WO2024111466A1

WO2024111466A1 - Photosensitive resin composition, cured product, organic el display device, electronic component, and semiconductor device

Info

Publication number: WO2024111466A1
Application number: PCT/JP2023/040893
Authority: WO
Inventors: 昭典佐伯; 聡亀本
Original assignee: 東レ株式会社
Priority date: 2022-11-25
Filing date: 2023-11-14
Publication date: 2024-05-30

Abstract

The purpose of the present invention is to provide a photosensitive resin composition that has suitable sensitivity, results in little residue after development, and yields a cured product having suitable light emission characteristics even after a reliability test.　This photosensitive resin composition includes a resin (A), a photosensitizer (B), and a compound (C) that is a compound represented by formula (1) and/or a compound represented by formula (2). In formula (1) and formula (2), R¹ and R² each independently represent a monovalent saturated hydrocarbon group having 1-10 carbon atoms. In formula (2), R³, R⁴, and R⁵ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1-10 carbon atoms. R⁶ and R⁷ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1-10 carbon atoms, or a monovalent hydroxyalkyl group having 1-10 carbon atoms. a represents 0 or 1.

Description

Photosensitive resin composition, cured product, organic EL display device, electronic component, and semiconductor device

The present invention relates to a photosensitive resin composition, a cured product, an organic electroluminescence display device, an electronic component, and a semiconductor device.

Polyimide resins have excellent heat resistance, electrical insulation, and mechanical properties, and are therefore widely used in applications such as pixel dividing layers in organic electroluminescence (EL) display devices and interlayer insulating films in semiconductors.

Generally, an organic EL display device has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposing first and second electrodes or by passing a current between them. Of these, photosensitive resin compositions that can be patterned by ultraviolet irradiation and that produce a cured product with good chemical resistance after curing are generally used as the materials for the planarization layer and the insulating layer.

On the other hand, the demand for higher reliability for organic EL display devices is becoming stricter every year, and materials that can maintain high light-emitting properties even after reliability tests under accelerated conditions such as light exposure are required for planarization layer materials and insulating layer materials.

Photosensitive resin compositions using polyimide-based or polybenzoxazole-based resins are preferably used because they have high heat resistance and generate little gaseous components from the cured product, making them capable of producing highly reliable organic EL display devices (see, for example, Patent Document 1). In addition, for example, photosensitive resin compositions containing phenolic compounds with specific structures have been proposed for the purpose of improving reliability and chemical resistance (see, for example, Patent Document 2).

JP 2002-91343 A International Publication No. 2019/065351

As mentioned above, the demand for high reliability of organic EL display devices is becoming stricter every year. For example, when the photosensitive resin composition described in Patent Document 1 is used as a material for a planarizing layer and an insulating layer, there is an issue that the light-emitting characteristics cannot be maintained after a reliability test under accelerated conditions such as light irradiation.

In addition, the technology of Patent Document 2, which contains a phenolic compound with a specific structure, provides good luminescence reliability and chemical resistance, but has issues such as slightly low sensitivity and a tendency to leave residues during patterning.

The present invention aims to provide a photosensitive resin composition that has good sensitivity, leaves little residue after development, and has good luminescence properties even after a reliability test when cured, as well as an organic EL display device, electronic component, and semiconductor device that include a cured product of the photosensitive resin composition.

In order to solve the above problems and achieve the above objectives, the present invention has the following configuration.

[1] A photosensitive resin composition comprising a resin (A), a photosensitizer (B), and a compound (C) which is a compound represented by formula (1) and/or a compound represented by formula (2).

In formula (1) and formula (2), R ¹ and R ² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. In formula (2), R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. R ⁶ and R ⁷ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent hydroxyalkyl group having 1 to 10 carbon atoms. a represents 0 or 1.

[2] The photosensitive resin composition according to [1], in which the total content of the compound (C) is 1 to 3,000 parts by mass per 100 parts by mass of the total amount of the resin (A).

[3] The photosensitive resin composition according to [1] or [2], wherein the compound (C) includes at least one selected from the group consisting of formulas (19) to (22).

[4] The photosensitive resin composition according to any one of [1] to [3], further comprising a compound (D) that has a boiling point at atmospheric pressure of 100°C or more and 170°C or less and does not fall under any of the resin (A), the photosensitizer (B), and the compound (C).

[5] The photosensitive resin composition according to [4], wherein the compound (D) includes a compound (D1) having a hydroxyl group.

[6] The photosensitive resin composition according to [4], wherein the ratio X/Y of the mass X of the compound (C) contained in the photosensitive resin composition to the mass Y of the compound (D) is 0.01 to 10.

[7] The photosensitive resin composition according to any one of [1] to [6], wherein the resin (A) contains an alkali-soluble resin (A1).

[8] The photosensitive resin composition according to [7], wherein the alkali-soluble resin (A1) contains one or more resins selected from the group consisting of polyimide resin (A1-1), polybenzoxazole resin (A1-2), and copolymer resin (A1-3) of repeating units of polyimide resin and repeating units of polybenzoxazole resin.

[9] The photosensitive resin composition according to [8], wherein one or more resins selected from the group consisting of the polyimide resin (A1-1), the polybenzoxazole resin (A1-2), and the copolymer resin (A1-3) contain a residue of a diamine represented by formula (10) and/or a residue of a diamine represented by formula (11).

In the formula, X ³ and X ⁴ each independently represent a direct bond, —SO ₂ —, —C(CH ₃ ) ₂ —, a divalent organic group represented by formula (12), —CH(CF ₃ )—, or —C(CF ₃ ) ₂ —.

In formula (12), * indicates a bond point.

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the photosensitizer (B) contains a photoacid generator (B1).

[11] The photosensitive resin composition according to any one of [1] to [10], further comprising a blackening agent (F).

[12] A cured product obtained by curing the photosensitive resin composition described in any one of [1] to [11].

[13] A cured product containing a resin (A) and containing a compound represented by formula (1) and/or a compound (C) represented by formula (2) in a total amount of 0.00001% by mass or more and 0.01% by mass or less relative to 100% by mass of the cured product.

[14] An organic electroluminescence display device comprising the cured product described in [12] or [13].

[15] An electronic component or semiconductor device comprising the cured product described in [12] or [13].

The present invention provides a photosensitive resin composition that has good sensitivity, produces little residue after development, and has good luminescence properties even after a reliability test when cured, as well as an organic EL display device, electronic component, and semiconductor device that include the cured product of the photosensitive resin composition.

1A to 1C are schematic diagrams illustrating a method for producing an organic EL display device having a pixel division layer in an example.

The present invention will be described in detail below.

In this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as the lower and upper limits.

Visible light refers to light with wavelengths in the range of 380 nm to less than 780 nm, and near-infrared light refers to light with wavelengths in the range of 780 nm to 1,000 nm.

Light-blocking properties refer to the ability to reduce the intensity of transmitted light compared to the intensity of light incident perpendicularly to the cured product.

In this specification, unless otherwise specified, the alkaline developer refers to an organic alkaline aqueous solution.

The photosensitive resin composition of the present invention contains a resin (A). Examples of the resin (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 alkaline developers.

Among these, from the viewpoint of reducing the environmental load, it is preferable that the resin (A) contains an alkali-soluble resin (A1) and the photosensitive resin composition can be developed using an alkali developer. The alkali-soluble resin referred to here means a resin whose dissolution rate is 50 nm/min or more, calculated from the decrease in film thickness when a solution of the resin dissolved in γ-butyrolactone is applied onto a silicon wafer and prebaked at 120°C for 4 minutes to form a prebaked film with a film thickness of 10 μm±0.5 μm, the prebaked film is immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23±1°C for 1 minute, and then rinsed with deionized water. The alkali dissolution rate of the alkali-soluble resin (A1) 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 obtained pattern.

Examples of the alkali-soluble resin (A1) include polyimide resins, polybenzoxazole resins, polyamideimide resins, polyamide resins, polymers containing radically polymerizable monomers, polysiloxane resins, cardo resins, phenolic resins, acrylic resins, and copolymers thereof. Two or more types of the alkali-soluble resins (A1) may be used in combination.

Among the above-mentioned alkali-soluble resins (A1), those that have excellent heat resistance, a small amount of outgassing at high temperatures, and excellent film properties such as chemical resistance are preferred. Specifically, it is preferred to include one or more resins selected from the group consisting of polyimide resins (A1-1), polybenzoxazole resins (A1-2), and copolymer resins (A1-3) of polyimide repeating units and polybenzoxazole repeating units.

When the total amount of the alkali-soluble resin (A1) contained in the photosensitive resin composition of the present invention is taken as 100 mass %, it is preferable that the composition contains a total of 50 mass % or more of one or more resins selected from the group consisting of the polyimide resin (A1-1), the polybenzoxazole resin (A1-2), and the copolymer resin (A1-3).

It is preferable that the alkali-soluble resin (A1) contains the polyimide resin (A1-1) and/or the copolymer resin (A1-3), and that the polyimide resin (A1-1) and/or the copolymer resin (A1-3) contains a residue of an acid dianhydride represented by any one of formulas (3) to (6).

^X1 in formula (5) represents a divalent organic group represented by any one of formulas (7) to (9).

In formula (8), ^X2 represents a direct bond or an oxygen atom. * represents a bonding point.

The polyimide resin (A1-1) and/or the copolymer resin (A1-3) contain the acid dianhydride residue, which improves the transmittance of the resin to ultraviolet rays such as i-line, thereby enabling the photosensitive resin composition to have a high sensitivity. In addition, the acid dianhydride residue represented by any one of formulas (3) to (6) suppresses intermolecular packing of the polyimide resin (A1-1) and the copolymer resin (A1-3), improves the solvent solubility and alkali solubility of the resin, and effectively suppresses the residue after development. The content of the acid dianhydride residue represented by any one of formulas (3) to (6) is preferably 30 mol% to 100 mol%, more preferably 45 mol% to 100 mol%, and particularly preferably 55 mol% to 100 mol%, based on the total amount of the acid dianhydride residues in the polyimide resin (A1-1) and the copolymer resin (A1-3) (100 mol%).

The polyimide resin (A1-1) and the copolymer resin (A1-3) may contain, in addition to the above-mentioned acid dianhydride residues, acid dianhydride residues derived from the following acid dianhydrides:

Specific examples of the other acid dianhydride residues include:
Residues of alicyclic tetracarboxylic dianhydrides such as 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentane acetic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, and 3,5,6-tricarboxy-2-norbornane acetic 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, residues of aromatic tetracarboxylic dianhydrides such as 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, and 3,4,9,10-perylenetetracarboxylic dianhydride;
Bis(3,4-dicarboxyphenyl)sulfone dianhydride, 4,4'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride, 2,2-bis(3-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride Examples of the aromatic acid dianhydride include residues of aromatic acid dianhydrides such as fluoropropane dianhydride, 2,2-bis(3-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, or compounds in which the aromatic rings of these compounds are substituted with alkyl groups or halogen atoms, and acid dianhydrides having an amide group. Two or more of these may be contained in combination.

It is preferable that one or more resins selected from the group consisting of the polyimide resin (A1-1), the polybenzoxazole resin (A1-2), and the copolymer resin (A1-3) contain a residue of a diamine represented by formula (10) and/or a residue of a diamine represented by formula (11).

In formulas (10) and (11), X ³ and X ⁴ represent a direct bond, —SO ₂ —, —C(CH ₃ ) ₂ —, a divalent organic group represented by formula (12), —CH(CF ₃ )—, or —C(CF ₃ ) ₂ —.

In formula (12), * indicates a bond point.

Since both of the diamine residues represented by formula (10) and formula (11) have a phenolic hydroxyl group, they can impart solubility in an alkaline developer and reduce development residues. In addition, when the diamine residue represented by formula (10) or formula (11) contains a structure of -C( _CF3 ) _2- , -C( _CH3 ) _2- , a divalent organic group represented by formula (12), or -CH( _CF3 )-, intermolecular packing is suppressed and solvent solubility can be improved, which is preferable.

When the total amount of all diamine residues contained in the polyimide resin (A1-1), the polybenzoxazole resin (A1-2), and the copolymer resin (A1-3) is taken as 100 mol%, the total content of the diamine residues represented by formula (10) and the diamine residues represented by formula (11) is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, and even more preferably 50 to 100 mol%.

Specific examples of diamine residues represented by formula (10) or formula (11) include residues of diamines such as 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (HA), 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane (HB), 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]-1,1,1-trifluoroethane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), bis(3-amino-4-hydroxyphenyl)sulfone, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (AZ-FDA), 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), and 1,1,1-trifluoro-2,2-bis(3-amino-4-hydroxyphenyl)ethane (BIS-AP-EF). Among these, from the viewpoint of solubility in an alkaline developer, it is preferable to contain one or more residues selected from the group consisting of BAHF, BAP, AZ-FDA, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane (HB), and 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (HA).

The polyimide resin (A1-1), the polybenzoxazole resin (A1-2), and the copolymer resin (A1-3) may also have other diamine residues in addition to the diamine residues described above.

Specific examples of the other diamine residues include aliphatic diamine residues and aromatic diamine residues. An aliphatic diamine residue means a residue of a diamine that does not have an aromatic ring. Examples of aliphatic diamine residues include residues of aliphatic alkyl diamines containing alkylene ether groups such as alkylene groups, polyethylene ether groups, polyoxypropylene groups, and tetramethylene ether groups, alicyclic diamines, and aliphatic diamines having a siloxane structure.

Examples of the aliphatic alkylenediamine residue include
Polymethylenediamines: tetramethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine,
Diamines containing polyethylene ether groups, such as Jeffamine KH-511, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, Jeffamine EDR-148, and Jeffamine EDR-176;
Polyoxypropylene diamines D-200, D-400, D-2000, D-4000, RP-409, RP-2009,
Tetramethylene ether group-containing diamines RT-1000 and HT-1100, and amino group-containing alkylene ether diamines HT-1000 and HE-1000 (all trade names, manufactured by HUNTSMAN Co., Ltd.)
Residues such as:

Examples of alicyclic diamine residues include residues of cyclohexyldiamine and methylenebiscyclohexylamine. Examples of aliphatic diamine residues having a siloxane structure include residues of bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.

In addition, when an aliphatic group having a siloxane structure is copolymerized to the extent that the heat resistance is not reduced, the adhesion to the substrate can be improved.

Other examples of aromatic diamine residues include:
Hydroxyl group-containing diamine residues such as 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, 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;
Sulfonic acid-containing diamine residues such as 3-sulfonic acid-4,4'-diaminodiphenyl ether,
thiol group-containing diamine residues such as dimercaptophenylenediamine;
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 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 residues of aromatic diamines such as (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-4,4'-diaminobiphenyl, and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl;
Examples of the diamine residues include those obtained by substituting a portion of the hydrogen atoms of these aromatic rings with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, or the like. These diamine residues can be used as they are, or as the corresponding diisocyanate compound or trimethylsilylated diamine. These can be used alone or in combination of two or more.

The polybenzoxazole resin (A1-2) and the copolymer resin (A1-3) preferably have a dicarboxylic acid residue and a bisaminophenol residue. The dicarboxylic acid residue here 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.

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, 2-fluoroterephthalic acid, 2-methoxyterephthalic acid, 2-phenoxyterephthalic acid, etc. These compounds may be used alone or in combination of two or more.

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, bis(3-amino-4-hydroxyphenyl)propane, 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)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene, etc. These compounds may be used alone or in combination of two or more.

The polyimide resin (A1-1), the polybenzoxazole resin (A1-2), and the copolymer resin (A1-3) may be end-capped with an end-capping agent such as a monoamine, an acid anhydride, a monoacid chloride, a monocarboxylic acid, or a monoactive ester. By capping the ends of the resin with an end-capping agent, the dissolution rate of the resin in an alkaline aqueous solution can be easily adjusted to a preferred range. Among these, it is preferable to use an end-capping agent having a phenolic hydroxyl group or a crosslinkable group. By using an end-capping agent having a phenolic hydroxyl group, the resin is made alkaline soluble, making it possible to reduce residues. In addition, by using an end-capping agent having a crosslinkable group, a crosslinking reaction proceeds during the heat curing process, making it possible to obtain a cured product with excellent chemical resistance.

Specific examples of the monoamines mentioned above that have 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, 3-aminophenol, and 4-aminophenol. In addition, examples of those having a photocrosslinkable group include 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-aminostyrene, 3-aminostyrene, and 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, and 4-aminobenzenesulfonic acid. Two or more of these may be used.

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. Those having a photocrosslinkable group include maleic anhydride, nadic anhydride, maleic acid, itaconic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, etc. 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, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and benzoic acid. In addition, for the above monocarboxylic acids, monoacid chloride compounds in which the carboxyl groups of these are converted to acid chlorides may be used, monoacid chloride compounds in which only one of the carboxyl groups of the above dicarboxylic acids is converted to acid chlorides may be used, and active 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 be used.

Also, multiple different end groups may be introduced by reacting multiple end-capping agents.

When a monoamine is used as the end-capping agent, the 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 (A1-1), the polybenzoxazole resin (A1-2), and the copolymer resin (A1-3). By setting the introduction ratio of the monoamine to preferably 1 mol% or more, more preferably 5 mol% or more, it is possible to effectively reduce the residue after development. Furthermore, by setting the introduction ratio of the monoamine to preferably 60 mol% or less, more preferably 50 mol% or less, it is possible to maintain a high molecular weight of the resin and maintain high chemical resistance and mechanical strength.

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 (A1-1), the polybenzoxazole resin (A1-2) and the copolymer resin (A1-3). 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 mechanical strength can be maintained.

Total amine compounds here refers to the total content of compounds that have amino groups, such as monoamines, diamines, and triamines.

The weight average molecular weight of the polyimide resin (A1-1), the polybenzoxazole resin (A1-2), and the copolymer resin (A1-3) is preferably 3,000 to 100,000 in terms of polystyrene by gel permeation chromatography. By making the weight average molecular weight 100,000 or less, more preferably 80,000 or less, and even more preferably 60,000 or less, good solvent solubility and good solubility in a developer can be effectively obtained. Furthermore, by making the weight average molecular weight 3,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more, high mechanical strength can be effectively obtained. In the present invention, the weight average molecular weight is determined by the method described below.

The polyimide resin (A1-1) may be, for example, a reaction product obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, or a tetracarboxylic diester dichloride with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine. These reaction products may also be dehydrated and cyclized by heating or by reaction with an acid or a base. Thus, a preferred embodiment of the polyimide resin (A1-1) has a tetracarboxylic acid and/or a derivative residue thereof, and a diamine and/or a derivative residue thereof.

The polyimide resin (A1-1) preferably has one or more repeating units selected from the group consisting of repeating units represented by formula (13), repeating units represented by formula (14), and repeating units represented by formula (15).

In formulae (13), (14) and (15), ^R8 represents an acid dianhydride residue, ^R9 represents a diamine residue, and ^R10 each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. * represents a bonding point.

The repeating unit represented by formula (13) represents a repeating unit in which all of the amic acid structures or amic acid ester structures in the repeating unit have been cyclically closed and imidized. Formula (14) represents a repeating unit in which some of the amic acid structures or amic acid ester structures in the repeating unit have been cyclically closed and imidized, with some remaining as amic acid structures or amic acid ester structures. Formula (15) represents a repeating unit in which none of the amic acid structures or amic acid ester structures in the repeating unit have been cyclically closed and all remain as amic acid structures or amic acid ester structures.

In the polyimide resin (A1-1), the number of repeating units represented by formula (13), the number of repeating units represented by formula (14), and the number of repeating units represented by formula (15) are p, q, and r, respectively, where p, q, and r are integers of 0 or more.

The imide ring closure rate of the polyimide resin (A1-1) is preferably 2% or more, more preferably 5% or more, and even more preferably 10% or more. An imide ring closure rate of 2% or more is preferable because it improves the dispersion stability when mixed with a pigment dispersion liquid, and it is possible to reduce the amount of outgassing at high temperatures, thereby improving the reliability of organic EL display devices.

The imide ring closure rate of polyimide resin (A1-1) can be determined by the method described below.

In formulas (14) and (15), the monovalent organic group having 1 to 20 carbon atoms in R ¹⁰ can be a monovalent hydrocarbon group having 1 to 20 carbon atoms. Examples of the monovalent hydrocarbon group include an alkyl group having 1 to 20 carbon atoms. 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. In order to reduce the generation of residues in the photosensitive composition, it is preferable that each R ¹⁰ is independently any one of a hydrogen atom, a methyl group, and an ethyl group.

The polyimide resin (A1-1) may also be a copolymer having one or more repeating units selected from the group consisting of repeating units represented by formula (13), repeating units represented by formula (14), and repeating units represented by formula (15), and a repeating unit other than the repeating units represented by formula (13), repeating units represented by formula (14), and repeating units represented by formula (15). When a copolymer is used, it is preferable to use a copolymer with a repeating unit of polybenzoxazole described below.

A preferred embodiment of the polybenzoxazole resin (A1-2) is, for example, one that can be obtained by reacting a bisaminophenol compound with a dicarboxylic acid or the 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 dehydrated and ring-closed by heating or by reaction with an acid, a base, acetic anhydride, a carbodiimide compound, or the like.

The polybenzoxazole resin (A1-2) preferably has one or more repeating units selected from the group consisting of repeating units represented by formula (16), repeating units represented by formula (17), and repeating units represented by formula (18).

In formula (16), formula (17) and formula (18), ^R11 represents a dicarboxylic acid residue, and ^R12 represents a bisaminophenol residue. The dicarboxylic acid residue is a structure obtained by removing two carboxyl groups from a dicarboxylic acid compound. The bisaminophenol residue is a structure obtained by removing two amino groups and two hydroxyl groups from a bisaminophenol compound.

The repeating unit represented by formula (16) represents a repeating unit in which all of the hydroxyamide structures in the repeating unit have been ring-closed to form oxazole. Formula (17) represents a repeating unit in which some of the hydroxyamide structures in the repeating unit have been ring-closed to form oxazole, with some remaining as hydroxyamide structures. Formula (18) represents a repeating unit in which the hydroxyamide structures in the repeating unit have not been ring-closed, and all remain as hydroxyamide structures.

In the polybenzoxazole resin (A1-2), the number of repeating units represented by formula (16), the number of repeating units represented by formula (17), and the number of repeating units represented by formula (18) are s, t, and u, respectively, where s, t, and u are integers of 0 or more.

The oxazole ring closure rate of the polybenzoxazole resin (A1-2) is preferably 0% or more and 95% or less, more preferably 0% or more and 85% or less, and even more preferably 0% or more and 75% or less. By having the oxazole ring closure rate within the above range, it is possible to improve the dispersion stability when mixed with a pigment dispersion liquid and reduce residues after development.

The oxazole ring closure rate of the polybenzoxazole resin (A1-2) is determined by the following method.

<Oxazole ring closure rate ( _ROX (%))>
Polybenzoxazole resin is dissolved in γ-butyrolactone (GBL) to a concentration of 35% by mass. This solution is 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 with a thickness of 4 to 5 μm. This wafer with the resin film is divided into two, and one of the two is cured in a clean oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.) at 140°C for 30 minutes under a nitrogen stream (oxygen concentration 20 ppm or less), and then further heated to 370°C for 1 hour to completely close the oxazole ring. The infrared transmission absorption spectra of the resin film before and after curing are measured using an infrared spectrophotometer (FT-720, manufactured by Horiba, Ltd.), and the intensities of the absorption peaks (near 1,050 cm ^-1 ) due to the C-O stretching vibration of oxazole (before curing: U, after curing: W) are determined. The peak intensity ratio is calculated by dividing the peak intensity (U) by the peak intensity (W), and the content of oxazole groups in the polymer before heat treatment, i.e., the oxazole ring closure rate, is determined.
R _OX (%) = (U/W) × 100.

The polybenzoxazole resin (A1-2) may be a copolymer having one or more repeating units selected from the group consisting of repeating units represented by formula (16), repeating units represented by formula (17), and repeating units represented by formula (18), and a repeating unit other than the repeating units represented by formula (16), repeating units represented by formula (17), and repeating units represented by formula (18). When a copolymer is used, it is preferable to use a copolymer with the repeating unit of the polyimide described above.

The copolymer resin (A1-3) can be obtained, for example, as a random copolymer by reacting the raw materials for the polyimide resin (A1-1) and the raw materials for the polybenzoxazole resin (A1-2) at once, or as a block copolymer having polyimide repeating units and polybenzoxazole repeating units by synthesizing the polyimide repeating units and the polybenzoxazole repeating units separately and then reacting the respective repeating units.

The copolymer resin (A1-3) preferably has both, for example, one or more repeating units of polyimide selected from the group consisting of repeating units represented by formula (13), repeating units represented by formula (14), and repeating units represented by formula (15), and one or more repeating units of polybenzoxazole selected from the group consisting of repeating units represented by formula (16), repeating units represented by formula (17), and repeating units represented by formula (18).

The resin (A) can be synthesized by a known method. Below, examples of the synthesis methods for the polyimide resin (A1-1), the polybenzoxazole resin (A1-2), and the copolymer resin (A1-3) are described.

The polyimide resin (A1-1) 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. The resin obtained by the above method may also be dehydrated and ring-closed by heating or chemical treatment with an acid or base.

The polybenzoxazole resin (A1-2) can be produced, for example, by a condensation reaction of a bisaminophenol compound with a dicarboxylic acid in a polymerization solvent. Specifically, a method of reacting a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and then adding a bisaminophenol compound to the reaction, or a method of dripping a solution of a dicarboxylic acid dichloride into a solution of a bisaminophenol compound to which a tertiary amine such as pyridine has been added, can be used.

The copolymer resin (A1-3) can be synthesized, for example, by combining the synthesis method of the polyimide resin (A1-1) and the synthesis method of the polybenzoxazole resin (A1-2).

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

The polymerization solvent is not particularly limited as long as it can dissolve the raw material monomers such as acid dianhydrides and diamines. For example, amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, and N,N'-dimethylpropyleneurea (DMPU), cyclic compounds such as γ-butyrolactone (GBL), γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone, and cyclic compounds such as γ-butyrolactone, γ-butyrolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone are usable. Examples include esters, 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, and dihydrolevoglucosenone (Cyrene, manufactured by Circa), etc.

The amount of the polymerization solvent used is preferably 100 to 1900 parts by mass, and more preferably 150 to 950 parts by mass, per 100 parts by mass of the resin (A).

The photosensitive resin composition of the present invention contains a photosensitizer (B). Examples of the photosensitizer (B) include a photoacid generator (B1) and a photopolymerization initiator (B2). By containing the photoacid generator (B1), an acid is generated in the light-irradiated portion, increasing the solubility of the light-irradiated portion in an alkaline aqueous solution, and a positive-type relief pattern in which the light-irradiated portion is dissolved can be obtained. In addition, by containing the photoacid generator (B1) and the crosslinking agent (I), the acid generated in the light-irradiated portion promotes the crosslinking reaction of the crosslinking agent (I), and a negative-type relief pattern in which the light-irradiated portion is insolubilized can be obtained. In addition, by containing the photopolymerization initiator (B2) and the radical polymerizable compound (H), the active radical generated in the light-irradiated portion advances the radical polymerization of the ethylenically unsaturated bond in the radical polymerizable compound, and a negative-type relief pattern in which the light-irradiated portion is insolubilized can be obtained. In the photosensitive resin composition of the present invention, it is preferable that the photosensitizer (B) contains the photoacid generator (B1) and exhibits positive photosensitivity. The photosensitizer (B) contains the photoacid generator (B1) and exhibits positive photosensitivity, which makes it easier to reduce variation in the opening dimensions of the pattern due to the processing process.

Examples of the photoacid generator (B1) include quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts.

The quinone diazide compound may be 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, or a polyhydroxy polyamino compound to which a sulfonic acid of quinone diazide is bonded via an ester bond and/or a sulfonamide bond. It is preferable that 50 mol % or more of the total functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinone diazide. It is also preferable that the compound contains two or more types of the photoacid generator (B1), which allows a highly sensitive photosensitive resin composition to be obtained.

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. In addition, 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.

Among the photoacid generators (B1), sulfonium salts, phosphonium salts, and diazonium salts are preferred because they adequately stabilize the acid component generated by exposure to light. Among these, sulfonium salts are preferred.

Specific examples of the photopolymerization initiator (B2) include the photopolymerization initiators described in paragraphs [0223] to [0276] of WO 2019/087985. Among them, it is preferable to include an oxime ester-based photopolymerization initiator from the viewpoint of achieving high sensitivity. Two or more of these may be included.

The content of the photosensitizer (B) is preferably 0.01 to 50 parts by mass per 100 parts by mass of the resin (A).

From the viewpoint of increasing sensitivity, the content of the photoacid generator (B1) in the photosensitizer (B) is preferably 0.01 to 50 parts by mass per 100 parts by mass of the resin (A). Of these, the content of the quinone diazide compound is preferably 3 to 40 parts by mass. In addition, the total amount of the sulfonium salt, phosphonium salt, and diazonium salt is preferably 0.5 to 20 parts by mass.

The content of the photopolymerization initiator (B2) in the photosensitizer (B) is preferably 0.1 to 20 parts by mass per 100 parts by mass of the resin (A). If it is 0.1 part by mass or more, sufficient radicals are generated by light irradiation, improving sensitivity. Also, if it is 20 parts by mass or less, there is no hardening of the unexposed parts due to the generation of excessive radicals, improving alkaline developability.

The photosensitive resin composition of the present invention contains compound (C), which is a compound represented by formula (1) and/or a compound represented by formula (2).

The compound represented by formula (1) is a levulinic acid alkyl ester, and the compound represented by formula (2) is a compound in which the carbonyl group of the levulinic acid alkyl ester is ketalized using a diol, triol, or tetraol compound. These compounds may be added as additives when preparing a photosensitive resin composition, or may be used as a solvent for the photosensitive resin composition. When the photosensitive resin composition contains the compound (C), it is possible to reduce residue after development, increase the sensitivity of the photosensitive resin composition, and improve the reliability of the cured product obtained by curing the photosensitive resin composition. Although the detailed mechanism is unknown, the principle by which the above effect is obtained is presumed as follows. For example, as described in International Publication No. 2019/065351, etc., highly polar and high boiling point solvents such as gamma-butyrolactone (GBL) are often used in photosensitive resin compositions for the purpose of improving coatability. A highly polar, high boiling point solvent such as GBL has the advantage of being highly soluble in solvents such as resins and slow drying, making it difficult for uneven coating to occur, while it has the disadvantage of being easily increased in development residue and easily reduced sensitivity due to its strong interaction with photosensitizers, which inhibits the interaction between the resin and the photosensitizer. In addition, a highly polar, high boiling point solvent such as GBL strongly interacts with resins, so that even after curing, a large amount of solvent remains in the cured product, and there is a concern that the remaining solvent becomes a source of gas generation and reduces the reliability of organic EL display devices and the like. In contrast, the compound (C) has good solubility in resins and additives, and has a weak interaction with resins and photosensitizers compared to highly polar, high boiling point solvents such as GBL, so it is difficult to inhibit the interaction between the resin and the photosensitizer, and it is thought that it is possible to reduce residue after development and increase sensitivity. In addition, since the compound (C) has a weak interaction with resins, it is thought that it is difficult to volatilize from the cured product during heat curing and remain in the cured product. As a result, it is possible to reduce gas generation from the cured product obtained after heat curing, and it is thought that it is possible to improve the reliability of organic EL display devices and the like. In addition, the inclusion of the compound (C) in the photosensitive resin composition makes it possible to improve the breaking elongation and crack resistance of the cured product, making it possible to obtain highly reliable electronic components or semiconductor devices. The mechanism by which the breaking elongation and crack resistance of the cured product are improved by including the compound (C) is believed to be that the compound (C) has good solubility in the resin and crosslinking agent and a moderate boiling point, which promotes the crosslinking reaction between the crosslinking agent and the resin during the heat curing process, resulting in a cured product with high crosslink density.

In addition, as described below, when the photosensitive resin composition of the present invention further contains a black agent (F) and the black agent (F) is a black pigment (F1), it is preferable to use the compound (C) as a dispersion medium because the storage stability of the black pigment dispersion obtained can be improved and the particle size of the black pigment (F1) can be made finer. Although the detailed mechanism is unclear, the compound (C) has a weaker interaction with the resin than a high-boiling point, highly polar solvent such as GBL. Therefore, when the compound (C) is used as a dispersion medium, the resin used as a dispersant is efficiently adsorbed to the surface of the black pigment (F1), and a steric repulsion effect is easily obtained, so that the dispersion stability of the black pigment (F1) is easily obtained and the particle size of the black pigment (F1) can be made finer.

The content of the compound (C) is preferably 1 to 3000 parts by mass, more preferably 20 to 2000 parts by mass, and even more preferably 50 to 1000 parts by mass, per 100 parts by mass of the total amount of the resin (A). By being within the above range, it becomes easier to obtain the effects of reducing development residues, increasing sensitivity, increasing reliability, improving the storage stability of the black pigment dispersion, and reducing the particle size of the black pigment (F1).

The content of the compound (C) is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, and even more preferably 3 to 45% by mass, relative to 100% by mass of the total amount of the photosensitive resin composition. By having the content of the compound (C) in the photosensitive resin composition within the above range, it becomes possible to control the amount of the compound (C) contained in the cured product obtained by curing the photosensitive resin composition within a preferred range. As a result, when used in an organic EL display device, it becomes possible to improve reliability.

Specific examples of the compound (C) include methyl levulinate, ethyl levulinate, propyl levulinate, butyl levulinate, pentyl levulinate, hexyl levulinate, heptyl levulinate, octyl levulinate, nonyl levulinate, and ketalized compounds obtained by reacting these compounds with polyhydric alcohol compounds such as propylene glycol and glycerin. Among these, the photosensitive resin composition of the present invention preferably contains at least one selected from the group consisting of formulas (19) to (22) as a specific example of the compound (C), and more preferably contains a compound represented by formula (19) and/or a compound represented by formula (20).

The photosensitive resin composition of the present invention preferably further contains a compound (D) that has a boiling point at atmospheric pressure of 100°C or more and 170°C or less and does not fall under any of the resin (A), the photosensitizer (B), and the compound (C). By containing the compound (D), the developability is improved and the occurrence of development residues can be suppressed.

It is more preferable that the compound (D) contains a compound (D1) having a hydroxyl group. This is because the inclusion of the compound (D1) provides a higher effect of reducing development residues.

Specific examples of the compound (D) that does not have a hydroxyl group include propylene glycol monomethyl ether acetate (boiling point 146°C), ethylene glycol monomethyl ether acetate (boiling point 145°C), and diethylene glycol dimethyl ether (boiling point 162°C).

Specific examples of compounds (D1) having a hydroxyl group include propylene glycol monomethyl ether (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), and diacetone alcohol (boiling point 166°C).

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

Furthermore, the ratio X/Y of the mass X of the compound (C) contained in the photosensitive resin composition of the present invention to the mass Y of the compound (D) is preferably 0.01 to 10, more preferably 0.05 to 5, and even more preferably 0.1 to 2. By having the ratio X/Y within the above range, the developability can be adjusted to a particularly preferred range, and the generation of development residues can be suppressed.

The photosensitive resin composition of the present invention preferably contains a solvent (E) other than the compound (C) and the compound (D). Examples of the solvent (E) 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 ethanol, isopropanol, 3-methyl-2-butanol, and 3-methyl-3-methoxybutanol;
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, and diacetone alcohol;
Polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, and dihydrolevoglucosenone (Cyrene, manufactured by Circa),
and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained.

The content of the solvent (E) is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and is preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less, per 100 parts by mass of the resin (A).

The photosensitive resin composition of the present invention preferably further contains a black agent (F). The black agent (F) refers to a compound that absorbs light of a visible light wavelength to color it black. Since an organic EL display device has a self-emitting element, when external light such as sunlight is incident outdoors, the visibility and contrast may be reduced due to the reflection of the external light. Therefore, a technology to reduce the reflection of external light may be required. Therefore, by including the black agent (F), the cured product of the photosensitive resin composition becomes black, and the light shielding property of shielding light that passes through the cured product of the photosensitive resin composition or light reflected from the cured product of the photosensitive resin composition can be improved. Therefore, it is suitable for applications such as a pixel division layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a thin film transistor (hereinafter, "TFT") planarization layer, an electrode planarization layer, a wiring planarization layer, a TFT protective layer, an electrode protective layer, a wiring protective layer, a gate insulating layer, a color filter, a black matrix, or a black column spacer. In particular, it is preferable as a light-shielding pixel division layer, electrode insulating layer, wiring insulating layer, interlayer insulating layer, TFT planarization layer, electrode planarization layer, wiring planarization layer, TFT protective layer, electrode protective layer, wiring protective layer, or gate insulating layer for an organic EL display device, and is suitable for applications requiring high contrast by suppressing external light reflection, such as a light-shielding pixel division layer, interlayer insulating layer, TFT planarization layer, or TFT protective layer.

Specific examples of the black agent (F) include those described in paragraphs [0281] to [0344] of International Publication No. 2019/087985. Among these, it is preferable to include a black pigment (F1) from the viewpoint of high shielding properties, high weather resistance, high chemical resistance, and resistance to fading when heated. In addition, among the black pigments (F1), it is preferable to use an organic black pigment (F1-1) from the viewpoint of excellent insulation properties and low dielectric properties. In particular, when used as an insulating layer such as a pixel division layer of an organic EL display device, a TFT planarization layer, or a TFT protective layer, it is possible to suppress light emission defects and improve reliability. In addition, among the organic black pigments (F1-1), from the viewpoints of improving sensitivity during exposure, reducing taper by controlling the pattern shape after development, suppressing changes in the pattern opening dimensional width before and after thermal curing, and improving halftone characteristics, it is preferable that the organic black pigment (F1-1) is one or more selected from the group consisting of benzofuranone-based black pigments, perylene-based black pigments, dioxazine-based black pigments, and azo-based black pigments, and benzofuranone-based black pigments are more preferable. By containing one or more selected from the group consisting of benzofuranone-based black pigments, perylene-based black pigments, dioxazine-based black pigments, and azo-based black pigments, the cured product of the photosensitive resin composition is blackened and has excellent hiding properties, so that the light-shielding properties of the cured product of the photosensitive resin composition can be improved. In particular, compared to general organic black pigments, the light-shielding properties per unit content ratio of the black pigment in the photosensitive resin composition are excellent, so that the same light-shielding properties can be imparted with a small content ratio. Therefore, the light-shielding properties of the cured product can be improved, and the sensitivity during exposure can be improved.

The organic black pigment (F1-1) may also contain a coating layer as described in paragraphs [0345] to [0359] of WO 2019/087985.

The content of the blackening agent (F) is preferably 10 to 200 parts by mass per 100 parts by mass of the resin (A).

The photosensitive resin composition of the present invention preferably contains a dispersant (G), particularly when the photosensitive resin composition contains a black pigment (F1) as the black agent (F). The dispersant (G) refers to a compound having a surface affinity group that interacts with the surface of the pigment and a dispersion stabilizing structure that improves the dispersion stability of the pigment. Examples of the dispersion stabilizing structure of the dispersant (G) include a polymer chain and/or a substituent having an electrostatic charge. Specific examples of dispersants that can be used include the dispersants described in [0371] to [0385] of WO 2019/087985. Among these, from the viewpoint of improving dispersion stability and improving resolution after development, the basic group or the structure in which the basic group forms a salt preferably has a tertiary amino group, a quaternary ammonium salt structure, or a nitrogen-containing ring skeleton such as a pyrrole skeleton, an imidazole skeleton, a pyrazole skeleton, a pyridine skeleton, a pyridazine skeleton, a pyrimidine skeleton, a pyrazine skeleton, a triazine skeleton, an isocyanuric acid skeleton, an imidazolidinone skeleton, a propylene urea skeleton, a butylene urea skeleton, a hydantoin skeleton, a barbituric acid skeleton, an alloxane skeleton, or a glycoluril skeleton.

When black pigment (F1) is contained as black agent (F), the content ratio of dispersant (G) in the photosensitive resin composition of the present invention is preferably 1 mass% or more relative to 100 mass% of the total amount of black pigment (F1) and dispersant (G). When the content ratio is 1 mass% or more, the dispersion stability of the black agent (F) can be improved, and the resolution after development can be improved. On the other hand, the content ratio of dispersant (G) is preferably 60 mass% or less. When the content ratio is 60 mass% or less, the heat resistance of the cured product can be improved.

The photosensitive resin composition of the present invention may further contain a radically polymerizable compound (H), and the photosensitizer (B) may contain a photopolymerization initiator (B2). By adopting such a configuration, as described above, the active radicals generated in the light-irradiated area promote radical polymerization of the ethylenically unsaturated bonds in the radically polymerizable compound, and a negative relief pattern can be obtained in which the light-irradiated area is insolubilized. As a result, the photosensitive resin composition becomes a negative-type photosensitive resin composition.

Specific examples of the radical polymerizable compound (H) include the radical polymerizable compounds described in paragraphs [0189] to [0222] of WO 2019/087985. Among these, it is preferable to contain a flexible chain-containing aliphatic radical polymerizable compound. A flexible chain-containing aliphatic radical polymerizable compound refers to a compound having multiple ethylenically unsaturated double bond groups and a flexible skeleton such as an aliphatic chain or an oxyalkylene chain in the molecule.

By including the flexible chain-containing aliphatic radical polymerizable compound, the curing reaction during light irradiation proceeds efficiently, and the sensitivity during light irradiation can be improved. In addition, when a black pigment (F1) is included as the black agent (F), the black pigment (F1) is fixed to the cured portion by crosslinking during UV curing of the flexible chain-containing aliphatic radical polymerizable compound, and the generation of residues after development originating from the black pigment (F1) can be suppressed. In addition, the change in the pattern opening dimensional width before and after thermal curing can be suppressed. The content of the radical polymerizable compound (H) is preferably 5 to 50 parts by mass per 100 parts by mass of the resin (A).

The photosensitive resin composition of the present invention preferably contains a crosslinking agent (I). The crosslinking agent (I) refers to a compound having a crosslinkable group capable of bonding with a resin. By including the crosslinking agent (I), the hardness and chemical resistance of the cured product can be improved. This is presumably because the crosslinking agent (I) can introduce a new crosslinking structure into the cured product of the photosensitive resin composition, thereby improving the crosslinking density.

In addition, by including the crosslinking agent (I), it becomes possible to form a pattern with a low taper shape after thermal curing. This is thought to be because the crosslinking agent (I) forms a crosslinked structure between the polymers, which inhibits the dense orientation of the polymer chains and maintains the reflowability of the pattern during thermal curing, making it possible to form a pattern with a low taper shape. As the crosslinking agent (I), a compound having two or more thermal crosslinkable groups in the molecule, such as an alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group, is preferred.

Specific examples of the crosslinking agent (I) that can be used include the crosslinking agents described in paragraphs [0407] to [0412] of WO 2019/087985.

The content of the crosslinking agent (I) is preferably 0.5 to 50 parts by mass per 100 parts by mass of the resin (A). If the content is 0.5 parts by mass or more, the hardness and chemical resistance of the cured product can be improved, and a pattern with a low taper shape can be formed after thermal curing. If the content is 50 parts by mass or less, the hardness and chemical resistance of the cured product can be improved, and a pattern with a low taper shape can be formed after thermal curing.

The photosensitive resin composition of the present invention may be a positive-type photosensitive resin composition further comprising a dissolution promoter (J), and the photosensitizer (B) may comprise a photoacid generator (B1). The dissolution promoter (J) supplements the alkaline developability of the photosensitive resin composition, and can improve the sensitivity in the positive-type photosensitive resin composition. The dissolution promoter (J) is preferably a compound having a phenolic hydroxyl group, and examples of the compound include Bis-z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-Pz, BisP-IPZ, BisC RIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP4HBPA (TetrakisP-DO-BPA), TrisPHAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCRPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, B Examples of compounds having a phenolic hydroxyl group include IR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOCF, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Chemicals Co., Ltd.), 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.

The content of the dissolution promoter (J) is preferably 1 to 40 parts by mass per 100 parts by mass of the resin (A).

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

The content ratio of the surfactant (K) in the photosensitive resin composition of the present invention is preferably 0.001 mass% or more of the entire photosensitive resin composition, and more preferably 0.005 mass% or more. When the content ratio is 0.001 mass% or more, the leveling property during application can be improved. On the other hand, the content ratio of the surfactant is preferably 1 mass% or less, and more preferably 0.5 mass% or less. When the content ratio is 1 mass% or less, defects occurring during application can be reduced.

The photosensitive resin composition of the present invention may contain additives (L) other than those described above. Examples of the additive (L) include the polyfunctional thiol compounds described in [0386] to [0398] of WO 2019/087985, the sensitizers described in [0399] to [0402] of WO 2019/087985, the polymerization inhibitors described in [0403] to [0406] of WO 2019/087985, the silane coupling agents described in [0413] to [0418] of WO 2019/087985, the surfactants described in [0419] to [0420] of WO 2019/087985, and the inorganic particles described in [0127] to [0130] of WO 2016/052268 and [0024] to [0025] of WO 2019/167461.

The photosensitive resin composition of the present invention can be produced, for example, by placing the resin (A), photosensitizer (B), compound (C), and other components, as well as other components as necessary, in a glass flask or stainless steel container, and stirring and dissolving them with a mechanical stirrer, dissolving them with ultrasonic waves, or stirring and dissolving them with a planetary stirring and degassing device.

The obtained photosensitive 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 (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., with polyethylene and nylon being preferred. When inorganic particles or pigments are contained in the photosensitive resin composition, it is preferable to use a leak filter with a pore size larger than these.

The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention. Examples of methods for curing the photosensitive resin composition include a method of curing the photosensitive resin composition by heating it, and a method of irradiating it with active actinic rays. By curing the photosensitive resin composition of the present invention, the heat resistance and chemical resistance of the cured product can be improved. The cured product is preferably in the form of a film, i.e., a cured film.

Next, we will explain the method for producing the cured product of the present invention.

The method for producing a cured product of the present invention preferably includes the following steps.
(1) applying the above-mentioned photosensitive resin composition onto a substrate to form a photosensitive resin film;
(2) drying the photosensitive resin film;
(3) exposing the dried photosensitive resin film through a photomask;
(4) a step of developing the exposed photosensitive resin film; and (5) a step of heat treating the developed photosensitive resin film.

In the above step (1), the photosensitive resin composition of the present invention is applied to a substrate by a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, or the like to obtain a photosensitive resin film of the photosensitive resin composition. Prior to application, the substrate to which the photosensitive resin composition is applied may be pretreated with an adhesion improver. For example, a method of treating the substrate surface using a solution in which the adhesion improver is dissolved at 0.5 to 20 mass % 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. Methods for treating the substrate surface 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 International Publication No. 2019/065351.

In the above step (2), the applied photosensitive resin film is dried under reduced pressure as necessary, and then heat-treated at 50°C to 180°C for one minute to several hours using a hot plate, oven, infrared, etc. to obtain a photosensitive resin film.

In the above step (3), the photosensitive resin film is irradiated with chemical radiation through a photomask having a desired pattern. Examples of chemical radiation used for exposure include ultraviolet light, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. After exposure to chemical radiation, post-exposure baking may be performed. By performing post-exposure baking, effects such as improved resolution after development or an increased tolerance range for development conditions can be expected. For post-exposure baking, an oven, a hot plate, infrared rays, a flash annealing device, or a laser annealing device can be used. 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. If the post-exposure baking time is within the above range, the reaction may proceed well and the development time may be shortened.

In the above step (4), the exposed photosensitive resin film is developed using a developer to remove a portion of the photosensitive resin film. The developer is preferably an aqueous solution of an alkaline compound such as tetramethylammonium hydroxide (TMAH), diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine. In some cases, polar solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone (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 to these aqueous alkaline solutions, either alone or in combination. Development methods that can be used include spray, paddle, immersion, and ultrasonic methods.

Next, it is preferable to rinse the pattern formed by development 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.

Next, the above step (5) is carried out. Residual solvents and components with low heat resistance can be removed by the heat treatment, so that heat resistance and chemical resistance can be improved. When the photosensitive resin composition of the present invention contains a polyimide resin, a polybenzoxazole resin, and/or a copolymer resin of a repeating unit of a polyimide resin and a repeating unit of a polybenzoxazole resin, an imide ring and an oxazole ring can be formed by the heat treatment, so that heat resistance and chemical resistance can be improved. In addition, when a thermal crosslinking agent is contained, a thermal crosslinking reaction can be promoted by the heat treatment, so that heat resistance and chemical resistance can be improved. This heat treatment is carried out by selecting a temperature and gradually increasing the temperature, or by selecting a certain temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is performed at 150°C and 250°C for 30 minutes each. Alternatively, a method of linearly increasing the temperature from room temperature to 300°C over 2 hours can be mentioned. 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 400°C or less, more preferably 350°C or less, and even more preferably 300°C or less.

Next, as an example of a method for producing a cured product of the present invention, a method for producing a cured film, which is one form of a cured product, using a photosensitive sheet formed from the photosensitive resin composition of the present invention in a sheet form will be described. Note that the photosensitive sheet here refers to a sheet-like photosensitive resin composition obtained by applying the photosensitive resin composition onto a peelable film and drying it.

When using a photosensitive sheet formed from the photosensitive resin composition of the present invention in a sheet form, if the photosensitive sheet has a protective film, this is peeled off, and the photosensitive sheet is placed opposite a substrate and bonded together by thermocompression to obtain a photosensitive resin film. The photosensitive sheet can be obtained by applying the photosensitive resin composition of the present invention onto a support film made of a peelable film such as polyethylene terephthalate, followed by drying.

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

The photosensitive resin film obtained by laminating a photosensitive sheet to a substrate can be formed into a hardened film by following the steps of exposing the photosensitive resin film to light, developing the exposed photosensitive resin film, and hardening it by heating, as described above.

Another embodiment of the cured product of the present invention is a cured product containing resin (A) and containing a compound represented by formula (1) and/or a compound (C) represented by formula (2) in a total amount of 0.00001% by mass or more and 0.01% by mass or less relative to 100% by mass of the cured product.

The content of the compound represented by formula (1) and the compound (C) represented by formula (2) in the cured product can be measured by the method described in the Examples. The total amount of the compound represented by formula (1) and the compound represented by formula (2) contained in the cured product is preferably 0.00005% by mass or more and 0.008% by mass or less, and more preferably 0.0001% by mass or more and 0.005% by mass or less, relative to 100% by mass of the cured product.

The above cured product can improve the reliability when used in an organic EL display device. Although the details of the mechanism by which the reliability of an organic EL display device is improved by the inclusion of compound (C) in the cured product are unknown, the inventors speculate on the following mechanism. Since the compound represented by formula (1) is a ketoester compound, it can form a chelate with an acidic compound between the carbonyl group and the ester bond. This makes it possible to suppress the generation of acidic gas from the cured product during a reliability test, suppresses corrosion of the electrodes of the organic EL display device, and improves reliability. In addition, the compound represented by formula (2) is a ketalized compound obtained by reacting the carbonyl group of a ketoester compound with a compound having two or more hydroxyl groups in the molecule, and it is speculated that a part of the ketal is eliminated to generate the same compound as formula (1) during the heating process in the process of forming the cured product and during the reliability test. Therefore, it is believed that the compound represented by formula (2) can also exhibit the chelate effect like the compound of formula (1), and the reliability of the organic EL display device can be improved.

The compound (C) contained in the cured product preferably contains at least one selected from the group consisting of formulas (19) to (22).

The organic EL display device of the present invention comprises the cured product of the present invention. Preferably, the organic EL display device of the present invention comprises the cured product of the present invention as one or more 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. In particular, the cured product obtained by curing the photosensitive resin composition of the present invention containing a black agent has excellent light-shielding properties and can improve the light resistance reliability of the organic EL display device. Therefore, the organic EL display device of the present invention preferably comprises the cured product of the present invention containing a black agent as one or more layers selected from the group consisting of a pixel division 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, and a gate insulating layer, and more preferably comprises the cured product of the present invention containing a black agent as one or more layers selected from the group consisting of a pixel division layer, an interlayer insulating layer, a TFT planarizing layer, and a TFT protective layer.

The electronic component of the present invention comprises the cured product of the present invention. The semiconductor device of the present invention comprises the cured product of the present invention. Specifically, the cured product of the present invention is suitable for use as an interlayer insulating film of an electronic component such as a SAW filter, a passivation film of a semiconductor element included in a semiconductor device, a surface protective film, an interlayer insulating film, etc., but is not limited thereto. The semiconductor device referred to here refers to a device that includes a semiconductor element or an integrated circuit integrating the semiconductor element as a component. The cured product obtained by curing the photosensitive resin composition of the present invention has excellent mechanical strength, so that a highly reliable electronic component or semiconductor device that does not crack even after a thermal cycle test can be obtained by having the cured product of the present invention. Examples of the configuration of the electronic component or semiconductor device of the present invention include, for example, the electronic components or semiconductor devices described in [0190] to [0208] of JP 2020-66651 A and [0183] to [0189] of WO 2021/085321 A, but are not limited thereto.

The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these embodiments. The names of the compounds used, for which abbreviations are used, are shown below.

(Acid dianhydride)
ODPA: 4,4'-oxydiphthalic anhydride 6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic 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.

(Diamine Compound)
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.)
AZ-FDA: 9,9-bis(3-amino-4-hydroxyphenyl)fluorene SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane.

(Dicarboxylic acid chloride)
OBBOC: 4,4'-oxybisbenzoic acid chloride (manufactured by Ihara Nikkei Chemical Industry Co., Ltd.).

(End-capping material that reacts with acid dianhydrides and dicarboxylic acid chlorides)
OAP: 2-aminophenol (Tokyo Chemical Industry Co., Ltd.)
MAP: 3-aminophenol.

(End-capping material that reacts with bisaminophenol compounds)
MAOC: methacryloyl chloride (Tokyo Chemical Industry Co., Ltd.)
(solvent)
NMP: N-methyl-2-pyrrolidone GBL: γ-butyrolactone PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether EL: ethyl lactate NS100: ethyl levulinate (NXTLEVEL Biochem BV)
NS200: Butyl levulinate (NXTLEVEL Biochem BV)
NS300: Ethyl levulinate propylene glycol ketal (formula (23), manufactured by NXTLEVVEL Biochem BV)
NS400: Ethyl levulinate glycerol ketal (formula (24), manufactured by NXTLEVVEL Biochem BV)

LVM: Methyl levulinate (Tokyo Chemical Industry Co., Ltd.)
LVP: Propyl levulinate (Tokyo Chemical Industry Co., Ltd.)
MPA: 3-methoxy-N,N-dimethylpropanamide (KJ Chemicals Co., Ltd.).

(others)
ITO: indium tin oxide TMAH: tetramethylammonium hydroxide DMFDMA: N,N-dimethylformamide dimethyl acetal BPAF: bisphenol AF.

[Common processing conditions]
In the following measurement and evaluation methods and examples and comparative examples, the following treatments were carried out under the following conditions unless otherwise specified.

(1) Pretreatment of ITO Substrate A glass substrate (manufactured by Geomatec Co., Ltd.; hereafter referred to as "ITO substrate") with 100 nm ITO formed on the glass by sputtering was subjected to a UV- _O3 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 heated at 130°C for 2 minutes using a hot plate (HP-1SA; manufactured by AS ONE Corporation) for dehydration and baking treatment before use.

(2) Development and Rinse The prebaked film was shower-developed with an alkaline developer of 2.38% by mass TMAH aqueous solution for 60 seconds using a small automatic photolithography developing apparatus (Takizawa Sangyo Co., Ltd. AD-2000), and then rinsed with deionized water for 30 seconds.

(3) 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 under a nitrogen atmosphere to form a cured film, which is one form of a cured product.

[Measurement and evaluation method]
(1) Weight Average Molecular Weight of Polyimide Resin The weight average molecular weight (Mw) in terms of polystyrene was measured using a GPC analyzer under the following conditions.
Measuring device: Waters 2695 (manufactured by Waters Corporation)
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% by mass of lithium chloride and 0.48% by mass of 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 (average value was taken as the weight average molecular weight of polyimide).

(2) 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 with a thickness of 4 to 5 μm. This wafer with the resin film was divided into two, and one of them was cured in a clean oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.) at 140°C for 30 minutes under a nitrogen stream (oxygen concentration 20 ppm or less), and 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.) to confirm the presence of absorption peaks of the imide structure due to polyimide (near 1,780 cm ^- 1 and near 1,377 cm ^-1 ), and the peak intensities near 1,377 cm ^-1 (before curing: S, after curing: T) were determined. The peak intensity ratio was calculated by dividing the peak intensity (S) by the peak intensity (T), and the content of imide groups in the polymer before heat treatment, i.e., the imide ring closure rate, was determined.
_RIM (%)=(S/T)×100.

(3) Pigment Particle Size The particle size of the pigment in the pigment dispersion or in the composition was measured using a nanoparticle analyzer. The pigment particle size was measured under the following conditions, and the _D50 (median size) value is shown in Table 1.
Measurement equipment: Nanoparticle analyzer SZ-100 (manufactured by Horiba, Ltd.)
Laser wavelength: 532 nm
Sample dilution solvent: PGMEA
Sample dilution ratio: 250 times (mass ratio)
Solvent viscosity: 1.25
Solvent refractive index: 1.40
Measurement temperature: 25°C
Measurement mode: scattered light Calculation conditions: polydispersion, broad Number of measurements: 2 (average value was taken as the pigment particle size).

(4) Film Thickness Measurement Film thickness was measured using a surface roughness/contour shape measuring instrument (SURFCOM1400D; manufactured by Tokyo Seimitsu Co., Ltd.) at a measurement magnification of 10,000 times, a measurement length of 1.0 mm, and a measurement speed of 0.30 mm/s.

(5) Evaluation of light-shielding properties The positive photosensitive resin compositions obtained in each Example and Comparative Example were applied to the surface of a transparent glass substrate ("Tempax" manufactured by AGC Technoglass Co., Ltd.) using a spin coater, adjusting the rotation speed so that the final cured film had a thickness of 1.5 μm, to obtain a coating film. The coating film was prebaked at 120° C. for 120 seconds under atmospheric pressure using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.) to obtain a prebaked film.

The prebaked film was then developed, rinsed, and dried to obtain a solid developed film. The developed film was then heat-treated (cured) to obtain a substrate for evaluating optical properties, which had a solid cured film with a thickness of 1.5 μm.

The intensities of incident light and transmitted light of the cured films obtained in each of the Examples and Comparative Examples were measured using an X-rite 361T (visual) densitometer, and the OD value of the cured films was calculated according to the following formula.
OD value = log ₁₀ (I ₀ /I)
Here,
I ₀ : Incident light intensity I: Transmitted light intensity.

In addition, (4) the thickness of the cured film was measured using the film thickness measurement method, and the light blocking ability per 1 μm of film thickness of each cured film was evaluated by calculating the OD value/film thickness.

(6) Sensitivity Evaluation of Positive Photosensitive Resin Composition The positive photosensitive resin compositions obtained in the Examples and Comparative Examples were applied onto a 100 mm x 100 mm ITO substrate by spin coating using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.) while adjusting the rotation speed so that the thickness of the prebaked film would be approximately 1.8 μm. The substrate was then prebaked at 100°C for 120 seconds using a buzzer hot plate (HPD-3000BZN; manufactured by AS ONE Co., Ltd.) to produce a prebaked film having a thickness of approximately 1.8 μm. The obtained prebaked film was exposed to ultraviolet light through a positive mask (manufactured by HOYA Corporation, stripe design line width 20 μm) using a double-sided alignment single-sided exposure device ("Mask Aligner"PEM-6M; manufactured by Union Optical Co., Ltd.) with a maximum exposure of 150 mJ/ ^cm2 (value on an i-line illuminometer) and decreasing the exposure amount in increments of 5 mJ/ ^cm2 , followed by development, rinsing, and drying to obtain a patterned substrate on which a photosensitive resin film was formed in a predetermined pattern. The patterned substrates with each exposure amount were used to evaluate sensitivity and development residue.

The presence or absence of residues in the openings of the resulting developed film was observed using an optical microscope. 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 judged as follows, and A, B, and C, which had a sensitivity of less than 95 mJ/ ^cm2 , were considered to be acceptable.
A: Sensitivity is less than 75 mJ/ ^cm2 . B: Sensitivity is 75 mJ/ ^cm2 or more and less than 85 mJ/ ^cm2 . C: Sensitivity is 85 mJ/ ^cm2 or more and less than 95 mJ/ ^cm2 . D: Sensitivity is 95 mJ/ ^cm2 or more.

(7) Evaluation of Development Residues In the same manner as in (6) above, the positive photosensitive resin compositions obtained in the Examples and Comparative Examples were applied onto an ITO substrate and prebaked to prepare a prebaked film having a thickness of about 1.8 μm. The obtained prebaked film was exposed to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp at a dose of 200 mJ/cm2 using a double-sided alignment single-sided exposure device (Mask Aligner PEM-6M; manufactured by Union Optical Co., Ltd.) through a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International Co., Ltd., having a 1:1 line & space pattern of 2 to 50 μm, each having areas with transmittances of 1%, 5%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 50%, and ⁶⁰ %). (value by an i-line illuminometer), the film was developed, rinsed, and dried to prepare a developed film of the photosensitive resin composition.

Using an FPD/LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the resolved pattern of the prepared post-development film was observed to check for the presence or absence of residues in the openings of the 20 μm line-and-space pattern at the location of the minimum exposure dose where the opening width becomes the same line width (20 μm) as the mask design. The results were judged as follows, and A, B, and C, where the area of the residues in the openings was less than 10%, were deemed to be acceptable.
A: No residue in the opening (less than 1%)
B: The area of the opening where the residue exists is 1% or more and less than 5%. C: The area of the opening where the residue exists is 5% or more and less than 10%. D: The area of the opening where the residue exists is 10% or more.

(8) Chemical Resistance Evaluation The photosensitive resin composition obtained in each Example and Comparative Example was applied to an alkali-free glass plate (OA-10 manufactured by Nippon Electric Glass Co., Ltd.) at an arbitrary rotation speed by spin coating to obtain a photosensitive resin film, which was then pre-baked for 2 minutes on a hot plate at 120°C as a drying process to obtain a photosensitive resin film. Then, the film was developed and rinsed. The developed and rinsed substrate with the photosensitive resin film was heat-treated (cured) to obtain a cured film having a film thickness of 2.0 μm. The cured film was then immersed in a stripping solution 104 manufactured by Tokyo Ohka Kogyo Co., Ltd. at 60°C for 10 minutes, the film thickness before and after the treatment was measured, and the amount of film loss due to the immersion treatment was determined. The evaluation was performed as follows, and A, B, and C, which were less than 0.10 μm in the amount of film loss, were deemed 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.

(9) Evaluation of the Light Emitting Reliability of the Organic EL Display Device The organic EL display devices obtained in Examples 1 to 23 and Comparative Examples 1 to 3 were placed on a hot plate heated to 80° C. with the display section (light emitting surface) facing up, and were driven by direct current at 10 mA/cm ² to emit light. After that, the pixel light emitting area ratio (area ratio of the light emitting section to the area of the light emitting pixel) was evaluated one hour later, and the power was once turned off to turn off the light. Next, light with an illuminance of 3.0 W/m ² at a wavelength of 420 nm, using a xenon lamp as a light source, was continuously irradiated onto the display section as simulated sunlight. After 100 hours and 500 hours from the start of irradiation, the display section was irradiated again, and the pixel light emitting area ratio was measured for 10 light emitting pixel sections located in the center, and the average value was calculated. Based on the pixel light emitting area ratio after one hour, the higher the pixel light emitting area ratio is maintained, the better the light emitting reliability is, and the display section was evaluated based on the following criteria, with A to C, where the area ratio of the light emitting section to the area of the light emitting pixel is 65% or more, being deemed to be pass, and D being deemed to be fail.
A: The area ratio of the light-emitting portion to the area of the light-emitting pixel is 95% or more. B: The area ratio of the light-emitting portion to the area of the light-emitting pixel is 80% or more but less than 95%. C: The area ratio of the light-emitting portion to the area of the light-emitting pixel is 65% or more but less than 80%. D: The area ratio of the light-emitting portion to the area of the light-emitting pixel is less than 65%.

(10) Elongation at Break The resin compositions obtained in Example 51 and Comparative Example 51 were applied to an 8-inch silicon wafer by spin coating using a coating and developing apparatus (ACT-8 manufactured by Tokyo Electron Limited) so that the film thickness after pre-baking for 3 minutes at 120°C was 11 μm, and then pre-baked. The wafer was then heated to 250°C at a rate of 3.5°C/min in an inert oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.) with an oxygen concentration of 20 ppm or less, and heat-treated at 250°C for 1 hour to form a cured film. When the temperature reached 50°C or less, the wafer was removed and immersed in 45% by mass hydrofluoric acid for 1 minute to peel off the cured film from the wafer. This film was cut into strips 1.5 cm wide and 5 cm long, and the elongation at break was measured by pulling at a tensile speed of 5 mm/min at room temperature of 23.0°C and humidity of 45.0% RH using a Tensilon (RTM-100, manufactured by Orientec Co., Ltd.). Measurements were performed on 10 strips per specimen, and the average of the top 5 points was calculated from the results. The results were judged as follows, with A, B, and C, which were elongations at break of 20% or more, being deemed to be acceptable.
A: The breaking elongation value is 40% or more. B: The breaking elongation value is 30% or more but less than 40%. C: The breaking elongation value is 20% or more but less than 30%. D: The breaking elongation value is less than 20%.

(11) Evaluation of crack resistance in thermal tests The following evaluation substrate was prepared for evaluating peeling in copper wiring. Cylindrical copper wiring with a thickness of 5 μm and a diameter of 90 μm was created on an 8-inch silicon wafer at equal intervals so that the center-to-center distance between the copper wirings was 150 μm. This was used as the evaluation substrate.

The resin compositions obtained in Example 51 and Comparative Example 51 were applied to the above evaluation substrates by spin coating using a coating and developing device (ACT-8 manufactured by Tokyo Electron Ltd.) so that the film thickness after heat treatment at 120°C for 3 minutes would be 8 to 12 μm, and then prebaked to produce resin films. Prebaking was performed at 120°C for 3 minutes in both cases.

Then, the resin film was heated in an inert oven (KOYO THERMO SYSTEMS CO., LTD., CLH-21CD-S) from 50°C to 250°C at a rate of 3.5°C/min under a nitrogen stream with an oxygen concentration of 20 ppm or less, and then heat-treated at 250°C for 1 hour to harden the resin film and obtain a cured film. The film thickness after pre-baking was measured using an optical interference film thickness measuring device (Dainippon Screen Mfg. Co., Ltd., "Lambda Ace" STM-602) with a refractive index of 1.629, and the film thickness of the cured film was measured with a refractive index of 1.773.

When the temperature dropped below 50°C, the evaluation board (hereafter referred to as the sample) was removed.

Next, the sample was placed in a thermal cycle tester (conditions: -65°C/30 min to 150°C/30 min) and subjected to 200 cycles. After that, the sample was removed and the presence or absence of cracks in the cured film was observed using an optical microscope. A total of 10 locations were observed, two locations each at the center of the substrate and at the four ends of the substrate, and the results were judged as follows. A, B, and C, which show four or fewer cracks, were deemed to be pass.
A: 0 cracks occurred. B: 1 to 2 cracks occurred. C: 3 to 4 cracks occurred. D: 5 or more cracks occurred.

(12) Measurement of the Amount of Compound (C) in the Cured Product The amount of compound (C) in the cured product was measured by the following procedure.
Step 1) Collection of desorbed gas The cured product with the non-alkali glass substrate obtained in (8) was cut into strips and placed in a heating vessel. The vessel was then heated under the following conditions, and the generated gas was collected in an adsorption tube. A specimen in which the same procedure was carried out without using a sample was used as a blank.
Heating temperature: 400°C
Heating time: 60 min
Atmosphere: Nitrogen 50 mL/min
Step 2) Thermal desorption GC/MS
The gas collected in the adsorption tube by the method of Procedure 1 was measured by thermal desorption GC/MS. The conditions for thermal desorption GC/MS are shown below.
Thermal desorption apparatus: TD-100 (Markes)
Primary thermal desorption conditions: desorption temperature 260°C, trap temperature -27°C, 15 min
Secondary thermal desorption conditions: 320°C, 5 min
GC device: 7890A (Agilent)
Column: DB-5MS 30m x 0.25mm ID, film thickness 1μm (Agilent J&W)
Column temperature: After being held at 40° C. for 4 minutes, the temperature was increased at a rate of 10° C./min and held at 280° C. for 22 minutes.
MS device: 5975C (Agilent)
Ionization method: Electron ionization (EI)
Monitor ion: m / z 29 to 600
Quantitative ion of LVM: m / z 130
Quantitative ion of LVP: m / z 158
NS100 quantification ion: m / z 144
NS200 quantification ion: m / z 172
NS300 quantification ion: m / z 202
NS400 quantification ion: m / z 218
Ion source temperature: 230° C.
Standard products: LVM, LVP (Tokyo Chemical Industry Co., Ltd.), NS100, NS200, NS300, NS400 (NXTLEVEL Biochem BV)
The standard was dissolved in methanol to prepare a standard solution, which was then appropriately diluted and 1 μL of the solution was taken and injected into an adsorption tube, which was then measured under the same conditions as the samples, and a calibration curve was prepared for quantification.

[Production, synthesis and preparation examples]
(Production Example 1) Fine Perylene Black Pigment PBk-1
1,000.00 g of "Spectrasense (registered trademark)" Black K0087 (manufactured by BASF) was heated in an oven at 250°C under atmospheric pressure/air for 1 hour, cooled to room temperature, and then deagglomerated in a ball mill to obtain a purplish black pigment. Then, physical micronization treatment was carried out by solvent salt milling according to the following procedure.

500.00 g of the above black pigment was mixed with 2.5 kg of grinding material (sodium chloride particles with an average primary particle size of 0.5 μm, which had been heated at 230° C. for 1 hour to reduce the moisture content to 0.1% by mass), and 250.00 g of dipropylene glycol, and the mixture was charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90° C. for 8 hours. The kneaded product was added to 5 L of warm water and stirred for 1 hour while maintaining the temperature at 70° C. to form a slurry. The mixture was filtered and repeatedly washed with water until the chloride ion content measured by ion chromatography was 50 ppm by mass or less, and the grinding material and dipropylene glycol were removed. The mixture was then dried in an oven at 100° C. under atmospheric pressure/air for 6 hours, and the dried aggregates were loosened in a ball mill to obtain a finely divided perylene black pigment PBk-1 consisting of an isomer mixture of the compound represented by formula (26) and the compound represented by formula (27). PBk-1 had an average primary particle diameter of 25 nm, a maximum primary particle diameter of 98 nm, and an average aspect ratio of 1.1. The chemical structure of PBk-1 was analyzed using MALDI-TOF MS.

(Synthesis Example 1) Dispersant A
A granular pigment, Daiwa Red 178 (manufactured by Daiwa Chemical Industries, Ltd.), was ground in a mortar and passed through a stainless steel sieve filter (opening diameter 38 μm) to remove coarse particles to obtain a powder. 50.00 g of the obtained powder was added to 950.00 g of a mixed solution of PGME:water in a mass ratio of 1:1 and stirred for 30 minutes to obtain a preliminary stirred solution. The preliminary stirred liquid was sent to a horizontal bead mill ("DYNO-MILL (registered trademark)" manufactured by Willy A. Bachofen) whose vessel was filled with 1.0 mmφ zirconia beads ("TORACERAM (registered trademark)" manufactured by Toray Industries, Inc.) at a filling rate of 75% by volume, and a wet media dispersion treatment was carried out by a circulation method at a peripheral speed of 10 m/s for 2 hours. After that, the light red filtrate that had been passed through a filtration filter was discarded, and the mixture was washed with water until the sulfate ion concentration as determined by ion chromatography fell below 50 ppm, and the residue was collected. The residue was dried under reduced pressure at 80°C for 24 hours to obtain a powdery dispersant A with a solid content of 100%.

Dispersant A is a mixture of a compound represented by formula (28), a compound represented by formula (29), and a compound represented by formula (30) in a mass ratio of 42:55:3. The chemical structure of dispersant A was analyzed using MALDI-TOF MS, and the mass ratio of the compounds constituting dispersant A was analyzed using LC-MS.

(Synthesis Example 2) 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 brought to 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. Then, filtration was performed to collect the precipitate. The precipitate was dried in a vacuum dryer to obtain a quinone diazide compound QD-a represented by formula (31).

In formula (31), * represents the bonding site with the oxygen atom.

(Synthesis Example 3) Quinone diazide compound QD-b
The synthesis was carried out in the same manner as in the synthesis example of the 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, to obtain a quinone diazide compound QD-b represented by formula (32).

In formula (32), * represents the bonding site with the oxygen atom.

(Synthesis Example 4) 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 cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 100 mL of acetone was added dropwise thereto. 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 off and dried in vacuum at 50°C.

30 g of the resulting 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 (Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was then introduced using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated when it was confirmed that the balloon was no longer deflating. 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.

(Synthesis Example 5) 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane (HB)
A hydroxyl group-containing diamine compound (HB) represented by the following formula was obtained in the same manner as in Synthesis Example 4, except that 18.3 g (0.05 mol) of BAHF was changed to 12.9 g (0.05 mol) of BAP.

(Synthesis Example 6) Polyamic acid ester (P1)
Under a dry nitrogen stream, 16.09 g (0.036 mol) of 6FDA was dissolved in 100 g of NMP in a three-neck flask. 17.52 g (0.029 mol) of HA obtained in Synthesis Example 4 was added together with 20 g of NMP, and the mixture was reacted at 40 ° C. for 2 hours. Next, 1.38 g (0.013 mol) of MAP was added together with 20 g of NMP as a terminal blocking agent, and the mixture was reacted at 40 ° C. for 1 hour. Then, a solution diluted with 12.95 g (0.109 mol) of DMFDMA and 20 g of NMP was added dropwise over 20 minutes. After the dropwise addition, the mixture was stirred at 40 ° C. for 2 hours. After the stirring was completed, the solution was cooled to 25 ° C., and then the solution was poured into 2 L of deionized water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with deionized water, and then dried for 20 hours in a vacuum dryer at 50° C. to obtain a powder of polyamic acid ester (P1), which is a form of polyimide. The weight average molecular weight of the polyamic acid ester (P1) was 32,500, and the imidization rate was 15%.

(Synthesis Example 7) Polyamic acid ester (P2)
A powder of polyamic acid ester (P2), which is a form of polyimide, was obtained in the same manner as in the synthesis example of polyamic acid ester (P1), except that GBL was used instead of NMP. The weight average molecular weight of the polyamic acid ester (P2) was 31,000, and the imidization rate was 20%.

(Synthesis Example 8) Polyimide resin (P3)
A powder of polyimide resin (P3) was obtained in the same manner as in the synthesis example of polyimide resin (P1), except that 1,3-dimethyl-2-imidazolidinone was used instead of NMP. The weight average molecular weight of polyimide resin (P3) was 31,300, and the imidization rate was 20%.

(Synthesis Example 9) Polyimide resin (P4)
Under a dry nitrogen stream, 16.09 g (0.036 mol) of 6FDA was dissolved in 100 g of NMP in a three-neck flask. 17.52 g (0.029 mol) of HA was added together with 20 g of NMP and reacted at 40 ° C for 2 hours. Next, 1.38 g (0.013 mol) of MAP was added as an end-capping agent together with 20 g of NMP and reacted at 40 ° C for 1 hour, and then stirred at 180 ° C for 4 hours. After stirring, the solution was poured into 2 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 50 ° C for 20 hours to obtain a powder of polyimide resin (P4). The weight average molecular weight of polyimide resin (P4) was 35,500, and the imidization rate was 99%.

(Synthesis Example 10) Polyimide resin (P5)
A powder of polyimide resin (P5) was obtained in the same manner as in the synthesis example of polyimide resin (P4), except that methyl levulinate was used instead of NMP. The weight average molecular weight of polyimide resin P5 was 31,700, and the imidization rate was 98%.

(Synthesis Example 11) Polyamic acid ester (P6)
Under a dry nitrogen stream, 21.0 g (0.035 mol) of the hydroxyl group-containing diamine (HA) obtained in Synthesis Example 4 and 0.54 g (0.0022 mol) of SiDA were dissolved in 100 g of MPA. 13.4 g (0.043 mol) of ODPA was added together 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 together with 20 g of MPA as an end-capping agent, and the mixture was reacted at 40° C. for 1 hour. Then, a solution in which 10.3 g (0.087 mol) of DMFDMA was diluted with 10 g of MPA was dropped. After the dropwise addition, the mixture was stirred for 2 hours at 40° C. After the stirring was completed, the solution was poured into 2 L of deionized water, and the precipitate of the polymer solid 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 (P6), which is a form of polyimide. The weight average molecular weight of the polyamic acid ester (P6) was 33,000 and the imidization rate was 10%.

(Synthesis Example 12) Polyhydroxyamide (P7)
Under a dry nitrogen stream, 33.0 g (0.090 mol) of BAHF was dissolved in 115 g of MPA. 4.43 g (0.027 mol) of NA was added to the mixture 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. A solution of 22.6 g (0.077 mol) of OBBOC dissolved in 50 g of MPA was added dropwise to the mixture so that the internal temperature did not exceed 0°C. After the dropwise addition, the mixture was stirred for 60 minutes at -15°C, and then stirred at room temperature for 120 minutes. After the reaction was completed, the solution was poured into 2 L of deionized water to collect 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 24 hours to obtain polyhydroxyamide (P7), which is a form of polybenzoxazole resin. The weight average molecular weight of polyhydroxyamide (P8) was 28,000.

(Synthesis Example 13) Polyhydroxyamide (P8)
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 temperature of 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 was completed, stirring was continued at -15°C for 60 minutes, and then stirring was performed at room temperature for 120 minutes. After the reaction was completed, the solution was poured into 3 L of deionized water to collect 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 24 hours to obtain polyhydroxyamide (P8), which is a form of polybenzoxazole resin. The weight average molecular weight of polyhydroxyamide (P8) was 32,000.

(Synthesis Example 14) Polyhydroxyamide (P9)
Under a dry nitrogen stream, 28.7 g (0.11 mol) of BAP was dissolved in 100 g of MPA, and the temperature of the solution was cooled to -15°C. A solution of 27.9 g (0.094 mol) of OBBOC dissolved in 50 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 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 dropwise addition, stirring was continued for 60 minutes at -15°C, and then stirring was performed at room temperature for 120 minutes. After the reaction was completed, the solution was poured into 3 L of deionized water to collect 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 24 hours to obtain polyhydroxyamide (P9), which is a form of polybenzoxazole resin. The weight average molecular weight of the polyhydroxyamide (P9) was 33,000.

(Synthesis Example 15) Phenol resin (P10)
The phenolic resin (P10) of this synthesis example was synthesized by the method described in Synthesis Example 5 of paragraph [0120] of WO 2012/141165.

(Synthesis Example 16) Acrylic resin (P11)
A methyl methacrylate/methacrylic acid/styrene copolymer (mass ratio 30/40/30) was synthesized by a known method (Patent No. 3120476; Example 1). 40 parts by mass of glycidyl methacrylate was added to 100 parts by mass of the copolymer, and the mixture was reprecipitated in deionized water, filtered, and dried to obtain an acrylic resin (P11) that is a polymer containing a radical polymerizable monomer.

(Synthesis Example 17) Polyamic acid ester (P12)
Polyamic acid ester (P12) was obtained in the same manner as in Synthesis Example of Polyamic acid ester (P6), except that 21.0 g (0.035 mol) of the hydroxyl group-containing diamine (HA) was changed to 17.4 g (0.035 mol) of the hydroxyl group-containing diamine (HB) obtained in Synthesis Example 5. The weight average molecular weight of polyamic acid ester (P12) was 32,000, and the imidization rate was 8%.

(Synthesis Example 18) Polyimide resin (P13)
Under a dry nitrogen stream, 10.88 g (0.036 mol) of TDA-100 was dissolved in 100 g of MPA in a three-neck flask. 14.39 g (0.029 mol) of HB was added together with 20 g of MPA, and the mixture was reacted at 40 ° C. for 2 hours. Next, 1.38 g (0.013 mol) of MAP was added together with 20 g of MPA as a terminal blocking agent, and the mixture was reacted at 40 ° C. for 1 hour, and then stirred at 180 ° C. for 4 hours. After stirring, the solution was poured into 2 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 50 ° C. for 20 hours to obtain a powder of polyimide resin (P13). The weight average molecular weight of the polyimide resin (P13) was 32,500, and the imidization rate was 100%.

(Synthesis Example 19) Polyhydroxyamide (P14)
Polyhydroxyamide (P14) was obtained in the same manner as in the synthesis example of polyhydroxyamide (P8), except that 29.2 g (0.80 mol) of BAHF was changed to 30.4 g (0.80 mol) of AZ-FDA. The weight average molecular weight of polyhydroxyamide (P14) was 33,200.

(Preparation Example 1) Preparation of Pigment Dispersion Bk-1 68.38 g of polyimide resin P1 was added to 900.00 g of a mixed solvent in which the mass ratio of PGME and EL as compound (D) and GBL as solvent (E) was 50:40:10, and the mixture was stirred for 30 minutes to dissolve. Further, 4.59 g of dispersant A was added, and after stirring for 30 minutes, 27.03 g of finely divided perylene black pigment PBk-1 was added and stirred for 30 minutes to obtain a preliminary stirring liquid. Next, the preliminary stirring liquid was sent to a vertical bead mill (Hiroshima Metal & Machinery Co., Ltd. "Ultra Apex Mill Advance" (registered trademark)) in which 0.05 mmφ zirconia beads "Treceram (registered trademark)" (manufactured by Toray Industries, Inc.) were filled in the vessel at a filling rate of 75 volume%, and a wet media dispersion treatment was performed for 5 hours at a peripheral speed of 10 m/s in a circulation system to obtain a pigment dispersion Bk-1 with a solid content of 10.00 mass%. The particle diameter (D ₅₀ ) of the pigment in the pigment dispersion Bk-1 was 200 nm.

(Preparation Example 2) Preparation of pigment dispersion Bk-2 Pigment dispersion Bk-2 was obtained in the same manner as in Preparation Example 1, except that NS100 was used as compound (C) instead of GBL in solvent (E). The particle size (D ₅₀ ) of the pigment in pigment dispersion Bk-2 was 170 nm.

(Preparation Example 3) Preparation of pigment dispersion Bk-3 Pigment dispersion Bk-3 was obtained in the same manner as in Preparation Example 1, except that NS100 was used as compound (C) instead of GBL in solvent (E) and polyimide resin P1 was changed to polyimide resin P2. The particle diameter (D ₅₀ ) of the pigment in pigment dispersion Bk-3 was 170 nm.

Preparation Example 4 Preparation of Pigment Dispersion Bk-4 Pigment dispersion Bk-5 was obtained in the same manner as in Preparation Example 1, except that NS100 was used as compound (C) instead of GBL in solvent (E) and polyimide resin P1 was changed to polyimide resin P4. The particle diameter (D ₅₀ ) of the pigment in pigment dispersion Bk-5 was 150 nm.

[Example 1]
Under yellow light, 2.08 g of polyimide resin P1 as resin (A), 0.168 g of QD-a and 0.125 g of QD-b as photoacid generator (B-1), 0.208 g of BPAF as dissolution promoter (J), 0.416 g of HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.; compound represented by formula (33)) as crosslinker (I), and 0.002 g of 10 mass% PGME solution of BYK-333 (manufactured by BYK Japan Co., Ltd.) as surfactant (K) were added to 17.0 g of a mixed solvent having a mass ratio of 20:40:40 as compound (D) and NS100 as compound (C), and the mixture was stirred for 30 minutes to dissolve the solids, thereby obtaining a homogeneous solution having a solid content of 15.00 mass%.

Then, the obtained solution was filtered through a 0.45 μmφ filter to obtain positive-type photosensitive resin composition 1. Next, various evaluations were performed using positive-type photosensitive resin composition 1 according to each of the measurement and evaluation methods (4) to (8).

　Next, a patterned cured film-formed substrate having a cured film obtained by curing the positive-type photosensitive composition 1, and an organic EL display device for evaluating the light emission reliability having the patterned cured film as a pixel dividing layer were produced by the following method.

Figure 1 shows the manufacturing process for an organic EL display device, including the process of forming a pixel division layer.

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 (1) (46 mm wide x 46 mm long square) by sputtering, and then etched to form a patterned metal reflective layer (2). Next, a 10 nm-thick ITO transparent conductive film was formed on the entire surface by sputtering, and then etched to form a second electrode (3) with the same pattern and an auxiliary electrode (4) as an extraction electrode. 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.

The positive photosensitive composition 1 was applied to the surface of the electrode formation substrate 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.

　A positive exposure mask with openings (rectangles of 30 μm wide x 165 μm long) arranged at an opening pitch of 50 μm was set on the coating film so that the vertical/horizontal edges of the patterned light-shielding portion of the positive exposure mask were parallel to the vertical/horizontal edges of the alkali-free glass substrate (1), respectively. Using a double-sided alignment single-sided exposure device ("Mask Aligner" PEM-6M manufactured by Union Optical Co., Ltd.), the prebaked film was irradiated with a pattern of 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 amount through the positive exposure mask to obtain an exposed film. Next, the developed film was obtained by developing and rinsing. Note that the positive exposure mask used was a mask with a patterned light-shielding portion made of chrome formed on the surface of a soda glass substrate.

Furthermore, the developed film was subjected to a heat treatment (cure) to form a hardened film, and a patterned hardened film-formed substrate with an aperture ratio of 18% was obtained, which had a patterned hardened film (5) with a thickness of 2.0 μm, in which openings (rectangles measuring 30 μm wide by 165 μm long) were arranged at an opening pitch of 50 μm within an area measuring 16 mm long by 16 mm wide in the center of the electrode-formed substrate. In the organic EL display device obtained after the process described below, the openings referred to here are the parts that will ultimately become the light-emitting pixel parts, and the patterned hardened film is the part that corresponds to the pixel dividing layer.

Next, an organic EL display device was produced using the patterned cured film-formed substrate. In order to form an organic EL layer (6) including a light-emitting layer by a vacuum deposition method, the patterned cured film-formed substrate was rotated with respect to the deposition source under deposition conditions with a vacuum degree of 1×10 ⁻³ Pa or less, and first, a film was formed with a thickness of 10 nm of compound HT-1 as a hole injection layer and a thickness of 50 nm of compound HT-2 as a hole transport layer. Next, on the light-emitting layer, a host material, compound GH-1, and a dopant material, compound GD-1, were deposited with a thickness of 40 nm. Then, as an electron transport material, compound ET-1 and compound LiQ were laminated with a volume ratio of 1:1 to a thickness of 40 nm.

Next, the compound LiQ was evaporated to a thickness of 2 nm, and then a silver/magnesium alloy (volume ratio 10/1) was evaporated to a thickness of 10 nm to form the first electrode (7).

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

The thickness mentioned here is the value displayed on a quartz crystal oscillator film thickness monitor.

Then, in a low humidity/nitrogen atmosphere, a cap-shaped glass plate was attached and sealed using an epoxy resin adhesive to obtain an organic EL display device. The light emission reliability of the organic EL display device was evaluated using the method described in Measurement/Evaluation Method (9), and the results are shown in Table 3.

[Examples 2 to 8, 12 to 23 and Comparative Examples 1 and 2]
Positive photosensitive resin compositions 2 to 8, 12, 13, and 15 to 26, cured films, and organic EL display devices were produced in the same manner as in Example 1, except that the positive photosensitive compositions were prepared according to the compositions shown in Tables 2 and 3. The evaluation results are shown in Tables 4 and 5.

[Example 9]
Under yellow light, in 1.524 g of NS100 as compound (C), 0.710 g of polyimide resin P1 as resin (A), 0.225 g of QD-a and 0.135 g of QD-b as photoacid generator (B-1), 0.270 g of BPAF as dissolution promoter (J), 0.495 g of HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.; compound represented by formula (33)) as crosslinker (I), and 0.014 g of 10% by mass PGME solution of BYK-333 (manufactured by BYK Japan Co., Ltd.) as surfactant (K) were added and stirred for 30 minutes to dissolve. Furthermore, 26.64 g of pigment dispersion Bk-2 was added and stirred for 30 minutes to obtain a uniform solution of 15.00% by mass of solids.

Then, the resulting solution was filtered through a 0.45 μm diameter filter to obtain positive-type photosensitive resin composition 9.

Then, a cured film and an organic EL display device were produced in the same manner as in Example 1, except that positive-type photosensitive resin composition 9 was used.

[Examples 10 and 11 and Comparative Example 3]
Positive photosensitive resin compositions 10, 11, and 14, cured films, and organic EL display devices were produced in the same manner as in Example 9, except that positive photosensitive resin compositions were prepared according to the compositions shown in Tables 2 and 3 using pigment dispersion Bk-3 in Example 10, pigment dispersion Bk-4 in Example 11, and pigment dispersion Bk-1 in Comparative Example 3. The evaluation results are shown in Tables 4 and 5.

[Example 51]
Under yellow light, 2.0 g of quinone diazide compound b, 3.0 g of HMOM-TPHAP, 0.04 g of an NS100 solution (solid content 5 mass %) of BYK-333 as a surfactant, and 15 g of NS100 and 15 g of PGME as a solvent were added to 10.0 g of polyimide resin P1, and the mixture was stirred for 30 minutes to obtain a homogeneous solution.

Then, the resulting solution was filtered through a 0.45 μm diameter filter to obtain a positive-type photosensitive resin composition 51.

Then, a cured film was prepared using the positive photosensitive resin composition 51 according to each of the measurement and evaluation methods (10) and (11).

[Comparative Example 51]
A positive photosensitive resin composition 52 was obtained in the same manner as in Example 51, except that PGMEA was used instead of NS100.

Then, a cured film was prepared using the positive photosensitive resin composition 52 according to each of the measurement and evaluation methods (10) and (11).

Table 6 shows the results of evaluation of the breaking elongation and crack resistance of the cured films of the compositions obtained in Example 51 and Comparative Example 51.

1: Non-alkali glass substrate 2: Metal reflective layer 3: Second electrode 4: Auxiliary electrode 5: Patterned cured film 6: Organic EL layer 7: First electrode

Claims

A photosensitive resin composition comprising a resin (A), a photosensitizer (B), and a compound (C) which is a compound represented by formula (1) and/or a compound represented by formula (2).

In formula (1) and formula (2), R 1 and R 2 each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. In formula (2), R 3 , R 4 and R 5 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. R 6 and R 7 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent hydroxyalkyl group having 1 to 10 carbon atoms. a represents 0 or 1.
The photosensitive resin composition according to claim 1, wherein the total content of the compounds (C) is 1 to 3,000 parts by mass per 100 parts by mass of the total amount of the resins (A).
The photosensitive resin composition according to claim 1 or 2, wherein the compound (C) comprises at least one selected from the group consisting of formulas (19) to (22).
The photosensitive resin composition according to claim 1 or 2, further comprising a compound (D) having a boiling point at atmospheric pressure of 100°C or more and 170°C or less, and not corresponding to any of the resin (A), the photosensitizer (B), and the compound (C).
The photosensitive resin composition according to claim 4, wherein the compound (D) includes a compound (D1) having a hydroxyl group.
The photosensitive resin composition according to claim 4, wherein the ratio X/Y of the mass X of the compound (C) contained in the photosensitive resin composition to the mass Y of the compound (D) is 0.01 to 10.
The photosensitive resin composition according to claim 1 or 2, wherein the resin (A) contains an alkali-soluble resin (A1).
The photosensitive resin composition according to claim 7, wherein the alkali-soluble resin (A1) contains one or more resins selected from the group consisting of polyimide resin (A1-1), polybenzoxazole resin (A1-2), and copolymer resin (A1-3) of repeating units of polyimide resin and repeating units of polybenzoxazole resin.
The photosensitive resin composition according to claim 8, wherein one or more resins selected from the group consisting of the polyimide resin (A1-1), the polybenzoxazole resin (A1-2), and the copolymer resin (A1-3) contain a residue of a diamine represented by formula (10) and/or a residue of a diamine represented by formula (11).

In the formula, X 3 and X 4 each independently represent a direct bond, —SO 2 —, —C(CH 3 ) 2 —, a divalent organic group represented by formula (12), —CH(CF 3 )—, or —C(CF 3 ) 2 —.

In formula (12), * indicates a bonding point.
The photosensitive resin composition according to claim 1 or 2, wherein the photosensitizer (B) contains a photoacid generator (B1).
The photosensitive resin composition according to claim 1 or 2, further comprising a blackening agent (F).
A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2.
A cured product comprising a resin (A), the cured product containing a compound represented by formula (1) and/or a compound (C) represented by formula (2) in a total amount of 0.00001 mass% or more and 0.01 mass% or less, relative to 100 mass% of the cured product.

In formula (1) and formula (2), R 1 and R 2 each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. In formula (2), R 3 , R 4 and R 5 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. R 6 and R 7 each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, or a monovalent hydroxyalkyl group having 1 to 10 carbon atoms. a represents 0 or 1.
An organic electroluminescence display device comprising the cured product according to claim 12.
An electronic component or semiconductor device comprising the cured product according to claim 12.