subsequent patterning by exposure and development, because this can prevent a decrease in sensitivity during development.

[0102] The acid generated from the thermal acid generator used in the present invention is preferably a strong acid, such as an arylsulfonic acid (e.g., p-toluenesulfonic acid, benzenesulfonic acid), an alkylsulfonic acid (e.g., methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid), or a haloalkylsulfonic acid (e.g., trifluoromethylsulfonic acid). These are used as a salt (e.g., onium salt) or as a covalently bonded compound (e.g., imidosulfonate). Two or more of these may be contained.

[0103] The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, based on 100 parts by mass of the total amount of the resin composition excluding the solvent. By including 0.01 parts by mass or more of the thermal acid generator, the crosslinking reaction and the cyclization of the unclosed ring structure of the resin are promoted, thereby further improving the mechanical properties and chemical resistance of the cured film. Furthermore, from the viewpoint of long-term reliability of the organic EL display device, the content is preferably 5 parts by mass or less, more preferably 2 parts by mass or less.

[0104] <Method of manufacturing resin composition> Next, a method for producing the resin composition of the present invention will be described. For example, the resin composition can be obtained by dissolving an alkali-soluble resin (a), a β-alkoxypropionamide (b), an amide group-containing tertiary amine compound (c), and, if necessary, a photosensitive compound, a radical polymerizable compound, a thermal crosslinking agent, a solvent, an adhesion improver, a surfactant, a compound having a phenolic hydroxyl group, inorganic particles, a thermal acid generator, etc.

[0105] Alternatively, instead of the alkali-soluble resin (a) described above, an alkali-soluble resin solution can be used, obtained by using a β-alkoxypropionamide (b) containing an amide group-containing tertiary amine compound (c) as a polymerization solvent for the alkali-soluble resin (a). Examples of dissolution methods include stirring and heating. When heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, typically room temperature to 80°C. The order in which the components are dissolved is not particularly limited; for example, compounds with low solubility can be dissolved sequentially. For components that tend to generate bubbles during dissolution by stirring, such as surfactants and some adhesion promoters, adding them last after dissolving the other components can prevent incomplete dissolution of the other components due to the generation of bubbles.

[0106] The resulting resin composition is preferably filtered through a filter to remove dust and particles. The filter pore size may be, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, or 0.02 μm, but is not limited to these. Filter materials include polypropylene (PP), polyethylene (PE), nylon (NY), and polytetrafluoroethylene (PTFE), with polyethylene and nylon being preferred.

[0107] <Resin sheet> The resin sheet of the present invention is formed from the resin composition.

[0108] The sheet of the present invention can be obtained by, for example, applying the above-described resin composition to a release substrate such as polyethylene terephthalate to obtain a coating film of the resin composition, and drying the coating film. A protective film may also be laminated thereon.

[0109] Examples of coating methods include spin coating, slit coating, dip coating, spray coating, and printing. Among these, slit coating is preferred because it allows coating with a small amount of coating liquid, which is advantageous for reducing costs. The amount of coating liquid required for slit coating is, for example, approximately 1 / 5 to 1 / 10 of that required for spin coating. Slit nozzles used for coating can be selected from those available from multiple manufacturers, including the "Linear Coater" manufactured by Dainippon Screen Mfg. Co., Ltd., the "Spinless" manufactured by Tokyo Ohka Kogyo Co., Ltd., the "TS Coater" manufactured by Toray Engineering Co., Ltd., the "Table Coater" manufactured by Chugai Ro Kogyo Co., Ltd., the "CS Series" and "CL Series" manufactured by Tokyo Electron Limited, the "Inline Slit Coater" manufactured by Cermatronics Trading Co., Ltd., and the "Head Coater HC Series" manufactured by Hirata Corporation. Coating speeds are typically in the range of 10 mm / s to 400 mm / s. The thickness of the coating film varies depending on the solid content and viscosity of the resin composition, but is usually applied so that the thickness after drying is 0.1 to 10 μm, preferably 0.3 to 5 μm.

[0110] Prior to application, the substrate to which the resin composition is to be applied may be pretreated with the adhesion promoter described above. Examples of pretreatment methods include treating the substrate surface with a solution of 0.5 to 20% by mass of an adhesion promoter dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate. Examples of substrate surface treatment methods include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

[0111] After coating, a vacuum drying process is performed as needed. Generally, the substrate on which the coating film is formed is dried under reduced pressure. For example, the substrate on which the coating film is formed is placed on proxy pins arranged in a vacuum chamber, and the vacuum chamber is depressurized to perform vacuum drying. In this case, to prevent haze and unevenness caused by a large amount of air flowing between the substrate and the vacuum chamber top plate during vacuum drying, it is preferable to adjust the height of the proxy pins to narrow the gap between the substrate and the vacuum chamber top plate. The distance between the substrate and the vacuum chamber top plate is preferably about 2 to 20 mm, more preferably 2 to 10 mm.

[0112] The reduced-pressure drying speed depends on factors such as the volume of the vacuum chamber, the capacity of the vacuum pump, and the diameter of the piping between the chamber and the pump, but is preferably set so that, for example, the pressure inside the vacuum chamber is reduced to 40 Pa after 60 seconds without a coated substrate present. Typical reduced-pressure drying times are often around 30 to 100 seconds, and the ultimate pressure inside the vacuum chamber at the end of reduced-pressure drying is usually 100 Pa or less with a coated substrate present. By setting the ultimate pressure to 100 Pa or less, it is possible to achieve a dry state with reduced stickiness on the surface of the coating film, thereby suppressing surface contamination and particle generation during subsequent substrate transport.

[0113] After coating or vacuum drying, the coating film is typically heated and dried. This process is also called pre-baking. Drying can be performed using a hot plate, oven, infrared radiation, or other methods. When using a hot plate, the coating film is heated directly on the plate or on a jig such as a proxy pin placed on the plate. Examples of proxy pin materials include metals such as aluminum and stainless steel, and synthetic resins such as polyimide resin and Teflon (registered trademark). Any heat-resistant proxy pin material can be used. The height of the proxy pin varies depending on the size of the substrate, the type of coating film, and the purpose of heating, but is preferably approximately 0.1 to 10 mm. The heating temperature and heating time vary depending on the type and purpose of the coating film, but a heating temperature of 50°C to 180°C and a heating time of 1 minute to several hours are preferred.

[0114] When the resin sheet is photosensitive, a pattern can be formed on the resin sheet, for example, by exposing the photosensitive resin sheet to actinic radiation through a mask having a desired pattern, and then developing the exposed resin sheet to form a desired pattern.

[0115] Examples of actinic radiation used for exposure include ultraviolet light, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. When the film has positive photosensitivity, the exposed area dissolves in the developer. When the film has negative photosensitivity, the exposed area hardens and becomes insoluble in the developer.

[0116] After exposure, the exposed areas are removed with a developer in the case of a positive-tone film, and the unexposed areas are removed with a developer in the case of a negative-tone film, to form the desired pattern. Examples of the developer include aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. These alkaline aqueous solutions may contain one or more polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide; alcohols such as methanol, ethanol, and isopropanol; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone. Examples of the developing method include spray, puddle, immersion, and ultrasonic methods.

[0117] Next, the pattern formed by development is preferably rinsed with distilled water. Alternatively, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

[0118] <Cured film> The cured film of the present invention can be obtained by curing the resin sheet or resin composition. By heat-curing the resin composition or resin sheet, components with low heat resistance can be removed, thereby further improving heat resistance and chemical resistance. In particular, when the resin composition or resin sheet of the present invention contains a polyimide precursor, a polybenzoxazole precursor, a copolymer thereof, or a copolymer selected from two or more of these and a polyimide, imide rings and oxazole rings are formed by heat-curing, thereby further improving heat resistance and chemical resistance.

[0119] The heat curing temperature is preferably 300°C or higher, more preferably 350°C or higher, from the viewpoint of further reducing the amount of outgassing from the cured film. On the other hand, from the viewpoint of improving the film toughness of the cured film, it is preferably 500°C or lower, more preferably 450°C or lower. Within this temperature range, the temperature may be increased stepwise or continuously. The heat curing time is preferably 30 minutes or longer, from the viewpoint of further reducing the amount of outgassing. Furthermore, from the viewpoint of improving the film toughness of the cured film, it is preferably 3 hours or shorter. For example, there may be mentioned a method in which heat treatment is performed at 150°C and 250°C for 30 minutes each, or a method in which heat treatment is performed while linearly increasing the temperature from room temperature to 300°C over 2 hours.

[0120] The resin composition, resin sheet, and cured film of the present invention are suitable for use as surface protection layers and interlayer insulating layers for semiconductor devices, insulating layers for organic electroluminescence (EL) devices, planarization layers for thin film transistor (TFT) substrates used in display devices using organic EL devices, wiring protection insulating layers for circuit boards, on-chip microlenses for solid-state imaging devices, and planarization layers for various displays and solid-state imaging devices. For example, they are suitable as surface protection layers and interlayer insulating layers for MRAM, which has low heat resistance, polymer memory (Polymer Ferroelectric RAM: PFRAM), which is a promising next-generation memory, phase change memory (Phase Change RAM: PCRAM), and Ovonics Unified Memory (OUM). They can also be used as insulating layers for display devices that include a first electrode formed on a substrate and a second electrode disposed opposite the first electrode, such as LCDs, ECDs, ELDs, and display devices using organic electroluminescent elements (organic electroluminescent devices). The following describes organic EL display devices, semiconductor devices, and semiconductor electronic components as examples.

[0121] <Organic EL display device> The cured film of the present invention is suitable for use as a planarizing layer and / or insulating layer in an organic EL display device having a drive circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate. Organic EL light-emitting materials are susceptible to degradation by moisture, which can have adverse effects such as a decrease in the area ratio of the light-emitting portion to the area of the light-emitting pixel. However, the cured film of the present invention has low water absorption, resulting in stable drive and light-emitting characteristics. Taking an active matrix display device as an example, a display device has a TFT and wiring located on the sides of the TFT and connected to the TFT on a substrate made of glass or various plastics, a planarizing layer on top of the TFT to cover the irregularities, and a display element on the planarizing layer. The display element and wiring are connected via contact holes formed in the planarizing layer.

[0122] When the cured film of the present invention is used as the planarizing layer, the film thickness is preferably 1.0 to 5.0 μm, more preferably 2.0 μm or more. By setting the planarizing layer within the above-mentioned range, the planarization layer can be made more precise and the planarization of densely packed TFTs and wiring can be improved. If the planarizing layer is made thick, outgassing increases, which causes a decrease in the light-emitting reliability of the organic EL display device. However, the cured film of the present invention has little outgassing, and therefore high light-emitting reliability can be obtained. Furthermore, since the TFTs and wiring can be arranged in the film thickness direction in order to achieve high definition, the planarizing layer is preferably multi-layered.

[0123] FIG. 1 shows a cross-sectional view of an example of a TFT substrate. Bottom-gate or top-gate TFTs (thin film transistors) 1 are arranged in a matrix on a substrate 6, and a TFT insulating layer 3 is formed to cover the TFTs 1. Wiring 2 connected to the TFTs 1 is also formed on the TFT insulating layer 3. A planarization layer 4 is further formed on the TFT insulating layer 3, burying the wiring 2. Contact holes 7 are formed in the planarization layer 4, reaching the wiring 2. An ITO (transparent electrode) 5 is formed on the planarization layer 4 and connected to the wiring 2 via the contact holes 7. The ITO 5 serves as an electrode for a display element (e.g., an organic EL element). An insulating layer 8 is formed to cover the periphery of the ITO 5. The organic EL element may be a top-emission type that emits emitted light from the side opposite the substrate 6, or a bottom-emission type that extracts light from the substrate 6 side. In this manner, an active matrix organic EL display device is obtained, in which TFTs 1 for driving each organic EL element are connected to each other.

[0124] The TFT insulating layer 3, the planarizing layer 4, and / or the insulating layer 8 can be formed by the steps of forming a photosensitive resin film made of the resin composition or resin sheet of the present invention, exposing the photosensitive resin film, developing the exposed photosensitive resin film, and heat-treating the developed photosensitive resin film, as described above. An organic EL display device can be obtained by a manufacturing method including these steps.

[0125] <Semiconductor electronic components, semiconductor devices> The cured film of the present invention can be suitably used as an interlayer insulating layer and / or a surface protective layer in semiconductor electronic components and semiconductor devices having electrodes, metal wiring, an interlayer insulating layer and / or a surface protective layer on a substrate. Because the cured film of the present invention has excellent mechanical properties, it can relieve stress from the encapsulating resin during mounting, suppress damage to the low-k layer, and provide a highly reliable semiconductor device.

[0126] Figure 2 shows an enlarged cross-sectional view of an example of a pad portion of a semiconductor device with bumps. A passivation layer 11 with input / output Al pads 10 and via holes is formed on a silicon wafer 9. An insulating layer 12 is then formed on the passivation layer 11. A metal layer 13 made of Cr, Ti, or the like is then formed to connect to the Al pads 10, and metal wiring 14 made of Al, Cu, or the like is then formed by electrolytic plating or the like. The metal layer 13 located around the solder bumps 18 is etched to insulate the pads from one another. A barrier metal 16 and solder bumps 18 are formed on the insulated pads. A scribe line 17 is formed when the insulating film 15 is processed.

[0127] Next, a method for manufacturing a semiconductor device will be described with reference to the drawings. FIG. 3 shows an example of a method for manufacturing a semiconductor device having bumps. In step 3a, a resin composition of the present invention is applied to a silicon wafer 9 on which an Al pad 10 and a passivation layer 11 have been formed, and a patterned insulating layer 12 is formed through a photolithography process. Next, in step 3b, a metal layer 13 is formed by sputtering. In step 3c, metal wiring 14 is formed on the metal layer 13 by plating. Next, in step 3d', a resin composition of the present invention is applied, and in step 3d, a pattern of insulating layer 15 is formed through a photolithography process. During this process, the resin composition constituting insulating layer 15 is processed into a thick film along scribe lines 17. Further wiring (so-called rewiring) can be formed on insulating layer 15. When forming a multilayer wiring structure of two or more layers, the above steps can be repeated to form a multilayer wiring structure in which two or more rewiring layers are separated by an interlayer insulating layer made of the cured film of the present invention. There is no upper limit to the number of layers in a multilayer wiring structure, but structures of 10 layers or less are often used. Next, in step 3e, a barrier metal 16 is formed, and in step 3f, solder bumps 18 are formed. Finally, the substrate is diced along the final scribe lines 17 to separate into individual chips, thereby obtaining semiconductor devices having bumps. [Example]

[0128] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Evaluations in the examples were carried out by the following methods.

[0129] (1) Weight-average molecular weight of alkali-soluble resin (a) The weight average molecular weight (Mw) of the alkali-soluble resin or alkali-soluble resin solution obtained in each Example and Comparative Example was measured in terms of polystyrene using a GPC (gel permeation chromatography) apparatus Waters 2690-996 (manufactured by Nihon Waters K.K.) with N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as the developing solvent.

[0130] (2) Evaluation of the content of β-alkoxypropionamide (b) and amide group-containing tertiary amine compounds (c) in the solvent The solvents used in each example and comparative example were analyzed by GC-MS using a GC-MS system (Agilent) under the following conditions: column temperature: 40-300°C, carrier gas: helium (1.5 mL / min), scan range: m / z 29-600. GC-MS analysis was performed using 3-dimethylamino-N,N-dimethylpropionamide (c-1) and N-[2-(dimethylamino)ethyl]-N-methylformamide (c-2) under the same conditions as above to create calibration curves, and the contents of β-alkoxypropionamide (b) and amide group-containing tertiary amine compound (c) were measured. The content of amide group-containing tertiary amine compound (c) relative to β-alkoxypropionamide (b) was calculated from the respective contents obtained.

[0131] (3) Evaluation of the content of amide group-containing tertiary amine compound (c) relative to alkali-soluble resin (a) 0.1 g of the alkali-soluble resin obtained in the Examples and Comparative Examples, or 0.3 g of the alkali-soluble resin solution obtained in the Examples and Comparative Examples, was dissolved in 1 mL of acetone, and the solution was subjected to GC-MS analysis in the same manner as above to measure the content of the amide group-containing tertiary amine compound (c) relative to the alkali-soluble resin (a).

[0132] (4) Evaluation of the content of β-alkoxypropionamide (b) relative to alkali-soluble resin (a) 0.03 g of the alkali-soluble resin (a) obtained in the Examples and Comparative Examples, or 0.1 g of the alkali-soluble resin solution obtained in the Examples and Comparative Examples, and 0.01 g of methyl 3-nitrobenzoate as an internal standard were dissolved in 0.7 g of deuterated dimethyl sulfoxide, and analyzed by NMR (GX-270, manufactured by JEOL Ltd.). The content of β-alkoxypropionamide (b) relative to the alkali-soluble resin (a) was measured from the area of each peak, using the area of the peak at around 3.9 ppm derived from methyl 3-nitrobenzoate as the standard.

[0133] (5) Esterification rate Using a nuclear magnetic resonance (NMR) apparatus (EX-270 manufactured by JEOL Ltd.), a mixed solution of 10 mg of the polyamic acid ester obtained in the examples and comparative examples and 0.8 g of deuterated dimethyl sulfoxide (DMSO-d6) was analyzed. 1 H-NMR was measured, and the integrated value of the peak derived from the aromatic protons of the resin was determined. The esterification rate of the polyamic acid ester was calculated from the area ratio to the peak derived from the methyl protons of the carboxylic acid alkyl ester. Since resins other than polyamic acid ester do not contain carboxylic acid alkyl ester, the esterification rate is indicated as "-" because it is not measurable.

[0134] (6) Evaluation of the content of the amide group-containing tertiary amine compound (c) relative to the alkali-soluble resin (a) in the resin composition The alkali-soluble resin (a) was separated from the varnish of the resin composition used in each Example and Comparative Example using a GPC separation apparatus (manufactured by Shimadzu Corporation), and the content of the alkali-soluble resin in the resin composition was determined.

[0135] Subsequently, the components other than the solid content obtained by GPC fractionation were concentrated using an evaporator, and then GC-MS analysis was carried out in the same manner as above to measure the content of the amide group-containing tertiary amine compound (c) in the resin composition. From the content of the alkali-soluble resin in the resin composition thus obtained and the content of the amide group-containing tertiary amine compound (c) in the resin composition, the content of the amide group-containing tertiary amine compound (c) relative to the alkali-soluble resin (a) was calculated.

[0136] (7) Storage stability The varnish obtained in each example and comparative example was applied to an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Limited), and baked at 120°C for 3 minutes to produce a pre-baked film with a thickness of 3.0 μm. The film thickness was measured using a Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. under the condition of a refractive index of 1.63. Thereafter, the varnish was exposed to light at an exposure dose of 50 to 300 mJ / cm using an i-line stepper NSR-2005i9C (manufactured by Nikon Corporation) through a mask having a pattern of 10 μm contact holes. 2 in the range of 5 mJ / cm 2 After exposure, the film was developed using the ACT-8 developing device with a 2.38 wt % aqueous solution of tetramethylammonium (hereinafter referred to as TMAH, manufactured by Tama Chemicals Co., Ltd.) as a developer until the film thickness was reduced to 0.5 μm, and then rinsed with distilled water and spun dry to obtain a pattern.

[0137] The obtained pattern was observed at a magnification of 20 times using an FDP microscope MX61 (Olympus Corporation), and the opening diameter of the contact hole was measured. The minimum exposure dose at which the opening diameter of the contact hole reached 10 μm was determined and used as the sensitivity.

[0138] The varnish was stored at 40° C., and the number of days until the sensitivity changed by 15% or more from the sensitivity on day 0 was counted.

[0139] (8) Development adhesion Using the same method as in (7), a 3.0 μm-thick prebaked film was formed on an 8-inch SiNx-coated silicon wafer. Subsequently, using an i-line stepper NSR-2005i9C (Nikon Corporation) exposure machine, the wafer was exposed through a mask with a 1-100 μm square convex pattern (islands) at the same exposure dose as the sensitivity determined in the sensitivity evaluation. After exposure, the wafer was developed using the ACT-8 developing system with 2.38 wt % TMAH as the developer until the film thickness was reduced to 0.5 μm. The wafer was then rinsed with distilled water and dried to obtain a pattern.

[0140] The obtained pattern was observed at 20x magnification using an FDP microscope MX61 (Olympus Corporation), and the minimum size of the convex pattern that adhered to the substrate without peeling was determined. The smaller the size of the convex pattern that adhered to the substrate without peeling, the higher the development adhesion.

[0141] (9) Chemical resistance A 3.0 μm-thick prebaked film was formed on an 8-inch silicon wafer using the same method as in (7). The resulting prebaked film was heated in an inert oven CLH-21CD-S (Koyo Thermo Systems Co., Ltd.) at an oxygen concentration of 20 ppm or less, increasing the temperature at a rate of 5°C / min up to 250°C, and then baked at 250°C for 1 hour to produce a cured film of the resin composition. After measuring the thickness of the cured film, the cured film was immersed in a 60°C mixed solution of 2-(2-aminoethoxy)ethanol / NMP / NMF / DMAc = 10 / 15 / 30 / 50 (by weight) for 30 seconds. After removing the cured film from the mixed solution, it was washed with pure water and then heated in an inert oven at an oxygen concentration of 20 ppm or less, increasing the temperature at a rate of 5°C / min up to 250°C, and then re-baked at 250°C for 1 hour. The film thickness was measured again, and the absolute value of the percentage of the change in film thickness after re-baking relative to the film thickness before immersion in the solution was calculated.

[0142] Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound (α) 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and the solution was cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise to the solution. After the addition was completed, the mixture was reacted at -15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered and dried in vacuo at 50°C.

[0143] 30 g of the solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, followed by 2 g of 5% palladium-carbon. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated by confirming that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain the hydroxyl group-containing diamine compound (α) represented by the following formula:

[0144] [ka]

[0145] Synthesis Example 2: Synthesis of amide group-containing tertiary amine compound (c-1) Under a dry nitrogen stream, 34.4 g (0.4 mol) of methyl acrylate was placed in a 500 ml flask, and 180.3 g (0.44 mol) of an 11% by weight solution of dimethylamine in methanol was added. The mixture was stirred at 40 ° C for 2 hours. Then, 0.77 g (0.004 mol) of a 28% by weight solution of sodium methoxide in methanol and 164.0 g (0.4 mol) of an 11% by weight solution of dimethylamine in methanol were added to the reaction mixture. The reaction mixture was stirred for 5 hours while cooling in a water bath so that the temperature did not exceed 40 ° C. After completion of the reaction, unreacted dimethylamine and methanol were removed by vacuum distillation, and 3-dimethylamino-N,N-dimethylpropionamide (c-1) was obtained as a nearly colorless liquid.

[0146] Synthesis Example 3: Synthesis of quinone diazide compound (d-1) 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to cool to room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise to the solution so that the temperature in the system did not exceed 35°C. After the addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The precipitate was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain quinone diazide compound (d-1) represented by the following formula:

[0147] [ka]

[0148] Synthesis Example 4 Synthesis of Adhesion Improver (e-1) In a 2 L separable flask, 110.7 g of 3-aminopropyltriethoxysilane and Add 845g of NMP, add 59.6g of phenyl isocyanate and 12g of NMP at room temperature. The resulting solution was slowly added dropwise at room temperature and stirred for 2 hours. After the reaction was completed, the solvent was removed to obtain an adhesion promoter (e-1) represented by the following formula.

[0149] [ka]

[0150] The names of the compounds shown in each Example and Comparative Example and the structure of the amide group-containing tertiary amine compound (c) are shown below. b-1: 3-Methoxy-N,N-dimethylpropionamide (Equamide M-100 (registered trademark) manufactured by Idemitsu Kosan) (SP value 10.3, calculated value) b-2:3-Butoxy-N,N-dimethylpropionamide (Equamide B-100 (registered trademark) manufactured by Idemitsu Kosan) (SP value 10.0, calculated value) c-1: 3-Dimethylamino-N,N-dimethylpropionamide (SP value 10.0, calculated value) c-2: N-[2-(dimethylamino)ethyl]-N-methylformamide (SP value 9.9, calculated value) e-2: 3-aminopropyltriethoxysilane NMP: N-methyl-2-pyrrolidone (SP value 11.2, literature value) PGMEA: Propylene glycol monomethyl ether acetate (SP value 8.7, calculated value) MIBK: Methyl isobutyl ketone (SP value 8.6, literature value) GBL: γ-butyrolactone (SP value 12.8, literature value) DMI: 1,3-dimethyl-2-imidazolidinone (SP value 11.4, calculated value)

[0151] [ka]

[0152] Example 1 The content of the amide group-containing tertiary amine compound (c) was evaluated using 1 L of solvent (b-1) as described above, and it was found that (b-1) contained 2000 ppm of (c-1). Next, (b-1) was continuously contacted with 100 ml of ion exchange resin (trade name "Amberlyst 16WET", manufactured by Organo Corporation (Rohm & Haas)) packed in an ion exchange resin tower, and purified until the content of (c-1) in (b-1) reached 100 ppm, to obtain purified solvent (b-1-100).

[0153] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenylethertetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of (b-1-100). To this solution, 29.3 g (0.08 mol) of BAHF and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter referred to as SiDA) were added along with 50 g of (b-1-100), and the mixture was allowed to react at 40 °C for 2 hours. Next, 2.18 g (0.02 mol) of 3-aminophenol (hereinafter referred to as MAP) was added as an end-capping agent along with 5 g of (b-1-100), and the mixture was allowed to react at 50 °C for 2 hours. A solution of 26.22 g (0.22 mol) of N,N-dimethylformamide dimethyl acetal diluted with 50 g of (b-1-100) was then added. After the addition, the mixture was stirred at 50°C for 3 hours. After stirring was completed, the solution was cooled to room temperature and then poured into 3 L of water to obtain 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 24 hours to obtain a polyamic acid ester (A), which is an alkali-soluble resin. The weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate were measured using the obtained resin as described above.

[0154] Next, 10.0 g of the polyamic acid ester (A) and 2.0 g of the quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of the amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0155] Example 2 In the same manner as in Example 1, purification was carried out until the content of (c-1) in the solvent (b-1) reached 500 ppm, to obtain a purified solvent (b-1-500).

[0156] Except for changing the solvent (b-1-100) to (b-1-500), an alkali-soluble resin, polyamic acid ester (B), was obtained in the same manner as in Example 1. The weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate of the obtained resin were measured as described above.

[0157] Next, 10.0 g of polyamic acid ester (B) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0158] Example 3 In the same manner as in Example 1, purification was carried out until the content of (c-1) in the solvent (b-1) reached 1000 ppm, to obtain a purified solvent (b-1-1000).

[0159] Except for changing the solvent (b-1-100) to (b-1-1000), an alkali-soluble resin, polyamic acid ester (C), was obtained in the same manner as in Example 1. The weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate of the obtained resin were measured as described above.

[0160] Next, 10.0 g of polyamic acid ester (C) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0161] Example 4 In the same manner as in Example 1, purification was carried out until the content of (c-1) in the solvent (b-1) reached 1800 ppm, to obtain a purified solvent (b-1-1800).

[0162] Except for changing the solvent (b-1-100) to (b-1-1800), an alkali-soluble resin, polyamic acid ester (D), was obtained in the same manner as in Example 1. The weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate of the obtained resin were measured as described above.

[0163] Next, 10.0 g of polyamic acid ester (D) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0164] Example 5 In the same manner as in Example 1, purification was carried out until the content of (c-1) in the solvent (b-1) reached 20 ppm, to obtain a purified solvent (b-1-1800).

[0165] Except for changing the solvent (b-1-100) to (b-1-20), an alkali-soluble resin, polyamic acid ester (E), was obtained in the same manner as in Example 1. The weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate of the obtained resin were measured as described above.

[0166] Next, 10.0 g of polyamic acid ester (E) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0167] Example 6 In the same manner as in Example 1, purification was carried out until the content of (c-1) in the solvent (b-2) reached 100 ppm, to obtain a purified solvent (b-2-100).

[0168] Except for changing the solvent (b-1-100) to (b-2-100), an alkali-soluble resin, polyamic acid ester (F), was obtained in the same manner as in Example 1. The weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate of the obtained resin were measured as described above.

[0169] Next, 10.0 g of polyamic acid ester (F) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0170] Example 7 An alkali-soluble resin, polyamic acid ester (G), was obtained in the same manner as in Example 1, except that 14.7 g (0.04 mol) of BAHF and 24.2 g (0.04 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 were used instead of 29.3 g (0.08 mol) of BAHF. Using the obtained resin, the weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate were measured as described above.

[0171] Next, 10.0 g of polyamic acid ester (G) and 2.0 g of quinone diazide compound (c-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0172] Example 8 An alkali-soluble resin, polyamic acid ester (H), was obtained in the same manner as in Example 1, except that 48.4 g (0.08 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 was used instead of 29.3 g (0.08 mol) of BAHF. The weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate were measured using the obtained resin as described above.

[0173] Next, 10.0 g of polyamic acid ester (H) and 2.0 g of quinone diazide compound (c-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0174] Example 9 Under a dry nitrogen stream, 29.3 g (0.08 mol) of BAHF, 1.24 g (0.005 mol) of SiDA, and 2.18 g (0.02 mol) of MAP (as an end-capping agent) were dissolved in 150 g of the solvent (b-1-100) obtained in Example 1. 31.0 g (0.10 mol) of ODPA was added along with 50 g of (b-1-100). The mixture was stirred at 60°C for 1 hour and then at 180°C for 5 hours. After stirring, the solution was poured into 3 L of water, and a white precipitate was collected. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain an alkali-soluble resin, polyimide (I). The weight-average molecular weight, β-alkoxypropionamide (b) content, and amide group-containing tertiary amine compound (c) content of the resulting resin were measured as described above.

[0175] Next, 10.0 g of polyimide (I) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above. Example 10 Under a dry nitrogen stream, 31.1 g (0.085 mol) of BAHF and 2.18 g (0.02 mol) of MAP were dissolved in 150 g of the solvent (b-1-100) obtained in Example 1 and 52.8 g (0.6 mol) of glycidyl methyl ether, and the solution was cooled to -15°C. A solution of 29.5 g (0.10 mol) of diphenyl ether dicarboxylic acid dichloride (manufactured by Nihon Nohyaku Co., Ltd.) dissolved in 50 g of (b-1-100) was added dropwise to the solution, ensuring that the internal temperature did not exceed 0°C. After the addition was complete, stirring was continued at -15°C for 6 hours. After the reaction was complete, the solution was poured into 3 L of water containing 10 wt% methanol, and a white precipitate was collected. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain an alkali-soluble resin, polyhydroxyamide (J). The weight average molecular weight, the β-alkoxypropionamide (b) content, and the amide group-containing tertiary amine compound (c) content were measured using the obtained resin as described above.

[0176] Next, 10.0 g of polyhydroxyamide (J) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of the amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0177] Example 11 Except for changing the solvent (b-1-100) to NMP, an alkali-soluble resin, polyamic acid ester (K), was obtained in the same manner as in Example 1. The weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate of the obtained resin were measured as described above.

[0178] Next, 10.0 g of polyamic acid ester (K), 2.0 g of quinone diazide compound (d-1), and 0.5 g of solvent (b-1-1000) containing 1000 ppm of the amide group-containing tertiary amine (c-1) obtained in Example 3 were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The content of the amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated using the obtained varnish as described above.

[0179] Example 12 Except for changing the number of times of washing with water after reprecipitation of the resin from three to two, an alkali-soluble resin, polyamic acid ester (L), was obtained in the same manner as in Example 1. Using the obtained resin, the weight-average molecular weight, the β-alkoxypropionamide (b) content, the amide group-containing tertiary amine compound (c) content, and the esterification rate were measured as described above.

[0180] Next, 10.0 g of polyamic acid ester (L) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0181] Example 13 Except for changing the number of times of washing with water after reprecipitation of the resin from three times to one time, an alkali-soluble resin, polyamic acid ester (M), was obtained in the same manner as in Example 1. Using the obtained resin, the weight-average molecular weight, the β-alkoxypropionamide (b) content, the amide group-containing tertiary amine compound (c) content, and the esterification rate were measured as described above.

[0182] Next, 10.0 g of polyamic acid ester (M) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. Using the obtained varnish, the content of the amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above, but the film loss during development was large, and it was not possible to form a residual pattern for development adhesion.

[0183] Example 14 In the same manner as in Example 1, the solvent (b-1) was purified until the concentration of (c-1) in the solvent (b-1) was below the detection limit (<1 ppm), and then an amide group-containing tertiary amine compound (c-2) was added to obtain a solvent (b-1-500') prepared so that the concentration of (c-2) in the solvent (b-1) was 500 ppm.

[0184] An alkali-soluble resin, polyamic acid ester (N), was obtained in the same manner as in Example 1, except that the solvent (b-1-100) was changed to (b-1-500'). The weight-average molecular weight and the amide group-containing tertiary amine compound (c) content were measured using the obtained resin as described above. The content of the amide group-containing tertiary amine compound (c), weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate in the resin composition were measured using the obtained resin solution as described above.

[0185] Next, 10.0 g of polyamic acid ester (N) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0186] Example 15 Under a dry nitrogen stream, 5 g of 2,2'-azobis(isobutyronitrile) and 5 g of t-dodecanethiol were dissolved in 150 g of propylene glycol monomethyl ether acetate (PGMEA). Then, 30 g of methacrylic acid, 35 g of benzyl methacrylate, and 35 g of tricyclo[5.2.1.02,6]decan-8-yl methacrylate were added, stirred at room temperature, and then heated and stirred at 70°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 heated and stirred at 90°C for 4 hours. After stirring, PGMEA was added to the resin solution until the solids concentration reached 30% by mass, yielding a 30% by mass solution (X') of the alkali-soluble acrylic resin (X). The resulting resin solution was used to measure the weight average molecular weight, the β-alkoxypropionamide (b) content, and the amide group-containing tertiary amine compound (c) content as described above.

[0187] Next, a varnish of a positive photosensitive resin composition was obtained by adding 2.0 g of quinone diazide compound (d-1) and 0.5 g of a solvent (b-1-1000) containing 1000 ppm of the amide group-containing tertiary amine (c-1) obtained in Example 3 to 30.0 g of a 30 mass % solution (X') of acrylic resin (X). The obtained varnish was used to evaluate the content of the amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0188] Example 16 Under a dry nitrogen stream, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 75.5 g of 37 wt% aqueous formaldehyde solution (0.93 mol of formaldehyde), and 0.63 g (0.005 mol) of oxalic acid dihydrate were dissolved in 260 g of methyl isobutyl ketone (MIBK). The reaction solution was refluxed for 7 hours to carry out a polycondensation reaction. The volatiles were then removed, and GBL was added to the dissolved resin until the solids concentration reached 30 wt%. This resulted in a 30 wt% solution (Y') of alkali-soluble novolak resin (Y). The resulting resin solution was used to measure the weight-average molecular weight, β-alkoxypropionamide (b) content, and amide group-containing tertiary amine compound (c) content, as described above.

[0189] Next, a varnish of a positive photosensitive resin composition was obtained by adding 2.0 g of quinone diazide compound (d-1) and 0.5 g of a solvent (b-1-1000) containing 1000 ppm of the amide group-containing tertiary amine (c-1) obtained in Example 3 to 30.0 g of a 30 mass % solution (Y') of novolak resin (Y). The obtained varnish was used to evaluate the content of the amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0190] Example 17 An alkali-soluble resin, polyamic acid ester (AC), was obtained in the same manner as in Example 3, except that a mixed solvent of (b-1-1000) and DMI in a mass ratio of 8:2 was used as the polymerization solvent instead of solvent (b-1-1000). Using the obtained resin solution, the content of amide group-containing tertiary amine compound (c), weight average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate in the resin composition were measured as described above.

[0191] Next, 10.0 g of polyamic acid ester (AC) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0192] Example 18 An alkali-soluble resin, polyamic acid ester (AD), was obtained in the same manner as in Example 4, except that a mixed solvent of (b-1-1800) and DMI in a mass ratio of 8:2 was used as the polymerization solvent instead of solvent (b-1-1800). Using the obtained resin solution, the content of amide group-containing tertiary amine compound (c) in the resin composition, weight average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate were measured as described above.

[0193] Next, 10.0 g of polyamic acid ester (AD) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0194] Comparative Example 1 In the same manner as in Example 1, purification was carried out until the content of (c-1) in the solvent (b-1) was below the detection limit (<1 ppm), to obtain a purified solvent (b-1-0).

[0195] Except for changing the solvent (b-1-100) to (b-1-0), an alkali-soluble resin, polyamic acid ester (O), was obtained in the same manner as in Example 1. The weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate of the obtained resin were measured as described above.

[0196] Next, 10.0 g of the polyamic acid ester (O) and 2.0 g of the quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of the amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0197] Comparative Example 2 Except for changing the solvent (b-1) from (b-1) to (b-1) instead of (b-1-100), an alkali-soluble resin, polyamic acid ester (P), was obtained in the same manner as in Example 1. The weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate of the obtained resin were measured as described above.

[0198] Next, 10.0 g of polyamic acid ester (P) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0199] Comparative Example 3 The amide group-containing tertiary amine compound (c-1) obtained in Synthesis Example 2 was added to the solvent (b-1) so that the concentration of (c-1) in the solvent (b-1) was 10,000 ppm, thereby obtaining a solvent (b-1-10000).

[0200] Except for changing the solvent (b-1-100) to (b-1-10000), an alkali-soluble resin, polyamic acid ester (Q), was obtained in the same manner as in Example 1. The weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate of the obtained resin were measured as described above.

[0201] Next, 10.0 g of polyamic acid ester (Q) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0202] Comparative Example 4 10.0 g of the alkali-soluble resin (K) obtained in Example 11 and 2.0 g of the quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of the amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0203] Comparative Example 5 Except for changing the solvent (b-1-100) to (b-1), an alkali-soluble resin, polyimide (R), was obtained in the same manner as in Example 7. The weight-average molecular weight, β-alkoxypropionamide (b) content, and amide group-containing tertiary amine compound (c) content of the obtained resin were measured as described above.

[0204] Next, 10.0 g of polyimide (R) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0205] Comparative Example 6 Except for changing the solvent (b-1-100) to (b-1), an alkali-soluble resin, polyhydroxyamide (S), was obtained in the same manner as in Example 10. The weight-average molecular weight, β-alkoxypropionamide (b) content, and amide group-containing tertiary amine compound (c) content of the obtained resin were measured as described above.

[0206] Next, 10.0 g of polyhydroxyamide (S) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0207] Comparative Example 7 Under a dry nitrogen stream, 29.3 g (0.08 mol) of BAHF, 1.24 g (0.005 mol) of SiDA, and 2.18 g (0.02 mol) of MAP (as an end-capping agent) were dissolved in 150 g of solvent (b-1). 31.0 g (0.10 mol) of ODPA was added along with 50 g of (b-1), and the mixture was stirred at 60°C for 1 hour, followed by stirring at 180°C for 5 hours. After stirring, the solvent was distilled off until the solids concentration of the solution reached 30% by mass, yielding a 30% by mass solution (R') of the alkali-soluble polyimide resin. The resulting resin solution was used to measure the weight-average molecular weight, β-alkoxypropionamide (b) content, and amide group-containing tertiary amine compound (c) content as described above.

[0208] Next, 2.0 g of quinone diazide compound (d-1) was added to 30.0 g of a 30% by mass solution (R') of polyimide (R) to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0209] Comparative Example 8 A varnish of a positive photosensitive resin composition was obtained by adding 10.0 g of the polyamic acid ester (K) obtained in Example 11, 2.0 g of the quinone diazide compound (d-1), and 0.1 g of the adhesion improver (e-1) obtained in Synthesis Example 4 to 30 g of GBL. The obtained varnish was used to evaluate the content of the amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0210] Comparative Example 9 10.0 g of the polyamic acid ester (K) obtained in Example 11, 2.0 g of the quinone diazide compound (d-1), and 0.1 g of the adhesion improver (e-2) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of the amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0211] Comparative Example 10 50 g of the polyamic acid ester (A) obtained in Example 1 was redissolved in 500 g of GBL. This solution was added to 3 L of water to obtain 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 24 hours to obtain a polyamic acid ester (T), an alkali-soluble resin. The weight-average molecular weight, β-alkoxypropionamide (b) content, amide group-containing tertiary amine compound (c) content, and esterification rate were measured using the obtained resin as described above.

[0212] Next, 10.0 g of polyamic acid ester (T) and 2.0 g of quinone diazide compound (d-1) were added to 30 g of GBL to obtain a varnish of a positive photosensitive resin composition. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0213] Comparative Example 11 A varnish of a positive photosensitive resin composition was obtained by adding 2.0 g of quinone diazide compound (d-1) to 30.0 g of the 30 mass % solution (X') of acrylic resin (X) obtained in Example 15. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0214] Comparative Example 12 A varnish of a positive photosensitive resin composition was obtained by adding 2.0 g of quinone diazide compound (d-1) to 30.0 g of the 30 mass % solution (Y') of novolak resin (Y) obtained in Example 16. The obtained varnish was used to evaluate the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0215] Comparative Example 13 A varnish of a positive photosensitive resin composition was obtained by adding 10.0 g of the alkali-soluble resin (K) obtained in Example 11, 2.0 g of the quinone diazide compound (d-1), and 0.5 mg of the amide group-containing tertiary amine compound (c-1) obtained in Synthesis Example 2 to 30 g of GBL. The obtained varnish was used to evaluate the content of the amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance as described above.

[0216] The compositions and evaluation results of each of the examples and comparative examples are shown in Tables 1 to 4.

[0217] [Table 1]

[0218] [Table 2]

[0219] [Table 3]

[0220] [Table 4] [Explanation of symbols]

[0221] 1: TFT (thin film transistor) 2: Wiring 3: TFT insulating layer 4: Flattening layer 5:ITO (transparent electrode) 6: Circuit board 7: Contact hole 8: Insulating layer 9: Silicon wafer 10: Aluminum pad 11: Passivation layer 12: Insulating layer 13: Metal (Cr, Ti, etc.) layer 14: Metal wiring (Al, Cu, etc.) 15: Insulating layer 16: Barrier metal 17: Scribe Line 18: Solder bump

Claims

1. The composition contains an alkali-soluble resin (a), a β-alkoxypropionamide (b), and an amide group-containing tertiary amine compound (c) having a structure represented by general formula (1), The alkali-soluble resin (a) contains a polyimide precursor, and the polyimide precursor is a polyamic acid ester having an esterification rate of 60% or more, the content of the β-alkoxypropionamide (b) relative to 100 parts by mass of the alkali-soluble resin (a) is 1 to 15 parts by mass, and the content of the amide group-containing tertiary amine compound (c) having a structure represented by general formula (1) relative to the alkali-soluble resin (a) is 1 to 10 ppm. 【Chemical 1】 (In general formula (1), R １ and R ２ represents a monovalent organic group having an alkyl group having 1 to 5 carbon atoms, R ３ and R ４ represents a monovalent organic group having a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

2. 2. The resin composition according to claim 1, wherein the β-alkoxypropionamide (b) is 3-methoxy-N,N-dimethylpropionamide or 3-butoxy-N,N-dimethylpropionamide.

3. 2. The resin composition according to claim 1, wherein the esterification rate of the polyamic acid ester is 75% or more.

4. The resin composition according to any one of claims 1 to 3, further comprising a photosensitive compound (d).

5. A resin sheet formed from the resin composition according to any one of claims 1 to 4.

6. A cured film obtained by curing the resin sheet according to claim 5.

7. A cured film obtained by curing the resin composition according to any one of claims 1 to 4.

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