Resin composition, cured film, electronic component, and organic el display device

Abstract

Disclosed is a resin composition which contains: component (A) that comprises one or more resins selected from the group consisting of a polyimide resin (A1), a polybenzoxazole resin (A2), and a copolymer resin (A3) of a structural unit of a polyimide resin and a structural unit of a polybenzoxazole resin; and component (B) that comprises levoglucosenone and / or dihydrolevoglucosenone.　The present invention provides: a resin composition with which it is possible to produce a cured film that has good chemical resistance, adhesion to a metal, flatness, and elongation at break; and an electronic component and an organic EL display device, each of which is provided with a cured film of the resin composition.

Description

Resin composition, cured film, electronic component, and organic EL display device

[0001] The present invention relates to a resin composition, a cured film, an electronic component, and an organic EL display device.

[0002] Polyimide resins and polybenzoxazole resins, which have excellent heat resistance, electrical insulation properties, mechanical properties, etc., have been widely used in the past for surface protection films and interlayer insulating films of semiconductor elements, and pixel dividing layers and planarizing layers of organic electroluminescence (hereinafter referred to as organic EL) display devices.

[0003] To obtain a thin film with excellent heat resistance and mechanical properties by thermally dehydrating and cyclizing a polyimide resin or polybenzoxazole resin coating, high-temperature baking at approximately 350°C is usually required. The process of thermally dehydrating and cyclizing a polyimide resin or polybenzoxazole resin coating to obtain a thin film with excellent heat resistance and mechanical properties is sometimes called baking (cure), and the change in the coating is sometimes called hardening. However, in view of the fact that recently used memory devices and molding resins used in semiconductor package fabrication are susceptible to high-temperature processes, and in view of semiconductor package reliability, there is a demand for polyimide-based resins, polybenzoxazole-based resins, and polyamide-imide-based resins that can be cured by baking at 250°C or less for surface protection films and interlayer insulating films and that have even better mechanical properties, chemical resistance, and adhesion.

[0004] Furthermore, in organic EL display devices and semiconductor devices, the density of pixels and wiring is increasing, and there is a demand for materials that are suitable for fine pattern processing and for flattening the surfaces of objects with irregularities.

[0005] To address the above-mentioned problems, for example, a resin composition containing a polyimide or polybenzoxazole resin with a specific structure, a thermal acid generator, and an antioxidant has been proposed for the purpose of improving breaking elongation and chemical resistance (see, for example, Patent Document 1). Also, a photosensitive resin composition containing a polyimide or polybenzoxazole resin and a phenolic resin with a specific structure has been proposed for the purpose of improving planarization properties and bending strength (see, for example, Patent Document 2).

[0006] International Publication No. 2017 / 188153 Japanese Patent Application Laid-Open No. 2022-34533

[0007] When the authors evaluated the planarization property using the resin composition described in Patent Document 1, they found that the planarization property required for the planarization layer of an organic EL display device could not be obtained. Furthermore, when the authors evaluated the breaking elongation and adhesion to metal materials using the photosensitive resin composition described in Patent Document 2, they found that the film was somewhat brittle and did not have sufficient breaking elongation, and that the adhesion to metal materials was low. As described above, the reality is that no resin composition is known that satisfies all of the requirements for breaking elongation, chemical resistance, planarization property, and adhesion.

[0008] Therefore, an object of the present invention is to provide a resin composition that can give a cured film that has good chemical resistance, adhesion to metal, flattening properties, and breaking elongation, and to provide an electronic component and an organic EL display device that are provided with a cured film of the resin composition.

[0009] In order to solve the above-mentioned problems, the present invention has the following configuration.

[0010] [1] A resin composition comprising: component (A), which is one or more resins selected from the group consisting of polyimide resins (A1), polybenzoxazole resins (A2), and copolymer resins (A3) of structural units of polyimide resins and structural units of polybenzoxazole resins; and component (B), which is levoglucosenone and / or dihydrolevoglucosenone.

[0011] [2] The resin composition according to [1], further comprising a component (D) which is a compound having a hydroxyl group and a boiling point at atmospheric pressure of 100°C or more and 200°C or less.

[0012] [3] The resin composition according to [2], wherein the ratio X / Z is 0.01 or more and 10 or less, where X is the mass of the (B) component and Z is the mass of the (D) component.

[0013] [4] The resin composition according to any one of [1] to [3], further containing a component (C) which is a compound represented by formula (1) and / or a compound represented by formula (2).

[0014]

[0015] In formula (1), R１ , R ２ and R ３ are each independently an alkyl group having 1 to 6 carbon atoms. ４ and R ５ are each independently an alkyl group having 1 to 6 carbon atoms. ６ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0016] [5] The resin composition according to [4], wherein the ratio X / Y is 1 or more and 1,000 or less, where X is the mass of the (B) component and Y is the mass of the (C) component.

[0017] [6] The resin composition according to any one of [1] to [5], further comprising a component (E) that is a photosensitizer.

[0018] [7] The resin composition according to [6], wherein the component (E) includes a component (E1) that is a photopolymerization initiator and / or a component (E2) that is a photoacid generator.

[0019] [8] The resin composition according to [7], wherein the component (E1) includes a component (E1-1) that is an oxime ester type photopolymerization initiator and / or a component (E1-2) that is a titanocene type photopolymerization initiator.

[0020] [9] The resin composition according to [7] or [8], further comprising a component (F) that is a radical polymerizable compound.

[0021]

[10] The resin composition according to any one of [1] to [9], wherein the component (A) comprises a polyimide resin (A1) and / or a copolymer resin (A3) of a structural unit of a polyimide resin and a structural unit of a polybenzoxazole resin, and the component (A) comprises a structural unit represented by formula (3):

[0022]

[0023] In formula (3), X １ represents a tetravalent organic group having 2 to 40 carbon atoms, which has any one of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 40 carbon atoms. １represents a divalent organic group having 2 to 40 carbon atoms, which has any one of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 40 carbon atoms. ７ and R ８ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having an ethylenically unsaturated double bond. * represents a bonding site.

[0024]

[11] Y in the formula (3) １ is a divalent organic group represented by formula (4) or formula (5).

[0025]

[0026] In formula (4) and formula (5), X ２ and X ３ each independently represents a direct bond, —SO ２ It represents -, -O-, or a divalent organic group having 1 to 20 carbon atoms. * represents the point of attachment to the amide structure, imide structure, amic acid ester structure, or amic acid structure.

[0027]

[12] The X ２ and X ３ are each independently a divalent organic group having 1 to 20 carbon atoms and not containing a fluorine atom.

[0028]

[13] A cured film obtained by curing the resin composition according to any one of [1] to

[12] .

[0029]

[14] An electronic component comprising the cured film according to

[13] .

[0030]

[15] An organic EL display device comprising the cured film according to

[13] .

[0031] According to the present invention, it is possible to obtain a resin composition that can give a cured film having good planarization properties, as well as good chemical resistance, adhesion to metals, and elongation at break, and to obtain an electronic component and an organic EL display device that have a cured film of the resin composition.

[0032] 1 is a cross-sectional view of a sample for evaluating planarization properties. 2 is a schematic diagram illustrating a method for producing an organic EL display device provided with a pixel dividing layer in an example.

[0033] The present invention will be described in detail below.

[0034] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0035] The resin composition of the present invention contains component (A), which is one or more resins selected from the group consisting of polyimide resins (A1), polybenzoxazole resins (A2), and copolymer resins (A3) composed of structural units of polyimide resins and structural units of polybenzoxazole resins. By containing component (A), it is possible to obtain a cured film that has a small amount of outgassing at high temperatures and is excellent in film physical properties such as chemical resistance.

[0036] The polyimide resin (A1) and the copolymer resin (A3) of a structural unit of a polyimide resin and a structural unit of a polybenzoxazole resin contained in the resin composition of the present invention include those that are expected to form an imide ring after curing, and therefore also include those that have a structure before ring closure to form an imide ring, i.e., an amide acid (or amic acid) or amide acid ester structure.

[0037] Furthermore, the polybenzoxazole resin (A2) and the copolymer resin (A3) of a structural unit of a polyimide resin and a structural unit of a polybenzoxazole resin contained in the resin composition of the present invention include those that are expected to form a benzoxazole ring after curing, and therefore also include those that have a structure before ring closure to an oxazole ring, i.e., a hydroxyamide structure.

[0038] Examples of the component (A) include resins that are soluble in organic developers such as ketone-based solvents, ester-based solvents, and amide-based solvents, and alkali-soluble resins that are soluble in alkali developers.

[0039] In particular, from the viewpoint of reducing environmental impact, it is preferable that the component (A) is an alkali-soluble resin and that the resin composition can be developed using an alkaline developer. The alkali-soluble resin referred to here means a resin whose dissolution rate is 50 nm / min or more, as determined from the film thickness reduction when a solution of the resin dissolved in γ-butyrolactone is applied to a silicon wafer and prebaked at 120°C for 4 minutes to form a prebaked film having a film thickness of 10 μm±0.5 μm, the prebaked film is immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23±1°C for 1 minute, and then rinsed with deionized water. The alkali dissolution rate of the component (A) is preferably 100 nm / min or more from the viewpoint of reducing development residue, and is preferably 15,000 nm / min or less from the viewpoint of improving the linearity of the resulting pattern.

[0040] When the total amount of resins contained in the resin composition of the present invention is taken as 100 mass%, it is preferable that the resin composition contain a total of 50 mass% or more of component (A), which is one or more resins selected from the group consisting of the polyimide resin (A1), the polybenzoxazole resin (A2), and the copolymer resin (A3).

[0041] The polyimide resin (A1) and the copolymer resin (A3) preferably have an acid dianhydride residue and a diamine residue, where the acid dianhydride residue refers to a residue obtained by removing two acid anhydride groups from an acid dianhydride compound, and the diamine residue refers to a residue obtained by removing two amino groups from a diamine compound.

[0042] The polyimide resin (A1) and the copolymer resin (A3) may have an acid dianhydride residue derived from the following acid dianhydride.

[0043] Specific examples of the acid dianhydride residue include 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione (hereinafter referred to as TDA-100), 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene- Residues of alicyclic tetracarboxylic dianhydrides such as 1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, and 3,5,6-tricarboxy-2-norbornaneacetic dianhydride, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3' '-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride The carboxylic acid residues include residues of aromatic tetracarboxylic acid dianhydrides such as bis(3,4-dicarboxyphenyl)methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, and 3,4,9,10-perylenetetracarboxylic acid dianhydride; bis(3,4-dicarboxyphenyl)sulfone dianhydride, 4,4'-oxydiphthalic anhydride (hereinafter, ODPA), 3,4'-oxydiphthalic anhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, and 2,2-bis(3,Examples of the dianhydride include 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 2,2-bis(3-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 2,2-bis(3-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, and compounds in which the aromatic rings of these compounds are substituted with alkyl groups or halogen atoms, and residues of aromatic acid dianhydrides such as acid dianhydrides having an amide group. Two or more of these may be contained in combination.

[0044] The component (A), which is one or more resins selected from the group consisting of the polyimide resin (A1), the polybenzoxazole resin (A2), and the copolymer resin (A3), preferably contains a residue of a diamine represented by formula (16) and / or a residue of a diamine represented by formula (17).

[0045]

[0046] In formula (16) and formula (17), X ２ and X ３ each independently represents a direct bond, —SO ２ It represents -, -O-, or a divalent organic group having 1 to 20 carbon atoms. * represents the point of attachment to the nitrogen atom.

[0047] The structures represented by formula (16) and formula (17) have a phenolic hydroxyl group, and therefore can impart solubility in an alkaline developer, thereby reducing development residues. ２ and X ３ are each independently -C(CF ３ ) ２ -, -CH(CF ３ ) - or -C(CH ３ ) ２ In the case of any one selected from the group consisting of X -, intermolecular packing is suppressed and solvent solubility can be improved, which is preferable. ２ and X ３are each independently a divalent organic group having 1 to 20 carbon atoms and not containing a fluorine atom, since this can improve the metal adhesion after a pressure cooker test (PCT). ２ and X ３ are each independently a divalent organic group represented by formula (18) or formula (19).

[0048]

[0049] In formulas (18) and (19), R ９ each independently represents an alkyl group having 1 to 4 carbon atoms, c represents an integer of 1 to 3, d represents 1 or 2, R １０ and R １１ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and * represents the point of attachment to the aromatic ring. ９ When a plurality of R are present, they may have the same structure or different structures. １０ and R １１ are not the same structure.

[0050] The X ２ and X ３ are each independently a divalent organic group represented by formula (18) or formula (19), which is preferable because it can improve the metal adhesion after PCT treatment and also improve the solvent solubility.

[0051] Among them, in the formula (18), the R ９ The total number of carbon atoms in the formula (19) is 1 or more and 5 or less, and １０ and the number of carbon atoms in R １１ The total number of carbon atoms in the R ９ The total number of carbon atoms in the formula (18) is 1 or more and 5 or less. ９ If there are multiple R ９The total number of carbon atoms in the R １０ and the number of carbon atoms in R １１ The total number of carbon atoms in R is 3 or more and 10 or less. １０ and R １１ The total number of carbon atoms in each of the R groups is 3 or more and 10 or less. ９ , R １０ , R １１ When the number of carbon atoms is within the above range, a photosensitive resin composition having good metal adhesion and solvent solubility after PCT treatment can be obtained without causing development residue or deterioration in sensitivity, which is preferable.

[0052] Specific examples of the divalent organic group in formula (18) or formula (19) include, but are not limited to, the structures shown below.

[0053]

[0054] In the above structure, * represents the point of attachment to the aromatic ring.

[0055] When the total amount of all diamine residues contained in the polyimide resin (A1), the polybenzoxazole resin (A2), and the copolymer resin (A3) is taken as 100 mol %, the total content of the diamine residues represented by formula (4) and the diamine residues represented by formula (5) is preferably 10 to 100 mol %, more preferably 30 to 100 mol %, and even more preferably 50 to 100 mol %.

[0056] Specific examples of the diamine residue represented by formula (4) or formula (5) include 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (hereinafter referred to as HA), 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]-1,1,1-trifluoroethane, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane, 9,9-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]fluorene, 2,2 bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter, BAHF), bis(3-amino-4-hydroxyphenyl)sulfone, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)propane (hereinafter, BAP), 1,1,1-trifluoro-2,2-bis(3-amino-4-hydroxyphenyl)ethane (hereinafter, BIS-AP-EF), and residues of diamines such as those represented by formulas (20) to (39). Among these, from the viewpoint of solubility in an alkaline developer, it is preferable to contain a residue of any diamine selected from the group consisting of BAHF, BAP, BIS-AP-EF, HA, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]-1,1,1-trifluoroethane, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane, and formulas (20) to (39). From the viewpoint of being able to improve metal adhesion after PCT treatment as well as being able to improve solvent solubility, it is more preferable to contain a residue of any diamine selected from the group consisting of formulas (20) to (39).

[0057]

[0058] The polyimide resin (A1), the polybenzoxazole resin (A2), and the copolymer resin (A3) may contain other diamine residues in addition to the above-mentioned diamine residues.

[0059] Specific examples of the other diamine residues include aliphatic diamine residues and aromatic diamine residues. The aliphatic diamine residue refers to a residue of a diamine that does not have an aromatic ring. Examples of the aliphatic diamine residue include residues of aliphatic alkyldiamines containing alkylene groups, polyethylene ether groups, polyoxypropylene groups, tetramethylene ether groups, etc., alicyclic diamines, and aliphatic diamines having a siloxane structure.

[0060] Examples of aliphatic alkylenediamine residues include tetramethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine, 8,13-dimethyloctadecanediamine, 8-methylnonadecanediamine, 9-methylnonadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, 8,13-dimethyloctadecanediamine-8,12-ene, polymethylenediamines such as Diamine H20 (trade name, manufactured by Okamura Oil Mills Co., Ltd.), Jeffamine KH-511, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, and Jeffamine EDR-1. 48, Jeffamine EDR-176 and other diamines containing a polyethylene ether group; polyoxypropylene diamines such as D-200, D-400, D-2000, D-4000, RP-409, and RP-2009; diamines containing a tetramethylene ether group such as RT-1000 and HT-1100; amino group-containing alkylene ether diamines such as HT-1000 and HE-1000 (all trade names, manufactured by HUNTSMAN Corporation); and dimer diamines such as Versamine (registered trademark) 551 and Versamine (registered trademark) 552 (manufactured by BASF Corporation), Priamine (registered trademark) 1073, Priamine (registered trademark) 1074, and Priamine (registered trademark) 1075 (manufactured by Cargill).

[0061] Examples of the alicyclic diamine residue include residues of cyclohexyldiamine, methylenebiscyclohexylamine, norbornanediamine, PRO-NBDA (trade name, manufactured by Mitsui Chemicals Fine Co., Ltd.), and the like.

[0062] Examples of aliphatic diamine residues having a siloxane structure include residues of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter, SiDA), bis(p-aminophenyl)octamethylpentasiloxane, etc. When an aliphatic group having a siloxane structure is copolymerized within a range that does not decrease heat resistance, adhesion to a substrate can be improved.

[0063] Other aromatic diamine residues include, for example, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, residues of hydroxyl group-containing diamines such as bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, and bis(3-amino-4-hydroxyphenyl)fluorene; residues of sulfonic acid-containing diamines such as 3-sulfonic acid-4,4'-diaminodiphenyl ether; residues of thiol group-containing diamines such as dimercaptophenylenediamine; 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl ) sulfone, bis(3-aminophenoxyphenyl) sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl} ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,Examples of suitable diamines include residues of aromatic diamines such as 4'-diaminobiphenyl and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, and residues of compounds in which some of the hydrogen atoms in these aromatic rings have been substituted with alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms, halogen atoms, or the like. These diamine residues can be used as they are, or as the corresponding diisocyanate compounds or trimethylsilylated diamines. These can be used alone or in combination of two or more.

[0064] The polybenzoxazole resin (A2) and the copolymer resin (A3) preferably have a dicarboxylic acid residue and a bisaminophenol residue, where the dicarboxylic acid residue refers to a residue obtained by removing two carboxyl groups from a dicarboxylic acid compound, and the bisaminophenol residue refers to a residue obtained by removing two amino groups and two phenolic hydroxyl groups from a bisaminophenol compound.

[0065] Examples of the dicarboxylic acid residue include residues of phthalic acid, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, 2,5-furandicarboxylic acid, 2,5-thiophenedicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 2-fluoroterephthalic acid, 2-methoxyterephthalic acid, 2-phenoxyterephthalic acid, etc. These compounds may be used alone or in combination of two or more.

[0066] Examples of the bisaminophenol residue include, but are not limited to, residues of 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 2,2-bis(3-amino-4-hydroxyphenyl)propane (hereinafter referred to as BAP), bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF), 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and 9,9-bis(3-amino-4-hydroxyphenyl)fluorene. These compounds may be used alone or in combination of two or more.

[0067] The polyimide resin (A1), the polybenzoxazole resin (A2), and the copolymer resin (A3) may be end-capping with an end-capping agent such as a monoamine, an acid anhydride, a monoacid chloride, a monocarboxylic acid, or a monoactive ester. Capping the ends of the resin with an end-capping agent can easily adjust the dissolution rate of the resin in an alkaline aqueous solution to a preferred range. Among these, it is preferable to use an end-capping agent having a phenolic hydroxyl group or a crosslinkable group. The use of an end-capping agent having a phenolic hydroxyl group imparts alkali solubility to the resin, thereby reducing residue. The use of an end-capping agent having a crosslinkable group also promotes a crosslinking reaction during the heat curing process, making it possible to obtain a cured film with excellent chemical resistance and elongation at break.

[0068] Specific examples of the monoamines having a phenolic hydroxyl 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, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol (hereinafter referred to as OAP), 3-aminophenol (hereinafter referred to as MAP), and 4-aminophenol (hereinafter referred to as PAP). Furthermore, examples of those having a photocrosslinkable group include 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-aminostyrene, 3-aminostyrene, 4-aminostyrene, and others include aniline, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, etc. Two or more of these may be used.

[0069] Among the acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds, those having a phenolic hydroxyl group include 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, etc. Furthermore, those having a photocrosslinkable group include maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride (hereinafter, NA), itaconic anhydride, itaconic acid, maleic acid, acrylic acid, methacrylic acid, 3-phenylacrylic acid, crotonic acid, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, and 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride. Other examples include acetic anhydride, succinic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride, 3-carboxythiophenol, 4-carboxythiophenol, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, terephthalic acid, phthalic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, trimellitic anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride. Furthermore, with respect to the above monocarboxylic acids, monoacid chloride compounds in which the carboxyl group of these monocarboxylic acids is converted to acid chloride may be used, or monoacid chloride compounds in which only one carboxyl group of the above dicarboxylic acids is converted to acid chloride may be used, or activated ester compounds obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide may be used. Two or more of these may also be used.

[0070] Furthermore, a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

[0071] When a monoamine is used as the end-capping agent, its introduction ratio is preferably 1 mol% or more and 60 mol% or less, based on 100 mol% of all amine compounds contained in the polyimide resin (A1), the polybenzoxazole resin (A2), and the copolymer resin (A3). By making the introduction ratio of the monoamine preferably 1 mol% or more, more preferably 5 mol% or more, the effect of reducing residue after development can be effectively obtained. Furthermore, by making the introduction ratio of the monoamine preferably 60 mol% or less, more preferably 50 mol% or less, the molecular weight of the resin can be maintained high, and high chemical resistance and breaking elongation can be maintained.

[0072] When an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound is used as the end-capping agent, the total introduction ratio thereof is preferably 1 mol part or more and 100 mol parts or less per 100 mol parts of all amine compounds contained in the polyimide resin (A1), the polybenzoxazole resin (A2), and the copolymer resin (A3). By setting the introduction ratio to preferably 1 mol part or more, more preferably 5 mol parts or more, the effect of reducing residue after development can be effectively obtained. On the other hand, by setting the introduction ratio to preferably 100 mol parts or less, more preferably 90 mol parts or less, the molecular weight of the resin can be maintained high, and high chemical resistance and elongation at break can be maintained.

[0073] The term "total amine compounds" as used herein refers to the total content of compounds having an amino group, such as monoamines, diamines, and triamines.

[0074] The weight-average molecular weight (Mw) of the polyimide resin (A1), the polybenzoxazole resin (A2), and the copolymer resin (A3) is preferably 3,000 to 100,000, as determined by gel permeation chromatography (GPC) in terms of polystyrene. By setting the Mw to 100,000 or less, more preferably 80,000 or less, and even more preferably 60,000 or less, good solvent solubility and good developer solubility can be effectively achieved. Furthermore, by setting the weight-average molecular weight to 3,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more, high elongation at break can be effectively achieved. In the present invention, Mw is determined by the method described below.

[0075] Examples of the polyimide resin (A1) include reaction products obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic acid dianhydride, or a tetracarboxylic acid diester dichloride with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine. These reaction products may also be subjected to dehydration ring closure by heating or by reaction with an acid or a base. Therefore, a preferred embodiment of the polyimide resin (A1) has a tetracarboxylic acid and / or a derivative thereof residue and a diamine and / or a derivative thereof residue.

[0076] The polyimide resin (A1) preferably has at least one structural unit selected from the group consisting of a structural unit represented by formula (6), a structural unit represented by formula (7), and a structural unit represented by formula (3).

[0077]

[0078] In formula (6), formula (7) and formula (3), X １ represents a tetravalent organic group having 2 to 40 carbon atoms, which has any one of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 40 carbon atoms. １ represents a divalent organic group having 2 to 40 carbon atoms, which has any one of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 40 carbon atoms. ７ and R ８each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having an ethylenically unsaturated double bond. * indicates a bonding site.

[0079] The structural unit represented by formula (6) represents a structural unit in which all of the amic acid structures or amic acid ester structures in the structural unit are cyclized and imidized. Formula (7) represents a structural unit in which some of the amic acid structures or amic acid ester structures in the structural unit are cyclized and imidized, resulting in some amic acid structures or amic acid ester structures. Formula (3) represents a structural unit in which none of the amic acid structures or amic acid ester structures in the structural unit are cyclized and all of the amic acid structures or amic acid ester structures are amic acid structures or amic acid ester structures.

[0080] When the number of structural units represented by formula (6), structural units represented by formula (7), and structural units represented by formula (3) in the polyimide resin (A1) is defined as p, q, and r, respectively, p, q, and r are integers of 0 or more. Among them, it is preferable that r is an integer of 1 or more, and the polyimide resin (A1) has a structural unit represented by formula (3). When the component (A) contains polyimide resin (A1) and the polyimide resin (A1) has a structure represented by formula (3), it is possible to improve sensitivity and reduce development residues when a photosensitizer is added to the polyimide resin (A1) to form a photosensitive resin composition, which is preferable. In addition, when R in formula (3) ７ and R ８ are each independently preferably an alkyl group having 1 to 10 carbon atoms or a monovalent organic group having an ethylenically unsaturated double bond, and more preferably an alkyl group having 1 to 3 carbon atoms or a monovalent organic group having an ethylenically unsaturated double bond. ７ and R ８ is an alkyl group having 1 to 10 carbon atoms or a monovalent organic group having an ethylenically unsaturated double bond, it is possible to adjust the solubility in the developer to a preferred range, and therefore it is possible to obtain a good pattern shape. ７ and R ８is a monovalent organic group having an ethylenically unsaturated double bond, which is preferable because, in addition to the above, the progress of a crosslinking reaction during heat curing can improve the breaking elongation and chemical resistance. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group, and examples of the monovalent organic group having an ethylenically unsaturated double bond include structures obtained by removing a hydroxyl group from 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA) and 2-hydroxyethyl acrylate.

[0081] In addition, Y in formula (3) １ is preferably a divalent organic group represented by formula (4) or formula (5).

[0082]

[0083] In formula (4) and formula (5), X ２ and X ３ each independently represents a direct bond, —SO ２ It represents -, -O-, or a divalent organic group having 1 to 20 carbon atoms. * represents the point of attachment to the amide structure, imide structure, amic acid ester structure, or amic acid structure.

[0084] The structures represented by formulas (4) and (5) have a phenolic hydroxyl group, and therefore can impart solubility in an alkaline developer, thereby reducing development residues. ２ and X ３ are each independently -C(CF ３ ) ２ -, -CH(CF ３ ) - or -C(CH ３ ) ２ In the case of any one selected from the group consisting of X -, intermolecular packing is suppressed and solvent solubility can be improved, which is preferable. ２ and X ３ are each independently a divalent organic group having 1 to 20 carbon atoms and not containing a fluorine atom, which is preferable because this can improve the metal adhesion after PCT treatment.

[0085] The imide ring closure rate of the polyimide resin (A1) is preferably 1% or more and 98% or less, more preferably 1% or more and 70% or less, and even more preferably 1% or more and 50% or less. An imide ring closure rate of 1% or more is preferable because it is possible to reduce the amount of outgassing at high temperatures and improve the reliability of organic EL display devices. Furthermore, an imide ring closure rate of 98% or less is preferable because it is possible to reduce residues after development and to increase the sensitivity of the resin composition.

[0086] The imide ring closure rate of the polyimide resin (A1) can be determined by the method described below.

[0087] The polyimide resin (A1) may be a copolymer having one or more structural units selected from the group consisting of structural units represented by formula (6), structural units represented by formula (7), and structural units represented by formula (3), and a structural unit other than the structural units represented by formula (6), structural units represented by formula (7), and structural units represented by formula (3). When a copolymer is used, it is preferably a copolymer with a structural unit of polybenzoxazole described below.

[0088] A preferred embodiment of the polybenzoxazole resin (A2) is, for example, a compound obtained by reacting a bisaminophenol compound with a dicarboxylic acid or a corresponding dicarboxylic acid chloride or dicarboxylic acid activated ester, and has a dicarboxylic acid residue and a bisaminophenol residue. The reaction product thus obtained may be subjected to dehydration ring closure by heating or by reaction with an acid, a base, acetic anhydride, a carbodiimide compound, or the like.

[0089] The polybenzoxazole resin (A2) preferably has, for example, one or more structural units selected from the group consisting of a structural unit represented by formula (8), a structural unit represented by formula (9), and a structural unit represented by formula (10).

[0090]

[0091] In formula (8), formula (9) and formula (10), X ２ represents a dicarboxylic acid residue, and Y ２indicates a bisaminophenol residue. A dicarboxylic acid residue is a structure obtained by removing two carboxyl groups from a dicarboxylic acid compound. A bisaminophenol residue is a structure obtained by removing two amino groups and two hydroxyl groups from a bisaminophenol compound.

[0092] The structural unit represented by formula (8) represents a structural unit in which all of the hydroxyamide structures in the structural unit have been ring-closed to form oxazoles. Formula (9) represents a structural unit in which some of the hydroxyamide structures in the structural unit have been ring-closed to form oxazoles, leaving some as hydroxyamide structures. Formula (10) represents a structural unit in which none of the hydroxyamide structures in the structural unit have been ring-closed to form oxazoles, leaving some as hydroxyamide structures.

[0093] When the numbers of the structural units represented by formula (8), the structural units represented by formula (9), and the structural units represented by formula (10) in the polybenzoxazole resin (A2) are denoted by s, t, and u, respectively, s, t, and u are integers of 0 or more.

[0094] The oxazole ring closure rate of the polybenzoxazole resin (A2) (hereinafter referred to as R ＯＸ The oxazole ring closure rate (sometimes referred to as "the oxazole ring closure rate") is preferably 0% or more and 90% or less, more preferably 0% or more and 70% or less, and even more preferably 0% or more and 50% or less. When the oxazole ring closure rate is within the above range, it is possible to reduce residues after development.

[0095] The oxazole ring closure rate of the polybenzoxazole resin (A2) can be determined by the following method. ＯＸ(%))> Polybenzoxazole resin (A2) was dissolved in γ-butyrolactone (hereinafter, GBL) to a concentration of 35% by mass. This solution was applied to a 4-inch silicon wafer by spin coating using a spinner 1H-DX (manufactured by Mikasa Co., Ltd.), and then baked on a hot plate at 120°C for 3 minutes to produce a resin film 4 to 5 μm thick. This wafer with the resin film was divided into two, and one half was cured in a clean oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen stream (oxygen concentration 20 ppm or less) at 140°C for 30 minutes, then further heated to 370°C for 1 hour to completely close the oxazole ring. The transmission infrared absorption spectra of the resin film before and after curing were measured using an infrared spectrophotometer FT-720 (manufactured by Horiba, Ltd.), and an absorption peak (1,050 cm) due to the C-O stretching vibration of oxazole was observed. －１ The peak intensity ratio obtained by dividing the peak intensity (U) by the peak intensity (W) is calculated using the following formula, and this is the content of oxazole groups in the polymer before heat treatment, i.e., the oxazole ring closure rate.

[0096] R ＯＸ (%)=(U / W)×100.

[0097] The polybenzoxazole resin (A2) may also be a copolymer having one or more structural units selected from the group consisting of structural units represented by formula (8), structural units represented by formula (9), and structural units represented by formula (10), and a structural unit other than the structural unit represented by formula (8), structural units represented by formula (9), and structural units represented by formula (10). When a copolymer is used, it is preferably a copolymer with the structural unit of the polyimide described above.

[0098] The copolymer resin (A3) can be obtained, for example, as a random copolymer by reacting the raw materials for the polyimide resin (A1) and the raw materials for the polybenzoxazole resin (A2) at once, or as a block copolymer having polyimide structural units and polybenzoxazole structural units by separately synthesizing polyimide structural units and polybenzoxazole structural units and then reacting the respective structural units.

[0099] The copolymer resin (A3) preferably has, for example, both one or more structural units of polyimide selected from the group consisting of a structural unit represented by formula (6), a structural unit represented by formula (7), and a structural unit represented by formula (3), and one or more structural units of polybenzoxazole selected from the group consisting of a structural unit represented by formula (8), a structural unit represented by formula (9), and a structural unit represented by formula (10).

[0100] Similarly to the polyimide resin (A1), the copolymer resin (A3) preferably has a structural unit represented by formula (3). When the component (A) contains the copolymer resin (A3) and the copolymer resin (A3) has a structure represented by formula (3), it is possible to improve sensitivity and reduce development residues when a photosensitizer is added to the copolymer resin (A3) to form a photosensitive resin composition, which is preferable.

[0101] In addition, like the polyimide resin (A1), the copolymer resin (A3) has a structural unit represented by formula (3), and Y in formula (3) １ is preferably a divalent organic group represented by formula (4) or formula (5). The structures represented by formulas (4) and (5) have a phenolic hydroxyl group, which can impart solubility in an alkaline developer and reduce development residues. ２ and X ３ are each independently -C(CF ３ ) ２ -, -CH(CF ３ ) - or -C(CH ３ ) ２ In the case of any one selected from the group consisting of X -, intermolecular packing is suppressed and solvent solubility can be improved, which is preferable. ２ and X ３ are each independently a divalent organic group having 1 to 20 carbon atoms and not containing a fluorine atom, which is preferable because this can improve the metal adhesion after PCT treatment.

[0102] The component (A) preferably contains a polyimide resin (A1) and / or a copolymer resin (A3) of a structural unit of a polyimide resin and a structural unit of a polybenzoxazole resin, and the component (A) contains a structural unit represented by formula (3), because when the component (A) is prepared into a photosensitive resin composition, it is possible to improve sensitivity and reduce development residues.

[0103] The component (A) can be synthesized by a known method. Examples of methods for synthesizing the polyimide resin (A1), the polybenzoxazole resin (A2), and the copolymer resin (A3) are described below.

[0104] The polyimide resin (A1) can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine compound in a polymerization solvent at low temperature, by obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with an amine in the presence of a condensing agent, or by obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with an amine. Alternatively, the resin obtained by the above-mentioned method may be dehydrated and ring-closed by heating or a chemical treatment with an acid or a base.

[0105] The polybenzoxazole resin (A2) can be produced, for example, by condensing a bisaminophenol compound with a dicarboxylic acid in a polymerization solvent. Specifically, there is a method in which a dehydration condensation agent such as dicyclohexylcarbodiimide (hereinafter referred to as DCC) is reacted with an acid and the bisaminophenol compound is added thereto, or a method in which a solution of a dicarboxylic acid dichloride is added dropwise to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine has been added.

[0106] The copolymer resin (A3) can be synthesized, for example, by combining the synthesis method for the polyimide resin (A1) and the synthesis method for the polybenzoxazole resin (A2).

[0107] The component (A) polymerized by the above method is preferably introduced into a large amount of deionized water or a mixture of methanol and deionized water, precipitated, filtered, dried, and isolated. This precipitation procedure removes unreacted monomers and oligomer components such as dimers and trimers, improving the film properties and chemical resistance after thermal curing.

[0108] The polymerization solvent may be any solvent as long as it can dissolve the raw material monomers, such as acid dianhydrides and diamines, and its type is not particularly limited. Examples of the polymerization solvent include amides such as N,N-dimethylformamide (hereinafter referred to as DMF), N,N-diethylformamide, N,N-dimethylacetamide (hereinafter referred to as DMAc), N-methyl-2-pyrrolidone (hereinafter referred to as NMP), N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as DMI), 3-methoxy-N,N-dimethylpropanamide (hereinafter referred to as MPA), 3-butoxy-N,N-dimethylpropanamide (hereinafter referred to as BPA), N,N'-dimethylpropyleneurea, N,N-dimethylisobutyramide (hereinafter referred to as DMIB), N,N-dimethylpropionamide (hereinafter referred to as DMPA), and 3-methyl-2-oxazolidone; γ-butyrolactone (hereinafter referred to as GBL); γ-butyrolactone (hereinafter referred to as GBL); Examples of the carboxylic acid ester include cyclic esters such as valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone; carbonates such as ethylene carbonate and propylene carbonate; glycols such as triethylene glycol; phenols such as m-cresol and p-cresol; esters such as methyl levulinate, ethyl levulinate, propyl levulinate, butyl levulinate, ethyl levulinate propylene glycol ketal, and ethyl levulinate glycerol ketal; acetophenone, sulfolane, dimethyl sulfoxide (hereinafter, DMSO); and dihydrolevoglucosenone (Cyrene, manufactured by Circa).

[0109] The amount of the polymerization solvent used is preferably 100 to 1,900 parts by mass, and more preferably 150 to 950 parts by mass, per 100 parts by mass of the component (A).

[0110] The resin composition of the present invention contains component (B), which is levoglucosenone and / or dihydrolevoglucosenone. Levoglucosenone refers to a compound represented by formula (11), and dihydrolevoglucosenone refers to a compound represented by formula (12).

[0111]

[0112] These compounds may be added as additives when preparing the resin composition, or may be used as a solvent for the resin composition. When the resin composition contains the component (B), it is possible to improve the planarization of the resin composition and the breaking elongation and chemical resistance of the cured film obtained by curing the resin composition. In this specification, planarization refers to the property of reducing the unevenness of the substrate surface, i.e., flattening, by applying the resin composition to a substrate with unevenness and curing it. Although the detailed mechanism is unknown, the principle by which the above effect is obtained is assumed as follows.

[0113] Regarding the improvement in planarization, levoglucosenone and dihydrolevoglucosenone are compounds with similar polarity to polyimide resins and polybenzoxazole resins, and therefore are presumed to interact strongly with these resins. Furthermore, because both levoglucosenone and dihydrolevoglucosenone have high boiling points, they are thought to remain in the resin film for a long time during the heat curing process. (Boiling point of levoglucosenone: 231°C, boiling point of dihydrolevoglucosenone: 227°C (both boiling points at atmospheric pressure).) Therefore, levoglucosenone and dihydrolevoglucosenone are thought to act as plasticizers in the resin film during the heat curing process, imparting fluidity during heat curing and resulting in improved planarization of the resin film. The resin film is a film formed by applying a resin composition to a substrate.

[0114] Furthermore, in terms of improving the breaking elongation and chemical resistance of the cured film, when the Hansen solubility parameters of levoglucosenone and dihydrolevoglucosenone are compared with those of commonly used polar solvents such as NMP and DMF, it is found that levoglucosenone and dihydrolevoglucosenone have a higher polarity. This suggests that levoglucosenone and dihydrolevoglucosenone promote nucleophilic reactions in the reaction system, accelerating the cyclization reaction of polyimide resins and polybenzoxazole resins, resulting in a cured film with excellent breaking elongation and chemical resistance. Furthermore, when the resin composition contains a crosslinking agent (described below), levoglucosenone and dihydrolevoglucosenone are also thought to be able to promote the reaction in which the crosslinking agent adds to the resin. Therefore, the inclusion of a crosslinking agent in the resin composition of the present invention is thought to enable further improvements in breaking elongation and chemical resistance.

[0115] The content of the component (B) is preferably 1 to 3,000 parts by mass, more preferably 20 to 2,000 parts by mass, and even more preferably 50 to 1,000 parts by mass, per 100 parts by mass of the total amount of the component (A). By being within the above range, it becomes easier to obtain the effects of improving the flattening property, the breaking elongation of the cured film, and the chemical resistance.

[0116] The component (B) refers to levoglucosenone or dihydrolevoglucosenone, and the resin composition of the present invention preferably contains dihydrolevoglucosenone as the component (B). By containing dihydrolevoglucosenone as the component (B), it is possible to improve the planarization properties and storage stability of the resin composition, as well as to improve the chemical resistance, breaking elongation, adhesion to metals, and transparency of the cured film obtained by curing the resin composition.

[0117] The resin composition of the present invention preferably further contains a component (C) which is a compound represented by formula (1) and / or a compound represented by formula (2).

[0118]

[0119] In formula (1), R １ , R ２ and R ３are each independently an alkyl group having 1 to 6 carbon atoms. ４ and R ５ are each independently an alkyl group having 1 to 6 carbon atoms. ６ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0120] The inclusion of component (C) promotes the ring-closing reaction of component (A), making it possible to improve breaking elongation and chemical resistance. Furthermore, since component (C) strongly interacts with component (A) and metal materials, the inclusion of component (C) can improve adhesion to metal materials.

[0121] The β-alkoxypropionamide, which is the compound represented by formula (1), is preferably MPA or BPA, from the viewpoints of improving the solubility of component (A), promoting the ring-closing reaction of component (A), and improving the breaking elongation and chemical resistance of the cured film.

[0122] In the present invention, the content of the β-alkoxypropionamide 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 component (A) from the viewpoint of accelerating the ring-closing reaction of the component (A) and improving the breaking elongation and chemical resistance of the cured film, while the content is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less, from the viewpoint of being able to form a desired patterned film when used as a developed film.

[0123] The compound represented by formula (2) is preferably DMPA or DMIB, from the viewpoint of accelerating the ring-closing reaction of component (A) and improving the breaking elongation and chemical resistance of the cured film.

[0124] In the present invention, the content of the compound represented by formula (2) is preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of component (A) from the viewpoint of accelerating the ring-closing reaction of component (A) and improving the breaking elongation and chemical resistance of the cured film, while the content is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less, from the viewpoint of being able to form a desired patterned film when used as a developed film.

[0125] In the resin composition of the present invention, the ratio X / Y, where X is the mass of the component (B) and Y is the mass of the component (C), is preferably 1 or more and 1,000 or less, more preferably 5 or more and 500 or less, even more preferably 10 or more and 450 or less, and particularly preferably 15 or more and 400 or less. As described above, both the component (B) and the component (C) can improve the breaking elongation and chemical resistance of the cured film, but by having X / Y within the above range, the breaking elongation and chemical resistance of the cured film can be improved without deteriorating the planarization properties of the resin composition and the adhesion of the cured film to metal materials.

[0126] The resin composition of the present invention preferably further contains a component (D) that is a compound having a hydroxyl group and a boiling point at atmospheric pressure of 100° C. or more and 200° C. or less. By containing the component (D), it is possible to improve the planarization property, as well as improve the developability, suppress the generation of development residues, and improve the sensitivity.

[0127] Specific examples of the component (D) include propylene glycol monomethyl ether (hereinafter, PGME; boiling point 120°C), methyl lactate (boiling point 145°C), ethyl lactate (boiling point 154°C), propyl lactate (boiling point 169°C), 1-butanol (boiling point 117°C), 1-pentanol (boiling point 138°C), 1-hexanol (boiling point 157°C), cyclohexanol (boiling point 161°C), 3-methoxybutanol (boiling point 161°C), ethylene glycol monomethyl ether (boiling point 124°C), diacetone alcohol (boiling point 166°C), tetrahydrofurfuryl alcohol (boiling point 176°C), and diethylene glycol monomethyl ether (boiling point 194°C).

[0128] The content of the component (D) in the resin composition of the present invention is preferably 5 to 3,000 parts by mass, and more preferably 10 to 1,000 parts by mass, per 100 parts by mass of the total amount of the component (A).

[0129] Furthermore, the ratio X / Z of the mass X of the component (B) to the mass Z of the component (D) contained in the resin composition of the present invention is preferably 0.01 to 10, more preferably 0.05 to 5, even more preferably 0.08 to 2, and particularly preferably 0.1 to 1. When the ratio X / Z is within the above range, it is possible to satisfy all of the properties of improved planarization, suppression of development residues, and improved adhesion and sensitivity.

[0130] The resin composition of the present invention preferably contains a photosensitizer component (E). The inclusion of component (E) can impart photosensitivity to the resin composition. Examples of the component (E) include a photoacid generator component (E2) and a photopolymerization initiator component (E1). The inclusion of the photoacid generator component (E2) generates acid in the irradiated areas, increasing the solubility of the irradiated areas in an alkaline aqueous solution, thereby producing a positive-tone relief pattern in which the irradiated areas are dissolved. Furthermore, the inclusion of the photoacid generator component (E2) and the crosslinking agent component (I) allows the acid generated in the irradiated areas to promote the crosslinking reaction of component (I), resulting in a negative-tone relief pattern in which the irradiated areas are insolubilized. Furthermore, the inclusion of the photopolymerization initiator component (E1) and the radically polymerizable compound component (F) allows the active radicals generated in the irradiated areas to promote radical polymerization of the ethylenically unsaturated bonds in the radically polymerizable compound, resulting in a negative-tone relief pattern in which the irradiated areas are insolubilized. Preferably, the component (E1) contains component (E1-1) which is an oxime ester-type photopolymerization initiator and / or component (E1-2) which is a titanocene-type photopolymerization initiator, and further contains component (F) which is a radical polymerizable compound. By including component (E1-1) and / or component (E1-2) and further including component (F), the sensitivity of the resin composition can be increased. In the resin composition of the present invention, the component (E) which is a photosensitizer preferably contains component (E2) which is a photoacid generator and exhibits positive photosensitivity. By including component (E) which is a photoacid generator and exhibiting positive photosensitivity, it becomes easier to reduce variations in pattern opening dimensions due to processing. Furthermore, by including component (E) which is a photosensitizer containing component (E1) which is a photopolymerization initiator and component (F) which is a radical polymerizable compound, and exhibiting negative photosensitivity, the sensitivity of the photosensitive resin composition can be increased.

[0131] Examples of the component (E2) that is a photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts.

[0132] Examples of the quinone diazide compound include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via an ester bond, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via a sulfonamide bond, and a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via an ester bond and / or a sulfonamide bond. It is preferred that 50 mol% or more of the functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinone diazide. It is also preferred that the photosensitive resin composition contain two or more types of the photoacid generator (E2), thereby enabling the production of a highly sensitive photosensitive resin composition.

[0133] The quinone diazide is preferably one having a 5-naphthoquinone diazide sulfonyl group or one having a 4-naphthoquinone diazide sulfonyl group. 4-naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure. 5-naphthoquinone diazide sulfonyl ester compounds have absorption extending to the g-line region of a mercury lamp and are suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure. Furthermore, a naphthoquinone diazide sulfonyl ester compound having both a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or both a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be contained.

[0134] Of the photoacid generators (E2), sulfonium salts, phosphonium salts, and diazonium salts are preferred because they appropriately stabilize the acid component generated by exposure, with sulfonium salts being particularly preferred.

[0135] Specific examples of the photopolymerization initiator component (E1) include the photopolymerization initiators described in paragraphs

[0223] to

[0276] of WO 2019 / 087985 and paragraphs

[0047] to

[0048] of WO 2019 / 194286. In particular, from the viewpoint of achieving high sensitivity, the component (E1) preferably contains an oxime ester photopolymerization initiator component (E1-1) and / or a titanocene photopolymerization initiator component (E1-2). Two or more of these may be contained.

[0136] The content of the component (E) which is the photosensitizer is preferably 0.5 to 50 parts by mass per 100 parts by mass of the component (A).

[0137] From the viewpoint of achieving high sensitivity, the content of the photoacid generator (E2) in the photosensitizer (E) component is preferably 0.5 to 50 parts by mass per 100 parts by mass of the component (A). Of these, the quinone diazide compound is preferably 3 to 40 parts by mass. The total amount of the sulfonium salt, phosphonium salt, and diazonium salt is preferably 0.5 to 20 parts by mass.

[0138] The content of the photopolymerization initiator component (E1) in the photosensitizer component (E) is preferably 0.5 to 20 parts by mass per 100 parts by mass of the component (A). When the content is 0.5 parts by mass or more, sufficient radicals are generated upon light irradiation, improving sensitivity. When the content is 20 parts by mass or less, curing of unexposed areas due to excessive radical generation does not occur, improving alkali developability.

[0139] The resin composition of the present invention may further include a radically polymerizable compound (Component (F)), and the photosensitizer (Component (E) may include a photopolymerization initiator (Component (E1)). By adopting such a configuration, as described above, active radicals generated in the light-irradiated area promote radical polymerization of the ethylenically unsaturated bonds in the radically polymerizable compound, thereby obtaining a negative relief pattern in which the light-irradiated area is insolubilized. As a result, the photosensitive resin composition becomes a negative-tone photosensitive resin composition.

[0140] Specific examples of the radically polymerizable compound component (F) include the radically polymerizable compounds described in paragraphs

[0189] to

[0222] of WO 2019 / 087985. Among these, it is preferable to contain a flexible-chain-containing aliphatic radically polymerizable compound. The flexible-chain-containing aliphatic radically polymerizable compound refers to a compound having, in the molecule, multiple ethylenically unsaturated double bond groups and a flexible skeleton such as an aliphatic chain or an oxyalkylene chain.

[0141] By including the flexible chain-containing aliphatic radical polymerizable compound, the curing reaction upon light irradiation can proceed efficiently, improving sensitivity upon light irradiation. Furthermore, changes in the pattern opening width before and after thermal curing can be suppressed. The content of the radical polymerizable compound, component (F), is preferably 5 to 50 parts by mass per 100 parts by mass of component (A).

[0142] The resin composition of the present invention may contain a solvent (Component (G)) other than the components (B), (C), and (D). Examples of Component (G) include ethers such as ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, and butyl lactate; alcohols such as methanol, ethanol, and isopropanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, and diacetone alcohol; polar aprotic solvents such as NMP, GBL, DMSO, 1,3-dimethyl-2-imidazolidinone, and 3-methyl-2-oxazolidone; and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained.

[0143] The amount of the component (G) is preferably 1,500 parts by mass or less, and more preferably 1,000 parts by mass or less, per 100 parts by mass of the component (A).

[0144] The resin composition of the present invention may be a positive-type photosensitive resin composition, further comprising a dissolution promoter (Component H), and the photosensitizer (Component E) further comprises a photoacid generator (Component E2). Component H supplements the alkaline developability of the photosensitive resin composition, thereby improving the sensitivity of the positive-type photosensitive resin composition. Component H is preferably a compound having a phenolic hydroxyl group, such as 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, or BisOIPP-CP. , Bis26X-IPZ, BisOTBP-CP, TekP4HBPA (tetrakisP-DO-BPA), TrisPHAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCRPA (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Mirex HBPX, Mirex PIRM, Mirex MDPR (trade names, manufactured by Mitsui Chemicals, Inc.), BIR-OC, BIP-PC, BIR-PC, Examples of compounds having a phenolic hydroxyl group include BIR-PTBP, BIR-PCHP, BIP-BIOCF, 4PC, BIR-BIPC-F, TEP-BIP-A (trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), bisphenol A, bisphenol AF (hereinafter referred to as BPAF), bisphenol B, bisphenol C, bisphenol S, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 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.

[0145] The content of the dissolution promoter (H) is preferably 1 to 40 parts by mass per 100 parts by mass of the component (A), since this allows for improved sensitivity while maintaining a good pattern shape.

[0146] The resin composition of the present invention preferably contains a crosslinking agent, component (I). A crosslinking agent refers to a compound having a crosslinkable group capable of bonding with a resin. The inclusion of component (I) can improve the breaking elongation and chemical resistance of the cured film. This is presumably because component (I) can introduce a new crosslinked structure into the cured film of the resin composition, thereby improving the crosslink density.

[0147] The component (I) is preferably a compound having two or more thermally crosslinkable groups in the molecule, such as alkoxymethyl groups, methylol groups, epoxy groups, or oxetanyl groups.

[0148] Specific examples of the component (I) that can be used include the crosslinking agents described in paragraphs

[0407] to

[0412] of WO 2019 / 087985.

[0149] The content of the component (I) is preferably 0.5 to 50 parts by mass per 100 parts by mass of the component (A). When the content is 0.5 to 50 parts by mass, the breaking elongation and chemical resistance of the cured film can be improved without impairing the storage stability of the resin composition or the transparency of the cured film.

[0150] The resin composition of the present invention may further contain a surfactant, component (J). A surfactant refers to a compound having a hydrophilic structure and a hydrophobic structure. By including an appropriate amount of component (J), the surface tension of the resin composition can be adjusted as desired, the leveling properties during application can be improved, and the thickness uniformity of the coating film can be improved. As component (J), a fluororesin-based surfactant, a silicone-based surfactant, a polyoxyalkylene ether-based surfactant, or an acrylic resin-based surfactant is preferred.

[0151] Specific examples of the component (J) include the surfactants described in paragraphs

[0419] to

[0420] of WO 2019 / 087985.

[0152] The content of the component (J) in the resin composition of the present invention is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, of the entire resin composition. A content of 0.001% by mass or more can improve leveling during application. On the other hand, the content of the surfactant is preferably 1% by mass or less, more preferably 0.5% by mass or less. A content of 1% by mass or less can reduce defects that occur during application.

[0153] The resin composition of the present invention may contain an additive (K) other than those described above. Examples of the additive (K) include the polyfunctional thiol compounds described in paragraphs

[0386] to

[0398] of WO 2019 / 087985, the colorants described in paragraphs

[0281] to

[0370] of WO 2019 / 087985, the dispersants described in paragraphs

[0371] to

[0385] of WO 2019 / 087985, and the dispersants described in paragraphs

[0399] to

[0402] of WO 2019 / 087985. the sensitizers described above, the polymerization inhibitors described in paragraphs

[0403] to

[0406] of WO 2019 / 087985, the silane coupling agents described in paragraphs

[0413] to

[0418] of WO 2019 / 087985, and the inorganic particles described in paragraphs

[0127] to

[0130] of WO 2016 / 052268 and paragraphs

[0024] to

[0025] of WO 2019 / 167461.

[0154] Examples of methods for producing the resin composition of the present invention include a method in which the components (A) and (B), and optionally other components, are placed in a glass flask or a stainless steel container, and stirred and dissolved using a mechanical stirrer or the like, an ultrasonic dissolving method, or a method in which the components are stirred and dissolved using a planetary stirring and degassing device.

[0155] The obtained resin composition is preferably filtered through a leak filter to remove dust and particles. The pore size of the leak filter is 0.5 to 0.02 μm, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, 0.02 μm, etc., but is not limited to these. The material of the leak filter includes polypropylene, polyethylene, nylon, polytetrafluoroethylene, etc., with polyethylene and nylon being preferred. When the resin composition contains inorganic particles, pigments, etc., it is preferable to use a leak filter with a pore size larger than these.

[0156] The cured film of the present invention is obtained by curing the resin composition of the present invention. Examples of methods for curing the resin composition include a method of curing the resin composition by heating it or a method of irradiating it with actinic rays. By curing the resin composition of the present invention, the heat resistance, breaking elongation, and chemical resistance of the cured film can be improved.

[0157] Next, the method for producing the cured film of the present invention will be described.

[0158] The method for producing a cured film of the present invention preferably includes steps (1), (2), and (5). When the resin composition of the present invention contains component (E) which is a photosensitizer and has photosensitivity, it preferably includes steps (3) and (4) in addition to the above: (1) a step of applying the above-described resin composition to a substrate to form a resin film, (2) a step of drying the resin film, (3) a step of exposing the dried resin film through a photomask, (4) a step of developing the exposed resin film, and (5) a step of heat-treating the developed resin film.

[0159] In the above step (1), the resin composition of the present invention is applied by spin coating, slit coating, dip coating, spray coating, printing, or the like to obtain a resin film of the resin composition. Prior to application, the substrate to which the resin composition is to be applied may be pretreated with an adhesion improver. For example, a method of treating the substrate surface using a solution in which 0.5 to 20% by mass of an adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate is used. Examples of substrate surface treatment methods include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment. Specific examples of adhesion improvers include the adhesion improvers described in

[0127] of WO 2019 / 065351.

[0160] In the above step (2), the applied resin film is subjected to a reduced pressure drying treatment as necessary, and then subjected to a heat treatment at a temperature in the range of 50°C to 180°C for 1 minute to several hours using a hot plate, an oven, infrared rays, or the like, to obtain a resin film.

[0161] In the above step (3), the resin film is irradiated with actinic radiation through a photomask having a desired pattern. Actinic radiation used for exposure includes ultraviolet light, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. After irradiation with actinic radiation, post-exposure baking may be performed. Post-exposure baking can be expected to improve the resolution after development or increase the tolerance for development conditions. Post-exposure baking can be performed using an oven, hot plate, infrared light, a flash annealing device, or a laser annealing device. The post-exposure baking temperature is preferably 50 to 180°C, more preferably 60 to 150°C. The post-exposure baking time is preferably 10 seconds to several hours. When the post-exposure baking time is within the above range, the reaction proceeds smoothly, and the development time may be shortened.

[0162] In the above step (4), the exposed resin film is developed using a developer to remove areas other than the exposed area. The developer is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. For example, in the case of a photosensitive resin composition that is not soluble in an alkaline aqueous solution, good solvents such as NMP, N-cyclohexyl-2-pyrrolidone, DMAc, cyclopentanone, cyclohexanone, GBL, and α-acetyl-γ-butyrolactone are preferred, while poor solvents such as toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water are preferred. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Two or more types of each solvent can also be used, for example, in combination. On the other hand, in the case of a photosensitive resin composition that is soluble in an alkaline aqueous solution, the developer used for development dissolves and removes the alkaline aqueous solution-soluble polymer, and is typically an alkaline aqueous solution containing an alkaline compound dissolved therein. Examples of alkaline compounds include 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. In some cases, polar solvents such as NMP, DMF, DMAc, DMSO, GBL, 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 alone or in combination to these aqueous alkaline solutions. Possible development methods include spray, paddle, immersion, and ultrasonic development.

[0163] Next, the pattern formed by development is preferably rinsed with deionized water. Here, too, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the deionized water for rinsing.

[0164] Next, the above-mentioned step (5) is carried out. Heat treatment can remove residual solvents and components with low heat resistance, thereby improving the heat resistance, elongation at break, and chemical resistance of the cured film. When the resin composition of the present invention contains a polyimide resin, a polybenzoxazole resin, and / or a copolymer resin composed of structural units of a polyimide resin and structural units of a polybenzoxazole resin, heat treatment can form imide rings and oxazole rings, thereby improving heat resistance, elongation at break, and chemical resistance. Furthermore, when a thermal crosslinking agent is contained, heat treatment can promote a thermal crosslinking reaction, improving heat resistance and chemical resistance. This heat treatment is carried out by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. One example is heat treatment at 150°C and 250°C for 30 minutes each. Alternatively, a method such as linearly increasing the temperature from room temperature to 300°C over 2 hours can be used. The heat treatment conditions in the present invention are preferably 180° C. or higher, more preferably 200° C. or higher, even more preferably 230° C. or higher, and particularly preferably 240° C. or higher. The heat treatment conditions are preferably 450° C. or lower, more preferably 350° C. or lower.

[0165] Next, as an example of a method for producing a cured film of the present invention, a method for producing a cured film using a photosensitive sheet obtained by forming the resin composition of the present invention containing the photosensitizer component (E) into a sheet will be described. Here, the photosensitive sheet refers to a sheet-like photosensitive resin composition obtained by applying the photosensitive resin composition to a release substrate and drying it.

[0166] When a photosensitive sheet formed from the resin composition of the present invention is used, if any protective film is present on the photosensitive sheet, the protective film is peeled off, and the photosensitive sheet and a substrate are placed opposite each other and bonded together by thermocompression to obtain a photosensitive resin film. The photosensitive sheet can be obtained by applying the resin composition of the present invention to a support film made of a peelable substrate such as polyethylene terephthalate, followed by drying.

[0167] Thermocompression bonding can be performed by a heat press treatment, a heat lamination treatment, a thermal vacuum lamination treatment, etc. The lamination temperature is preferably 40°C or higher in terms of adhesion to the substrate and embeddability. Furthermore, the lamination temperature is preferably 140°C or lower to prevent the photosensitive sheet from curing during lamination, which would reduce the resolution of pattern formation in the exposure and development steps.

[0168] The photosensitive resin film obtained by laminating a photosensitive sheet to a substrate can be formed into a cured film by following the steps of exposing the resin film, developing the exposed resin film, and heat curing.

[0169] The electronic component of the present invention comprises the cured film of the present invention.

[0170] A cured film formed from the resin composition of the present invention can be used as an insulating film or a protective film that constitutes an electronic component.

[0171] Here, examples of electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (ICs), and memories, as well as passive components such as resistors, capacitors, and inductors. Electronic components using semiconductors are also called semiconductor devices or semiconductor packages.

[0172] Specific examples of the cured film in electronic components that can be suitably used include a passivation film for a semiconductor, a surface protection film for a semiconductor element, a TFT (Thin Film Transistor), etc., an interlayer insulating film such as an interlayer insulating film between rewirings in multilayer wiring for high-density packaging of 2 to 10 layers, an insulating film for a touch panel display, a protective film, and an insulating layer for an organic electroluminescent device, but the film is not limited thereto and can have various structures.

[0173] Furthermore, the electronic component of the present invention preferably comprises a substrate on which the cured film of the present invention is formed. The substrate surface on which the cured film is formed can be appropriately selected depending on the application and process. Examples of the substrate include a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, ceramics, gallium arsenide, metal, and epoxy resin. A silicon substrate, a silicon carbide substrate, or a gallium nitride substrate is preferred.

[0174] The organic EL display device of the present invention comprises the cured film of the present invention. Preferably, the organic EL display device of the present invention comprises the cured film of the present invention as one or more layers selected from the group consisting of a pixel dividing layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT planarizing layer, an electrode planarizing layer, a wiring planarizing layer, a TFT protective layer, an electrode protective layer, a wiring protective layer, a gate insulating layer, a color filter, a black matrix, and a black column spacer.

[0175] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The names of the compounds used, for which abbreviations are used, are shown below. ODPA: 4,4'-oxydiphthalic anhydride TDA-100: 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione (manufactured by New Japan Chemical Co., Ltd.) BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Central Glass Co., Ltd.) BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Wakayama Seika Kogyo Co., Ltd.) SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane OBBOC: 4,4'-oxybisbenzoyl chloride (manufactured by Ihara Nikkei Chemical Industry Co., Ltd.) MAP: 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) NA: 5-norbornene-2,3-dicarboxylic anhydride, OAP: 2-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.), MAOC: methacryloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), MPA: 3-methoxy-N,N-dimethylpropanamide (manufactured by KJ Chemicals Co., Ltd.), DMIB: N,N-dimethylisobutyramide, DMPA: N,N-dimethylpropionamide, NMP: N-methyl-2-pyrrolidone, PGME: propylene glycol monomethyl ether, GBL: γ-butyrolactone, CHN: cyclohexanone, HEMA: 2-hydroxyethyl methacrylate, ITO: indium tin oxide, TMAH: tetramethylammonium hydroxide, DMFDMA: N,N-dimethylformamide dimethyl acetal, BPAF: bisphenol AF.

[0176] [Common Processing Conditions] In the following measurement and evaluation methods, and in the examples and comparative examples, the following processing was carried out under the following conditions unless otherwise specified.

[0177] (1) Pretreatment of ITO Substrate A glass substrate (manufactured by Geomatec Co., Ltd.; hereinafter referred to as "ITO substrate") on which a 100 nm ITO film was formed by sputtering was subjected to an ozone cleaning treatment for 100 seconds using a tabletop optical surface treatment device PL16-110 (manufactured by Sen Special Light Sources Co., Ltd.). A Si wafer (manufactured by Electronics and Materials Corporation) was subjected to a dehydration bake treatment by heating at 130°C for 2 minutes using a hot plate HP-1SA (manufactured by AS ONE Corporation).

[0178] (2) Heat Treatment (Cure) The developed film was heated in a high-temperature inert gas oven INH-9CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) at 250° C. for 1 hour in a nitrogen atmosphere to form a cured film.

[0179] [Measurement and Evaluation Methods] (1) Weight-average molecular weight of component (A) The resin or resin solution obtained in each synthesis example was measured for polystyrene-equivalent weight-average molecular weight (Mw) using a GPC analyzer under the following conditions. Measuring device: Waters 2695 (manufactured by Waters) Column temperature: 50 ° C. Flow rate: 0.4 mL / min Detector: 2489 UV / Vis Detector (measurement wavelength 260 nm) Developing solvent: NMP (containing 0.21 mass% lithium chloride and 0.48 mass% phosphoric acid) Guard column: TOSOH TSK guard column (manufactured by Tosoh Corporation) Column: TOSOH TSK-GEL a-2500 and TOSOH TSK-GEL a-4000 (both manufactured by Tosoh Corporation) in series Number of measurements: 2 (the average value was taken as the weight-average molecular weight of the polyimide).

[0180] (2) Esterification Rate Using a nuclear magnetic resonance (NMR) spectrometer EX-270 (manufactured by JEOL Ltd.), a mixed solution of 10 mg of the polyamic acid ester obtained in each synthesis example and 0.8 g of deuterated DMSO (DMSO-d6) was measured. １H-NMR was measured, and the integrated value of the peak derived from the aromatic protons of the resin was determined. The esterification rate of the polyamic acid ester was calculated from the area ratio of the peak derived from the methyl protons of the carboxylic acid ester and the ethylenically unsaturated double bond group. Since resins other than polyamic acid ester do not contain carboxylic acid esters, the esterification rate is indicated as "-" because it is not measurable.

[0181] (3) Imide ring closure rate (R ＩＭ (%)) The polyimide resin obtained in each synthesis example was dissolved in GBL to a concentration of 35% by mass. This solution was applied to a 4-inch silicon wafer by spin coating using a spinner 1H-DX (manufactured by Mikasa Co., Ltd.), and then baked on a hot plate at 120°C for 3 minutes to produce a resin film 4 to 5 μm thick. This wafer with the resin film was divided into two, and one was cured in a clean oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen stream (oxygen concentration 20 ppm or less) at 140°C for 30 minutes, then further heated to 320°C for 1 hour to completely close the imide ring. The transmission infrared absorption spectra of the resin film before and after curing were measured using an infrared spectrophotometer FT-720 (manufactured by Horiba, Ltd.), and the absorption peak (1,780 cm) of the imide structure due to polyimide was detected. －１ Near 1,377 cm －１ After confirming the existence of the 1,377 cm －１ The peak intensity ratio (before curing: S, after curing: T) near the peak intensity (S) was calculated by dividing the peak intensity (S) by the peak intensity (T) using the following formula, and this was taken as the content of imide groups in the polymer before heat treatment, i.e., the imide ring closure rate.

[0182] R ＩＭ (%)=(S / T)×100.

[0183] Resins other than polyimide (including polyamic acid ester) do not have polyimide structural units, and therefore the imide ring closure rate is not measurable and is indicated by "-".

[0184] (4) Evaluation of the Contents of the Compounds Represented by Formula (1) and Formula (2) Relative to Component (A) 0.03 g of component (A) obtained in each Synthesis Example, or 0.1 g of a solution of component (A) obtained in a Synthesis Example, and 0.01 g of methyl 3-nitrobenzoate as an internal standard were dissolved in 0.7 g of deuterated DMSO, and the solution was analyzed using an NMR system GX-270 (manufactured by JEOL Ltd.). Using the area of ​​the peak at around 3.9 ppm derived from methyl 3-nitrobenzoate as the standard, the contents [parts by mass] of the compounds represented by formula (1) and formula (2) relative to 100 parts by mass of component (A) were measured from the area of ​​each peak.

[0185] (5) Film Thickness Measurement Using a surface roughness and contour shape measuring instrument SURFCOM 1400D (manufactured by Tokyo Seimitsu Co., Ltd.), the film thickness was measured at a measurement magnification of 10,000 times, a measurement length of 1.0 mm, and a measurement speed of 0.30 mm / s.

[0186] (6) Sensitivity Evaluation The photosensitive resin compositions obtained in Examples 18 to 24 and Comparative Examples 4 and 5 were applied by spin coating onto a 100 mm x 100 mm ITO substrate using a spin coater MS-A100 (manufactured by Mikasa Co., Ltd.) by adjusting the rotation speed so that the thickness of the prebaked film would be approximately 1.8 μm. The substrate was then prebaked at 110°C for 120 seconds using a buzzer hot plate HPD-3000BZN (manufactured by AS ONE Corporation) to produce a prebaked film with a thickness of approximately 1.8 μm. The resulting prebaked film was exposed to ultraviolet light at 150 mJ / cm using a manual exposure machine MA-1200 (manufactured by Nippon Kaken Co., Ltd.) through a positive mask (manufactured by HOYA Corporation, stripe design line width 20 μm). ２ (value of i-line illuminometer) as the maximum exposure, and 5 mJ / cm ２ The exposure dose was reduced for each exposure, followed by development, rinsing, and drying to obtain a patterned substrate with a photosensitive resin film formed in a predetermined pattern. Using the patterned substrates with each exposure dose, sensitivity and development residue were evaluated. Development was performed using an AD-2000 compact automatic photolithography developing apparatus (manufactured by Takizawa Sangyo Co., Ltd.) by shower development using an alkaline developer of 2.38% by mass TMAH aqueous solution. The development time was adjusted as follows:

[0187] Positive photosensitive resin composition (Examples 18 to 21, Comparative Example 4): The developing time was adjusted so that the film thickness loss in the unexposed areas was 0.5 μm, and rinsing was performed with deionized water.

[0188] Negative-type photosensitive resin composition (Examples 22 to 24, Comparative Example 5): The prepared prebaked film was spray-developed with a 2.38 mass% TMAH aqueous solution using a compact photolithography developing device AD-2000 (manufactured by Takizawa Sangyo Co., Ltd.), and the time it took for the prebaked film (unexposed area) to completely dissolve (Breaking Point; hereinafter, B.P.) was measured. The developing time was set to 1.5 times the B.P., and rinsing was performed with deionized water.

[0189] The openings in the resulting developed film were observed using an FPD / LSI inspection microscope OPTIPHOT-300 (Nikon Corporation), and the minimum exposure dose at which the opening width became the same line width (20 μm) as the mask design was taken as the sensitivity. The sensitivity was determined as follows, and the sensitivity was 110 mJ / cm ２ A: Sensitivity is less than 80 mJ / cm. ２ B: Sensitivity is less than 80 mJ / cm ２ 95mJ / cm or more ２ C: Sensitivity is less than 95 mJ / cm ２ 110mJ / cm or more ２ D: Sensitivity is less than 110 mJ / cm ２ That's all.

[0190] (7) Chemical Resistance Evaluation The resin compositions obtained in each Example and Comparative Example were applied to an alkali-free glass plate OA-10 (manufactured by Nippon Electric Glass Co., Ltd.) by spin coating at an arbitrary rotation speed to obtain a resin film, which was then pre-baked on a hot plate at 120°C for 2 minutes as a drying process. The resin film-coated substrate was heated at 250°C for 1 hour in a nitrogen atmosphere using a high-temperature inert gas oven INH-9CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured film with a film thickness of 2.0 μm. The cured film was then immersed in Stripper 106 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 40°C for 5 minutes, and the film thickness before and after the treatment was measured to determine the amount of film loss due to the immersion treatment. The results were evaluated as follows, and A, B, and C, which indicate a film loss of less than 0.10 μm, were considered to be acceptable. A: The amount of film loss is less than 0.03 μm B: The amount of film loss is 0.03 μm or more and less than 0.06 μm C: The amount of film loss is 0.06 μm or more and less than 0.10 μm D: The amount of film loss is 0.10 μm or more (8) Evaluation of Planarization Property Figure 1 shows a cross section of a sample for evaluation of planarization property. The sample resin composition was applied by spin coating using a spin coater MS-A100 (manufactured by Mikasa Co., Ltd.) onto a 100 mm square stepped substrate 1 on which five parallel line patterns, each 1.2 μm thick (height), 5 μm wide, and 15 mm long, were patterned at 5 μm intervals in the central part of the substrate, and the substrate was prebaked at 110° C. for 120 seconds to produce a prebaked film so that the film thickness h0 at a flat part on the substrate on which the pattern was not formed, away from the pattern and not affected by the pattern (for convenience, the point where the measurement was performed is referred to as "measurement point A"), was 3.7 μm. Subsequently, the obtained substrate with the film was subjected to a curing process in which the temperature was raised to 250°C at a rate of 5°C / min in an oxygen concentration of 20 ppm or less using a high-temperature inert gas oven INH-9CD-S (manufactured by Koyo Thermo Systems Co., Ltd.), and the substrate was heated at 250°C for 1 hour, producing a cured film having a film thickness of approximately 2.5 μm at measurement point A. The surface step of the obtained cured film was measured using a Surface Profiler P-15 (manufactured by KLA Tencor Corporation), and the average value of heights h1 to h3 from the baseline 10 of the film present on the line patterns of three line patterns excluding the outermost two of the five line patterns was taken as the surface step h.The baseline 10 was defined as the line connecting the smallest film thicknesses of the recesses on the left and right of each mountain-like resin film portion where h1 to h3 were measured, as seen in Figure 1. A specific example is described below. In Figure 1, the baseline was the straight line connecting the bottoms a1 and a2 of the step shape, and h1 was defined as the length from the top b1 of the step shape to the intersection of a line drawn perpendicular to the substrate surface with the baseline. h2 was defined as the length from b2 to the intersection of a line drawn perpendicular to the substrate surface with the baseline, with the line connecting a2 and a3 being the baseline. h3 was defined as the length from b3 to the intersection of a line drawn perpendicular to the substrate surface with the baseline, with the line connecting a3 and a4 being the baseline. Planarization was evaluated based on the surface step height h as follows, with A, B, and C being considered acceptable, with a surface step height h of less than 0.4 μm. A was the most favorable result. A: The surface step h is less than 0.2 μm. B: The surface step h is 0.2 μm or more and less than 0.3 μm. C: The surface step h is 0.3 μm or more and less than 0.4 μm. D: The surface step h is 0.4 μm or more.

[0191] (9) Breaking Elongation Evaluation The resin compositions obtained in each example and comparative example were applied to an 8-inch silicon wafer by spin coating using an ACT-8 coating and developing apparatus so that the film thickness after pre-baking at 120 ° C for 3 minutes was 15 μm. After pre-baking, an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) was used to raise the temperature to 250 ° C at a rate of 4.0 ° C / min at an oxygen concentration of 20 ppm or less, and then heat-treated at 250 ° C for 1 hour. When the temperature reached 50 ° C or less, the silicon wafer was removed and immersed in 45% by mass hydrofluoric acid for 5 minutes to peel off the cured film of the resin composition from the wafer. This film was cut into strips 1 cm wide and 9 cm long, and using a Tensilon RTM-100 (manufactured by Orientec Co., Ltd.), it was stretched at a room temperature of 23.0 ° C, a humidity of 45.0% RH, and a tensile speed of 50 mm / min, and the breaking elongation was measured. Measurements were performed on 10 strips per specimen, and the top five results were averaged. The results were judged as follows, with AA, A, B, and C, which had breaking elongation values ​​of 15% or more, being considered pass. AA: Breaking elongation value of 60% or more A: Breaking elongation value of 45% or more but less than 60% B: Breaking elongation value of 30% or more but less than 45% C: Breaking elongation value of 15% or more but less than 30% D: Breaking elongation value less than 15%.

[0192] (10) Adhesion Test After Pressure Cooker Test (PCT) Treatment An adhesion test to a metal material was carried out by the following method.

[0193] A substrate (copper-sputtered substrate) having a metal material layer formed on its surface by copper sputtering on a silicon wafer to a thickness of 200 nm was prepared. The resin compositions obtained in each of the Examples and Comparative Examples were applied to the substrate in the same manner as in (9) and then subjected to a heat treatment to obtain a cured film.

[0194] The heat-treated film was cut into a grid of 10 rows and 10 columns at 2 mm intervals using a single-edged blade. Next, a pressure cooker test (PCT) was performed using a HAST CHAMBER EHS-212MD (manufactured by Espec Corporation) under saturated conditions of 121°C and 2 atmospheres for 400 and 800 hours. The number of squares that peeled out of 100 squares was counted using "Sellotape" (registered trademark), and the adhesion properties between the metal material and the cured resin film were evaluated. The peel test was evaluated as follows, with A, B, and C being graded as passing, with the number of peeled squares being less than 20. A: 0 peeled squares; B: 1 or more but less than 10; C: 11 or more but less than 20; D: 21 or more peeled squares.

[0195] (11) Evaluation of Light Emission Reliability of Organic EL Display Devices The organic EL display devices obtained in Examples 18 to 24 and Comparative Examples 4 and 5 were placed on a hot plate heated to 80°C with the display section (light emitting surface) facing up, and a current of 10 mA / cm ２ The pixel light-emitting area ratio (the area ratio of the light-emitting portion to the area of ​​the light-emitting pixel) was evaluated one hour after the device was driven by DC current at 400 V, and the power was then turned off. ２ The display was continuously irradiated with light of 10 ...

[0196] Synthesis Example 1: Synthesis of quinone diazide compound QD-a Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to reach room temperature. A solution of 15.18 g of triethylamine dissolved in 50 g of 1,4-dioxane was added dropwise to the system so that the temperature was 35°C or less. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The mixture was then filtered, and the precipitate was collected. This precipitate was dried in a vacuum dryer to obtain quinone diazide compound QD-a represented by formula (13).

[0197]

[0198] In formula (13), * represents the bonding site with the oxygen atom.

[0199] Synthesis Example 2: Synthesis of quinone diazide compound QD-b> A quinone diazide compound QD-b represented by formula (14) was obtained by the same method as in the synthesis example for quinone diazide compound QD-a, except that 36.27 g (0.135 mol) of 4-naphthoquinone diazide sulfonyl chloride was used instead of 36.27 g (0.135 mol) of 5-naphthoquinone diazide sulfonyl chloride.

[0200]

[0201] In formula (14), * represents the bonding site with the oxygen atom.

[0202] Synthesis Example 3: Synthesis of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (HA) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and the solution was cooled to −15°C. To this solution, a solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise. After completion of the dropwise addition, the mixture was stirred at −15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered and dried in vacuo at 50°C.

[0203] 30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, and 2.0 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated when it was confirmed that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound (HA) represented by the following formula:

[0204]

[0205] Synthesis Example 21: Synthesis of diamine (DAP-B) A 500 mL four-neck flask equipped with a stirrer, thermocouple, and dropping funnel was charged with 26.70 g (0.086 mol) of BisP-HTG (4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol, manufactured by Honshu Chemical Industry Co., Ltd.) and 100 mL of glacial acetic acid, and the mixture was stirred. The internal temperature was raised to 50°C in a water bath. To this was added 2 mL (0.026 mol) of concentrated nitric acid dropwise over 1 hour, followed by ice cooling to lower the internal temperature to 13°C, and then 13.3 mL (0.149 mol) of concentrated nitric acid was added dropwise over 1 hour. Stirring was continued for 3 hours, and the precipitated yellow crystals were filtered, washed successively with 40 mL of glacial acetic acid and 80 mL of deionized water, and dried under reduced pressure to obtain the dinitro form.

[0206] Next, 54.06 g (0.135 mol) of the dinitro compound, 180 mL (3.71 mol) of hydrazine monohydrate, and 900 mL of ethanol were placed in a 2 L four-neck flask equipped with a stirrer, thermocouple, Dimroth condenser, and dropping funnel, and the mixture was stirred under ice cooling. 0.9 g of 5% palladium-carbon (Wako Pure Chemical Industries, Ltd.) suspended in 30 mL of ethanol was added dropwise over 1 hour. The solution was then refluxed for 2 hours, and the palladium-carbon was removed by filtration while washing with 300 mL of ethanol. All of the solvent was removed by heating under reduced pressure, and the residue was washed with 75 mL of ice-cold ethanol, filtered, and then washed with 75 mL of deionized water and 150 mL of diethyl ether, followed by drying under reduced pressure, to obtain the diamine (DAP-B) represented by the following formula:

[0207]

[0208] Synthesis Example 22: Synthesis of diamine (HC) Diamine (HC) represented by the following formula was obtained in the same manner as in Synthesis Example 3, except that 17.0 g (0.05 mol) of DAP-B obtained in Synthesis Example 21 was used instead of BAHF.

[0209]

[0210] Synthesis Example 4: Synthesis of Polyimide (a-1) Under a dry nitrogen stream, 21.3 g (0.058 mol) of BAHF, 0.86 g (0.0034 mol) of SiDA, and 1.50 g (0.014 mol) of MAP as an end-capping agent were dissolved in 150 g of MPA. 21.4 g (0.069 mol) of ODPA was added to the solution along with 30 g of MPA, and the mixture was reacted at 60°C for 1 hour, followed by stirring at 180°C for 4 hours. After stirring, the solution was poured into 3 L of deionized water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with deionized water, and then dried in a vacuum dryer at 80°C for 20 hours to obtain a powder of polyimide (a-1).

[0211] Synthesis Example 5: Synthesis of Polyimide (a-2) Under a dry nitrogen stream, 19.6 g (0.054 mol) of BAHF, 3.95 g (0.015 mol) of BAP, and 1.67 g (0.015 mol) of MAP as an end-capping agent were dissolved in 150 g of MPA. To this solution, 18.98 g (0.061 mol) of TDA-100 and 4.74 g (0.015 mol) of ODPA were added along with 30 g of MPA, and the mixture was reacted at 60°C for 1 hour, followed by stirring at 180°C for 4 hours. After stirring, the solution was poured into 3 L of deionized water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with deionized water, and then dried in a vacuum dryer at 80°C for 20 hours to obtain a powder of polyimide (a-2).

[0212] Synthesis Example 18: Synthesis of polyimide (a-15) A powder of polyimide (a-15) was obtained in the same manner as in Synthesis Example 4, except that 19.8 g (0.058 mol) of the diamine (DAP-B) obtained in Synthesis Example 21 was used instead of 21.3 g (0.058 mol) of BAHF.

[0213] Synthesis Example 6: Synthesis of Polyamic Acid Ester (a-3) Under a dry nitrogen stream, 22.0 g (0.037 mol) of the hydroxyl-containing diamine (HA) obtained in Synthesis Example 3 and 0.54 g (0.0022 mol) of SiDA were dissolved in 100 g of MPA. To this solution, 13.4 g (0.043 mol) of ODPA was added along with 20 g of MPA, and the mixture was stirred at 40°C for 2 hours. Then, 0.95 g (0.0087 mol) of MAP was added as an end-capping agent along with 20 g of MPA, and the mixture was allowed to react at 40°C for 1 hour. Subsequently, a solution prepared by diluting 10.3 g (0.087 mol) of DMFDMA with 10 g of MPA was added dropwise. After the dropwise addition, stirring was continued for 2 hours at 40°C. After stirring, the solution was poured into 2 L of deionized water, and the polymer solid precipitate was collected by filtration. The polymer solid was then washed three times with 2 L of deionized water and dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyamic acid ester (a-3), which is a form of polyimide.

[0214] Synthesis Example 7: Synthesis of polyamic acid ester (a-4) A polyamic acid ester (a-4), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 6, except that the solution was added to 3 L of deionized water, the precipitate of polymer solid was collected by filtration, and the precipitate was further washed six times with 3 L of deionized water.

[0215] Synthesis Example 8: Synthesis of Polyamic Acid Ester (a-5) 24.8 g (0.080 mol) of ODPA was placed in a 2-liter separable flask, and 20.8 g (0.16 mol) of HEMA and 310 g of MPA were added. 12.7 g (0.16 mol) of pyridine was added with stirring at room temperature to obtain a reaction mixture (ODPA-HEMA). After the heat generated by the reaction had ceased, the mixture was allowed to cool to room temperature and then allowed to stand for a further 16 hours.

[0216] Next, under ice cooling, a solution of 28.9 g (0.14 mol) of DCC in 180 g of MPA was added to the reaction mixture over 40 minutes with stirring. Subsequently, a suspension of 82.2 g (0.14 mol) of HA and 1.99 g (0.008 mol) of SiDA in 230 g of MPA was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 24.8 g (0.080 mol) of ODPA was added, and stirring was continued at room temperature for 3 hours. Then, 3.49 g (0.032 mol) of MAP was added, and stirring was continued at room temperature for 1 hour. The precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction solution.

[0217] The reaction solution was poured into 3 L of deionized water to obtain a white precipitate, which was collected by filtration, washed twice with deionized water, washed once with isopropanol, and then dried in a vacuum dryer at 50°C for 72 hours to obtain polyamic acid ester (a-5), which is a form of polyimide.

[0218] Synthesis Example 9: Synthesis of Polyamic Acid Ester (a-6) Polyamic acid ester (a-6), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 6, except that DMIB was used instead of MPA.

[0219] Synthesis Example 10: Synthesis of Polyamic Acid Ester (a-7) Polyamic acid ester (a-7), which is one form of polyimide, was obtained in the same manner as in Synthesis Example 6, except that DMPA was used instead of MPA.

[0220] Synthesis Example 11: Synthesis of Polyamic Acid (a-8) Under a dry nitrogen stream, 22.0 g (0.037 mol) of the hydroxyl group-containing diamine (HA) obtained in Synthesis Example 3 and 0.54 g (0.0022 mol) of SiDA were dissolved in 100 g of MPA. To this solution, 13.4 g (0.043 mol) of ODPA was added along with 20 g of MPA, and the mixture was stirred at 40°C for 2 hours. Then, 0.95 g (0.0087 mol) of MAP was added as an end-capping agent along with 20 g of MPA, and the mixture was stirred at 60°C for 2 hours. After stirring, the solution was poured into 2 L of deionized water, and the precipitated polymer solid was collected by filtration. The mixture was further washed three times with 2 L of deionized water, and the collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours to obtain polyamic acid (a-8), a form of polyimide.

[0221] Synthesis Example 12: Synthesis of polyamic acid ester (a-9) Polyamic acid ester (a-9), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 6, except that NMP was used instead of MPA.

[0222] Synthesis Example 13: Synthesis of polyamic acid ester (a-10) Polyamic acid ester (a-10), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 6, except that GBL was used instead of MPA.

[0223] Synthesis Example 19: Synthesis of polyamic acid ester (a-16) Polyamic acid ester (a-16), which is one form of polyimide, was obtained in the same manner as in Synthesis Example 6, except that 21.2 g (0.037 mol) of the diamine (HC) obtained in Synthesis Example 22 was used instead of 22.0 g (0.037 mol) of the hydroxyl group-containing diamine (HA).

[0224] Synthesis Example 20: Synthesis of polyamic acid ester (a-17) Polyamic acid ester (a-17), which is one form of polyimide, was obtained in the same manner as in Synthesis Example 7, except that 21.2 g (0.037 mol) of the diamine (HC) obtained in Synthesis Example 22 was used instead of 22.0 g (0.037 mol) of the hydroxyl group-containing diamine (HA).

[0225] Synthesis Example 14: Synthesis of Polyhydroxyamide (a-11) Under a dry nitrogen stream, 33.0 g (0.090 mol) of BAHF was dissolved in 115 g of MPA. To this was added 4.43 g (0.027 mol) of NAOH along with 15 g of MPA, and the mixture was stirred at 85°C for 2 hours. After stirring, the solution was cooled to -15°C. To this was added a solution of 22.6 g (0.077 mol) of OBBOC dissolved in 50 g of MPA, with the internal temperature not exceeding 0°C. After the dropwise addition, stirring was continued for 60 minutes at -15°C, followed by 120 minutes of stirring at room temperature. After the reaction was complete, the solution was poured into 2 L of deionized water, and the white precipitate was collected. The precipitate was collected by filtration, washed three times with deionized water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain polyhydroxyamide (a-11), which is a type of polybenzoxazole resin.

[0226] Synthesis Example 15: Synthesis of Polyhydroxyamide (a-12) Under a dry nitrogen stream, 29.2 g (0.80 mol) of BAHF and 3.07 g (0.028 mol) of OAP were dissolved in 120 g of MPA, and the solution was cooled to −15°C. A solution of 27.7 g (0.094 mol) of OBBOC dissolved in 60 g of MPA was added dropwise thereto so that the internal temperature did not exceed 0°C. After the dropwise addition, stirring was continued for 60 minutes at −15°C, and then at room temperature for 120 minutes. After the reaction was completed, the solution was poured into 3 L of deionized water, and a white precipitate was collected. The precipitate was collected by filtration, washed three times with deionized water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain polyhydroxyamide (a-12), a form of polybenzoxazole resin.

[0227] Synthesis Example 16: Synthesis of Polyhydroxyamide (a-13) Under a dry nitrogen stream, 28.7 g (0.11 mol) of BAP was dissolved in 100 g of MPA, and the solution was cooled to -15°C. To this solution, a solution of 27.9 g (0.094 mol) of OBBOC dissolved in 50 g of MPA was added dropwise so that the internal temperature did not exceed 0°C. After the addition was complete, stirring was continued for 30 minutes at -15°C. Next, a solution of 3.48 g (0.033 mol) of MAOC dissolved in 30 g of MPA was added dropwise so that the internal temperature did not exceed 0°C. After the addition was complete, stirring was continued for 60 minutes at -15°C, and then for 120 minutes at room temperature. After the reaction was complete, the solution was poured into 3 L of deionized water, and the white precipitate was collected. The precipitate was collected by filtration, washed three times with deionized water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain polyhydroxyamide (a-13), which is a type of polybenzoxazole resin.

[0228] Synthesis Example 17: Synthesis of Phenolic Resin (a-14) Phenolic resin (a-14) of Synthesis Example 17 was synthesized by the method described in Synthesis Example 5 in paragraph

[0120] of WO 2012 / 141165.

[0229] Table 1 shows the measurement results of the constituent components (molar ratio), molecular weight (Mw), esterification rate [%], and the content [parts by mass] of the compounds represented by formula (1) and formula (2) for Synthesis Examples 4 to 16 and 18 to 20.

[0230]

[0231] Example 1 Under yellow light, 4.20 g of polyimide resin (a-1) as component (A), 0.840 g of HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.; a compound represented by the following formula (15)) as component (I) serving as a crosslinking agent, and 0.004 g of BYK-302 (manufactured by BYK Japan KK) as surfactant (K) were added to 28.6 g of a mixed solvent containing PGME and ethyl lactate as component (D) and dihydrolevoglucosenone (product name: Silene, manufactured by Sigma-Aldrich) as component (B) in a mass ratio of 45:45:10, and the mixture was stirred for 30 minutes to dissolve the components, yielding a homogeneous solution with a solid content of 15.0% by mass.

[0232]

[0233] The resulting solution was then filtered through a 0.45 μmφ filter to obtain Resin Composition 1 shown in Table 2-1. Next, using the resulting Resin Composition 1, various measurements and evaluations were performed using the methods (7) to (10) described above, and the results are shown in Table 3-1. [Examples 2 to 17, 25 to 29 and Comparative Examples 1 to 3] Resin compositions 2 to 17, 25 to 27, and 30 to 34 and cured films were produced in the same manner as in Example 1, except that resin compositions were prepared according to the formulations shown in Tables 2-1 to 2-3. In Example 3, levoglucosenon manufactured by Tokyo Chemical Industry Co., Ltd. was used. The evaluation results are summarized in Tables 3-1 to 3-2.

[0234] [Example 18] Under yellow light, 29.5 g of a mixed solvent containing PGME and ethyl lactate as the component (D) and dihydrolevoglucosenone (product name: Shiren, manufactured by Sigma-Aldrich) as the component (B) in a mass ratio of 35:35:30 was added to 4.20 g of polyimide resin (A-1) as the component (A), 0.504 g of QD-a and 0.504 g of a photoacid generator as the component (E) which is a photosensitizer. QD-b, 0.420 g of BPAF as component (J) serving as a dissolution promoter, 0.840 g of HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.; a compound represented by formula (15)) as crosslinking agent (I), and 0.005 g of BYK-333 (manufactured by BYK Japan KK) as component (K) serving as a surfactant were added, and the mixture was stirred for 30 minutes to dissolve the components, yielding a homogeneous solution with a solid content of 18.0% by mass.

[0235] Thereafter, the obtained solution was filtered through a 0.45 μmφ filter to obtain a positive-type photosensitive resin composition 18 shown in Table 2-2. Next, using the positive-type photosensitive resin composition 18, various measurements and evaluations were carried out by the methods (6) to (10) above, and the results are shown in Table 3-1.

[0236] Next, a patterned cured film-formed substrate having a cured film obtained by curing the positive photosensitive composition 18, and an organic EL display device for evaluating light-emitting reliability having the patterned cured film as a pixel dividing layer were produced by the following methods.

[0237] FIG. 2 shows a manufacturing process of an organic EL display device, including a process of forming a pixel dividing layer.

[0238] A 10-nm-thick thin film of silver / copper alloy (volume ratio 10:1) was formed on the entire surface of an alkali-free glass substrate (3) (a square measuring 46 mm wide x 46 mm long) by sputtering, followed by etching to form a patterned metal reflective layer (4). Next, a 10-nm-thick ITO transparent conductive film was formed on the entire surface by sputtering, followed by etching to form a second electrode (5) and an auxiliary electrode (6) as an extraction electrode, both of the same pattern. The substrate was then ultrasonically cleaned for 10 minutes with "Semicoclean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.) and washed with deionized water to obtain an electrode-formed substrate.

[0239] The surface of the electrode-formed substrate was coated with the positive photosensitive composition 18 using a spin coater, adjusting the rotation speed so that the final thickness of the pixel division layer would be 2.0 μm, to obtain a coating film. Next, the coating film was prebaked at 120° C. under atmospheric pressure for 120 seconds using a hot plate (HPD-3000BZN manufactured by AS ONE Corporation) to obtain a prebaked film.

[0240] A positive exposure mask with openings (rectangles measuring 30 μm wide and 165 μm long) arranged at a pitch of 50 μm was set on the coating film so that the vertical and horizontal edges of the patterned light-shielding portion of the positive exposure mask were parallel to the vertical and horizontal edges of the alkali-free glass substrate (3), respectively. Using a manual exposure machine MA-1200 (manufactured by Dai Nippon Scientific Research Institute Co., Ltd.), the prebaked film was pattern-irradiated with exposure light using a mixture of j-line (313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) from an ultra-high pressure mercury lamp at the minimum required exposure dose, thereby obtaining an exposed film. The positive exposure mask was then developed and rinsed to obtain a developed film. The positive exposure mask used was a mask with a patterned light-shielding portion made of chromium formed on the surface of a soda glass substrate.

[0241] Furthermore, the developed film was subjected to a heat treatment (curing) to form a cured film, and a patterned cured film (7) having a thickness of 2.0 μm and having openings (rectangles measuring 30 μm wide x 165 μm high) arranged at a pitch of 50 μm within a 16 mm long x 16 mm wide area in the center of the electrode-forming substrate was obtained, resulting in a patterned cured film-formed substrate with an aperture ratio of 18%. The curing was carried out using a high-temperature inert gas oven INH-9CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) under conditions of an oxygen concentration of 20 ppm or less, heating to 250°C at a rate of 5°C / min, and heat treatment at 250°C for 1 hour. In the organic EL display device obtained after the process described below, the openings referred to here are the portions that will ultimately become the light-emitting pixel portions, and the patterned cured film is the portion corresponding to the pixel dividing layer.

[0242] Next, an organic EL display device was produced using the substrate on which the patterned cured film was formed. －３ The patterned cured film-formed substrate was rotated relative to the evaporation source under evaporation conditions of 0.1 Pa or less, and first, a 10 nm thick film of compound HT-1 was formed as a hole injection layer, and a 50 nm thick film of compound HT-2 was formed as a hole transport layer. Next, compound GH-1 as a host material and compound GD-1 as a dopant material were evaporated onto the light-emitting layer to a thickness of 40 nm. Thereafter, compound ET-1 and compound LiQ were laminated as electron transport materials at a volume ratio of 1:1 to a thickness of 40 nm.

[0243] Next, the compound LiQ was vapor-deposited to a thickness of 2 nm, and then a silver / magnesium alloy (volume ratio 10 / 1) was vapor-deposited to a thickness of 10 nm to form a first electrode (9).

[0244] The chemical structures of the compounds (HT-1, HT-2, GH-1, GD-1, ET-1, and LiQ) used to form the organic EL layer are shown below.

[0245]

[0246] The thickness referred to here is the value displayed on a quartz crystal oscillation type film thickness monitor.

[0247] Thereafter, a cap-shaped glass plate was attached and sealed using an epoxy resin adhesive under a low humidity / nitrogen atmosphere to obtain an organic EL display device. The light emission reliability of the organic EL display device was evaluated using the method described in (11) above, and the results are also shown in Table 3-1.

[0248] [Examples 19 to 21, 30 to 35 and Comparative Example 4] Positive photosensitive resin compositions 19 to 21, 28, 35 to 40, cured films, and organic EL display devices were produced in the same manner as in Example 18, except that positive photosensitive compositions were prepared according to the formulations shown in Tables 2-2 and 2-3. The evaluation results are summarized in Tables 3-1 and 3-2.

[0249] [Example 22] Under yellow light, 28.4 g of a mixed solvent containing PGME and ethyl lactate as the component (D) and dihydrolevoglucosenone (product name: Silene, manufactured by Sigma-Aldrich) as the component (B) in a mass ratio of 35:35:30 was added to 4.20 g of polyimide resin (A-1) as the component (A), 0.204 g of IN-a, a photopolymerization initiator, and 0.204 g of a radical polymerizable compound ( 1.680 g of 4G as component (F), 0.084 g of MW-390 (manufactured by Sanwa Chemical Co., Ltd.) as component (I) serving as a crosslinking agent, 0.060 g of KBM-303 (manufactured by Shin-Etsu Chemical Co., Ltd.) as other additives, and 0.005 g of BYK-302 (manufactured by BYK Japan KK) as component (K) serving as a surfactant were added, and the mixture was stirred for 30 minutes to dissolve, thereby obtaining a uniform solution with a solid content of 18.0 mass %.

[0250] Thereafter, the obtained solution was filtered through a 0.45 μmφ filter to obtain a negative-type photosensitive resin composition 22 shown in Table 2-2. Next, using the negative-type photosensitive resin composition 22, various measurements and evaluations were carried out by the methods (6) to (10) above, and the results are shown in Table 3-1.

[0251] Next, a cured film and an organic EL display device were produced in the same manner as in Example 18, except that the negative photosensitive resin composition 22 was used and a negative exposure mask was used. The results of evaluation by the method (11) above are also shown in Table 3-1.

[0252] [Examples 23 and 24 and Comparative Example 5] Negative photosensitive resin compositions 23, 24, and 29, cured films, and organic EL display devices were produced in the same manner as in Example 22, except that negative photosensitive resin compositions were prepared according to the compositions shown in Tables 2-2 and 2-3. The evaluation results are summarized in Tables 3-1 and 3-2.

[0253]

[0254]

[0255]

[0256] The components listed in Tables 2-1 to 2-3 above are as follows.

[0257] (A) Component (a-1), (a-2), (a-15): The above-mentioned polyimide resin (a-3) to (a-7), (a-9), (a-10), (a-16), (a-17): The above-mentioned polyamic acid ester resin (a-8): The above-mentioned polyamic acid (a-11) to (a-13): The above-mentioned polyhydroxyamide (a-14): The above-mentioned phenolic resin (B) Component (b-1): Dihydrolevoglucosenone (product name: Silene, manufactured by Sigma-Aldrich) (b-2): Levoglucosenone (manufactured by Tokyo Chemical Industry Co., Ltd.) (C) Component (c-1): MPA (compound represented by formula (1)) (c-2): DMIB (compound represented by formula (2)) (c-3): DMPA (compound represented by formula (2)) (D) Component (d-1): PGME (a compound having a hydroxyl group and a boiling point of 120°C at atmospheric pressure) (d-2): ethyl lactate (a compound having a hydroxyl group and a boiling point of 154°C at atmospheric pressure) Component (E) (e-1): QD-a (a compound described in Synthesis Example 1) (e-2): QD-b (a compound described in Synthesis Example 2) (e-3): NCI-930 (manufactured by ADEKA Corporation) (e-4): bis(η ５(2,4-chloropentadien-1-yl)-bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium (IV) (manufactured by Tokyo Chemical Industry Co., Ltd.) component (F) (f-1): NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.) component (G) (g-1): GBL (a compound having no hydroxyl groups and a boiling point of 204°C at atmospheric pressure) (g-2): CHN (a compound having no hydroxyl groups and a boiling point of 156°C at atmospheric pressure) component (H) (h-1): BPAF (manufactured by Tokyo Chemical Industry Co., Ltd.) component (I) (i-1): HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) (i-2): MW-390 (manufactured by Sanwa Chemical Co., Ltd.) component (J) (j-1): BYK-302 (manufactured by BYK Japan Co., Ltd.) (K) component (k-1): KBM-303 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0258]

[0259]

[0260] The above results show that the resin compositions of the examples have excellent planarization properties, elongation at break, and chemical resistance, and also have excellent adhesion to metal materials. Comparative Examples 1 and 2, which did not contain component (B), resulted in poor planarization properties. Comparative Example 3, which did not contain component (A), resulted in poor elongation at break, chemical resistance, and adhesion to metal materials.

[0261] The resin composition of the present invention is suitable for use in bank layers of organic EL display devices, planarizing layers of TFT substrates for driving organic EL display devices, and insulating films and protective films constituting electronic components, including active components having semiconductors such as transistors, diodes, integrated circuits (ICs), and memories, as well as passive components such as resistors, capacitors, and inductors.

[0262] The cured film of the present invention is suitable for use as a bank layer in an organic EL display device, a planarizing layer in a TFT substrate for driving an organic EL display device, or an insulating film or protective film constituting an electronic component, such as an active component having a semiconductor, such as a transistor, a diode, an integrated circuit (IC), or a memory, or a passive component, such as a resistor, a capacitor, or an inductor.

[0263] 1: Stepped substrate 2: Cured film 3: Alkali-free glass substrate 4: Metal reflective layer 5: Second electrode 6: Auxiliary electrode 7: Patterned cured film 8: Organic EL layer 9: First electrode 10: Baseline

Claims

1. A resin composition comprising component (A), which is one or more resins selected from the group consisting of polyimide resins (A1), polybenzoxazole resins (A2), and copolymer resins (A3) consisting of structural units of polyimide resins and structural units of polybenzoxazole resins, and component (B), which is levoglucosenone and / or dihydrolevoglucosenone.

2. The resin composition according to claim 1, further comprising component (D), which is a compound having a hydroxyl group and a boiling point at atmospheric pressure of 100°C or higher and 200°C or lower.

3. The resin composition according to claim 2, wherein the ratio X / Z, where X is the mass of the component (B) contained in the resin composition and Z is the mass of the component (D), is 0.01 or more and 10 or less.

4. The resin composition according to claim 1 or 2, further comprising a component (C) which is a compound represented by formula (1) and / or a compound represented by formula (2). In formula (1), R １ , R ２ and R ３ are each independently an alkyl group having 1 to 6 carbon atoms. ４ and R ５ are each independently an alkyl group having 1 to 6 carbon atoms. ６ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

5. The resin composition according to claim 4, wherein the ratio X / Y, where X is the mass of the component (B) and Y is the mass of the component (C), is 1 or more and 1,000 or less.

6. The resin composition according to claim 1 or 2, further comprising a component (E) which is a photosensitizer.

7. The resin composition according to claim 6, wherein the component (E) comprises a component (E1) which is a photopolymerization initiator and / or a component (E2) which is a photoacid generator.

8. The resin composition according to claim 7, wherein the component (E1) comprises a component (E1-1) which is an oxime ester type photopolymerization initiator and / or a component (E1-2) which is a titanocene type photopolymerization initiator.

9. The resin composition according to claim 8, further comprising a component (F) which is a radically polymerizable compound.

10. The resin composition according to claim 1 or 2, wherein the component (A) comprises a polyimide resin (A1) and / or a copolymer resin (A3) of a structural unit of a polyimide resin and a structural unit of a polybenzoxazole resin, and the component (A) comprises a structural unit represented by formula (3). In formula (3), X １ represents a tetravalent organic group having 2 to 40 carbon atoms, which has any one of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 40 carbon atoms. １ R represents a divalent organic group having 2 to 40 carbon atoms, which has any one of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 40 carbon atoms. ７ and R ８ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having an ethylenically unsaturated double bond. * indicates a bonding site.

11. Y in the formula (3) １ The resin composition according to claim 10, wherein is a divalent organic group represented by formula (4) or formula (5). In formula (4) and formula (5), X ２ and X ３ each independently represents a direct bond, —SO ２ It represents -, -O-, or a divalent organic group having 1 to 20 carbon atoms. * represents a bonding point that bonds to an amide structure, an imide structure, an amic acid ester structure, or an amic acid structure.

12. The above X ２ and X ３ The resin composition according to claim 11, wherein each of the groups is independently a divalent organic group having 1 to 20 carbon atoms and not containing a fluorine atom.

13. A cured film obtained by curing the resin composition according to claim 1 or 2.

14. An electronic component comprising the cured film according to claim 13.

15. An organic EL display device comprising the cured film according to claim 13.

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