Resin composition, resin sheet and 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 possess excellent heat resistance and electrical insulation properties. Therefore, photosensitive resin compositions containing these heat-resistant resins are used as surface protective layers, interlayer insulating layers, insulating layers for organic field elements and organic EL display elements, and planarization layers for TFT substrates used in display devices. In recent years, with the miniaturization and reduction of electronic devices, the increasing resolution of display elements and the miniaturization and integration of semiconductor devices have led to various technical problems in the materials used for these insulating films or protective films. Among these, development adhesion is a particularly significant problem; when the development adhesion between the photosensitive resin composition used for forming fine patterns and the substrate is poor, peeling often occurs. Therefore, a method of adding an aminosilane coupling agent to the photosensitive resin composition to improve development adhesion is known (see Non-Patent Literature 1).

[0003] However, if the amount added is large, when stored as a resin composition containing o-quinone diazide compounds, which are widely used as photosensitive agents in photoresists, the amino groups of the aminosilane coupling agent react with the o-quinone diazide compounds, leading to a gradual decrease in sensitivity. To solve this problem, a method has been proposed in which an isocyanate compound or a carbonate ester derivative is reacted with an aminosilane coupling agent to produce a resin composition containing a polyimide precursor and an o-quinone diazide compound (Patent Document 1). However, the resin composition obtained by this method has the problem that sufficient adhesion to the substrate cannot be obtained because the amino groups are modified. [Prior art documents] [Patent Documents]

[0004]

Patent Document 1

Non-Patent Document 1

Summary of the Invention

Problems 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 Problems

[0006] The present invention relates to a resin composition containing an alkali-soluble resin (a), β-alkoxypropionamide (b), and a tertiary amine compound containing an amide group (c), wherein the content of the tertiary amine compound containing an amide group (c) with respect 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 Description of the Drawings

[0008] [Figure 1] It is a cross-sectional view of an example of a TFT substrate. [Figure 2] It is an enlarged cross-sectional view of an example of a pad portion of a semiconductor device having bumps. [Figure 3] It is a schematic view showing an example of a method for manufacturing a semiconductor device having bumps.

Modes for Carrying Out the Invention

[0009] Embodiments of the present invention will be described in detail.

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

[0011] In the present invention, the alkali-soluble resin (a) preferably has acidic groups in the structural units of the resin and / or at the ends of its main chain in order to impart alkali solubility. Examples of acidic groups include carboxyl groups, phenolic hydroxyl groups, and sulfonic acid groups. Furthermore, the alkali-soluble resin (a) preferably has fluorine atoms in order to impart water repellency.

[0012] The alkali-soluble resin (a) in the present invention includes, but is not limited to, polyimide, polyimide precursor, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, polyamide, polymers of radical polymerizable monomers having alkali-soluble groups, and phenolic resins. Two or more of these resins may be included. Among these alkali-soluble resins, polyimide, polybenzoxazole, polyamideimide, any of their precursors, or copolymers selected from two or more of them are preferred due to their high developability, excellent heat resistance, and low outgassing at high temperatures, and polyimide, polyimide precursor, polybenzoxazole precursor, or copolymers selected from two or more of them are more preferred. Furthermore, from the viewpoint of further improving sensitivity, polyimide precursor or polybenzoxazole precursor is even more preferred. Furthermore, from the viewpoint of ease of synthesis, polyimide precursor is particularly preferred. Here, polyimide precursor refers to a resin that is converted to polyimide by heat treatment or chemical treatment, and examples include polyamic acid and polyamic acid ester, with polyamic acid ester being preferred from the viewpoint of improving 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 higher, and more preferably 75% or higher. The esterification rate of the polyamic acid ester is, for example 1 The polybenzoxazole precursor can be calculated by measuring the 1H-NMR spectrum, using the area ratio of the integral value of the peak originating from aromatic protons in the resin to the peak originating from methyl protons in the alkyl carboxylate. A polybenzoxazole precursor refers to a resin that is converted to polybenzoxazole by heat treatment or chemical treatment, such as 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]

Chem.

[0015] In general formula (1), X represents an organic group having a valence of 2 to 8, and Y represents an organic group having a valence of 2 to 11. R 5 and R 7 represent a hydroxyl group or a sulfonic acid group, and each may be a single one or a mixture of different ones. R 6 and R 8 represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. r, s, and u represent integers from 0 to 3, and t represents an integer from 0 to 6. However, r + s + t + u > 0.

[0016]

Chem.

[0017] In general formula (2), E represents an organic group having a valence of 4 to 10, and G represents an organic group having a valence of 2 to 8. R 9 and R 10 represent a carboxy group, a sulfonic acid group, or a hydroxyl group. A plurality of R 9 and R 10 may be the same or different from each other. p and q each independently represent an integer from 0 to 6.

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

[0019] In the above general formula (1), X(R 5 ) r (COOR 6 ) srepresents an acid residue. X is a 2- to 8-valent organic group, and among these, an organic group with 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic 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'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, and 2,2-bis(2,3-dicarboxyphenyl) Examples of tetracarboxylic acids include tetracarboxylic acids such as cyphenyl)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, as well as aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, and aliphatic tetracarboxylic acids containing cyclic aliphatic groups such as 1,2,3,4-cyclopentanetetracarboxylic acid. Two or more of these may be used.

[0021] [ka]

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

[0023] Of the acids mentioned above, in the case of tricarboxylic acids and tetracarboxylic acids, one or two carboxyl groups are (COOR) in general formula (1). 6 This corresponds to ).

[0024] These acids may be used as is, or they may be used as acid anhydrides, active esters, or active amides. Examples of active esters include N-hydroxysuccinimide ester compounds obtained by reacting the carboxyl group of an acid with N-hydroxysuccinimide, and examples of active 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 acidic dianhydride. E is a tetravalent to decavalent organic group, and among these, an organic group with 5 to 40 carbon atoms containing an aromatic ring or a cyclic aliphatic group is preferred.

[0026] Specifically, the acid dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic acid 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, and bis(3,4-dicarboxyphenyl) Examples include aromatic tetracarboxylic dianhydrides such as ether dianhydrides, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenic acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorenic acid 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 acid dianhydrides with the structures shown below; aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride; and aliphatic tetracarboxylic dianhydrides containing cyclic aliphatic groups such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride. Two or more of these may be used.

[0027] [ka]

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

[0029] The above general formula (1) Y(R 7 ) t (COOR 8 ) u and G(R) of the above general formula (2) 10 ) q The '' represents a diamine residue. Y is a 2-11 valent organic group, and G is a 2-8 valent organic group, with organic groups having 5-40 carbon atoms containing an aromatic ring or a cyclic aliphatic group being 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'-di Examples 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, aromatic diamines such as 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, and compounds in which at least some of the hydrogen atoms of these aromatic rings are substituted with alkyl or halogen atoms; aliphatic diamines containing cyclic aliphatic 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 R represents an oxygen atom, C(CF3)2 or C(CH3)2. 21 ~R 24 Each of these independently represents either a hydrogen atom or a hydroxyl group.

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

[0034] Furthermore, by sealing the ends of these resins with monoamines, acid anhydrides, acid chlorides, monocarboxylic acids, or active ester compounds that have acidic groups, resins with acidic groups at the ends 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-aminona Examples 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 acid anhydrides include phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic anhydride. 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, and 1-mercapto-5-carboxynaphthalene. Two or more of these may be used.

[0038] Preferred examples of acid chlorides include monoacid chloride compounds in which the carboxyl group of the monocarboxylic acid is acid-chlorinated, and monoacid chloride compounds in which only one carboxyl 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 acid-chlorinated. Two or more of these may be used.

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

[0040] End-captives introduced into resins can be easily detected by the following methods. For example, a resin containing an end-captive is dissolved in an acidic solution and decomposed into its constituent amine and acid components. The end-captive can then be easily detected by gas chromatography (GC) or NMR measurement. Alternatively, resins containing end-captives can be analyzed using pyrolysis gas chromatography (PGC), infrared spectroscopy, and 13It can also be detected by measuring the 1C-NMR spectrum.

[0041] From the viewpoint of further enhancing the effect of improving development adhesion, the resin composition of the present invention may contain an alkali-soluble resin (a) that is a β-alkoxypropionamide (b) and an amide group-containing tertiary amine compound (c). Such an alkali-soluble resin (a) can be achieved by using a β-alkoxypropionamide (b) containing an amide group-containing tertiary amine compound (c) as the 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 known methods. One method for producing polyamic acid, a polyimide precursor, is to react a tetracarboxylic dianhydride with a diamine compound in a solvent at a low temperature.

[0043] Other methods for producing polyamic acid esters, which are also polyimide precursors, include, in addition to the method of reacting the polyamic acid with an esterifying agent as described above, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting it with an amine in a solvent in the presence of a condensing agent; and a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then acid-chloridating the remaining dicarboxylic acid and reacting it with an amine in a solvent. From the viewpoint of ease of synthesis, it is preferable to include a step of reacting the polyamic acid with an esterifying agent. There are no particular limitations on the esterifying agent, and known methods can be applied, but N,N-dimethylformamide dialkyl acetal is preferred because the resulting resin is easy to purify.

[0044] One method for producing polyhydroxyamide, a polybenzoxazole precursor, is to react a bisaminophenol compound with a dicarboxylic acid in a solvent. Specifically, this involves reacting a dehydrating condensation agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding the bisaminophenol compound. Another method involves adding a solution of dicarboxylic acid dichloride dropwise to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine has been added.

[0045] One method for producing polyimide is to dehydrate and cyclize the polyamic acid or polyamic acid ester obtained by the method described above in a solvent. Methods for dehydration and cyclization include chemical treatment with acids or bases, and heat treatment.

[0046] One method for producing polybenzoxazole is to dehydrate and cyclize the polyhydroxyamide obtained by the method described above in a solvent. Methods for dehydration and cyclization include chemical treatment with acids or bases, and heat treatment.

[0047] Examples of polyamide-imide precursors include polymers of tricarboxylic acid, the corresponding tricarboxylic acid anhydride, or tricarboxylic acid anhydride halide with a diamine compound, with polymers of trimellitic anhydride chloride and aromatic diamine compounds being preferred. Methods for producing polyamide-imide precursors include, for example, reacting tricarboxylic acid, the corresponding tricarboxylic acid anhydride, or tricarboxylic acid anhydride halide with a diamine compound in a solvent at low temperature.

[0048] Methods for producing polyamide-imide include, for example, reacting trimellitic anhydride with an aromatic diisocyanate in a solvent, and dehydrating and cyclizing the polyamide-imide precursor obtained by the aforementioned method in a solvent. Methods for dehydration and cyclization include chemical treatment with acids or bases, and heat treatment.

[0049] In the present invention, the method for producing the alkali-soluble resin (a) preferably contains β-alkoxypropionamide (b) as the polymerization solvent. β-alkoxypropionamide has high solubility for the alkali-soluble resin (a) and can dissolve the alkali-soluble resin (a) without using NMP, which is a concern for its effects on living organisms. From the viewpoint of ease of solvent production, 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) in the present invention may include a solvent other than β-alkoxypropionamide (b) as the polymerization solvent. Examples of solvents other than 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-pyro Lydone (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 values) N,N-dimethylisobutyrate (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), deltavalerolactone (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 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 / 10mmHg, converted to atmospheric pressure boiling point: 313°C, SP value 14.3, calculated value). The solubility parameter (SP value) in this invention is based on the literature value described in "Basic Science of Coatings" (page 65, by Yuji Harasaki, Maki Shoten). Furthermore, for values ​​where SP values ​​were not specified, the values ​​used were calculated from Fedors' methods for atom and atomic group evaporation energy and molar volume, as described in "Basic Science of Coatings" (page 55, by Yuji Harasaki, Maki Shoten).

[0051] In addition to the β-alkoxypropionamide (b) and the amide group-containing tertiary amine compound (c), it is preferable to include an organic solvent (d) having a solubility parameter of 10.4 or higher and 13.0 or lower. By including an organic solvent with a solubility parameter higher than that of the β-alkoxypropionamide (b), such as 3-methoxy-N,N-dimethylpropionamide (SP value 10.3, calculated value) and 3-butoxy-N,N-dimethylpropionamide (SP value 10.0, calculated value), and the amide group-containing tertiary amine compound (c), such as 3-dimethylamino-N,N-dimethylpropionamide (SP value 10.0, calculated value), the reaction efficiency of the esterification step of the polyamic acid described above can be increased, and the esterification rate of the resulting polyamic acid ester can be improved. From the viewpoint of improving the esterification efficiency of the polyamic acid, a solvent having a urea bond is particularly preferred. Solvents containing urea bonds include 1,3-dimethyl-2-imidazolidinone (SP value 11.4, calculated value) and N,N-dimethylpropylene urea (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 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, and more preferably 10% or more, relative to 100% of the polymerization solvent. By setting it within this range, a polyamic acid ester with a high esterification rate can be obtained. On the other hand, when the obtained alkali-soluble resin is used as a photosensitive resin composition as described later, from the viewpoint of suppressing the residue of organic solvents on the film after firing, it is preferably 50% or less, and more preferably 40% or less.

[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 Each is independently a monovalent organic group having an alkyl group with 1 to 5 carbon atoms, R 3 and R 4 Each of these independently represents a monovalent organic group having either a hydrogen atom or an alkyl group with 1 to 5 carbon atoms.

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

[0057] When using β-alkoxypropionamide (b) containing an amide group-containing tertiary amine compound (c) as a polymerization solvent for alkali-soluble resin (a), after the polymerization reaction is complete, it is reprecipitation 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 the amide group-containing tertiary amine compound (c). The content can be adjusted by appropriately adjusting the selection of the poor solvent during reprecipitation, the flow rate during reprecipitation, and the number of washes. From the viewpoint of further enhancing the effect of improving developability, it is preferable to include β-alkoxypropionamide (b) and the amide group-containing tertiary amine compound (c) in 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 β-alkoxypropionamide (b). By including β-alkoxypropionamide (b) and an amide group-containing tertiary amine compound (c), the adhesion of the resin composition of the present invention after development can be improved.

[0059] β-alkoxypropionamide (b) may be included in the alkali-soluble resin (a) by being used as a polymerization solvent for the alkali-soluble resin (a). From the viewpoint of further enhancing the effect of improving developability, it is preferable to include β-alkoxypropionamide (b) in the alkali-soluble resin (a) by using it as a polymerization solvent for the alkali-soluble resin (a) as described above, rather than adding it to the resin composition.

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

[0061] In the present invention, the content of β-alkoxypropionamide (b) is preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of alkali-soluble resin (a), from the viewpoint of improving developability and adhesion. On the other hand, from the viewpoint of forming a desired patterned film when used as a developable film, it is preferably 15 parts by mass or less, and more preferably 7 parts by mass or less. Development adhesion refers to the adhesion between the film and the substrate after development. When the coating film of the resin composition of the present invention is dried using the method described later, and then exposed and developed, 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 β-alkoxypropionamide (b) and an amide group-containing tertiary amine compound (c), the adhesion of the resin composition of the present invention after development can be improved.

[0063] As described above, the amide group-containing tertiary amine compound (c) may be included in the alkali-soluble resin (a) by being used as part of the polymerization solvent for the alkali-soluble resin (a). From the viewpoint of further enhancing the effect of improving developability, it is preferable to include a specified amount of the amide group-containing tertiary amine compound (c) by using β-alkoxypropionamide (b) containing the amide group-containing tertiary amine compound (c) as the polymerization solvent for the alkali-soluble resin (a), 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 resulting alkali-soluble resin (a) is used as a photosensitive resin composition, it is preferable that the amide group-containing tertiary amine compound (c) has a structure represented by the following general formula (3).

[0065] [ka]

[0066] In general formula (3), R 1 and R 2 Each is independently a monovalent organic group having an alkyl group with 1 to 5 carbon atoms, R 3 and R 4 Each of these independently represents a monovalent organic group having either a hydrogen atom or an alkyl group with 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, and more preferably 10 ppm or more, relative to the alkali-soluble resin (a), from the viewpoint of improving developability. On the other hand, from the viewpoint of improving the storage stability of the resin composition, it is 90 ppm or less, and more preferably 50 ppm or less.

[0068] <Photosensitive compound (d)> The resin composition of the present invention preferably contains a photosensitive compound (d) and can be 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 acid upon light irradiation, and the photopolymerization initiator (d2) is a compound that undergoes bond cleavage and / or reaction upon exposure, generating radicals.

[0069] By including a photoacid generator (d1), acid is generated in the light-irradiated area, increasing its solubility in the alkaline aqueous solution and allowing for the production of a positive relief pattern where the light-irradiated area dissolves. Alternatively, by including the photoacid generator (d1) and an epoxy compound or a thermal crosslinking agent described later, the acid generated in the light-irradiated area promotes the crosslinking reaction of the epoxy compound or thermal crosslinking agent, resulting in a negative relief pattern where the light-irradiated area becomes insoluble. On the other hand, by including a photopolymerization initiator and a radical polymerizable compound described later, radical polymerization proceeds in the light-irradiated area, resulting in a negative relief pattern where the light-irradiated area becomes insoluble.

[0070] Examples of photoacid generators (d1) include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. It is preferable to contain two or more photoacid generators to obtain a highly sensitive photosensitive resin composition.

[0071] Examples of quinone diazide compounds include those in which the sulfonic acid of quinone diazide is esterified to a polyhydroxy compound, those in which the sulfonic acid of quinone diazide is sulfonamide bonded to a polyamino compound, and those in which the sulfonic acid of quinone diazide is esterified and / or sulfonamide bonded to a polyhydroxypolyamino compound. 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 diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of mercury lamps and is suitable for i-line exposure. The 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of mercury lamps and is suitable for g-line exposure. In the present invention, it is preferable to select the 4-naphthoquinone diazidosulfonyl ester compound or the 5-naphthoquinone diazidosulfonyl ester compound depending on the exposure wavelength. Furthermore, the same molecule may contain a naphthoquinone diazidosulfonyl ester compound having both a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group, or it may contain both a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound.

[0073] The above-mentioned quinone diazide compounds can be synthesized from a compound having a phenolic hydroxyl group and a quinone diazidesulfonic acid compound by any esterification reaction. Using these quinone diazide compounds improves resolution, sensitivity, and residual film ratio.

[0074] Among the photoacid generators (d1), sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts are preferred because they appropriately stabilize the acid components generated by exposure. Sulfonium salts are particularly preferred. Furthermore, sensitizers and other additives may be included as needed.

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

[0076] Examples of photopolymerization initiators (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 included. From the viewpoint of further improving sensitivity, α-aminoketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and oxime ester-based photopolymerization initiators are even more preferred.

[0077] Examples of α-aminoketone-based photopolymerization initiators 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 acylphosphine oxide-based photopolymerization initiators 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 oxime ester-based photopolymerization initiators 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- Examples include [9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-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-carbazole-3-yl]ethanone-1-(O-acetyl)oxime, or 1-(9-ethyl-6-nitro-9H-carbazole-3-yl)-1-[2-methyl-4-(1-methoxypropane-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, and more preferably 1 part by mass or more, per 100 parts by mass of the total of the alkali-soluble resin (a) and the radical polymerizable compound described later, from the viewpoint of further improving sensitivity. On the other hand, from the viewpoint of further improving resolution and reducing the taper angle, it is preferably 25 parts by mass or less, and more preferably 15 parts by mass or less.

[0081] <Radical polymerizable compounds> The resin composition of the present invention may further contain a radical polymerizable compound. Radical polymerizable compounds are compounds that have multiple ethylenically unsaturated double bonds in their molecules. During exposure, radical polymerization of the radical polymerizable compound proceeds due to radicals generated from the aforementioned photopolymerization initiator (d2), and a negative pattern can be obtained by insolubilizing the light-irradiated area. Furthermore, by including a radical polymerizable compound, the photocuring of the light-irradiated area is accelerated, and sensitivity can be further improved. In addition, the crosslinking density after thermal curing is improved, which can improve the hardness of the cured film.

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

[0083] Examples of radical polymerizable compounds 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, and 2,2-bis[ Examples 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, or acid-modified, ethylene oxide-modified, and propylene oxide-modified versions thereof.

[0084] In the resin composition of the present invention, the content of the radical polymerizable compound is preferably 15 parts by mass or more, and 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 viewpoint of further improving sensitivity and reducing the taper angle. On the other hand, from the viewpoint of further improving the heat resistance of the cured film and reducing the taper angle, it is preferably 65 parts by mass or less, and more preferably 50 parts by mass or less.

[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 heat-reactive functional groups in its molecule, such as an alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group. By including a thermal crosslinking agent, the alkali-soluble resin (a) or other additive components can be crosslinked, improving the heat resistance, chemical resistance, and hardness of the film after heat curing. Furthermore, the amount of outgassing from the cured film can be further reduced, improving the long-term reliability of the organic EL display device.

[0086] Preferred examples of compounds 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 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, HMOM-TPHAP (all are 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 are 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. , “Epolite” 4000, “Epolite” 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 Co., Ltd.), GAN, GOT (all manufactured by Nippon Kayaku Co., Ltd.), “Epicote” (registered trademark) 828, “Epicote” 1002, “Epicote” 1750, “Epicote” 1007, YX8100-BH30, E1256, E4250, E4275 (all manufactured by Japan Epoxy Resin Co., Ltd.), “E Examples include "Piclon" (registered trademark) EXA-9583, HP4032 (both manufactured by DIC Corporation), VG3101 (manufactured by Mitsui Chemicals, Inc.), "Tepic" (registered trademark) S, "Tepic" G, "Tepic" P (all manufactured by Nissan Chemical Industries, Ltd.), "Denacol" EX-321L (manufactured by Nagase ChemteX Corporation), NC6000 (manufactured by Nippon Kayaku Co., Ltd.), "Epotote" (registered trademark) YH-434L (manufactured by Toto Kasei Co., Ltd.), EPPN502H, NC3000 (manufactured by Nippon Kayaku Co., Ltd.), and "Epiclon" (registered trademark) N695, HP7200 (all manufactured by DIC Corporation).

[0088] Preferred examples of compounds having at least two oxetanyl groups include, for example, etanacol EHO, etanacol OXBP, etanacol OXTP, etanacol OXMA (all manufactured by Ube Industries, Ltd.), and oxetanized phenol novolacs.

[0089] The thermal crosslinking agent may be included in combination of two or more types. The thermal crosslinking agent content is preferably 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of the total resin composition excluding the solvent. If the thermal crosslinking agent content is 1 part by mass or more, the chemical resistance and hardness of the cured film can be further improved. Furthermore, if the thermal crosslinking agent content 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 is also excellent.

[0090] <Solvent> The resin composition of the present invention may further contain a solvent. By including a solvent, it can be made into a varnish, which can improve its applicability.

[0091] As solvents, 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, dioxane, acetone, methyl ethyl Ketones, including 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; ethyl 2-hydroxy-2-methylpropionate; 3-methoxypropyl 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 include n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate and other esters, 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 present.

[0092] The solvent content is not particularly limited, but is preferably 100 to 3000 parts by mass, and more preferably 150 to 2000 parts by mass, per 100 parts by mass of the total photosensitive resin composition excluding the solvent. Furthermore, the proportion of 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 reducing the proportion of 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 aromatic amine compounds with alkoxy group-containing silicon compounds. Two or more of these may be included. By including these adhesion improvers, the development adhesion to substrates such as silicon wafers, ITO, SiO2, and silicon nitride can be improved when developing the resin film. Furthermore, resistance to oxygen plasma and UV ozone treatment used for cleaning can be improved. 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] <Surfactants> The resin composition of the present invention may further contain a surfactant as needed to improve wettability with the substrate. Examples of surfactants include fluorine-based surfactants such as the SH series, SD series, and ST series from Toray Dow Corning Ltd., the BYK series from BIC Chemie Japan Ltd., the KP series from Shin-Etsu Chemical Co., Ltd., the Disform series from NOF Corporation, the "Megafac®" series from DIC Corporation, the Florard 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-based surfactants such as the Polyflow series from Kyoeisha Chemical Co., Ltd. and the "Disparon®" series from Kusumoto Kasei Co., Ltd.

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

[0096] <Compounds containing phenolic hydroxyl groups> For the purpose of compensating for the alkali developability of the resin composition of the present invention, it may contain a compound having a phenolic hydroxyl group. Examples of compounds 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, Chilentris-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 Chemicals Industry Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaph Examples include talene, 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 including these compounds having phenolic hydroxyl groups, the resulting photosensitive resin composition is almost insoluble in alkaline developer before exposure, but readily dissolves in alkaline developer after exposure, resulting in less film loss during development and easier development in a short time. Therefore, sensitivity is easily improved.

[0097] The content of such compounds having phenolic hydroxyl groups is preferably 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of alkali-soluble resin. By keeping it 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. Preferred specific examples of inorganic particles include, for example, silicon dioxide, titanium dioxide, 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 inorganic particle content is preferably 5 to 90 parts by mass per 100 parts by mass of the total resin composition excluding the solvent.

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

[0101] The thermal decomposition initiation temperature of the thermal acid generator used in the present invention is preferably 50°C to 270°C, and more preferably 250°C or lower. Furthermore, it is preferable to select a thermal acid generator that does not generate acid during drying (pre-baking: approximately 70 to 140°C) after coating the resin composition of the present invention onto the substrate, but generates acid during the final heating (curing: approximately 100 to 400°C) after patterning by exposure and development, as this suppresses 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 aryl sulfonic acids like p-toluenesulfonic acid and benzenesulfonic acid, alkyl sulfonic acids like methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and butanesulfonic acid, and haloalkylsulfonic acids like trifluoromethylsulfonic acid. These are used as salts such as onium salts, or as covalent compounds such as imidosulfonates. Two or more of these may be included.

[0103] The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of the total 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 the long-term reliability of the organic EL display device, the content is preferably 5 parts by mass or less, and more preferably 2 parts by mass or less.

[0104] <Method for producing resin compositions> Next, a method for producing the resin composition of the present invention will be described. For example, a resin composition can be obtained by dissolving an alkali-soluble resin (a), a β-alkoxypropionamide (b), and an amide group-containing tertiary amine compound (c), and optionally 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 obtained by using a β-alkoxypropionamide (b) containing an amide group-containing tertiary amine compound (c) as the polymerization solvent for the alkali-soluble resin (a) can be used. Dissolution methods include stirring and heating. When heating, the heating temperature should preferably be set within a range that does not impair the performance of the resin composition, and is usually room temperature to 80°C. Furthermore, the order in which each component is dissolved is not particularly limited; for example, compounds with lower solubility can be dissolved sequentially. In addition, for components that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, adding them last after dissolving the other components can prevent poor dissolution of other components due to bubble generation.

[0106] The resulting resin composition is preferably filtered using a filtration filter to remove dirt and particles. The filter pore size can be, but is not limited to, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, or 0.02 μm. The material of the filtration filter can be polypropylene (PP), polyethylene (PE), nylon (NY), or polytetrafluoroethylene (PTFE), with polyethylene or nylon being preferred.

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

[0108] The sheet of the present invention can be obtained, for example, by applying the aforementioned resin composition onto a releaseable substrate such as polyethylene terephthalate to obtain a coating film of the resin composition, and then drying it. A protective film may be further laminated.

[0109] Coating methods include, for example, 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 cost reduction. The amount of coating liquid required for slit coating is about 1 / 5 to 1 / 10 of that required for spin coating, for example. As for the slit nozzles used for coating, several manufacturers' products are available, such as Dainippon Screen Manufacturing Co., Ltd.'s "Linear Coater," Tokyo Ohka Kogyo Co., Ltd.'s "Spinless," Toray Engineering Co., Ltd.'s "TS Coater," Chugai Ro Kogyo Co., Ltd.'s "Table Coater," Tokyo Electron Limited's "CS Series" and "CL Series," Thermatronics Trading Co., Ltd.'s "In-line Slit Coater," and Hirata Kiko Co., Ltd.'s "Head Coater HC Series." Coating speeds are generally in the range of 10 mm / second to 400 mm / second. The thickness of the coated film varies depending on the solid content concentration and viscosity of the resin composition, but it is usually applied so that the film 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 will be applied may be pre-treated with the adhesion-improving agent described above. Examples of pre-treatment methods include treating the substrate surface with a solution obtained by dissolving the adhesion-improving agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate at a concentration of 0.5 to 20% by mass. Examples of substrate surface treatment methods include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

[0111] After coating, vacuum drying is performed as needed. It is common to vacuum dry the substrate together with the coated film. For example, one method is to place the substrate with the coated film on proxy pins placed in a vacuum chamber and vacuum dry by reducing the pressure inside the vacuum chamber. At this time, it is preferable to adjust the height of the proxy pins so as to narrow the gap between the substrate and the top plate of the vacuum chamber in order to suppress the haze and unevenness that occurs due to the large amount of air flowing between the substrate and the top plate of the vacuum chamber during vacuum drying. The distance between the substrate and the top plate of the vacuum chamber is preferably about 2 to 20 mm, and more preferably 2 to 10 mm.

[0112] The vacuum drying rate depends on factors such as the vacuum chamber volume, vacuum pump capacity, and the diameter of the piping between the chamber and the pump. However, it is preferable to set the vacuum drying rate to a condition where, for example, the pressure inside the vacuum chamber is reduced to 40 Pa after 60 seconds, even without a coated substrate. The typical vacuum drying time is often between 30 and 100 seconds, and the pressure reached inside the vacuum chamber at the end of vacuum drying is usually 100 Pa or less with a coated substrate. By reducing the pressure to 100 Pa or less, a dry state with reduced stickiness on the surface of the coated film can be achieved, thereby suppressing surface contamination and particle generation during subsequent substrate handling.

[0113] After coating or vacuum drying, it is common to heat-dry the coated film. This process is also called pre-baking. Drying is done using a hot plate, oven, or infrared heating. When using a hot plate, the coated film is heated either directly on the plate or held on a jig such as proxy pins placed on the plate. Proxy pins can be made of metal materials such as aluminum or stainless steel, or synthetic resins such as polyimide resin or "Teflon" (registered trademark). Any material with heat resistance can be used for proxy pins. The height of the proxy pins varies depending on the size of the substrate, the type of coated film, and the purpose of heating, but 0.1 to 10 mm is preferable. Heating temperature and time vary depending on the type and purpose of the coated film, but a heating temperature of 50°C to 180°C and a heating time of 1 minute to several hours are preferable.

[0114] If the resin sheet is photosensitive, a pattern can be formed on it. For example, a photosensitive resin sheet can be exposed to a chemical beam by irradiating it through a mask having the desired pattern, and then developed to form the desired pattern.

[0115] Chemical beams used for exposure include ultraviolet light, visible light, electron beams, and X-rays. In this invention, it is preferable to use the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp. If the image is positive-type photosensitive, the exposed area dissolves in the developer. If the image is negative-type photosensitive, the exposed area hardens and becomes insoluble in the developer.

[0116] After exposure, the desired pattern is formed by removing the exposed areas with a developer in the case of a positive film, or the unexposed areas in the case of a negative film. Preferred developers are 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. To these alkaline aqueous solutions, 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 may be added. Development methods include spray, paddle, immersion, and ultrasonic methods.

[0117] Next, it is preferable to rinse the pattern formed by development with distilled water. 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 aforementioned resin composition or resin sheet, components with low heat resistance can be removed, thereby further improving heat resistance and chemical resistance. In particular, if 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 them and polyimide, heat curing forms imide rings and oxazole rings, thereby further improving heat resistance and chemical resistance.

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

[0120] The resin composition, resin sheet, and cured film of the present invention are suitably used as surface protection layers and interlayer insulating layers for semiconductor elements, insulating layers for organic electroluminescence (EL) elements, planarization layers for thin-film transistor (TFT) substrates used to drive display devices using organic EL elements, wiring protection insulating layers for circuit boards, on-chip microlenses for solid-state image sensors, and planarization layers for various displays and solid-state image sensors. For example, they are suitable as surface protection layers and interlayer insulating layers for MRAM with low heat resistance, polymer memory (PFRAM) and phase-change memory (PCRAM, Ovonics Unified Memory: OUM), which are promising as next-generation memories. They can also be used as insulating layers for display devices including a first electrode formed on a substrate and a second electrode provided opposite the first electrode, such as LCDs, ECDs, ELDs, and display devices using organic electroluminescent elements (organic electroluminescent devices). The following explanation will use organic EL display devices, semiconductor devices, and semiconductor electronic components as examples.

[0121] <Organic EL display device> The cured film of the present invention can be suitably used in the planarization layer and / or insulating layer of an organic EL display device having a drive circuit, a planarization layer, a first electrode, an insulating layer, an emissive layer, and a second electrode on a substrate. Organic EL emissive materials are susceptible to degradation by moisture, which can have adverse effects such as a decrease in the area ratio of the emissive part to the area of ​​the emissive pixel. However, since the cured film of the present invention has a low water absorption rate, stable drive and emissive characteristics can be obtained. Taking an active matrix type display device as an example, it has a TFT and wiring located on the side of the TFT and connected to the TFT on a substrate such as glass or various plastics, a planarization layer covering the irregularities thereon, and a display element further provided on the planarization layer. The display element and the wiring are connected via contact holes formed in the planarization layer.

[0122] When the cured film of the present invention is used as the planarization layer, the film thickness is preferably 1.0 to 5.0 μm, and more preferably 2.0 μm or more. By keeping the planarization layer within the above range, the flatness of densely packed TFTs and wiring can be improved by increasing the resolution. If the planarization layer becomes thicker, outgassing increases, which can cause a decrease in the light emission reliability of the organic EL display device. However, since the cured film of the present invention produces less outgassing, high light emission reliability can be obtained. Furthermore, for the sake of increasing the resolution, it is preferable that the planarization layer be multilayered so that TFTs and wiring can be arranged in the film thickness direction as well.

[0123] Figure 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 the substrate 6, and a TFT insulating layer 3 is formed covering the TFTs 1. Wiring 2 connected to the TFTs 1 is provided on the TFT insulating layer 3. Furthermore, a planar layer 4 is provided on the TFT insulating layer 3, embedding the wiring 2. Contact holes 7 reaching the wiring 2 are provided in the planar layer 4. ITO (transparent electrode material) 5 is formed on the planar layer 4, connected to the wiring 2 via these contact holes 7. Here, the ITO 5 becomes the electrode for the 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 light from the side opposite the substrate 6, or a bottom-emission type that extracts light from the substrate 6 side. In this way, an active-matrix type organic EL display device is obtained in which each organic EL element is connected to a TFT 1 for driving it.

[0124] The TFT insulating layer 3, planarization layer 4, and / or insulating layer 8 can be formed by the steps described above: 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. An organic EL display device can be obtained by a manufacturing method having these steps.

[0125] <Semiconductor electronic components, semiconductor equipment> The cured film of the present invention can be suitably used as an interlayer insulating layer and / or 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 having bumps. A passivation layer 11 having Al pads 10 for input / output and via holes is formed on a silicon wafer 9. Furthermore, an insulating layer 12 is formed on the passivation layer 11, and a metal layer 13 made of Cr, Ti, etc. is formed to connect to the Al pads 10, and metal wiring 14 made of Al, Cu, etc. is formed by electroplating or the like. The metal layer 13 located around the solder bumps 18 is etched to insulate the pads from each other. Barrier metal 16 and solder bumps 18 are formed on the insulated pads. Scrive lines 17 are formed when the insulating film 15 is processed.

[0127] Next, the method for manufacturing a semiconductor device will be explained using drawings. Figure 3 shows an example of a method for manufacturing a semiconductor device having bumps. In step 3a, the resin composition of the present invention is applied to a silicon wafer 9 on which an Al pad 10 and a passivation layer 11 are formed, and a patterned insulating layer 12 is formed via a photolithography process. Then, in step 3b, a metal layer 13 is formed by sputtering. In step 3c, metal wiring 14 is deposited on the metal layer 13 by plating. Next, in step 3d', the resin composition of the present invention is applied, and in step 3d, a pattern of the insulating layer 15 is formed via a photolithography process. At this time, the resin composition constituting the insulating layer 15 is processed into a thick film using a scribe line 17. Further wiring (so-called rewiring) can be formed on the insulating layer 15. When forming a multilayer wiring structure of two or more layers, the above steps are 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 the multilayer wiring structure, but structures with 10 layers or less are commonly used. Next, in step 3e, a barrier metal 16 is formed, and in step 3f, solder bumps 18 are formed. Finally, the chips are separated by dicing along the last scribe line 17 to obtain semiconductor devices having bumps. [Examples]

[0128] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Each evaluation in the examples was performed using the following method.

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

[0130] (2) Evaluation of the content of β-alkoxypropionamide (b) and amide group-containing tertiary amine compound (c) in the solvent. The solvents used in each example and comparative example were subjected to GC-MS analysis using a GC-MS instrument (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 on 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, thereby measuring the content of β-alkoxypropionamide (b) and amide-containing tertiary amine compound (c). From the obtained content values, the content of amide-containing tertiary amine compound (c) relative to β-alkoxypropionamide (b) was calculated.

[0131] (3) Evaluation of the content of amide group-containing tertiary amine compound (c) in alkali-soluble resin (a) GC-MS analysis was performed in the same manner as described above on a solution prepared by dissolving 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, in 1 mL of acetone, 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) in 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, were dissolved in 0.7 g of deuterated dimethyl sulfoxide with 0.01 g of methyl 3-nitrobenzoate as an internal standard, and analyzed by NMR (JEOL Ltd., GX-270). The area of ​​the peak around 3.9 ppm derived from methyl 3-nitrobenzoate was used as a reference, and the content of β-alkoxypropionamide (b) relative to alkali-soluble resin (a) was measured from the peak area of ​​each.

[0133] (5) Esterification rate Using a nuclear magnetic resonance (NMR) spectrometer (EX-270, manufactured by JEOL Ltd.), the 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 ¹H-NMR was measured, and the integral value of the peak originating from aromatic protons in the resin was determined. The esterification rate of the polyamic acid ester was calculated from the area ratio with the peak originating from methyl protons of the alkyl carboxylate ester. Resins other than polyamic acid esters do not contain alkyl carboxylate esters, so the esterification rate is not measurable and is indicated with "-".

[0134] (6) Evaluation of the content of amide group-containing tertiary amine compound (c) relative to alkali-soluble resin (a) in the resin composition. For each example and comparative example, the varnish of the resin composition was separated using a GPC preparative (manufactured by Shimadzu Corporation) to separate the alkali-soluble resin (a), and the content of the alkali-soluble resin in the resin composition was determined.

[0135] Next, the components other than the solids obtained by GPC preparative analysis were concentrated using an evaporator, and then GC-MS analysis was performed in the same manner as described 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 and the content of the amide group-containing tertiary amine compound (c) in the resin composition obtained in this way, 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 varnishes obtained in each example and comparative example were applied to an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Ltd.), 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 conditions of a refractive index of 1.63. Subsequently, using an i-line stepper exposure machine NSR-2005i9C (manufactured by Nikon Corporation), exposure was performed through a mask with a 10 μm contact hole pattern at an exposure dose of 50-300 mJ / cm². 2 Within the range of 5 mJ / cm 2 Each exposure was performed. After exposure, using the ACT-8 developing apparatus, a 2.38 wt% aqueous tetramethylammonium solution (hereinafter referred to as TMAH, manufactured by Tama Chemical Industry Co., Ltd.) was used as the developer until the film thickness was reduced to 0.5 μm. After that, the film was rinsed with distilled water, shaken dry, and the pattern was obtained.

[0137] The obtained patterns were observed at 20x magnification using an FDP microscope MX61 (manufactured by Olympus Corporation), and the aperture diameter of the contact holes was measured. The minimum exposure dose at which the aperture diameter of the contact holes reached 10 μm was determined and defined as the sensitivity.

[0138] The aforementioned varnish was stored at 40°C, and the number of days it took for the sensitivity to change by 15% or more from the sensitivity on day 0 was investigated.

[0139] (8) Development adhesion A pre-baked film with a thickness of 3.0 μm was formed on an 8-inch SiNx-coated silicon wafer using the same method as in (7). Subsequently, using an i-line stepper exposure machine NSR-2005i9C (manufactured by Nikon), the wafer was exposed through a mask having a convex pattern (island) of 1 to 100 μm squares, at the same exposure dose as the sensitivity determined in the sensitivity evaluation above. After exposure, the wafer was developed using the ACT-8 developing apparatus with 2.38 wt% TMAH as the developing solution until the film thickness was reduced to 0.5 μm, then rinsed with distilled water, shaken dry, and the pattern was obtained.

[0140] The obtained patterns were observed at 20x magnification using an FDP microscope MX61 (manufactured by Olympus Corporation) to determine the minimum size of the convex patterns that adhered firmly to the substrate without peeling. A smaller size of the convex patterns that adhered firmly to the substrate without peeling indicates higher development adhesion.

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

[0142] Synthesis Example 1: Synthesis of a 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 mixture 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. After the addition was complete, the mixture was allowed to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered off and vacuum-dried at 50°C.

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

[0144] [ka]

[0145] Synthesis Example 2: Synthesis of an amide group-containing tertiary amine compound (c-1) Under a stream of dry nitrogen, 34.4 g (0.4 mol) of methyl acrylate was added to a 500 ml flask, and 180.3 g (0.44 mol) of an 11% methanol solution of dimethylamine was added. The mixture was stirred at 40°C for 2 hours. Then, 0.77 g (0.004 mol) of a 28% methanol solution of sodium methoxide and 164.0 g (0.4 mol) of an 11% methanol solution of dimethylamine were added to the reaction mixture. The reaction mixture was stirred for 5 hours while cooling in a water bath to keep the temperature below 40°C. After the reaction was complete, unreacted dimethylamine and methanol were removed by vacuum distillation to obtain 3-dimethylamino-N,N-dimethylpropionamide (c-1) 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 diazidosulfonylic acid chloride were dissolved in 450 g of 1,4-dioxane and allowed to rise to room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise, ensuring the system temperature did not exceed 35°C. After addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitated material was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain the quinone diazide compound (d-1) represented by the following formula.

[0147] [ka]

[0148] Synthesis Example 4: Synthesis of adhesion improver (e-1) In a 2L separable flask, add 110.7g of 3-aminopropyltriethoxysilane and Add 845g of NMP, and at room temperature, add 59.6g of phenyl isocyanate and NMP12 The solution containing 0g was slowly added dropwise at room temperature, and the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the solvent was removed to obtain the adhesion improver (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®, manufactured by Idemitsu Kosan Co., Ltd.) (SP value 10.3, calculated value) b-2:3-Butoxy-N,N-dimethylpropionamide (Equamid B-100®, manufactured by Idemitsu Kosan Co., Ltd.) (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 Using 1 L of solvent (b-1), the content of the amide group-containing tertiary amine compound (c) was evaluated as described above, and it was found that (b-1) contained 2000 ppm of (c-1). Subsequently, (b-1) was continuously brought into contact with 100 ml of ion exchange resin (product name "Amberlist 16WET", manufactured by Organo (Rohm & Haas)) packed in an ion exchange resin column, and purified until the amount of (c-1) in (b-1) became 100 ppm, obtaining the purified solvent (b-1-100).

[0153] Under a stream of dry nitrogen, 31.0 g (0.10 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereafter referred to as ODPA) was dissolved in 500 g of (b-1-100). To this, 29.3 g (0.08 mol) of BAHF and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereafter referred to as SiDA) were added along with 50 g of (b-1-100), and the mixture was reacted at 40°C for 2 hours. Next, 2.18 g (0.02 mol) of 3-aminophenol (hereafter referred to as MAP) was added along with 5 g of (b-1-100) as a terminal encapsulant, and the mixture was reacted at 50°C for 2 hours. After that, a solution of 26.22 g (0.22 mol) of N,N-dimethylformamide dimethyl acetal diluted with 50 g of (b-1-100) was added. After adding the ingredients, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature, and then 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 polyamic acid ester (A), which is an alkali-soluble resin. 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.

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

[0155] Example 2 In the same manner as in Example 1, the solvent (b-1) was purified until the concentration of (c-1) in the solvent reached 500 ppm, obtaining the purified solvent (b-1-500).

[0156] A polyamic acid ester (B), which is an alkali-soluble resin, was obtained in the same manner as in Example 1, except that the solvent (b-1-100) was changed to (b-1-500). 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.

[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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

[0158] Example 3 In the same manner as in Example 1, the solvent (b-1) was purified until the concentration of (c-1) in the solvent reached 1000 ppm, obtaining the purified solvent (b-1-1000).

[0159] A polyamic acid ester (C), which is an alkali-soluble resin, was obtained in the same manner as in Example 1, except that the solvent (b-1-100) was changed to (b-1-1000). 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.

[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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

[0161] Example 4 In the same manner as in Example 1, the solvent (b-1) was purified until the concentration of (c-1) in the solvent reached 1800 ppm, obtaining the purified solvent (b-1-1800).

[0162] A polyamic acid ester (D), which is an alkali-soluble resin, was obtained in the same manner as in Example 1, except that the solvent (b-1-100) was changed to (b-1-1800). 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.

[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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

[0164] Example 5 In the same manner as in Example 1, the solvent (b-1) was purified until the concentration of (c-1) in the solvent reached 20 ppm, obtaining the purified solvent (b-1-1800).

[0165] A polyamic acid ester (E), which is an alkali-soluble resin, was obtained in the same manner as in Example 1, except that the solvent (b-1-100) was changed to (b-1-20). 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.

[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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

[0167] Example 6 In the same manner as in Example 1, the solvent (b-2) was purified until the concentration of (c-1) reached 100 ppm, obtaining the purified solvent (b-2-100).

[0168] A polyamic acid ester (F), which is an alkali-soluble resin, was obtained in the same manner as in Example 1, except that the solvent (b-1-100) was changed to (b-2-100). 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.

[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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

[0170] Example 7 A polyamic acid ester (G), which is an alkali-soluble resin, 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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

[0172] Example 8 A polyamic acid ester (H), which is an alkali-soluble resin, 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. 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.

[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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

[0174] Example 9 Under a stream of dry nitrogen, 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-cap encapsulant 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 to this solution along with 50 g of (b-1-100), and the mixture was stirred at 60°C for 1 hour, followed by stirring at 180°C for 5 hours. After stirring, the solution was added to 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 polyimide (I), an alkali-soluble resin. Using the obtained resin, the weight-average molecular weight, β-alkoxypropionamide (b) content, and amide group-containing tertiary amine compound (c) content 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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above. Example 10 Under a stream of dry nitrogen, 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 Nippon Soda Co., Ltd.) dissolved in 50 g of (b-1-100) was added dropwise, ensuring 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 added to 3 L of water containing 10% by weight of methanol, 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 polyhydroxyamide (J), an alkali-soluble resin. Using the obtained resin, the weight-average molecular weight, β-alkoxypropionamide (b) content, and amide group-containing tertiary amine compound (c) content were measured 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 for a positive-type 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.

[0177] Example 11 A polyamic acid ester (K), which is an alkali-soluble resin, was obtained in the same manner as in Example 1, except that the solvent (b-1-100) was changed to NMP. 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.

[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 for a positive-type 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.

[0179] Example 12 Except for changing the number of water washes after resin reprecipitation from three to two, an alkali-soluble polyamic acid ester (L) was obtained in the same manner as in Example 1. 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.

[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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

[0181] Example 13 A polyamic acid ester (M), which is an alkali-soluble resin, was obtained in the same manner as in Example 1, except that the number of washes with water after reprecipitation of the resin was changed from three to one. 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.

[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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above. However, significant film loss occurred during development, and it was not possible to form a residual pattern for development adhesion.

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

[0184] A polyamic acid ester (N), which is an alkali-soluble resin, was obtained in the same manner as in Example 1, except that the solvent (b-1-100) was changed to (b-1-500'). Using the obtained resin, the weight-average molecular weight and the amide group-containing tertiary amine compound (c) were measured as described above. Using the obtained resin solution, the content of the amide group-containing tertiary amine compound (c), the weight-average molecular weight, the β-alkoxypropionamide (b) content, the amide group-containing tertiary amine compound (c) content, and the esterification rate in the resin composition were measured 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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

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

[0187] Next, 30.0 g of a 30% by mass solution (X') of acrylic resin (X) was mixed with 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 to obtain a varnish for a positive-type 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.

[0188] Example 16 Under a stream of dry nitrogen, 70.2 g (0.65 mol) of m-cresol, 37.8 g (0.35 mol) of p-cresol, 75.5 g (0.93 mol) of 37 wt% formaldehyde aqueous 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 (hereinafter abbreviated as MIBK). Subsequently, the reaction mixture was refluxed and a polycondensation reaction was carried out for 7 hours. After that, volatile components were removed, and GBL was added to the dissolved resin until the solid content concentration reached 30 mass%, to obtain a 30 mass% solution (Y') of the alkali-soluble resin novolac resin (Y). Using the obtained resin solution, the weight-average molecular weight, β-alkoxypropionamide (b) content, and amide group-containing tertiary amine compound (c) content were measured as described above.

[0189] Next, 30.0 g of a 30% by mass solution (Y') of novolac resin (Y) was mixed with 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 to obtain a varnish for a positive-type 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.

[0190] Example 17 A polyamic acid ester (AC), which is an alkali-soluble resin, 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 the solvent (b-1-1000). Using the obtained resin solution, the content of the amide group-containing tertiary amine compound (c), the weight-average molecular weight, the β-alkoxypropionamide (b) content, the amide group-containing tertiary amine compound (c) content, and the 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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

[0192] Example 18 A polyamic acid ester (AD), which is an alkali-soluble resin, 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 the solvent (b-1-1800). Using the obtained resin solution, the content of the amide group-containing tertiary amine compound (c), the weight-average molecular weight, the β-alkoxypropionamide (b) content, the amide group-containing tertiary amine compound (c) content, and the esterification rate in the resin composition 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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

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

[0195] A polyamic acid ester (O), which is an alkali-soluble resin, was obtained in the same manner as in Example 1, except that the solvent (b-1-100) was changed to (b-1-0). 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.

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

[0197] Comparative Example 2 A polyamic acid ester (P), which is an alkali-soluble resin, was obtained in the same manner as in Example 1, except that the solvent (b-1-100) was changed to (b-1). 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.

[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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

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

[0200] A polyamic acid ester (Q), which is an alkali-soluble resin, was obtained in the same manner as in Example 1, except that the solvent (b-1-100) was changed to (b-1-10000). 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.

[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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated 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 for a positive-type 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.

[0203] Comparative Example 5 Polyimide (R), an alkali-soluble resin, was obtained in the same manner as in Example 7, except that the solvent (b-1-100) was changed to (b-1). Using the obtained resin, the weight-average molecular weight, β-alkoxypropionamide (b) content, and amide group-containing tertiary amine compound (c) content 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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

[0205] Comparative Example 6 Polyhydroxyamide (S), an alkali-soluble resin, was obtained in the same manner as in Example 10, except that the solvent (b-1-100) was changed to (b-1). Using the obtained resin, the weight-average molecular weight, β-alkoxypropionamide (b) content, and amide group-containing tertiary amine compound (c) content 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 for a positive-type 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.

[0207] Comparative Example 7 Under a stream of dry nitrogen, 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-cap encapsulant were dissolved in 150 g of solvent (b-1). 31.0 g (0.10 mol) of ODPA was added to this solution 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 removed from the solution until the solid content concentration reached 30% by mass, obtaining a 30% by mass solution (R') of the alkali-soluble resin polyimide (R). Using the obtained resin solution, the weight-average molecular weight, β-alkoxypropionamide (b) content, and amide group-containing tertiary amine compound (c) content were measured 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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

[0209] Comparative Example 8 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 were added to 30 g of GBL to obtain a varnish for a positive-type 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.

[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 for a positive-type 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.

[0211] Comparative Example 10 50 g of 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 polyamic acid ester (T), which is an alkali-soluble resin. 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.

[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 for a positive-type photosensitive resin composition. Using the obtained varnish, the content of amide group-containing tertiary amine compound (c) in the resin composition, development adhesion, storage stability, and chemical resistance were evaluated as described above.

[0213] Comparative Example 11 To 30.0 g of a 30% by mass solution (X') of the acrylic resin (X) obtained in Example 15, 2.0 g of quinone diazide compound (d-1) was added to obtain a varnish for a positive-type 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.

[0214] Comparative Example 12 To 30.0 g of a 30% by mass solution (Y') of the novolac resin (Y) obtained in Example 16, 2.0 g of quinone diazide compound (d-1) was added to obtain a varnish for a positive-type 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.

[0215] Comparative Example 13 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 were added to 30 g of GBL to obtain a varnish for a positive-type 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.

[0216] The composition and evaluation results of each example and comparative example are shown in Tables 1-4.

[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: Al 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: Scribeline 18: Handa 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, a polybenzoxazole, a polyamideimide, a precursor of any of these, and / or a copolymer selected from two or more of these, 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. 【Chemistry 1】 (In general formula (1), R 1 and R 2 represent monovalent organic groups having an alkyl group of 1 to 5 carbon atoms, and R 3 and R 4 represent hydrogen atoms or monovalent organic groups having an alkyl group of 1 to 5 carbon atoms.)

2. A coating composition comprising 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, a polybenzoxazole, a polyamideimide, a precursor of any of these, and / or a copolymer selected from two or more of these, the content of the β-alkoxypropionamide (b) relative to 100 parts by mass of the alkali-soluble resin (a) is 5 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 50 ppm. 【Chemistry 2】 (In general formula (1), R 1 and R 2 represent monovalent organic groups having an alkyl group of 1 to 5 carbon atoms, and R 3 and R 4 represent hydrogen atoms or monovalent organic groups having an alkyl group of 1 to 5 carbon atoms.)

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

4. The resin composition according to any one of claims 1 to 3, wherein the alkali-soluble resin (a) contains a polyimide precursor.

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

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

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

8. A cured film obtained by curing the resin composition according to any one of claims 1 to 5.

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