Positive-type photosensitive resin composition, cured product, organic EL display device, method for producing the cured product

Abstract

The purpose of the present invention is to provide a positive photosensitive resin composition which has high sensitivity, good development adhesion and high heat resistance, while providing a cured product thereof with high folding resistance, and which enables the achievement of high reliability if a cured product thereof is used in an organic EL display device. The present invention provides a positive photosensitive resin composition which contains (A) one or more substances that are selected from the group consisting of a polyimide, a polyimide precursor and a copolymer of those, (B) one or more substances that are selected from the group consisting of a polybenzoxazole, a polybenzoxazole precursor and a copolymer of those, (C) a polyhydroxystyrene and / or a copolymer of a polyhydroxystyrene and a polystyrene, (D) a quinonediazide compound, and (E) a solvent, wherein: the content of the component (B) is 10 parts by mass to 100 parts by mass relative to 100 parts by mass of the component (A); and the content of the component (C) is 1 part by mass to 90 parts by mass relative to 100 parts by mass of the component (A).

Description

[Technical Field]

[0001] The present invention relates to a positive-type photosensitive resin composition, a cured product using the same, an organic EL display device comprising the cured product, and a method for producing the cured product. [Background technology]

[0002] Many products using organic electroluminescent (hereinafter referred to as "organic EL") display devices have been developed for display devices with thin displays, such as smartphones, tablet PCs, and televisions.

[0003] Generally, an organic EL display device has a drive circuit, a planarization layer, a first electrode, a pixel division layer, an emissive layer, and a second electrode on a substrate, and can emit light by applying a voltage or current between the opposing first and second electrodes. Among these, photosensitive resin compositions that can be patterned by ultraviolet irradiation are generally used as the material for the planarization layer and the material for the pixel division layer. In particular, photosensitive resin compositions using polyimide-based resins are preferred because the resin has high heat resistance and generates little gas from the cured product processed at a low temperature of about 200 to 270°C, thus enabling the creation of highly reliable organic EL display devices (see, for example, Patent Document 1).

[0004] On the other hand, the demand for high reliability in organic EL display devices is becoming stricter year by year. For planarization layer materials and pixel splitting layer materials, there is a need for highly reliable materials that do not experience a decrease in luminous brightness or pixel shrinkage even after reliability testing under accelerated conditions such as high temperature, high humidity, and light irradiation. Here, pixel shrinkage refers to the phenomenon in which the luminous brightness decreases or the pixels fail to light up from the edges.

[0005] Furthermore, in order to shorten the exposure time due to reasons such as the increasing size of the substrate and the need to improve productivity, photosensitive resin High sensitivity is required for lipid compositions. On the other hand, high-sensitivity materials have the problem of poor developability, so good developability is required for photosensitive resin compositions.

[0006] Furthermore, in recent years, there has been a surge in the development of flexible organic EL display devices formed on resin film substrates. Flexible organic EL display devices have structurally flexible parts and / or parts that are fixed in a bent state, and bending stress is applied to the planarization layer and pixel division layer in these bent parts. In such flexible organic EL display devices that include these bent parts, high bending resistance is required for the materials used in the planarization layer and the pixel division layer.

[0007] Against this backdrop, there is a strong demand for the development of photosensitive resin compositions that enable highly sensitive patterning, possess high heat resistance and bending resistance, and produce highly reliable cured products.

[0008] To address these challenges, siloxane resins are being investigated as photosensitive resin compositions capable of achieving high sensitivity (see, for example, Patent Document 2). Furthermore, as a photosensitive resin composition that can impart high bending resistance, the addition of specific phenolic hydroxyl group-containing compounds and phenolic antioxidants to the photosensitive resin composition is being investigated (see, for example, Patent Document 3). [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Publication No. 2002-91343 [Patent Document 2] Japanese Patent Publication No. 2006-178436 [Patent Document 3] International Publication No. 2019-065351 [Overview of the Initiative] [Problems that the invention aims to solve]

[0010] However, the materials proposed in the above-mentioned patent documents do not have sufficient performance for applications with even stricter reliability requirements, such as automotive displays. In view of the above problems, the present invention aims to provide a photosensitive resin composition that has high sensitivity, good developability and adhesion, high heat resistance, and high bending resistance of the cured product, and that is highly reliable when the cured product is used in an organic EL display device. [Means for solving the problem]

[0011] The present invention is as follows: [1] (A) one or more selected from the group consisting of polyimides, polyimide precursors and copolymers thereof, (B) one or more selected from the group consisting of polybenzoxazoles, polybenzoxazole precursors and copolymers thereof, (C) polyhydroxystyrene and / or copolymers of polyhydroxystyrene and polystyrene, (D) quinone diazide compounds and (E) solvents, The content of component (B) is 10 to 100 parts by mass per 100 parts by mass of component (A), A positive-type photosensitive resin composition in which the content of component (C) is 1 to 90 parts by mass per 100 parts by mass of component (A). [2] When the content of component (A) is [PI] (mass), the content of component (B) is [PB] (mass), and the content of component (C) is [PH] (mass), The positive-type photosensitive resin composition according to [1], wherein the mass ratio [PI] / ([PB]+[PH]) is in the range of 0.5 ≤ [PI] / ([PB]+[PH]) ≤ 5.0. [3] The positive-type photosensitive resin composition according to [2], wherein the relationship between [PB] and [PH] is [PB] > [PH]. [4] The positive-type photosensitive resin composition according to [3], wherein the mass ratio of [PB] and [PH] is in the range of 1.01 ≤ [PB] / [PH] ≤ 55.00. [5] A positive-type photosensitive resin composition according to any one of [1] to [4], wherein the (C) component comprises polyhydroxystyrene. [6] The positive photosensitive resin composition according to any one of [1] to [5], wherein the (E) solvent contains a polar aprotic solvent. [7] The positive photosensitive resin composition according to [6], wherein the content of the polar aprotic solvent is 1 to 30% by mass based on 100% by mass of the (E) solvent. [8] The positive photosensitive resin composition according to any one of [1] to [7], wherein the solid content concentration of the positive photosensitive resin composition is 3 to 30% by mass. [9] The positive photosensitive resin composition according to any one of [1] to [8], wherein the component (B) includes a resin having a structural unit represented by the following formula (1) as a main chain.

[10] The positive photosensitive resin composition according to any one of [1] to [9], further containing (F) a thermal acid generator.

[11] The positive photosensitive resin composition according to

[10] , wherein the (F) thermal acid generator contains a thermal acid generator having a sulfonic acid ester structure.

[12] The photosensitive resin composition according to

[10] or

[11] , wherein the (F) thermal acid generator contains a compound represented by the following formula (2).

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

[12] .

[14] When analyzed by reaction thermolysis GC / MS, a compound represented by the following formula (3), a compound represented by the following formula (4), and a compound represented by the following formula (5) are detected, and the detection peak intensity ratio is such that when the compound represented by the formula (4) is taken as 1, the compound represented by the formula (3) is 0.1 to 1, and the compound represented by the formula (5) is 0.1 to 3. A cured product.

[15] An organic EL display device including the cured product according to

[13] or

[14] .

[16] (1) A step of applying the positive photosensitive resin composition according to any one of [1] to

[12] to a substrate to form a positive photosensitive resin film, (2) a step of drying the positive photosensitive resin film, (3) a step of exposing the dried positive photosensitive resin film through a photomask, (4) a step of developing the exposed positive photosensitive resin film, and (5) a step of heat-treating the developed positive photosensitive resin film in this order. A method for producing a cured product.

Advantages of the Invention

[0012] The present invention provides a photosensitive resin composition that exhibits high sensitivity, good development adhesion, high heat resistance, and high bending resistance of the cured product, resulting in a highly reliable photosensitive resin composition when the cured product is used in an organic EL display device. [Brief explanation of the drawing]

[0013] [Figure 1] This is a cross-sectional view of an organic EL display device in which a planarization layer and a pixel splitting layer have been formed. [Figure 2] This is a schematic diagram of the substrate for an organic EL display device. [Modes for carrying out the invention]

[0014] Embodiments of the present invention will be described in detail. The positive-type photosensitive resin composition of the present invention contains (A) one or more selected from the group consisting of polyimide, polyimide precursors and copolymers thereof (hereinafter sometimes referred to as component (A)), (B) one or more selected from the group consisting of polybenzoxazole, polybenzoxazole precursors and copolymers thereof (hereinafter sometimes referred to as component (B)), (C) polyhydroxystyrene and / or a copolymer of polyhydroxystyrene and polystyrene (hereinafter sometimes referred to as component (C)), (D) a quinone diazide compound, and (E) a solvent. The content of component (B) is 10 to 100 parts by mass per 100 parts by mass of component (A), The positive-type photosensitive resin composition is such that the content of component (C) is 1 to 90 parts by mass per 100 parts by mass of component (A).

[0015] By having a content of component (B) of 10 to 100 parts by mass per 100 parts by mass of component (A), a cured product with good heat resistance and bending resistance can be obtained. By having a content of component (C) of 1 to 90 parts by mass per 100 parts by mass of component (A), the sensitivity of the resin composition is improved and the developability is improved. By containing the three components (A) to (C), it is possible to provide a photosensitive resin composition that has high sensitivity, good developability, high heat resistance and bending resistance of the cured product, and high reliability when the cured product is used in an organic EL display device.

[0016] The positive-type photosensitive resin composition of the present invention contains one or more selected from the group consisting of (A) polyimides, polyimide precursors, and copolymers thereof. Component (A) may contain a polyimide containing known polyimide structural units, a polyimide precursor containing known polyimide precursor structural units, and known copolymers thereof. In the present invention, component (A) is defined as a resin having imide bonds in its main chain. Furthermore, if component (A) contains structural units of polyimide and / or polyimide precursors along with structural units of polybenzoxazole and / or polybenzoxazole precursors, it shall be designated as component (A). Component (A) preferably has an alkali-soluble group. Alkali solubility means that when a solution of the resin dissolved in γ-butyrolactone is applied to a silicon wafer, pre-baked at 120°C for 4 minutes to form a pre-baked film with a thickness of 10 μm ± 0.5 μm, the dissolution rate determined from the reduction in film thickness when the pre-baked film is immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide at 23 ± 1°C for 1 minute, and then rinsed with pure water, is 50 nm / min or more.

[0017] To impart alkali solubility, it is preferable that the resin has acidic groups in its structural units and / or at the ends of its main chain. Examples of acidic groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and thiol groups. Furthermore, it is preferable that component (A) contains fluorine atoms, which imparts water repellency to the interface between the film and the substrate when developing with an alkaline aqueous solution, thereby suppressing the penetration of the alkaline aqueous solution into the interface. The fluorine atom content of component (A) is preferably 5% by mass or more from the viewpoint of preventing the penetration of the alkaline aqueous solution into the interface, and preferably 20% by mass or less from the viewpoint of solubility in alkaline aqueous solutions.

[0018] (A) Component is synthesized by known methods.

[0019] Polyimide precursors can be synthesized by, for example, reacting a tetracarboxylic dianhydride with a diamine compound at low temperatures if they are polyamic acids, or by reacting a tetracarboxylic dianhydride with a diamine compound at low temperatures, followed by partial esterification of the amidic acid structure with N,N-dimethylformamide dimethylacetal, 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 obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-chloridating the remaining dicarboxylic acid and reacting it with an amine.

[0020] In the case of polyimides, for example, they can be obtained by dehydrating and cyclizing the polyamic acid or polyamic acid ester obtained by the method described above by heating it in a solvent or by chemical treatment with an acid or base.

[0021] (A) The tetracarboxylic dianhydrides used in component (A) include, specifically, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2 Examples include aliphatic tetracarboxylic dianhydrides such as ,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorenic acid dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorenic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, butanetetracarboxylic dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic dianhydride. Two or more of these tetracarboxylic dianhydrides may be used as component (A).

[0022] (A) Specific examples of diamine compounds used in component (A) include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl} ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl- Examples include 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, or compounds in which at least some of the hydrogen atoms of these aromatic rings are substituted with alkyl or halogen atoms, as well as aliphatic cyclohexyldiamines, methylenebiscyclohexylamines, and diamines with the structures shown below. Two or more of these diamine compounds may be used.

[0023] [ka]

[0024] R 3 and R 6 These represent, independently, an oxygen atom, C(CF3)2, or C(CH3)2. 4 , R 5 and R 7 ~R 14 Each of these independently represents either a hydrogen atom or a hydroxyl group.

[0025] Furthermore, in order to improve the storage stability of the positive-type photosensitive resin composition, it is preferable to encapsulate the main chain ends of these components (A) with known end-capturing agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. To improve the chemical resistance of the resin cured product obtained by firing, monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds having at least one alkenyl group or alkynyl group can also be used as end-capturing agents.

[0026] The content of end-capturing agents such as monoamines, acid anhydrides, acid chlorides, and monocarboxylic acids is preferably 1 mol% or more, and more preferably 5 mol% or more, based on 100 mol% of the total sum of all monomer components constituting component (A), from the viewpoint of improving storage stability. Furthermore, from the viewpoint of obtaining a resin with good film properties, it is preferably 40 mol% or less, and more preferably 30 mol% or less, based on 100 mol% of the total sum of all monomer components constituting component (A). Multiple different end groups may be introduced into component (A) by reacting multiple end-capturing agents.

[0027] The positive-type photosensitive resin composition of the present invention contains one or more selected from the group consisting of (B) polybenzoxazole, polybenzoxazole precursor, and copolymers thereof. In the present invention, component (B) is defined as a resin that does not contain imide bonds in its main chain. Component (B) may contain a polybenzoxazole containing a known polybenzoxazole structural unit, a polybenzoxazole precursor containing a known polybenzoxazole precursor structural unit, and known copolymers thereof.

[0028] In the present invention, component (B) preferably has an alkali-soluble group. To impart alkali solubility, it is preferable that component (B) has an acidic group in its structural unit and / or at the end of its main chain. Examples of acidic groups include carboxyl groups, phenolic hydroxyl groups, sulfonic acid groups, and thiol groups. Furthermore, it is preferable that component (B) has a fluorine atom, which imparts water repellency to the interface between the film and the substrate when developing with an alkaline aqueous solution, thereby suppressing the penetration of the alkaline aqueous solution into the interface. The fluorine atom content in component (B) is preferably 5% by mass or more from the viewpoint of preventing the penetration of the alkaline aqueous solution into the interface, and preferably 20% by mass or less from the viewpoint of solubility in alkaline aqueous solutions.

[0029] Component (B) is synthesized by known methods.

[0030] In the case of polybenzoxazole precursors, they can be obtained by condensing a bisaminophenol compound with a dicarboxylic acid. Specifically, this can be done by reacting a dehydrating condensation agent such as dicyclohexylcarbodiimide (DCC) with an acid and adding the bisaminophenol compound, or by adding a solution of dicarboxylic acid dichloride dropwise to a solution of a bisaminophenol compound with a tertiary amine such as pyridine.

[0031] In the case of polybenzoxazoles, for example, they can be obtained by dehydrating and cyclizing the polybenzoxazole precursor obtained by the method described above by heating it in a solvent or by chemical treatment with an acid or base.

[0032] Examples of dicarboxylic acids used in component (B) include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, etc. Examples of tricarboxylic acids include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc. Examples of tetracarboxylic acids include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis( Examples include 3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. Two or more of these dicarboxylic acids may be used in component (B).

[0033] Specific examples of the bisaminophenol compound used in the (B) component include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3, ,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, or a compound in which at least a part of the hydrogen atoms of these aromatic rings is substituted with an alkyl group or a halogen atom, an aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and a diamine having the structure shown below. The bisaminophenol compound used in the (B) component may be used in combination of two or more of these.

[0034]

Chemical formula

[0035] R 3 and R 6 each independently represents an oxygen atom, C(CF3)2, or C(CH3)2. R 4 , R 5 and R 7 ~R 14 each independently represents a hydrogen atom or a hydroxyl group.

[0036] Furthermore, in order to improve the storage stability of the positive-type photosensitive resin composition, it is preferable to encapsulate the main chain ends of these (B) components with known end-captive agents such as monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds. To improve the chemical resistance of the resin cured product obtained by firing, monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds having at least one alkenyl group or alkynyl group can also be used as these end-captive agents.

[0037] The content of end-capturing agents such as monoamines, acid anhydrides, acid chlorides, and monocarboxylic acids is preferably 1 mol% or more, and more preferably 5 mol% or more, based on 100 mol% of the total sum of all monomer components constituting component (B), from the viewpoint of improving storage stability. Furthermore, from the viewpoint of obtaining a resin with good film properties, it is preferably 40 mol% or less, and more preferably 30 mol% or less, based on 100 mol% of the total sum of all monomer components constituting component (B). Multiple different end groups may be introduced into component (B) by reacting multiple end-capturing agents.

[0038] The content of component (B) of the positive-type photosensitive resin composition is 10 to 100 parts by mass per 100 parts by mass of component (A). If the content of component (B) is less than 10 parts by mass per 100 parts by mass of component (A), the bending resistance decreases. The content of component (B) is preferably 20 parts by mass or more. On the other hand, if the content of component (B) exceeds 100 parts by mass per 100 parts by mass of component (A), the heat resistance decreases. The content of component (B) is preferably 95 parts by mass or less per 100 parts by mass of component (A).

[0039] Component (B) preferably contains a resin whose main chain consists of structural units represented by formula (1). Including a resin whose main chain consists of structural units represented by (1) improves bending resistance.

[0040] [ka]

[0041] In formula (1), R 1 and R 2 Each of these independently represents a divalent to octavalent organic group with 2 to 30 carbon atoms. p represents an integer from 0 to 4, and q represents an integer from 1 to 4.

[0042] The positive-type photosensitive resin composition of the present invention contains (C) polyhydroxystyrene and / or a copolymer of polyhydroxystyrene and polystyrene. (C) "Containing polyhydroxystyrene and / or a copolymer of polyhydroxystyrene and polystyrene" means containing either polyhydroxystyrene, a copolymer of polyhydroxystyrene and polystyrene, or both.

[0043] Component (C) of the present invention is synthesized by known methods.

[0044] Component (C) can be obtained by addition polymerization of a phenol derivative having an unsaturated bond. Examples of phenol derivatives having an unsaturated bond include hydroxystyrene, dihydroxystyrene, allylphenol, coumaric acid, 2'-hydroxychalcone, N-hydroxyphenyl-5-norbornene-2,3-dicarboxylic acid imide, resveratrol-4-hydroxystilbene, etc., and two or more of these may be used. Alternatively, it may be a copolymer with a monomer that does not contain a phenolic hydroxyl group, such as styrene. This makes it easier to adjust the alkali dissolution rate of component (C).

[0045] The content of component (C) is 1 to 90 parts by mass per 100 parts by mass of component (A). If the content of component (C) is less than 1 part by mass per 100 parts by mass of component (A), the sensitivity decreases. Preferably, the content of component (C) is 3 parts by mass or more per 100 parts by mass of component (A). On the other hand, if the content of component (C) exceeds 90 parts by mass per 100 parts by mass of component (A), the development adhesion decreases. Preferably, the content of component (C) is 70 parts by mass or less per 100 parts by mass of component (A).

[0046] The preferred weight-average molecular weight of component (C) can be determined by gel permeation chromatography (GPC) on a polystyrene basis, and from the viewpoint of sensitivity, it is preferably 1000 or more, more preferably 3000 or more, and even more preferably 4000 or more. From the viewpoint of development adhesion, it is preferably 10000 or less, more preferably 8000 or less, and even more preferably 7000 or less.

[0047] (C) Component preferably contains polyhydroxystyrene from the viewpoint of sensitivity.

[0048] In the positive-type photosensitive resin composition of the present invention, when the content of component (A) is [PI] (mass), the content of component (B) is [PB] (mass), and the content of component (C) is [PH] (mass), the mass ratio [PI] / ([PB]+[PH]) is preferably in the range of 0.5 ≤ [PI] / ([PB]+[PH]) ≤ 5.0. When [PI] / ([PB]+[PH]) is 0.5 or more, heat resistance can be improved. [PI] / ([PB]+[PH]) is more preferably 1 or more. On the other hand, when [PI] / ([PB]+[PH]) is 5 or less, sensitivity can be improved. [PI] / ([PB]+[PH]) is more preferably 4 or less.

[0049] It is preferable that the relationship between [PB] and [PH] is [PB] > [PH]. Having [PB] > [PH] improves development adhesion. It is preferable that the relationship between [PI], [PB], and [PH] is [PI] > [PB] > [PH]. Having [PI] > [PB] > [PH] improves the heat resistance of cured products processed with low-temperature curing at around 200-270°C.

[0050] The mass ratio of [PB] and [PH] is preferably in the range of 1.01 ≤ [PB] / [PH] ≤ 55.00. When the mass ratio of [PB] / [PH] is 1.01 or higher, development adhesion can be improved. The mass ratio of [PB] / [PH] is more preferably 1.50 or higher, and even more preferably 2.00 or higher. On the other hand, when the mass ratio of [PB] / [PH] is 55.00 or lower, sensitivity can be improved. The mass ratio of [PB] / [PH] is more preferably 30.00 or lower, and even more preferably 10.00 or lower.

[0051] The positive-type photosensitive resin composition of the present invention contains (D) a quinone diazide compound.

[0052] (D) By including a quinone diazide compound, acid is generated in the light-irradiated area, increasing its solubility in the alkaline aqueous solution, and a positive-type relief pattern in which the light-irradiated area dissolves can be obtained.

[0053] Examples of (D) quinone diazide compounds include polyhydroxy compounds to which quinone diazide sulfonic acid is ester-bonded, polyamino compounds to which quinone diazide sulfonic acid is sulfonamide-bonded, and polyhydroxypolyamino compounds to which quinone diazide sulfonic acid is ester-bonded and / or sulfonamide-bonded. When the total amount of hydroxyl groups or amino groups of these polyhydroxy compounds or polyamino compounds in (D) quinone diazide compounds is taken as 100 mol%, it is preferable that 50 mol% or more are esterified or sulfonamidated with quinone diazide sulfonic acid. Furthermore, the positive-type photosensitive resin composition (D) may contain two or more types of quinone diazide compounds.

[0054] (D) Among quinone diazide compounds, naphthoquinone diazidesulfonic acid ester compounds can be preferably included. Naphthoquinone diazidesulfonic acid ester compounds can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazidesulfonic acid compound, and can be synthesized by known methods. By using these naphthoquinone diazidesulfonic acid ester compounds, resolution, sensitivity, and residual film rate can be further improved.

[0055] The compounds having phenolic hydroxyl groups used here include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, and BisRS-26X. , DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPH Preferred examples include compounds such as AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, manufactured by Asahi Organic Chemicals Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylenebisphenol, and BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), to which naphthoquinone diazide-4-sulfonic acid or naphthoquinone diazide-5-sulfonic acid is introduced via an ester bond; however, other compounds can also be used.

[0056] The naphthoquinone diazide sulfonic acid-4-ester compound has absorption in the i-line region of mercury lamps and is suitable for i-line exposure, while the naphthoquinone diazide-5-sulfonic acid compound has absorption extending to the g-line region of mercury lamps and is suitable for g-line exposure. The photosensitive resin composition of the present invention can contain either the naphthoquinone diazide-4-sulfonic acid compound or the naphthoquinone diazide-5-sulfonic acid compound, and can also contain a naphthoquinone diazide sulfonic acid compound that uses both a naphthoquinone diazide-4-sulfonyl group and a naphthoquinone diazide-5-sulfonyl group in the same molecule, or can contain a mixture of the naphthoquinone diazide-4-sulfonic acid compound and the naphthoquinone diazide-5-sulfonic acid compound.

[0057] (D) The content of the quinone diazide compound is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more, per 100 parts by mass of the polyimide resin (A), from the viewpoint of improving sensitivity during exposure. Furthermore, from the viewpoint of reducing outgassing from the cured product, it is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less, per 100 parts by mass of the polyimide resin (A).

[0058] The positive-type photosensitive resin composition of the present invention contains (E) a solvent. (E) By including a solvent, it can be made into a varnish, which improves its applicability.

[0059] The solvent (E) may be a polar aprotic solvent such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, or dimethyl sulfoxide; an ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tetrahydrofuran, or dioxane; an ether such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, or diacetone. The product may contain solvents such as ketones like chol, esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethyl lactate, other esters such as ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, methyl acetoacetate, ethyl acetoacetate, etc., and aromatic hydrocarbons such as toluene and xylene, either alone or in combination.

[0060] From the viewpoint of improving coatability, it is preferable that the (E) solvent contains a polar aprotic solvent. Preferred polar aprotic solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0061] The content of solvent (E) is preferably such that the solid content concentration of the positive-type photosensitive resin composition is 3 to 30% by mass. If the solid content concentration is less than 3% by mass, the coating properties deteriorate, and 5% by mass or more is more preferable. Furthermore, if the content of solvent (E) exceeds 30% by mass, the storage stability of the positive-type photosensitive resin composition deteriorates, and 20% by mass or less is more preferable. Here, solid content concentration refers to the concentration of components other than (E) solvent in the positive-type photosensitive resin composition.

[0062] Furthermore, the content of the polar aprotic solvent is preferably 1 to 30% by mass relative to 100% by mass of the (E) solvent. If it is 1% by mass or more, the solubility of components (A), (B), and (C) can be improved, and the linearity of the pattern after development can be improved. The content of the polar aprotic solvent is more preferably 3% by mass or more relative to 100% by mass of the (E) solvent. Furthermore, if the content of the polar aprotic solvent is 30% by mass or less relative to 100% by mass of the (E) solvent, the solvent drying performance during pre-baking is improved, and the development adhesion is improved. The content of the polar aprotic solvent is more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to 100% by mass of the (E) solvent.

[0063] The positive-type photosensitive resin composition of the present invention may contain known compounds such as thermal crosslinking agents.

[0064] Examples of thermal crosslinking agents include DML-PC, DML-PEP, DMOM-PC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP, HMOM-TPPA (all are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), “NIKALAC” (registered trademark) MX-270, and “NIKA Thermal crosslinking agents having methylol groups and / or alkoxymethyl groups, such as "LAC" (registered trademark) MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.), epoxy groups such as "Denacol" EX-850L, "Denacol" EX-201-IM (trade name, manufactured by Nagase ChemteX Co., Ltd.), VG3101L (trade name, manufactured by Printec Co., Ltd.), "TEPIC" (registered trademark)-S, "TEPIC"-L, "TEPIC"-VL, "TEPIC"-FL, "TEPIC"-UC (trade name, manufactured by Nissan Chemical Industries, Ltd.). Thermal crosslinking agents having oxetane groups such as OXT-121, OXT-221, OX-SQ-H, OXT-191, PNOX-1009, RSOX (all trade names, manufactured by Toagosei Co., Ltd.), bismaleimide thermal crosslinking agents such as 1,2-bis(maleimide)ethane, 1,3-bis(maleimide)propane, 1,4-bis(maleimide)butane, 1,5-bis(maleimide)pentane, 1,6-bis(maleimide)hexane, 2,2,4-trimethyl-1,6-bis(maleimide)hexane, 4,4'-methylenebi Examples include aromatic polyisocyanates such as phenylene isocyanate (MDI) and tolylene diisocyanate (TDI); aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, and lysine diisocyanate; and alicyclic polyisocyanates such as isophorone diisocyanate (IPDI) and 4,4'-methylenebis(cyclohexyl isocyanate) (H12MDI) as thermal crosslinking agents.

[0065] From the viewpoint of improving the chemical resistance of the cured product, the content of the thermal crosslinking agent is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of component (A). Furthermore, from the viewpoint of reducing outgassing from the cured product and further improving the reliability of the organic EL display device, the content of the thermal crosslinking agent is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less, per 100 parts by mass of component (A).

[0066] The positive-type photosensitive resin composition of the present invention may contain (F) a thermal acid generator. The thermal acid generator is a compound that generates acid when heated, and the thermal decomposition start temperature of the thermal acid generator is preferably 120°C or higher, more preferably 130°C or higher, and even more preferably 140°C or higher. By setting the thermal decomposition temperature to 120°C or higher, it is possible to prevent the generation of acid in the process of drying the coated positive-type photosensitive resin film by applying heat during pattern processing (sometimes referred to as the pre-bake process). Furthermore, the thermal decomposition start temperature of (F) the thermal acid generator is preferably 250°C or lower, more preferably 240°C or lower, and even more preferably 230°C or lower. By setting the thermal decomposition temperature to 250°C or lower, sufficient acid can be generated in the heating process. In the present invention, by generating acid in the heating process, the crosslinking reaction of the thermal crosslinking agent can be promoted, and as a result, the amount of unreacted crosslinkable groups remaining in the cured product can be significantly reduced. If unreacted crosslinking groups remain in the cured product, gaseous components are generated during reliability testing, causing undesirable phenomena such as a decrease in brightness and pixel shrinkage in organic EL display devices. However, the crosslinking-promoting effect of the acid generated from the thermal acid generator can significantly improve the reliability of organic EL display devices.

[0067] In the positive-type photosensitive resin composition of the present invention, the (F) thermoacid generator only needs to have the function of generating acid when heated, and compounds that have the function of generating acid when exposed to light such as ultraviolet light in addition to heat are also included in the definition of a thermoacid generator. However, (D) quinone diazide compounds are defined as not being included in the (F) thermoacid generator even if they generate acid when heated.

[0068] (F) The acid generated from the thermal acid generator is preferably a strong acid, for example, aryl sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, alkyl sulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid, or camphor sulfonic acid.

[0069] (F) Examples of thermal acid generators include sulfonium salts and sulfonic acid esters. Two or more of these may be included. In the case of sulfonium salts, it is preferable to include a compound selected from the group consisting of monoarylsulfonium salts and trialkylsulfonium salts, from the viewpoint of generating heat by heating.

[0070] (F) Among thermal acid generators, it is preferable to include a thermal acid generator having a sulfonic acid ester structure because it has a high effect in improving the reliability of organic EL display devices. For example, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, phenyl methanesulfonate, methyl ethanesulfonate, ethyl ethanesulfonate, propyl ethanesulfonate, butyl ethanesulfonate, phenyl ethanesulfonate, methyl propanesulfonate, ethyl propanesulfonate, propyl propanesulfonate, butyl propanesulfonate, phenyl propanesulfonate, methyl butanesulfonate, ethyl butanesulfonate, propyl butanesulfonate, butyl butanesulfonate, phenyl butanesulfonate, methyl octanesulfonate, ethyl octanesulfonate, propyl octanesulfonate, butyl octanesulfonate, phenyl octanesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, phenyl p-toluenesulfonate, methane Examples include methoxyphenyl sulfonate, methoxyethyl methanesulfonate, methoxyethyl p-toluenesulfonate, “Irgacure” (registered trademark) PAG103, PAG121 (trade name, manufactured by BASF Japan Ltd.), PA-411, PA-480 (trade name, manufactured by Heraeus K.K.), and other thermal acid generators having a sulfonic acid ester structure include PAI-01, PAI-101, PAI-106, PAI-1001, PAI-10 Examples include 02, PAI-1003, PAI-1004 (product name, manufactured by Midori Chemical Co., Ltd.), SP-082, SP-601, SP-606, SP-607, SP-612 (product name, manufactured by ADEKA Corporation), NIT, MIN, ILP-110, ILP-110N, ILP-118, ILP-113, PA-223, PA-298 (product name, manufactured by Heraeus K.K.), NAI-105, NAI-106, NAI-109 (product name, manufactured by Midori Chemical Co., Ltd.).

[0071] Furthermore, it is particularly preferable that the (F) thermal acid generator contains the compound shown in formula (2). By including the compound in formula (2) in the (F) thermal acid generator, the volatility of the (F) thermal acid generator during curing (heat treatment) is reduced, and acid can be efficiently generated from the (F) thermal acid generator during curing, resulting in a greater crosslinking effect and thus improving the reliability of the organic EL display device. In addition, by including the compound shown in formula (2) in the (F) thermal acid generator, solubility in alkaline developer is more easily improved compared to cases where the compound in formula (2) is not included, thus improving exposure sensitivity.

[0072] [ka]

[0073] (In formula (2), R 15 R is a divalent to tetravalent group with 1 to 10 carbon atoms. 16 Each of these independently represents an alkyl group having 1 to 10 carbon atoms, which may have substituents, or an aryl group having 6 to 20 carbon atoms, which may have substituents. Examples of substituents include hydroxyl groups, halogen atoms, cyano groups, vinyl groups, acetylene groups, or linear or cyclic alkyl groups having 1 to 10 carbon atoms. (a represents an integer from 2 to 4.) From the standpoint of not reducing exposure sensitivity, in equation (2), R 15 R is a divalent group having 1 to 6 carbon atoms, which may have substituents, 16 Each of these is preferably independently a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms, which may have substituents.

[0074] Examples of compounds described in formula (2) above include compounds having multiple alcoholic hydroxyl groups (sometimes referred to as polyhydric alcohol compounds) or compounds having multiple phenolic hydroxyl groups (sometimes referred to as polyhydric phenolic compounds), in which the alcoholic hydroxyl groups or phenolic hydroxyl groups are esterified with methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, octanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, etc. Specific examples of dihydric alcohol compounds among polyhydric alcohol compounds include methanediol, ethanediol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol. Specific examples of polyhydric alcohol compounds with a valency of three or higher include propanetriol, butanetriol, pentanetriol, hexanetriol, heptanetriol, octantriol, nonanetriol, decanetriol, and pentaerythritol. Specific examples of polyhydric phenolic compounds include dihydroxybenzene, trihydroxybenzene, and tetrahydroxybenzene.

[0075] The content of the compound represented by formula (2) is preferably 20% by mass or more in 100% by mass of (F) the thermal acid generator, from the viewpoint of easily obtaining the effects of improving exposure sensitivity and improving the reliability of organic EL display devices. More preferably 50% by mass or more, even more preferably 70% by mass or more, and particularly preferably 100% by mass.

[0076] (F) The content of the thermal acid generator is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, when the total mass of components (A) and (B) is 100 parts by mass, from the viewpoint of further improving the reliability of the organic EL display device. Furthermore, the content of the thermal acid generator is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, when the total mass of components (A) and (B) is 100 parts by mass, from the viewpoint of imparting high heat resistance to the cured product.

[0077] The positive-type photosensitive resin composition of the present invention may contain a colorant. The colorant refers to a known organic pigment, inorganic pigment, or dye. The colorant is preferably an organic pigment and / or an inorganic pigment.

[0078] Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, copper phthalocyanine, surene pigments, benzofuranone pigments, or metal complex pigments.

[0079] Examples of inorganic pigments include titanium dioxide, zinc oxide, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, manganese violet, or cobalt violet.

[0080] Examples of dyes include azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine, or polymethine dyes.

[0081] For the purpose of improving the contrast of organic EL display devices, the color of the colorant is preferably black, which can block visible light across the entire wavelength range. It is preferable to include a colorant in the positive-type photosensitive resin composition that contains at least one selected from organic pigments, inorganic pigments, and dyes, so that the cured product is black. To achieve this, the above-mentioned black organic pigment and black inorganic pigment may be included, or a pseudo-black color may be obtained by mixing two or more organic pigments and dyes. In the case of pseudo-black coloring, it can be obtained by mixing two or more of the above-mentioned red, orange, yellow, purple, blue, green, and other organic pigments and dyes. It should be noted that the positive-type photosensitive resin composition of the present invention does not necessarily have to be black; a colorant that changes color during heat curing, resulting in a cured product that is black, may be used.

[0082] Of these, from the viewpoint of ensuring high heat resistance, it is preferable to include organic pigments and / or inorganic pigments, and a coloring agent that exhibits black coloration when cured. Furthermore, from the viewpoint of ensuring high insulating properties, it is preferable to include organic pigments and / or dyes, and a coloring agent that exhibits black coloration when cured. In other words, in order to achieve both high heat resistance and insulating properties, it is preferable to include organic pigments and a coloring agent that exhibits black coloration when cured.

[0083] The colorant content is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, based on the total amount of the positive-type photosensitive resin composition excluding the solvent, from the viewpoint of obtaining the necessary coloring properties for the cured product. Furthermore, from the viewpoint of obtaining good storage stability, the colorant content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on the total amount of the positive-type photosensitive resin composition excluding the solvent.

[0084] If a positive-type photosensitive resin composition contains a pigment, it is preferable that it also contains a dispersant. By including a dispersant, the colorant can be uniformly and stably dispersed in the positive-type photosensitive resin composition. The dispersant is not particularly limited, but polymeric dispersants are preferred. Examples of polymeric dispersants include polyester-based polymeric dispersants, acrylic-based polymeric dispersants, polyurethane-based polymeric dispersants, polyallylamine-based polymeric dispersants, or carbodiimide-based dispersants. More specifically, a polymeric dispersant is a polymer compound whose main chain consists of polyamino, polyether, polyester, polyurethane, polyacrylate, etc., and which has polar groups such as amines, carboxylic acids, phosphoric acids, amine salts, carboxylate salts, or phosphates in its side chains or main chain ends. The polar groups adsorb to the pigment, and the steric hindrance of the main chain polymer stabilizes the dispersion of the pigment.

[0085] Dispersants are classified into (polymer) dispersants having only an amine value, (polymer) dispersants having only an acid value, (polymer) dispersants having both an amine value and an acid value, or (polymer) dispersants having neither an amine value nor an acid value. However, (polymer) dispersants having both an amine value and an acid value, or (polymer) dispersants having only an amine value, are preferred, and (polymer) dispersants having only an amine value are more preferred.

[0086] From the viewpoint of obtaining good dispersion stability, the dispersant content is preferably 1 part by mass or more, and more preferably 3 parts by mass or more, per 100 parts by mass of pigment. Furthermore, from the viewpoint of maintaining the heat resistance of the cured product, it is preferably 100 parts by mass or less, and more preferably 50 parts by mass or less, per 100 parts by mass of pigment.

[0087] The positive-type photosensitive resin composition used in the present invention may contain an adhesion improver. Examples of adhesion improvers include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, as well as zirconia chelating agents, titanium chelating agents, aluminum chelating agents, and compounds obtained by reacting aromatic amine compounds with alkoxy group-containing silicon compounds. Two or more of these may be included. By including these adhesion improvers, adhesion to substrates such as silicon wafers, ITO, SiO2, and silicon nitride can be improved when developing the positive-type photosensitive resin film. Furthermore, resistance to oxygen plasma and UV ozone treatment used for cleaning can be improved. The adhesion improver content is preferably 0.1 to 10% by mass relative to the total amount of the positive-type photosensitive resin composition excluding the solvent.

[0088] The positive-type photosensitive resin composition used in the present invention may contain a surfactant to improve wettability with the substrate, if necessary. Commercially available compounds can be used as surfactants. Specifically, examples of silicone-based surfactants include the SH series, SD series, and ST series from Toray Dow Corning Silicone, the BYK series from Bic Chemie Japan, the KP series from Shin-Etsu Silicone, the Disform series from Nippon Oil & Fats Co., Ltd., and the TSF series from Toshiba Silicone Co., Ltd. Examples of fluorine-based surfactants include the Megafac® series from Dainippon Ink & Industrial Co., Ltd., the Florard series from Sumitomo 3M Co., Ltd., the Surflon® series and Asahi Guard® series from Asahi Glass Co., Ltd., the EF series from Shin Akita Chemical Co., Ltd., and the Polyfox series from Omnova Solutions Co., Ltd. Examples of surfactants consisting of acrylic and / or methacrylic polymers include the Polyflow series from Kyoeisha Chemical Co., Ltd. and the Disparon® series from Kusumoto Chemical Co., Ltd., but are not limited to these.

[0089] The surfactant content is preferably 0.001 to 1% by mass relative to the total amount of the positive-type photosensitive resin composition excluding the solvent.

[0090] The positive-type photosensitive resin composition used in the present invention may contain a compound having a phenolic hydroxyl group if necessary to supplement the alkali developability of the photosensitive resin composition. Examples of compounds having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, Bi sOTBP-CP, TekP-4HBPA (TetrakisP-DO-BPA), TrisPHAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCR-PA, BisOFP- Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis23 6T-OCHP, Methylene Tris-FR-CR, BisRS-26X, BisRS-OCHP, (product name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, B IR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Yokuzai Kogyo Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, Examples include 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, and 8-quinolinol. By including these compounds having phenolic hydroxyl groups, the resulting positive-type photosensitive resin composition is almost insoluble in alkaline developer before exposure, but readily dissolves in alkaline developer after exposure, resulting in less film loss during development and easier development in a short time. Therefore, sensitivity is easily improved.

[0091] The content of such compounds having phenolic hydroxyl groups is preferably 1% by mass or more and 20% by mass or less, based on the total amount of the positive-type photosensitive resin composition excluding the solvent.

[0092] Furthermore, the positive-type photosensitive resin composition used in the present invention may also contain inorganic particles. Preferred specific examples include, but are not limited to, silicon dioxide, titanium dioxide, barium titanate, alumina, and talc. The primary particle size of these inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

[0093] The inorganic particle content is preferably 5 to 90% by mass relative to the total amount of the positive-type photosensitive resin composition excluding the solvent.

[0094] Next, a method for producing the positive-type photosensitive resin composition of the present invention will be described. For example, a positive-type photosensitive resin composition can be obtained by dissolving component (A), component (B), component (C), (D) a quinone diazide compound, (E) a solvent, and optionally an adhesion improver, surfactant, colorant, inorganic particles, etc.

[0095] Dissolution methods include stirring and heating. When heating, the heating temperature should preferably be set within a range that does not impair the performance of the positive-type photosensitive resin composition, and is usually between room temperature and 80°C. Furthermore, the order in which each component is dissolved is not particularly limited; for example, compounds with lower solubility can be dissolved sequentially. In addition, for components that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, adding them last after dissolving the other components can prevent poor dissolution of other components due to bubble generation.

[0096] The obtained positive-type photosensitive resin composition is preferably filtered using a filtration filter to remove impurities. The filter pore size can be, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, or 0.02 μm, but is not limited to these. The material of the filtration filter can be polypropylene (PP), polyethylene (PE), nylon (NY), or polytetrafluoroethylene (PTFE), with polyethylene or nylon being preferred. If the positive-type photosensitive resin composition contains pigments or particles, it is preferable to use a filtration filter with a pore size larger than the size of these particles.

[0097] The cured product of the present invention is a cured product obtained by curing a positive-type photosensitive resin composition. The cured product is obtained by heat-treating the positive-type photosensitive resin composition. Known methods such as using a hot plate, oven, or infrared radiation can be used for the heat treatment. Preferred heat treatment conditions will be described later in the product manufacturing method (5) step of heat-treating the developed positive-type photosensitive resin film.

[0098] Next, a method for producing a cured film using the positive-type photosensitive resin composition of the present invention will be described in detail. The method for manufacturing the cured product is: (1) A step of applying the above-mentioned positive-type photosensitive resin composition to a substrate to form a positive-type photosensitive resin film. (2) A step of drying the positive-type photosensitive resin film (pre-baking step), (3) A step of exposing a dried positive-type photosensitive resin film through a photomask, (4) A process of developing the exposed positive-type photosensitive resin film and (5) A process of heat-treating the developed positive-type photosensitive resin film. It includes them in this order.

[0099] (1) In the step of applying the above-described positive-type photosensitive resin composition to a substrate to form a positive-type photosensitive resin film, the positive-type photosensitive resin composition of the present invention is applied by spin coating, slit coating, dip coating, spray coating, printing, etc., to obtain a positive-type photosensitive resin film of the positive-type photosensitive resin composition. Prior to application, the substrate to which the positive-type photosensitive resin composition is to be applied may be pre-treated with the adhesion improver described above.

[0100] For example, one method involves treating the substrate surface using a solution obtained by dissolving an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate at a concentration of 0.5 to 20% by mass. Methods for treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

[0101] (2) In the process of drying the positive-type photosensitive resin film, the coated positive-type photosensitive resin film is subjected to vacuum drying as needed, and then heat treatment is performed using a hot plate, oven, infrared rays, etc., at a temperature of 50°C to 180°C for 1 minute to several hours to obtain the positive-type photosensitive resin film.

[0102] Next, (3) the step of exposing the dried positive-type photosensitive resin film through a photomask will be described. Chemical rays are irradiated onto the positive-type photosensitive resin film through a photomask having a desired pattern. Chemical rays that can be used for exposure include ultraviolet rays, visible light, electron beams, and X-rays, but in this invention, it is preferable to use the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp.

[0103] Post-exposure baking may be performed after chemical irradiation. Post-exposure baking can be expected to improve resolution after development or increase the tolerance range of development conditions. Post-exposure baking can be performed using an oven, hot plate, infrared, flash annealing device, or laser annealing device. The post-exposure baking temperature is preferably 50 to 180°C, and 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 will proceed well and the development time may be shortened.

[0104] (4) In the step of developing the exposed positive-type photosensitive resin film, the exposed positive-type photosensitive resin film is developed using a developer to remove areas other than the exposed parts. As the developer, aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine are preferred.

[0105] In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added to these alkaline aqueous solutions, either individually or in combination. Possible development methods include spraying, paddle development, immersion, and ultrasonic development.

[0106] Next, it is preferable to rinse the pattern formed by development with distilled 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 distilled water for rinsing.

[0107] Next, (5) the developed positive-type photosensitive resin film is subjected to a heat treatment step. Since residual solvents and components with low heat resistance can be removed by the heat treatment, heat resistance and chemical resistance can be improved. The positive-type photosensitive resin composition of the present invention can form imide rings and oxazole rings by heat treatment, thus improving heat resistance and chemical resistance. Furthermore, if a thermal crosslinking agent is contained, the thermal crosslinking reaction can be advanced by heat treatment, further improving heat resistance and chemical resistance. From the viewpoint of improving the heat resistance of the cured product, the heat treatment temperature is preferably 200°C or higher, more preferably 220°C or higher, even more preferably 230°C or higher, and particularly preferably 240°C or higher.

[0108] On the other hand, from the viewpoint of avoiding the effects of thermal degradation of the TFT element, a temperature of 400°C or lower is preferred, more preferably 350°C or lower, and even more preferably 270°C or lower. Within this temperature range, the temperature may be increased in stages or continuously. From the viewpoint of improving the heat resistance of the cured product, the heat treatment time is preferably 30 minutes or more, and more preferably 45 minutes or more. Also, from the viewpoint of productivity, it is preferably 180 minutes or less, and more preferably 120 minutes or less. For example, a method of heat treatment at 150°C and 250°C for 60 minutes each can be used, or a method of heat treatment while linearly increasing the temperature from room temperature to 250°C over 2 hours can be used.

[0109] The cured product of the present invention is preferably a cured product formed from the positive-type photosensitive resin composition of the present invention. In another embodiment of the cured product of the present invention, when analyzed by reaction pyrolysis GC / MS, the compound represented by formula (3), the compound represented by formula (4), and the compound represented by formula (5) are detected, and the detection peak intensity ratio is such that, with the compound represented by formula (4) being 1, the compound represented by formula (3) is 0.1 to 1, and the compound represented by formula (5) is 0.1 to 3.

[0110] [ka]

[0111] (In equations (3), (4), and (5), R 17 ~R 23 Each of these independently represents a monovalent organic group having 1 to 30 carbon atoms, which may contain a hydrogen atom or a heteroatom.

[0112] Examples of monovalent organic groups having 1 to 30 carbon atoms that may contain the heteroatom in formulas (3), (4), and (5) include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0113] The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in linear and branched alkyl groups is usually 1 to 30, preferably 1 to 20 and more preferably 1 to 10 from the viewpoint of maintaining high heat resistance and high bending resistance of the cured product. The number of carbon atoms in cyclic alkyl groups is usually 3 to 30, preferably 3 to 20 and more preferably 3 to 10 from the viewpoint of maintaining high heat resistance and high bending resistance of the cured product. Examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, and decyl group.

[0114] The alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in linear and branched alkenyl groups is usually 2 to 30, preferably 2 to 20 and more preferably 2 to 10 from the viewpoint of maintaining high heat resistance and high bending resistance of the cured product. The number of carbon atoms in cyclic alkenyl groups is usually 3 to 30, preferably 3 to 20 and more preferably 3 to 10 from the viewpoint of maintaining high heat resistance and high bending resistance of the cured product. Examples of alkenyl groups include ethenyl, propenyl, isopropenyl, butenyl, pentenyl, hexenyl, nonenyl, and decenyl groups.

[0115] The alkynyl group may be linear, branched, or cyclic. The number of carbon atoms in linear and branched alkynyl groups is usually 2 to 30, preferably 2 to 20 and more preferably 2 to 10 from the viewpoint of maintaining high heat resistance and high bending resistance of the cured product. The number of carbon atoms in cyclic alkynyl groups is usually 3 to 30, preferably 3 to 20 and more preferably 3 to 10 from the viewpoint of maintaining high heat resistance and high bending resistance of the cured product. Examples of alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, and hexynyl groups.

[0116] The aryl group is the remaining atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting the aromatic ring from an aromatic hydrocarbon, and includes those having a hydroxyl group, the alkyl group, the alkenyl group, or the alkynyl group as a functional group. The number of carbon atoms in the aryl group is usually 6 to 30, and preferably 6 to 20. Examples of aryl groups include phenyl group, hydroxyphenyl group, alkylphenyl group, and alkylhydroxyphenyl group. From the viewpoint of balancing high heat resistance and bending resistance of the cured product, hydroxyphenyl group and alkylhydroxyphenyl group are preferred. Examples of alkylphenyl groups include methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, methylethylphenyl group, propylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, tert-butylphenyl group, pentylphenyl group, hexylphenyl group, cyclohexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, and decylphenyl group. Examples of alkylhydroxyphenyl groups include methylhydroxyphenyl group, ethylhydroxyphenyl group, dimethylhydroxyphenyl group, propylhydroxyphenyl group, methylethylhydroxyphenyl group, propylhydroxyphenyl group, isopropylhydroxyphenyl group, butylhydroxyphenyl group, isobutylhydroxyphenyl group, tert-butylhydroxyphenyl group, pentylhydroxyphenyl group, hexylhydroxyphenyl group, cyclohexylhydroxyphenyl group, heptylhydroxyphenyl group, octylhydroxyphenyl group, nonylhydroxyphenyl group, and decylhydroxyphenyl group.

[0117] From the perspective of balancing high heat resistance and bending resistance of the cured material, R 2 , R 3 , R 4 Preferably, at least one of the groups is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group. More preferably, the group contains both an alkyl group and a hydroxyphenyl group and / or an alkylhydroxyphenyl group.

[0118] When the cured product is analyzed by reaction pyrolysis GC / MS, the compounds shown in formula (3), formula (4), and formula (5) are detected. If the peak intensity ratio of the detected compounds is set to 1 for the compound shown in formula (4), then the compound shown in formula (3) is 0.1 to 1, and the compound shown in formula (5) is 0.1 to 3. This makes it easier to obtain a cured product with high heat resistance and high bending resistance.

[0119] The compounds contained in the cured product of the present invention will now be described. The compound represented by formula (3) can be obtained, for example, as a structure or residue derived from (C) polyhydroxystyrene and / or a copolymer of polyhydroxystyrene and polystyrene. The compound represented by formula (4) can be obtained, for example, as a structure or residue derived from (A) polyimide, polyimide precursors and copolymers thereof. The compound represented by formula (5) can be obtained, for example, as a structure or residue derived from (B) polybenzoxazole, polybenzoxazole precursors and copolymers thereof.

[0120] A cured product formed using the positive-type photosensitive resin composition of the present invention can be used in a display device that includes a first electrode formed on a substrate and a second electrode provided opposite to the first electrode, specifically, for example, a planarization layer of a liquid crystal display device, a planarization layer and / or pixel division layer of an organic EL display device. The following explanation will use an organic EL display device as an example.

[0121] The organic EL display device of the present invention comprises the cured material. Specifically, it is preferable that the organic EL display device has a drive circuit, a planarization layer, a first electrode, a pixel division layer, an emissive layer, and a second electrode on a substrate, and that the planarization layer and / or pixel division layer contain the cured material. Taking an active matrix type display device as an example, it has a thin-film transistor (hereinafter referred to as TFT) and wiring located on the side of the TFT and connected to the TFT on a substrate such as glass or a resin film, and has a planarization layer thereon so as to cover the irregularities, and further has a display element provided on the planarization layer. The display element and the wiring are connected via contact holes formed in the planarization layer. In particular, in recent years, flexible organic EL display devices have become mainstream, and it is preferable that the substrate having the aforementioned drive circuit is made of a resin film.

[0122] The organic EL display device of the present invention preferably has at least a portion of the cured material that is flexible and / or fixed in a bent state. By using the cured material obtained by curing the positive-type photosensitive resin composition or photosensitive resin sheet of the present invention, an organic EL display device with excellent bending resistance can be obtained. The radius of curvature of the flexible and / or fixed in a bent state is preferably 0.1 mm or more, and preferably 5 mm or less. If the radius of curvature is 0.1 mm or more, bending resistance at the bent portion can be ensured, and if it is 5 mm or less, design features such as a narrow bezel can be ensured.

[0123] The organic EL display device of the present invention is bendable at any suitable part. For example, the organic EL display device may be bendable in the center, like a foldable display device, or it may be bendable at the edges from the viewpoint of maximizing design and display screen size. Furthermore, the organic EL display device may be bendable along its longitudinal direction or along its short direction. Depending on the application, it may be necessary for specific parts of the organic EL display device to be bendable (for example, some or all of the four corners may be bendable diagonally).

[0124] Figure 1 shows a cross-sectional view of an example of an organic EL display device in which a planarization layer and a pixel division layer are formed. Bottom-gate or top-gate type TFTs 1 are arranged in a matrix on a substrate 6, and a TFT insulating layer 3 is formed covering these TFTs 1. Wiring 2 connected to the TFTs 1 is provided on the TFT insulating layer 3. Furthermore, a planarization layer 4 is provided on the TFT insulating layer 3, embedding the wiring 2. Contact holes 7 reaching the wiring 2 are provided in the planarization layer 4. ITO (transparent electrode) 5 is formed on the planarization layer 4, connected to the wiring 2 via these contact holes 7.

[0125] Here, ITO5 becomes the electrode for the display element (e.g., an organic EL element). A pixel division layer 8 is formed to cover the periphery of ITO5. The organic EL element may be a top-emission type that emits light from the side opposite the substrate 6, or a bottom-emission type that extracts light from the substrate 6 side. In this way, an active-matrix type organic EL display device is obtained in which each organic EL element is connected to a TFT 1 for driving it.

[0126] The TFT insulating layer 3, planarization layer 4, and / or pixel splitting layer 8 can be formed by the steps of forming a positive-type photosensitive resin film made of the positive-type photosensitive resin composition of the present invention, exposing the positive-type photosensitive resin film, developing the exposed positive-type photosensitive resin film, and heat-treating the developed positive-type photosensitive resin film. An organic EL display device can be obtained by a manufacturing method having these steps.

[0127] Furthermore, cured products formed using the positive-type photosensitive resin composition of the present invention can be used as insulating films and protective films constituting electronic components. Here, examples of electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (hereinafter referred to as ICs), and memories, and passive components such as resistors, capacitors, and inductors. Electronic components using semiconductors are also referred to as semiconductor devices. Specific examples of cured products within electronic components include semiconductor passivation films, semiconductor elements, surface protective films for TFTs, interlayer insulating films in multilayer wiring for high-density mounting of 2 to 10 layers, insulating films and protective films for touch panel displays, etc. However, the invention is not limited to these applications and can take various structures.

[0128] Furthermore, the substrate surface on which the cured product is formed can be appropriately selected depending on the application and process, but examples include silicon, ceramics, metal, glass, epoxy resin, etc., and multiple of these may be arranged on the same surface. Examples of electronic devices having a surface protective film or interlayer insulating film on which the cured product of the present invention is arranged include MRAMs with low heat resistance. In other words, the cured product of the present invention is suitable for use as a surface protective film for MRAMs.

[0129] Furthermore, polymer memory (Polymer Ferroelectric RAM: PFRAM) and phase-change memory (PCRAM, or Ovonics Unified Memory: OUM), which are promising next-generation memory technologies in addition to MRAM, are likely to utilize new materials with lower heat resistance compared to conventional memory. Therefore, the cured product of the present invention is also suitable for use as a surface protective film for these technologies.

[0130] Furthermore, it is also suitably used in fan-out wafer-level packages (hereinafter referred to as fan-out WLPs). A fan-out WLP is a semiconductor package in which an expanded portion is provided around the semiconductor chip using an encapsulating resin such as epoxy resin, rewiring is performed from the electrodes on the semiconductor chip to the expanded portion, and solder balls are mounted on the expanded portion to secure the required number of terminals.

[0131] In fan-out WLP, wiring is installed so as to straddle the boundary line formed by the main surface of the semiconductor chip and the main surface of the encapsulating resin. That is, an interlayer insulating film is formed on a substrate composed of two or more materials, namely a semiconductor chip with metal wiring and encapsulating resin, and wiring is formed on the interlayer insulating film.

[0132] In addition to the above, in semiconductor packages in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is installed so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. In this embodiment as well, an interlayer insulating film is formed on a substrate composed of two or more materials, and wiring is formed on the interlayer insulating film. The cured product obtained by curing the positive-type photosensitive resin composition of the present invention has high adhesion to semiconductor chips with metal wiring and also has high adhesion to encapsulating resins such as epoxy resin, and is therefore suitable for use as an interlayer insulating film provided on a substrate composed of two or more materials. [Examples]

[0133] The present invention will be described below with reference to examples, but the present invention is not limited to these examples. That is not the case. Examples 1 to 14 shall be interpreted as Reference Examples 1 to 14. The positive-type photosensitive resin compositions in the examples were evaluated by the following method.

[0134] (1) Sensitivity evaluation The positive-type photosensitive resin compositions obtained in each of the examples and comparative examples described below were coated onto an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Ltd.), and a pre-baked film with a thickness of 3.0 μm was prepared by baking on a hot plate at 120°C for 3 minutes. The film thickness was measured using a Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. under conditions of a refractive index of 1.63.

[0135] Subsequently, using the Nikon i-line stepper exposure machine NSR-2005i9C, exposure was performed through a mask with a 10 μm contact hole pattern, applying 50-300 mJ / cm².2 At this exposure level, 10 mJ / cm² 2 The exposure was performed in steps. After exposure, the film was developed using the ACT-8 developing apparatus with a 2.38% by mass aqueous solution of tetramethylammonium (hereinafter referred to as TMAH, manufactured by Tama Chemical Industry Co., Ltd.) for a time when the film thickness during development was 0.5 μm. After rinsing with distilled water, the film was shaken dry to obtain the pattern.

[0136] The resulting developed film pattern was observed at 20x magnification using an FDP microscope MX61 (manufactured by Olympus Corporation). The minimum required exposure to reach a contact hole aperture diameter of 10 μm was determined, and this was set as the exposure sensitivity, resulting in 200 mJ / cm². 2 The following were deemed acceptable. A lower sensitivity value indicates higher sensitivity and is preferable.

[0137] (2) Evaluation of bending resistance The positive-type photosensitive resin compositions obtained in each of the examples and comparative examples described below were applied to a polyimide film substrate by spin coating at an arbitrary rotation speed to obtain a positive-type photosensitive resin film. As a drying step, the film was pre-baked on a hot plate at 120°C for 2 minutes to obtain a positive-type photosensitive resin film. Next, using an automatic developing device (AD-2000, manufactured by Takizawa Sangyo Co., Ltd.), the film was shower-developed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide for 90 seconds, and then rinsed with pure water for 30 seconds. The developed positive-type photosensitive resin film-coated substrate was cured (heat-treated) in an oven at 250°C under a nitrogen atmosphere for 60 minutes to obtain a cured product with a film thickness of 2.0 μm.

[0138] Next, ten pieces of polyimide film substrate containing the cured material were cut to a size of 50 mm x 10 mm. The cut polyimide films were then stored in an air atmosphere at 100°C for 500 hours. Afterward, with the cured material side facing outward, the polyimide film substrate was folded 180° along a 25 mm vertical line and held for 30 seconds. After 30 seconds, the folded polyimide film substrate was unfolded, and the folded portion along the 25 mm vertical line on the cured material surface was observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation) to evaluate the change in the appearance of the cured material surface. The bending test was performed in the range of curvature radius from 0.1 to 2.0 mm, and the minimum curvature radius (mm) at which no peeling of the cured material from the polyimide film substrate or appearance changes such as cracks occurred on the cured material surface was recorded. A smaller minimum curvature radius (mm) value indicates higher bending resistance and is preferable.

[0139] (3) Reliability testing of organic EL display devices <Fabrication of Organic EL Display Devices> Figure 2 shows a schematic diagram of the substrate used. First, a 100 nm transparent ITO conductive film was formed on the entire surface of a 38 × 46 mm alkali-free glass substrate 11 by sputtering and etched as the first electrode 12. At the same time, an auxiliary electrode 13 was also formed to extract the second electrode. The obtained substrate was ultrasonically cleaned for 10 minutes with "Semicoclean 56" (product name, manufactured by Furuuchi Chemical Co., Ltd.) and then washed with ultrapure water. Next, a positive-type photosensitive resin composition (varnish) according to each example and comparative example described later was applied to the entire surface of this substrate by spin coating and pre-baked on a hot plate at 120°C for 2 minutes. This film was UV exposed using a parallel light mask aligner (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Inc.) with an ultra-high pressure mercury lamp as the light source (mixed g-line, h-line, and i-line) via a photomask. After UV exposure, it was developed with a 2.38% TMAH aqueous solution to dissolve only the exposed areas, and then rinsed with pure water. The resulting patterned substrate was cured in an inert oven (CLH-21CD-S, manufactured by Koyo Thermo Systems Co., Ltd.) at 250°C under a nitrogen atmosphere for 60 minutes. In this way, a pixel division layer 14 was formed, limited to the effective area of ​​the substrate, with openings measuring 50 μm in width and 260 μm in length, arranged at a pitch of 155 μm in the width direction and 465 μm in the length direction, with each opening exposing the first electrode. In this manner, a pixel division layer with an aperture ratio of 18% was provided in the effective area of ​​the substrate, which was a rectangle with sides of 16 mm, and the thickness of the pixel division layer was approximately 2.0 μm.

[0140] Next, after nitrogen plasma treatment as a pretreatment, an organic EL layer 15 was formed by vacuum deposition. The vacuum level during deposition was 1 × 10⁻⁶. -3 The temperature was below Pa, and the substrate was rotated relative to the deposition source during deposition. First, compound (HT-1) was deposited as a hole injection layer at 10 nm, and compound (HT-2) was deposited as a hole transport layer at 50 nm. Next, compound (GH-1) as a host material and compound (GD-1) as a dopant material were deposited on the light-emitting layer to a thickness of 40 nm with a doping concentration of 10%. Then, compound (ET-1) and compound (LiQ) were layered as electron transport materials in a volume ratio of 1:1 to a thickness of 40 nm. The structures of the compounds used in the organic EL layer are shown below.

[0141] [ka]

[0142] Next, a 2nm layer of compound (LiQ) was deposited, followed by a 60nm layer of Mg and Ag in a volume ratio of 1:10 to form the second electrode 16. Finally, the device was sealed by bonding a cap-shaped glass plate using an epoxy resin adhesive under a low-humidity nitrogen atmosphere, and four 5mm square light-emitting devices were fabricated on a single substrate. The film thickness mentioned here refers to the value displayed on a quartz crystal-wavelength film thickness monitor.

[0143] <Reliability Evaluation> The fabricated organic EL display devices were stored in an air atmosphere at 100°C. Every 100 hours, the organic EL display devices were removed and driven by DC at 10 mA / cm² to emit light, and the luminescent area of ​​each light-emitting pixel was measured. The reliability of the organic EL display device (in hours) was defined as the minimum time at which the luminescent area after the UV irradiation test became 50 or less, with the initial luminescent area before the reliability test set to 100. A reliability of 500 hours or more was considered acceptable. A longer minimum time at which the luminescent area after the UV irradiation test becomes 50 or less is preferable as it indicates superior reliability.

[0144] (4) Heat resistance evaluation The positive-type photosensitive resin compositions obtained in each of the examples and comparative examples described below were applied to an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Ltd.), and a pre-baked film with a thickness of 3.0 μm was prepared by baking on a hot plate at 120°C for 3 minutes. Subsequently, using the developing apparatus of the ACT-8, the film was developed with a 2.38 mass% aqueous solution of tetramethylammonium (hereinafter referred to as TMAH, manufactured by Tama Chemical Industry Co., Ltd.) for a time at which the film thickness during development was reduced to 0.5 μm. After rinsing with distilled water, the film was shaken dry. Then, it was cured in an inert oven (CLH-21CD-S, manufactured by Koyo Thermo Systems Co., Ltd.) in a nitrogen atmosphere at 250°C for 60 minutes. The resulting cured product was peeled off with hydrofluoric acid to obtain a film. A 10 mg sample of the obtained single-layer film was packed into an Al clamp cell to prepare a TGA measurement sample. Thermogravimetric analysis was performed using a TGA-50 (Shimadzu Corporation) under a nitrogen atmosphere, while increasing the temperature by 10°C per minute. A temperature of 320°C or higher was considered acceptable for a 5% weight reduction from the weight at 200°C. A higher temperature for a 5% weight reduction from the weight at 200°C indicates higher heat resistance and is preferable.

[0145] (5) Evaluation of development adhesion The positive-type photosensitive resin compositions obtained in each of the examples and comparative examples described below were coated onto an 8-inch silicon wafer by spin coating using a coating and developing apparatus ACT-8 (manufactured by Tokyo Electron Ltd.), and a pre-baked film with a thickness of 3.0 μm was prepared by baking on a hot plate at 120°C for 3 minutes. The film thickness was measured using a Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. under conditions of a refractive index of 1.63. Subsequently, exposure was performed using an i-line stepper NSR-2005i9C (manufactured by Nikon Corporation) through a mask having a pattern of closed sections with a diameter of 3 to 100 μm, at the exposure amount corresponding to the exposure sensitivity obtained in (1). After exposure, development was performed using the ACT-8 developing apparatus with a 2.38 mass% tetramethylammonium aqueous solution (hereinafter referred to as TMAH, manufactured by Tama Chemical Industry Co., Ltd.) for a time at which the film thickness during development was 0.5 μm. After rinsing with distilled water, the film was shaken dry to obtain the pattern.

[0146] The resulting developed film patterns were observed at 20x magnification using an FDP microscope MX61 (manufactured by Olympus Corporation). 100 observation points were taken per size, and the minimum closed pattern with 90 or more patterns remaining intact was identified. A film was considered acceptable if patterns of 10 μm or less remained intact. A smaller minimum closed pattern with 90 or more patterns remaining is preferable because it indicates superior development adhesion.

[0147] (6) Evaluation of pattern linearity after development The patterns of the developing films obtained in (5) were observed at 20x magnification using an FDP microscope MX61 (manufactured by Olympus Corporation). 100 50 μm closed patterns were observed, and if 90 or more patterns showed no shape abnormalities, the result was considered good (A); if 80 or more patterns showed no shape abnormalities, the result was considered somewhat good (B); and if fewer than 80 patterns showed no shape abnormalities, the result was considered poor (C).

[0148] <Compositional analysis by reaction pyrolysis GC / MS> To 61 μg of the cured product obtained in (4), 3 μL of reaction reagent (tetramethylammonium hydroxide) was added, and thermal decomposition was performed at a heating temperature of 400°C using a multi-shot pyrolizer PY-3030D (Frontier Labs). Analysis was then performed using a gas chromatograph-mass spectrometer JMS-Q1000GC(K9) (JEOL Ltd.), with a stainless steel capillary column (0.25 mm inner diameter × 30 m, stationary phase: 5% phenylpolydimethylsiloxane) as the GC column, the GC temperature was raised from 40°C (held for 3 minutes) at a rate of 20°C / min to 320°C, the inlet temperature was 300°C, the column flow rate was 1.5 mL / min, the ionization method was EI (electron ionization), the mass number range was m / z 20~800, and the scan speed was 0.5 sec / scan.

[0149] The compounds used in the examples and comparative examples are listed below.

[0150] Synthesis Example 1: Synthesis of Hydroxyl Group-Containing Diamine Compounds 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and the mixture was cooled to -15°C. A solution of 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise. After the addition was complete, the mixture was allowed to react at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered off and vacuum-dried at 50°C.

[0151] 30 g of solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve. 2 g of 5% palladium-carbon was added. Hydrogen was introduced using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated when it was confirmed that the balloon no longer deflated. After the reaction was complete, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

[0152] [ka]

[0153] Synthesis Example 2: Synthesis of Polyimide Precursor (P1) Under a stream of dry nitrogen, 62.0 g (0.20 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of N-methyl-2-pyrrolidone (hereinafter referred to as NMP). 96.7 g (0.16 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 was added together with 100 g of NMP, and the mixture was reacted at 20°C for 1 hour, followed by 50°C for 2 hours. Next, 8.7 g (0.08 mol) of 3-aminophenol was added as a terminal encapsulant along with 50 g of NMP, and the mixture was reacted at 50°C for 2 hours. Then, a solution of 47.7 g (0.40 mol) of N,N-dimethylformamide dimethyl acetal diluted with 100 g of NMP was added dropwise over 10 minutes. After the addition, the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature, and then added to 5 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target polyimide precursor (P1).

[0154] Synthesis Example 3: Synthesis of Polyimide (P2) Under a stream of dry nitrogen, 58.6 g (0.16 mol) of BAHF and 8.7 g (0.08 mol) of 3-aminophenol as an end-capturing agent were dissolved in 300 g of N-methyl-2-pyrrolidone (NMP). 62.0 g (0.20 mol) of ODPA was added along with 100 g of NMP, and the mixture was stirred at 20°C for 1 hour, followed by stirring at 50°C for 4 hours. Then, 15 g of xylene was added, and the mixture was stirred at 150°C for 5 hours while azeotropically stirring with water. After stirring, the solution was added to 5 L of water, and a white precipitate was collected. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target polyimide (P2).

[0155] Synthesis Example 4: Synthesis of Polybenzoxazole Precursor (P3) Under a stream of dry nitrogen, 41.3 g (0.16 mol) of diphenyl ether-4,4'-dicarboxylic acid and 43.2 g (0.32 mol) of 1-hydroxy-1,2,3-benzotriazole were reacted to obtain a mixture of 0.16 mol of dicarboxylic acid derivatives. This mixture was then dissolved in 73.3 g (0.20 mol) of BAHF in 570 g of NMP, and the mixture was reacted at 75°C for 12 hours. Next, 13.1 g (0.08 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride dissolved in 70 g of NMP was added, and the mixture was stirred for another 12 hours to complete the reaction. After filtering the reaction mixture, it was added to a water / methanol = 3 / 1 (volume ratio) solution to obtain a white precipitate. This precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain the target polybenzoxazole (PBO) precursor (P3). P3 had the structural unit represented by formula (1) described above.

[0156] Synthesis Example 5: Synthesis of Polyhydroxystyrene (P4) To a mixture of 2400 g of tetrahydrofuran and 2.56 g (0.04 mol) of sec-butyllithium as an initiator, 105.75 g (0.6 mol) of pt-butoxystyrene was added and polymerized with stirring for 3 hours. Then, 12.82 g (0.4 mol) of methanol was added to terminate the polymerization. Next, to purify the polymer, the reaction mixture was poured into 3 L of methanol, and the precipitated polymer was dried. The obtained polymer was dissolved in 1.6 L of acetone, and 2 g of concentrated hydrochloric acid was added at 60°C and stirred for 7 hours to deprotect pt-butoxystyrene and convert it to hydroxystyrene. After the reaction was complete, the solution was poured into water to precipitate the polymer, and the obtained precipitate was washed three times with water. After that, it was dried in a vacuum dryer at 50°C for 24 hours to obtain the target polyhydroxystyrene (P4).

[0157] Synthesis Example 6: Synthesis of Acrylic Resin (P5) A methyl methacrylate / methacrylic acid / styrene copolymer (mass ratio 30 / 40 / 30) was synthesized by a known method (Patent No. 3120476; Example 1). 100 parts by mass of the copolymer was mixed with 40 parts by mass of glycidyl methacrylate, and the mixture was re-precipitation with purified water, filtered, and dried to obtain an acrylic resin (P5), which is a polymer containing a radically polymerizable monomer.

[0158] Synthesis Example 7: Synthesis of Quinone Diazide Compounds Under a stream of dry nitrogen, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 5-naphthoquinone diazidosulfonylic acid chloride were dissolved in 450 g of 1,4-dioxane and allowed to rise to room temperature. To this, 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise, ensuring that the temperature in the system did not exceed 35°C. After addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitated material was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain quinone diazide compound 1, represented by the following formula.

[0159] [ka]

[0160] <Thermo-crosslinking agent containing epoxy groups> TEPIC-VL; “TEPIC” (registered trademark)-VL (an epoxy thermal crosslinking agent containing an isocyanuric ring structure, the compound shown in the chemical formula below, manufactured by Nissan Chemical Industries, Ltd.)

[0161] [ka]

[0162] <Heat acid generator> BTS; p-toluenesulfonate butyl (a thermal acid generator having a sulfonic acid ester structure but not satisfying formula (2), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) F1; 1,3-propanediol di-p-toluenesulfonic acid (a thermal acid generator having a sulfonic acid ester structure and satisfying formula (2), manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) F2; 1,4-Butanediol dimethanesulfonate (a thermal acid generator having a sulfonic acid ester structure and satisfying formula (2), manufactured by Tokyo Chemical Industry Co., Ltd.)

[0163] [ka]

[0164] <Solvent> PGME; Propylene glycol monomethyl ether GBL; γ-Butyrolactone Example 1 Under a yellow light, 100g of (P1) obtained in Synthesis Example 2 was weighed as component (A), 65g of (P3) obtained in Synthesis Example 4 as component (B), 25g of (P4) obtained in Synthesis Example 5 as component (C), 20g of quinone diazide compound 1 obtained in Synthesis Example 7 as quinone diazide compound (D), and 15g of TEPIC-VL as a thermal crosslinking agent. These were then dissolved in 1823g of PGME and 203g of GBL. The resulting solution was then filtered through a 1μm pore size filter to obtain positive-type photosensitive resin composition A. The evaluations described in (1) to (6) above were performed using the obtained positive-type photosensitive resin composition.

[0165] Examples 2-19, Comparative Examples 1-7 Using the same method as in Example 1, positive-type photosensitive resin compositions B to S and positive-type photosensitive resin compositions a to g were obtained using the types and amounts of compounds as shown in Tables 1 and 2. The obtained positive-type photosensitive resin compositions were used to perform the evaluations described in (1) to (6) above.

[0166] The compositions and evaluation results of the examples and comparative examples are shown in Tables 1 and 2.

[0167] [Table 1-1]

[0168] [Table 1-2]

[0169] [Table 2]

[0170] Examples 1 to 19 all yielded good results in terms of sensitivity, bending resistance, reliability of the organic EL display device, heat resistance, development adhesion, and pattern linearity. In contrast, Comparative Example 1, which did not use component (A), showed inferior reliability and heat resistance. Comparative Examples 2 and 7, which had a high concentration of component (C), showed inferior development adhesion. Comparative Example 3, which had a high concentration of component (B), showed inferior heat resistance. Comparative Examples 4 and 6, which had a low concentration of component (B), showed inferior bending resistance. Comparative Example 5, which did not use component (C), showed inferior sensitivity.

[0171] Example 20 The thermal decomposition products of the cured photosensitive resin composition O were analyzed using the method described in <Compositional Analysis by Reaction Pyrolysis GC / MS> above. The analysis results show the structures obtained in the cured product, with peaks attributed to the structure shown in formula (3) (1015-1025 seconds), peaks attributed to the structure shown in formula (4) (1335-1345 seconds), and peaks attributed to the structure shown in formula (5) (1860-1870 seconds).

[0172] [ka]

[0173] These results confirm that the cured product of the photosensitive resin composition O contained compounds represented by formula (3), formula (4), and formula (5), and that the peak intensity ratio of the detected compounds was 0.5 for the compound represented by formula (3) and 1 for the compound represented by formula (5), with the compound represented by formula (4) being set to 1. [Explanation of Symbols]

[0174] 1: Circuit board 2: TFT 3: TFT insulating layer 4: Wiring 5: Flattening layer 6: Contact Hole 7:First electrode 8: Pixel splitting layer 9: Organic EL layer 10:Second electrode 11: Glass substrate 12:First electrode 13: Auxiliary electrode 14: Pixel division layer 15: Organic EL layer 16:Second electrode

Claims

1. (A) one or more selected from the group consisting of polyimides, polyimide precursors and copolymers thereof, (B) one or more selected from the group consisting of polybenzoxazoles, polybenzoxazole precursors and copolymers thereof, (C) polyhydroxystyrene and / or copolymers of polyhydroxystyrene and polystyrene, (D) quinone diazide compounds, (E) solvents, and (F) a thermal acid generator. The content of component (B) is 10 to 100 parts by mass per 100 parts by mass of component (A), The content of component (C) is 1 to 90 parts by mass per 100 parts by mass of component (A), A positive-type photosensitive resin composition wherein the (F) thermal acid generator contains a compound represented by formula (2). 【Chemistry 1】 (In formula (2), R １５ R is a divalent to tetravalent group with 1 to 10 carbon atoms. １６ Each of these independently represents an alkyl group having 1 to 10 carbon atoms, which may have substituents, or an aryl group having 6 to 20 carbon atoms, which may have substituents. Examples of substituents include hydroxyl groups, halogen atoms, cyano groups, vinyl groups, acetylene groups, or linear or cyclic alkyl groups having 1 to 10 carbon atoms. (a represents an integer from 2 to 4.)

2. When the content of component (A) is [PI] (mass), the content of component (B) is [PB] (mass), and the content of component (C) is [PH] (mass), The positive-type photosensitive resin composition according to claim 1, wherein the mass ratio [PI] / ([PB]+[PH]) is in the range of 0.5 ≤ [PI] / ([PB]+[PH]) ≤ 5.

0.

3. The positive-type photosensitive resin composition according to claim 2, wherein the relationship between [PB] and [PH] is [PB] > [PH].

4. The positive-type photosensitive resin composition according to claim 3, wherein the mass ratio of [PB] and [PH] is in the range of 1.01 ≤ [PB] / [PH] ≤ 55.

00.

5. The positive-type photosensitive resin composition according to claim 1, wherein the (C) component comprises polyhydroxystyrene.

6. The positive-type photosensitive resin composition according to claim 1, wherein the solvent (E) contains a polar aprotic solvent.

7. The positive-type photosensitive resin composition according to claim 6, wherein the content of the polar aprotic solvent is 1 to 30% by mass relative to 100% by mass of the (E) solvent.

8. The positive-type photosensitive resin composition according to claim 1, wherein the solid content concentration of the positive-type photosensitive resin composition is 3 to 30% by mass.

9. The positive-type photosensitive resin composition according to claim 1, wherein the (B) component comprises a resin having a structural unit represented by formula (1) as its main chain. 【Chemistry 2】 (In formula (1), R １ and R ２ Each of these independently represents a divalent to octavalent organic group with 2 to 30 carbon atoms. p represents an integer from 0 to 4, and q represents an integer from 1 to 4.

10. A cured product obtained by curing the positive-type photosensitive resin composition according to claim 1.

11. An organic EL display device comprising the cured product described in claim 10.

12. (1) A step of applying the positive-type photosensitive resin composition according to any one of claims 1 to 9 to a substrate to form a positive-type photosensitive resin film. (2) A step of drying the positive-type photosensitive resin film, (3) A step of exposing a dried positive-type photosensitive resin film through a photomask. (4) A step of developing the exposed positive-type photosensitive resin film, and (5) A process of heat-treating the developed positive-type photosensitive resin film. A method for producing a cured product containing the following in this order.

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